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org/materials | Journal of Materials Chemistry

Evolution of conductivity, structure and thermochemical stability

of lanthanum manganese iron nickelate perovskites
Elena Konysheva* and John T. S. Irvine
Received 28th April 2008, Accepted 1st August 2008
First published as an Advance Article on the web 23rd September 2008
DOI: 10.1039/b807145d

A series of solid solutions in the La0.8Sr0.2MnO3
d (LSM)–xLa0.95Ni0.6Fe0.4O3d (LNF) system were

synthesised by solid-state reaction to investigate the effect of Ni/Fe substitution for Mn on their DC
electrical conductivity, structure and thermochemical stability. A non-linear change in structure,
conductivity, magnetic properties and thermochemical stability of solid solutions was observed with the
increase in the Ni/Fe content. A new phase (100  x)LSM$xLNF with orthorhombic symmetry was
found in the concentration range 35 # x < 70 mol%, and exhibits the lowest value of the conductivity
and the highest activation energy in the single-phase concentration range 43 # x # 53. This is, most
probably, caused by a low concentration of Mn3+–O–Mn4+ units available for small polaron motion
through the B sublattice. The compositions containing more than 50 mol% Ni in the B sublattice shows
metallic-like conductivity behaviour. The temperature of the semiconducting metallic transition
decreases with increase in the Ni concentration. All compositions had good thermochemical stability in
air, in contrast to that under reducing conditions. The higher the Ni/Fe content in the sample, the faster
the reduction of the solid solutions occurred in non-humidified Ar–H2 (95 : 5) atmosphere. The overall
oxygen stoichiometry of the solid solutions is discussed.

Introduction B sublattice is of great importance for understanding general

Mixed metal oxides with perovskite structure reveal a wide
range of attractive properties such as good electrocatalytic
activity, high electronic and ionic conductivity, and nowadays
they are considered as promising materials for application in
high-efficiency power devices. LaNiO3d perovskite exhibits
metallic-type conductivity.1,2 However, its thermochemical
stability is not good enough for application as cathode and
cathode current collectors in solid-oxide fuel cells at intermediate
temperature.3 The thermochemical stability of this material
could be improved by substitution of different transition
elements (Fe, Co, Mn, Cr etc.) for Ni.4,5 It was found that the
LaNi1xFexO3d and LaNi1xCoxO3d compositions have
better thermochemical stability than LaNiO3d and metallic-type
conductivity was observed at temperatures higher than 200  C.5,6
Improved electrocatalytic activity was also reported even at a
relatively low temperature (400–500  C).7 The LaNi0.6Fe0.4O3d
(LNF) composition was found to possess the highest value of
electronic conductivity.5 All authors reported5–7,9 that the LNF
composition (stoichiometric and with A-site deficiency) had
rhombohedral symmetry (space group R-3c, no. 167). It is
known, that La0.8Sr0.2MnO3
d is isostructural with LNF and
has similar lattice parameters at room temperature.10,11 In addi-
tion, it possesses the highest electronic conductivity among
La1xSrxMnO3
d perovskites.12,13 An incorporation of a third
transition element into the B sublattice could be the next step in
the modification of the electrical properties and thermochemical
stability of these materials. Moreover, the study of perovskite
systems containing more than two 3d-transition elements in the
School of Chemistry, University of St Andrews, St Andrews, Fife, UK
KY16 9ST. E-mail: ek31@st-andrews.ac.uk
trends in multi-component oxide systems and for engineering
of complex oxide materials with controlled physical–chemical
properties.
Therefore, the present work aimed to study the electrical
conductivity, crystal structure and thermochemical stability of
the complex manganese-, nickel- and iron-containing perovskites
formed in the La0.8Sr0.2MnO3
d–La0.95Ni0.6Fe0.4O3d system.
During this investigation the Ni : Fe ratio was kept fixed to
minimise the effect of the redistribution of electronic density
between Ni and Fe with variation of Ni or Fe concentration.
Experimental
La0.8Sr0.2MnO3
d (LSM) and La0.95Ni0.6Fe0.4O3d (LNF)
powders were produced by combustion spray pyrolysis
and supplied by PRAXAIR Inc., USA. Compositions in the
(100  x)LSM$xLNF (x ¼ 2–98 mol%) series were obtained by
mechanical mixing of the corresponding powders in relevant
proportions and followed by calcination in air at 1350  C for 5 h.
Chemical composition and the corresponding abbreviation used
in the text are listed in Table 1. Possible contamination of the
samples by carbon was checked by using an elemental analyser
1110 CHNS CE Instrument (ThermoQuest Italia S.P.A,
Rodano, Italy).
Powder X-ray diffraction (XRD) data were recorded at room
temperature in air in transmission mode on a STOE Stadi-P
diffractometer with CuKa radiation (Stoe & Cie Darmstadt,
Germany) and in reflection mode on a Philips analytical X-ray
PW1710 diffractometer with CuKa radiation (Nederlandse
Philips Bedrijven B.V., Almelo, The Netherlands) to identify
phase composition and structure of the compositions

