CEMS

Jointly published by Journal of Radioanalytical and Nuclear Chemistry, Articles,
Elsevier Science S. A, Lausanne and Vol. 202,Nos 1-2 (1996) 103-199

Akad~miai Kiad6, B udapest
Review
APPLICATIONS OF CONVERSION ELECTRON

MOSSBAUER SPECTROMETRY (CEMS)
K. NOMURA,* Y. UJIHIRA,**A. VI~RTES***
*School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-Ku, Tokyo 113 (Japan)
**Research Centerfor Advanced Science and Technology, The University of Tokyo,
Kamaba-4-6-1, Meguro-Ku, Tokyo 153 (Japan)
***Department of Nuclear Chemistry, E6tv6s Lor6nd University, H-1518 Budapest 112, P.O. Box 32 (Hungary)
(Received March 13, 1995)
Contents
II. Instrumentation for Conversion Electron M6ssbauer Spectrometry (CEMS) 105

A. Methodology 105
B. Integral CEMS 110
1. Probing depth 110
2. Sensitivity 111
3. Detectors 111
a) Gas proportional counter 111
b) Parallel plate avalanche counter 114
c) Gas counter for low temperature 114
d) Gas counter for high temperature 115
e) Electron multipliers 116
f) Scintillation detector 117
C. Combination of CEMS, XMS and TMS 117
D. Depth Selective CEMS (DSCEMS) 119
1. Electron energy spectra 119
a) Proportional counters 119
b) Electron spectrometers 120
2. Electron energy spectrometers 122
3. DSCEMS analysis 124
4. Glancing Angles CEMS (GACEMS) 125
5. Low energy electron 57Fe MOssbauer spectrometry (LEEMS) 128
Ill. Applications of CEMS 131

A. Corrosion of steel 13I
1. Basics of corrosion products 131
2. Wet corrosion study by CEMS 134
3. Passive films I36
4. Environmental corrosion of weathering steel 136
5. Thermal corrosion 137
B. Surface finishing of steel 137
1. Phosphating of steel 137
2. Oxalating of steel 140
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K. NOMURA et al.: APPLICATIONS OF CONVERSIONELECTRON
3. Nitriding of steel 140

4. Boronizing of steel 141
5. Galvanizing of steel 142
6. Carbnrizing of steel 144
C. Metal alloy and amorphous alloy 144
L Metal alloy 144
a) Ni/Fe alloy 144
b) Fe/Ti alloy 144
c) Other crystalline alloys 145
2. Amorphous alloy 146
3. Hydrogenation 148
4. Surface improvement by laser irradiation 148
D. Artificial oxide films 150
1. Oxide films of single crystal 150
2. Polycrystalline oxide surface 156
a) Perovskite oxide 156
b) Surfaces of other oxides 156
E. Ultra thin films and multilayers 158
1. Magnetic order in ultra thin films and their interfaces 158
2. Langmuir-Blodgett layers 162
F. Surface and interface reaction 162
G. Ion implanted layers 164
1. Fe ion implantation 165
a) In semiconductors and metals 165
b) Fe ion implantation in ceramics 168
2. Other ion implantations in iron and steels 169
a) N ion implantation 169
b) B ion implantation 172
c) C ion implantation 172
d) P ion implantation 174
e) AI ion implantation 175
f) Ti ion implantation 176
g) Ni ion implantation 176
h) Si ion implantation 177
3. Ion beam mixing (irradiation effect) 177
a) AI/Fe layer ~77
b) Cu/Fe layer 179
c) Ni/Fe layer 179
d) Pd/Fe layer 179
e) Zr/Fe and the multilayers 179
f) Irradiation effects in metals and alloys 180
g) Irradiation effects in metal and ceramic interface 150
h) Irradiation effects in polymers 180
H. ngSn CEMS 181
1. Metal and alloy films 181
2. Oxide film 182
3. Ion implantation and ion beam irradiation 184
I. CEMS using other nuclei 186
J. Other applications of CEMS 186
1. In-beam M6ssbauer spectrometry 186
2. Source experiment 187
IV. Summary 187
References 157
104
K: NOMURAet al.: APPLICATIONSOF CONVERSIONELECTRON
Since Rudolf L. Mtssbauer found the phenomenon of recoil-free T-ray resonance

absorption by the ~91Irnucleus in 1958,1,2 the Mtssbauer effect has been applied in many fields
such as physics, chemistry, material science, mineralogy, metallurgy, biology and So on, and
M6ssbauer spectrometry has now become one of the most powerful nuclear analytical
methods, providing unique information about magnetic, electronic, and lattice properties of
solid Mtissbauer spectrometry (TMS) has been used commonly to get the bulk information
for solids since the discovery of the Mtssbauer effect. On the other hand, scattering
experiments, carded out by detecting '/-rays,i X-rays and electrons re-emitted after the
M~ssbauer effect, have proved to be useful for non-destructive surface analysis of solids.
Among the scattering mode techniques, conversion electron Mtissbauer spectroscopy (CEMS)
has been considerably developed and frequently used because it provides information on solid
surface layers. The depth information on solid surface layers obtained by CEMS depends on
the energy of electrons detected. If electrons re-emitted after the MOssbauer effect can be
detected with a highly resolved electron energy spectrometer, the thinner layer on the surface
can be analysed layer by layer. This method is called depth selective conversion electron
M~ssbauer spectroscopy (DSCEMS). However, the efficiency of detection of electrons in
DSCEMS is small, and the system requires careful energy analysis in a high vacuum chamber
and needs a long measuring time. The applicatio n of DSCEMS has so far been limited to the
analysis of solid surfaces containing enriched M6ssbauer isotopes such as 57Fe. The most
frequently used CEMS technique is integral CEMS (ICEMS) because M/Sssbauer spectra of
surface layers of materials containing a 2% natural abundance of 57Fe can be obtained by
detecting all electrons without discrimination of electron energy and, without a strong "/-ray
source. The term ICEMS is used only when it is to be distinguished from DSCEMS. CEMS has
also been called Resonant Electron Mtssbaner Spectroscopy (REMS). However, CEMS is
used in general.
The applications of CEMS techniques have increased steadily in various fields for last
15 years. Most references concerning CEMS and its applications can be found in the
"Conversion Electron Mtssbauer Spectroscopy Handbook". 3 However, the handbook does not
contain the contents of the papers, but a list of all papers published up to 1982. The number
of publications of CEMS studies reached about a hundred a year recently. 4
There are many books useful for learning the general principles of the Mt~ssbauer
effect.5,6,7,8.9.1~ There are many articles reviewing the applications of CEMS to each
field. I1,12,I3~4,15 A book on Mtssbauer studies of surface layers, t6 concerning theoretical and
practical problems of the use of Mtssbauer spectroscopy for studying solid surfaces, its
applications, and development, was published~recently. An International Conference on the
Applications of the M/Sssbauer Effect has been held every two years and the recent
proceedings have also been published in Hyperfine Interactions.
We have surveyed both the references published in the last decade and those previous
papers, Considered to be important for understanding the principle of CEMS and the further
development of the applications of CEMS, so as to be helpful especially for researchers
intending to begin CEMS studies from now.
II. INSTRUMENTATION
FOR CONVERSION ELECTRON MOSSBAUER SPECTROMETRY
A. Methodology
The measurement system of the M6ssbauer effect is composed of 7-ray source, acceleration
driving devices coupled to a controller, absorber, detector, multichannel analyser and computer
for accumulation of data. For example, 57C0, ~19mSnand ~3~Sm are used as typical '/-sources
105
K. NOMURAet al.: APPLICATIONS OF CONVERSION ELECTRON
for 57Fe, 119Sn and 151Eu Mbssbauer spectrometry, respectively. The decay scheme of the "/-ray
source leading to 57Fe is shown in Fig. 1. Source matrices need to have Debye-Waller fractions
close to 1, narrow resonant line widths and neither quadrupole interactions nor magnetic
interactions. On the basis of the geometrical arrangements shown in Fig. 2, the methods for
measuring MSssbauer spectra are divided into three categories as follows. Transmission
M6ssbauer Spectrometry (TMS), Emission MSssbauer spectrometry (EMS) and Scattering
57Fe ( i 4 . 4 k e V )
57~ l.Tm
\
~i00%
57Co 270d
5/2 -
3~/2 ~Complex /99.84%,

- 366.8
3/2. i4.4
1/2- i 7~1
S~Fe
Fig. 1. Energy of radiations: YM;14.39 keV, 71; 122.0keV, Y2; 136.4keV, gab; 6.5 keV, Half-life ?M; 9.8 9 10-s sec,
conversion coefficient?M;9.00, isotopic abundance;2.19%, magnetic moment ground state; +0.09024 nm,
magnetic moment excited state;4).154 nm, quadmpolemoment3/2 state; + 0.285b,resonar- .ross section;
2.43- lif t8 cm2, natural width; 4.655.10-12 keV, velocity width; 0.09699 rmn/sec, and recoil energy;
1.951. 10-3 keV (from Ref. 4)
Mbssbauer Spectrometry (SMS). The SMS can be further subgrouped into three methods,
SGMS, XMS and CEMS, which are discriminated by the scattered radiations detected -,/-rays,
X-rays or electrons - after resonant "/-ray absorption.
MSssbauer parameters obtained by SMS are inherently the same as those developed for
conventional TMS. The resonance peaks appear by energy transitions of the 57Fe atomic
nucleus between the excited state (nuclear spin: I = 3/2) and the ground state (I = 1/2). The
hyperfine structures observed are due to the electron states, electric quadrupole interaction and
magnetic dipole interaction around '/-ray resonance nucleus as shown in Fig. 3. Isomer shift
(IS) comes from interactions between the nucleus and electrons accommodated in the ls
orbital. The electrostatic energy of a nuclear level shifts due to the variation of electronic
charge density around nucleus. Quadrupole splitting (QS) arises from the interaction between
an electric field gradient (EFG) and nuclear quadrupole moment, eQ. Magnetic splitings due
to the interaction between magnetic moment and magnetic fields (H~,) are also observed. The
relative intensity ratio of sextet p e ~ s observed in the CEM spectrum of iron is different from
that in the TM spectrum because the magnetic moments in the bulk and the surface are
generally at random and parallel to the surface, respectively.
106
K. NOMURA et al,: APPLICATIONS OF CONVERSIONELECTRON
(a) (c)
> !..r..,.a.,.Y.~-I 7 ray <~> 7 ray
Source [;i;;,t!~;,#,:;i:~i!;:?;2;!~:i: i i} ~ , r a v
Source L_J Detector
Sample
(b)
II Xray I
<__>';'ray ~-] 7ray
< ............
ZZII.~ .................
> .........................
~ .................~ Sample
Source Detector Source II 1...1..e_
~ r Detector
+Sample Standard
Absorber
Fig. 2. Arrangement of equipments for MOssbauer spectromelry. (a) Transmission mode, (b) emission mode,
(c) scatteringmode: scatteredresonance7-rayor X-ray detected,and (d) 2 ~rbackscatteringmode: conversion
electrons or X-ray detected
The inner conversion process in the excited iron nucleus Iv is shown in Fig. 4. The
conversion efficiency (c~: the emission probability ratio of conversion electrons and scattered
y-rays) is 8.5, and the conversion efficiency of K shell electrons is 7.6. Therefore, K shell
electrons are produced with the probability of 0.8 ( = 7.6(8.5 + 1)). The energy of K electrons
is 7.3 keV, which is the y-ray energy (14.4 keV) minus the binding energy (7.1 keV). In the
process, transition of electrons from the L shell to the K shell is followed by the emission of
K X-ray and Auger electrons. As the fluorescent efficiency (mE) of the K X-ray is 0.34, the
probability of the K X-ray is 0.27 ( = 0.8 - 0.34) and the energy is 6.4 keV. The emission
probability of 5.4 = 5.6 keV (KLM) and 6.3 keV) (KLM) Auger electrons is 0.53 ( = 0.8 9
9 0.66). Therefore, K inner conversion electrons, Auger electrons, K X-rays, and resonant
y-rays are produced with the probability of 80%, 53%, 27%, and 10%, respectively. Total
probability of 57Fe resonant electrons reaches 133%9 The occurrence of 1198n (0~ = 5.2) is
ahnost the same as that of STFe and each probability is also shown in Fig. 4. The total
probability of u9Sn resonant electrons is 159%.
The statistical quality of TMS, XMS, and CEMS measurements depends on the thickness
of iron as shown in Fig. 5. H,~8 The detection of, electrons is advantageous for iron samples
less than about 500 nm in thickness. Thick samples between 0.4 and 4 Ixm can be effectively
measured by XMS, and TMS or SGMS is advantageously applied to samples thicker than
4 I.tm. CEMS provides information on thin solid layers less than 300 nm thickness, whereas
SGMS and XMS give the information of thick surface layers about 20 txm and 10 I.tm in
thickness respectively. The experimental line width increases with the increase of effective
thickness of the absorber. However, the line width is relatively narrow in CEM spectra as
compared with TM and XM spectra.
.On the basis of the report'by GANCEDO et al.} 9 the advantages and disadvantages of STFe
ICEMS methodology can be summarized as follows.
107
K. NOMURAet al.: APPLICATIONSOF CONVERSIONELECTRON
/iEq=+ e2qQ
b 6 ----~
4=a 4.a
8 o ! :
0
Velocity 0 Velocity
: H,n//Vzz m
--:3/z
Is . Qs
~ . Q 3/z / -.-----W~-"-'---~ -1/2
I-3/2 ............ #::17.. . . . . . . . t/2
= " S o u r c e " Absorber "- Magnetic F i e l d -1/a
g -A5 _, go-g.,_
"- "'=i g " - " I -'-i g~ ":! g.+/kEq-~ g,=~/z~~
1 1 ,
,, ,,
8 [ ,: o=Zlz:H
I P~ , ~[ P~
-.ab.- Velocity
6
Fig. 3. Energystates of 57Fenucleusin the excited (I = 3/2) and groundstates (I = 1/2) and M0ssbauerspectra
(I) Advantages
(1) The penetration depth for 7.3 keV K-conversion electrons is below 300 nm and the
energy lost in about 5 nm is negligible.
(2) The approximate energy distribution function for electrons related to depth and detection
angle with energy can be calculated.
(3) Electrons are very easy to detect efficiently.
(4) Non-resonant electrons from the photoelectric effect can be differentiated.
(5) The line widths of resonant peaks do not depend so much on the thickness of thicker
samples and the saturation of peak intensity is not observed.
(6) The intensity ratio of magnetic split peaks obtained can yield effective information on
the configuration of magnetic spin in the surface layer.
(II) Disadvantages
(1) Compton scatterin and the phbtoelectric effect produce "non-resonant electrons".
(2) Loss of electron energy in their passage through matter cannot be calculated.
108
K.NOMURAetal.:APPLICATIONSOFCONVERSIONELECTRON
14.4keV Tray
10% ?.~keV K electrons
STCo 6keVI{I,L Auger

r a y l O 0 % ~ ~
14.4keY
27% 6:3keVXray
23.8keV T ray
N 16% 9
~ 1 9 . 8 k e Y L elecf~rons
~fray 100%,~
23.8keY ~?
rays 84%
75% 2.8keV Auger
9%3.6keg Xray electrons
Fig. 4. Inner conversion process after M0ssbauer Effect of 57Fe and UgSn nuclei
..._. 7 - ~ " ~ .
lO-I
_ ~ . / \ \
I-i
t~
o ,, -
i0-~ -.1 ~I.-~-~' . / \ ~
,,-I
Gr
lO-- <i. \
/
lO-4 I I 1
10 10z 103 10~ 10~-
Iron Film Thickness (nm)
Fig. 5. Comparison of the statistica quality Q of the 57Fe M6ssbauer spectra for iron measured with the detection
of scattered y-ray, X-ray and electron with Q values calculated from the formulas derived in [Ref. 18],
(from Ref. 11)
109
(3) Electrons do not move through matter in straight lines.

(4) Only windowless detectors may be used.
(5) Magnetic split peaks of complex CEM spectra do not always follow the constant
intensity ratio. Some fitting must be done on the some assumption.
B. Integral CEMS
1. Probing depth
Using various thick Fe films prepared on stainless steel,THOMAS et al) ~ showed that
65% of total resonant electrons come from a surface thickness of 60 nm and that 96% come
from a thickness of 300 rim. LILJEQUIST zt made a theoretical analysis of contributions to
the relative.signal for stainless steel in the experiments of THOMAS et al. Contributions of
Auger, K-conversion, L-conversion, X-ray photoelectron (XPE), and X-ray photoelectron
(XPE) are shown in Fig. 6, 'a as a function of depth. It is clear that almost of all Auger and
K conversion electrons are emitted from about 100 nm depth. Using the assumption that
eleclron attenuation in a surface film follows a simple exponential law, BA1NBRIDGE
(1975) n produced a quantitative treatment of CEM spectra for a duplex oxide film grown on
pure iron. The effective mass absorption coefficients for the attenuation of 7.3 keV electrons
are 2.5.104 cmZ/g in pure iron2~ and 1.1.104 cm2/g in iron oxides z3 and the attenuation
coefficient for 5.4 keV electrons is 1.73.104 cm~/g in iron oxides. 23 A relationship between
oxide thickness and relative spectral area was established by GRAHAM et al (1978). 24
Electropolished iron substrates were oxidized at 513 K in 0.66 Pa oxygen. Using magnetite
films of thicknesses between 26.5 and 425 nm, the following relationship was deduced:
d(nm) = 1.95 9 102 In (1 - 0.01P)
where d is the oxide thickness and P the percentage of Mtssbauer peaks due to oxide.
1.0- Iss/Itot
o
4~
\~Auger
~
~0.5-
,x:l
"~ K cony. \ \ ~
L conv.~ . . . . .
>.dFo
5'0 16o (~)
Depth
Fig. 6. Contributionsto the relative stainlesssteel signal in THOMAS et al. e• (Ref. 20), according to the
Liljequist theory (From Ref. 21)
110
K. NOMURA et al.: APPLICATIONS OF CONVERSION ELECTRON
The probing depth is determined by the escape range of conversion electrons, Auger
electrons and secondary electrons in the absorber. The range of low energy electrons (1-10
keV) in a solid can be estimated using FELDMAN's expression2s as follows:
R = 25(A/p Z"a)E~
Where n = 1.2/(1 - 0.29 log Z), E is the electron energy (keV), R is the range (nm), A is
the atomic or molecular weight, Z is the atomic number or electron number/a molecular, and
p is the density (g/cma). This expression is convenient for estimating the maximum thickness
of various samples that can be observed by integral CEMS techniques. A theoretical analysis
on ICEMS of natural iron absorbers was proposed, 26 and the resonant emission of secondary
electronsa7 and the changes of internal conversion coefficients for the M1 transitions in ions2s
were considered and the weight functions for ICEMS 29 were determined.
2. Sensitivity
An attractive feature of CEMS is its high sensitivity. Typical isotopes for the CEMS
technique are listed in Table 1. H The lowest quantities are 1014 atoms, cm -2 for SVFe, 1015
atoms, cm -2 for ngSn, and 1016 a t o m s , cm -2 for ~SaEu. The sensitivity depends on nuclear,
atomic and solid states. The maximum magnitude of the resonance ~/is given by the following
expression t~ for thin single line scater.
No - N~ 1 a ~o
N= <rl=~fJan l+a
where N= and N are the count rates at non-resonance and off-resonance, respectively, f~ and
fa are the recoilless fractions for the source and the absorber, t~ is the internal conversion
coefficient, 6o is the resonant absorption cross section, ~ is the photoeffect cross section and
n is abundance of the resonant isotope. In practice, the observed magnitude is smaller than
q. The non-resonant background is Caused by secondary electrons, produced by non-resonant
y- and X-rays scattered from the counter and samples as weli as high energy 7-rays. As seen
in Table 1, 57Fe and ttgsn CEMS can be easily performed. Since t51Eu nuclei have high inner
conversion efficiency, ~5~Eu CEMS is more useful than aSaEn TMS. The S/N ratios of
MSssbauer spectra are improved by filtering out low energy X-rays and "/-rays, for example,
with 2-3 rnm of Lucite for 57Fe, 25 gm of Pd for H9Sn, or 2 mm of Cu for 197Au.
3. Detectors
The detectors normally used for CEMS are divided into the two typical types of gas
counter and electron spectrometer. Many kinds of detectors have been developed for different
purposes: ICEMS, DSCEMS, low temperature CEMS, and high temperature CEMS.
a) Gas proportional counter
TERRELL and SPIJKERMAN (1968) made a simple and excellent proportional counter
for CEMS and XMS. 3~ Many proportional counters have been designed specially for CEMS
and XMS 3~ and SGMS. 32 A back-scatter 2re gas proportional counter has high detection
efficiency for low energy electrons of about 10 keV. Since He gas is insensitive to incident
X-rays and 7-rays, CEM spectra are acquired easily in flowing He + CH 4 gas. XMS spectra
also can be obtained by changing to an Ar + 10% CH 4 flow-gas mixture. It is necessary to
place a Lucite plate (2 mm thick) in front of the incident window to reduce the detection of
X-rays emitted from the 7-source, and to count the 6.3 keV resonance Fe X-rays.
111
K. N O M U R A et al.: APPLICATIONS OF CONVERSION ELECTRON
o o o o O o o o o
~ 0
< ~ ~gg
<
g gg~g g
CN E
O= o
g g d d ~
db d ~g d .g~
m m
4 2 ~g
~ ~ eg g ~d 4m ~
0 ~
"~ >
9,-t 0
o ~ xx O 0 0 0 ~ O O C O 0 0 0 0 ~ O 0
~ ~
C
0
r ~ CO
:0
0 ~ N
~ 0
~ m
~D 0
9 0 " , 0 . . . . . O
<
m 0
112
The operating voltage depends on the diameter of amode wire, the distance between the
anode and sample cathode in counter body, the gas pressure and the percentage of quenching
gas included for a proportional counter. The large volume of this gas flow detector makes it
unsuitable for detecting STFe conversion electrons because the range of 7.3 keV electrons in
He gas is at highest 5 ram. A typical and simple gas flow detector for STFe CEMS is shown
in Fig. 7. 33 One face of the sample inside the counter acts as the cathode. A higher utility rate
was achieved from a counter with a single wire housing than with a multiwire housing. ~4"~s
The fraction of the background noise due to the 122 and 136 keV T-rays was 65% in the
energy region 2-5 keV. 36 The improvement of reflection efficiency and S/N is of most
importance for shortening measuring time. The sensitive area of sample is near the anode
wire. The higher applied voltage reduces S/N by increasing detection of nonresonance
electrons from the counter wall. Starting from the theory of phenomena in gas detectors under
space charge conditions, a general expression for the multiplication factor was obtained. 37 The
operational maximum range of the gas Counters used in CEMS is at the border between the
proportional counter and Geiger-Miiller domains.
When resonance electrons of enriched STFe samples are selected with a small energy
window, the shape of resonance lines sometimes become asymmetric. It is due to the gain
o10 z,0 3o 4o.

oNol
t $gas
fF
Yray ~e ~II I
Fig. 7~A back scattered type of gas flow counter for CEMS. A: gas inlet and outlet, B: anode, C: W anode
(0 30 p.m), D: holes for gas, E: AI body, F: H.V. connector, G: A1 window (15 ~tm thick), H: sample,
i: screw, J: supporter (from Ref. 33)
113
shift of gas multiplication after the count rate increased drastically on resonance. Further,
attention should be paid to the ohmic contact between counter body and sample in practice
because the charging of the sample affects the electric field in the counter in a long
measurement. An electrically conductive film, such as thin carbon, must be applied to an
insulating sample. The properties of the gas scintillator were used to detect electrons for
CEMS by VARTANOV and ZEMSKOV. 38 However, the measuring system is less effective
than gas multiplication.
b) Parallel plate avalanche counter
A parallel plate avalanche counter (PPAC) has been developed for CEMS. sg,4~ A flat
plate of graphite is used as the anode for working in the avalanche region. In PPAC, any
organic polyatomic gas can be used as the counting gas, acetone vapour being preferred
normally.42 Powder samples dissolved in ketone were painted on copper plate and
were measured using a PPAC filled with ketone gas. The advatltage of this counter is that an
insulated sample can be measured by CEMS, albeit without energy selection of the emitted
resonance electrons. All resonance electrons detected could give the higher S/N. The utility
of the PPAC for lJgSn CEMS was demonstrated.43 A gas filled resonance counter equipped
' with enriched 57Fe stainless steel microfoil provides the highest S/N. 44 It was applied to low
and intermediate energy M0ssbauer transition45 and to selective double excitation. 4~
c) Gas counter for low temperature
Mtssbauer measurements at various temperatures give many types of information. It is
desirable to measure CEM spectra at as low temperature as possible. Pure He gas and He gas
mixtures with 5% quenchers of H 2, N 2, CH 4, and CO can be used at 77 K by placing a gas
8
(a) ? -
- (b?-J .",
X : "'~
4 " \\
onv22 \
f l
O0 4 8 12 16
Energy (keV)
Fig. 8. Pulse height spectra recorded at 100 K using Ar + 5% CH4 (a) on and (B) off resonance,and He + 5% CO
(c) on and (d) off resonance (from Ref. 48)
114
I-I. V .
A , 5.
A i i.-:*, t
7r
!,~4-
!lX_z,0 =
~CEMS. . . . ~S
Fig. 9. Gas tlow proportional detector designed for simultaneous measurements of CEMS and XMS at 150 to
300 K. A: anode, B: carbon coated thin film, C: sample, D: Cu rod, E: shelter (Pd+ Cu) (From Ref. 49)
counter inside the cryostat normally used for TMS. The most stable speration was achieved
with He + 5% CO at 77 K. 47 A gas flow counter, set outside cryostat, could be operated at
100--400 K. 4s,49The pulse height spectra recorded at 100 K are shown in Fig. 8.48 NOMURA
and UJIHIRA also designed a gas flow proportional counter with two separated cells for
simultaneous measurement of CEMS and XMS at 100-300 K in 1986 as shown in Fig. 9. I n
this type of counter, it was hard to control the temperature precisely and to keep it constantly
low for several days. KASTNER et al., 50 and KAMZIN et al: 1~2 also developed a dual
chamber proportional counter for CEMS and XMS in the temperature range 100-700 K. It
was easy to achieve the operation at liquid N 2 temperature. However, at lower temperature
than liquid N 2 temperature, it was not easy to keep the gas-filled counter working stably
because of the tendency of impurity or quenching gas in He to condense. Recently
FUKUMURA et al. developed a gas counter which could be operated at various temperatures
down to 15 K as shown in Fig. 10:3e435 The purified He, Ne, H e + 5 % N 2 or H e + 10% CO
made it possible to operate a proportional counter at low temperatures between 15 and 300K,
though gas multiplication decreased with lowering temperature and the proportional counting
region of applied voltage became narrow. A cryogenic gas counter for CEMS can be made
to operate even under strong magnetic fields: 6
d) Gas counter for high temperature
In the initial stage of developing a gas cou/ater for high temperature, a gas chamber was
insered into an electric furnace: 7 INABA et al. (1981) 57 made a high temperatm'e gas flow
counter with the sample heated up to 740 K. The sample was heated by a "hot finger" while
the detector body was kept cool. 59 A different type of gas counter with a halogen lamp heater 60
were made in order to heat the samples only. This type of heated gas counter can work well
only below 600 K. The higher temperature the gas counter is operated at, the smaller the
recoilless fraction, the more reactive is the quenching gas to the surface of sample, and the
higher the thermal electron background count. However, gas reactivity was utilized in a study
of the gas sensing mechanism of sensor materials because various flammable gases could be
used as a quenching gas by including them in the He counting gas: 1
115
Compressor
He Gas
Vacu~
Fig. I0. C_o,ostat and counter assembly. 1: Cooling water for the compression; 2: pressure buffer balloon;
3: pressure gauge; 4: valve for heat exchanging helium gas; 5: bellows (vibration absorber); 6: expansion
engine; 7: insulation flange; 8: connector for signals and high voltage bias; 9: vacuum valve; 10: counter
gas inlet; 11:5 mm diameter SU8 tube for signal and high voltage lead; 12: heat exchange space filled
with helium gas; 13: proportional counter; 14: $HV connector for HV bias; I5: counter room; I6: copper
radiation shield; I7 and 18: heater and thermocouple for controlling temperature; 19: windows;
20: vacuum space; 21: outer vacuum jacket; 22: 57Co source for CEMS; 23: velocity transducer for
CEMS; 24: counter body; 25: anode wire (30 I,tm gold-coated tungsten wire); 26: specimen (a sm"nple
foil for CEMS measurements or 5vCo source for examining the counter operation); 27: collimator
(2 mm thick lead p~ate); 28: absorber (3 mm thick Lucite plate) (from Refs 53-55)
e) Eleclron multipliers
Channei electron multipliers such as the c h a n n e l m m and the channelplate s2 have i n h e r e n t l y
no energy resolution, end require a v a c u u m chamber. The channel electron multiplier has been
used for [CEMS at low temperature, S A W I C K I and his group have develeped the convenient
detectors using channel elecU'on multipliers. 6~ The typical detector for CEMS operated at low
temperatures between 4 arid 300 K is shown in Pig. 11 64 The sample and the channel electron
multiplier m'e installed in a sideways scattering geometry and cooled together either by using
a conventional Dewar or by inserting a detector chamber into a liquid He or iiquid N 2
container. A T K I N S O N and C R A N S H A W ~ consmacted the same detector so that the electrons
1!6
are quided away from the specimen by a controlling electric field, and enter the channeltron
with the optimum energy for detection. Count rate and spectra quality depend on geometry
and a properly shaped and graded collimator. The efficiency of channel electron multiplier
increased three times by coating the cone with MgO because the normal efficiency was about
10%' for several-keV electrons. 6~
Source | ~'~&-~ f ,Multiplier
7 ---Sample
vH:cguhUmHea~er-~ Cooling
"Block
icm
Fig. l 1. A configuration for lhe measurements of CEM spectra between 4 and 400 K (from Ref. 64)
f) Scintillation detector
The increase of the detection efficiency is a major consideration for CEMS in high
vacuum. A extremely 10w noise scintillation detector (SCD: Hamamatsu R1635-02 or R2557
photomultiplier with P-47 thin-layer phosphor) was used to detect several-keV electrons in
high vacuum as shown in Fig. 12. 67 The electron energy spectra of an 90% enriched STFe foil
are shown in Fig. 13. 67 The SCD is superior to the channeltron by one order of magnitude.
There was greater improvement achievable for samples with normaI isotope abundance than
for enriched ones. 67 SCD is advantageous for an electrostatic cylindrical mirror analyzer even
for DSCEMS 6~ although cooling is necessary in order to reduce the noise of the
photomuRiplier. UHV-ICEMS e• 69 were peffolTned under high vacuum. SCD is more
useful for lower temperature performance because the background count of the photomultiplier
can be further reduced2 ~ The performance of a channeltron and a low-noise SCD for
UHV-ICEMS applications was compared on the basis of measurements on different
samples. 7t,7z Criteria, limitations and possible improvements in high-performance M6ssbauer
spectroscopy, were discussed in assessing the different types of detectors in -racuum such as
channeltron, P-47 CsICl'I), and plastics. 73,74The channeltron provides higher performance due
to the substantial conMbufion of low energy (50-100 keV) electrons to the MiSssbauer spectra.
SCD is not sensitive to electrons of energy less than about 3 keV.
C. Combination of CEMS, XMS and TMS

A detector assembly combined with two proportional counters, designed for CEMS and
XMS, has been developed since 1974. 75 The detector was equipped with retard electrodes in
117
IW and signal
Cooli.ng feed-through
.\ H ~ ~ H ~ ~HU\HV~Chamber
. . . . .
Photomult~~'~!]
P h 6 t o m u l t i p l i e r H~"~[J:}U ~+---Turnable
(ttamamatsu ~[fi~.]] fl s h u t t e r
~:cl~uur:.l~ig~r
gg~~QuaQuartz disc
P-47 grafns Al-film

Fig. 12. A schematicdrawing of the scintillationdetectorunit (fromRef. 67)
A S e i n t i l l a t i o n Detector
OChanneltron
' ' ' ' K-Conversion
4C
KLL Auger
A
20
0 I I I I I I I I
3 4 5 6 7 8
(keY)
Fig. 13. Electron energy distributions from an uncovered 57Co source placed into the sample position of the
CMA and using the following eleclron-detector: a) chaaneltron (Valvo X919L); b) scintillation counter
(Hamamatsu R1635-02 photomultiplier, cooled to 243 K, equipped with a P--47 phosphor film with
- 1.5 ~tm average grain size). The count rate values are normalized to 1 at 2.5 keV. The signal amplitude
discriminator levels were set just above electronic noise (from Ref. 67)
118
the XMS sensitive volume so the incident 7- and X-radiation was as low as possible. It is also
possible to reduce the incident 7- and X-ray flux reaching the detector to some degree by
using a thin-waUed chamber for incident y-rays.
Another type of combined counter was constructed as shown in Fig. 14,75 the surface, sub-
surface and bulk of amorphous ribbons were measured simultaneously using a triple combination
,Source [ " i
C~S CEMS TMS
Fig. 14. Experimental set-up for simultaneous CEMS, CXMS and TMS measurement(from Refs 76, 78)
of CEMS, XMS and TMS by GONCER's group. 76,77,78,79,g0,81 The counters for y-rays, X-rays
and electrons were separated and shielded to minimize the mutual perturbation. In order to
shorten measuring time and to find the different states among surface layer, sublayer and bulk,
a combination counter is very useful from the viewpoint of practical measurement.
A combination counter with dual chambers was also used to measure CEM and XM spectra
together with reflection and scattering y-ray M6ssbauer spectra under total exte_mal reflection, s2
D. Depth Selective CEMS

