J186 Journal of The Electrochemical Society, 157 共5兲 J186-J190 共2010兲

0013-4651/2010/157共5兲/J186/5/$28.00 © The Electrochemical Society

The Spectroscopic Properties and Structural Occupation

of Eu3+ Sites in LiMgPO4 Phosphor
Suyin Zhang,a Yanlin Huang,a and Hyo Jin Seob,z
a
College of Chemistry, Chemical Engineering and Materials Science, Soochow University,
Suzhou 215123, China
b
Department of Physics, Pukyong National University, Busan 608-737, Republic of Korea

Eu3+-doped LiMgPO4 was prepared by a high temperature solid-state reaction. The phase formation was confirmed by X-ray
powder diffraction measurements. The site-selective excitation and emission spectra were investigated in the 5D0 → 7F0 region by
using a pulsed, tunable, and narrowband dye laser. Two crystallographic sites for Eu3+ ions doped in LiMgPO4 were observed from
the luminescence and structure features. Absorption and emission peaks at 579.0 nm were caused by the Eu3+ site, which
⬘,
substitutes the Li+ ion located in the channel of the LiMgPO4 structure along the 关010兴 direction, creating cation vacancies VLi
while absorption and emission peaks at 579.9 nm were caused by a cluster of Eu3+ ions. The decay times of the two Eu3+ sites
were measured. The defect structures and charge compensation mechanism of Eu3+ doping in LiMgPO4 were discussed.
© 2010 The Electrochemical Society. 关DOI: 10.1149/1.3356975兴 All rights reserved.

Manuscript submitted December 21, 2009; revised manuscript received February 5, 2010. Published April 6, 2010.