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Table 1 Chemical composition of some compounds synthesised, oxygen content and the corresponding abbreviations used in the text
Abbreviation Composition (theoretical)
LSM La3+0.8Sr2+0.2Mn3+O3
d
98LSM$02LNF La3+0.803Sr2+0.196Mn3+0.98Ni3+0.012Fe3+0.008O3
d
52LSM$48LNF La3+0.872Sr2+0.104Mn3+0.52Ni3+0.288Fe3+0.192O3
d
30LSM$70LNF La3+0.905Sr2+0.06Mn3+0.3Ni3+0.42Fe3+0.28O3
d
20LSM$80LNF La3+0.92Sr2+0.04Mn3+0.2Ni3+0.48Fe3+0.32O3d
10LSM$90LNF La3+0.935Sr2+0. 02Mn3+0.1Ni3+0.54Fe3+0.36O3d
LNF La3+0.95Ni3+0.6Fe3+0.4O3d
a b
Assuming Sr substitution is compensated by oxygen vacancies. The oxygen content was determined from weight change of samples during their
reduction in non-humidified Ar–H2 (95 : 5). c At 900  C.
synthesised. The diffraction data were refined by the Rietveld
method.14,15
X-Ray photoelectron spectroscopy (XPS) was used to char-
acterise the chemical state of elements in the solid solutions. La
3d, Mn 2p, Fe 2p, O 1s and C 1s core level spectra were recorded
on powders with an ESCALAB II spectrometer (V.G., UK)
using Al (hv ¼ 1486.4 eV) radiation. It should be mentioned that
it was not possible to investigate oxidation states of Ni due to the
interference with La (La 3d3/2 as split doublet together with Ni
2p3/2, both at 853 eV, other Ni signals are weak and/or broad).
Applying the procedure based on the fixed ratio between the La
3d5/2 and La 3d3/2 peak areas (theoretical value is 1.5) also did not
allow Ni contribution in the La 3d3/2 peak to be distinguished for
all samples. The analysing aperture was about 3 mm in diameter.
The overall chemical stoichiometry and thermochemical
stability were analysed by thermal gravimetric analysis (TGA)
on a NETZSCH TG 209 instrument (NETZSCH-Geraetebau
GmbH, Selb, Germany). Measurements were carried out on
powders in air and Ar–H2 (95 : 5) in a temperature range of
25–800  C at a heating/cooling rate of 5  C min1. The initial
weight of samples was about 60 mg. The magnetic susceptibility
measurements were performed in a field of 0.0035 T using
a magnet with the NETZSCH TG 209 instrument.16 The effect of
buoyancy was corrected by blank runs with an alumina crucible
under corresponding gas atmospheres.
Electrical conductivity was measured on sintered pellets by the
standard four-terminal DC method between 25 and 900  C in
ambient air, using heating and cooling rate of 1–2  C min1. A
current of 100 mA (model: Keithley 220, Keithley Instruments
Inc, USA) was applied in both directions, and resistance
was calculated as a gradient of potential vs. current. This was
converted to conductivity using the geometrical factor of the
sample. A jig specially designed for the four-terminal method
was used. In the jig all probes were made of thick Pt wires (1 mm
thickness). The distance between the current probes was 10 mm.
The potential probes were situated between the current probes,
with a distance between the potential and current probes of
3 mm. The length of bars (samples) was 12–15 mm. Au paste
(T10112, Metalor Technologies Ltd, UK) was applied as an
electrode to improve contact between samples and current/
potential probes. In addition, Pt paste (A-3786, Metalor Tech-
nologies Ltd, UK) was used with some compositions. 4 thin
strips of Au or Pt pastes were painted around the bar at the same
distances as the probes in the jig. In addition, Au or Pt foil strips
were co-fired to improve contact between the sample and the
5148 | J. Mater. Chem., 2008, 18, 5147–5154
Oxygen content Oxygen content
(theoretical)a (experimental, at 800  C)b
2.900 2.940
0.005
2.901 2.934
0.005
2.912 2.958
0.012c
2.918 2.956
0.005
2.920 2.830
0.005
2.923 2.899
0.005
2.925 2.872
0.005
probes. Before experiments with real samples the jig was tested
with the gold foil as the sample to identify contact losses at the
interface between Pt wires (jig) and Au foil/paste with tempera-
ture variation (25–900  C). Samples with different thickness were
also tested, and finally samples with a thickness of about 1 mm
were chosen for measurements.
The microstructure characterisation of the {Pt paste–ceramic}
interface was carried out with a Jeol-JSM-5600 scanning electron
microscope (JEOL, Tokio, Japan) equipped with an energy
dispersive X-ray (EDX) spectrometer of the Inca-energy 200 type
(Oxford Instruments, Eynsham, UK).
Results
Electrical conductivity and effect of stray impurities
The compositional dependencies of the electrical conductivity of
the synthesised solid solutions and the values of activation energy
(Ea) are presented in Fig. 1 and Fig. 2. First we would like to
discuss the results obtained in the tests with electrodes prepared
from gold paste and then compare them with those found in tests
with electrodes prepared from platinum paste. The value of
conductivity showed a non-linear dependence with increase
in the LNF content, Fig. 1a. The LSM and 90LSM$10LNF
possessed nearly the same value of conductivity in a temperature
range of 500–900  C. The difference in the value of the conduc-
tivity became more significant with decreasing temperature
(500–50  C). The (100  x)LSM$xLNF compositions containing
between 43 and 53 mol% of LNF exhibited the lowest value of
the conductivity. The activation energy increased gradually