1. Electron energy spectra
a) Gas proportional counter
Many researchers have proposed the feasibility of DSCEMS on the basis of scattered
electron energy distributions obtained with a 2~ gas flow counter. 83,s4,sS.86,s7 However, it was
not easy to accomplish the layer analysis precisely because the energy resolution of a
119
1,0
~, B
.
"x
.4.a
%
0.6
9 .
,,-,4 . 9 ~176
4.-.a
c~
,--4
• -'% \
0.2
5 10 {5
Electron E n e r g y (keY)
Fig. 15. The on-resonance electron pulse-height spectra recorded for a stainless steel scatterer with (A) and
without (B) application of the X-ray--elec~xoncoincidencetechnique (from Refs 88, 89)
proportional counter is too poor to discriminate 7.3-6.4 keV conversion electrons from the
photoelectrons emitted from 6.4 keV X-rays. BARA and B O G A C Z 8~ investigated the
performance of X-ray and e- coincidence for recording 57Fe DSCEM spectra, using a assemble
of He and Ar gas flow proportional counters. The coincidence technique efficiently reduces
the detector background and increases the magnitude of the MSssbauer effect. Spectrum A in
Fig. 15. represents only the K shell conversion electron selected. A reduction of electron beam
intensity caused by X-ray and e- coincidence resulted in a prolongation of spectrum storage
time by a factor of 2.82. A pronounced DSCEM spectra can be achieved both by selecting
the angle of the incident y-ray beam in addition to selecting the energy of the emitted electrons.
Eight DSCEM spectra were simult~teously recorded using a duplex layer of haematite (48 nm)
and magnetite (t92 rim) on a metallic iron substrate. The selected electron energy intervals,
the angles of incident y-rays relative to the normal to the sample surface and the percentages
of the total spectrum, contributed by each phase are indicated in Fig. 1639 The application
of the X-ray and e- coincidence technique for selection of the K shell conversion electrons
can improve the DSCEM spectra.
Proportional counters have a small efficiency for the low energy seconda13, electrons~
whereas channel electa-on multipliers have a larger efficiency for low energy electrons than
for high energy electrons.
b) Electron spectrometers
DSCEM spectra can be obtained in high vacuum by selecting electrons with a certain
range of energy and analyzing them in electrostafc or magnetic fields. BAVERSTAM et al. 9~
proposed in 1973 a method to deterrrfine the shape of line profiles from electrons scattered in
120
K, NOMURAet al.: APPLICATIONSOF CONVERSIONELECTRON
F~O~! 2 a 4 5 6
~,_ ,, . , o . ~.o . L .L .g_ .~.
11q
:eV
101
13,
~eV
10
1384 ~eV
I0
15,
:eV
i0,
15, :eV
lOq
15q
eV
i 0 0 ~ ~ "~" ~
1 1 [ t i !
-I0 -5 0 5 10
Velocity (ram/s)
Fig. 16. The depth selectiveand ang|e sensitiveCEM spectra.A to C recordedby registeringelectronsof selected
energies, C to F recorded at selectedangles of incidence(from Ref. 89)
thin fihus or foils. DSCEM spectra of layers with known thickness and depth (0.3 gm for
57Fe and 3 ~tm for '19Sn) were measured with the use of a [3:spectrometer. The change of the
energy distribution of resonance electrons was determined by BONCHEV et al. 93 The clear
experimental evidence of a sharp resolution in CEM spectra was demonstrated using a high
resolution electrostatic electron spectrometer by SHIGEMATSU et ai.gz
Electron energy spectra associated with the decay of 57Co to 57Fe were measured with an
ellipsoidal mirror analyzer as shown in Fig. 17.93 Spectrum B was obtained after covering the
121
3000 K-Conversion
LXY-Auger
2500-~" KLL-Auger
2oo, f
/I A
~ 1501 i B /l --160eV
~ ooo i L-Conversion
500 onversion
ll2eV ~,~ l
1 1 I I I I --l------- I
-T-"- ",t--&_.k_ ..... ,t -.------b--~--.--I ~,
0 i 2 3 4 5 6 ? 8 9 10 11 12 13 14 15 16
Energy (keY)
Fig. 17. Electron spectra associated with the decay of 57Co to 57Fe measured with an elfipsoid,{1 mirror analyzer.
The spectrum obtained for the 30 pCi 57Co source electroplated obtained after covering the source with
6.2 nm layer of iron (from Ref. 93)
source with 6.2 nm layer of Fe, in which energy loss was characterized due to inelastic
scattering electrons. The energy resolution of the spectrometer was set for 1.2 and 3% at
7.3 keV. The energy distributions from measured Mtssbauer spectra were consistent with
those of the Monte Carlo calculation by LILJEQUIST. 94 The range of depths was determined
by a nondestructive layer-by-layer analysis of materials. 95,96 The energy spectra of 7.3 keV
electrons passing through iron films covered with different thickness are necessary to
determine weight coefficients. High resolution electron spectrometers for DSCEMS cannot be
used for measurements at low temperature because of the low counting efficiency and
complexity.
2. Electron energy spectrometers

In 1961 KANKELEIT 97 employed a magnetic wedge spectrometer for detecting the
30.5 keV K shell conversion electrons generated by 100.1 keV y-transition in ~szW.
MITROFANOV and SHPINEL 98 used a double lens [3-spectrometer for detecting conversion
electrons from 119Sn. BONCHEV et alY~ demonstrated the possibility of energy resolved
DSCEMS with a magnetic solenoid [3-spectrometer. The complicated electron analyzers gave
excellent energy resolution but with a great decrease of luminosity.
Various types of elecU'on analyzer for CEMS have been developed by many
researchers68'99,1~176176176
as shown in Table 2. To compensate for luminosity, electrons have to
be recorded with a poor energy resolution. The forwards scattering geometry is limited to thin
samples. A cylindrical mirror type electrostatic electron spectrometer with a back scattering
geometry 1~176176 was designed and improved to measure DSCEM spectra at 77.3-293 K. 1~176
An ultra high vacuum system for application to DSCEMS, I~176 a magnetic sector
[3-spectrometer,11~and a high transmission orange type magnetic electron spectrometer m were
122
Table 2. Electron energy spectrometers f o r CEMS
Type Energy Detection Sample S/N References year

r e s o l u t i o n e f f i c i e n c y dimension, r a t i o
at 7.3 keV, for
[%] [%] r mm a~-~TFe
150" spherleal
sector 2.0 0.27 lOx4 3 / 92 / (1980)
ellipsoldal
mirror retard,
grid 9 35 5 1 / i01 / (1981)
second order
focusing c y l i n d r i c a l
mirror 0.2-0.5 7 / 104 / (1982)
a double
cylindrical
mlrror-analyser 0.i 3 / i05 / (1984)
mini-orange
magnetic filter 8 2 / 99 / (1984)
cyltndrtcal
mirror 4 7 / 1.03 / (1986)
eylindrlcal
mirror 3.0 6.4 7.3 / 88 / (1988)
retarding field 6 i0 I0 / 114 / (1988)
analyser 4 7 / 113 / (1988)
spheric
electrostatic 2 13 4 / 102 / (1989)
spheric
electrostatic 2.7 8 / 115 / (1990)
iron f r e e
orange type I 20 / 111 / (1990)
magnetic s e c t o r
B -spectrometer 0.7 0.6 lx15 / 110 / (1990)
constructed recently, Microchannel plate detectors were used (energy range from 0 to about
20 keV) so as to m e a s u r e simultaneously a m o m e n t u m range of about 4% with a resolution
of 0,5%. The spin-dependent relative conversion coefficients in iron and iron oxide were
measured.~a
The retarding-field electron spectrometer for D S C E M S ~13 was constructed and improved
so as to allow for energies up to 25 keV and samples with diameters up to 10 ram. H4 T h e
energy resolution could be varied between about 0.1 and 6% and the total transmission was
10% of 2n. The temperature of the sample could be controlled between 25 and 100 K. A thin
iron layer on a stainless steel substrate was measured in a U H V chamber with a base pressure
of 2 . 10 ~ Pa? ~4 A high transmission (14%) spherical electrostatic electron spectrometer was
constructed to work from T = 4 K to 350 K Y 5 However, the experiments at lower than 20 K
were not easy under 1.33. 10 -6 Pa because of the possibility of the s a m p l e ' s being covered
by impurities. H5
To suppress the increased background at high. temperature, the detector w a s s e t at a
negative potential of - 2 0 V and the screening grid at a positive potential o f + 20 V. The
equipment for C E M S was combined with thin film evaporation and a heater to analyse
deposition film at 800 K and under a pressure of 1,33 - 10~ to 10 v paT3
123
3. DSCEMS analysis
SMIT and STAPELE n6 presented an analytical method enabling DSCEM spectra to be
obtained from ICEM spectra and etch experiments as follows.
Weight functions give the probability, that electrons energy loss originates from a certain
depth in the sample. The number of electrons, N(v), that are emitted after nuclear resonant
absorption and counted in a CEM experiment at a velocity v of the absorber with respect to
the T-ray source, can be written as
d
N(v) = ~ T(x)A(x,v) dx
o
Where d is the thickness of the absorber, A(x, v) is the number of nuclear deexcitations
at depth x per unit of depth and T(x) is a response function of the absorber, or weight function.
The function T(x) is composed of two terms. The first gives the chance that conversion or
Auger electrons emitted after a resonant absorption at depth x are detected. The other terms
of T(x) yield the probability of detecting a photon emitted after a MSssbauer nuclear
absorption at depth x. If the thickness of the top layer and the MSssbauer spectrum of the
bulk are known, the MSssbauer spectrum of the layer can be calculated. By repeatedly
removing thin layers from the sample and subsequently measuring the CEM spectrum, a set
of spectra can be obtained, from which it is possible to extract the spectra belonging to the
removed layers.
La, Ga substituted yttrium iron garnet (YIG) film (about 5% enriched 57Fe) was grown
using the liquid phase epitaxy method on a gadolinium gallium garnet (GGG) substrateY 6
The sample was implanted with 10 ~4 Ne ions. cm -2 at 200 keV. The layers were removed
(a) (b)
:'.
.' ..,: ~. ~.
:.,.
~. -'~ ;': 9 .?~
.....: ".;'j,/'...:" .... 30nm

-'"; -/ ~/ .....' .... 30~120nr~
:% .& 9 :, .~
/ -: .,.. 120nm /: <~' \ 120~150nm
._/.,'"..f /kj",, 15Onto ..~:%:/":~:?::(:?;;:"i>:.... 150 ~ 200 n m

,." ,...
f- :\ :" "/\".... 200nm
,/-",,: -,,?_/',._.:.....~'~-:'...., 250nm

....." : - ' J '~'~'-'-._:'"-':-"-"""-,. bulk
-'5 6 :5 6
Velocity (mm/s) Velocity (mm/s)
Fig. 18. (a) 57Fe CEM speclra of a La, Ga substitutedYIG film implanted with 10~4Ne ions. cm 2 of 200 keV
taken at various depths. (b) Layer spectra derived from the observed CEM spectra shown in Fig. 18a
(from Ref. 116)
124
K, NOMURA et al.: APPLICATIONS OF CONVERSION ELECTRON
chemically by etching with a strong phosphoric acid solution at 390 K. The observed 57Fe.
CEM spectra are shown in Fig. 18a), and the spectra of layers calculated in Fig. 18b). This
method is more simple, and substantially less time-consuming than techniques involving
electron spectrometers. KUPRIN and NOVAKOVA 117 studied systematically 57Fe DSCEMS
on samples with rough surfaces by changing the high voltage of a proportional counter, which
affected the depth profile. LILJEQUIST et al. have studied the theoretical expressions of
CEMS and DSCEMS since 1978. 21 The total transmission into various angular and ~nergy
intervals from different depths in a STFe absorber have been computed mainly by the Monte
Carlo method. The K- and L-conversion electrons as well as the Auger electrons and the
resonant photoelectrons were taken into account. H8 The surface roughness on conversion
electron scattering did not affect the CEM spectra so much. t~ Programs ft;r the i clonte Carlo
simulation in STFe DSCEMS have also been developed by LILJEQUIST. 12~
4. Glancing angles CEMS (GACEMS)

In 1976 TRICKER et al. TM constructed a gas detector for the study of the angular effect
in such a way that the incident~T-ray to sample angle could be varied. The background
increased at grazing incidence because photoelectrons, which wou~d have been produced
beyond the escape depth at normal incidence, were released closer to the surface and could
escape into the detector. However, this study suggested that glancing incident CEMS could
be applied to the analysis of thinner surface layers.
The detection of electrons at large angles leads to a drastic contraction of the weight function
toward the surface. 122A complete mapping of the K- and L-conversion electron weight functions
for 57Fe DSCEMS was obtained by Monte Carlo simulation of 6.106 electron histories.
Analyzer Channeltron
- -- lensl-~ Sarce I
Fig. 19. Schematic view of the electron spectrometer for DCEMS studies showing the 150~ spherical sector
electron analyzer, electrostatic inlet lens, MOssbauerabsorber (sample),57CoMOssbauersource and ion
sputter fun, all parts being placed in an ultra high vacuum. (from Refs 92, 124)
125
200
io" .~~
200( 7.2key
]I ]I ~A /I ]I 7.3 10"
30i
"-"50 46"
0
4~
o 7.1 (D 400
(D
q-~
r-~ 50 60"
6.9
_.A~ _. 30
50C
72"
] / 6.0
-8-6-4-z 0 z 4 8
Velocity (mm/s) Velocity (ram/s)
Fig. 20. a) DSCEM spectra at 0= 10~ (almost perpendicular electron emission) for various electron-energy
settings V between 7.3 and 6.6 keV, obtained from the test absorber, i.e., a 21.0+ 1.0 nm thick layer of
tz- 57Fe (95% enriched) on a stainless steel substrate(19% enriched), b) DSCEM spectra at the electron
energy setting V= 7.2 keV, for electron emission angles 0 = 10%46~ 60~and 72~obtainedfrom the same
absorber as in Fig. 20 a) (from Ref. 124)
It was suggested that a surface layer with a mean depth < 1 nm could be observed at extreme
glacing angles ( 0 = 80~176 The angular effect of CEMS was also considered for thinner
surface layer by TOPALOV and PRIOKOVA. n3 The depth selectivity in 57Fe DSCEMS
was experimentally investigated by using a high-resolution electron-energy analyzer as shown
in Fig. 19. 92 DSCEM spectra were measured in ultra-high vacuum (6.6- 109 Pa) at different
electron energies (Fig. 20a) from 6.5 to 7.3 keV (with 2.7% energy resolution) and a different
electron-emission angles 0 relative to the absorber surface normal (from 0 = 10 to 72,
Fig. 20b), using a thin ~-Fe layer on a stainless-steel substrate. 124 The weight functions of K
conv~sion electron calculated are shown in Fig. 21. i24 It was confirmed that the surface signal
was ~ h a n c e d by measuring at glancing angles relative to the sample surface. The influence
of surface roughness on the surface selectivity in 57Fe GACEMS was small, lz5,~2~The electron
scattering for GACEMS was analysed by improving the conventional computational
procedures.~27
The ultra thin surface layers can be analysed at angles where total external reflection (TER)
takes place. Although the analysed layer under TER conditions is very thin (minimum
penetration; 2-3 nm), the techni/tue has not been widely used because of the very low
luminosity at glancing angles. Substantial progress was achieved by detecting the conversion
126
2~" 3keV (a)
o., ov
~176 500 I000
tO
0
r, 7.3keV
4,-4 / (b)
q~
t~
7.2keV
7.1keV
6.gkeV
!ev
500 idoo
Depth (k Fe)
Fig. 21. Some typical theoretical K conversion-electronweight functions T ~v(x) calculated for the speclrometer
with 2.7% FWHM energy resolution. Curves are labeled by setting (V) value, corresponding to energy
E by V=V/E= 1.007. The selected angular interval is 0= 10~_+6~ in (a) and 0= 72~ + 6~ in (b), depth
(2") is measured in Fe = 0.0786 ~tg/cm2 (from Ref. 124)
and Auger electrons instead of the specularly reflected 7-quanta. RGM spectra 12s and CEM
spectra ~29were obtained under TER conditions. The reflection coefficient of 7r- and G-polarized
radiation from an isotropic medium are almost equal, and the anisoptropic behaviour of the
reflection process needs not to be accounted for. The main contribution to the background
comes from the yield of nonresonant photoelectrons. CEM and XM spectra were
simultaneously measured together with reflection spectra under by a Russian group. 82
GAM spectra are formed by scattering by both the electron shell and the nucleus. The
latter contribution is varied experimentally by changing the y-ray energy. In the absence of
nuclear resonant interactions the critical angle for a metal iron mirror is 0c = 3.8 mrad for
radiation with energy 14.4 keV. Although it took one month to get MiSssbauer spectra using
a 3.7 GBq y-source, the distinctive four Mt~ssbauer spectra were measured simultaneously by
detection of the 7-radiation specularly reflected by electrons and nuclei (RGM spectrum),
conversion and Auger electrons (CEM spectrum), characteristic X-ray (CXM spectrum) and
7-radiation resonantly scattered by nuclei (SGM spectrum) as shown in Fig. 22. The
asymmetry of the lines is due to the fact that the refraction angles and the penetration depth
of refracted radiation differ for energies less or greater than the exact resonance energy. The
line broadening is caused by saturation effects which arise even for very thin layers due to
grazing propagation angles of the refracted radiation.
127
1.7o-1 '
t1 , 0 0 ~ "'~'~""
1,02-{ 9 I
o9~-1 ~ z . ,
0.92-
-10.0 -5.0 0 ,5.0 +10.0

Relative Velocity (mm/s)
Fig. 22. M0ssbauer spectra of the pure iron film obtained from: (a) secondary electrons, (b) reflected 7-radiation,
(c) characteristic X-ray radiation, and (d) scattered "f-radiation(from Ref. 82)
The computer simulation on GAMS theory showed that the shape of the resonant spectrum
of the reflected wave intensity, in the case of a resonant film, differs considerably from the
case of a semiinfinite resonant mirror) 3~ This shape strongly depends on the thickness and
the properties of the film and of the nonresonant substrate.
5. Low energy electron 5'TFe MSssbauer spectroscopy (LEEMS)

The process involved in low energy electrons passing through matter was connected with
the problems of DSCEMS by GROZDANOV et al. in 1979. TM LMM Auger electrons of about
600 eV were employed for CEMS by STANIEK et al. 132 Resonant emission of secondary
electrons was considered by SAWICKI and TYLISZCZAK. 27 LEE et al. (1987) x33', have
developed a theoretical description in order to take advantage of greater electron yields and
to provide enhanced surface sensitivity using lower energy electrons such as LMM and MNN
Auger electrons. ZABINSKI and TATARCHUK 134,135pointed out the possible use of very low
energy ( - 1 0 eV) electrons emitted directly by the 57Fe atom. LEE and TATARCHUK
(1990) 136 studied angular and energy distributions of backscattered low energy resonant and
128
nonresonant electrons from iron films both theoretically and experimentally. Emerging
electrons with energies below 50 eV come from low energy Auger cascades, low energy
shake-off electrons and secondary electrons being attributed to higher energy events. The large
number of low energy electrons permitted relatively short acquisition times (ca 1 h) and
enhanced surface sensitivity associated with the short range of very low energy electrons.
4 1 2 3
0 10 20am
Fig. 23. Orange spectromter; l: drive; 2: source; 3: absorber;4: coil; 5: e--detector;6: proportionalcounter (from
Ref. 137)
KLINGELHOFER obtained CEM spectra with very low energy electrons (0 to 15 eV) with
a high transmission orange type magnetic spectrometer as shown Fig. 23.137 This technique is
named as low energy electron MOssbauer spectroscopy (LEEMS). The em-iched 57Fe stainless
steel showed a high resonance effect of about 700% with count rates of 103 s-1, compared to
750% and 60 s-~ at the K-edge. Indeed, a sharp peak at energies below about 20 eV can be
seen in Fig. 24.137 The surface sensitivity of the resonant low energy electrons was determined
using nonresonant 56Fe metal and 56Fe stainless steel foils, coated with about 2 nm and 5 nm
57Fe, respective/y, and exposed to air after evaporation. ~38 Two-layer structures can be
distinguished from 5 nm thick samples. '39 LEEMS is significantly more sensitive to the surface
than conventional DSCEMS, but not as sensitive as Auger electron MOssbauer spectroscopy
(AEMS) using LMM-Auger electrons of 5004500 eV.
LILJEQUIST and LANG t4~ also investigated the intensity and surface sensitivity to be
expected by LEEMS from theoretical considerations. The weight function was calculated for
SVFe CEMS. Internal conversion electrons or KLL, KLM and KMM Auger electrons have an
129
Is
4000-
t~ 20
x ZO00-
== lO. O
, ~, ~---~K
8 15eV 730 3400 7900 i4i00
730 3400 7900 14100

Electron energy/eV
Fig. 24. Resonant electron energy spectntm for the 57Fe--SS sample (i.e. difference between electron spectra,
obtained for source and absorber nearly at resonance and far from resonance). A voltage of spectra,
obtained for source and absOrber nearly at resonance and far from resonance. A voltage of -200 V is
applied to the sample (from Ref. 137)
1.0
0.8 a)
4-.}
9,-4 O. 9
0.4 i , , , ~
O.I "-.., 4)
0.( .... 100. . . . 2 0 0 : ' ' 3 0 0 ' ' "4

Fe-overlayer ( X)
1.0
0.8-i.'.... 1)
0.6.
0.4. , ..
O. ' ~ " - ~
i 4) .................
0. o .... 10o .... 200. . . . 360 .... 400
Fe-overlayer ( ~ )
Fig. 25. Comparison with experimental data from KLINGELHOFER and KANKELEIT (Ref. 137). Surface
(oxide) and bulk (stainless steel) signals, as functions of the thickness of a 56Fe overlayer. The signals
are normalized to unity for zero overlayer thickness. These data have been computed with the simulation
model, assuming a surface layer thickness of 2Fe urn. a) With e,~c = 5Fe nm, and 6n = 8 R = 1.0. b) With
2"~ = 10Fe nm, and ~ = ,3~ = 0.5. 1) Bulk signal, computed data. 2) Bulk signal, experimental data.
3) Surface signal, computed data. 4) Surface signal, experimental data (from Ref. 140)
130
initial energy of > 5 keV as "high energy electrons", followed by low energy Auger electrons
(LMM, MMM, MMN) as "secondary electrons". A single internal conversion event in metallic
iron should imply an average of about 6.5 ejected electrons per Mtissbauer effect, of which
about 1.5 are contributed from high energy electrons and about 5.0 from low energy Auger
and shake-off electrons.a41 Most of the low energy Auger electrons have energies below
100 eV, and most of the shake-off electrons have energies below 15 eV.
SEILER m gave a semiempiricat formula for the case of a normally incident primary
electron beam
~(Er) = 1.11 8mE~.35(1 - exp (2.3EI.3s))
here, ~5(Er) is the secondary electron yield per incident electron as a function of E r = E/E,,
where E is the kinetic energy of the incident electron and E~ the kinetic energy E at which
8,, has its maximum value 8~. The values of E~ and 8,, depend on the surface material. For
an iron surface, E m = 4 0 0 eV mad 8,~ = 1.1-1.3.
LILJEQUIST and LANG 14~ assumed that the value of 8,, is increased by a factor of 2,
since primary electrons are emitted in essentially random directions from the surface. The
secondary electrons yield should have g - 1 for an Fe surface.
For the secondary electron yield, it was assumed that each K-conversion electron escaping
from the absorber surface is followed by ~ secondary electrons, while each escaping
relaxation electron is followed by 8R secondary electrons. The surface (S) and bulk (B)
M~Sssbauer signals are obtained by
o d
The weight function T(x) is the probability of a de-excitation at depth x. The surface selectivity
is defined as follows,
S
Q- S+B
Q depends on d. This theoretical treatment was compared with experimental data 137 as shown
in Fig. 25. The oxide layer mass thickness was estimated as about 2 nm Fe. There is a
discrepancy with experiment which may be somewhat decreased by adjusting escape depth
(XEsc) and the secondary yield. ZABINSKI and TATARCHUK also tried to determine weight
functions empirically. ~35 However, it is difficult to determine the LEEMS weight function in
general, because of the complex range of electrons of many different origins and of the
material variation in the secondary electron scattering at very low energies, whereas the weight
functions of conventional ICEMS aand DSCEMS can now be computed with considerably
better accuracy. ~4~
IIL APPLICATIONS OF CEMS

A. Corrosion o f steel
1. Basics of iron corrosion products
The structure and chemical state of corrosion layers on steel should be characterized by
non-destructive methods because corrosion products contain intermediate products, which are
not always stable. Scattering Mtssbauer techniques are among the most powerful methods for
analysing corroded surface layers of thicknesses between several nm and several tens of nm
131
0 0
e~
~g
I
O i O
r., i t.~
L
-~
I ~o o i o
ed r 9
,--4 ~
O i
,-.4 i
s,. %"
a
O
t. L-
=~1
d:z
0 ~, 0
1~121 ~176
9-~ ,-4 ~
~
,4
O 0
u.~ ,?
132
Table 4. M ~ s s b a u e r parameters for corrosion products of iron
Site Temp. I.S. Q.S. HL.

Compound
(Valence) (K) (mm/s) (mm/s) (T)
a -Fe - RT 0 33.3
FeO F e =* RT 0.93 0.8 -
Feo.90 FeZ'(A) RT 0.91 0.46 -

Fe2*(B) RT 0.86 0.78 -
Fe304 Fea*(A) RT 0.24 0 49.3

Fe2",Fe~*(B) RT 0.65 0 46.2
Fe~*(A+B) 77 0.44 0 51.4
Fe='(B) 77 0.94 -0.76 49.9
a Fea03 Fe 3. RT 0.39 0.42 51.8
83 0.3 -0.5 54.2
7 Fez03 (A,B) RT 0.3 50.2

a FeOOH Fe a* RT 0.61 38.9
B FeOOH Fe 3" RT 0.39 0.62 -
200 0.4 0.i 41.7
80 0.38 0.64 48.5
7 FeOOH Fe 3" RT 0.38 0.76
Fe(0H)2 Fe ~* RT 1.18 2.92
5Ve=O~.9H=0 Fe ~" RT 0.37 0.54

85 0.4 0.5 42.5
from Ref.154 )
although full information on the corroded surfaces cannot be obtained from M 6 s s b a u e r spectra
without k n o w l e d g e of the fundamental characteristics and structure of basic iron oxides, m
The characteristics and crystal structure of iron oxides, oxyhydroxides, and hydroxides are
shown in Table 3.
Hematite, (z-Fe:O 3, is red brown and has a trigonal system ( a = 0 . 5 0 3 5 nm, c =
= 1.375 nm). ~44 T h e magnetic transition (Neel) temperature is 965 K, and the spin is parallel
to (001) face arid normal to (001) face under and above 260 K (Morin transition temperature),
respectively. T h e Morin temperature of 57.5 n m particles is 166 K245
Magnetite, Fe304,is black and has a cubic system (a = 0.83963) nm). Fe(llI) ions occupy both
tetrahedral (A) and octahedral (B) sites in an inverse spinel structure. Electron hopping occurs
between Fe(II) and Fe(III) in B sites above 119 K ( T j Verwey transition temperature). FeOI) and
133
Fe(m) occupying B sites cannot be distinguished at room temperature. T v of 10 nm Fe304 particles

is 100 K. ~'~ Maghematite, y-Fe304 is brown and has a cubic system (a = 0.8338 nm) of spinel type.
Wiistite, FeO, is a cubic system of nonstoichiometric Fe~_xO (0.046<x<0.13). The Neel
temperature is 198 K.
Goethite, a-FeOOH, is yellow and. has an orthorhombic structure (a = 1.00 nm, b =
= 0.303 nm, c = 0.464 nm), which is based on a hexagonal closepacked, framework of oxygen.
The Neel temperature of goethite is 393 K. Goethite is produced in pH 6.5-7.5 at 298-310 K
or by air oxidation of Fe(OH) z and Fe(OH)3 in an alkaline solution, j47 Heated at 553-593 K,
~-FeOOH is transformed to o~-Fe20~.
Akaganeite, 13-FeOOH, has a tetragonal sla'ucture (a = 1.048 nm, c = 0.3023 nm), which is
based on body centred cubic oxygen. The Neel temperature is 293 K. Akaganeite is
precipitated-by slowly heating a FeCI 3 solution. ~I-FeOOH is transformed to o~-F%O3 by heating
to over 573 K.
Lepidocrocite, y-FeOOH, has an orthorhombic system (a = 0.388 nm, b = 1.254 nm, c =
= 0.307 nm). Its Neel temperature is .50 K. It is most often found as the main constituent of
rust layers of iron in wet corrosion. Heated in air, it is transformed into y-Fe203 at 573 K and
c~-Fe~O3 at 723 K.
~i-FeOOH has a hexagonal crystal structure (a = 0.4449 nm). It is produced ~ o m the
precipitation of sulfate solution and H202, and it is transformed into a-FeOOH by drying at
323 K.
In the rusting process, green rust I, green rust II and amorphous oxyhydroxides (5Fe203 -
9 9H20) ~4g are produced as intermediate compounds. Green rust I and 1I have hexagonal
structures with Fe(II)/Fe(I11)=2/1 and Fe(II)/Fe(Ig)= 1/1 of Fe(OH) 2 and Fe(OH) 3,
respectively, The M,6ssbauer parameters of these iron o x i d e s ~49,~5~ a r e shown in
Table 4. ts4
2. Wet corrosion study by CEMS

The general advantages of MOssbauer spectroscopy applied to the study of corrosion have
been described by MEISEL. ~55 CEMS is an useful technique for analysing final and stable
oxides produced on surface layers of iron and steels, the inner corrosion of hot water pipes,
the effect of corrosion inhibitors, and the influence of aggressive components, and XMS for
the nondestructive analysis of sublayer rusting beneath a coating. ~55
Great attention has to be paid to the drying process because ferrous species sometimes
change to ferric species during the drying. Unstable ferrous species cannot be detected unless
wet samples are first cooled and dried in vacuum. NOMURA and UJIHIRA analysed the
corrosion layers produced in solutions containing CI-, SO24-, and NO53 by CEMS. The doublets
of high spin ferrous compounds were observed in CEM spectra of iron plate, dipped in S Q
and NO 3 solutions. In NO 3 solution, a y-FeOOH layer was produced on the surface with high
spin ferrous species and a magnetite layer was developed beneath the ,/-FeOOH layer/$6
~-FeOOH was not produced even by dipping in 0.5M NaC1 solution for several days, but it
was found that the retarding supply of dissolved oxygen to the initial corrosion layers under
the presence of chloride ions allowed the production of ~-FeOOH. The CEM spectra measured
at dry ice temperature are shown in Fig. 26. ~57It was found that 13-FeOOH was grown beneath
ferric oxyhydroxides with an increase of dipping period time in the presence of less dissolved
oxygen. ~57When steel was oxidized in alkaline solutions containing N O 3 and N O 2 at boiling
point, black layers on the surface were produced. The CEM spectra of the black layers
consisted of distorted magnetically split peaks and doublet peaks, due to ferrimagnetic and
superparamagnetic magnetite, respectively/s8,159 The existence of C1- in the alkaline solutions
promoted the production of the reddish-brown rust, which was ccomposed of 13- and y-FeOOH.
In rust layers on an iron plate corroded in a 0.02M KCI solution, there existed a magnetite
134
T i . 1 I I ,G-Fe
~Fe(~ll " ""'" ":l

, , ' , 'Fe(lll, a-Fe I
, ,' ,., , ,~-Fe00H]
8
(d)
:,._..~...~ ~!.. . - ....

t.JFe(~l)
I ~ T i i ~ot - F e
I I 1 T I ~ i i
I 01 t
-10.0 .0 10.0
Velocity (ram/s)
Fig. 26. Dry ice temperature CEM spectra of the corrosion layers form on iron by immersing in 3% sodium
chloride solulion of inilial pH 6.5 at 318 K for (a) 12 h (pH changed to 7.0), (b) 24 h (.pH changed to
7.3), (c) 48 h (pH changed to 7.7) and (d) 96 h (pH changed to 8.0) (from Ref. 157)
layer below an outer "y-FeOOH layer. The CEM spectrum displayed three ferric sextets in
its lepidocrocite part with magnetic fields of 44.8, 44.2, and 38.7 T at 10 K. They were
attributed to Fe 3+ ions having zero, one and more C1- ions as first nearest neighbours,
respectively. 160
Corrosion products formed in nuclear power plants are predominantly nonstoichiometric
ferrous cation deficient magnetite and lepidocrocite. Small quantities of goethite and haematite
were found in some samples. 16t Surface oxides produced on an iron surface during discharge
in water, ]62 and the corrosion process and its inhibition 163 were studied by CEMS and other
electron spectroscopies. The high corrosion resistance of stainless steel X1CrNil815 against
boiling HNO~ was found to be due to an SiO 2 layer formed on the surface. Almost no iron
oxides were formed, although the composition of the alloy close to the metal surface was
slightly influenced, t63
135
Corrosion layers formed on two metallic glasses, Fes~1320and Fe~oNit0(MoB)z0, by exposing

to an SO2-polluted humid atmosphere, were analysed by ICEMS, XPS, XRD and EAS364 The
iron-containing corrosion products were the same compounds for pure iron in the same
environment, but different relative concentrations were clearly evidenced by ICEMS.
Elemental sulphur, Ni(OH)2 and B(OH)3, were found by XPS, XRD and AES.
Paints, varnishes, greases and oils are coated on metal surfaces. The temporary, protective
layers are typically 25 g m for paints and 15 gm per layer for varnishes. 6.3 keV fluorescence
X-rays are able to penetrate the protective layers, but then meets the large escape depth of
the metal substrate (i0 ~tm). To enhance the surface sensitivity of the XMS technique, an STFe
layer of approximately 20 nm was deposited onto mild steel, and then annealed. ~65X M spectra
were recorded before and after exposure of the coated samples to various aggressive
environments. XM spectra were not clear enough to identify the product because the
annealing promoted dilution of the 57Fe. The 57Co EMS is recommended over XMS for
characterizing the substrate interface under a protective layer. When there is a very small
amount of 57Co source on the intersurface, the y-ray, which can penetrate the thick coating,
can be detected with high sensitivity using standard absorbers with enriched 57Fe and a
resonant counter.
3. Passive films
It is hard to analyse uilra thin layers, such as passive layers, by ICEMS. However, sample
surfaces enriched with SVFe can be measured by DSCEMS. The first stages of corrosion of
iron in water and the passivating influence of H20 2 were studied by DSCEMS. ~6~The results
showed that a thin (4 nm) passive layer was detectable by DSCEMS. At room temperature,
corrosion was inhibited at H202 concentrations of 0.006 and 16.8%, while intermediate
concentrations led to the formation of y-FeOOH. The corrosion was not fully inhibited at
358 K.
AES, ICEMS, and DSCEMS showed that the layer formed on steel in a phosphate buffer
consists of y-FeOOH367 Only a thin intermediate layer formed between the cubic substrate
and the y-FeOOH was responsible for the passivity. 167,168The passive layer formed on steel
by anodic oxidation in 0.5M N ~ S O 4 solution contained iron only in the trivalent state. ~69The
thickness of the layer increased with the applied potential as well as with the passivating time.
Corrosion products on iron formed in a solution were measured with a proportional counter
at various temperatures of 6.3, 78 and 300 K. 170,171The layers consisted Of small particles of
y-Fe203. The passivation of low carbon steel was studied in a solution of 0.5M Na~SO4 +
+ 0.001M NaHSO 3 at pH 3.5172 and pH 6.5.173 The rate of the dissolution of iron was much
higher through the thick passive film formed in the presence of HSO? ions ~68than that formed
in the solution of 0.5M NaSO 4 without HSO? ions. It was found that the major components
were y-FeOOH and Fe3C, and that FeSO 4 - H20 could be identified on the low carbon steel as
a minor component. ~72,~74
The presence of sulfite ion induces pitting corrosion. At pH 3.5, Fe3C was detected in
most cases, and FeSO 4 - H20 was also detected after a polarization time of 90 min. 173 At
pH 6.5, the passive film contained only amorphous iron(III)-oxide or oxyhydroxide.
4. Environmental corrosion of weathering steel