Rare-earth 共RE兲-doped phosphors have gained considerable in-
terest due to their wide range of applications in display devices,
lamp phosphors, white light generation, etc.1,2 Usually, the local
structures, e.g., coordination numbers 共CNs兲 and degree of distortion
by defects, have an important influence on the spectroscopic prop-
erties of RE ions doped in a host.3
The phosphates with an ABPO4 formula 共A and B are monova-
lent and divalent cations, respectively兲 are a large family of mono-
phosphates with the different structure types depending on the rela-
tive size of the A and B ions.4 In recent years, the luminescence
properties of RE-doped ABPO4 monophosphates have gained in-
creasing interest. For example, Eu2+-doped KSrPO4,5 NaCaPO4,6
KBaPO4,7 LiBaPO4,8 LiSrPO4,9 and ABaPO4 共A = Na, K兲 10 have
recently been reported to be new materials for their potential appli-
cations as new luminescence hosts. To the best of our knowledge,
the luminescence properties of the monophosphates ABPO4 with A
as a small monovalent cation Li+ and B as a small bivalent cation
共Fe, Mg, Co, or Ni兲 have not yet been reported. These compounds
adopt the olivine 共Mg2SiO4兲 structure type, for example, as in Li+
and Mg2+; the resulting compound is LiMgPO4. In the present work,
the luminescence and spectroscopic parameters of the Eu3+-ion
doped LiMgPO4 have been investigated. The motivations for this
study are as follows.
First, over the past years, there was considerable research into
developing phosphate-olivine LiMPO4 共M = Fe, Mg, Co, or Ni兲
compounds for the next generation of lithium rechargeable
batteries.11,12 The distribution of metal cations at different atomic
sites in a structure plays a significant role in tailing the physical
properties of the material for device applications. At present, the
survey on the microstructure of the impurity-doped LiMgPO4 com-
pound was only limited by theoretical calculations,13 X-ray diffrac-
tion 共XRD兲,13,14 electron paramagnetic resonance spectrum,14,15 IR
spectroscopy,14 and NMR studies of 7Li and 31P.11 Even some in-
teresting works have been reported with the help of these methods;
however, the luminescence of the structural probe ion is another
channeling technique. The 5D0 → 7F0 emission lines of Eu3+ can
reveal the presence of crystallographic inequivalent sites or clusters
in a given host matrix.16 By applying the site-selective excitation
spectroscopic techniques 共dye laser with continuous wavelength in
the region of 7F0 → 5D0 of Eu3+兲, the crystallographic properties of
Eu3+ ions and the defect distributions in this host could be well
defined.
Secondly, on the aim of luminescence studies, it seems interest-
ing to study whether it is possible to build the large Eu3+ ion 共the
ionic radius with CN = 6 is 0.947 Å兲17,18 into the LiMgPO4 lattice
and present different luminescence properties. In LiMgPO4, Mg2+
z
E-mail: hjseo@pknu.ac.kr
and Li+ have ionic radii of 0.72 and 0.76 Å 共CN = 6兲,
respectively.17,18 In many host matrices, the substitution sites of RE
ions could be well-defined on the basis of the charge and the size
between the doped and the substituted ions. For example, in
SrY2O4 19 and LaPO4,20 the dopant Eu3+ ions are accommodated in
the Y3+ and La3+ sites, respectively. However, in some cases, RE
ions have no obvious substitution site available, especially in a host
with small cations. For example, in the hosts of LiNbO3 21 and
LiTaO3,22 the doped RE ion has a different charge with respect to
the host cations 共Li+, Ta5+, and Nb5+兲 and also a different ionic
radius 共Li+, Ta5+, and Nb5+ are smaller than the RE ions兲. Conse-
quentially, the local structure and the occupation around the RE ions
are not easily determined. The aim of this investigation is therefore
to investigate the local structure of the site or sites occupied by Eu3+
ions in LiMgPO4 by a local structure probe ion of the Eu3+ ion.
In this work, Eu3+-doped LiMgPO4 was synthesized by a solid-
state reaction. The excitation and site-selective emission spectra
have been investigated under pulsed dye laser excitation in the
5
D0 → 7F0 region of Eu3+-doped LiMgPO4. The microstructure and
the charge compensation of Eu3+ ions in the LiMgPO4 lattices were
discussed. The decay curves of the Eu3+ luminescence were mea-
sured. This is helpful for the luminescence investigation of RE ions
doped in this kind of phosphate host.
Experimental
The preparation of LiMgPO4:Eu3+ was carried out by a solid-
state synthesis. The raw materials were high purity Li2CO3,
4共MgCO3兲·Mg共OH兲2·5H2O 共magnesium carbonate basic pentahy-
drate兲, NH4H2PO4, and Eu2O3. Here, Mg was introduced from
4共MgCO3兲·Mg共OH兲2·5H2O because this available chemical had a
better sintering ability than MgO and MgCO3 according to our ex-
perience. The doping level of Eu3+ was 1.0 mol %. The starting
materials with stoichiometric amounts were ground together in an
agate mortar. The mixture was first heated up to 300°C and kept at
this temperature for 5 h. After a second homogenization in the mor-
tar, the sample was heated up to 650°C and was kept at this tem-
perature for 10 h. After that, the sample was mixed and heated at
800°C for 20 h.
The XRD patterns were collected on a Rigaku D/Max-2000 dif-
fractometer operating at 40 kV, 30 mA with Bragg–Brentano geom-
etry by using Cu K␣ radiation 共␭ = 1.5418 Å兲 and were analyzed
using Jade-5.0 software. The optical excitation and emission spectra
were recorded by a Perkin-Elmer LS-50B luminescence spectrom-
eter and a Hitachi F-4500 fluorescence spectrophotometer.
For the excitation and site-selective emission measurements, the
excitation source was a dye laser 共Spectron Laser Sys. SL4000兲
pumped by the second harmonic 共532 nm兲 of a pulsed Nd:yttrium
aluminum garnet laser 共Spectron Laser Sys. SL802G兲. The pulse
energy was about 5 mJ with a 10 Hz repetition rate and a 5 ns

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 Journal of The Electrochemical Society, 157 共5兲 J186-J190 共2010兲 J187

3500 7 5

(131)
F0- D0

(011)

(120)
M: 579

(211)
3000

(200)

(221)
2
(a)
(101)
(111)

(041)
(031)

(112)

(223)
012)
(140)
Intensity (a. u.)

(321)
2500

(040)
(220)

Intensity (a. u.)