in the same concentration range (from 0 to 43 mol%) and
attained the maximum for the composition with 48 mol% LNF,
Fig. 2. The value of conductivity increased and the activation
energy decreased with further increase in the Ni/Fe content. The
LSM and LNF showed metallic-like type of conductivity at
temperature higher than 775 and 300  C, Fig. 2, respectively,
which is in accord with previous results.5,6,12 These compositions
exhibited a semiconductor type of conductivity at low tempera-
ture (25–775  C and 25–300  C for LSM and LNF, respectively).
However, the semiconductor behaviour was observed for all the
(100  x)LSM$xLNF compositions with increase in the LNF
content from 2 to 70 mol% over a wide temperature range (50–
900  C). A metal-like conductivity behaviour was observed for
the 20LSM$80LNF composition only between 860–900  C, The
composition containing 90 mol% of LNF possessed metallic-like
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Fig. 1 Electrical conductivity of the (100  x)LSM$xLNF composition
as a function of LNF content at different temperatures: (a) Au, (b) Pt;
Po2 ¼ 0.21.
Fig. 2 The activation energy (Ea) of conductivity as a function of LNF
content evaluated from electrical conductivity temperature dependencies
taken with gold (C) and Pt (,). The temperature range is written near
the symbols. Data are presented for region with semiconducting-type
conductivity.
type of conductivity over a wider temperature range (635–
900  C) and only 02LSM$98LNF composition showed metallic-
type conductivity in the same temperature range like LNF.
The same compositions were then tested with electrodes
prepared from platinum paste. In this case, the compositional
dependencies of the electrical conductivity of the samples showed
a similar trend, Fig. 1. The value of the activation energy
This journal is ª The Royal Society of Chemistry 2008
remained nearly the same, Fig. 2. However, the absolute value of
conductivity was lower as compared to that tested with the gold
paste for all compositions besides the LNF, Fig. 1a,b.
Since the electronic conductivity (se) is proportional to the
number of charge carries (n), their charge (e) and mobility (m)
se ¼ n  e  m (1)
one may assume that either the concentration of main charge
carriers or their mobility decreases if ceramics were tested with
platinum paste. In semiconductors, in general, the number of
mobile electrons is small. This number may be increased by
raising the temperature to promote more electrons from the
valance band to the conduction band or by doping with impu-
rities that provide either electrons or holes. On the other hand,
the presence of stray impurities could lead to an opposite effect,
further decreasing the number of mobile carriers or forming new
microphases with different electrical properties. Microstructure
characterisation of the {Pt paste–30LSM$70LNF} interface,
Fig. 3, showed, that in addition to the main elements (platinum,
nickel, iron and manganese), zinc and lead were revealed.
Zinc mainly concentrated at the interface between Pt and the
30LSM$70LNF ceramic sample. Lead penetrated into the
sample to a depth of about 15 mm, probably, along grain
boundaries since the concentration of Pb within 15 mm was
almost the same, Fig. 3. Possibly, manganese- and lead-
containing microphases with different transport properties are
formed. This seems to be reasonable since only in the case of the
LNF, the value of conductivity was independent of the type of
the paste utilised (Au or Pt). In addition, one can not completely
rule out contamination of the grain boundaries with a lead
silicate glass with low electrical conductivity (species such as lead
silicates are often used as an addition to pastes to improve
electrode adhesion). One can assume that a formation of
a surface layer with low electrical conductivity and variation of
a grain boundary constituent could lead to a difference observed
in the value of conductivity for the compositions tested with
platinum and gold pastes.
Structure of solid solutions
Fig. 4 presents powder X-ray diffraction spectra taken of the
LSM, LNF, 52LSM$48LNF and 47LSM$53LNF compositions
in transmission mode at room temperature. The normalised unit
cell volume and room temperature lattice parameters of the solid
solutions synthesised are presented as a function of LNF content
in Fig. 5. The LSM and LNF perovskites exhibited rhombohe-
dral symmetry (space group R-3c, no. 167). The room temper-
ature lattice parameters for these phases are presented in
hexagonal setting, Fig. 5b. Two very weak diffraction peaks
corresponding to NiO were found in the XRD pattern of the
LNF composition recorded in the reflection mode before and
after calcination at 1350  C. In the case of the 52LSM$48LNF
and 47LSM$53LNF, the principal reflections of the ortho-
rhombic cell dominate and are marked on the XRD patterns
(space group Pbnm; standard setting: Pnma, no. 62), Fig. 4. Since
the rhombohedral (Rh) and orthorhombic (OR) unit cell
volumes (V) contain different number of formula units (Z(Rh) ¼ 6
and Z(OR) ¼ 4), the normalised unit cell volume (Vn) containing
J. Mater. Chem., 2008, 18, 5147–5154 | 5149
 Fig. 3 SEM image as well as elements mappings of the {Pt paste–30LSM$70LNF} interface.