Corrosion of steel induced by acid rain has been the subject of electrochemical and CEMS
studies. ~7s The surface oxides of weathering steel, ASTM A242 Type l, were analysed by
CEMS and XMS after exposure for 5.5 years in marine or industrial environments. ~v6 In an
industrial environment, a-FeOOH existed mainly in the form of small particles which
exhibited superparamagnetic relaxation. In a marine environment, the clusters of c~-FeOOH
were smaller in size and had a larger distribution of particle size, and c~-FeOOH was present
136
below a layer of T-FeOOH and ferrihydrite, t77 Atmospheric corrosion products of coated
weathering steel exposed for 13 years were analysed by XMS and CEMS: 7s The magnetic
hyperfine fields of fine o~-FeOOH and ferrihydrite observed in CEM spectra were smaller than
those in XM spectra measured at 160 K.
The rusts formed on pure iron and weathering steel after exposure to several wet-dry cycles
in an SO:polluted atmosphere have been studied. 179 Poorly crystallized o~-FeOOH and
quasi-amorphous ferrihydrite were identified as the main corrosion products. The rusts had
different particle size for pure iron and weathering steel samples. An intermediate corrosion
layer of superparamagnetic o~-FeOOH was formed only on weathering steel: g~ The surface
layers of iron plates exposed to the ambient atmosphere in different places were analysed by
CEMS to study the relationship between air pollution and corroded iron) ~l
The corrosion products of steel exposed to a sulfur dioxide (0.16 vol%) environment1~2in
hydrogen sulfide-nitrogen and hydrogen sulfide-oxygen environments ~s3 and in a hydrogen
chloride atmosphere ~84have been analysed by CEMS. The corrosion products from a Brazilian
oil refinery were confirmed to be FeS z, FeTS~ and FeS: s5
The hydrolytic oxidation of surface layers of iron fluoride hydrate x86 and the oxidation
process in polished steel ~g7have been studied. The effect of polishing a stainless steel sample
was also analysed by CEMS and XPS: 8g
5. Thermal corrosion
The surface contamination on iron in a vacuum system was studied by DSCEMS) s9 In an
oil-diffusion-pumped system iron carbonate was found after ix'on was annealed at 1023 K for
several hours.
The initial oxidation on an 100 nm thick 57Fe single crystal (110) face was studied at
548 K in the pressure range 2.7 - 10~ to 1.0~ P a : ~ Only magnetite was formed at 2.7.10 -2 and
1.0-6 Pa and a magnetite/haematite conversion occurred at 0.27 Pa. DSCEMS was used to
measure qualitatively the depth distribution of the oxide phases.
Silicon steel (Fe-3% Si) after a thermal pretreatment was covered by insulating layers,
consisting of an outer layer of ferric oxides and a large amount of inner Fe~SiO4 (fayalite)
layer. An additional wustite was contributed as shown in Fig. 27) 9~ The clusters of SiO4 was
formed by internal oxidation/63 The f-factor of fayalite was determined experimentally
(ff~y,~to/fa-Fe=0"47 +0"04) j91 When silicon steel (Fe-3w%Si) was annealed in H 2/H20 at
elevated temperatures, a92 carbide was formed in the temperature ranges from 773 K to 993 K,
indicating that decarburization was hindered. Above 1073 K, the layer consisted of fayalite
and iron oxides. At 1120 K, the onset of iron oxide was found to be formed at the oxygen
potential a 0 = 0.33) 92
It was shown from CEMS that the oxidation of an ultra-thin 310 stainless steel foil
deviated from the expected oxidation behaviour due to the effects of chromium depletion: 3
The oxide layers on stainless steels (SUS304 and 316) heated up to 1073 K were analysed by
CEMS. 194.t95 It was found that iron ferrite compounds were produced in the top rust layers on
stainless steel heated up to 873 K, whereas above 873 K paramagnetic iron species were
produced in the intermediate layer. The paramagnetic peaks are considered to be due to a
superparamagnetism of fine e~-Fe203, which is dispersed in Cr203 layers.
B. Surface finishing of steel

1. Phosphating of steel
Phosphating of steel has been widely used for industrial applications: 6,196 BERRY
(1979) 39. investigated the phosphating of iron surfaces by CEMS. Iron phosphating led to the
inclusion of hydrolyzed iron(III) species in the irun(II) phosphate compounds. Exposure of
137
104
I0~
102
.,-4
I01
i0 i c~, u(d)
,' , (b,)]
I(a)
I0~
(D
;>
..-4 102
r
101
10(
I I
<eL
,',
(b21 I(a) ,I
-10 "5 6 5 10
Velocity (ram/s)
Fig. 27. 1CEM spectra of two samples of silicon iron after the first anneal. The solid fines show the contributions
from c~-Fe(a), fayalite (b), Fe3§ oxide (c) and wustite (d) (from Ref. 191)
the surface coating to water vapour gave a partial oxidation of iron(II) phosphate to an iron(III)
hydrate. Phosphating of iron and steel with different phosphate solutions led to various
coatings that differed in morphology and compound composition. The states of iron in zinc
phosphate coating, calcium zinc phosphate coating ~99and manganese phosphate coating 2~ have
been characterized. Phosphophillite, Zn2Fe(PO4) 2 94HzO , Scholzite, (Ca2Zn)(PO4) ~ - 2H20, and
Hureaulite, (Mn,Fe)~H2(PO4). 4HzO , are the main constituents of zinc, calcium-zinc and
manganese phosphating on iron and steel, respectively. A little Fe(m) compound was included in
many phosphate coatings, whereas Fe(II) phosphate compounds were grown in the coatings
with the increase of dipping time. M6ssbauer parameters of phosphate compounds synthesized
are listed in Table 5. The peak ratio, (172+ Ps)/(P, + Pa), of substrate iron beneath the coatings
138
K. NOMURA etM.:APPLICATIONSOF CONVERSIONELECTRON
Table 5. M~ssbauer parameters of iron species produced in various

phosphate coatings and oxalate coatlngs
Iron Products IS (mm/s) QS (mm/s) remarks
Vlvlanlte
Fe3(PO4),.SHzO 1.25 8.04 ( from Ref.2O5 )
1.21 2.54 i
FezPO4.4H20 0.42 0.59 i
Amorphous Fe(PO4)?H20 0.37 0.78 i by Fe phosphatlng
Barbosallte
Fe3(PO4)~(OH)z 1.12 2.02 !i Fe2+ ratlo: i
0.36 0,5 i Fe3§ : 2
Phosphophylllte
Zn2Fe(PO4)u.4H20 1.26 3.40 by Zn phosphating
Zn=Fe(PO4I=-2H20 1.16 2.54 > 168"C~dehydration of
i.i 2.1 phosphophyllite
r(Zn,Fe)3(P04)2 1.26 1.99 > 277"C (8-eoordl.slte)
1.15 2,71 (5-eoordl.site)
Seholzite
Zn=Ca(PO4)=.2H20 1.27 2.3 by Ca and Zn p h o s p h a t i n g
Hureaullte
(Mn,Fe)sH=(PO4)4.4HzO 1.26 2.47 by Mn phosphatlng
1.23 1.58
1.23 1.20
Wolfeite
(Mn,Fe)=(PO4)(OH) 1.25 1.88 >350"C dehydration
1.18 2.38 of hureaullte
i.I 1,77
FeC20,-2H~O 1.17 1.75 on mild steel

FeC204-2H20 1.19 1.69 on sns304
( from Ref.202,203,207 )
decreased with the increase of the phosphating periods as shown in Fig. 28. '99 It suggested
that the roughness of iron substrate increases with phosphating. It was confirmed t h a t
particularly deep etching on ferrite areas due to zinc phosphating caused a considerable
reduction limit} ~
Barbosalite was found as one of the precipitates in the phosphating bath. The thermal
products of phosphophyllite, the thermal behavior of zinc phosphate coatingsz~ and many
kinds of iron phosphate compounds z~ were investigated by Mtissbauer spectrometry. Natural
single crystal vivanite2~ samples were also studied by TMS and CEMS. An additional
doublet appearing in the samples after vacuum treatment was ascribed to a tetrahydrate
phosphate compound appearing at the surface due to dehydration. Heating at 413 K in dry
air for 15 to 240 min. caused a higher oxidation and decomposition rate at the surface region
139
K. NOMI.NA et al.: APPLICATIONS OF CONVERSION ELECTRON
than in the bulk of vivianite2~ although the surface region of oxidized vivianite had higher
resistance against oxidation than the bulk. TM The highest rate of the conversion Fe2+---rFe3+
was found in air around 390 K for pure vivianite, while the samples ground together with
boron nitrite showed a very different behaviour. The oxidation process was considered to be
due to two competing processes: oxidation by oxygen diffusing into the vivianite fl'om outside
and auto oxidation by decomposing crystal'water. 20~
1.4
i\
\
_ \
\
\
o"81. 0- "•..
0~.~
.,.-~
bl r
N0.
O O 0.
~,4.a
6
I I ...... I
30 60 90
Immersing ~ime (s)
Fig. 28. Effect of immersing time on peak ratio of (P2 + P5)/(PI + P6) of Fe substrate beneath zinc phosphate
coating
2. Oxalating of steel
Mild and stainless steel were treated in an oxalate solution. The QS of the Fe(II) oxalate
produced on the stainless steel was slightly smaller than that of the Fe(//) oxalate on mild
steel. The thermal properties of axalate coating were similar to those of FeC204 - 2H~O. It was
confirmed from the results of CEMS that the oxalate coating works better as a lubricant rather
than as a corrosion-resistant material, especially at the surface of stainless steel. 207
3, Nitriding of steel
Several CEMS studies of nitrided surface of iron have been performed since 1978. 208
Mrssbauer parameters of iron-r~;trogen-carbon compounds are listed in Table 62o9 for the
analysis of surface treatment of steel. By comparing these with TM spectra of chemically
synthesized nitrite powder, it was confirmed that nitrided surfaces are mixtures of Fe4N and
Fe3N structures with a certain nonstoichiometry, z0~
Among the various methods for alloying with these elements, surface treatment by use of
ion implantation2o9 and laser beam z~0 have been of particular interest recently. These
applications will be described in other sections.
!40
K. NOMURA et al.: APPLICATIONS OF CONVERSION ELECTRON'
Table 6. M~ssbauer parameters for iron-nitrogen-carbon phases by

various process
Process ! Phase IS(mm/s) QS(mm/s) H , , (T)
Iron, gas i a''-Fe~6N2 0.05 29.7

nitriding 0.18 40.7
0.18 31.4
Iron, gas T'-Fe4N 0.24 34.1

nitriding 0.52 21.6
-0.15 21.9
Iron, gas e-Fe2.• 0.24 29.8

nltrldlng X=I.2 0.33 23.8
................................................
~...........................................................
i...............................................
!.............................................
i'
Iron, gas ! s-Fe2N 0.4 0.27

nitriding
Iron, gas X-l.2 0.25 29.0/30.0

nitriding 0.3<X<2.7 i -0.30 0/23.5
and c a r b o - 0.3<X<1.2 i 0.40/0.60 0/14.5
nitriding X=O i 0.31/0.49 0.28/0.86
( from Ref.209 )
4. Boronizing of steel
The surface layer slructures of steel2H and iron212,2~3boronized in crystalline boron powder
were characterized by CEMS and XMS. In addition to an inner Fe2B layer and an intermediate
FeB layer, a third compound of FeB x = (2"> 1) was contained in an outer layer of the boride
coatings.2~ Carbon free Fe-Ni alloys (12 and 20 w% Ni) were analysed by XRD, XMS and
CEMS after boriding at 1273 K for 20 hours. 2~4 Besides (Fe~NiI_)2B and Fe~li~_~B, a third
boride phase rich in boron was detected in the outer borided layers of the alloy specimens.
(Fe~li~ ,)2B was present only in the deeper part and the outer surface layers consisted of a
nickel and boron rich boride and a superparamagnetic oxide.
Pure Fe2B and FeB powders were compacted and oxidized for 1 h in flowing oxygen in
the 573 K-723 K temperature ranges. 215 Both oxides and oxygen-free compounds were
produced by oxidation. These Mfssbauer parameters are listed in Table 7.
Three F e - C - C r alloys containing up to 5.64 w% Cr were borided for 15 hrs at 1123 K
with a B4C-base powder mixture and then the borided layers were characterized by using
CEMS, XMS, XRD, metallography and microhardness measurements. 216 T~-e mechanical
ha mess of the innermost F%B single-phase layers was related to the extent of
crystallographic order. The influence of chromium on the thermochemical boriding of iron
alloys was studied using powder of a 13 w% Cr steel borided with mixtures by widely
varying boron potentials. 217
The process occurring at the surface of iron in contact with fluoride activated B4C powder
mixture at 1123 K was investigated by CEMS.2~8 The possibility of passing from iron boriding
to iron siliciding was shown by dilution of SiC with different silicon compounds. Single phase
and compounds of boride coatings were grown on iron using B4C - base powder mixtures
oxidized for 1 h in gaseous oxygen at temperatures up to 1123 K as shown in Fig. 29. 219
141
Table 7. M ~ s s b a u e r p a r a m e t e r s of p u r e iron and F e - C - C r alloy

b o r i d e d at I O 0 0 " C for 1 5 B
Sample (pure iron* *IS QS Hi,

and F e - C - C r a l l o y at
1000 " C for 15 hr.) (mm/s) (mm/s) (T)
sextet ~ FeBx
XMS 0.02 0.24 9.4
(l<x=2)
........................................................................................
i...........................................................................................v
CEM 0.06 0.13 11.7

sextet 8 FeB
~6MS 0.08 0.12 11.8
sextet B FezB XMS -0.03 0.06 28.8
CEM -0.ii 0 33.0

sextet a aFe
XMS -0.12 0 32.8
Fe-C-l.28wt%Cr 0.i0 0.05 233

sextet o
Fe-C-5.65wt%Cr . . . . . . . . . . . .
Fe-C-I.26wt%Cr 0.25 0.26 107

sextet n
Fe-C-5.SSwt%Cr 0.28 0.29 107
Fe-C-l.26wt%Cr 0.26 0,28 81

sextet
Fe-C-5.65wt%Cr 0.24 0.27 91
Fe-C-l.26wt%Cr . . . . . . . . . . . .
sexZet 8
Fe-C-5.85wt%Cr -0.75 2.07 ....
*IS r e f e r r e d to Rh (from R e f . 2 1 3 and 218)
5. Galvanizing of steel
Fe-Zn intermetallic compounds produced on galvanized steel were characterized by
CEMS. 2z~ From the top surface the phases consisted of the (, t~ lp (palisade), 81k (compact)
and /" phases. The M6ssbauer parameters are listed in Table 8. n~ The structures of the
electro-deposited Fe-Zn alloys were as follows, nz (1) The deposits of 0.9-17 w% Fe had
hexagonal structures corresponding to the iron supersaturated r/-phase. (2) The deposits of
18.5-40 w% Fe had bcc stxuctures similar to the F-phase. (3) The deposits of more than
50 w% Fe had a bcc structure corresponding to the zinc-supersaturated a-phase. The
morphology of the Fe-Zn intermetallic phase was classified into three types: outburst
structure, fine granular structure, and pillar-like structure. The formation of the outburst
structure was accelerated by decreasing solute carbon content in steels. Phosphorus inhibited
this formation when solute carbon was combined with a carbide forming element such as Nb
or Ti. For electrodeposited Fe-Zla alloys with > 52 at% Zn, CEM spectra consisted of a-phase
and Zn-Fe intermediate phase. TM Average H~ and IS values were correlated with Zn
concentration.
142
| K. NOMURA et al.: APPLICATIONS OF CONVERSION ELECTRON
(a)
1.08
i. OC ---~ ....... ! ~
o= (b) II. ,,1
.,--I
(D
>
'+.a
'~ J \
-
= 1.OC
,--4
1.0~ (c)
t
1.0 ~ " i
tI L--It ]I
t ,, t ,, t ,, IVIi v]i i
' ' 6 '.'4'-'8

Velocity (rams -i)
Fig. 29. Room tempeature XM spectra for polyphase boride coatings oxidized for 1 hr at (a) 673 K, (b) 773 K
and (c) 1t23 K I) Fe203 (fine particles); II) Fe in B203 glass; IID FeB and FeBx; IV) FeeB; V) a-Fe;
VI) Fe3BO6; VII) a-Fe203 (from Ref. 219)
Table 8. M o s s b a u e r p a r a m e t e r s of the Fe-Zn Intermetall[c phases on

g a l v a n i z e d steel[.
Phase IS QS FWlIM Peak i n t e n s i t y katlo

[mm/s) (mm/s (mm/s) (hrenb/Area ~)
0 . 4 9 • 0.01 0.44• 0.44

6 ,~ 0 . 4 5 • 0.01 0 . 3 8 • 0 03 0.41• 0.05 b 0.93• 0.30
0.39• 0.05 ~
6
6 ,, 0 . 4 2 • 0.01 0 . 4 4 • 0 01 0.48• 0.02 b 1.45• 0.09
0.32• 0.02 c
0 . 0 8 7 • 0.002 0 . 4 1 • 0.01 0.30• 0.02 b 0.25• 0.02

0.36• 0.01 ~
R e l a t i v e to m e t a l l i c Fe. ( from Ref.220 )

Peak at iD.wer velocity.
Peak at hlghcr veloelty.
143
6. Carburizing of steel
CEM spectra revealed that the uppermost surface layer of a carburized and quenched steel
was almost qt-austenite and that the surface layer of this sample consisted of c~-martensite and
"/-austenite. Iron carbide was not formed in the surface layer of a carburized and annealed
steel.2Z3 9
The transformation of retained austenite phase in low-alloy steel,224 and the origin of the
remarkable work hardening at the surface of a'high manganese steel (Hadfield steel)zz5 were
investigated by CEMS. The decarburizing occurred at the surface, cx-martensite had no relation
to work hardening. A spring steel Fe62SiCrs,zz6 was treated thermomechanically at high
temperature, and the distribution of interstitial carbon in iron alloys and the isochronal kinetics
of the aging of martensite zz7 were studied by CEMS.
C. Metal alloy and amorphous alloy

1. Metal alloy
a) Ni/Fe alloy
Iron-nickel alloys in a taenite lamellaz28 and the surface change of lattice constant and
hyperfine fields on the impurities of Fe-36Ni alloy were investigated by CEMS and
XMS. 229,23~On (Fe0.65Ni0.ss)l_~Mnx (x = 0.026) prepared by diffusion of Mn into a Feo.65Ni0.s5
foil, the diffusion coefficient of Mn in Fe0.65Nio.s5 at 1300 K was determined to be about
10-~ cm 2. s-~.TM The depth sensitivity of DSCEMS offers the possibility of checking the
homogeneity of an alloy as a function of the sample thickness.
Nickel-qt iron interfaces obtained by growing films of Fe on a Ni substrate were studied
and the following results were obtained: a) intermixing is two atomic layers, b) Fe atoms
deposited on structural defects of the Ni(II) surface are magnetically polarized, c) Fe
epitaxially grown on Ni is highly susceptible at room temperature. Moreover the Ni-Fe
interface shows Neel-type magnetic anisotropy. ~32
Soft magnetic Fe-Ni-Cr alloys233 in as-rolled and amended form were investigated by
CEMS. The magnetic moments of the annealed samples with Cr > 1 w% are preferentially
oriented in the plane of the ribbons.
Duplex stainless steel consisted of about 17% ferromagnetic ferrite and 83% paramagnetic
austenite. The hyperfine field of the ferromagnetic ferrite showed the phase decomposition
after annealing for over 100 h at 723 K. TM
The crystallographic structure and morphology of as-sputtered Fe-Ni-Cr films and the
(bcc)---~'/(fcc) phase transformation were investigated using the CEMS technique. 23~ The
bulk of 304 stainless steel (SS) normally has the fcc structure which is nonmagnetic at room
temperature (austenitic "/-phase); the Neel temperature is approximately 60 K. Sputter-
deposited austenitie 304 SS films have a crystalline structure different from the parent material
at the deposition temperature lower than 650 K. The bcc ferromagnetic c~-phase was stable
up to abouf 750 K, and the c~---~]t-phase transformation occured at temperatures higher than
750 K. The activation energy Q was estimated to be 366 kJ. tool-~,
b) Fe/Ti alloy
The surface layex ~ of actived iron (FeTi)236 and reactions occurring in thin films of FeTi
during initial activation and cyclic deactivation for hydrogen storage23v were analysed by
CEMS and XPS. As shown in Fig. 30, CEM spectra of a protective Pd coated specimen
showed the singlet of FeTi (IS = ~ . 1 5 mm/s) for annealing and reduction treatments. Thin
Ti and TiN films on an iron substrate were studied by CEMS. The intermixing of Ti with Fe
in Ti and TiN films onto argon plasma exposed iron substrate at various temperature and
144
K. NOMURAet al.: APPLICATIONSOF CONVERSIONE ~ O N
CEIdS XPS Schematic

Fe 2pv2_v2 Ti 2pvz_v3
a) As ~ ~ Fe +s ' Fe o T1-+4 Ti
"o t-'-. ~e,Q,.c~. 0.,~ ..:,,
Fabricated ~ II "-~ AAFe/TiPL i I . . . . . I
~lt "111~ i ~I\ I t e l l , lunm I
b)Annealed /I "
,,!A I
A, I
I----:-,,0.:-.---.I
9 l.'~ *"
// - V" I\I I I
Ik~ L'-J-
FeTi I
c) ReducedA [ ~ A l ~ i I--~e~- ^ ' _ d ~ l
28 -4 0 4 '8 458.5 453.8V////~/~O)'////A

u (ram/s) 710.7 706.8
Binding Energy (eY)
Fig. 30. CEMS and XPS spectra of an uncoated FeTi sample used to investigatecycfic deactivation mechanism
(from Ref. 237)
negative bias resulted in the appearance of an amorphous FeTid_x phase. Furthermore, a

comparison of CEM spectra before heating in UHV showed rather strong influence of thermal
treatments on Fe/Ti as well as Fe/TiN interfaces. 23s
Very thin films of TiN and T i f f i n were prepared by physical vapour deposition on iron
at 773 K to investigate the phenomena occurring at the coating substrate interface during
d e p o s i t i o n . 239 The preliminary depositions of Ti films led to the formation of a-'Fe(Ti) solid
solution. Either cr solid solution or Fe-Ti intermetallic compounds were formed,
depending on the amount of deposited Ti.
Low carbon steel surfaces coated with Ti and TiN by sputter deposition at room
temperature were also analysed by CEMS, c~-Fe(Ti) alloy and amorphous Fe~Til_~ phases were
produced at the interface of samples coated with films of Ti(25 nm thick). In samples with a
TiN layer (25 nm thick), only some oxidic Fe could be detected, probably due to the reaction
of Fe with the residual gas in the sample preparation chamber.
c) Other crystalline alloys

The surface of neodymium-iron-boron sintered magnets was studied by STFe CEMS and
XRD} 4~The as-polished surfaces of Nd2Fe~4B in sintered Ndt4Fe77B8 permanent magnets and
the surface after controlled oxidation at 873 K in a 10-6 Pa vacuum were studied by CEMS,
XRD and SEM. TM
The surface 'of high resistance magnetic dielectrics and the transient layer in the F%_~AI~
alloy with x = 0 . 1 , 0.2 and 0.3 on a silicon substrate 242 was studied by CEMS. The alloy
exhibits a D O 3 type of structure. The origin of this low-field part as well as the broadening
of the line-widths were discussed. 243 The deformed Fe-Si-A1 alloyTM and the surface of
Fe-Si-AI alloy powders of granular aud plane types were analysed by TMS and CEMS,
145
respective!y.245 The hyperfine distributions P(H) between granular and plane types were
different, and the P(H) of the surface were a little smaller than that of the bulk of powders.
These powders exhibited DO 3 Structure after annealing.
Fe-Si-A1 alloy films deposited on a cooled substrate contained superparamagnetic
components in addition to magnetic components, The fine grains yielded a random orientation
of magnetic spins in the films. After annealing the sputtered films above 773 K, the spin
orientation became perpendicular to the surface, probably through the growth of columnar
crystals accompanied by the diffusion of Si substrate into the films. 246
Iron and iron-cobalt (40 at%) thin films in the range 20-1500 nm were deposited on
various rotating substrates in UHV conditions (2.10-\Pa). 2~7 The spin orientation, deduced
from CEM spectra, rotated from in plane (less than 100 nm) to out of plane (nearly
perpendicular) position when the thickness increased. This behaviour was related to the
columnar structure observed by TEM and explained by the enhanced surface diffusion in the
low residual pressure. At low evaporation rate, the columnar axis must be oriented toward the
vapour beam direction. 247 The spins stayed along the film nnnnal up to 573 K and then the
random orientation was obtained when the annealing temperature reached about 873-973 K.
2, Amorphous alloy
CEM spectra of FexGe~_~ amorphous thin films were measured at low temperature and
analysed 248 to characterize the structure and magnetic properties of sputtered thin films of
Fe079Geo2j. MASSENET and DAVER (1977) 249 have studied on a series of amorphous
FexGe~_~thin films. QS and IS measured forx ranging from 0.08 to 0.53 were 0.5 and0,35 m/s,
respectively. When no ferromagnetic order was observed, the Fe atoms had no magnetic moment
for x < 0.4 because the d'levels were too wide as a result of hydridization with the sp Ge states.
For higher concentration, the Fe atoms ordered ferromagnetically at low temperature.
It was found from CEMS that an amorphous iron was produced by thermal decomposition
of earbonyl iron in liquid phaseY ~ The amorphous iron film contained about 4% carbon, which
contributed to the stability of the amorphous state.
Amorphous FeSi films deposited at 77 K and at room temperature were studied by CEMS.
The QS values in the CEM spectra were larger by aboat 0.04 ram. s-t than the QS obtained
from TM spectra. Further, QS was found (a) to decrease with the thickness of the film,
and (b) to be 25% larger for an amorphous film than for a crystallized one (of the same
thickness). The crystallization was found to start at 513 K for a 30 nm thick film. TM
The Fe-Si thin films,252 the compositionally modulated Fe~Si/Si amorphous films, 253,254
amorphous FeBSi and (Fe78B13Sig)/silicon films255,~6 have been characterized by CEMS.
Amorphous Fe83Bt7 ribbon 257 and Fe80Bz0 metaglass258 were also analysed by CEMS, using
a proportional gas detector for conversion electrons with discrete energy intervals of 11.5 to
14.5 keV, 6.6 to 9.1 keV, and 5.1 keV, and X-ray with 6.4 keV as shown in Table 9. 257 The
crystallization of dull and shiny surfaces and bulk was compared for amorphous
Fe~0.sBlzSi45C3, Fes0.sB12Sir.sC1259 and FevsB~ISigC2 metaglasses. 66 The lowering of the
crystallization temperatures was observed in the surface of the ribbon samples. This implied
the increase of carbon concentration and the decrease of silicon in the surface layers. Further,
the transformation in the surfaces caused the magnetic moment of the amorphous iron
component to be perpendicular to the ribbon plane because of stress to the bulk. The first step
of the crystallization process is the precipitation of ~-Fe and Fe-Si(several at%) phases and
the second is the transformation of the remaining amorphous phase into FezB. However, the
formation of Fe3C was detected in the surface of o~-Feso,sB12Si4.sC3,259The temperature range
of the FeroMg4o amorphous thin films to crystal transition was determined by CEMS and
TEM? ~~ A superparamagnetic like behaviour of the films was revealed by measurement at
77 K.
146
Table 9. Phase composition o f d i f f e r e n t layers o f F e . a B . 7 alloy

ribbon
Detected Depth of Contribution of Phases into

radiation the layer MSssbauer spectrum (%)
(From the shinY) AmorpHous FezB, Fe~B, a-Fe

side state
Electrons
ll.5-14.5keV 100 nm 19 19 28 34
6.8- 9.1keV 150 nm 25 21 25 29
i.i- 5,1keV 250 nm 33 17 24 26
Xrays 20 ~m 86 5 - 9
i from Ref.257
A crystallization of amorphous (a) Fe42Ni4zBltFe40Ni4oB20and Fe25N~55B20was studied by

annealing samples up to 773 K in argon and in vacuum. TM The surfaces were crystallized in
the same way as the bulk into fcc-(Fe,Ni) andorthorhombic (0) (Fe,Ni)3B. Annealing
c~-(Fe,Ni,B) in argon caused the depletion of o-(Fe,Ni)3B faster tha n annealing in vacuum
within the same temperature range. By the oxidation of Fe42Ni4zB~6 at 673 K in air, o~-FezO3
y-FezO 3 and Fe2BO ~ were produced. The Fe-based oxides do not have any effect on the
depletion of o~-(Fe,Ni)B761
57Fe CEM and TM spectra of metaglass (Fe4oNi4oP,4B6)262 were obtained simultaneously.
The differences in bulk and surface states were observed and summarized as follows: 1) The
surface exhibits larger mean magnetic fields than the bulk, 2) Magnetic moments in the
surfaces are more aligned in the plane of the ribbon than in the bulk. 3) After armealing at 545 K
the stmfaces exhibit larger magnetic fields than the bulk but the degree of alignment of
tile magnetic moments in the plane of the ribbon is reduced. Primary crystallization was
revealed in a surface layer 100 nm thick on the rough side of amorphous Fe40Ni40Pj4B6 ribbon
over three years natural aging. 263
The ionic character of the amorphous state in electrodeposited Fe-Ni-P samples has been
studied. A Fe~sNiz3P~ sample gave rise to two doubles (IS I =0.27 mm/s, QS; =0.51 mm/s,
and IS2 = 1.22 ram/s, QS 2 = 2.54 mm/s)764
Melt spinning ribbons of alloys containing a variable amount of Cr(4-10 at%) and
Si(0-2 at%) have been studied by CEMS. A strong magnetic texture and a hyperfine field
distribution were dependent on Cr concentration, and the iron concentration near the shiny
face was higher than near the dull face. The depth dependence of iron concentration variation
was small on crystallized specimens. 265
The CEM spectra of Cdo.95Feo.05Te thin films grown by r.f. sputtering on quartz and silicon
substrates showed the presence of Fe z+ and Fe 3§ which were associated with the amorphous
and polycrystalline phase, respectively, in the films. 266,267
The ionicity of iron was studied in order to determine the amorphous tO crystalline ratio
in CdFeTe films 26s and amorphous Tb-Fe films, z69
The structural relaxations and diffusive transporff7~ and the thermal oxidation of
Fe67CoLsB~4Si~ metaglass TM were studied by CEMS. Crystallization of the amorphous
Fe75C%B16 alloy 272 was also studied by CEMS and TMS. Non-uniform nucleation of the
primary et-Fe-Co phase on both contact and free surfaces of annealed amorphous FevsCogBz6
alloy was observed in its early crystallization stage, whereas to traces of volume crystallization
were observed in TM spectra7 7z The amount of crystalline phase on the contact ribbon side
(dull side) surpassed that on the free one by a factor of three.
147
K. NOMURA etal.: APPLICATIONS OF CONVERSION ELECTRON
3. Hydrogenation
The role of light interstitial elements in metal has been reviewed and discussed. 2t~
Hydrogen, nitrogen, and carbon, residing on interstitial sites of the host lattices, are capable
of inducing noticeable changes in the physical properties of the material. Hydrogen uptake by
different intermetallic compounds can lead to completely different results, depending on the
chemical affinity between hydrogen and the constituent elements of the compounds. The
several distinct hydride phases with considerable hydrogen content can usually be found and
identified by M6ssbauer spectrometry. Alternations of the intermetallic hydride are frequently
observed and discussed. 2~~
The effect of hydrogenation in Fe89Zr~ amorphous alloys was studied. 273 A magnetically
split spec~um resulted from increasing the hydrogen content. The changes of M/Sssbauer
parameters depended on the annealing temperature before the hydrogenation as well as on the
cathodic potential of hydrogenation. The magnetic states of amorphous Feg0Zrl0 and FeglHf9
varied with the charge of hydrogen 274 because hydrogen was trapped near the Zr sites and the
magnetic interaction among iron atoms was enhanced.
4. Surface improvement by laser irradiation

Laser irradiation can improve hardness, wear and corrosion resistance of the surface
without affecting the bulk material. The CEM spectra of laser treated samples are shown in
Fig. 312~~ and the depth profiles in Fig. 32. 2~~ On the top layer; austenite increased and
martensite decreased. XMS was also used to analyse CO 2 laser-treated samples of cast iron.
The depth profile revealed by phase analysis was discussed in connection with the initial
microstructure.275 The surface of a mild steel(C45) substrate was alloyed with
chromium-boride CrB 2 with a high power continuous-wave CO s laser,z76 The XM spectra of
the laser alloyed surface are shown in Fig. 33. Three sextets with H~, of 33.5 T, 30.8 T, and
27.7 T were attributed to mart6nsite containing Cr. The B and Cr effects could not be resolved
because the reduction of H~n to 3.0 T due to neighbouring B atoms was very close to the
reduction due to a neigbouring B atom. The single line with IS = --0.08 mrrgs was attributed
to austenite whereas the doublet with IS=0.08 mm/s and Q S - 0 . 6 9 mm/s arose
from interstitial atoms. Two magnetically split sextets with Hi~ 18.2 and 11.5 T was
attributed to orthorhombic (Fe,Cr)3B. XM spectra of an unalloyed sample were fitted with two
sextets due to martensite and a single peak due to the retained austenite.
Plates of a 0.38C-Ni--Cr-Mo steel and a 1(2-1.5Cr steel were coated with graphite277 and
then irradiated using a continuous, wave CO 2 laser beam with an incident power density of
11.6 kW - cm -2 and a beam translation speed of 4.5 m . min -~. These steels were also studied
by CEMS. In the case of laser treated surfaces of a Feg3Si~7alloy and a low-carbon steel with
Ni and AI, the short range order in the surface layers was found to be similar to that before
irradiation.~Ts
The as-cut and laser melted surfaces of single phase crystalline Fe2Y, Fe23Y6, Fe~Zr, Fe2B
and FeB ingots were studied. 279 A new phase with a low hyperfine field was observed for the
Fe-Y and Fe2Zr ingots even on the as-cut surface due to the mechanical processing. The
amorphous phase by laser melti,g was formed for only Fe2B, while c~-FeB modification
appeared both for mechanical processing and laser melting of FeB.
The structure of nanosecond-pulse laser-melted surfaces of different evaporated layers with
the iron-boron system between 17 and 56 at% B content28~ was studied using CEMS. A
considerable decrease (about 10%) of the width of the iron hyperfine field distribution was
observed for the laser-melted surface. Amorphous alloys were obtained in the 17-33 at% B
composition range by laser melting, although no amorphous alloy was obtained for the
equsiatomic FeB ingot or the evaporated amorphous Fe44B56 film. In the latter case the laser
148
X 210 Cr 12 A rough surface

1.06 sample 4 II
1.o4!laser treated/~ 0 ttm
1.02
1.00
'_SL_
1.10
O
,---I
1.05
o'a
.,--4
1.00
Ei i .03
r-r-I
1.02
~
1.01
.q-a
1.00
(1) A 000 m
1.01
1 O(
1.06
1.04
1.02
1.00
-6 -4 -2 0 2 4 6
Velocity (mm/s)
Fig. 31. CEM spectra of the steel after laser tr6atment at different levels below the surface (from Ref. 210)
melting resulted in the low temperature crystalline or-FeB modification, indicating the
important role of surface nucleation. 280
In the case of F e - Z r ingots in the 25-80 at% Zr composition range, TM disorder and
amorphization were observed even on the as-cut surfaces due to the mechanical processing.
Besides a significant enhancement of the non-crystalline fraction, the surface melting by ns
laser pulses also resulted in the appearance of new metastable phases. Solidification via an
extremely high cooling rate thus produced an amorphous phase. TM Coatings ,,g Ni and Co
b a s .i alloys were prepared by laser alloying and analysed by CEMS. 282 The annealing effect
of laser pulses from ruby and neodymium glass on 57Fe ion implanted in silicon was
investigated. 283 The irradiation by a ruby laser with a power density of 1.5 J . cm -2 and a Nd
laser with power densities > 10 J. cm -2 gave a quadmpole doublet. This was approximately
due to the precipitation of FeSi 2.
149
~X 210 Cr 12
lO0rsample 4 -1000
1laser treated
r2700 W
80(. 1.2 • • • -800
~ 60- -600 ~
eSS
[ ] martensite
>
.,-I • 0 austenite (D
40- Ak carbide -400 -~
=
20- -200
]
0.6
~ idoo
depth (/z m)
Fig. 32. Depth profile of the fractional areas of the various phases and of the mechanical hardness after laser
irradiation. The carbon concentrationsof the austenite phase (in wL%) are indicated in the figure (from
Ref. 210)
D. Artificial oxide films