(121)

(117)
579.6

(220)
(122)
2000
579.9
300 K
1500
1
(b)
1000 150 K

500
0 10 K
20
2 Theta (Degrees)
Figure 1. XRD patterns of 共a兲 pure and 共b兲 Eu3+-doped LiMgPO4 in this
work and JCPDS card no. 32-0574.
duration. The samples were placed in a liquid helium flow cryostat
for measurements at low temperatures. The luminescence was dis-
persed by a 75 cm monochromator 共Acton Research Corp. Pro-750兲
and observed with a photomultiplier tube 共Hamamatsu R928兲. Suit-
able filters were used to eliminate the intense laser scattering.
The excitation spectra of the 7F0 → 5D0 transition were obtained
by monitoring the total luminescence by setting the monochromator
in zero order of diffraction to pass all the 5D0 → 7FJ 共J = 1, 2, 3,
and 4兲 emission in which a 580 nm cutoff filter was used. Time-
integrated signals from a digital storage oscilloscope 共LeCroy
9310A兲 were recorded for the emission and excitation spectra under
pulsed laser excitation.
The crystal phase formation.— Figure 1 shows the XRD pat-
terns of pure and Eu3+-doped LiMgPO4 and the Joint Committee on
Powder Diffraction Standards 共JCPDS no. 32-0574兲. By a compari-
son between them, the position and intensity of the diffraction peaks
are the same. No impurity lines were observed. All peaks are well
indexed to a LiMgPO4 single phase and labeled in Fig. 1. These
results agree well with the reported data of pure LiMgPO4.14
Photoluminescence.— The photoluminescence excitation and
emission spectra of LiMgPO4:Eu3+ are shown in Fig. 2. In the ex-
citation spectrum 共Fig. 2a兲, the broad bands ranging from 200 to 300
nm with a maximum at 254 nm are the charge-transfer 共CT兲 transi-
tions from the 2 p orbit of O2− to the 4 f orbit of Eu3+, while the
PDF#32-0574
0
30 40 50
575 576 577 578 579 580 581
Wavelength (nm)
Figure 3. 共Color online兲 The excitation spectra in the region of 7F0 → 5D0
transition in LiMgPO4:Eu3+ at 10, 150, and 300 K. The luminescence were
monitored at the luminescence corresponding to the 5D0 → 7FJ 共J = 1, 2, 3,
and 4兲 by setting the monochromator at zero wavelength position, and a 580
nm filter was used. To compare 1 spectrum with another, the intensities of 3
spectra were normalized to 1, and the spectra at 150 and 300 K have been
shown by some shifts.
other weak peaks in the longer wavelength region located at 361,
383, 394, and 465 nm are assigned to the direct excitation of the f–f
shell transitions of the Eu3+ ions.
The emission spectra under the 254 nm excitation are shown in
Fig. 2b. The spectrum consists of many sharp lines ranging from 580
to 710 nm, which are associated with the transitions from the excited
Results state 5D0 to 7FJ 共J = 0, 1, 2, 3, and 4兲 levels of Eu3+. The red
emission at 613 nm is an electric dipole transition, while the orange
emission at 588 nm is a typical magnetic dipole transition. The
emission spectra are dominated by the transitions of 5D0 → 7F1.
Except the transition from 5D0, no emission from the higher level,
e.g., 5D1,2, was detected. Usually, in a monophosphate, the vibration
energy of the P–O bond is high 共ca. 1000 cm−1兲.23 This means that
only two to three phonons are needed to fill the energy gap of
2000 cm−1 between 5D1 and 5D0 共as well as between 5D2 and 5D1兲.
Thus, only the 5D0 → 7FJ 共J = 0, 1, 2, 3, and 4兲 emission of Eu3+
could be observed in Fig. 2. This Eu3+-doped LiMgPO4 phosphor is
air-stable and moisture-stable and can keep the same luminescence
after being exposed to the air for several months.

The excitation spectra of 7F0 → 5D0 transition.— Eu3+ 共4f6

configuration兲 is widely used as a probe of the surrounding symme-
1.4
try because the emission and excitation lines between the 5D0 and
(a) λem=588 nm (b) λex=254 nm 7
1.2 F0 levels are nondegenerate. This reveals the presence of crystallo-
graphic nonequivalent sites in a given host matrix.3 To examine the
D0- F1
Intensity (a. u.)