Fig. 4 XRD patterns of the LSM, LNF, 52LSM$48LNF and

47LSM$53LNF compositions after calcination at 1350  C for 5 h. XRD
patterns were recorded in the transition mode on STOE diffractometers.

one B-site cation was evaluated in accordance with the geometry

of cells as:

Vn ¼ V/Z (2)
The normalised unit cell volume was comparable for rhombo-
hedral and orthorhombic phase in the concentration range
between 35 and 70 mol% of LNF. This means that a change in
symmetry from rhombohedral to orthorhombic could comfort-
ably take place. And in general it agrees with the phase rule
(‘‘ss’’ stands for ‘‘solid solution’’): Ass phase with rhombohedral
symmetry (region I), a mixture of two Ass and Css phases with
different symmetries (region II), Css phase with orthorhombic
symmetry (region III), a mixture of two Css and Bss phases with
different symmetries (region IV), Bss phase with rhombohedral
symmetry (region V), Fig. 5a. In the regions I, V and III with
a high LSM content (x < 30), a high LNF content (x $ 70) and
an LNF content between 48 and 60 mol%, respectively, the
normalised unit cell volume decreases continuously, which can
be assigned as single-phase regions. The unit cell volume is
practically constant in the concentration range between 35 to
48 mol% of LNF. Completely the same trend is observed between
Fig. 5 The normalised unit cell volume (a) and the lattice parameters (b)
as a function of LNF content evaluated for phases with rhombohedral
(Rh) and orthorhombic (OR) symmetries. The dashed lines indicate
possible phase boundaries.
60 and 70 mol% of LNF. Two phases, most probably, coexist in
the II and IV regions. It should be mentioned that the boundaries
of the concentration regions defined above could vary with an
increase in temperature.
Thermogravimetric analysis (TGA)
Processes taking place at the solid–gas interface could affect
the properties of a solid oxide, therefore thermogravimetric
analysis was used for characterisation of nickel-, manganese- and
iron-containing perovskites. For comparison, the samples were
tested under different gas atmospheres. The data obtained are
presented in Fig. 6.