1. Oxide films of single crystal
Magnetic single crystalline films of garnet have been extensively used as magnetic-bubble
memory, magneto-optical isolator and microwave devices. Several additives are doped into
garnet crystal, and ions are implanted into surface regions of these films to suppress hard
bubble formation, to enlarge a Faraday rotation and to improve temperature dependency of
magnetic properties. The various garnet films are prepared with a reactive ion-beam method
as well as fiquid phase epitaxy.
Yttrium-iron-garnet CYIG) has fenimagnetism and a cubic svucture, which is formulated as
[C]3[A]z[D]30~z. The unit cell is composed ot eight sublattices. [C] ions locate in dodecahedral
sites (24c). [A] and [D] ions of iron occupy octahedral sites (16a) and tetrahedral sites (24d),
respectively. CEMS characterization of ion implanted bubble garnets has been reviewedY 4
La, Ga: YIG implanted with 10 ~4 Ne ions 9 cm -2 was analysed layer by layer. 285 57Fe
DSCEMS was implemented by removing thin layers from a garnet sample and measuring the
ICEM spectraJ ~6 Magnetic properties of bubble garnet films were studied by DSCEMS. z86
150
K. NOMURA et al,: APPLICATIONS OF CONVERSION ELECTRON
i.(}2
1.00 ..L
r i i i i
I I l I I
I I 1 , t I
I I / I I I
L I I I ,, I I
O
9~ 1. OI .A_
L..I
9 .~-I i t I i v l
II .... l ~ I l I
, I I ..I I I
l~ I I I I I I
.,--I
1.06
1.0:
1.0C ~_
I 1 [ 1 I
I I, I I I
1.04
1.00
I
-6
!
-'4 -'z '

I
,,
0 2 4
.
V e l o c i t y (mm/s)
.
Fig. 33. XM spectra of the surfaces. (a) sample 1: CrB2 alloyed 1750 W, (b) sample 2: CrB2 alloyed 1250 W,
. . .
6
t
(c) sample 3: unalloyed 1750 W, (d) unlreated (from Ref. 276)
The spin-tilt angle from the surface normal increased from the bulk value up to 30 degree at
the top of the surface as shown in Fig. 34. This phenomenon was explained by the widening
of the domain wall with toward the surface# 87
5VFe-enriched, epitaxial Y~3FesO12 films were implanted with 50 keV and 100 keV Ne ions
with a dose of 4 , 1014 Ne* cm-L DSCEMS was performed at 300 K and 30 K ) 8g The 50 and
t00 keV-implanted samples formed an amorphous layer on top of an almost unperturbed YIG
layer and a buried amorphous layer, respectively. The high temperature annealing effect of
ion implanted garnets z89 were studied by CEMS together with X-ray standing waves 29~ or
X-ray double-axis spectroscopy# 91 The magnetic and structural properties of calcium-doped
YIG films formed by annealing in a hydrogen atmosphere TM were investigated. The orientation
of the easy axis of magnetization was different between the two layers: it is in plane in the
151
O@Electron
Spectrometer
z ~ k P r o p g r t i 0 i i a l ....
Counter
~ [~llTransmission
,~ 0 b) - new surface
b) after etching
z0
1.5 ,,
1.0
~1.5:(c)
OAF] a-site
O~kll b-site
1 9~
.--4
" a-site
u
E
O. 5 b-site
I
0 0.1 0.2 0 3 0.4 0.5
Depth (~zm)
Fig. 34. Spin-flit angles from the surface normal direction (a), spectral area ratios of d to a sites patterns (b),
and linewidths for two sites (c), as a function of the depth (from Ref. 287)
film bulk (particularly in the [011] or [011] directions) and lies along the < 111 > directions
in the thin surface layer. The behaviour of the easy axis of magnetization in the two layers
was explained as a pure magnetostrictive effect} 9~
The specific chemical effect of hydrogen implantation of 57Fe-enriched YIG was compared
with a pure damage effect from a shallow Ne ion implantation by GEMS. ~92,293The MSssbauer
parameters obtained by computer fitting of four sextets in YIG are listed in Table 10. Ne and
H implantations affect the tetrahedral sites preferentially. Moreover, for about 15% of H
implantation the presence of a new "dH" magnetic sites among the tetrahedral sites was clearly
correlated with the ~ormation of O-H bonds. 294 The remaining 85% responsible for the
reduction of iron gave rise to the broadening of Mtssbauer peaks and the decrease of hyperfine
field.
Y3FesOI2(YIG), Y3A150~z(YAG) and Gd3GasO~2(GGG ) single crystal garnets were
implanted 29s with 10 H Fe-cm-L For YIG and YAG large a-Fe203 particles were formed after
annealing, and the Morin transition was observed, whereas for GGG no Morin transition was
observed.
152
Table i0. M~ssbauer Parameters of vlr~!n fIG single crystal obtained by

computer fitting of the spectra measure d . IS : Isomer shlft(referred to
a Iron), Hs, : hyperflne field, QS : Quadrupole splitting, W :
linewldth, RI : relative Intensity
Channeltron setup
Room temp. Lig.N, temp.
a site IS (am/s) 0.38(2) 0.52(3)

H,, (T) 49.4(2) 55.1(1)
QS (am/s) 0.10(6) 0.09(3)
W (ma/s) 0.30(2) 0.42(2)
RI 0.23(2) 0.22(2 )
a' site IS (ma/s) 0.38(3) 0.43(3)

Hr, (T) 48.0(3) 54.5(2)
QS (ma/s) -0.1i(5) -0.11(6)
W (am/s) 0.30(2) 0.42(2)
RI 0.16(2) 0.18(2)
site IS (am/s) 0.13(2) 0.23(3)

H,n (T) 40.4(4) 47.5(1)
QS (am/s) 0,09(5) 0.08(8)
W (mm/s) 0.39(3) 0.47(2)
RI 0.37(2) 0.40(4)
d" site IS (ma/s) 0.18(1) 0.32(1)

}I,, (T) 38.7(3) 46.1(1)
QS (mm/s) -0.09(3) -0.22(4)
W (am/s) 0.38(3) 0.47(5)
RI 0.24(2) 0.21(4)
( from Ref.294 )
Substitution of Bi ion into to YIG increases the Farady rotation of YIG from 200 to
l0 s deg/cm. Sputtered Bi3F%O~2(BilG), YIG and BiYIG were compared. The hyperfine
field at the tetrahedral site (d) increased to 42,6 T by substitution of Bi ion, indicating a
decrease in the intrasublattice exchange interaction rather than the decrease of the tetrahedrat
iron moment, z96 Under the effect of the diamagnetic dilution of the diamagnetic yttrium
sublattice the magnetization of BilG decreased with respect to YIG, 297
CEM spectra of a (111) oriented single crystalline BilG were also measured at 6, 78, 290
and 670 K. 2~'s QS values for octahedral (a) and tetrahedral (d) sites measured at 670 K are
smaller than those found in other related garnets, R3Fe5OIz with R = Lu-Sm. The various QS
values against the reciprocal volume, 1/V (V = a3, a is the lattice constant) are shown in
Fig. 35. The magnetic and quadrupole hyperfine interactions indicated continuous effects of
lattice expansion. The temperature dependence of the sublattice magnetization has been
explained by the two sublattice molecular field model} 98 YIG films substituted by Bi, Ti, Ga
and La was studied b y CEMS} ~9 Ti-doping increased the transparency.
Single crystal iron borate (FeaBO6) is also expected to be used in magneto-optical
applications. The phase transitions in single crystal Fe~BO6 were studied by simultaneous
153
Bi Sm Gd Dy Y YbLu
! ; i i i
1.( - (b)
O.
co
"~0.6
v
o.4
(a)
0.2
1 1 I I I
4.9 5.1 5.3 5.5
1/V ( X l O -4 ~-3)
Fig. 35. Dependence of the qaadrupole splitlings of various iron garnets upon the reciprocale volume (from Ref.
298) (a) a sile, (b) d site
J 4 5 6
.Vu --
i;t: 9
::2
/
2,.
e
J
i
'A
Pd
p
r~
Pt
p
?.: tI
'i
.z 'j
Fig, 36. Multi purpose detector, 1) 57Co sQurce; 2) collimator;, 3) sample; 4) beryllium foil; 5) heater; 6) point
supports (from Ref. 300)
154
12.5 ,._....;...
11.5 ( :~
10. , , , 1 I , I I I I I
-4 -2 0 2 4 6
9 ,--~ :. . , . "..~.',. '.-:,

ir~-' i i / i 1 r I I t i I
-4 -2 0 2 4 6
Velocity (mm/s)
Fig. 37. M6ssbauer spectra of Fe3BO6 at 498 K obtained by detection of the "l-rays in a transmission geometry
(a), detection of the characteristic X-rays (b), detection of the conversion electrons (c), and detection of
the conversion electrons and characteristic X-rays (d) (from Ref. 301)
m e a s u r e m e n t s of C E M S , X M S and T M S as shown in Fig. 36. 3o0 Fe3BO 6 is an orthorhombic

structure, with space group Pmna, and s h o w s an antiferromagnedsm with a week
felTomagnetic m o m e n t below the Neel temperature T N = 507.7 K. At 415 K, the crystal shows
a spin reorientation phase transition. The M6ssbauer spectra of Fe3BO ~ obtained at 498 K are
shown in Fig. 37? ~ The C E M spectrum (c) is a superposition of paramagnetic doublets. X M
spectrum (b) is a superposition of CEM and TM spectra. The transition of the crystal to
paramagnetic state begins from the surface of the crystal below the Neel temperature. T h e
spectrum (d) was obtained by flowing Ar + 5 % CH 4 gas in a CEMS counter with a sample
not covered by a thin foil. This m e a s u r e m e n t detected was both the characteristic X-rays and
conversion electrons, whose contribution about 40%. Surface and bulk magnetic properties
of antiferromagnetic single FeBO 3 cD, stal below T N = 348.3 K 3~ were also studied.
155
K. NOMURA etM.:APPLICA~ONS OF CONVERSION ELECTRON
Table ii. Average Mossbauer parameters of Fe implanted YBazCuaO~
Components Doublet A i Doublet B Doublet C
IS(ram/s) 0.21mm/s i 0.25mm/s 0.23mm/s
QS(mm/s) 1.08mm/s ! O.~8mm/s i 1.51mm/s
2. Polycrystalline oxide surface

a) Perovskite oxide
The surface and bulk properties of high-temperature superconductor YBa2(Cu~_~Fe)3OT_y
were compared by CEMS and TMS measurements at room temperature. Local states of
implanted S7Fe in YBa~Cu3Or.4 and YBa2Cu3Or. 9 pellets3~ were tested. The CEM spectra of
~7Fe in YBCO were decomposed to three distinct symmetric doublets 3~ as shown in Table 11.
A model was proposed, based on the crystal structure and an enhanced oxygen content at the
grain surfaces. 3~ Fully c-axis oriented thin fihns of YBa2(Cui_~TFex)3Ov_y3~176 were studied by
varying the Fe- and O-content and the substrate. 3~ For all iron concentrations (x = 0.15%, 1%,
3% and 6%), iron was homogeneously distributed in the films. For x = 0.15%, 1%, and 3%
the c-axis length was the same as for undoped films, and for x = 6% it was enlarged. The
surface of the films got smoother with increasing x. The crytical temperature Tc values for
x = 0.15% and 1% were the same as for the undoped films, although Tc values were reduced
for x = 3% and 6%. CEM spectra for all x values were fitted with only three quadmpole
doublets (A, B, and C). The MSssbauer parameters with different relative intensities for
different x values are shown in Fig. 38. 303 The quadrupole splitting of doublet B decreased
with increasing x values. The Elebye-Waller factor did not change significantly with x. 3~ For
two quadrupole doublets, the main component of the EFG lay in the a- and b-plane, and for
the third doublet it was parallel to the c-axis. The EFG of all three doublets showed
approximately axial symmetry. 3~ 500 MeV ~zTIirradiation of thin films of YBa2(Cu0.9757Fe)307
on < 100 > SrTiO 3 substrate 3~ resulted in the appearance of a fourth quadrupole doublet in
the CEM spectra (QS = .1.1 mm/s, IS = 1.26 mm/s), whose intensity increased with increasing
fluences? ~ The Debye-Waller factor of the new Fe-species was only about 60% of that of
the species A, B and C. The latent racks with about 2.6 nm radius were mainly formed of
the "green phase" Y2BaCuOs. Response of epitaxial YBa2Cu307 films after ion irradiation was
studied by the measurement of critical currents, magnetic relaxation, far infrared reflecfivity
and CEMS. 3w The substitution of Cu(2) by Fe in the films was the highest. The CEM spectrum
of a reduced film showed that the direction of the magnetic hyperfine field for doublet C is
perpendicular to the c-axis, m
The orientation of magnetic iron ions in Y2CaFe3.gCo0.1GeOl2,312 and nonstoichiometric
perovskite, Ba1_xCarFeO34,313were also studied by CEMS. The Mtissbauer parameters changed
depending on oxygen vacancy. The new magnetic species with intermediate H~, was produced
by mixing Ba and Ca in addition to iron species in octahedral and tetrahedral sites due to
oxygen deficient. The magnetic properties of these perovskite oxides were affected by
absorption of CO 2.
b) Surfaces of other oxides
The initial stages of the oxidation of biotite was originally studied by CEMS in 1976. 3~4
CEM spectra of spinel oxides CoFe2_~AI~O4 (x = 0.1, 0.3, 0.6, 0.8 and 1.0) 3~5 were measured.
The fraction of Co 2§ ions at the tetrahedral lattice sites increased linearly with the aluminium
content, although a difference befween powder and bulk samples was observed. 3~5
Iron and AI203 were simultaneously ion-beam sputtered on polycrystalline an alumina
substrate at room temperature to produce ultrafine particles of iron embedded in the insulating
156
0.4 (a), i t , , , i
..A ........ r ........ ix"

2.0 ~ " ~ . . . . . . . . D . . . . . . . . . . --,Q2
0.~
~A 9 UA
1.51 ~ - o OB
"~0.~ OB 9 " ...... : . . . . . Ac
z~C
"--" 0. 1! 1.0
O'3
._= . . . . . . . . ~ . . . . . . . . . . . . . ~ . <]
0.0 0.5 r --/~ ........ ix .............
-0 U, 9,,,, ...... 0.0 , i , i , I , i i I , i

"'0 1 2 3 4 5 6 1 2 3 4 5 6
X~, (%) X~o (%)
(d) . . . . . .
0.6 . . . . . . 60
O. ~ ; ' - ~ . . . . . . . -o . . . . . . . . . . . . . ~." 5C
ol
. . . . . . -z/~ t-d ....... -9. :~,'-':. . . . . . . o-.
0A ix ...... 4C
.~176 ~--~ ..... ~A
O. ..-a- ..... tJ 3Z 9
..-4
"'El ....................... I3" .~ 7.C a . . ~ AC
o. [3A
9 -""'~
o. OB
.,-I AC C)
(
1 2 3 4 5 6
X~, (~) X~~ (%)
Fig. 38. (a)IS, (b) QS, (c) linewid!h, and (d) relative area of the doublets A, B and C vs. x of YBa-zCu3 xFexO7
(from Ref. 308)
matrix. T h e doublet with IS = 0.28 m m 9 s -~ and QS = - 1 . 0 5 m m 9 s-~ was associated with a

Fe > state corresponding to (Fe~Al~_,)203 due to substitutional iron into alumina or to small
superparamagnetic F%O 3 particles. T h e doublet with IS = 0.08 r a m . s ~ was due to partially
oxidized iron under very small paramagnetic or superparamagnetic iron clusters dispersed in
alulnina. T h e third doublet with IS = - 0.02 m m . s -~ and QS = 4).43 man 9 sq would be due
to iron perturbed less o x y g e n atoms in its neighbourhood. 3~6
T h e decrease of magnetic m o m e n t in the surface of magnetite Fe304 films 317 and the phase
transformation on the surface of magnetite single crystaP 18 were studied by CEMS.
Magnetite-coating on iron 3~* and oxide films on stainless steeP 2~ were developed as a pH
electrode and analysed by m e a n s of CEMS5 ~4 The thin hematite films for photoelectrode were
prepared on semiconductive oxide films by a spray pyrolysis method and analysed by C E M S
at room temperature 32~ and at dry ice temperature. 3= The grains of ot-F%O 3 produced by a
spray pyrolysis of a FeCI3 solution were dependent on the semiconductive substrate type.
Superparamagnetism of ~-Fe~_O3 was not observed on the SnO 2 films, but on Z n O and WO3
s~ ,strates.
The d y n a m i c s of piezoelectric polymer materials at high frequencies was m e a s u r e d with
CEMS.323
Coatings using repeating Fe/Ag sandwich layers underneath silica provide enhanced
protection against atomic oxygen attack on both volatile and non-volatile substrates. Silver
preferentially migrated out of the layered metal network, nucleated as A g O at and within the
pinholes and served to block the transport of reacti.ve oxygen towards the substrate. 324 CEMS
was used as an effective technique for evaluating coating effect by non-destructively
monitoring oxidation at the coating-substrate interface. -n4
157
E. Ultra thin films and multilayers

1. Magnetic order in ultra thin films and their interfaces
G R A D M A N N (1991)325,326reviewed the overall changes of magnetic properties in surfaces

and interfaces. A theoretical review of surface magnetism was given by MATHON. 327 Surface
magnetism can be analysed from the theoretical treatment of ultra thin slabs 32s or from the
experiments with ultra thin magnetic films. 329 In situ CEMS instrumentation for analysis of
monolayer magnetism was developed by KORECKI and G R A D M A N N ? 30 An enhanced
exchange interaction in the surface layer has been introduced in local theoretical models. It
W(.110}//k.(30 OK)/Ag(300K)
1701D =
O.
160
222
59d
570
585
"0.98
x
to 573
o
r,D
123C 9 1.09 ; A427
121C
325
31E
-8-6-4-20246 ""~-8-6-4-2 0 2 4 6 8
Fig. 39. CEM spectra of Fe(1 lO) films consisting of (D + 0.05) bulk atomic layer of pure 57Fe, prepared on
W(110) at TF~= 300 K, coated by Ag at Thg= 300 K. The spectra were measured at Tm= 295 K. They
were fitted by one single line (a') and four sextets [(a"), (b), (c) and (d)], with relative intensities as
indicated by the finger prints (from Ref. 333)
158
is known that the enhancement above about 50% results in a ferromagnetic surface even above
the Curie temperature of the bulk,
R A D O TM had noted in 1957 that the surface or first layer magnetization m, should follow
the Bloch law,
rn, = (1 - b 1 T3a)
with a spin-wave parameter of the first layer b I = 2b 0, enhanced twice in comparison with the
bulk parameter b o .
The magnetic hyperfine field H~n (T) follows the same temperature dependence as the
magnetic m o m e n t m of the electron shell. The proportionality between Hin (T) and m (T)
25~
W(110)/0.82 (475K)/Ag (3 IOK)
23C t T=274K
&-.
0
X 21 s ';~. .~2" '~ ~ ;"~.--t--,'3
co
301
~i=2 8
2K
28~
28~ .... " -:
z8c8
-8-6-4-2 0 2 4 6 8- 4-'z 6 . 8
Fig. 40. CEM spectra of a film W(110)/0.82 (475 K)/AG (310 K) (0.82 bulk layers of STFe(ll0), prepared at
T v e = 475 K, coated by Ag at Tag = 310 K, fitted by a superposition of one magnetic component
(11/6:12/5 : 13/4=2.6 : 0.3 : 1) corresponding to magnetization along [ll0], and one nonmagnetic single
line. Line broadening at 87 K by vibrations in the cooling system. For all other temperatures, the line
width (FWHM) is given b y / ' = 0.40 + 0.06 mm/s (from Ref. 334)
159
is known from bulk materials. Therefore, local analysis of m (T) becomes feasible using
a probe layer of 5VFe. WALKER et al. confirmed the enhancement of thermal decrease
near F e ( l l 0 ) / A g ( l l l ) interfaces. 332 For a probe of 1.5 atomic layers of SVFe near the
Ag-coated surface of a fitm of 30 atomic layers, a Bloch law with b~ = 12- 10 -6 K -3/2 was
obtained. It showed 324 a surface enhancement b~ /b o = 2.3, compared with the bulk value
b o = 5.2. 10 4 K -3~.
A detailed analysis of F e ( l l 0 ) films on W ( l l 0 ) , coated by Ag, again showed the
enhanced thermal decrease of the first monolayer, where the centre of the film followed
nearlY the bulk Bloch law. Comparison of b~ = 13.3.10 -6 K -3n in the Ag-coated surface
with b~ = 6.2- 10 4 K -3a from the film centre resulted in an enhancement b o / b o = 2.15.
The magnetic moments are enhanced in free surface of transition metal ferromagnets. The
reduction of H~, (T) in the first monolayer was combined with an enhancement of the magnetic
moment by at least 20%, as shown in Fig. 39. 333 The CEM spectra of pseudomorphic films
measured at low temperatures are shown in Fig. 40. TM
For a Ag-coated ferromagnetic monolayer Fe(110) on W(110), 334.335 a reduction of H~, (0)
from 34 T (in bulk) on 12 T in the submonolayer was connected with an increase of the
magnetic moment from 2.22 to 2.53(12) P-B-
The layer-by-layer analysis of 57Fe/Ag superlattices and epitaxial 21-monolayer Fe(110)
films on W(110) was carried out using in situ CEMS. 336.337,338The temperature dependency of
H~, for films of different thickness is shown in Fig. 41. 339 The local structure of the H~, (T)
36, 36
_~.~ High field component
35! 9 W(llO)/8.6/Ag 35
L"-----._"~ 0W(110)/5.3/A.g
34
33
32 32
v
z2
:ff 21 ', 30
2O
19 ""- 19
Low field co %" o
18
T 1 I -. ~
i00 200 300 460

Temperature (K)
Fig. 41. The temperature dependence of the magnetic hypeffine field for films of different thickness. All data
were fitled to HI,(T)= Hi~(0)(l - bT3;2) as indicated by solid lines (from Ref. 339)
160
near Fe(110)-surfaces was analysed for the Ag-coated surface at 90 < T < 300 K and for the
free surface at 300 K. 34~The data of the free surface were extrapolated to the ground state,
resulting in a clear spatial oscillation, H~, being reduced in the first monolayer by 0.75 T and
enhanced in the second monolayer by 0.77 T.
Strongly reduced Hin values of Fe(100) near W(100) can be explained 34~ by a spatial
oscillation. Spin-wave parameters in the first monolayer were enhanced by a factor 2.6 in the
Fe/W and a factor 3.1 in the Fe/Ag interface, respectively, indicating a moderate reduction of
exchange in this interface. In the first monolayer below Ag, two components of Fe were
observed with different hyperfine fields. TM
Ultrathin films (10 to 17 monolayers) of fcc Fe(100) grown epitaxially on Cu(100) were
found to be paramagnetic at 295 K by 57Fe CEMS in UHV. 342 Below TN = 65 • 5 K, fcc-Fe
films are magnetically ordered and show a small average hyperfine field of 1.1 T at 29 K for
10 monolayers, indicating a small atomic magnetic moment. The fcc Fe(100) stabilized at a
lattice constant/c~[ose to that of Co has an antiferromagnetic ground state, 342
The magnetic properties of (111) Cu/Fe multilayers grown on Cu underlayers of several
thicknesses (200-50-5 nm) on cleaved mica have been investigated by CEMS and SQUID
magnetometry. 343The results suggested that 2.5 monolayers of y-Fe fnterfaced with Cu evolved
partially from paramagnetic to ferromagnetic states as the Cu underlayer thickness was
reduced to 5.0 rim.
Magnetic hyperfine fields near the Fe/Cr interface in epitaxial thin film structures with
(110) and (100) orientation were analysed by in situ CEMS.344,345The Hi, at room temperature
in the first Fe monolayer (ML) at the interface was strongly reduced to 22.0 T(110) and 20.9
T(100), whereas the 2nd and 3rdML revealed a slightly increased Hin of 33.7 T as compared
with the Fe bulk value of 33,4 T. The temperature dependence of the H~n at the interface
showed a T -3a spin wave law. The spin wave parameters are enlarged-with respect to the bulk
value, indicating a reduced exchange interaction, The temperature dependenceof the local
magnetization for the interface atom layers was found to be much smaller than that of the
magneto-resistance (MR) effect.
The H~n at the interface with noble metal differs only slighdy from the Hi, (0) in the center
of the films. There is a positive correlation between H~o and IS at Fe/Cu, Fe/Ag, and Fe/Au
as shown in Fig. 42. 346
The FeZr multilayer films 346,347 annealed in ultra-high vacuum were not completely
amorphous: only a maximum thickness of 14 interfacial c~-Fe is transferred into the
amorphous phase between 620 and 660 K. The thin amorphous layer acts as a diffusion barrier
and prohibits further growth of the amorphous interfacial layer. Iron segregation in Zr-Fe
alloys was studied. For the samples with the overall composition Fe0.67Zr0.33, Fe0.sZr05 and
Fe0.33Z0.67, an amorphous phase was formed. 347 The growth and the crystallization of the
intermetallic compound FeZr 3 for the rich zirconium sample were discussed. 347 A Au/Si
interface, 348 and a Fe-AI thin-film349.350 were characterized by CEMS.
Fe/Fe-N multilayered films prepared by an alternation of Fe sputtering and nitrogen
plasma exposure TM were analysed by CEMS. Fine crystals of s and Fe2N grains were
produced in plasma exposure rather than thermally stable y-Fe4N. The Fe/Fe-N multilayered
fihns showed good soft magnetic properties.
In Y/Fe/Y layered structures the Fe interlayer grew in an amorphous structure up to a
critical thickness of dr =2.3 nm. The average magnetic moment of c~-Fe amounts was
= (1.2 + 0.2)/.t B and the fenomagnetic Curie temperature was T~ = (80-+ 3)K? 52
In situ CEMS in ultrahigh vacuum was employed to study the average Fe-spin orientation
and hyperfine fields in zero external field in uncoated and Tb-coated 57Fe films deposited
either onto a clean Tb(0001) single-crystal surface or onto (bulk like) i~olycrystalline Tb or
Ag films. At 30 K, the spectra of 1.5 nm thick uncoated Fe Films on Tb(0001) indicated
structurally disordered (amorphous) Fe layers, whereas spectra of 3.0-3.5 nm thick Fe films
161
W(110)/20§
37 , , , , ,.
1 35
34 ~bulk
,4
3:
3~ I 1 t 1 I
0.05 0.09 0.13
IS (m~/'s)
Fig. 42. The ground state values of magnetic hyperfine field combined with isomer shift for Fe(110) interface
with noble metals (from Ref. 346)
exhibited a preferential Fe-spin orientation perpendicular to the film plane at - 3 0 K

irrespective of the substrates used. 353
2. Langmuir-Blodgett layers
Mono- and multilayers of ferric stearate were formed on oxidized silicon wafers by the
Langmuir-Blodgett technique. 3s4,355Heating of samples in air up to 523 K ted to a desorption
of the fatty acid chains, while the ferric irons were left on the substrate surface. They formed
a rather homogeneous, closed oxide layer. The iron oxides are most probably in the form of
crystalline and amorphous 7-FeOOH. 329 By a subsequent heating in hydrogen gas or exposure
to nascent hydrogen, a part of the iron oxide layer was reduced to the metallic state (cc-Fe).
The CEM spectra (Fig. 43) 329 show the formation of a mixture of different iron species (Fe 3§
Fe 2§ Fe0). The surface iron ions were found to exhibit a reasonably high recoilless fraction.
CEMS is useful for identifying iron species even if the surface is covered by less than one
monolayer. Oxidic and metallic Fe/Ni multilayers were prepared from Langmuir-Blodgett
films. The results observed by CEMS were different from those obtained from disordered bulk
alloys. 356
F. Surface and interface reaction

EYNATTEN et al. (1991) 357 studied the interface between polymers and metallic iron.
Chemical changes of metallic iron can be detected with a resolution of less than a monolayer.
First results of UV-light (60 mW/cm 2) induced changes of these interfaces to the copolymer
of polyvinylidenefluoride/trifluoroethylene (VDF/TrFe) or poly carbonate, respectively. The
162
T = 530~
t•
//V~
Fe 3§
,-~ Fe 2+
~
ul
, ,/
.4-a
8 T = SO0~
! 1 I I !
-I0 -5 0 5 I0
Velocity (ram/s)
Fig. 43. CEM spectra of thermodesorbed samples with I1 ML after heating in I-Iz gas for 15 rain at 803 K and
773 K (from Ref. 329)
production of Fe 3+ saturated for longer times of irradiation at a value of about 4%, equivalent
to about one monolayer of iron compound if the Debye-Waller factor would be half of the
value of metallic iron. The high spin Fe 2§ was dominating for long times of irradiation.
To investigate lubricant substrate interfaces, stoichiometric MoS 2 single crystals coated
with 57Fe films were investigated by CEMS. 358 Four different compounds were found to form
at the MoS 2/Fe interface, depending on annealing temperature, sulfur content in the MoS 2
and defect density. The undamaged MoS 2 basal plane was inert toward reaction with iron,
whereas the presence of excess sulfur and defects promoted the reaction. FeMozS 6 was found
to be preferentially oriented with respect to the MoS z habit plane. Excess sulfur within
molybdenite migrated to iron overlayers to form overlayers of troilite or pyrohotite depending
on the annealing temperature. The interfaces of TaS 2 and Fe layers on quartz, prepared by
DC and RF sputterings, also were characterized by CEMS. 359
The surface of iron fluoride hydrate was observed by CEMS at low glancing angles. 36~
The reaction of ct- and q(-Fe203 with flammable gas, TM the reaction between hydrogen fluoride
and iron oxide surface films in the presence and absence of oxygen and water vapor, 3~2 and
the oxidation of siderate 363 have been investigated by CEMS.
Thin layers of-~TFe (2.5 nm, l0 nm and 70 nm thickness), vacuum evaporated onto A1 and
Si plates, have been investigated by CEMS, UHV-ICEMS and DSCEMS. 3~3B The phase
analysis of the layers indicated the presence of metallic iron and one or two iron compounds,
formed with the residual gas during evaporation as shown in Fig. 44. These products were
rather stable iron nitrides, which were distributed through out the whole layer.
163
15(]
130 ~!~ . 2.5rim
I I' I I
o ~ 11 !I
x 3z /l ii'if
-4~
= 29 t k :; ":-~" , ~,7
320 I~
,I!
i'~
I!,
!]
7Onto
/il ~ ~ ~11 /~
5 .i !./,,vt.,i..ii!:]\
-10 -5 0 5 1'0
Velocity (ram/s)
Fig. 44. Integral CEM spectra of 57Fe layers of 2.5 nm, 10 nm and 70 nm evaporated onto oxidized Si, A1 and
AI, respectively(from Ref. 61)
G. Ion implanted layers

The effect due to ion implantation depends on various factors: beam parameters, nature
of materials, and substrate temperatures.
CEMS has most often been used to characterize ion implanted surface layers because the
location of implanted ions from the surface is almost consistent with the sensitive depth of
CEMS. Together with CEMS the other analytical methods for depth profile of elements such
as Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), secondary
ion mass spectroscopy (SIMS), Rutherford backscattering spectroscopy (RBS) and nuclear
reaction analysis (NRA) have been used. AES, XPS and SIMS are destructive techniques,
whereas RBS and NRA are non-destructive analytical methods of element profiles. RBS takes
advantage of the significantly lower Coulomb barrier for low atomic number elements with a
depth resolution of 10 to 20 nm. When characterizing crystalline products in implanted iron
and steels, grazing incidence X-ray diffraction (GXRD) can be used supplementally.
Ion implantation techniques were first performed in order to improve the electric property
of semiconductors. To improve the surface property of metals, light elements such as nitrogen,
boron, carbon and phosphorous have been implantated into the metals, and irradiation with
Ar, Kr and Xe ions is effective to mix the multilayers and heterolayers for new materials.
164
K, NOMURA et al.: APPLICATIONS OF CONVERSION ELECTRON
1. Fe ion implantation
a) In semiconductors and metals
57Fe implanted into semiconductor solids36s and Single crystals of graphite366 have been
studied by CEMS. Hyperfine interactions of 57Fe implanted into 3d, 4d and 5d metallic hosts
were comparable with fast quenched dilute alloys.367 Fig. 45 presents isomer shift data for
iron implanted into various matrices." The concentration of iron implanted was about one to
three atomic percent, but IS values for the implanted 57Fe were different from those for the
dilute alloy obtained by thermal equilibrium because of a high degree of atomic disorder in
matrix.
In Si and Ge implanted with 57Fe at the energy of 70 keV and the doses from 5 9 1014 to
1016 c m -2, the QS values increased with the lowering of iron dose) 66 In 3 at% Fe implanted
in Si and Ge, a rather small temperature dependence of the electric field gradient was observed
and interpreted in terms of the T -3n relationship.3s9
Factors influencing the final landing site of implanted ions in semiconductorsy~ and the
defect configuration in semiconductors and metals on high dose implantationTM were reviewed
by Langouche. At high doses ( > 10 ~6 atoms, cm-2) of 57Fe implanted into Si(lI) single crystals,
the measured hyperfine interaction values were the same as those in the bulk amorphous
Fe~Si~ samples. At low dose, the IS value was the same as that of the stoichiometric
crystalline phases but the QS value was different,m
Evidence for fast diffusion of 57Fe implanted in copper was shown by DSCEMS. 373 The
copper-iron alloys produced by 57Fe implantation374at doses between 1 9 10 ~s and 5 9 10 ~6 ions
9cm-2 and the aging behaviour of the implanted alloys375 were characterized by CEMS.
A significantly different spectrum observed for the highest dose was associated both with the
effect of sputtering and with the presence of widely spread damaged regionsP74
L2pJ L3pJ L 3d 14pa L 4d 15pJ L 4f J" 5d 16pJ
-0. ~ sr (0)1z
c .ATi TboLuxH
"~ Ac~- ~ ~d
~C Mg Zn~Ge ~ T ~Ir~
O. 5 . Se Ag~,/wTe ' ~ A u
11 o
I I I 1 I I I I I I I
0 20 40 60 80 100
Atomic Number
Fig. 45. Systematics of the isomer shifts for the one to three atomic percent iron alloys obtained by implantation
of 57Fe ions (50-100 keV) in various matrices - black points. The open points are for the corresponding
alloys obtainedby diffusionor alloyingat thermal equilibrium(from Ref. 11)
165
Valve
I
Ta:
i
,I
:Ion Beam
To D r i v e ~
v~ :ton
~6
v.
Shutter tOUr o Terminals