1.0
CT 254 nm site distributions of Eu3+ ions in LiMgPO4, the excitation spectra
and site-selective emission spectra were measured. Figure 3 shows
5

0.8
the excitation spectra corresponding to the 7F0 → 5D0 transition,
D0- F2

obtained by monitoring the total luminescence at 10, 150, and 300

7

0.6
D0- F4

K.
5

0.4 The excitation spectra consist of the strongest line at 579.0 nm

F0- L6

D0- F3

and a weak broad peak at 579.9 nm, which are labeled Eu3+共M兲 and
F0- D2

D0- F0

5
5

0.2
7
5

Eu3+共M⬘兲, respectively. No other line corresponding to the 7F0

7

5
7

0.0 → 5D0 transition was detected in the temperature range of 10–300

300 400 600 650 700 K. The occupation probability of the major site Eu3+共M兲 is domi-
nant. The minor site Eu3+共M⬘兲 is weakly occupied due to its weak
Wavelength (nm) excitation intensity. The results in Fig. 3 clearly indicate that the
Figure 2. 共Color online兲 The photoluminescence 共a兲 excitation and 共b兲 emis- Eu3+ ions occupy one intrinsic crystallographic site and other dis-
sion spectra of LiMgPO4:Eu3+. turbed sites in LiMgPO4.

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 J188 Journal of The Electrochemical Society, 157 共5兲 J186-J190 共2010兲

D0- F1
2.4 (a) 300 K Table I. The emission wavelengths (nm) and wave numbers

7
2.2 „cm−1… corresponding to the 5D0 \ 7FJ (J = 1, 2, 3, and 4) tran-

D0- F2
2.0 sitions in LiMgPO4:Eu3+.

D0- F3
Intensity (a. u.)

D0- F4
1.8

7
5

7
1.6 Sites

5
1.4 M excited at 579 nm R=0.47 M M⬘
1.2
−1
1.0 Transitions nm cm nm cm−1
0.8 5
D 0 → 7F 0 579.0 17,271 579.9 17,244
0.6 R=2.65
M' excited at 579.6 nm 5
D 0 → 7F 1 587.8 17,013 588.4 16,995
0.4
593.5 16,850 593.5 16,849
0.2 M' excited at 579.9 nm R=3.15 595.0 16,807 596.5 16,764
0.0 5
D 0 → 7F 2 612.4 16,330 612.4 16,329
580 600 620 640 660 680 700 720 615.7 16,242 616.0 16,234
Wavelength (nm) 619.1 16,152 617.8 16,186
621.4 16,093 619.6 16,139
2.2 623.2 16,046
5
D 0 → 7F 3
D0- F1

643.9 15,530 634.3 15,765

2.0
7

(b) 10 K 647.2 15,451 651.1 15,359

1.8
5

648.7 15,415
1.6
D0- F4
D0- F2

650.2 15,380
Intensity (a. u.)

D0- F3

7
7

1.4 651.4 15,352

653.5 15,302
5
5

1.2 R=0.35
M excited at 579 nm 5
D 0 → 7F 4 683.2 14,637 683.5 14,631
1.0
685.0 14,599 686.2 14,573
0.8 688.3 14,529 689.5 14,503
0.6 690.7 14,478 692.8 14,434
0.4 694.3 14,403 695.2 14,384
M' excited at 579.9 nm 696.7 14,353 699.1 14,304
0.2 R=3.2
699.4 14,298 701.8 14,249
0.0 707.2 14,140
580 600 620 640 660 680 700