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Fig. 6 Mass change vs. temperature in air (a), apparent weight in air
with magnetic field (b), as well as mass change and temperature vs. time in
non-humidified Ar–H2 (95 : 5) (c).
All compositions including solid solutions with a high LNF
content (70 # x # 100) exhibited good thermal stability in air,
Fig. 6a. Samples weight was constant during thermocycling.
Only LSM showed a slight reversible oxygen loss up to 0.7%.
This could indicate on slight reduction of manganese ions to low
oxidation state at elevated temperatures. This means that the
overall oxygen stoichiometry is nearly constant and variation in
oxidation state and concentration of transition element in the B
sublattice could be more important for understanding of the
changes in the structure and the conductivity observed.
Magnetic susceptibility experiments carried out in air, Fig. 6b,
showed that apparent weight of the LSM sample increased up to
3.4 wt% at 38  C. This is in good agreement with the Curie
temperature (TC), which was defined for the La0.8Sr0.2MnO3
single crystal in the experiments measuring the magneto-
resistance.17,18 It is known from the literature that the
La0.8Sr0.2MnO3 undergoes a paramagnetic-to-ferromagnetic
transition at TC. At a low doping level (2% LNF), the apparent
weight of the 98LSM$02LNF sample became higher by about
2% ( 5.4 wt%) at a similar temperature to the LSM and
exhibited similar behaviour with an increase in temperature.
The apparent weight of the (100  x)LSM$xLNF compositions
(x $ 10) was stable, Fig. 6b. One can conclude that the
This journal is ª The Royal Society of Chemistry 2008
appearance of metal-like conductivity at high temperatures for
the compositions with a high LNF content can not be caused
by magnetic ordering/disordering on the B sublattice.
Fig. 6c illustrates thermochemical stability of the complex
perovskites during thermo-cycling under reducing conditions. In
the present study we would like to discuss briefly the stage when
an initial strong weight loss of samples was observed, region I.
For both LNF and 52LSM$48LNF compositions an initial
strong weight loss was observed at nearly the same temperature
(around 380–400  C). The lower the Ni/Fe content in the sample,
the less the weight loss was. Reduction of Mn in the LSM began
at slightly higher temperature and showed slower kinetics at this
stage, Fig. 6c. Notice that the average oxidation state of Mn in
the LSM is higher than in the 52LSM$48LNF (cf. next section).
According to the literature19 at 1000  C LaNiO3d and LaFeO3
completely decompose to La2O3 and Ni or Fe at PO2  1012–
1013 and 1016–1017 atm, respectively, and LaMnO3 to La2O3
and MnO at PO2  1015 atm. One can assume that a strong
weight loss observed at this stage for the LNF and
52LSM$48LNF is mainly caused by the reduction of nickel
cations to a low oxidation state. In the case of the
52LSM$48LNF, the reduction of manganese cations could also
take place after partial or full nickel cation reduction. The
detailed quantitative analysis of the region I (Fig. 6c and ref. 20)
is presented in Table 2. In addition, an expected weight loss for
the same samples was evaluated on the basis of the weight loss
measured by TGA for the LSM and LNF; with the assumption
that Ni and Mn have the same oxidation state in the
52LSM$48LNF as in the parent LNF and LSM phases and
contribute to the weight loss simultaneously and proportionally
to their content in the 52LSM$48LNF, Table 2. At the earlier
stage of the 52LSM$48LNF reduction, the measured weight loss
is higher than the calculated one, indicating a higher average
transition metal oxidation state in the B sublattice than it was
assumed, Table 1. CHNS analysis carried out for the LSM, LNF
and 52LSM$48LNF compositions showed a very low carbon
content ( 0.01–0.02%), which is at the detection limit of the
method. This also confirms that the discrepancy observed for the
measured and calculated weight losses of the 52LSM$48LNF can
not be explained by a contribution from stray impurities.
Finally, the oxygen content in these compositions was esti-
mated from the weight changes of samples during their isothermal
(800 and 900  C) reduction followed by decomposition in non-
humidified Ar–H2 (95 : 5), Table 1. In addition, the theoretical
value of the oxygen content in the (100  x)LSM$xLNF
compositions was evaluated with the assumption that all
3d-transition metal cations in the B sublattice have oxidation
state 3+. The LSM and solid solutions with a high LSM content
as well as the 52LSM$48LNF have higher oxygen content
compared to the theoretical value. It is explained for the LSM as
coexistence of Mn cations in different oxidation states in the B
sublattice.21 In the case of the 52LSM$48LNF, an interpretation
of this result could be more difficult due to coexistence of several
oxidation states for all three elements (Mn, Ni and Fe).22 The
LNF and solid solutions with a high LNF content (70 < x # 100)
have slightly low oxygen content as compared to the theoretical
value, indicating an existence of anion vacancies in the oxygen
sublattice. If only Fe3+ cations were in the LNF, the average
oxidation state of Ni in the LNF in air would amount to 2.8+.
J. Mater. Chem., 2008, 18, 5147–5154 | 5151
Table 2 Detailed analysis of the reduction curves presented in Fig. 6c

Weight loss (%)

Content of
elements in the B Isothermal
sublattice of the reduction at 800  C
sample   
86 min (449 C) 95 min (493 C) 100 min (520 C) for 12 min20

Samples Ni Mn TGA Calc.a TGA Calc.a TGA Calc.a TGA Calc.a

LNF 0.6 — 0.74 1.54 1.84 1.18

52LSM$48LNF 0.288 0.52 0.74 0.47 1.14 0.97 1.22 1.20 1.10 0.91
LSM — 1 0.23 0.44 0.61 0.66
a
Based upon of the weight loss measured by TGA for the LSM and LNF; with the assumption that Ni and Mn have the same oxidation state in the
52LSM$48LNF as in the parent LNF and LSM phases and contribute to the weight loss simultaneously and proportionally to their content in the
52LSM$48LNF.