I
Fig. 46. Cross section of inslrument for in situ CEMS of isotope separator implantedsamples. Viewed from above
(from Ref. 377)
CEMS apparatus for in situ studies of ion beam-modifed metals has been developed as
shown in Fig. 46. 376,377An in-situ CEM spectrometer 377was used to study the defect association
and clustering of 57Fe implanted in AI and Cu. The substitional monomer fractions are shown
in Fig. 47 and Fig. 48. For 57Fe implanted into Cu at 120 K, the substitutional fraction ~ )
was less than 0.5 of the value expected for a random distribution and it fell to zero after
annealing at 600 K, where more extensive Fe clustering occurred. For 57Fe implanted into A1
at 120 K, f~ was somewhat smaller than expected for a random distribution of impurity but
much larger than after implantation at room temperature. 377 An apparent inconsistency was
observed between ion implantation experiments by recoil implantation of Coulomb excited
atoms and by conventional ion implantation. 378
57Fe implantation and post A1 implantation in aluminium foil were performed at the low
energy of 27 keV and the CEMS showed the formation of intermetallic compounds FeA16 and
F%A1s during the ion bombardmentY 9 The aging behaviottr of 57Fe ions implanted A1 with a
38 kV isotope separator was examined by CEMS at 77 K. The spectrum changed at
temperatures below 373 K, suggesting supersaturation of the lattice vacancies? ~0
Ni-Ti 50 at% alloy was amorphized under 57Fe ion implantation at 300 K. The short-range
order, structural relaxation, crystallization and diffusion of S7Fe were studied after annealing
(300-900 K). Amorphous Fe-Ti-C phase was produced by Fe ion implantation and its role
TM
in tribological behaviour was investigated28z The Fe implanted gadolinium was also studied
by CEMSY 3 High dose implantation of Fe into metals and semiconductors have been
performed with energies up to 1 MeV at the UNILAC injector) ~4 Unusually high
concentrations of 70 at% Fe for Si with doses of 10 ~s Fe ions. cm -2, and 20 at% Fe for Cu
with 10 t7 Fe ions- cm -z were obtained.
166
K. NO/vlURA et al.: APPLICATIONS OF CONVERSION EI..ECq'RON
+ Lonwgrth & Jain (implanted)[

SVFe Cu • Sawlcki s (implanted)l
9 de Wa~?~l-& Ziaang (implanted)l
O Window ( quenched)l
,,\o \
o.~- _
-"
+ 3_ \ o
• \~ o \ \
\ +
0 i t ",,\ i \
0.1 1 10
Average conc. (96)
Fig. 47. Substitutional monomer fractions ~ ) of Fe in implanted and quenched 57FeCu samples. Drawn line:
expectation for random (binomial) impurity distribution with 12 neighbours; broken lines for 52 and 100
neighbours (from Ref. 377)
XSawicki's (implanted)
5~Fe A1 l d e Waard & Zhang
(implanted)
t*
q-~
1.(
~ (quenched)i
0.5
_x X~x o~
x 12~
I 1 • I \
0.1 1 10
Average conc. (%)
Fig. 48. Substitutional monomer fractions (/s) of Fe in implanled and quenched 57FeAI samples. Drawn line:
expectation for random (binomial) impurity dislribution (12 neighbours) (from Ref. 377)
167
Nickel foils were implanted 385 with 57Fe+ in the range 0.1 to 2.5 9 10 ~7 ions. cm-L At low
fluence a Ni(Fe)' solid solution was formed. When the fluence was increased FeNi 3 was first
produced, then FeNi together with a small amount of Fel_~Ni~ with x = 0.3~).4 even if the
predicted value was lower than 0.55. Although ion implantation and ion beam mixing can
lead to the formation of Invar alloys~ it is difficult to obtain only one phase with these
techniques.
b) Fe ion implantation in ceramics

Ceramics such as MgO, A12033~6 and ZRO2387 were implanted with 57Fe§ ions and the
~samples were annealed under various atmospheres (02, H 2, Ar). In a single crystal of
sapphire.implanted with 100 keV 57Fe to a dose of 3.4 9 1015 ions 9 cm-2,'the CEM spectra
even at 15 K temperature did not show magnetic sextet of high spin Fe 3§ In this case
of low dose all irons Were in two charge states of Fe2§ = 0.9 mm/s, QS = 2.19 mrn/s)
and Fe3*(2)(IS = 1.34 mm/s, QS = 2.26 ram/s). 388 In A1203 implanted at room temperature
with 1.2. 1017 STFe+ ions. cm -z at 110 keV, 389,39~ the iron atoms were found to be in
different chemical states: (1) a single line with IS = -0.08 mm/s (small c~-iron precipitates;
Fe~ (2) the doublet with IS = 0.08 mm/s and QS = 0.40 mm/s (Fe 4§ ions located in a
distorted FeO 6 octahedra), and (3) the two doublets with IS = 1.00 mm/s and IS =
= 0.55 mm/s (Fe z+ i n FeAlzO 4 and cationic or anionic vacancy configurations). Fluence
dependence of the components in CEM spectra is shown in Fig. 49. 39z Relative amounts
of the components produced were different between the substrate temperatures during
implantation. An amorphous surface layer was produced by implantation of Fe ion in
AlzO 3 at the substrate temperature of 77 K during implantation. TM Fe 4+ ions completely
disappeared at 673 K. After heating at 1273 K, all iron atoms were oxidized into Fe 3~
and formed two populations of (Fe~AlI_x)203 precipitates. The magnetic component would
be large hematite-like precipitates (x > 0.9) located along grain boundaries. The hematite
precipitates were grown at 1473 K. 389 The total amount of iron was distributed among
~-Fe203 and ~-(Fel_xAlx)zO3 precipitates. For highest temperature annealing up to 1873 K,
only substitutional iron remained. 39~In reducing hydrogen atmosphere iron did not migrate
up to 1273 K. As a result, first the FeA1203 contribution increased and in most cases
large c~-Fe precipitates were formed together with hercynite containing some defects.
Further annealing at 1473 K completed the clustering of iron, decomposed partially
FeA1203 and produced oxide precipitates at the surface of the grains. The hyperfine
parameters corresponded to 7-Fe203. At 1673 K the total iron disappeared from the
implanted layer, s93
CuO (small metallic precipitates), FeO (small c~-iron precipitates), Fe2+(FeA1204), Fe 4§
(metastable state), ZrO and Zrz*(ZrO2) were produced in the as-implanted region with Cu, Fe,
or Zr, respectively. By thermal treatments between 873 and 1273 K, a complete surface
oxidation occurred and some precipitates appeared along grain boundaries. Annealing at
temperatures range from 1273 to 1873 K led to the drastic changes of surface composition. TM
These results were reviewed and the comparison between implantation and annealing effects
on single-crystalline and polycrystalline materials is conducted. 394 The main differences were
attributed to grain boundaries. Fe implantation at 160 keV and 1017 ions. cm -z in sapphire
reduced in iron precipitates with .an average size of 2.5 nm. Two doubles of the Fe(II) state
were ascribed to the FeAI203 spinel compound and to a spinel structure associated with oxygen
vacancies. Two other doublets were assigned to the Fe(IV) with high spin configurations. At
973-1073 K, the Fe precipitates grew and remained superparamagnetic whatever the matrix
structure. The Fe(III) oxidation, state had different hyperfine parameters in single and
polycrystals. In polycrystals the doublet was characteristic of the mixed oxide (Fet ~AI~)~O3
with some typical sextet of F%O 3 slightly began to appear. In the single crystal only one
168
Ion f l u e n c e Ion f l u e n c e
( X I 0 ~ i o n s . c t a -2) ( X 1 U s Lons.cm -~)
.0 z 4 6 8 lo o z 4 6 s to
~ ' ' , j.<~4 r , , , , ,~
20 L_ ,. 2+ ~ *A
oi-,/" , , ,I I- '~' ,
40[ l , ~ i ' '1 0t I I i I,/
.--~ ..... o ~001~ J i I I iA
0L ~ r p| N40
~'10/+-.7." , l I I1 4
,0b ------+ ,
Ok I I I ,I
40, , i I I 4~ 0!
40 I I I ~ q
(a) 0~" 110 210 Fe~, i o-~i , I ] (b)

30 I0 20 30
Concentration Fe/AI (%) Concentration Fe/AI (%)
Fig. 49. (a) Fluence dependence of the different componentspresent in the MOssbauerspectra of AI203 implanted
with 160 keV, Fe at 77 K. (b) Fluence dependence of the componentspresent in the M6ssbauer spectra
of iron-implanted crys{allineAI203 (300 K) (from Ref. 392)
doublet was attributed to the Fe(Fex ~A1)203 spinel detected) 94 At 1473 K Fe203 precipitates
were preferentially identified in the polycrystal whereas only the spinel phase was observed
in the single crystal. At 1673 K the remaining iron might be incorporated into the alumina
lattice in the (F%_xAI.+)aO3 solid solution or in the form of small particles of diamond cubic
F%O 3 containing aluminium? 94
A ZrO 2 fihn was implanted at room temperature 3s7 with 100 keV 57Fe+ to a fluence of 8 9
9 10 ~6 ions. cm -2. The oxidation of iron was very fast and completed around 673 K for the
ZrO 2 film. The powder samples of 57FezO3 and ~6FezO3 were implanted with 56Fe and STFe ions,
respectively, 39s to study local states of implanted and displaced iron ions in o~-FezO3.3% The
implanted and displaced iron atoms appeared in three different states: (1) regular subsitutional
positions of Fe203, (2) as magnetite Fe304-type structures and (3) paramagnetic FeOl_x state.
In 5VFe implanted samples some enhancement of the FeOt~ fraction was found in comparison
with the SSFe implanted haematite. 39-~ Silver arsenic sulfide (AgAsS2) glass 397 and lithium
fluoride 3~ implanted with 57Fe ions were also characterized by CEMS.
2. Other ion implantation in iron and steels

a) N ion implantation
Ion implantation produces point defects and compressive stresses in the implanted layers.
The vacuum heat treatment anneals out the point defects, stabilizes the compressive stresses,
and favours migration of nitrogen atoms towards grain boundaries and dislocation pipes
leading to their passivation there by inhibiting the oxidation of the iron foils.
169
Nitrogen implantation is effective in improving the mechanical properties of steels such

as microhardness, friction and wear rates. MAREST 399reviewed nitrogen implantation in iron
and steels in 1988 and considered the nitrogen distribution, the microstructural changes, the
influence of various parameters depending on the irradiation or on the implanted steels, the
effects of thermal treatments, the texture effect and the oxidation mechanism. Since the energy
of implanted nitrogen used was commonly about 20 to 100 keV, the distribution extended to
about 150 nm thickness. The assignment of M6ssbauer parameters to specific phases has been
made by comparison with literature parameters of nitrogen compounds (cg-martensite (N),
a"-Fe16N2, 3t-Fe4N, e~ or ~-Fe2N, e-Feq§ and of e-Feq§ carbonitrides. These parameters
are listed{n Table 12.
The evolutions of nitrogen implanted steels by annealing can be schematically summarized
as f o l l o w s : 399
For 2. 1017 N § cm -z
c~-(N)martensite
0_Fe3(C,N) 523 K ) e_Fe3(C,N) 723 K e.Fe3.2N or
a"-FelsN 2
For 4 . 1 0 ~7 N +- cm -z
523 K 723 K 883 K

e-FeqN ~ e-Feq(C,N) ) e-Fe3.2N ) og'_FelaN
For 6 . 1 0 L7 N § cm -2
~_FeaN 523 K ; E_Fe.z(C,N) 723 K ) g-Fe3(C,N) 773 K ) ct'-martensite

~-Fea(C,N) + "/-Fe4N
LONGWORTH and HARTLEY (1987) have investigated chemical states of compounds

formed after nitrogen implantation of various doses in pure iron. They produr~'~ a phase
diagram of the implanted iron-nitrogen system. 4~176Iron implanted with nitrogen and
phosphorus, 4~ monocrystalline iron,4~ 9Cr18 stainless bearing steel, and C40 medium-carbon
steel,4~ implanted with nitrogen, were studied by CEMS. The oxidation behaviour of N +
implanted iron-nickel (FesoNiso) alloy, 4~ and the effects of a-particle irradiation fluence on
nitrogen-implanted compounds in low-carbon steel4~ have been studied. For 3BNCD4 steel
samples, implanted with nitrogen, steel layers followed one upon the other in which first
Fe2§ with 0.3 < y < 2.7, then Fez§ with 0 < x < 0.3, and finally austenite containing 10 at%
nitrogen, predominantly. 407
~SN implanted (E = 40 keV, D---2. 1017 ions. cm -2) iron and two steel types, 100Ca and
42CD4, 4~ were characterized by the 15N(p,ctqt)~2C reaction and CEMS. When iron foils
implanted at a dose of 2 . 1 0 ~ ions. cm ~ of 80 keV N~ were treated by thermal oxidation,
the as-imPlanted samples exhibited enhanced oxidation while the implanted and annealed
samples showed considerably reduced oxidation. 4~ These, results were supported by the
oxidation of iron foils implanted with Ar+ and of iron films with stresses on substrates of
molybdenum.
Bearing steel implanted with N* (2 - I0 ~7 ions - cm -~ at 60 keV) 713 K were measured

by CEMS and XMS as shown in Fig. 50. 4~~The following microstructures were modified:
(1) reduced near-surface (about 100 nm) austenite content, (2) formation of Cr-modified
Fe nitrides, and (3) N trapping in carbides thereby forming complex Fe-Cr carbonitrides. 4~
The thermal behaviour of the carbonitrides was strongly affected by the He particles
(10 L5 a - cm-2). 4"
170
"~ d ~d i
d dd'd dd i
d gd 1
d dd i
d ~d i ,
d dd i ~
o
~,~
O O
~,q 4.a z d
d dd d ~d ~ dd d dd d ~d d d~ d dd
~ I- *
r . . . . . . . , 9 9 o
r.. dg d dd g gd
I
J ~ ~ ~ ~ ~ ~.~ ~.~
~4~ d~d'~4dd ddddl~dd o~od ~d~o
~ ~
0 ~ 0 0 O0 0 O~ 0 0 ~ 0 O0 0 0 ~ 0 O~ 0
0 i~ ''~
~ ~ o ~ i ~o ~ ~o . . . . . .
dddg~ ! d4~ g'd4~ o o~;~ o i o ~ ~ o oo;~ o
~ ~.~ ~. ~ .. ~ ~. ~ ~. ~ ~. ~
O~ 0 0 ~ 0 O~ 0 O~ 0 0 ~ 0 0 0
0
o
171
For N ion implanted in anstenitic 18/9-stainless steel: 12CEMS analysis allowed resolution
of five iron environments having a different quantity of nearest and next nearest interstitial N
atoms. The relative line intensities of the subspectra agreed well with the statistical model of
a binomial distribution based on a random arrangement of nitrogen interstitials on octahedral
sites. 41~AISI 304L stainless steel samples were implanted at room temperature with 100 keV
N or C ions with a 4.1017 ions. cm -2 fluence, and were annealed at a temperature of 633 K
for 4 and 100 hours: 13Pure Fe and AISI 304 SS were implanted with N* ion to doses as high
as 1 9 1019 ions- cm -2 while the target was held at elevated temperatures, 373 K and 873 K.
Thick layers, containing y-Fe2N, were produced by holding the Fe target near 673 K while
thick layers containing either e-(Fe, Cr, Ni)2+AN, y-phase high N solid solution, or mixed
o~-phase/y-CrN was produced in 304 stainless steel, depending on the dose and the hold
temperature. The highest dose resulted in the e-(Fe, Cr, Ni)xN phase at 673 K, but in the
y-CrN phase at 773 K and 873 K. Because N was preferentially associating with Cr rather
than Fe, implantation of 304 SS at higher temperatures and doses of 1 9 1019 ions 9 cm -2 caused
decomposition of the austenite into a mixed ferrite/y-CrN microstrueture.414
(Fe, Cr)2N and (Fe, COx phases formed after implantation were fairly stable after
100 hours of annealing. The partial dissolution of these phases led to the formation of
magnetic components attributed to e((N) or (C)-martensites. The thermal stability of nitride
phases was greatly increased by alloying elements such as Cr and A1 as compared to pure
a-Fe implanted with N ion. 4a5 The thermal stability of nitrite phases upon 1 h annealing was
greatly increased as a result of co-implanting either Cr or A1 with N ion as compared to pure
ct-Fe implanted only with N ion. The increased trapping of N atom is related to the higher
formation energy of Cr- or Al-containing nitrides. The enhanced stability of nitrides, especially
of the y-phase in the FeCr and FeA1 model systems, resulted from the higher trapping
efficiency of N in such materials. 4a6 Microstructure and tribology of carbon, nitrogen, and
oxygen implanted ferrous materials417 also were studied by CEMS.
b) B ion implantation
The boron and carbon ion implanted irons were studied by CEMS. 4tg A ball beating steel
was implanted at room temperature with UB ions of 20, 35 and 50 keV energies a: 5 9 1016 to
2 9 1017 ions 9cm -z fluences. 4~9 The 11B (a,~x') reaction at 6.04 MeV was used to determine the
boron distribution profiles. The high fluence led to amorphization of the surface. Fe2B, Fe3B
and Fel_~13x phases were distinguished in boron implanted ball bearing. 419 A thin amorphous
layer was formed in the topmost region of all three different types of steel, armco iron,
X90CrMoV18, and austenitic X10CrNiTi189 when boron ions were implanted at room
temperature using 100 keV beam energy in a dose range of 2 to 1 0 . 1 0 a7 ions 9cm z. An
additional doublet was accounted for as boron atoms on interstitial sites in the direct
neighbourhood of the probe Fe atoms. 4z0
c) C ion implantation
Steel (210Cr46) was implanted in two steps with 5. l017 cm -z carbon ions at 50 keV and
with 2.1017 cm -z carbon ions at 20 keV. The CEM spectrum of the untreated steel showed
about 82% martensitic (sextets 1, 2 and 4) and 18% austenitic fractions (doublet and singlet)
as shown in Table 13721 Sextet 3 is due to the introduction of chromium into the iron lattice
which leads to a decrease of the hyperdine field by about 2.2 T. After implantation, the
martensitic fractions strongly decreased, and two subspectra (sextets 5 and 6) appeared in
addition to the crystalline phase of FezC.
To investigate new effects such as the "long range effect", which is defect formation at
depths exceeding the ion range in materials under high dose implantation (1016 to
5 . 10 ~7 cm-Z), the multiply charged ions Al% Ti +" and C +~ were implanted into a-iron. 42z In
the case of the implantation dose, 2 . 1 0 : C ions 9cm -2, it resulted in e-carbide formation
172
K. NOMURA et al.: A P P L I C A T I O N S OF CONVERSION ELECTRON
o
.c/
2.
o
r
o ~
E
o
o I
L ~ O I ~0 ~ ~ t~
0 0 0,1 r 0
O
I I
o I
N I
O
~d
E
o ..
0
~176
O ~
o
~ N . . . .
N 0 0 0 0 O0
1 1 1 1 I
~ ,-4
~ .~
~4
0 0 0 0 0 0 ~ 0
173
1.091
XMS
100- I I-flAI-
G 1
1.26 ~
9,-,,I
r/l
~ ~.00
2 .07
~-~ - b ~~ XMS
, ,.--,I
.4..a
1.00 ~ Y~'-~'~ " "~

1"08 b [I CEMS -
1.00 t--JN2 lt74
I I 1
-4 0 4
Velocity (mm/s)
Fig. 50. XMS and CEMS data and computer fits from (a) unimplanted 400 ~ steel and (b) N-implanted
440 ~ steel (from Ref. 410)
(Fe2C), which then partially transforms into cementite (F%C) due to substrate heating caused
by irradiation. The implantation of C ions did not show the decreased wear even in the case
of 8. 10 ~7 cm -2 doses, though microhardness increased.
d) P ion implantation
Phosphorus ion implanted iron has been studied. 4~3,424,425The mean projected range for
phosphorus in iron was 22_+ 14, 39 +22, and 7 2 + 38 nm for 50~ 100 and 200 keV,
respectively. The samples, P2 (50 keV), P4 (100 keV) and P6 (200 keV), implanted with
5. 1017 cm 2 phosphorus ions showed fairly uniform behaviour. Paramagnetic Fe2P-like
structures could be detected in all three samples. The lines of the two quadrupole doublets
were very broad (0.66 ram/s). They could be explained only by amorphous fractions with
174
, 9 , a:-Fe
, ,,'!..': :" : }FezP
) FezP
>. 104
i0~
IOC
i0~
~ i0~
..~ IOC
10C
104
102
100
104
i0~
lOG
Velocity (ram/s)
Fig. 51. CEM spectra of sample P4 as implanted (100 keV, 5 - 10t7 pcm-2) and annealed for 1 h at different
temperalures (from Ref. 425)
widely spread hyperfine fields. F%P-like structures and another magnetic c o m p o n e n t

(IS = 0.12 ram/s, QS = - 0 . t 8 mm/s, Hi~ = 2 0 . 2 T) were found in sample P5 (1 - 10 I7 c m -2
200 keV). Annealing at temperatures up to 673 K and 773 K resulted in a precipitation
of Fe2P and Fe3P (4 sextets), respectively. This fact could be seen at 873 K most distinctly.
The Fe3P began to decrease at 973 K as shown in Fig. 51. 424
e) A1 ion implantation
Iron samples were implanted with A1 ions at 50, 100 and 200 keV, respectively, w i ~
doses between 5 . 10 ~6 and 5. l017 cm-2. 426,427 Independent of energy, at doses up to
2 - 10 ~7 cm -2, further magnetic fractions with a Fe3Al-like structure were formed besides
oc-iron.42~ The CEM spectra of A1 implanted iron included (1) a central line with IS = 0.2 mrn/s
(nonmagnetic alloy phase), (2) a magnetic hyperfine field distribution with a maximum near
30 T and an average IS = 0.05 mm/s (a magnetic Fe3Al-like disordered phase), and (3) a sextet
at 33 T, IS = 0 mlrds (bulk o'-Fe). 429 DSCEM spectra are shown in Fig. 52. 429 At high dose
A1 implantation of 1 - 10 ~8 cm 2 the component with QS = 0.5 mm/s and IS = 0.2 mm/s was
produced. The FeAI like order was transformed into a Fe3A1 like order between 673 K and
873 K. At 973 K the influence of the aluminium implantation was strongly decreased and
(z-iron was the predominant phase. 43~ The increased implantation dose of A1 into o~-Fe to
5 . 1017 ions. cln -2 resulted in a decreased degree of ordering and possibly partial
amorphization. An ordered Fe3AI phase, including a partial amorphous phase, was produced
as a result of A1 implantation. 422
175
5 X 10 ! Z 50 keV Ai --~5'Fe
~ 6600eV
0ov
v
,,-4
4..1
i-..4
ID
,,-4
4~
r
~l ~ 12750e~ ~ ~
,--.4
~,i . ll0500eV
i0 30
H,.(T)
-8 -4 0 4 8
Velocity (ram/s)
Fig. 52. DCEM spectra and calculated hyperfine field distribution of the 57Fe foil (sample 5a) at various selected
electron energies (every resolution ~ E / E - 3%), plotted from top to bottom in the order of increasing
probing depths (from Ref. 429)
f) Ti ion implantation
The AIS1 M2 high steel implanted with 110 keV Ti ions at 293 K and with fluences
varying between 5 9 1016 and 4.1017 Ti + 9 cm -2 was characterized by CEMS. The profiling was
done using the 48Ti(p,7)ggv resonant nuclear reaction at 1362,keV and the sputtering yield
measurements of ironY~
Ti clusters and small dispersion carbides were formed in the surface of a - F e after Ti
implantation, which increased microhardness and decreased the wear and friction coefficient
by a factor of 2.5. 422 Increasing the irradiation dose to 5. 1017 Ti ions. crn4 results in the
formation of titanium carbide (TIC).
g) Ni ion implantation
Thin films (70 nm) of 57Fe deposited on SiO2 substrates were implanted with 0.5, 2.5, 5
and 10. 10 I~ 64Ni- cm -2 at 80 keV. 432 The RBS technique at 5,7 MeV a-particles was used to
determine the nickel depth in the implanted surface. Saturation was nearly reached for the
highest implanted fluence due to the high sputtering yield. FeNi alloys with different
compositions and structures were formed: Fe(Ni) solid solution, bcc Fe-ricb phase, fcc Ni-rich
zone and fcc FeNi invar alloys231
176
h) Si ion implantation
Si ion implanted into iron with different energies (100, 200 and 300 keV) and ion doses
(2. i017 to 1 9 1018 cm -1) was investigated by CEMS. 433 A singlet line was observed in CEM
spectra of iron implanted with 100 keV, 5- 10 ~ Si- cm -2 and 200 keV, t - 10 TM Si- cm -2. As
the single had IS = 0.22 m m . s-~ and no QS, FeSi or FeSi2 could be excluded, and the singlet
referred to isolated iron. The line became narrower by anne~iling at 573 K, and 673 K, and
was due to precipitation processes. The components with 32 T and 19.8 T, which were formed
at 773 K and 873 K, were attributed to the short range order of Fe3Si. After annealing at
973 K the peak intensity of Si/Fe compound decreased from 70% to 33% and t~-Fe dominated
in the CEM spectra. The Si diffused thermally and the concentration decreased in the
investigated range, and silicide compounds could not be formed.
3. Ion beam mixing (irradiation effect)

PRINCIPI et al.434 reviewed the effect of irradiation with Ar, Kr and Xe ions of bimetallic
systems. Fe/Pd, Fe/A1. Beam mixing is a new technique to induce changes in composition
and in structure of thin layers of deposited material on a substrate. The deposited layers are
mixed by cascade collisions and diffusive process connected with the mobility of defects
created by radiation damage. One of the advantages of ion beam mixing is that results can be
obtained at irradiation doses ten times lower than in the case of direct ion implantation. The
process is generally far from the thermodynamic equilibrium and so can induce the formation
of unusual surface structures. The typical configurations for ion beam mixing are monolayers
and bilayers, and multilayer targets. The depth is of the same order of ion range of 100 keV
Ar + or 200 keV Kr + in metallic iron films: 34 Ion beam mixing and substrate surface tailoring
may be used to enhance the adhesion at metal-glass, metal-ceramic and metal-polymer
interfaces. Some recent publications on the chemical and structural nature of such bonding
were reviewed, with special reference to the roles of interface chemistry and morphology: 35
a) A1/Fe layer
The ion beam mixing of bilayer and multilayer Fe/A1 samples 436,437was performed. (1) The
mixing of A1/Fe (A1 on top) films took place starting at 2.5 9 1015 ions. cm -z. (2) Iron atoms
moved fast toward the surface at 10~6 ions. cm -z, and (3) a bcc Fe/At solid solution was
formed 438 at 3.6 9 1016. A Fe/A1 bilayer (iron on top), kept at three different temperatures (77,
300 and 500 K) during bombardment in the dose range from 3. l0 Is to 1 - 1017 ions. cm 4,
was characterized by Vasconcellos et al) 49 (1) Ion beam mixing induced interdiffusion and
phase formation at temperatures lower than thermal annealing. (2) Irradiation led to an
intermediate state, (3) The stoichiometric Fe2A15 or FeA16 phases were formed under into
bombardment at 500 K.
A i-netastable Fe55A145 was detected by GODBOLE et al.439 in 100 keV A r irradiated
specimens of 30 nm iron coated aluminium. Fe3A1 and Fe phases were precipitated by
annealing at 873 K.
In the spectrum of the as irradiated sample the presence of two unresolved doubles D1
and D2 was recognized. Doublet D1 had parameters close to those found for an amorphous
(z-AlsrFe~4 phase prepared by SCHERER et al.: 4~ and doublet D2 was due to a substantially
similar structure but perturbed by possible extended defects, created by irradiation. When
Fe/A1 multilayer samples were irradiated by Xe ions~37 at 1.5 9 10 ~6 ions 9cm -2 at room and
liquid N 2 temperatures, a bcc disordered solid solution was formed and the ordering started
at 470 K. The ion beam irradiated Fe/A1 multilayer specimen was structurally disordered and
inhomogenous, and the subsequent annealing produced a phase evolution.
AI/Mn and AI/Fe multitayers were mixed at various temperatures (450, 493 and 77 K)
with an 800 keV Xe § ion beam. 44~ A dose of about 3 9 1016 ions-cm -2 was necessary to obtain
homogeneous alloys at 77 K, while the quasicrystalline phases were formed at 450 K (AIMn)
177
or 493 K (A1Fe) for a dose o f 8 9 10 z~ ions. cm -z. In the A1Fe alloys, the local environments
of the Fe atoms showed different characteristic evolutions for amorphous and quasicrystalline
phases with a combination of several sites, of which the relative proportions varied at each
intermediate mixing stage.
The ion beam mixing in Fe/A1 bilayer structures at low temperature did not induce
amorphous phase formation. 442 Multilayers of overall composition around Fe2oA180 subjected
to Xe bombardment at 7 7 K produced amorphous alloys. The icosahedral structure was
obtained by bombardments at 300 K . The initial multilayered thin film structures had
thickness from 10/2 nm to 10/42 nm of Fe/A1.
The ion beam mixing was accomplished by means of Ar+ and Xe § bombardments at a
fluence of..5 9 10 '~ cm -2, with ion energies of 100 and 300 keV, respectively. The analyses
showed the presence of amorphous equilibrium phases. The electrochemical corrosion
behaviout44~ of ion beam-mixed Fe/A1 and Fe/C were studied by CEMS.
Ion-beam mixing of the A1-Fe-Mn system with 100 keV A r and their subsequent
transformation upon thermal annealing were studied by CEMS and X-ray diffraction. 444,445The
mixed states were comprised both binary (Fe-AI, Fe-Mn, Mn-A1) and ternary (A1-Fe-Mn)
metastable phases. XRD patterns were obtained for the as deposited and ion-beam mixed
samples annealed at 673 K for 200 min. The X-ray diffraction patterns for the as-deposited
and annealed sample showed presence of a tertiary A1FeMn phase with ~-Mn structure along
with binary FeA1, Fe2A15, MnA16, [~-FeMn4, and A1Mn phases. 445 The MGssbauer parameters
of Fe-A1 intermetallic compounds are listed in Table 14,446 which are useful for the
comparison with the CEM parameters of ion beam mixed layers.
Table 14. 57Fe M~ssbauer Parameters for Aluminum Rich Iron Alloys~
Composition l.S.{mm/s) q.S.(mm/s) Line Width(mm/s)
AI-Fe (0.1954) 0
0.36 0
AI~Fe2 0.289 0.462 0.350

(-0.18) 0.5
Alx3Fe4 0.010 0 0.265

0.202 0 0,265
0.392 0 0.265
(0.010) 0 0,245
(0.210) 0 0.285
(0.415) 0 0.245
AI~Fe (0.223) 0.288 0,266

0.22 0.26
Ai-Fe(solid 0.43 0
solution) 0.440 0 0.252
0.422 0 0.242
(0.429) 0 0.229
Isomer shifts in parentheses have been adjusted to be relative to

a -iron foil.
( from Ref.448 )
178
K. NOMURA et aL: APPLICATIONS OF CONVERSIONELECTRON
b) Cu/Fe layer
40Ar (E = 225 MeV) and 13zXe (E = 120 MeV) ion radiation of Cu-0.2% SVFe alloys
accelerated the diffusion processes. In the case of amorphous alloys the degree of disorder
increased and the chemical short range order changed due to irradiation. The magnetic
amisotropy was decreased and the volume was increased by defects induced. 447
The internal oxidation of an oxygen-bombarded impurity element (fe) in a crystalline host
(Cu) was studied by C E M S : 48 Annealing of 57Fe-implanted copper at 673 K resulted in the
formation of host coherent precipitates of 7-Fe ( < 4 nm) in the non-oxidized copper and of
a solid solution of ferrous iron in the surface cuprous oxide forming "molecular" units of
Cu20 9 FeO. Ferric ions was not formed on ion bombardment with oxygen and the 7-Fe
precipitates were converted to o~-Fe203 ( < 6 nm) and possibly also CU*Fe§ z- (delafossite).
c) Ni/Fe layer
100 keV Ar + irradiation of Fe/Ni bilayers (with iron on top) was effective in the formation
of an heterogeneous Fe-Ni alloy with a structure partly bcc and partly fcc: 49 The high dose
irradiation of Ni-Fe bilayers (Ni on top) brought up to a migration of iron atoms toward the
surface. 45~ Layered thin samples of 100 nm 56Fe/3 nm 57Fe/43 nm Ni(coating) or 100 nm
S6Fe/3 nm S6Fe/63 nm Ni(coating) were irradiated with 100 keV Ar + or 200 keV Kr 2§ ions, 4s~
at doses up to 6- 1016 ions- cm -2. The resonant 58Ni(p,'y)sgCu reaction at Ep = 1424 keV was
used to obtain depth profiles of Ni concentration. Three distinct Fe-Ni phases were identified
by their hyperfine magnetic fields in the ion beam mixed region after irradiation: a solid
solution of Ni in bcc ot-Fe (33 T), an fcc Fe-Ni alloy (28 T) (possibly either NisFe462 or
Fe0.64Nio.36 invar alloy), 453 and a non-magnetic Fetich fcc Fe (7-Fe) phase.
Nickel was electrodeposited on one side and chromium on the other side of a sheet of
(z-iron enriched with 57Fe (85%). The electrodeposited Ni and Cr contained oxygen and it
could be separated by 500 keV Xe § irradiation. The separated oxygen formed an amorphous
metal-oxide interphase at the interface of iron substrate and electrodeposited Ni o r Cr, 454
Fe65Nis5 as multilayers evaporated in UHV were irradiated with 200 keV Kr ions at doses
in the range 1 9 1015-5 9 1016 ions. cm -2 in order to characterize the mixing process as a
function of the fluence. 455 A partial bcc to fcc phase transformation occurred even at the lowest
irradiation dose and went on when the irradiation dose was increased. A remarkable
enhancement of the fcc lattice parameter, due to interstitial inclusions of Kr atoms, occurred
at 4 9 1016 Kr 2+ - cm -2 dose. The bcc phase almost disappeared in the sample irradiated at
8.5 9 1015 Kr 2§ cm-:, and simultaneously a magnetic Fcc Fe-Ni phase (47 at% Ni content)
and a small amount of a nomagnetic fcc Fe--Ni phase were formed.
d) Pd/Fe layer
Analysis of Pd/Fe bilayers on SiO 2 before and after mixing with 200 keV Kr z§ was
performed using R B s and CEMS by GUPTA et al.456 A 5 nm thick 57Fe layer remained
unmixed at either the Pd/Fe interface or the Fe-substrate interface. This was attributed either
to a y-Fe phase, or to an increased lattice spacing of the ct-Fe itself, possibly due to
incorporation of Kr in the lattice. The broad peaks corresponded to Fea_~Pdx phase with average
composition x = 0.72. A disordered FePd 3 phase was formed predominantly in the mixed
region.
e) Zr/Fe and other multilayers
The amorphization of Fe-Zr multiIayers due to ion-beam mixing and solid state reaction
was studied using the CEMS and CXMS. ha the case of the amorphous Fe-Zr phase, the
diffusion of Fe was importantY 7 The ion beam mixing at Fe/Si,458,459 Fe/Ge, 46~ Fe]~/46I and
Fe/Mo interfaces462 were also studied by CEMS.
179
f) Irradiation effect in metals and alloys