Wavelength (nm)
Figure 4. The emission spectra of 5D0 → 7FJ 共J = 1, 2, 3. and 4兲 under the
site-selective excitation into Eu3+共M兲 at 579 nm and Eu3+共M⬘兲 at 579.6 and
579.9 nm at 共a兲 300 and 共b兲 10 K. The R values in the figure are the inte-
grated intensity ratio of 共 5D0 → 7F2兲/共 5D0 → 7F1兲.
The site-selective emission spectra.— The site-selective emis-
sion spectra under the M- and M⬘-line excitations at 10 and 300 K
for LiMgPO4:Eu3+ are shown in Fig. 4. The different emission spec-
tra due to the 5D0 → 7FJ 共J = 1, 2, 3, and 4兲 transitions are ob-
served. The emission spectrum under the site-selective excitation
into the Eu3+共M兲 site shows the strong sharp emission lines corre-
sponding to the transitions of 5D0 → 7FJ 共J = 1, 2, 3, and 4兲. The
emission spectra under the excitation into Eu3+共M⬘兲 show several
groups of broad lines. According to the emission spectra at 10 K
共Fig. 4b兲, the wavelengths and energies of the 5D0 → 7FJ 共J = 0, 1,
2, 3, and 4兲 transitions within each Eu3+ site were derived and are
listed in Table I.
Dependence of luminescence decay on temperature.— The lu-
minescence decay curves of the 5D0 emission after the M and M⬘
line excitations at different temperatures were measured. The typical
decay curves at 10 and 300 K are shown in Fig. 5. At 10 K, the
decay of Eu3+共M兲 共Fig. 5a兲 is single exponential, while the decay of
Eu3+共M⬘兲 presents a nonexponential curve. With the increase in
temperature, the decay curves of Eu3+共M⬘兲 sites become an expo-
nential profile at 300 K, as shown in Fig. 5b.
The exponential decay curve can be fitted into a single exponen-
tial function as
I = I0 exp共− t/␶兲
兰⬁0 tI共t兲dt
␶avg = 关2兴
兰⬁0 I共t兲dt
The luminescence lifetimes of the Eu3+ ions are calculated as a
function of temperature. The 5D0 decay time in the Eu3+共M兲 site is
a constant of 2.28 ms from 10 to 150 K and then drops at higher
temperatures, presenting a typical temperature quenching behavior,
while the 5D0 decay time in the Eu3+共M⬘兲 site has a nearly constant
value 共about 1.8 ms兲 for the different temperatures 共10–300 K兲.
Discussion
The structure description of LiMgPO4.— LiMgPO4 crystal has
an orthorhombic structure with the space group of Pnma and a
parameter of a = 10.147 Å, b = 5.909 Å, c = 4.692 Å, and
Z = 4.13 It belongs to the ordered olivine-type structure. The struc-
ture contains tetrahedral PO4 and octahedral LiO6 and MgO6 groups.
Tetrahedrally coordinated P5+ cations are located in 4 c sites and
bridge the Mg共Li兲O6 chains to form an interconnected three-
dimensional structure. The Li+ and Mg2+ ions occupy two distinct
crystallographic sites. The divalent Mg2+ ions are randomly distrib-
uted over 4c sites on the mirror plane of the space group 共Cs sym-
metry兲. The Li+ ions are octahedrally coordinated and situated on 4a
sites 共Ci symmetry兲. MgO6 and LiO6 groups are connected by shar-
ing edges and corners.25
This structure may be described as chains 共along the c-direction兲
of the edge-sharing Mg共Li兲O6 octahedral, which are cross-linked by
the PO4 groups to form a three-dimensional network. The MgO6
distorted octahedra are corner-shared and cross-linked by the PO4
groups, forming a three-dimensional network, with perpendicular
tunnels along the 关010兴 and 关001兴 directions. The tunnels are occu-
关1兴 pied by Li+ ions.13

where I0 is the initial emission intensity for t = 0 and ␶ is the life- The major Eu3⫹共 M 兲 site.— There are two sites in LiMgPO4 for
time. The average decay time ␶avg of the nonexponential curve for the possible substitution of Eu3+, i.e., Li+ and Mg2+. The octahe-
Eu3+共M⬘兲 was evaluated using the equation24 drally coordinated Li+ and Mg2+ have the ionic radii of 0.76 and