X-Ray photoelectron spectroscopy

X-Ray photoelectron spectroscopy (XPS) was used to study
chemical states of Mn, Fe, La and O in (100  x)LSM–xLNF.
The Mn 2p, Fe 2p, La 3d5/2 and O 1s core level spectra are shown
in Fig. 7 and Fig. 8. It should be mentioned initially that an
interpretation of the XPS spectra is not simple because the core-
level binding energies of a certain element may be subject to
variations (typically up to a few eV) depending on the chemical
state (i.e. oxidation state, lattice sites, molecular environment
etc.) of the atom. Therefore, a direct comparison of data recor-
ded for perovskites with XPS spectra measured for MnO (Mn2+),
Mn2O3 (Mn2+ and Mn3+) and MnO2 (Mn4+) could lead to
misunderstanding. The data measured in the present investiga-
tion were compared with XPS spectra for the LaMnO3,23 for
which the oxidation state of Mn was defined as 3+ from neutron
diffraction studies of the magnetic properties.
Comparison of the Mn 2p3/2 XP spectra for the solid solutions
synthesised clearly indicates an irregularity in change of the Fig. 8 La 3d5/2 and O1s XPS spectra of the (100  x)LSM$xLNF
chemical state of Mn with increase in the Ni/Fe content. The Mn compositions.
2p3/2 peak in the LaMnO3 and LSM XP spectra can be centred at
640.4 and 642.1 eV, respectively, ref. 23 and Fig. 7. This indicates
that the LSM has fractions of both Mn3+ and Mn4+ cations. In interpreted in different ways. It may mean either a slight decrease
the case of the 98LSM$02LNF, a slight shift to a low binding in the concentration of Mn4+ cations or a change from low (LS)
energy (EB ¼ 641.97 eV) was observed, Fig. 7. The result could be to high (HS) spin of Mn3+ cations. In the latter case, this should
be accompanied by an increase in the effective ionic radius of
Mn3+ cations (r(LS) ¼ 0.58 and r(HS) ¼ 0.65 Å)24 and as a conse-
quence the increase in the room lattice parameters, as observed
for the 98LSM$02LNF, Fig. 5. The oxidation state of Fe could
also vary, but the intensity of the Fe 2p peak in the
98LSM$02LNF XP spectrum was too low to be accurately
analysed. A shift of up to 1.2 eV (EB ¼ 640.9 eV) was observed
in the Mn 2p3/2 XP spectrum of the 52LSM$48LNF as compared
to that for the LSM, Fig. 7. Most probably, the concentration
of Mn4+ cations decreases essentially, thereby reducing the
number of Mn3+–O–Mn4+ groups available for polaron motion.
The fraction of Mn4+ cations seems to be higher in the
30LSM$70LNF composition (EB ¼ 641.6 eV) as compared to the
52LSM$48LNF, Fig. 7.
The broad Fe 2p3/2 XP spectra of the LNF and 52LSM$48LNF
compositions could be centred at 710.4 and 710.6 eV, indicating
Fig. 7 Mn 2p and Fe 2p XPS spectra of the (100  x)LSM$xLNF a very small difference in oxidation state of iron in the LNF
compositions. and 52LSM$48LNF compositions, Fig. 7. Unfortunately, one