Using 57Fe CEMS, the structural and compositional changes at near surface of the
amorphous Fe-13% B - 9 % Si and Fe-15% Cr-9% Ni stainless steel specimens were clarified
after the bombardment of 25 kV accelerated He + i o n s : 63 Radiation damage in stainless steel
SS 302, 4~ ion-implanted layers of ferrite ,garnet~s and phase transitions of Fe--40 at% A1,
induced by ion implantation,466:*7. '~s were studied by CEMS. Ion-beam mixing on iron metallic
glass (Fe67, Co~sB14, Sil)469 were also studied by CEMS.
A sigle crystal of 17/13 stainless steel was irradiated by Xe ion and characterized using
RBS and CEMS. 300 keV Xe ions induced martensitic transformation in the austenitic steel. 47~
The magnetic anisotropy changed in radiation damage in Fe-0.83% Mn--0.13% C steel
irradiated with 120 MeV 132Xe ions at room temperature. This indicated the segregation of
alloying elements due to irradiation.471
A rapidly quenched Nis057FelP19 amorphous alloy472 was irradiated by Xe ions (100 keV,
1015-1017 Xe ions. cm-2). The observed changes of the quadrupole splitting distributions were
associated with changes in the short range order of amorphous alloy due to irradiation.
The effects of Kr post-bombardment on iron-carbonitrides produced by N-implantation in
a low carbon steel were studied. 473 The Kr bombardment strongly affected the thermal
behaviour of the precipitates, raising their temperature of dissolution. It was suggested that
Kr vacancy complexes are responsible for a nitrogen inhibited diffusion, which turns out in
a retention of the iron-carbonitrides at higher temperature.
g) Irradiation effect in metal and ceramic interface
Ion-beam mixing at the Fe/AI~O3 interface was revealed by CEMS; 474,475Metallic iron films
deposited on sapphire substrates were mixed at room temperature with Ne, At, Kr, and Xe
' ions in wide dose and energy ranges. The ratio Fe3+/Fe2+ induced at the interface was found
to be controlled as well as the subsequent adhesion enhancement. This effect was optimized
in the particular case of a Fe/A1203 system mixed with neon ions as shown by the pin pull
test results. 476 Thermal annealing in the low temperature range ( < 872 K), which seems to
promote the spinel phase formation, produces an additional positive effect on adhesion 477
The interracial reaction between Nb and Fe/A1203 was enhanced by Ar ion i r r a ~ , n o n and
the rupture of Fe-O bonding caused by irradiation was 'also observed: 78 The subsequent
thermal annealing of the irradiated bilayers led to the interdiffusion between Nb and free Fe
precipitated from the oxide, with an Fe-Nb phase of ferromagnetic character possibly forming
at the interface region.
The interface of Fe/SiO 2 irradiated with 100 keV Ar ions was characterized by C E M S : 79
A FeTSiOi0 phase was produced together with an Fe-Si-O complex after ion beam mixing.
ct-Fe was precipitated and the ratio Fea§ 2+ increased after annealing the mixing sample at
723 K. The Fe/SiO 2 couple was also irradiated with 200 keV Kr ions 48~ in the dose range
2.5 9 1015 to 3.5 9 1016 ions 9 cm-L The presence of small Fe clusters, Fe/oxide and Fe/silicate
phases was recognized at the interface. The structural changes in the interfacial region after
thermal annealings were correlated to corresponding changes in optical properties. The
samples with three layers (Si/500 nm 56Fe/2.5 nm 57Fe/15 nm 56Fe) were irradiated with
20 MeV C1§ at 1013 ions- cm -2. The adhesion was improved markedly in the sapphire and
silica.480
The chemical reactions induced by 40 keV He* ions in tx-FeqO3 and Fe30 4 were
investigated by CEMS. 481 Magnetite was formed upon the bombardment of tz-Fe203, whereas
no change was observed in Fe30 4.
h) Irradiation effect in polymers
An ion beam mixing at the films of iron and polyethylene4s2 and of Fe (5-10 nm thick)
on PVC substrates with 48 MeV BI*+ ions483 were studied. Substantial radiation induced
alterations were observed in the CEM spectra. WAPPLING reviewed CEMS study on the
180
Table 15. Mossbauer parameters for the different components formed

during irradiation and f o r some p o s s i b l e c o r r e s p o n d i n g compounds
Component IS (mm/s) QS (mm/s)
D1 O. 38 O. 85
D2 1.04 2.48
D3 1.48 2.60
FeF2 component i. 37 2.79

FeFz 0.49 0 9
Fe(OH) 2 1.16 3.0
Fe z. 0.38 0.71
Fe-C 0.3 0.8
FeClz 0.44 0
Fel-xO 0.84-0.90 0.62
( From Ref.484 )
metal-polymer systems irradiated with heavy ions. 484 Three doublets (D1, D2 and D3) were
observed by irradiation with 16 MeV S 3§ ions on Fe-Teflon as shown in Table 15. The T
components (D1, D2 and D3) were associated with FetE, Fe-F and FeF 2 compounds, (f-
respectively.
H. HgSn CEMS
1. Metal alloy films

ngSn CEMS 'was studied by MITROFANOV and SHPINEL 495 in 1964, and YAGNIK et
al.486 also designed a back-scatter proportional detector for ~gSn CEMS, which is rectangular
in shape, 13.97 • 10.16 • 3.18 cm. Unenriched SnO 2 powder gave a 950% effect above base
line. The energy and angular distributions of 19.6 keV conversion electrons in thin foils of
ll9Sn were analysed by PROYKOVA et al., 487,488 and the electron penetration of thin films was
also studied by a Monte Carlo method. 489
WILLIAMSON and DEB 490 studied on amorphous-S~_xSn x (H) alloys films prepared by
dc and rf sputtering of composite Si~Sn targets in Ar-H z gas mixtures, ngSn CEMS revealed
led the Sn to be incorporated into the films on at least four distinct sites; (1) substitutional
Sn in the amorphous-Sit_xSnx (H) matrix, (2) crystalline I~-Sn precipitates, (3) Sn4§ similar to
SnO 2, and (4) Sn 2+ similar to SnO. The substitutional Sn in the amorphous-Si (H) matrix was
well characterized by a QS of 0.46 + 0.05 mm/s.
The composition, structure, magnetic properties and stability of Fe~Sn thin films produced
by co-evaporation with dc magnetron sputtering were studied. 491,492The results of RBS, AES,
XRD and CEMS indicated the formation of a homogeneous solid solution of 9.8 at% Sn above
(three times) the limit of equilibrium solid solubility.493 The films presented saturation
magnetization and remanence similar to those of pure iron, but a much smaller coercivity.
Thermal treatment or aging let to second-phase precipitation, which was accompanied by a
growth of coercivity and remanence. 492
181
VERTES et al. (1982) 494 studied electrodeposited and cast brass containing 1-4 mg fin by
CEMS. Tin phases were formed with copper but not with zinc. The phases identified were ~,
~t, ~ and rl. Their ratio depended on the tin concentration and on the preparation process of
the brass.
The Fe~Sn intermetallic compositions on electro-deposited tin were analysed and it was
found that the fully alloyed layers of FeSn2, FeSn + FeSn2, FeSn, FeSn + Fe3SnC and Fe3SnC
were formed by thermal treatment for 30 min at 573, 673,773, 873 and 973 K, respectively. 49s
2.' Oxide films

SnO2_Xhas a semiconducting property in transparent films and inflammable gas sensors.
Surface tin layers deposited by an electroless process, 496 nanocrystalline tin dioxide
materials, H7 and SnO 2 films obtained by sputtering and sol-gel route 497 were studied by
CEMS. The textured SnO 2 films with different thicknesses in the range of 60-1120 nm
prepared by chemical vapour deposition were characterized by CEMS coupled with XRD
and AES. 498 The 20 nm thick interface layer between SnO 2 and the glass substrate was
formed by the mutual penetration of Si and Sn atoms. SnO 2 existed in polycrystalline
state with preferred crystal face orientation. MORENO et al. 499 studied thermal evaporated
thin S n - O films subjected to annealing treatments in air in the range 473-1173 K and
in Ar in the range 473-773 K followed by annealing in air up to 1373 K. The presence
of the intermediate oxide Sn304 was detected by CEMS and a tentative hyperfine structure
for the Sn 1§ site in Sn304 was obtained.
Gas sensitivity5~176
and characterization50~ of metal oxides mixed SnO z films prepared by
spray pyrolysis were investigated. The chemical state of tin oxide changed depending on the
kinds of metal oxide additives in the tin oxide and the degree of spillover of exposed hydrogen
gas. CO selectivity of tin-bismuth oxide s0z was compared with that of the other fin oxides 6~
by in situ CEMS. In high temperatures CEMS up to 773 K, reduced Sn(II) species could not
be observed, but the MOssbauer parameters changed at the temperature of gas sensing as
shown in Fig. 53. 61
0.08
" •0.04 .•SnOzBiz03

~ -0.04 ..LZ.
-0.08
160 200 3~0 460 560

T e m p e r a t u r e (~
Fig. 53. Change in IS obtained by in situ CEMS for Sn-Bi (5 : 1) oxide and Sn oxide/Pd film (from Ref. 61)
182
K. NOMURA el al.: APPLICATIONS OF CONVERSION ELECTRON
(a) i~Sn(II)
.qnflVl IA,, ~7:~,{

9"\ , " t ~1
...l.a
o,~1
(b)
o;
r
9. ,,, '.,. s !
4-~ ::~. ; ":~.1 ,
or,,-I
:. ,.....". 9 . ._:__::_<.:_.--::. .... ~,:,~:._,_ ~:.:..-. :'~

4-:'
9 - -~..-..-,-.. 9 . u ,t_.__ 4 - ""
2.
I I I I I J I I I I I [ I I
z"". ', I
i I
r i
t ,-1 I
- ,,/: i~ . t I / , W
/
I ..,,. " ." , " . . '.'V.i ~,..\, " -" ," ,"?L ~,~:. ~'-~-. '--.:;-
i ' : . . . . - - - t.d t------a I
-5 0 5
Velocity (ram/s)
Fig. 54. HOSnCEMS spectra of (a) tin film treated by H3PO4, (b) Mn phosphate coating lreated in SnCI2 solution,
and (c) Zn phosphate coating treated in SnCI2 solution (from ReL 506)
N O M U R A et al. characterized transparent conductive films of indium tin oxides (ITO), 5~

prepared on glass by Ar ion sputtering, ion plating and electron beam melting in vacuum. ITO
films, produced from ITO sputtering target materials with higher solubility of tin oxide,
showed lower electric resistivity. Amorphous ITO films had larger QS than crystalline ones.
The tin oxide films, prepared by CVD of SnCI 4 in methanol-containing HF, were exposed in
hydrogen plasma and hydrogen gas, and the change of these films was also assessed by
CEMS 504
Tin phosphate sputtered films, and converted tin phosphate coatings on iron and steel 5~176
were characterized by CEMS. Sn(IV) species was observed in sputtered tin phosphate coating
whereas Sn(II) phosphate was observed as main components in converted phosphate coatings
183
Table 16. M~ssbauer parameters o f xX*Sn c o m p o u n d s o b t a i n e d from

CEblS analysis
Components IS(mm/s) qS(mm/s) r(mm/s)
in amorphous Si 1.90 --- 1.20 ~ Ref.518
in metallic Sn 2.56 --- 0.70 ~ Si wafer

(~-Sn) implanted with x1~Sn
in ~rystalllne Si 1.70 --- 0.65
assoc, w i t h vacancy 2.28 --- i.i Rapid quenching
in amorphous Ge-Sn 1.95 --- i.i
amorphous SnOx 0.08 0.76 0.93 Ref.518

a-Sn 2.0 --- 0.90
crystalline Sn0x -0.03 0.51 0.89
crystalline Sn0x 0.01 0.49 0.81
Converted Sn (II) 3.6 1.4 --- Ref.505
phosphate coating 3.1 1.9 ---
0.01 0.4 ---
RF sputtered Sn -0.14 0.64 1.08 Ref.506

phosphate 0.12 1.09 ---
RF sputtered Sn -0.19 0.61 0.90

phosphate, heated 0.65 1.61
powder 3.53 1.49

Sn3(PO4)= 2.92 1.85
as shown in Fig. 54. 505 The MSssbauer parameters of these in c o m p o u n d s are listed in
Table 16. Analysis of there doublets were performed, assuring that the peak ratio of each
doublet was equal.
3. I o n implantation and ion beam irradiation

The surface layers of pure iron samples treated by both direct ion implantation of Sn § and
by radiation e n h a n c e m e n t of tin were analysed by means of RBS and l!gSn CEMS. 5~ T h e
presence of a m o r p h o u s phases was more pronounced on the directly implanted samples, while
there was a tendency for the formation of intermetallic c o m p o u n d s in the radiation enhanced
samples. The thermal evolution of the phases was consistent with the equilibrium phase
diagram for the F e - S n system. After annealing in v a c u u m at 823 K, only an unidentified
singlet (IS = 1.60 r a m . s ') was observed. This was due to tin segregation at the grain
boundaries of the substrate.
184
VI~RTES et al. 5~ also studied the effect of ion-beam irradiation on the composition and
structure of some Co~Sn eleCtrodeposits. A transformation of dissolved tin and cubic CoSn
to y-C%Sn z was observed. The effect of Xe § irradiation and of subsequent annealing on Fe/Sn
bilayer was studied by 119Sn CEMS. 5~ The Xe § irradiation caused effective intermixing of fin
and iron layers. [~-tin was not detected in the irradiated samples. Despite successive annealings,
the ion beam mixing of the bilayer favoured the formation of Fe3Sn2.5~
Films of Fe (20 rim) and Sn (40 nm) were deposited onto A1 supports and irradiated with
100 keV Xe ions at a dose of 5-1015 ions. cm -~. Scanning electron microscope (SEM)
examination showed that the irregular morphology of deposited Sn was considerably flattened
by irradiation, which also produced sputtering of Sn. The formation of various intermetallic
phases was enhanced by irradiation. Their thermal stability under annealing at temperature up
to 523 K was also investigated.51~
Silicon and tin (12 at% to 60 at% Sn) multilayers with total thickness 200 nm were
deposited at room temperature on beryllium and glass plate substrates under high vacuum
( < 5- 10 -7 mbar). TM The samples were irradiated at room temperature with Xe § ions of
900 keV energy with fluences of 0.1 - 1015 to 2 . 1 0 ~8 ions. cm -2. After irradiation, the
relative population of a substitutional Sn site depended on composition and irradiation
fluence. These films showed semiconductor behaviour with electrical resistivity of Sn
implanted silicon, 512 and ion beam mixing in the Sn-Si system 5x3 were studied by CEMS.
DE WAARD (1992) 514reviewed the formation of isolated molecules of composition SnO x
in silver and SnFx in copper. Ion beam interaction techniques were used for the identification
of these molecules. 5~ Local structure and thermal behaviour of 119Sn ion implanted
tin-aluminium and -nickeP 15 were investigated by CEMS.
The thermal oxidation behaviour of a high-carbon steep 16and an austenitic stainless steel5t7
treated, by tin ion implantation and radiation enhanced tin diffusion, respectively, were
investigated by CEMS. Significant reduction of the oxidation rate constant as well as
pronounced enhancement of the adherence of the oxide scale to the steel substrate were
observed for the treated high carbon steel. 515 However, the austenitic stainless steel treated lost
its natural protection against oxidation. This distinctive behaviour was due to the precipitation
of Ni--Sn intermetallic compounds. 516
Silicon preamorphized using HgSn§ implantation, the amorphous Ge-Sn thin films
deposited by sputtering, and this films of semiconductor SnO x deposited by reactive sputtering
were characterized by 1198n CEMS 518 as shown in Table 16.
The 119Sn implantation at 4 . 10 I6 cm -2 (180 keV) and higher was performed in sapphire
(A1202).519 The CEM spectra indicated that tin species was distributed between the Sn(II) and
Sn(IV) states in the amorphous films. The Sn(II) component (IS = 3.2 mm/s, QS = 2.1 mm/s,
F W H M = 1.3 mm/s) was assigned to a SnA1204 environment rather than SnO. The values of
QS and FWHM for the Sn(IV) component given were comparable to those of SnO 2 or SnA1205
but the IS values were systematically negative and lower than the IS for these compounds.
The lower IS values could be due to (1) a high ionicity of the Sn~3 bonding or (2) a decrease
in the electron density at the Sn nucleus due to a lower pressure expected by the amorphous
A120 ~ matrix on small SnO 2 or SnAlzO3 precipitates. The asymmetry of the Sn(II) and Sn(IV)
doublets is caused either by an orientation effect of the electric field gradient with respect to
the 3, beam, or an anisotropy in the Goldanski-Karyagin effect. If the tin is present in small
precipitates, the symmetry is broken at the surface, ~and this fact introduces the
Goldanski-Karyagin effect. All tin states became Sn(IV) with asymmetry doublet by annealing
up to temperatures of 1173 K.
185
I. CEMS using other nuclei

The CEM spectra of the 77.3 keV y-ray transition in 197Au were measuredfor the first
time with the use of a channel electron multiplier at low temperatures) 2~ The high
magnitude of the resonant effect was obtained using thin gold films. Single MgO crystals
implanted at room temperature with 180 keV Au 9 ions (dose: 8.1016 i o n s - c m -2) were
investigated at 4.2 K 197Au CEMS. 522 The isomer shifts measured after implantation
(IS = -1.09 mm/s) and after annealing at 1173 K (IS = -1.30 mm/s) indicated precipitation of
Au atoms in a metallic state (maximum diameter: about 20 nm).
~5~Eu Mfssbauer spectra of surface-oxidized Eu(II) sulfate were measured by TMS and
CEMS. 523 The photochemical reduction of Eu(IlI) oxalate to a Eu(lI) species after irradiation
with a low-pressure mercury lamp was demonstrated by the CEMS technique and ESR.
CEM si~ectra of ~81Ta (6.2 keV y-rays) were observed. 524 CEM spectra for tantalum single
crystal and oil surfaces (mean depth 33.0 nm) were compared with TM spectra for tantalum
foils (bulk). Although no broadening of lines was observed for carefully polished single crystal
surface, CEM spectra of the surfaces showed considerably broader lines than TM spectra of
the bulk. The line-width and isomer shift indicated an increase of concentration of absorbed
residu~ gases at the foil surface.
~93Ir CEMS was studied by using 73.0 keV "y-ray.~25 Mtissbauer shape parameters for ~83W
and 19~Irin metallic tungsten and iridium, 5z~ and for ~srI'b in terbium-aluminium (TbAI2) and
terbium oxide (Tb407) 5z7 were also studied by CEMS. Relation of contact densities with isomer
shifts for 35.46 keV M1 transition of tellurium-125 s28 was obtained.
17~ CEM spectrum was first observed by detecting low energy electrons emitted after
the 84.3 key y-ray absorp~on in ytterbium using a 50 mCi I7~FmAI~ source, a 5 mg/cm 2 Yb
metal absorber enriched with 67% 17~ and a channel electron multiplier kept at liquid helium
temperature? 29 A resonant signal of up to 1.5% was obtained. The measurements were not as
easy as would be expected. The low effect was due to contributions from the photoelectrons
generated by XSrays and n0nresonant y-rays.
J. Other applications of CEMS

1. In-beam Mrssbauer spectrometry
In-beam M6ssbauer recoil ion implantation can be applied to the study of interstitial jump
processes by using PPA resonant counters successfully to detect the excited y-rays. 53~ After
implantation of Coulomb excited 57Fe into metals (cr A1, Nb and Au) at low temperature,
a relatively large part of the implanted atoms ended up in interstitial positions yielding large
QS. In c~-Zr, the interstitiaal line showed a clear quadrupole relaxation accompanied by a
sharp decrease of the resonance intensity between 40 K and 100 K. This effect was interpreted
as localized fast jumps of 57Fe atoms in the octahedral cage of the hcp Zr lattice. The special
features of this technique in comparison with more conventional radioactive ion implantation
are stressed. TM At low temperatures a dynamic behaviour of the Fe interstitial can be described
in some cases as localized motion and in others as onset of long-range interstitial diffusion.
The particular advantage of in-beam Mtissbauer spectroscopy (IBMS) is the extreme dilution
of 57Fe nuclei in the host lattice. Interfering effects are essentially excluded. This is the main
difference to the more standard technique of implanting radioactive 57Co decaying into STFe
(about 10 I~ atoms/cmZ). During an IBMS measurement, a dose of 10 H atoms/cm 2 is
accumulated in the samples. If the spectra are recorded directly after implantation (about
100 ns), there is no time for agglomeration or out-diffusion of the implanted atoms. Using
the pulsed beam from an accelerator, time-differential in-beam Mfssbauer spectra (TDIBMS)
can be recorded by measuring the time between the beam pulse and the decay of the resonantly
excited absorber nucleus) 32 TDIBMS offers the unique possibility of observing the
186
implantation process in the 100 ns range where only very few other techniques are applicable.
However, an intense ion beam and a long measuring time are necessary to accumulate enough
statistics for each time window.
2. Source experiment
A vibration-free conversion electron detector was constructed for M~ssbauer source
experiments with extremely low doping levels ( - 1 ppm) of 57Co. It still yielded more
than a sixfold enhancement in S/N ratio over standard TM methods. The'lightweight
detector ( - 25 g) may be mounted directly on a conventional transducer without limiting
the performance. This allows low temperature source measurements to be made by moving
the detector and fixing the sample/source in a cryostat. 533
IV. SUMMARY
CEMS is an unique analytical technique for investigation of chemical state, structure and
magnetism in surface and subsurface layers on functional substance and solid materials. Many
principle techniques and applications of CEMS have been discussed in this article. The
experimental techniques and detectors for CEMS have been described in particular detail so
that the detectors can easily be designed to suit an intended application of CEMS. CEM
spectra can be also analysed by a conventional method using the large quantity of data
obtained by both TMS and CEMS, and the different chemical states between the surface and
the bulk can be easily distinguished. CEMS techniques have come to be one of the most
indispensable analytical methods for surface and subsurface characterization of solid and
materials. Integral CEMS is now popular. In situ CEMS and DSCEMS, especially LEEMS
and GACEMS, will be expected to apply more to surface analysis of thinner films of new
materials, and to interface analysis of artificial multilayers, with improvementg in the electron
detection system.
The authorsare gratefulto Prof. GRADMANand Dr. H. REUTHERfor their suggestionsconcerningthis review
article.
References
1. R. L. MOSSBAUER, Z. Physik, 151 (1958) 124.

2. R. L. MOSSBAUER,Naturwissenschaften,45 (1958) 538.
3. J. G. STEVEN, V. E. STEVENS, ConversionElectronMOssbauerSpectroscopyHandbook,MOssbauerEffect
Data Center, 1982.
4. J. G. STEVENS, Hyperfine Interact., 58 (1990) 2693.
5. V. I. GOLDANSKII, R. H. HERBER, Chemical Appficationsof M(JssbauerSpectroscopy, Academic Press,
New York, 1968.
6. N. N. GREENWOOD, T. C. GIBB, MOssbauerSpectroscopy, Chapman & Hall, London, 1971.
7. R. L. COHEN (Ed.), Applicationof MOssbauerSpectroscopy,AcademicPress, New York, 1976.
8. U. GONSER (Ed.), M0ssbauer Spectroscopy, Topics in Appfied physics, Vol. 5, Springer-Verlag Berlin,
Heidelberg, New York, 1975.
9. L. MAY (Ed.), An Inlroductionto MOssbauerSpectroscopy,AcademicPress, New York, 1968.
10. A. Vt~RTES, L. KORECZ, K. BLrRGER, MSssbaner Spectroscopy, Studies in physical and theoretical
chemistry 5, Elsevier ScientificPublicationCompany, Amsterdamq3xford-NewYork, 1979.
11. J. A. SAWICKI, in: IndustrialApplicationsof the Mt~ssbauerEffect, G. J. LONG and J. G. STEVENS (Eds),
Plenum Press, New York and London, 1986, p. 83.
187
12. J. J. SPIIKERMAN, CEMS, in: MOssbauerEffect Methodology, I. J. GRUVERMAN (Ed.), Vol. 7, Plenum
Press, New York, 1971, p. 85.
13. G. P. HUFFMAN, Theoretical expressions for analysis of multilayer surface films by electron re-emission
M0ssbaner spectroscopy, in: MOssbauerEffect Methodology, I. J. GRUVERMAN, (Ed.), Vol. 10, Plenum
Press, New York, 1976, p. 209.
14. M. J. TRICKER, CEMS and its recent,development, in: MOssbauer spectroscopy and its Chemical
Applications (Adv. in Chem. Ser. No. 194)i J. G. STEVENS and G. K. SHENOY (Eds), Am. Chem. Soc.,
Washington DC, 1981.
15. Y. UJIHIRA, Analytical applications of conversion electron MOssbauerspectrometry (CEMS), Rev. Anal.
Chem., 8 (1985) 125.
16. G. N. BELOZERSKI, MOssbauerStudies of Surface Layers, Elsevier Science Publ., Amsterdam, 1993.
17. F. E. WAGNER, J. Phys. (Paris) Colloq., C6, 37 (1976) 673.
18. R. OSWALD, M. OHRING, J. Vac. Sci. Tech., 13 (1976) 40.
19. J. R. GANCEDO, M. GRACIA, J. F. MARCO, CEMS Methodology, Hyperfine Interact., 66 (1991) 83.
20. J. M. THOMAS, M. J. TRICKER, A. P. WINTERBOTrOM, J. Chem. Soc. Farad. Trans., (1975) 1708.
21. D, LIIAEQUIST,T. EKDAHL, U. BAVERSTAM, Nucl. lnstrum. Methods, 155 (1978) 529.
22. J. BAINBRIDGE, Nucl. Instmm. Methods, 128 (1975) 531.
23. M. J. GRAHAM, D. F. MITCHELL, D. A. CHANNING,Oxidation of Metals, 12 (1978) 247.
24. M. J. GRAHAM, D. F. MrrcHELL, D. A. CHANNING,Oxidation of Metals, 12 (1978) 373.
25. C. FELDMAN, Phys. Rev., 117 (1960) 455.
26. D. LILJEQUIST,Nucl. Instrum. Methods, 179 (1981) 617.
27. J. A. SAWlCKI, 1". TYLISZCZAK, Nucl. Inslrum. Methods, 216 (1983) 501.
28. K. MAKARILrNAS,E. MAKARIUNIENE,Liet. Fiz. Rinkinys; 25 (1985) 111.
29. F. SALVAT, R. MAYOL, J. D. MARTINEZ, J. PARELLADA, Nucl. Instrum. Methods in Phys. Res., B6
(1985) 547.
30. J. H. TERRELL, J. J. SPIJKERMAN, Appl. Phys. Lett., 13 (1968) 11.
31. K. R. SWANSON, J. J. SPIJKERMAN, J. Appl. Phys., 41 (1970) 3155.
32. B. KEISCH, Nucl. lnstrum. Methods, 104 (1972) 237.
33. K. NOMURA, Y. UJIHIRA, Bunseki-Kagaku, 34 (1985) T5.
34. D. HANZEL, P. GRIESBACH, W. MEISEL, P. G~TLICH, Hyperfine Interact., 71 (1992) 1441.
35. M. INABA, K. NOMURA, Y.'UJIHIRA, J. de Physique,41 (1980) C1-115.
36. T. TORIYAMA, K. UEOKA, Hyperfine Interact, 29 (1986) 1525.
37. V. KUNCSER, G, F1LOTI,Nucl. Instr. and Meth. in Phys. Res., B82 (1993) 186.
38. V. S. VARTANOV, B. G. ZEMSKOV, Izmer. Tekh., (1987) 51.
39. J. R. GANCEDO, M. GRACIA, Hyperfine Interact., 28 (1986) 1097.
40. L. SBRIZ, M. VILLAGRAN,G. VALCONI,J. Radioanal. Nucl. Chem., 128 (1988) 387.
41. M. VILLAGRAN, L. SBRIZ, G. VALCON1, J. Radioanal. Nucl. Chem., 153 (1991) 375.
42. L. SBRIZ, M. VILLAGRAN,G. VALCONI, J. Radioanal. Nucl. Chem., 133 (1989) 211.
43. G. WEYER, Hyperfine Interact., 58 (1990) 2561.
44. J. G. MULLEN. J. STEVENSON,Nucl. Inslrum. Methods, 153 (1978) 77.
45. J. G. MULLEN, A. DJEDID, C. HOLMES, G. SCHUPP, L. CROW, W. YELON, Nucl. Insmam.Methods in
Phys. Res., B14 (1986) 323.
46. S. BOCQUET, R. J. POLLARD, J. D. CASHION, Hyperfine Interact., 58 (1990) 2503.
47. Y. ISOZUMI, M. KURAKADO,R. KATANO, Nucl. Instrum. Methods, 204 (1983) 571.
48. D. C. COOK, Hyperfine Interact,, 29 (1986) 1463.
D. C. COOK, E. AGYEKUM, Nucl. Instrum. Methods in Phys. Res., B12 (1985) 515.
49. K. NOMURA, M. TASAKA, Y. UJIHIRA, HyperfineInteract., 41 (1988) 681.
50. A. KASTNER, G. LUGERT, G. BAYREUTHER, Hyperfine Interact., 42 (1988) 1145.
51. A. S. KAMZIN, V. P. RUSAKOV, Prib. Tekh. Eksp., (1988) 56.
52. A. S. KAMZIN, L. A. GRIGOR'EV, Prib. Tekh. Eksp., (1990) 77.
53. K. FUKUMURA, A. NAKANISHI, T. KOBAYASHI,R. KATANO, Y. ISOZUMI,Nuch Instrum. Methods
in Phys. Res., 861 (1991) 127.
54. K. FUKUMLrRA, T. KOBAYASHI, A. NAKANISHI,R, KATANO, Y. ISOZUMI Hyperfine Interact., 69
(1991) 755.
55. K. FUKU-MURA,R. KATANO, T. KOBAYASHI,A. NAKANISHI,Y. ISOZUMI,Nucl. Instrum. Methods
in Phys. Res., A.301 (1991) 482.
56. T. FUJI/, N. HOSOITO,R. KATANO, Y. ISOZUMI, Nucl. Instrum. Methods in l:;hys. Res., B76 (1993) 207.
57. Y. ISOZUMI, M. KURAKADO,~R. KATANO, Nucl. Instrum. Methods, 166 (1979) 407.
58. M. INABA, H. NAKAGAWA, Y. UJ1HIRA,Nucl. lnstrum. Methods, 180 (1981) 131.
188
59. X. ZHOU, A. H. MORRISH, Nucl. Inslrum. Methods in Phys. Res., B18 (1987) 215.
60. D. BODIN, J. P. EYMERY, Nucl. Inslrum. Methods in Phys. Res., B16 (1986) 424.
61. K. NOMURA, S. S. SHARMA, Y. UJIHJRA, Nucl. Inslrum. Methods in Phys. Res., B76 (1993) 357.
62. H. SATO, M. MITSUHASHI, Hyperfme Interact., 58 (1990) 2535.
63. J. A. SAWICKI, T. TYLISZCZAK, O. GZOWSKI, Nucl. Instrum. Methods, 190 (1981) 433.
64. J. A. SAWICKI, Nucl. Instrum. Methods in Phys. Res., B16 (1986) 483,
65. R. ATKINSON, T. E. CRANSHAW, Nucl. Inslrum. Methods., 204 (1983) 577.
66. A. A. MANALIO, K. BURIN, G. M. ROTHBERG, Sci. Instrum., 52 (1981) 1490.
67. ZS. KAJCSOS, CH. SAUER, A. HOLZWARTH, R. KURZ, W. ZINN, M. A. C. LIGTENBERG, G. VAN
ALLER, Nucl. Inslrum. Methods in Phys. Res., B34 (1988) 383.
68. CH. SAUER, A. HOLZWARTH, ZS. KAJCSOS, W. ZINN, Nucl. Instrum. Methods in Phys. Res., B34
(1988) 377.
69. ZS. KAJCSOS, CH. SAUER, W. ZINN, R. KURZ, W. MEYER, M. A. C. LIGTENBERG, Hyperfme
Interact., 58 (1990) 2519.
70. ZS. KAJCSOS, CH. SAUER, W. ZINN, M. A. C. LIGTENBERG, Hypeffine Interact., 71 (1992) 1479.
71. ZS. KAJCSOS, CH. SAUER, W. ZINN, Hyperfine Interact., 51 (1989) 1147.
72. ZS. KAJCSOS, CH. SAUER, W. ZINN, R. KURZ, W. MEYER, M. A. 'C. LIGTENBERG, Hyperfine
Interact., 58 (1990) 2519.
73. ZS. KAJCSOS, CI-I. SAUER, W. ZINN, W. MEISEL, H. SPIERING,M. ALFLEN, P. GOTLICH, Hyperfine
Interact., 71 (1992) 1469.
74. ZS. KAJCSOS, W. MEISEL, P. GRIESBACH, P. GQrLICH, M. A. C. LIGTENBERG, V. GRADMANN,
E. LEHRBERGER, M. PRZYBYLSKI, Hyperfine Interact., 71 (1992) 1483.
75. Y. ISOZUMI, D. I. LEE, I. KADAR, Nucl. Instrum. Methods, 20 (1974) 23.
76. P. SCHAAF, U. GONSER, Hypeffine Interact., 57 (1990) 2101.
77. U. GONSER, P. SCHAAF, Fresenius J. Anal. Chem., 341 (1991) 131.
78. P. SCHAAF, A. KRAMER, F. AUBERTIN, U. GONSER, Z. Metallkunde, 82 (1991) 815.
79. D. LILJEQUIST, B. B. RINGSTROM, Nucl. Instrum. Methods, 160 (1979) 131.
80. U. GONSER, P. SCHAAF, F. AUBERT1N, Hyperfine Interact., 66 (1991) 95.
81. P. SCHAAF, A. KRAEMER, L. BLAES, G. WAGNER, F. AUBERTIN, U. GONSER, Nucl. Inslrum.
Methods in Phys. Res., B53 (1991) 184.
82. S. MI-IRKAEV, M. A. ANDSREEVA, V. G. SEMENOV, G. N. BELOZERSKII, O. V. GRISHIN, Nucl.
Instrum. Methods in Phys. Res., B74 (1993) 545.
83. M. MATSUO, H. SATO, T. TOMINAGA, Radiochem. Radioanal. Lett., 48 (1981) 253.
84. H. NAKAGAWA, Y. UJIHIRA, M. INABA, Nucl. Instrum. Methods, 196 (1982) 573.
85. M. TAKAFUCH/, T. KOBAYASHI,Nucl. lnstrum. Methods in Phys. Res., B9 (1985) 223.
86. Y. YONEKURA, T. TORIYAMA, J. ITOH, K. HISATAKE,Hyperfine Interact., 16 (1983) 1005.
87. J. J. BARA, B. F. BOGACZ, Hyperfine Interact., 29 (1986) 1575.
88. J. 1. BARA, B. F. BOGACZ, Nucl. Instrum. Methods in Phys. Res., A238 (1985) 469.
89. J. 1. BARA, B. F. BOGACZ, Hypeffine Interact., 58 (1990) 2497.
90. U. BAVERSTAM, C. BOHM, B. RINGSTROM, T. EKDAHL, Nucl. Instrum. Methods, 108 (1973) 439.
91. TSV. BONCHEV, A. MINKOVA, G. KUSHEV, M. GROZDANOV, Nucl. Instrum. Methods, 147 (1977)
481.
92. T. SHIGEMATSU, H. D. PFANNES, W. KEUNE, American Phys. Soci., 45 (1980) 1206.
93. J. ITOH, T. TORIYAMA, K. SANEYOSHI,K. HISATAKE, Nucl. Instrum. Methods, 205 (1983) 279.
94. D. LILJEQUIST, Hyperfine Interact., 57 (1990) 1963.
95. A. I. CHUMAKOV, G. V. SMIRNOV, Zh. Eksp. Teor. Fiz., 89 (1985) 1810.
96. YU. F. BABIKOVA, O. M. VAKAR, P. L. GRUZIN, YU. V. PETRIKIN, Priklyad. Spektrosk., 11 (1982)
228.
97. E. KANKELEIT,Z. Phys., 164 (1961) 442.
98. K. P. MITROFANOV,V. S. SHPINEL, Soviet Phys., JETP 13 (1964) 233.
99. S. C. PANCHOLI, H. DE WAARD, J. L. W. PETERSEN, A. VAN DER WIIK, J. VAN KLINKEN, Nucl.
Instrum. Methods in Phys. Res., A221 (1984) 577.
100. A. I. CHUMAKOV, G. V. SMIRNOV, Nucl. lnstrum. Methods in Phys. Res., B28 (1987) 307.
101. M. DOMKE, B. KYVELOS, G. KAINDL, Hyperfine Interact., 10 (1981) 1137.
102. Z. M. STADNIK, H. R. BORSJE, A. E. M. SWOLFS, W. H. A. LEENDERS, J. C. FUGGLE, Rev. Sci.
lnstrum., 60(4) (1989) 708.
103. J. KORECKI, U. GRADMANN, Hyperfine Interact., 28 (1986) 931.
104. D. VARGA, I. Ki~d)2~R, A. KOVER, I. CSERNY, G. MORIK, V. BRABEC, O. DRAGOUN, A. KOVALIK,
J. ADAM, Nucl. Inslr. Methods, 192 (1982) 277.
189
t05. CH. BRIANCON, B. LEGRAND, R. J. WALEN, TS. VYLOV, A. MINKOVA, A. INOYATOV, Nucl. Instr.,
221 (1984) 547.
106. H. SATO, M. MATSUO, M. TAKEDA, N. MORIKAWA, T. TOMINAGA, Int. J. Appl. Radiat. Isot., 34
(1983) 709.
107. M. MATSUO, H. SATO, T. TOMINAGA, Radiochim. Acta, 35 (1984) 227.
108. I. P. JAIN, Y. K. VIJAY, L. K. MALHOTRA, A. VERMA, R. CHANDRA, Hyperfine Interact., 35 (1987)
1045.
109. I. P. JAIN, Y. K. VIJAY, R. CHANDRA, Vacuum, 41 (1990) 1776.
110. V, YU. RYZHYKH, M. I. BABENKOV, B. V. BOBYKIN, V. S. ZHDANOV, A. K. ZHETBAEV, Nucl.
lll. B. STAHL, G. KLINGELHOFER, H. JAGER, H. KELLER, TH. REITZ, E. KANKELEIT, Hyperfine
Interact., 58 (1990) 2547.
112. G. KLINGELHOFER, U. IMKELLER, E. KANKELEIT, Hyperfine Interact., 54 (1990) 577.
113, H, M. VAN NOORT, A. A. VAN GORKUM, J. Phys. E: Sci. Instrum., 21(1988) 587.
114. H, M. VAN NOORT, F, J. FERGUSON, C. J. G. VERWER, A. A. VAN GORKUM, J. M. E. VAN
LAARHOVEN, C. J. M. DENISSEN, Nucl. Inslrum. Methods in Phys. Res., B34 (1988) 391.
115. P. AURIC, A. BAUDRY, M. BOGE, L ROCCO, L. TRABUT, Hyperfine Interact., 58 (1990) 2491.
116. P. H. SMIT, R. P. VAN STAPELE, Appl. Phys., A28 (1982) 113.
117. A. P, KUPRIN, A. A. NOVAKOVA, Nucl. Instrum. Methods in Phys. Res., B62 (1992) 493.
118. D. LIIAEQUIST, C. BOHM, T. EKDAHL, Nucl, Instrum. Methods, 177 (1980) 495.
119. D. LIIAEQUIST, M. ISMAIL, NucL Instrum. Methods in Phys. Res., A239 (1985) 273.
120, D. LILJEQUIST, Report IS: US/P-85-20, ESA-86-97049; Order No. N86-28642/4/GAR (1985) 92.
121. M_J. TRICKER, A. G. FREEMAN, A. P. WINTERBOTTOM, J. M. THOMAS, Nucl. Instrura. Methods, 135
(1976) 117.
122. D. LIIAEQLFIST, M. ISMAIL, Phys. Res., B, 31 (1985) 4131.
123. P. TOPALOV, A. PRO1KOVA, Nucl. Instrum. Methods in Phys. Res., Sect. A, A236 (1985) 142.
124. D. L1LFEQUIST, M. ISMAIL, K. SANEYOSHI, K. DEBUSMANN, W. KEUNE, R, A. BRAND,
W. KIAUKA, Phys. Rev., B, 31 (1985) 4137.
125. M. ISMAIL, D. LILJEQUIST, Hyperfine Interact., 29 (1986) 1509.
126, T. S. LEE, B. L TATARCHUK, Hyperfine Interact., 42 (1988) 1149.
127. D. LILJEQUIST, Hyperfine Interact., 57 (1990) 1963.
128. S. BERNSTEIN, E, C. CAMPBELL, Phys. Rev., 132 (1963) 1625.
129. J. C. FROST, B. C. C. COWIE, S. N. CHAPMAN, J. P. MARSHALL, Appl. Phys. Lett., 47 (1985) 581.
130. S. M. IRKAEV, M. A. ANDREEVA, V. G. SEMENOV, G. N. BELOZERSKII, O. V. GRISHIN, Nucl.
131. M. GROZDANOV~ TS. BONCHEV, V. LILKOV, Nucl. Instrum. Methods, 165 (1979) 231.
132. S. STANIEK, T. SHIGEMATSU, W. KEUNE, H. D. PFANNES, J. Magn. Magn. Mater., 35 (1983) 347.
133. T. S. LEE, T. D. PLACEK, J. A. DUMESIC, B. J. TATARCHUK, Nucl. Instrum. Methods in Phys. Res., B18
(1987) 182.
134. J. S. ZABINSKI, B. J. TATARCHUK, Nucl. Inslrum. Methods in Phys. Res., B31 (1988) 576.
135. J. S. ZABINSKI, B. J. TATARCHUK, NucL Instrum. Methods in Phys. Res., B51 (1990) 41.
136. T. S. LEE, B. J. TATARCHUK, Hyperfine Interact., 57 (1990) 1949.
137. G. KLINGELHOFER, E. KANKELEIT, Hyperfine Interact., 53 (1990) 1905.
138. G. KLINGELHOFER, U. IMKELLER, E. KANKELEIT, B. STAHL, Hyperfine Interact., 69 (1992) 819.
139. G. KLINGELHOFER, U. IMKELLER, E. KANKELEIT, B. STAHL, Hyperfine Interact., 71 (1992) 1445.
140. D. LILIEQUIST, H. LANG, Nucl. lnstrura. Methods in Phys. Res., B52 (1990) 83.
141. J. S. ZABINSKI, 13. J. TATARCHUK, Nucl. Instrum. Methods in Phys. Res, B42 (1989) 379.
142.H. SEILER, J. App. Phys., 54 (1983) RI..
143. T. MISAWA, K. HASIMOTO, S. SHIMODAIRA, Corres. Sci., 14 (1974) 131.
144. W. KUNDIG, H. BOMMEL, G. CONSTABARIS, R. H. LINDQUIST, Phys. Rev., 142 (1966) 327.
145. D. SCHROEER, R. C. NINIGER, Jr., Phys. Rev. Lett., 19 (1967) 632.
146. H. TOPSOE, S. MORUP, Int. Conf, MOssbauer Spectroscopy Proc., Vol. 1 (1975) 321.
147. S. HANADA, K. KUMA, Bull. Chem. Soc. Japan, 49 (1976) 3695.
148. P. C. BHAT, M. P. SATHYAVATHIAMMA, N. G. PUTTASWMY, R. M, MALLYA~ Corros. Sci., 23
(1983) 733.
149. T. PEEV, M. K. GEORGIEVA, S. NAGY, A. VFS,RTES, Radiochem. Radioanal. Lett., 33 (1978) 265.
150. I. DEZSI, A. VI~RTES, M. KOMOR, Inorg. Nucl. Chem. Lett., 4 (1968) 649.
151. A. VI~RTES, K. L,/~Z.~, K. KELEMEN, L. BOGNAIN, Radiochem. Radioanal. Lett., 4 (1970) 375.
152. H. LEIDHE[SER, Jr., I. CZ, NAGY, Corros. Sci., 24 (1984) 569.
190
153. G. M. SIMMONS, E. KELLERMAN, H. LEIDHEIZER,Jr., Corros., 29 (1973) 227.