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 Journal of The Electrochemical Society, 157 共5兲 J186-J190 共2010兲
1 measure of the Eu3+ ion’s site symmetry. A higher symmetry of the
Ln[Intensity (a. u.)]
3+
Eu (M) τ=2.28 ms
0.1
3+
0.01 Eu (M') τ=1.79 ms
0.000 0.003 0.006
Time (second)
Ln[Intensity (a. u.)]
0.1
Eu (M) τ=1.56 ms
0.01
3+
Eu (M') τ=1.71 ms
1E-3
0.003
Time (second)
Figure 5. The luminescence decay curves of LiMgPO4:Eu3+ at 共a兲 10 and 共b兲
300 K after the excitation of 579 nm by monitoring 5D0 → 7F1 emission of
587.8 nm in Eu3+共M兲 and after the excitation of 579.9 nm by monitoring
612.4 nm in Eu3+共M⬘兲.
0.72 Å, respectively. The charge and size of both ions are very
different from those of Eu3+ 共the ionic radius is 0.947 Å兲. However,
on the basis of structure spatiality in LiMgPO4, there is a consider-
able preference for the substitution of Li+ by the Eu3+ ion.
The Li+ ions occupy the structural tunnels in the three-
dimensional network forming strips running zigzag along b. The
average bond distances of Li–O and Mg–O are 2.143 and 2.105 Å
within polyhedra LiO6 and MgO6, respectively. The average O–O
edge lengths in polyhedra LiO6 and MgO6 are 3.015 and 2.921 Å,
respectively.13 In spite of a considerable difference between the
ionic radii of Li+ and Eu3+, it is reasonable that the Eu3+ ions may
occupy probably the Li+ sites because the compact space of the
Mg2+ ions in LiMgPO4 offers very small sites for the Eu3+ ions,
while the Li+ ion has a great adaptability to adjust the mismatch due
to Eu3+ doping because it locates in the tunnels in the LiMgPO4
structure.
Goñi et al.14 conducted the structure refinement of
Li1−3xFexMgPO4 共0 ⬍ x ⬍ 0.1兲. During the calculation process,
atomic fractions were constrained so that every Fe3+ ion displaces
three Li+ cations from their sites. Attempts to locate the doped Fe3+
ions in the Mg2+ positions were carried out, but the results were
unsuccessful.14
According to the Judd–Ofelt theory, if the Eu3+ ions occupy an
inversion symmetry site, the orange-red emission, magnetic transi-
tion 5D0 → 7F1 is the dominant transition. On the contrary, the elec-
tric dipole transition 5D0 → 7F2 is the dominant transition.26 There-
fore, the intensity ratio of R = I共 5D0 → 7F2兲/I共 5D0 → 7F1兲 is a
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J189
(a) 10 K
crystal field around Eu3+ results in a smaller value.3
In the site-selective emission spectra of the Eu3+共M兲 site in Fig.
4, the magnetic-dipole transition 5D0 → 7F1 is the most prominent
group, while the 5D0 → 7F2 transitions are very weak. The intensity
ratios R are 0.35 and 0.47 at 10 and 300 K, respectively. These
values are quite small in comparison with those of other Eu3+-doped
monophosphates, such as GdPO4:Eu3+ 共R = 0.715兲,27 LaPO4:Eu3+
共R = 0.924兲, and YPO4:Eu3+ 共R = 0.978兲.28 The results indicate that
the major Eu3+ ion occupies the inversion center site. This undoubt-
edly points to the fact that the dominated Eu3+共M兲 is from the Eu3+
ion that substitutes Li+.
0.009 Because both ionic radius and charge are not the same for the
Eu3+ and Li+ ions, it is inevitable to create some defect centers or
Li+ vacancies for charge compensation. The dopant ion Eu3+ is in a
structurally disordered environment. Usually, the presence of the
(b) 300 K
5
D0 → 7F0 transition suggests that this Eu3+ local site environment
must be described by one of the following point groups: Cn, CS, or
C2v. The numbers of the crystal-field components for Eu3+共M兲
共Table I兲, i.e., the three emission lines in the 5D0 − 7F1 region and
3+
four emission lines in the 5D0 → 7F2 region, point to an orthorhom-
bically distorted Eu3+ ion site with the C2v symmetry.
The minor Eu3⫹共 M ⬘兲 site.— The inhomogeneous broadening ef-
fects are observed for the excitation 共Fig. 3兲 and emission spectra
共Fig. 4兲 of the Eu3+共M⬘兲 site. This is associated with a disordered