5152 | J. Mater. Chem., 2008, 18, 5147–5154 This journal is ª The Royal Society of Chemistry 2008
can not directly compare these data with that measured for the
LaFeO323 because the Mössbauer study showed a significant
difference in the fine structure of the LaFeO3 and
LaFe0.6Ni0.4O3d perovskites.8 The comparison with the XP
spectra measured for La0.8Sr0.2Mn1xFexO3d perovskites25 and
database for surface spectroscopy26 allowed the presence of Fe3+
and Fe2+ cations in the LNF and 52LSM$48LNF compositions to
be assumed. According to EXAFS and XANES,27 Fe3+ cations are
mainly present in the LaNi0.6Fe0.4O3d composition synthesised
by a co-precipitation method and finally sintered at 700  C. A
slight variation observed in the oxidation state could be caused by
either the difference in the sensitivity limits for XPS and EXAFS
or the effect of thermal treatment on properties of these materials.
The chemical states of La and O in the La 3d5/2 and O 1s XP
spectrum of the 52LSM$48LNF essentially differs from those for
the LSM or LNF, Fig. 8. This could give additional evidence,
that the 52LSM$48LNF phase has a different structure
compared to the LSM or LNF.
Discussion
Solid solutions formed in the regions with a high LSM (x < 30)
content showed a rhombohedral symmetry (group R3-c, no. 167)
like the parent LSM. However, an interesting correlation was
observed in the concentration region with small doping level of
LSM, Fig. 5 region I. An expansion of the unit cell volume by
2.6% was observed for the 98LSM$02LNF; both a and c
parameters increased, Fig. 5. The apparent weight change of the
composition on heating in the magnetic susceptibility experiment
increased as well. Mn 3p3/2 peak in the XP spectrum slightly
shifted to a low binding energy. The change from a low to a high
spin of Mn3+ cations was assumed. One can presume that
magnetic ordering occurs in the B sublattice of the
98LSM$02LNF. The a parameter is practically constant with
further increase in the LNF concentration up to 30 mol%,
whereas the c parameter gradually decreases. At the same time,
the apparent weight of the composition in the magnetic suscep-
tibility experiment did not change with further increase in the
LNF content, Fig. 6b. An ordering/disordering in the c direction
of the B sublattice seems to be important for the understanding
of the magnetic properties of these perovskites.
Formation of a new phase with orthorhombic structure was
observed at room temperature in the concentration range
between 35 and 70 mol% of LNF. The 52LSM$48LNF and
47LSM$53LNF compositions showed the lowest value of the
electronic conductivity at 100  C. The concentration range,
where solid solutions possess a low conductivity, became wider
(43 # x # 53) with increasing temperature, Fig. 1a. Mn cations
occupy 52% sites in the B sublattice, Table 1, which is higher than
the percolation threshold.28 According to XPS, manganese in the
form of Mn 3+ cations is mainly present on the B sublattice of the
52LSM$48LNF composition and the concentration of Mn4+
cations seems to be negligible. This fact can explain the relatively
high value of activation energy (Ea ¼ 0.3 eV) and low value of
conductivity observed for 52LSM$48LNF, assuming the trans-
port of main charge carries through the polaron mechanism. The
oxidation state of iron in 52LSM$48LNF is nearly the same as in
the LNF and could be represented by a mixture of Fe3+ and Fe2+
cations. Since, the oxygen content in LNF and 52LSM$48LNF is
This journal is ª The Royal Society of Chemistry 2008
known from TGA, Table 1, the oxidation state of Ni can be
evaluated. The average oxidation state of Ni amounts to 2.8+
and 3.3+ in the LNF and 52LSM$48LNF, respectively, if we
assume all Fe3+. The value evaluated seems to be reasonable for
LNF. In the case of 52LSM$48LNF, the average oxidation state
of Ni is slightly higher. One can conclude that all three cations in
the B sublattice of 52LSM$48LNF exist in high oxidation
state (Ni3.3+, Mn3+ and Fe3+/Fe2+). This is in contradiction
with the tendencies known for ternary systems. The average
oxidation state of Mn cations tends to reduce with Fe substitu-
tion in the La0.8Sr0.2Mn1xFexO3
d series (for instance,
La3+0.802Sr2+0.190Mn3+0.362Mn4+0.141Fe3+0.503O3.04) and to
increase in the LaMn1xNixO3
d series (for instance,
La3+Ni2.7+0.25Mn3.34+0.75O3.09).25,29,30 On the other hand, effective
ionic radii of Ni3+, Mn3+ and Fe3+/Fe2+ cations are very close
in contrast to that for Ni2+ (rNi2+ ¼ 0.70 Å; rNi3+(LS) ¼ 0.56 Å;
rNi3+(HS) ¼ 0.60 Å; rMn3+(LS) ¼ 0.58 Å; rFe3+(LS) ¼ 0.55 Å; rFe2+(LS) ¼
0.61 Å).24 In this case, Me–O bonds formed through the B sub-
lattice could be more equivalent, structure becomes less distorted
and more stable. The tolerance factor (t) calculated for
52LSM$48LNF, eqn (3),31 amounts to 0.996.
dAO
t¼ pffiffiffi (3)
dBO 2
Here dA–O and dB–O represent the average distances. Notice, that
52LSM$48LNF showed better thermochemical stability under
reducing conditions during the thermo-cycling, Fig. 6c, and in
the long-term compared to LSM and LNF.20
Finally, we would like to discuss the total conductivity in the
region with a high LNF content (x $ 70). Solid solutions formed
in this region exhibited at room temperature a rhombohedral
symmetry (group R3-c, no. 167) like the LNF compositions and
did not the change oxygen content during thermal cycling in air.
However, a type and value of the total conductivity changed
dramatically with the temperature change, Fig. 1. The
30LSM$70LNF containing 30 mol% Mn in the B sublattice
showed semiconducting-type conductivity. The value of Ea is
comparable for both LSM and 30LSM$70LNF. It is reasonably
assumed that charge transport in the 30LSM$70LNF composi-
tion occurs through the small polaron mechanism. LaNiO3d