154. G. W. SIMMONS, H. LEIDHEISER, Jr., Applications of M6ssbauer spectroscopy, Vol. 1, Academis Press,
New York, 1976, p. 85.
155. W. MEISEL, Spectrochimica Acta, 39B (1984) 1505.
156. Y. UJIHIRA, K. NOMURA, Journal de Physique, 41 (1980) C-39t.
157. K. NOMURA, M. TASAKA, Y. UJIHIRA, Corros., 44 (1988) 131.
158. K. NOMURA, Y. UJIHIRA, Applicationsof the M6ssbauerEffect, Gordon and Breach, Sci. PUN., New York,
1985, p. 1185.
159. K. NOMURA, Y. UJ1HIRA,J. Mater. Sci., 19 (1984) 2664.
160. PH. REFAIT, PH. BAUER, J. M. R. GENIN, Hyperfine Interact., 69 (1991) 831.
161. J. LIPKA, J. BLAZEK, D. MAJERSKY, M. MIGLIERINI,M. SEBERINI,J. CIRAK, I. TOTH, R. GRONE,
Hyperfine Interact., 53-58 (1990) 1969.
162. N. R. BULAKH, S. V. GHAISAS, S. A. KULKARNI, S. M. KANETKAR, S. B. OGALE, Hyperfine
Interact., 41 (1988) 641.
163. W. MEISEL, Hyperfine Interact., 45 (1989) 73.
164. J. DAVALOS, J. F. MARCO, M. GRACIA, J. R. GANCEDO, J. M. GRENECHE, Hypertine Interact., 53-58
(1990) 1809.
165. J. S. BROOKS, S. THORPE, Hyperfine Interact., 47 (1989) 159.
166. G. BELOZERSKII, C. BOHM, T. EKDAHL, D. LILJEQUIST,Corros. Sci., Vol. 22, No. 9 (1982) 831.
167. W. MEISEL, U. STUMM, C. THILMANN, R. GANCEDO, P. GUTLICH, ttyperfine Interact., 41 (1988)
669.
168. W. MEISEL, U. STUMM. P. GOTLICH, Fres. Z. Anal. Chem., 333 (1989) 555.
169. U. STUMM, W. MEISEL, P. GOTLICH, Hypeffine Interact., 53-58 (1990) 2115~
170. T. KOBAYASHI, K. FUKUMURA, Y. ISOZUMI,R. KATANO, Hyperfine Interact., 53-58 (1990) 1923.
171. T. KOBAYASHI, K. FUKUMURA, Y. ISOZUM/, R. KATANO, Hypeffine Interact., 39 (1988) 419.
172. M. L. VARS/~d'~YJ,CS. VI~RTES, A. VI~RTES, L. KISS, W. MEISEL, P. GRIESBACH, P. GUTLICH,
J. Electrochem. Soc., 139 (t992) 1301.
173. CS. VI~RTES, M. L. VARS~YI, W. MEISEL, A. VI~RTES,P. G~ILICH, L. KISS, Eleclrochem. Acta, in
press.
174. CS. Vt~RTES, M. L. VARS,~.NYI, A. Vt~RTES, E. KUZMANN, W. MEISEL, P. GOTLICH, Hyperfine
Interact., 69 (1991) 731.
175. CS. Vt~RTES, M. L. VARS,i2qYI, W. MEISEL, AI Vt~RTES, P. G[ITLICH, Nucl. Instrum. Methods in Phys.
Res., B76 (1993) 20.
176.13. C. COOK, Hyperfine Interact., 28 (1986) 891.
177. S. R. SEREJ, D. C. COOK, Hyperfine Interact., 41 (1988) 701.
178. K. NOMURA, Y. UJIHIRA, Hyperfine Interact., 29 (1986) 1467.
179. J. DAVALOS, J. F. MARCO, M. GRACIA, J. R. GANCEDO, Hyperfine Interact., 66 (1991) 63.
180. J. DAVALOS, M. GRACIA, J. F. MARCO, J. R. GANCEDO, Hyperfine Interact., 69 (1991) 871.
181. M. MATSUO, T. KOBAYASHI,Nucl. Inst. B76 (1993) 418.
182. M. FUJ1NAMI, Y. UJIHIRA, Appl. Surf. Sci., 17 (1984) 265.
183. M. FUJINAMI, Y. UJIHIRA, Appl. Surf. Sci., 17 (1984) 276.
184. A. HANDA~J. KOBAYASHI, Y. U]IHIRA, Appl. Surf. Sci., 20 (1985) 581.
185. M. 1. DA COSTA, Jr., L I. KUNRATH, J. T. MOROI J. B. M. DA CUNHA, G. ENGLERT,
L. U. COMPARSI, 1. L. MULLER, Nucl. Inst. B76 (1993) 168.
186. P. L. CROUSE, C. M. STANDER, Corros. Sci., 33 (1992) 13.
187. E. G. DA SILVA, G. P. A. COSTA, A. A. G. CAMPOS, AZEVEDO, A. L. TENUTA, Scr. MetaU. Mater.,
25 (1991) 331.
188. CS. VI~RTES, G. VASS, E. KUZMANN, K. ROMI-J~NY1, M. L. VARS,~dgYI,A. VI~RTES,L Radioanal.
Nucl. Chem., 186 (1994) 447.
189. B. B. RINGSTRROM, U. BAVERSTAM, C. BOHM, L Vac. Sci. TechnoL, 16 (1979) 1013.
190. M. DOMKE, B. KYVELOS, Corros. Sci., 23 (1983) 921.
191. W. MEISEL, P. GRIESBACH, H. 1. GRABKE, P. GOTLICH, Hyperfine Interact., 57 (1990) 2001.
192. P. GRIESBACH, W. MEISEL, P. GUTLICH, Hyperfine Interact., 69 (1991) 811.
193. I. STEWART, M. J. TRICKER, Corms. Sci., 26 (1986) 1041.
194. K. NOMURA, Y. UJIH1RA,J. Mater. Sci., 25 (1990) 1745.
196. G. LORIN, Phosphating of Metals, Finishing Publications (1974) 57.
197. R. J. HILL, Am. Mineral, 62 (1977) 812.
198. F. J. BERRY, J. Chem. Soc., Dalton Trans. (1979) 1736.
191
K. NOMURA et at.: APPLICATIONS OF CONVERSION ELECTRON
199. K. NOMURA, Y. UJIHIRA, R. KOJIMA, Proceedings of Indian National Science Academy, Phys. Sci. Spec.
Vol., Indian National Science Academy, New Delhi, 1982, p. 311.
200. K. NOMIYRA, Y. UJ1HIRA, J. Mater Sci., 17 (1982) 3437.
201. M. CARBUCICCHIO, G. PALOMBARINI, G. SAMBOGNA, Hyperfine Interact., 53-58 (1990) 1775.
202. K. NOMURA, Y. UJIHIRA, J. Analytical and Applied Pyrolysis, 5 (1983) 221.
203. E. MATI1/e;VICH, J. DANON, J. Inorg. Nucl. Chem., 39 (1977) 569.
204. M. J. TRICHER, L. A. ASH, W./ONES, J. Inorg. Nucl. Chem., 41 (1979) 891.
205. D. HANZEL, W. MEISEL, P. GOTLICH, Hyperfme Interact., 57 (1990) 2201.
206. D. HANZEL, W. MEISEL, P. GOTLICH, Solid State Commnn., 76 (1990) 307.
207. K. NOMURA, Y. UJIHIRA, J. Mater. Sci., 18 (1983) 1751.
208. K. YAMAKAWA, F. E. FUJ1TA, Metallurgical Transact. A, 9A (1978) 91.
209. G. PRINCIPI, S. LO RUSSO, C. TOSELLO, Industrial Applications of M0ssbauer Effect, G. J. LONG and
G. J. STEVENS (Eds), Plenum Press, New York, 1986.
210. F. AUBERTIN, S. ABEL, G. WAGNER, P. SCHAAF. U. GONSER, Hyperfme Interact., 47 (1989) 379.
211. A. HANDA, Y. UJIHIRA, J. Mater. Sci., 18 (1983) 1887.
212. M. CARBUCICCHIO, L. BARDANI, J. Mater. Sci., 15 (1980) 711.
213. M. CARBUCICCHIO, L. BARDANI, J. Mater. Sci., 15 (1980) 1483.
214. G. PRINCIPI, A. GUPTA, C. BADINI, Hyperfine Interact., 69 (1991) 479.
215. M. CARBUCICCHIO, R. REVERBERI, G. PALOBARINI, G. SAMBOGNA, Hyperfine Interact., 46 (1989)
473.
216. M. CARBUCICCHIO, E. ZECCHI, J. Mater. Sci., 18 (1983) 3355.
217. M. CARBUCICCHIO, G. SAMBOGNA, Thin Solid Films, 126 (1985) 299.
218. M. CARBUCICCHIO. A. CASAGRANDE, G. PALOMBARINI, Hyperfine Interact., 53-58 (1990) 1769.
219. M. CARBUCICCHIO, G. PALOMBARINI, G. SAMBOGNA, Hyperfine Interact., 69 (1991) 843.
220. M. J. GRAHAM, P. E. BEAUBIEN, G. I. SPROULE, J. Mater. Sci., 15 (1980) 626.
221. M. GHAFARI, M. SAITO, Y. HIROSE, Y. NAKAMURA, Nucl. Instmm. Methods in Phys. Res., B76 (1993)
306.
222. Y. SHIMA, M. TERASAKA, K. NAKAOKA, T. HARA, T. HONMA, Tetsuto Hagane, 72 (1986) 954.
223. A. HANDA, Y. UJIHIRA, I. OKABE, J. Mater. Sci., 16 (198l) 1999.
224. S. SKRZYPEK, E. KOLAWA, J. A. SAWICKI, T. TYLISZCZAK, Mater. Sci. Eng., 66 (1984) 145.
225. S. NASU, H. TANIMOTO, F. E. FUJITA, Hyperfine Interact., 57 1-4 (I990) 2009.
226. C. PIETZSCH, U. TI-IIEME, Isotopenpraxis, 24 (1988) 405.
227. O. N. C. UWAKWEH, J. P. BAUER, J. M. R. GENIN, Metall. Trans. A, 21A (1990) 589.
228. A. CHRISTIANSEN, L. LARSEN, H. R. POULSEN, N. O. R. POULSEN, L. VISTISEN, J. M. KNUDSEN,
Phys. Sci., 29 (1984) 94.
229. M. INABA, K. NOMURA, Y. UJIHIRA, Jap. J. Metal., 52 (1988) 1121.
230. M. INABA, K. NOMURA, Y. UJIHIRA, Jap. J. Metal., 53 (1989) 356.
231. G. KRETrEK, B. HUCK, J. HESSE, Hyperfine Interact., 53-58 (1990) 1935.
232. G. B. FRATUCELLO, E. COLOMBO, O. DONZELL1, F. RONCONI, Hyperfine Interact., 45 (1989) 255.
233. M. GHAFARI, T. OKIYAMA, T. TAKEMOTO, Y. KAWAI, Y. NAKAMURA, Nucl. Instrum. Methods in
Phys. Res., B76 (1993) 37.
234. K. MARIMOTO, A. KIRIHIGASHI, S. NASU, Nucl. Inslrum. Methods in Phys. Res., B76 (1993) 295;
235. B. BOUBEKER, J. P. EYMERY, M. F. DENANOT, E. L. H. SAYOUTY, J. Magnetism and Magnetic
Materials, 133 (1994) 470.
236. D. KHATAMIAN, F. D. MANCHESTER, J. M. DANIELS, J. Less-Common Met., 130 (1987) 511.
237. J. H. SANDERS, B. J. TATARCI-~.JK,Hyperfine Interact., 53-58 (1990) 2083.
238. D. HANZEL, W. MEISEL, P. GUTLICH; Hyperfine Interact., 69 (1991) 807.
239. M. CARBUC1CCHIO, G. PALOMBARINI, Hypeffine Interact., 53-58 (1990) 1783.
240. S. HIROSAWA, H. TANIMOTO, S. NASU, K. TOKUttARA, J. Appl. Phys., 70 (1991) 6369.
241. S. HIROSAWA, H. TANIMOTO, S. NASU, Nucl. Instr. Methods in Phys. Res., B76 (1993) 373.
242. H. M. VAN NOORT, Solid State Commun., 48 (1983) 495.
243. L. DOBRZYNSKI, T. GIEBLrLTOWICZ, M. KOPCEWICZ, M. PIOTROWZKIAND, K. SZYMANSKI,
Phys. Slat. Sol., (a), 101 (1987) 567.
244. K. NOMURA, Y. UJIHIRA, M. SUEKI, N. KAWASHIMA, t-Iyperfine Interact., 54 (1990) 839.
245. K. NOMURA, Y. UJIH/RA, N. KAWASHIMA, Nucl. Instram. Methods in Phys; Res., B76 (1993) 199.
246. K. NOMURA, Y. UJIHIRA, A. YANAGITANI, Hyperfine Interact., 88 (1994) 73.
247. J. F. DINHUT, J. P. EYMERY, J. Magnetism and Magnetic Materials, 93 (1991) 252.
248. O. MASSENET, H. DAVER, Solid State Commun., 25 (1978) 917.
249. O. MASSENET, H. DAVER, Solid State Commun., 21 (1977) 37.
192
250. K. NOMURA, J. TANAKA, Y. UJIHIRA, T. TAKAHASHI, Y. UCHIDA, Hyperfine Interact., 56 (1990)

1711.
251. R. S. OSWALD, M. RON, M. OHRING, Solid State Commun., 26 (1978) 883.
252. B. MARTINEZ, A. LABARTA, J. TEJADA, HyperfineJnteract.,52 (1989) 321.
253. X. D. MA, Y. H. LIU, L. M. MEI, J. Magn. Magn. Mater., 95 (1991) 199.
254. X. D. MA, Y. H. LIU, L. M. MEI, J. Phys.: Condens. Matter, 3 (1991) 7139.
255. L. MEI, W. LI, S. BI, J. Phys. Colloq., C8 (1988) 1759.
256. S. BI, W. LI, L. MEI, Chin. Sci. Bull., 34 (1989) 823.
257. A. A. NOVAKOVA, A. P. KUPRIN, G. A. SIROTYNINA,G. V. SIDOROVA,Nucl. Inslrum. Methods in
Phys. Res., B76 (1993) 109.
258. J. A. CUSIDO, J. TEIADA, J. Mater. Sci. Lett., 5 (1986) 75.
259. M. FUJINA_MI,Y. UJIHIRA, J. Non-Cryst. Solids, 69 (1985) 361.
260. A. FNIDIKI, J. P. EYMERY, M. F. DENANOT, Hypeffine Interact., 45 (1989) 295.
261. J. W. KONDORO, F. AUBERTIN, S. J. CAMPBELL, U. GONSER, J. Non-Cryst. Solids, 143 (1992) 147.
262. O. DONZELLI, G. FRATUCELLO, F. RONCONI, Hyperfine Interact., 69 (1992) 779.
263. A. A. NOVAKOVA, G. V. SIDOROVA, Hypertine Interact., 45 (1989) 337.
264. E. KUZMANN, CS. VI~RTES,A. VI~RTES,S. VITKOVA,G. RAICHEWSKI,HyperfineInteract., 69 (1991)
607.
265. P. AURIC, J. M. GRENECHE, O. DE BOUVIER, J. J. RAMEAU, J. Magn. Magn. Mater., 82 (1989) 243.
266. E. G. DA SILVA, R. B. SCORZELLI, F. S. SINENCIO,O. A. FREGOSO,J. G. M. ALVAREZ, Solid State
Commun., 72 (1989) 1059.
267. M. PRZYBYLSKI, U. GRADMANN, J. De Physique, Colloque C8, 49 (1988) 1705.
268. F. S. SINENCIO, J. G. M. ALVAREZ, O. ZELAYA, A. HERRERA, F. LARIOS, O. A. FREGOSO, J. M.
FIGUEROA, G, C. PUENTE, A. D. GONGORA, E. G. DA SILVA, R. B. SCORZELLI, M. H. FARIAS, L.
C. ARAIZA, G. SOTO, Thin Solid Films, 193/194 (1990) 382.
269. J. P. EYMERY, A. FNIDIKI, R. KRISHNAN, M. TESSIER,J. P. VrITON, Phys. Rev. B: Condens. Matter,
38 (1988) 11931.
270. S. B. OGALE, Y.V. BHANDARKAR,P. P. PATIL, S. M. KANETKAR, V. G. BHIDE, Hypeffine Interact.,
27 (1986) 289.
271. Y. V. BHANDARKAR, S. M. KANETKAR, S. B. OGALE, S. V. GHAISAS, C, G. BHIDE, J. Appl. Phys.,
59 (1986) 4158.
272. T. ZEMCIK, K. ZAVETA, I. SKORVANEK,J. Mater. Sci., 28 (1993) 654.
273. E. KUZMANN, A. VI~RTES, Y. UJIHIRA, M. FUJINAMI, P. KOV,/~CS, T. ANDO, T. MASUMOTO,
Hyperfine Interact., 45 (1989) 279.
274.1. TANAKA, K. NOMURA, Y. UJIHIRA, A. VI~RTES,H. KIMURA,T. MASUMOTO, Hyperfine Interact.,
55 (1990) 1071.
275. P. SCHAAF, V. BIEHL, U. GONSER, M. BAMBERGR, PH. BAUER, J. Mater. Sci., 26 (1991) 5019.
276. P. SCHAAF, V. BIEHL, U. GONSER, M. BAMBERGER, M. LANGOHR,F. MAISENHALDER,Hyperfine
Interact., 53-58 (1990) 2095.
277. M. CARBUCICCHIO, G. PALOMBARINI, Thin Solid Films, 126 (1985) 293.
278. O. SCHNEEWEISS,K. VOLENIK, Hyperfine Interact., 46 (1989) 527.
279. CS. FETZER, L. GRANASY, T. KEIvlENY,I. VINCZE, Hyperline Interact., 53-58 (1990) 1823.
280. CS. FETZER, L. GRANASY, T. KE/vlENY,E. KOTAI, M. TEGZE, I. VINCZE, W. HOVING,F. VAN DER
WOUDE, American Phys. Soci., 42 (1990) 548.
281. CS. FETZER. GY. FAIGEL, L. GRANASY, T. KEIvlENY,M. TEGZE, I. VINCZE, Hyperfine Interact., 59
(1990) 48 t.
282. O. SCHNEEWEISS, K. VOLENIK, S. LIBOVICZKY,A. SEDLACEK, Hyperfine Interact., 53-58 (1990)
2105.
283. S. DAMGAARD, M. ORON, J. W. PETERSEN, YU. V. PETRIKIN, G. WEYER, Phys. Star. Sol., (a)59
(1976) 63.
284. P. J. PICONE, A. H. MORRISH, J. Appl. Phys., 53 (1982) 2471.
285. P. H. SMIT, H. A. ALGRA, J. M. ROBERTSON, Appl. Phys., 22 (1980) 299.
286. J. ITOH, Y. YONEKURA, T. TORIYAMA, H. MIYASAKA,K. HISTAKE, Hyperfine Interact., 16 (1983)
771.
287. J. ITOH, K. SANEYOSHI, T. TORIYAMA, K. HISATAKE,J. Appl. Phys.i 60 (1986) 1461.
288. C. J. M. DEN1SSEN, Hyperfine Interact., 53-58 (1990) 157%
289. X. Z. ZHOU, R. J. POLLARD, A. H. MORRISH, IEEE Trans. Magn., MAG-21 (1985) 1703.
290. G. BALESTRINO, S. LAGOMARSINO, B. MATURI, A. TUCCIARONE, IEEE Trans. Magn., 20 (1984)
1864.
193
291. G. BALESTRINO, S. LAGOMARSINO, A. TUCCtARONE, Thin Solid Films, 125 (1985) 263.
292. G. MAREST, A. PEREZ, J. L. PONTHEN1ER,p. GERARAD,J. M. ROBERTSON, J. Appl. Phys., 55 (1984)
2560.
293. G. MAREST, A. PEREZ, P. GERARD, J. M. MACKOWSKI, Phys. Rev. B: C0ndens. Mlatter, 34 (1986)
4831.
294. G. MAREST, A. PEREZ, P. GERARD, J. M. MACKOWSKI,Phys. Rev. B, 34 (1986) 4831.
295. G. MAREST, N. KORN1LIOS,A. PEREZ, F. RAVEL, P. GXERARD, B. GILLES, M. BRUNEL, Hyperfine
Interact., 35 (1987) 943.
296. M. PARDAVI-HORV,g,TH; L. BOTYYidg, I. S. SZOCS, P. E WIEGEN, M. GOMI, J. Mag. Mater., 83
(1990) 23.
297. M. P. HORVATH, L. BoTrY~dq, I. S: SZOCS, P. E. WIEGEN, M, GOMI, Hyperiine Interact., 54 (1990)
639.
298. T. FUJII, M. TAKANO, R. KATANO, y. BANDO, Y. ISOZUMI, T. OKUDA, J. Magn, Magn. Mater., 92
(1990) 261.
299. K. NOMURA, T. HANAI, R. SADAMOTO, Y. UJIHIRA, T. RYUO, M. TANNO, Hyperfine Interact., 84
(1994) 421.
300. A. S. KAMZIN, L. A. GRIGOR'EV, Soy. Tech. Phys. Lett., 16 (1990) 616.
301. A. S. KAMZIN, L. A. GRIGOR'EV, Soy. Phys. Tech. Phys., 35 (1990) 840.
302. A. S. KAMZIN, L. A. GRIGOR'EV, Sov. Tech. Phys. Lett., 16 (1990) 580.
303. G, MAREST, E. B. SAITOVITCH, Hyperfine Interact., 66 (1991) 401.
304. X. Z. ZHOU, A. H. MORRISH, Q. A. PANKHURST, M. RAUDSEPP, J. Phys., Colloq. (Proc. Int. Congr.
Magn., 188) 3, C8 (1988) 2213.
305. J. DENGLER, G. RITYER, G. S. ISCHENKO, B. ROAS, L. SCHULTZ, B. MOLNftR, D. L. NAGY,
I. S. SZOCS, Hypeffine Interact., 55 (1990) 1267.
306. J. DENGLER, G. RIqTER, G. S. ISCHENKO, B. ROAS, L. SCHULTZ, B. MOLN,gdt, D. L. NAGY,
L S. SZCdCS, Physica C (Amsterdam) 162 (1989) 1297.
307. J. DENGLER, G, ERRMANN~ G. R/TrER, O. BAUER, G, S. ISCHENKO, B. ROAS, Hypeffine Interact.,
66 (1991) 373.
308. J. DENGLER, G. ERRMANN, G. Rrlq~R, J. MARKL, G. S. ISCHENKO, B. ROAS, Hyperline Interact.,
70 (1992) 1197.
309. J. DENGLER, G. RI'ITER, G. S. ISCHENKO, B. ROAS, L. SCHULTZ, B. MOLN,g~R, D. L. NAGY,
I. S. SZI)CS, Hyperfine Interact,, 55 (1990) 1267.
310. G. S. ISCHENKO, B. HANSEL, B. ROAS, J. DENGLER, G. RITI~R, S. KLAUMUE~'~ZER,
H. E. HOENIG, H. W. NEUMUELLER, J. SCHUTZMANNet al., Prog. High Temp. Superco ., zl (1990)
361.
311. J. DENGLER, G. ERRMANN, G. RITI'ER, O. BAUER, G. S. ISCHENKO, B. ROAS, Hypeffine Interact.,
66 (1991) 373.
312. A. MAZIEWSKI, E. JACKIEW1CZ, A. KOTLICKI,P. GOEMERT, Solid State Commun., 73 (1990) 487.
313. K. NOMURA, Y. SUGAWARA, H. LI, Y. UJIHIRA, Hyperfine Interact., 69 (1991) 879.
314. M. J. TRICKER, A. P. WINTERBOTI'OM, A. G. FREEMAN, J. Chem. Soc. Dalton (1976) 1289.
315. H. M. VAN NOORT, J. W. D. MARTENS, W. L. PEETERS, Mater. Res. Bull., 20 (1985) 41.
316. F. THIMON, G. MAREST, N. MONCOFFRE, S. JOSHI, S. B. OGALE, Nuct. Instrum. Methods in Phys.
Res., B80/81 (1993) 1241.
317. C, ORTIZ, C. HWANG, A, H. MORR1SH, X. Z. ZHOU, J. Mater. Res, 5 (1990) 824.
318. A. A. NOVAKOVA, A. P. KUPRIN, Nuel. Inst. Methods in Phys: Res., B76 (1993) 213.
319. K. NOMURA, Y. UJIHIRA, Analyt. Sci., 3 (t987) 125.
320. K. NOMURA, Y. UJIHIRA, Analyt. Chem., 60 (1988) 2564.
321. K. NOMURA, Y. UJIHIRA, K. ITOH, K. HONDA, Thin Solid Film, 128, Nos 3, 4 (1985) 225.
323. G. VON EYNATTEN, E. FUKADA, K. DRANSFELD, Hyperfine interact., 42 (1988) 1095.
324. J. H. SANDERS, B. J. TATARCHUK, Thin Solid Films, 192 (1990) 79.
325. U. GRADMANN, J. Magn. Magn. Mater., 100 (1991) 481.
326. M. PRZYBYLSKI, J. KORECKI, U. GRADMANN, Appl. Phys., A52 (1991) 33.
327. J. MATHON, Rep. Progr. Phys., 51 (1988) 1.
328, A. J. FREEMAN, C. L. FU, J. Appl. Phys., 61 (1987) 3356.
329. W. MEISEL, P. GUTLICH; Surface and Interface Analysis, 19 (192) 450.
330. J. KORECKI, U. GRADMANN, Phys. Rev. Lett., 55 (1985) 2491.
331. G. T. RADO, Bull. Am. Phys. Sot., 2 (1957) 127.
332, J. C. WALKER, R. DROSTE, G. STERN, J. TYSON, J. Appl. Phys., 55 (1984) 2500.
194
333. M. PRZYBYLSKI, I. KAUFMANN, U. GRADMANN, Phys. Rev.B, 40 (1989) 8631.