distribution of the crystal-field strength. Moreover, as shown in Fig.
3, the excitation spectra have similar shapes showing an indepen-
dence of temperatures. To confirm this, the emission spectra were
0.006 measured under the different excitations at 579.6 and 579.9 nm
separately chosen on the broad excitation spectra of Eu3+共M⬘兲 共la-
beled by arrows in Fig. 3兲. The shape and peak position of the broad
emission are not influenced by the excitation energy. This indicates
that the Eu3+共M⬘兲 site is a family of sites or several families of sites
with almost identical environments.
Magnetic susceptibility measurements on Li1−3xFexMgPO4 共0
⬍ x ⬍ 0.1兲 show the forming clusters associated with the Li+ va-
cancies in the structure. The cluster of the Fe3+ ions yields the ex-
istence of antiferromagnetic interactions despite the low concentra-
tion of magnetic ions in the compounds. Considering that the
magnetic Fe3+ ions are located inside the tunnels of the structure
along 关010兴, the size of the clusters was suggested to be variable,
ranging from dimers, trimers, and so on.
So, the assignment for the Eu3+共M⬘兲 site to the cluster of Eu3+ in
LiMgPO4 lattices is reasonable. Under the site-selective excitation
in Eu3+共M⬘兲 at 10 and 300 K, emission lines of 5D0 − 7FJ 共J = 1, 2,
3, and 4兲 became broader. This indicates an inhomogeneous distri-
bution of the Eu3+ ions. In this lower symmetry, three and five split
lines are observed for the 5D0 → 7FJ 共j = 1 and 2兲 transitions, re-
spectively 共Table I兲. The numbers of split lines indicate that the
crystallographic symmetry of Eu3+共M⬘兲 ions is Cs. The higher R
values 共Fig. 4兲 indicate a considerably distorted crystallographic en-
vironment of Eu3+共M⬘兲 that could be comparable to that of Eu3+
ions in glasses. Also, the formation of the clusters in LiMgPO4 leads
to the complicated excitation and emission spectra.
In this experiment, the doping level of Eu3+ 共1.0 mol %兲 may be
too high in terms of the great difference of charge and size between
Eu3+ and Li+. Consequently, the remaining investigations of lumi-
nescence in a very low Eu3+-doped LiMgPO4 should be conducted
in future experiments.
The ABPO4-type host lattice is formed with monovalent alkali
metal ions 共A+ = Li+, Na+, K+, and Rb+兲 and divalent alkaline earth
ions 共B2+ = Mg2+, Ca2+, Sr2+, and Ba2+兲 in which all of the ions are
larger than Eu3+ ions except for only the Li+ and Mg2+ ions in the
LiMgPO4 lattice. A usual substitution of the larger dopant ion for the
smaller cation in a host lattice gives rise to the distortion of the
lattice site. It is expected that the luminescence properties of
 J190 Journal of The Electrochemical Society, 157 共5兲 J186-J190 共2010兲
Eu3+-doped LiMgPO4 is different from other Eu3+-doped ABPO4
共A+ = Na+, K+, and Rb+ and B2+ = Ca2+, Sr2+, and Ba2+兲. In fact,
the clustering of Eu3+ ions is only observed in LiMgPO4, as reported
here. In the reported RE-ion-doped monophosphates ABPO4 共A+
= Na+, K+, and Rb+ and B2+ = Ca2+, Sr2+, and Ba2+兲, no clustering
of RE ions has been observed.29-31 In the Eu3+-ion-doped LiMgPO4,
the clustering is due to the smaller Li sites for Eu3+, together with
charge compensation.
The doping mechanism of Eu3⫹ in LiMgPO4.— Because of the
heterovalence character of Eu3+ → Li+ substitution in LiMgPO4, the
positive charge excess 共Eu3+
Li 兲 requires charge compensation. This
••
could be realized by the formation of two Li+ vacancies forming the
dipole complexes of 关共Eu3+ Li 兲 − 2V⬘ Li兴. This kind of mechanism has
••
also been confirmed in Fe3+-doped LiMgPO4, where Fe3+ ions sub-
stitute the Li+ ions in the channels of the LiMgPO4 structure along
the 关010兴 direction, creating cation vacancies V⬘Li.14 However, even
when the Li+ ions left vacancies in the structure, ionic mobility in
LiMgPO4 was not observed.11 It was suggested that when Fe3+ sub-
stituted Li+ ions, they would push the Li+ neighbors into the chan-