with Ni3+ is known as a metallic conductor with a relatively
narrow conduction band.22 Metallic-like conductivity was
observed for the (100  x)LSM$xLNF (x $ 80) compositions
containing nearly 50 or more mol% Ni in the B sublattice in
a variable temperature range, Fig. 1 and Table 1. This is in
a good agreement with the fact that the LaNi0.4Fe0.6O3d
composition showed semiconductor-type conductivity in
a temperature range of 50–800  C unlike LaNi0.6Fe0.4O3d,
which possessed metallic-type conductivity over a wide temper-
ature range (200–800  C).5,8 It seems that high occupancy of the
sites in the B sublattice by Ni (50% or more) is one of the main
requirements for the realisation of the metallic-like conductivity
in the solid solution synthesised in the present study and maybe
in B-site substituted LaNiO3d perovskites.
Conclusions
A continuous increase in the [Ni + Fe] : Mn ratio leads to non-
linear change in structure, conductivity, magnetic properties and
J. Mater. Chem., 2008, 18, 5147–5154 | 5153
thermochemical stability as well as oxidation states of manganese
and iron in the (100  x)LSM$xLNF series of solid solutions.
The total electrical conductivity of the solid solutions
decreased dramatically in the concentration range 43 # x # 53.
This is, most probably, caused by a formation of a new phase
with orthorhombic structure. As compare to the LSM, a decrease
in the average oxidation state of Mn cations in this phase was
revealed by X-ray photoelectron spectroscopy, indicating a low
concentration of Mn3+/Mn4+ couples available for polaron
hopping motion.
A wide variation in value and type of conductivity was
observed for the (100  x)LSM$xLNF compositions (70 # x #
100) containing more than 48 mol% Ni in the B sublattice,
in spite of all these solid solutions exhibited rhombohedral
structure at room temperature. A semiconductor behaviour is
prevalent at low temperatures whereas metallic-like conductivity
seems to be dominant at high temperatures. The temperature of
the semiconducting–metallic transition decreases with further
increase in the Ni content between 48 and 60 mol%. All these
compositions showed good thermochemical stability in air and
their apparent weight during magnetic susceptibility experi-
ments remained constant. This indicates that the shift in the
temperature of the semiconducting–metallic transition can not
be explained by either the change in the overall oxidation state
or magnetic ordering/disordering in the B sublattice of the
(100  x)LSM$xLNF compositions (70 # x # 100). Further
high-temperature investigation should be carried out to give
insight into the nature of metallic conductivity in perovskites at
high temperatures.
Acknowledgements
We would like to thank Dr S. Frances for XPS measurements,
Mrs S. Williamson for carrying out the elemental analysis as well
as St Andrews Fuel Cell Ltd and the Engineering and Physical
Sciences Research Council for financial support.
References
1 H. W. King, K. M. Castelliz, G. J. Murphy and A. S. Rizkalla, J. Can.
Ceram. Soc., 1986, 55, 10.
2 K. P. Rajeev and A. K. Raychaudhuri, Phys. Rev. B, 1992, 46, 1309.
5154 | J. Mater. Chem., 2008, 18, 5147–5154
3 J. Drennan, C. P. Travares and B. C. H. Steele, Mater. Res. Bull.,
1982, 17, 621.
4 M. Hrovat, N. Katsarakis, K. Reichmann, S. Bernik, D. Kuscer and
J. Holc, Solid State Ionics, 1996, 83, 99.
5 R. Chiba, F. Yoshimura and Y. Sakurai, Solid State Ionics, 1999, 124,
281.
6 J. Knudsen, P. B. Friehling and N. Bonanos, Solid State Ionics, 2005,
176, 1563.
7 S. Li., J. Sun, X. Sun and B. Zhu, Electrochem. Solid-State Lett., 2006,
9, A86.
8 K. Świerczek, J. Marzec, D. Pa1ubiak, W. Zaja˛c and J. Molenda, Solid
State Ionics, 2006, 177, 1811.
9 H. Falcon, A. E. Goeta, G. Punte and R. E. Carbonio, J. Solid State
Chem., 1997, 133, 379.
10 M. Mamak, G. S. Metraux, S. Petrov, N. Coombs, G. A. Ozin and
M. A. Green, J. Am. Chem. Soc., 2003, 125, 5161.
11 D. Grossin and J. G. Noudem, Solid State Sci., 2004, 6, 939.
12 J. H. Kuo, H. U. Anderson and D. M. Sparlin, J. Solid State Chem.,
1990, 87, 55.
13 C. C. T. Yang, W. C. J. Wei and A. Roosen, Mater. Chem. Phys.,
2003, 81, 134.
14 H. M. Rietveld, Acta Crystallogr., 1967, 22, 151.
15 H. M. Rietveld, J. Appl. Crystallogr., 1969, 2, 65.
16 D. Baskar and S. B. Adler, Rev. Sci. Instrum., 2007, 78, 023908.
17 T. V. Ramakrishnan, J. E. Enderby, R. L. Johnston,
A. S. Alexandrov, H. von Lohneysen, P. Coleman,
R. L. McGreevy, Y. Iye and C. N. R. Rao, Philos. Trans.: Math.,
Phys. Eng. Sci., 1998, 356, 41.
18 S. E. Lofland, S. M. Bhagat, K. Ghosh, R. L. Greene,
S. G. Karabashev, D. A. Shulyatev, A. A. Arsenov and
Y. Mukovskii, Phys. Rev. B, 1997, 56, 13705.
19 T. Nakamura, G. Petzow and L. J. Gauckler, Mater. Res. Bull., 1979,
14, 649.
20 E. Konysheva and J. T. S. Irvine, unpublished results.
21 F. W. Poulsen, Solid State Ionics, 2000, 129, 145.
22 P. A. Cox, Transition Metal Oxides, Clarendon Press, Oxford, 1995,
p. 283.
23 D. J. Lam, B. W. Veal and D. E. Ellis, Phys. Rev. B, 1980, 22,
5730.
24 R. D. Shannon and C. T. Rewitt, Acta Crystallogr., Sect. B, 1969, 25,
925.
25 M. R. Pai, B. N. Wani, B. Sreedhar, S. Singh and N. M. Gupta,
J. Mol. Catal. A, 2006, 246, 128.
26 Database for Surface Spectroscopy (http://www.lasurface.com) and
NIST XPS Database (http://srdata.nist.gov/xps/index.htm).
27 M. Bevilacqua, T. Montini, C. Tavagnacco, E. Fonda, P. Fornasiero
and M. Graziani, Chem. Mater., 2007, 19, 5926.
28 S. Kirkpatrick, Rev. Mod. Phys., 1973, 45, 574.
29 M. Petitjean, G. Caboche, E. Siebert, L. Dessemond and
L.-C. Dufour, J. Eur. Ceram. Soc., 2005, 25, 2651.
30 M. C. Sanchez, G. Subfas, J. Perez-Cacho, J. Garcia and J. Blasco,
J. Synchrotron Radiat., 2001, 8, 901.
31 V. M. Goldschmidt, Naturwissenschaften, 1926, 14, 477.
This journal is ª The Royal Society of Chemistry 2008