334. U. GRADMANN, G. LIU, H. J. EL/VIERS,M. PRZYBYLSKI, Hyperfine Interact., 53-58 (1990) 1845,
335. U. GRADMANN, M. PRZYBYLSKI, H. J. ELMERS, G. L1U, Appl. Phys. A, 49 (1989) 563.
336. F. A. VOLKENING, B. T. JONKER, J, J. KREBS, N, C. KOON, G. A. PRINZ, J. Appl. Phys., 63 (1988)
3869.
337. F. A. VOLKENING, B. T. JONKER, J. J. KREBS, G. A. PRINZ, N. C. KOON, J. Phys. Colloq., C8 (1988)
1699.
338. J. KORECKI, U. GRADMANN, Hyperfine Interact., 28 (1986) 931.
339. J. KORECKI, M. PRZYBYLSKI, U. GRADMANN, J. Magn. Magn. Mater., 89 (1990) 325.
340. J. KORECKI, U. GRADMANN, Europhys. LelI., 2 (8) (1986) 651.
341. G. LIU, U. GRADMANN, J. Magn. Magn. Mater., 118 (1993) 99.
342. W. A. A. MACEDO, W. KEUNE, Phys. Rev. Lett, 61, 4 (1988) 475.
343. O. DONZELLI, G. FRATUCELLO, F. RONCONI, J. TEJADA, Z. RACH/D, X. X. ZHANG, Hyperfine
Interact., 68 (1991) 303.
344. J, LANDES, CH. SAUER, R. A. BRAND, W. ZINN, S. MANTL. ZS. KAJCSOS,J. Magn. Magn. Mater., 86
(1990) 71.
345. J, LANDES, CH. SAUER, R. A. BRAND, W. ZINN, ZS. KAJCSOS, Hyperfine Interact., 57 (1990) 1941.
346. M. PRZYBYLSKI, U. GRADMANN, K. KROP, Hyperfine Interact., 57 (1990) 2045.
347. A. PAESANO, Jr., S. R. TEIXEIRA, L. AMARAL, Hyperfine Interact., 67 (1991) 665.
348. J, A. SAWICKI, A. P. HITCHCOCK, T. TYLISZCZAK, Physica B (Amsterdarn),~158 (1989) 681.
349. M. A. Z. VASCONCELLOS, S. R. TEIXEIRA, I?. H. DIONISIO,W. H. SCHREINER, L L R. BAUMVOL,
Nucl. Instrum. Methods in Phys. Res., A280 (1989) 557.
350. A. FNIDIKI, J. P. EYMERY, J. Phys. Colloq., C8 (1988) 1735.
351. H. ONE, M. I'qJJINAGA, T. YONEMOTO, T. MIYAGAWA, Y. KITANO, J. Magn. Magn. Mater., 118
(1993) 352.
352. S. ~ANDSCHLr/-/, J. LANDES, U. KOBLER, CH. SALTER, G. KISTERS, A. FUSS, W. ZINN, J. Magn.
Magn. Mater., 119 (1993) 254.
353. B. SCHOLZ, R. A. BRAND, W. KEUNE, Phys. Rev., 50 (1994) 2537.
354. W. MEISEL, P. GI3TLICH, Hypeffine Interact,, 69 (1991) 815.
355. W. MEISEL, P. TIPPMANN-KRAYER, H. MOHWALD, P. GLITLICH, Fresenius J. Anal. Chem., 341
(1991) 289,
356. T. FALDUM, W. MEISEL, P. GI~ILICH, Hyperfine Inter'act. (1994) in press.
357. G. VON EYNA'IT"EN,K. NNOTHHELFER, K. DRANSFELD, Hypeffine Interact., 69 (1991) 759.
358. I. S. ZABH~SK1, B. J. TATARCHUK, Hypeffine Interact., 53-58 (1990) 2141.
359. T, S. LEE, T. GEORGE, B, J. TATARCHUK, J. R. WILLIAMS,Jr., D. L. EDWARDS, Hyperfine Interact.
(1994) in press.
360. P. L. CROUSE, C. M. STANDER, J. Phys. Chem. Solids, 49 (1988) 1145.
361. M. FUJINAML Y. UJIHIRA, J. Mater. Sci., 20 (1985) 1859.
362. P. L. CROUSE, J. Phys. Chem. Solids, 50 (1989) 369.
363. A. FNIDIKI, J. P. EYMERY, Ann. Chim. (Paris), 8 (1983) 237.
364. ZS. KAJCSOS. W. MEISEL, E. KUZMANN, C. TOSELLO, M. L GRATTON, A. VI~RTES,P. GU'I~ICH,
D. L. NAGY, Hypertine Interact., 57 (1990) 1883.
365. J. STANEK, J. SAWICKI, B. SAWICKA, Nucl. lnstrum. Methods, 130 (1975) 613.
366. M. J. TRICKER, R. K. THORPE, J. H. FREEMAN, G. A. GARD, Phys. Smt. Soli. A, 33 (1976) K97.
367. B. D. SAWICKA, J. SAWICKI, J. STANEK, Phys. Lett., 59 (1976) 59.
368. B. D. SAWICKA, J. SAWICKI, J. STANEK, Nucl. Instrum. Methods, 130 (1975) 615.
369. B. D. SAWICKA, J. A. SAWICKI, J. STANEK, T. TYLISZCZAK, J. KOWALSK/, Phys. Star. Sol. A, 56
(1979) 451.
370. G. LANGOUCHE, Hyperfine Inleracl., 45 (1989) 199.
371. G. LANGOUCHE, Hypeffine Interact., 68 (199l) 95.
372. P. ZHANG, L. URHAHN, 1. DEZSI, A. VANTOMME, G. LANGOUCHE, Hyperfine Interact.', 53-58 (1990)
1667.
373. T. SHIGEMATSU, S. STANIEK, R. A. BRAND, W. KEUNE, R. H. NUSSBAUM, H. D. PFANNES,
D. L1L,IEQUIST,G. LONGWORTH, R. ATKINSON,Hyperfine Interact., 15 (1983) 383.
374. G. LONGWORTH, R. JA/N, J. Phys. F: Metal Phys., 8 (t987) 351.
375. R. JAIN, G. LONGWORTH,J. Phys. F: Met,'d Phys., 8 (1987) 363.
376. M. HANS, G. K. WOLF, F. E. WAGNER, Hyperfine Interact., 53-58 (1990) 1569.
378. G. LANGOUCHE, Hyperfine Interact., 72 (1992) 217.
379. W, X. HU, G. L. ZHANG, W. H. LIU, F. XU, y. G. LI, Hyperfine Interact., 70 (1992) 935.
195
380. K. SASSA, Y. ISHIDA, K. KANEKO, J. de Physique, Colloque, C2, 40 (1979) 556.

381. D. BODIN, P. MOINE, J. P. EYMERY, Nucl. Inslrum. Methods in Phys. Res., B23 (1987) 337.
382. D. L. W1LLIAMSON, I. L. SINGER, R. WEI, P. J. J. WILBUR, Nucl. Inst., B76 (1993) 2t0.
383. E. KOLAWA, T. TYLISZCZAK, B. D. SAWICKA,J. A. SAWlCKI, M. DRWIEGA,Phys. Stat. Sol. A, 102
(1987) 181.
384. G. MULLER, G. KLINGELHOFER,P. SCHWALBACH, E. KANKELEIT,Nucl. Instrum. Methods in Phys.
Res., B50 (1990) 384.
385. G. MAREST, J. PARELLADA, G. PRINCIPI, C. TOSELLO, Nucl. Instr. Methods in Phys. Res., B80/81
(1993) 309.
386. G. MAREST, Surface and Interface Analysis, 12 (1988) 509.
387. G. MAREST, C. DONNET, J. A. SAWICKI, Hyperfine Interact., 53-58 (1990) 1605.
388. K. FUKUMURA, T. KOBAYASHI, M. OHKUBO, T. HIOKI, Y. ISOZUMI, Hypeffine Interact., 70 (1992)
889.
389. C. DONNET, H. JAFFREZIC, G. MAREST, N. MONCOFFRE, J. TOUSSET, Nucl. Inslrum. Methods in
Phys. Res., B50 (1990) 410.
390. G. MAREST, C. DONNET, N. MONCOFFRE, J. TOUSSET, Hyperfine Interact., 56 (1990) 1613.
391. C. DONNET, G. MAREST, N. MONCOFFRE, J. TOUSSET, A. RAHIOUI, C. ESNOUF, M. BRUNEL,
Nucl. Instrum. Methods in Phys. Res., B59/60 (1991) 1205.
392. C. J. McHARGUE, P. S. SKLAD, J. C. McCALLUM, C. W. WHITE, A. PEREZ, G. MAREST, Nucl.
393. C. DONNET, G. MAREST, N. MONCOFFRE, J. TOUSSET, Nucl. Instrum. Methods in Phys. Res., B59/60
(1991) 1177.
394. N. MONCOFFRE, Nucl. Instrum. Methods in Phys. Res., B59/60 (1991) 1129.
395. H. BINCZYCKA, G. MAREST, N. MONCOFFRE, J. STANEK, Hyperfine Interact., 53-58 (1990) 1557.
396. H. BINCZYCKA, B. FORNAL, G. MAREST, N. MONCOFFRE, J. STANEK, Radiat. Eft. Defects Solids,
116 (1991) 97.
397. E. A. BYCHKOV, YU. G. VLASOV, V. A. DRAVIN, V. G. SEMENOV,J. Non-Cryst, Solids, 113 (1989)
203.
398. J. KOWALSKI, J. A. SAWICKI, J. STANEK, G. MAREST, A. PEREZ, B, D. SAWICKA,
T. TYLISZCZAK, Nucl. Instrum. Methods in Phys. Res., 209 (1983) 1145.
399. G. MAREST, Defect and Diffusion Forum, 57-58 (1988) 273.
400. M. KOPCEWlCZ, J. JAGIELSKI, G. GAWLIK, A. TUROS, Nucl. Instrum. Methods in Phys. Res., B68
(1992) 417.
401. H. REUTHER, Phys. Stat. Soli. A, 93 (1986) 201.
402. G. TERWAGNE, G. VAN TENDELOO, S. E. DONNELLY,J. Appl. Phys, 65 (1989) 4225.
403. M. WU, Z. TONG, Q. ZHANG, Y. JIN, S. WANG, Nucl. Instrum. Methods in Phys. Res., B52 (1990) 44.
404. R. FRATTINI, G. PRINC1PI, S. LO RUSSO, B. TIVERON, C. TOSELLO, J. Mater. Sci., 17 (1982) 1683.
405. Y. S. DORIK, S. M. CHAUDHARI, S. V. GHAISAS,S. B. OGALE, V. G. BHIDE, J. Appl. Phys.k 60 (1986)
2959.
406. S. M. M. RAMOS, L, AMARAL, M. BEHAR, O. MAREST, A. VASQUEZ,F. C. ZAWISLAK, Hyperfine
Interact., 46 (1989) 483.
407. M. CARBUCICCHIO, L. BARDANI, S. TOSTO, J. Appl. Phys., 57 (1981) 1589.
408. G. MAREST, C. SKOUTARIDES, T. BARNAVON, J. TOUSSET, S. FAYEULLE, M. ROBELET, Nucl.
Instrum. Methods in Phys. Res., 209 (1983) 259.
409. Y. S. DORIK, V. G. BHIDE, S. M. KANETKAR, S. V. GHAISAS, S. M. CHAUDHARI, S. B. OGALE,
J. Appl. Phys., 56 (1984) 2566.
410. F. M. KUSTAS, M. S. MISRA, D. L. WlLLIAMSON,Nucl. Instrum.Methods in Phys. Res., B31 (1988) 393.
41l. S. M. M. RAMOS, L. AMARAL, M. BEHAR, G. MAREST, A. VASQUEZ, C. ZAWISLAK, Mater. Sci.
Engi., All5 (1989) 31.
412. G. WAGNER, R. LEUTENECKER, U. GONSER, Flyperfine Interact., 53-58 (1990) 1653.
413. M. A. EL KHAKANI, G. MAREST, N. MONCOFFRE,J. TOUSSET, Nucl. Instrum. Methods in Phys. Res.,
B59/60 (1991) 817.
414. D. L. W/LLIAMSON, O. OZTURK, S. GLICKK, R. WEI, P. J. WILBUR, Nucl. Inslrum. Methods in Phys.
Res., B59/60 (1991) 737.
415. M. KOPCEWICZ, J. JAGIELSKI, A. TUROS, M. LUKASIAK,Hyperfine Interact., 70 (1992) 1385.
416. M. KOPCEWICZ, J. JAGIELSKI, A. TUROS, G. GAWLIK, Nucl. Instrum. Methods in Phys. Res., B80/81
(1993) 327.
417. D. L. WILLIAMSON,Nucl. Inst. Methods in Phys. Res., B76 (1993) 262.
418. M. FUJINAMI, Y. UJIHIRA, H. REUTHER, E. RICHTER, Hyperfine Interact., 42 (1988) 985.
196
419. N. MILLARD, G. MAREST, N. MONCOFFRE, J. TOUSSET, Surface and Coatings Technology, 51 (1992)
446.
420. A. KRAMER, F. AUBERTIN, U. GONSER, Hyperfine Interactions, 84 (1994) 289.
421. H. REUTHER, E. RICHTER, I. S. SZ!)CS, Phys. Stat. Sol. A, 118 (1990) 409.
422. A. D. POGREBNJAK, O. G. BAKHAREV, V. A. MARTYNENKO, V. A. RUDENKO, R. BRUSA,
A. ZECCA, R. OECHSNER, H. RYSSEL, I. A. TIKttOMIROV, A. I. RYABCHIKOV, Nucl. Instrum.
Methods in Phys. Res., B94 (1994) 8t.
423, H. REUTHER, Nucl. Inslrum. Methods in Phys. Res., B30 (1988) 61.
424. H. REUTHER, Phys. Star. Sol. A, 93 (1986) 201.
425. H. REUTHER, Isotopenpraxis, 24 (1988) 419.
426. H. REUTHER, E. RICHTER, Phys. Res., 13 (1990) 460.
427. H. REUTHER, Nucl. Instrum. Methods in Phys. Res., B53 (1991) 167.
428. H. REUTHER, Hyperfine Interact., 56 (1990) 1637.
429. H. REUTHER, I. NIKOLOV, S. KRUL1ER, R. A. BRAND, W. KEUNE, Nucl. Instrum. Methods in Phys.
Res., B80/81 (1993) 348.
430. H. LADSTATTER, B. STAHL, O. GEISS, R. GILLERT, M. HARTICK, G. KLINGELHOFER,
P. SCHWALBACH, KANKELEIT, Nucl. Inst. Methods in Phys. Res,, B76 (1993) 29.
431. M. A. EL KHAKANI, H. JAFFREZIC, G. MAREST, N. MONCOFFRE, J. TOUSSET, Mater. Sci. Eng.,
All5 (1989) 37.
432. G. MAREST, M. A. EL KHAKANI, Nucl. Insla-urn.Methods in Phys. Res., B59/60 (1991) 833.
433. H. REUTHER, Surface and Interface Analysis, 22 (1994) 547.
434. G. PRINCIPI, Hyperfine Interact., 66 (1991) 149.
435. J. E. E. BAGLIN, Nucl. Instmm. Methods in Phys. Res., B65 (1992) 119.
436. A. FNIDIKI, J. P. EYMERY, Scr. Metall., 19 (1985) 847.
437. C. JAOUEN, J. P. EYMERY, E. L. MATH, J. DELAFOND, Mater. Sei. Eng., 69 (1985) 483.
438. F. G. DOYLE, F. G. YOST, S. T. PICRAUX, D. M. FOLLSTAEDT, L. E. POPE, J. A. KNAPP, Nucl. Instr.
Methods in Phys. Res,, B718 (1985) 166.
439. V. P. GODBOLE, S. M. CHAUDHARI, S. V. GHAISAS,S. M. KANETKAR, S. B. OGALE, V. G. BHIDE,
Phys. Rev., B31 (1985) 5703.
440. W. W. HU, C. R. CLAYTON, H. HERMAN, J. K. HIRVONEN, Sci. Metall., 12 (1978) 697.
441. J. C. PLENET, A. PEREZ, J. RIVORY, O. LABORDE, Nucl. Inslrum. Methods in Phys. Res., B80/81 (1993)
379.
442. J. L. ALEXANDRE, M. A. Z. VASCONCELLOS,R. HUBLER, S. R. TEIXEIRA,I. J. R. BAUMVOL, Nucl.
443. S. M. KANETKAR, Y. S. DORIK, S. M. CHAUDHARI, S. V. GHAISAS, S. B. OGALE, V. G. BHIDE,
Thin Solid Films, 136 (1986) 45.
444. D, M. PHASE, J. PATANKAR, V. N. KULKARNI, 8. B. OGALE, Radiat. Eft., 106 (1988) 297.
445. S. N. YEDAVE, S. M. CHAUDHARI, S. M, KANETKAR, S. B. OGALE, S. V. GHAISAS, J. Appl. Phys.,
67 (1990) 710.
446. T. BIRCHALL, D. HODGSON, Industrial Applications of the M0ssbauer Effect, G. J. LONG a n d
J. G. STEVENS (Eds), Plenum Publishing Corporation, New York, 1986, p. 189.
447. E. KUZMANN, I. N. SPIROV, Materials Science Forum, 97-99 (1992) 665.
448. W. H. GRIES, B. D. SAWICKA, J. A. SAWICKI,Nucl. Inslrum. Methods in Phys. Res., B18 (1987) 291.
449. L. M. GRATI'ON, A. GUPTA, W. KELrNE, S. LO RUSSO, J. PARELLADA, G. PRINCIPI, C. TOSELLO,
Mater. Sci. Eng., Al15 (1989) 161.
450. M. A. EL KHAKANI, G. MAREST, N. MONCOFFRE, J. TOUSSET, Nucl. Instrum. Methods in Phys. Res.,
in press.
451.C. TOSELLO, L. M. GRATI'ON, W. KEUNE, R. A. BRAND, S. LO RUSSO, J. PARELLADA,
J. M. FERNANDEZ, G. MAREST, M. A. E. KHAKANI,G. PRINCIPI, A. GUPTA, Nucl. Instrum. Methods
in Phys. Res., B59/60 (1991) 545.
452. A. D. MARWICK, R, C. PILLER, T. E. CRANSHAW, J. Phys. F: Met. Phys., 17 (1987) 37.
453. H. FRANCO, H. R. RECHENBERG, J. Phys. F: Met. Phys., 15 (1985) 719.
454. A. VI~RTES, E. KUZMANN, G. VIS-RTES,Z. S. NAGY, E. KOTAY, G./VlF.ZF,y, Hyperfine Interact., 42
(1988) 1013.
455. C. TOSELLO, F. FERRARI, R. BRAND, W. KEUNE, G. MAREST, M. A. EL KHAKANI,
J. PARELLADA, G. PRINCIPI, S. LO RUSSO, V. RIGATO, S. ENZO, Nucl. Instrum. Methods in Phys.
Res., B80/81 (1993) 417.
456. A. GUPTA, G. PRINCIPI, G. BATrAGLIN, S. LO RUSSO, Q. ZHANG, Hyperfine Interact,, 53 (1990)
1587.
197
457. M. KOPCEWICZ, D. L. WILLIAMSON,F. E. CECIL, Hyperfine Interact., 53 (1990) 1599.

458. V. P. GODBOLE, V. G. BHIDE, S. V. GHAISAS,S. M. KANETKAR,R. S. JOSHEE, S. B. OGALE, Mater.
Res. Soc. Symp. t:'roc., 25 (1984) 241.
459. S. B. OGALE, R. JOSHEE, VI P. GODBOLE, S. M. KANETKAR, V. G. BHIDE, J. AppL Phys., 57 (1985)
2915.
460. J. PATANKAR, Y. V. BHANDARKAR, S. M. ,KANETKAR, S. B. OGALE, V. G. BHIDE, Nucl. Inslrum.
Methods in Phys. RSes., B7 (1985) 720.
461. A. P. KUPRIN, I. G. MURZIN, Nucl. Inslrum. Methods in Phys. Res., B76 (1993) 218.
462. R. JOSHEE, D. M. PHASE, S. V. GHAISAS, S. M. KANETKAR, S. B. OGALE, V. G. BHIDE, J. AppL
Phys., 59 (1986) 388.
463. S. NASU, F. E. FUJITA, Hyperfine Interact., 29 (1986) I279.
464. G. MUKHOPADHYAY, D. DAS, C. K. MAJUMDAR, K. R. P. M. RAO, Philos. Mag. Lett., 63 (1991) 315.
465. SH~ SH. BASHK1ROV, N. G. IVOILOV, E. S. ROMANOV, Izv. Akad. Nauk SSSR, Ser. Fiz., 54 (1990)
1769.
466, A. FNIDIKI, J. P. EYMERY, Scr. Metall., 19 (1985) 329.
467. A. FN[DIKI, D. BODIN, J. P. EYMERY, Hypeffine Interact., 29 (I986) 1179,
468. J. P. EYMERY, A. FNIDIKI, Diffus. Defect Data, 57 (1988) 229.
469. Y. V. BHANDARKAR, S. V. GHAISAS, S. B. OGALE, J. Appl. Phys,, 64 (1988) 677.
470. N. HAYASHI, I. SKAMOTO, H. TANOUE, NucL Instmm. Methods in Phys. Res., B76 (1989) 268.
471. E. KUZMANN, I. N. SPIROV, A. YU. DIDYK, Mater. Sci. Forum, 97-99 (1992) 671.
472. G. PRINCIPI, C. TOSELLO, E. KUZMANN, A. VI~RTES,Materials Science Forum, 97 (1992) 393,
473. C. E. FOERSTR, L. AMARAL, N. MONCOFFRE, M. BHAR, NaeL Inslram. Methods in Phys. Res., B80/81
(1993) 316.
474. S. B. OGALE, D. M. PHASE, P. P. PATIL, S. M. KANETKAR, S. V. GHAISAS,V. G. BI~DE, S. K. Date,
475. S. B. OGALE, D. M. PHASE, S. M. CHAUDHARI, S. V. GHAISAS, S. M. KANETKAR, P. P. PATIL,
V. G. BHIDE, S. K. DATE, Phys. Rev. B, 35 (1987) 1593.
476. E, ABONNEAU, A. PERSEZ, G. FUCHS, M. TREILLEUZ, Nucl. Instrum. Methods in Phys. Res., B59/60
(1991) 1183.
477. A. PEREZ, E. ABONNEAU, G. FUCHS, M. TREILLEUX, C. J. McHARGUE, D. H. JOSLIN, Nucl.
Inslrum. Methods in Phys. Res., B65 (1992) 129.
478. J. LI, B. X. LIU, Nucl. Instrum Methods in Phys. Res., B31 (1988) 407.
479. S. BHAGWAT. S. N. YEDAVE, D. M. PHASE, S. M. CHAUDHARI, S. M. KANETKAR, S. B. OGALE,
Phys. Rev. B, 40 (1989) 700.
480. G. PRINCIPI, P. POLATO, A. PACCAGNELLA, A. MADDALENA, S. LO RUSSO, G. BATTAGLIN,
481. Y. ARATONO, C. SAGAWA, M. NAKASH/MA,M. NADAKA, K. JOJOU, M. SAEK1, Hyperfine Interact.,
70 (1992) 905.
482. P. P. PATIL, N. KULKARNI, S. V. GHAISAS, S. B. OGALE, V. G. BHIDE, S. K. DATE, Hyperfine
Interact., 35 (1987) 919.
483. P. A. INGEMARSSON, T. ERICSSON, G. POSSNERT, R. WAPPL1NG, Hypeffine Interact., 46 (1989) 549.
484. R. WAPPLING, Nucl. Inslmm. Methods in Phys. Res., B76 (1993) 22.
485. K, P. M1TROFANOV, V. S. SHPINEL, Soviet Phys., JETPI3 (1964) 233.
486. C. M. YAGNIK, R. A. MAZAK, R. L. COLLINS, Nucl. Instrum. Methods in Phys. Res., 114 (1974) 1.
487. A. PROYKOVA, A. MINKOVA, B. SLAVOV, TS. BONCKEV, Bulg. J. Phys., V, 3 (1978) 248.
488. A. PROYKOVA, Bulg. J. Phys., VI, 1 (1978) 28.
489. A. PROYKOVA, NucL Instrum. Methods, 160 (1979) 321.
490. D. L. WILLIAMSON, S. K. DEB, J. Appl. Phys., 54 (1983) 2588.
491. P. H. DIONISIO, A. VASQUEZ, B. HALLOUCHE, D. M. MOSCA, Jr., S. R. TEIXERIA,
W. H. SCHR INER, Hyperfine Interact., 67 (1991) 493.
492. P. H. DIONISIO, A. VASQUEZ, B. HALLOUCHE, D. H. MOSCA, Jr., S. R. TEIXEIRA,
W. 14. SCHREINER, A. A. PASA, Thin, Solid Films, 217 (1992) 152.
493. S. M. DUBIEL, W, ZNAMIROWSKI,Hyperfine Interact., 9 (1981) 477.
494. A. Vt~RTES, A. P. PCHELNIKOV, V. V. LOSEV, M. SUBA, M. V. LAKATOS, 1. CZ. NAGY, Radiochem.
Radioanal. Letters, 53 (1982) 167.
495. M. FUJINAMI, K. YOSHJDA, Y. UJIHIRA, M. TERASAKA, J. Mater. Sci., 20 (1985) 4099.
496. H. M. VAN NOORT, B. C. M. MEENDERINK, A. MOLENAAR, J. Eleclrochem. Soc., 133 (1986) 263.
497. G. PRINCIPI, A. MADDALENA, A. GUPTA, R. DAL MASCHIO, S. DIRE, Hyperfine Interact., 69 (1992)
619.
198
498. H. TANG, R. LIU, H. ZHOU, Y. HSIA, Hyperfine Interact., 41 (1988) 713,

499. M. S. MORENO, J. DESIMONI, R. C. MERCADER, A. G. BIBILONI,Hyperfine Interact., 67 (1991) 657.
500. K. NOMURA, S. S. SHARMA, Y. UJIHIRA, A. FUEDA, T. MURAKAMI, J. Mateer. Sci., 24 (1989) 937.
501. S. S. SHARMA, K. NOMURA, Y. UJIH1RA,J. Mater. Sci., 25 (1991) 4101.
502. S. S. SHARMA, K. NOMURA, Y. UJ1HIRA,J. Appl. Phys., 71 (1992) 2000.
502. K. NOMURA, Y. UJIHIRA, S. S. SHARMA, K. MATSUMOTO, Hyperfine Interact., 57 (1990) 2015.
504. K. NOMURA, Y. UJIHIRA, S. TANAKA, K. MATSUMOTO, Hyperfine Interact., 42 (1988) 1207.
505. K. NOMURA, Y. U.IIHIRA,R. KOJIMA. J. Mater. Sci., 27 (1992) 2449.
506. K. NOMURA, Y. UJIHIRA, O. TAKAI, R. KOJIMA. Hyperfine Interact., 69 (1991) 549.
507. P. H. DIONISIO, C. SCHERER, S. R. TEIXEIRA,I. J. R. BAUMVOL,Nucl. Instrum. Methods in Phys. Res.,
B16 (1986) 345.
508. A. Vt~RTES, G. PRINCIPI, L. M. GRATI"ON, C. TOSELLO, I. CZ. NAGY, J. Radioanal. Nucl. Chcm.
Letters, 96, 2 (1985) 175.
509.1. CZ. NAGY, A. V~TES, L. M. GRATTON, C. TOSELLO, G. PRINCIPI,J. RadioanaL Nucl. Chem., 136
(1989) 275.
510. S. MONCHER, G. PRINCIPI, L. M. GRATTON, C. TOSELLO, I. CZ. NAGY, A. VI~RTES, Hyperfme
Interact., 46 (1989) 535.
51l. G. MASSOURAS, J. A. ROGER, A. PEREZ, G. FUCHS, L. Romana (1989) 509.
512. E. M. SCHERER, J. P. DE SOUZA, C. M. HASENACK, I. J. R. BAUMVOL. Secimond. Sci. Technol., 1
(1986) 241.
513. K. G. PRASAD, M. B. KURUP, A. BHAGAWAT,Nucl. Instrum. Methods in Phys. Res., B15 (1986) 698.
514. H. DE WAARD, Hypeffine Interact., 72 (1992) 229.
515. H. BINCZYCKA, B. MICZKO, J. A. SAWICKI,J. STANEK, M. DRWlEGA, T. TYLISZCZAK,Mater. Sci.
Eng., 69 (1985) 519.
516. P. H. DIONISIO, I. J. R. BAUMVOL. Phys. Stat. Sol. A, 101 (1987) 63.
517. P. H. DIONISIO, B. A. S. DE BARROS, Jr., I. J. R. BAUMVOL, Phys. Stat. Sol. A, 118 (1990) 473.
518. F. C. STEDILE, W. H. SCHREINER, P. H. DIONISIO,I. J. R. BAUMVOL,Nucl. Instrum. Methods in Phys.
Res., A280 (1989) 552.
519. C.'J. McHARGUE, P. S. SKLAD, J. C. McCALLUM, C. W. WHITE, A. PEREZ, E. ABONNEAU,
G. MAREST, Nucl. Instrum. Methods in Phys. Res., B46 (1990) 74.
520. J. A. SAWICKI, T. TYLISZCZAK,J. STANEK, B. D. SAWICKA,J. KOWALSKI,Nucl. Instrum. Methods,
215 (1983) 567.
521. J. A. SAWlCKI, B. D. SAWICKA, Hyperfine Interact., 16 (1983) 1013.
522. J. A. SAWICKI, G. ABOUCHACRA, J. SERUGHETTI, A. PEREZ, Nucl. Inslrum. Methods in Phys. Res.,
B16 (1986) 355.
523. S. YAMAUCHI, Y. MINAI, T. WATANABE,T. TOMINAGA,J. Radioanal. Nucl. Chem., Lett., 96 (1985)
513.
524. D. SALOMON, P. J. WEST, G. WEYER, Hyperfine Interact., 5 (1977) 61.
525. J. A. SAWICKI, B. D. SAWICKA, F. E. WAGNER, Nucl. Instrum. Methods in Phys. Res., B62 (1991) 253.
526. B. R. BULLARD, J. G. MULLEN, G. SCHUPP, Phys. Rev., 43 (1991) 7405.
527. B. R. BULLARD, L G. MULLEN, Phys. Rev., 43 (1991) 7416.
528. T. MIURA, Y. HATSUKAWA, M. YANAGA, K. ENDO, H. NAKAHARA,M. FUJIOKA, E. TANAKA,
A. HASHIZUME, Hyperfine Interact., 30 (1986) 371.
529. J. A. SAWICKI, L. NIESEN, H. DE WAARD, Nucl. Instrum. Methods in Phys. Res., B83 (1993) 454.
530, Y. YOSI-IIDA,Hyperfine Interact., 47 (1989) 95.
531. R. SIELEMANN, Y. YOSHIDA, Hyperfine Interact., 68 (1991) 119.
532. M. HART1CK, P. SCHWALBACH, M. CIANI, M. DRODT, B. KECK, R. SIELEMANN, B. STAHL,
L. WENDE, E. KANKELEIT, Hyperfine Interact., 84 (1994) 317.
533. L. X. LIAO, D. H. RYAN, Z. ALTOUNIAN, Rev. Sci. Instrum., 64 (1993) 679.
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Jointly published by Journal of Radioanalytical and Nuclear Chemistry, Articles,

Elsevier Science S. A, Lausanne and Vol. 202,Nos 1-2 (1996) 103-199

APPLICATIONS OF CONVERSION ELECTRON

(Received March 13, 1995)

II. Instrumentation for Conversion Electron M6ssbauer Spectrometry (CEMS) 105

Ill. Applications of CEMS 131

3. Nitriding of steel 140

IV. Summary 187

Since Rudolf L. Mtssbauer found the phenomenon of recoil-free T-ray resonance

3~/2 ~Complex /99.84%,

= " S o u r c e " Absorber "- Magnetic F i e l d -1/a

STCo 6keVI{I,L Auger

i0-~ -.1 ~I.-~-~' . / \ ~

(3) Electrons do not move through matter in straight lines.

d(nm) = 1.95 9 102 In (1 - 0.01P)

o10 z,0 3o 4o.

Source | ~'~&-~ f ,Multiplier

C. Combination of CEMS, XMS and TMS

P-47 grafns Al-film

C~S CEMS TMS

D. Depth Selective CEMS

2. Electron energy spectrometers

Table 2. Electron energy spectrometers f o r CEMS

Type Energy Detection Sample S/N References year

.....: ".;'j,/'...:" .... 30nm

._/.,'"..f /kj",, 15Onto ..~:%:/":~:?::(:?;;:"i>:.... 150 ~ 200 n m

f- :\ :" "/\".... 200nm

,/-",,: -,,?_/',._.:.....~'~-:'...., 250nm

4. Glancing angles CEMS (GACEMS)

2~" 3keV (a)

-10.0 -5.0 0 ,5.0 +10.0

5. Low energy electron 5'TFe MSssbauer spectroscopy (LEEMS)

730 3400 7900 14100

0.( .... 100. . . . 2 0 0 : ' ' 3 0 0 ' ' "4

IIL APPLICATIONS OF CEMS

Table 4. M ~ s s b a u e r parameters for corrosion products of iron

Site Temp. I.S. Q.S. HL.

FeO F e =* RT 0.93 0.8 -

Feo.90 FeZ'(A) RT 0.91 0.46 -

Fe304 Fea*(A) RT 0.24 0 49.3

a Fea03 Fe 3. RT 0.39 0.42 51.8

83 0.3 -0.5 54.2

7 Fez03 (A,B) RT 0.3 50.2

B FeOOH Fe 3" RT 0.39 0.62 -

200 0.4 0.i 41.7

80 0.38 0.64 48.5

7 FeOOH Fe 3" RT 0.38 0.76

Fe(0H)2 Fe ~* RT 1.18 2.92

5Ve=O~.9H=0 Fe ~" RT 0.37 0.54

Fe(m) occupying B sites cannot be distinguished at room temperature. T v of 10 nm Fe304 particles

2. Wet corrosion study by CEMS

~Fe(~ll " ""'" ":l

:,._..~...~ ~!.. . - ....

Corrosion layers formed on two metallic glasses, Fes~1320and Fe~oNit0(MoB)z0, by exposing

4. Environmental corrosion of weathering steel

B. Surface finishing of steel

Table 5. M~ssbauer parameters of iron species produced in various

Iron Products IS (mm/s) QS (mm/s) remarks

FeC20,-2H~O 1.17 1.75 on mild steel

Table 6. M~ssbauer parameters for iron-nitrogen-carbon phases by

Process ! Phase IS(mm/s) QS(mm/s) H , , (T)

Iron, gas i a''-Fe~6N2 0.05 29.7

Iron, gas T'-Fe4N 0.24 34.1

Iron, gas e-Fe2.• 0.24 29.8