nels, leaving vacancies as the nearest neighbors of the doped iron. In
Li1−xFexMgPO4, Li共Fe兲–O distances undergo a progressive enlarge-
ment with the increase in x, while the MgO6 octahedra become more
regular and smaller. Coulomb repulsion between the negatively
charged ions avoids any jumps back to the vacant sites.11
In Eu3+ doping in LiMgPO4, the crystal-field strength of Eu3+
could be weaker because of the repulsion and the enlargement of
Li共Eu兲–O distances. This effect is reflected by the CT position. The
CT band of Eu3+ in Fig. 2 is found at the wavelength of 254 nm
共39.3 ⫻ 103 cm−1兲. Hoefdraad32 reported that the position of the
CT band of Eu3+ in many oxide compounds is nearly fixed in an
octahedral coordination; i.e., the CT position is in the region of
41.4 ⫻ 103–43.4 ⫻ 103 cm−1. For example, in the olivine-
structured compounds of NaLuGeO4, LiLuSiO4, and LiYGeO4, the
CT values of Eu3+ are 43.4 ⫻ 103, 43.2 ⫻ 103, and 41.4
⫻ 103 cm−1, respectively.32 The CT location of Eu3+ in LiMgPO4
共39.3 ⫻ 103 cm−1兲 shows a redshift. The peak position of the CT
band in different host lattices is related to the crystal-field environ-
ment about Eu3+ ions. Usually, the weaker the crystal field or the
longer the Eu–O bond is, the longer the wavelength of the CT band
position will be. This indicates that the crystal field of Eu3+ in
LiMgPO4 is weaker than the common Eu3+ ions with CN = 6 in an
oxide compound.
In general, another charge compensation mechanism related to
the interstitial oxygen Oi⬙ is possible: Li+ → Eu3+ + Oi⬙. This
mechanism can form the dipole complexes of 关共Eu3+ Li 兲 − Oi⬙兴. Usu-
••
ally, in the oxides, the reaction energy to create Oi⬙ is higher than
that of cation vacancy.33 The defect Oi⬙ tends to increase the CN of
Eu3+, resulting in an increase in its atomic radius.22 This is unfavor-
able for the substitution of Li+. So, it is difficult for this possible
mechanism in LiMgPO4:Eu3+.
Due to the obvious differences of ionic radius and charge be-
tween the Eu3+ and Li+ ions, another consideration is also possible;
i.e., the Eu3+ ions take an interstitial position in lattice rather than
replace any Li+ ions. However, the XRD pattern of the Eu3+-doped
sample 共Fig. 1兲 shows a pure crystal phase of LiMgPO4. The lumi-
nescence measurements also did not show any information for this
occupation in an interstitial position.
Conclusions
3+
Eu -doped LiMgPO4 was prepared by a high temperature solid-
state reaction. Structural characterizations reveal that the phosphor
derives from the olivine structure with a space group of Pnma. The
CT transition band of the Eu3+ ion in LiMgPO4 is located at 254 nm.
Under UV excitation, all the emission lines are the transitions from
the 5D0 to 7FJ 共J = 0, 1, 2, 3, and 4兲 levels and the dominant emis-
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sion is 5D0 − 7F1. The excitation spectrum corresponding to the
7
F0 → 5D0 transition consists of the strongest line at 579.0 nm 共M兲
and a weak and broad peak at 579.9 nm 共M⬘兲, indicating that the
Eu3+ ions occupy one intrinsic crystallographic site and a disturbed
site in LiMgPO4. The major Eu3+共M兲 site occupies the inversion
center site, which substitutes the Li+ ion in the channel of the
LiMgPO4 structure, creating cation vacancies VLi ⬘ . The excitation
spectra corresponding to the minor Eu3+共M⬘兲 site show an inhomo-
geneous broadening and an independence on temperatures. The
Eu3+共M⬘兲 site was assigned to the clustering of Eu3+ in LiMgPO4
lattices.
Acknowledgments
This work was financially supported by the Korea Science and
Engineering Foundation 共KOSEF兲 grant funded by the Korean gov-
ernment 关Ministry of Education, Science and Technology 共MEST兲,
no. 2009-0078682兴.
Pukyong National University assisted in meeting the publication costs of
this article.
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