Accepted Manuscript

Theoretical and experimental evidences of defects in LiMgPO4

D.G. Kellerman, N.I. Medvedeva, M.O. Kalinkin, A.I. Syurdo, V.G. Zubkov

PII: S0925-8388(18)32449-6
DOI: 10.1016/j.jallcom.2018.06.328
Reference: JALCOM 46664

To appear in: Journal of Alloys and Compounds

Received Date: 22 March 2018

Revised Date: 25 June 2018
Accepted Date: 26 June 2018

Please cite this article as: D.G. Kellerman, N.I. Medvedeva, M.O. Kalinkin, A.I. Syurdo, V.G. Zubkov,
Theoretical and experimental evidences of defects in LiMgPO4, Journal of Alloys and Compounds
(2018), doi: 10.1016/j.jallcom.2018.06.328.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT
Theoretical and experimental evidences of defects in LiMgPO4
D.G. Kellerman1*, N.I.Medvedeva1, M.O. Kalinkin1, A.I.Syurdo2,3, V.G. Zubkov1
1
Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Russia
2
Institute of Industrial Ecology, Ural Branch, Russian Academy of Sciences, Russia
3
Department of Experimental Physics, Ural Federal University, Russia

*Corresponding author:

PT
Institute of Solid State Chemistry
91, Pervomaiskaya st., Ekaterinburg, 620990 Russia
tel.: 7+343-3623442

RI
E-mail address: kellerman@ihim.uran.ru

SC
ABSTRACT
The phosphate LiMgPO4 with orthorhombic olivine-type structure was synthesized by

U
the conventional solid state reaction route and its optical properties were examined by the
experimental and theoretical methods. Using diffuse-reflectance (DR) spectroscopy we
AN
observed two absorption stages at 5.5 eV and at 4.4 eV, which were attributed to the
fundamental band gap and energy levels of defects within the band gap, respectively. These
experimental results were confirmed by ab initio calculations. We observed
photoluminescence and thermoluminescence (TL) in undoped LiMgPO4. Emission
M

components were detected in the UV, visible and NIR regions. These multicolor emissions
indicate the presence of various defects in LiMgPO4 and each color is due to different
electronic transitions. The thermoluminescence of undoped LiMgPO4 shows that defects in
D

LiMgPO4 serve as traps during irradiation. The TL glow curve with a sufficiently large light
sum consists of five overlapping peaks in the temperature range 300-600 K.
TE

Keywords
Defects, LiMgPO4, Ab initio calculations, Luminescence, Optical gap,
EP

Thermoluminescense
C

1. Introduction
AC

Phosphates of the general formula ABPO4 (where A and B are monovalent and
divalent cations, respectively) are in the focus of both fundamental and applied research for
their electrochemical [1-5], ferroelectric [6-8] and optical [9-10] properties. It is well known
that these phases represent a large family of monophosphates, whose structures depend on
the ratio between A and B sizes [11]. For small A and B ions, such as Li+ and Mg2+ with
ionic radii of 0.76 and 0.72 Å, respectively [12], the olivine structure is typical [13]. The
orthorhombic structure of LiMgPO4 (space group Pnma) contains tetrahedral PO4 and
octahedral LiO6 and MgO6 groups sharing edges and corners. The strips of LiO6 octahedra
are interconnected with MgO6 octahedra and PO4 tetrahedra [14]. Due to excellent chemical
 ACCEPTED MANUSCRIPT
stability, charge stabilization and facile synthesis, LiMgPO4 is a suitable host lattice for
various luminescent ions [15]. Recently, LiMgPO4 doped with Eu, Tb, Sm, and B [16-18]
attracted much attention as a material for dosimetric applications. The energy release can be
stimulated either by heating (thermally stimulated luminescence, TSL) or by irradiation with
light quanta of proper energy (optically stimulated luminescence, OSL). The stored energy is
released as light at luminescence centers. The doped LiMgPO4 was shown to be an
alternative to traditional Al2O3:C [19-20]. It is known that solid-state luminescent dosimetry

PT
based on radiation energy storage makes use of electrons trapped between the valence and
conduction bands. The trapping sites are bulk and surface defects, which are were well

RI
studied in alkaline and alkaline-earth based compounds. Defects of different nature are
detected by both optical methods [21-24] and EPR [25-26], and were modeled using first-

SC
principle calculations [27-30]. In many studies, defects in MgO were considered with respect
to catalysis [31-33] and dosimetric application [34]. There are no studies of defects in pure

U
or doped LiMgPO4, although such information is extremely important for the development
of dosimetric materials with improved properties. In the present work, we report on the
AN
electronic structure, defects and optical properties of pure LiMgPO4 examined using the
experimental and theoretical methods.
M

2. Experimental
D

The phosphate LiMgPO4 was synthesized by the conventional solid state reaction
method. The appropriate amounts of raw materials – Li2CO3 (lithium carbonate, 99.99%),
TE

3MgCO3*Mg(OH)2*3H2O (magnesium carbonate, 99.9%), and NH4(H2)PO4 (ammonium

dihydrogen phosphate, 99.99%) – were mixed and milled until the average particle size was
EP

less than 1 µm. The mixture was pre-heated for 5 h at 300 oC in air in alumina crucibles with
covers. After the second homogenization in an agate mortar, the sample was heated to 650 oC
C

and kept at this temperature for 20 h. After the third homogenization, the sample was pressed
into tablet and thermally treated at 950 oC for 20 h in air.
AC

The X-ray diffraction data were collected at room temperature using a STADI-P
transmission diffractometer (STOE) equipped with a scintillation detector. Polycrystalline
silicon (a=5.43075(5) Å) was used as an internal standard. The lattice parameters were refined
with the full-profile Rietveld analysis using the FULLPROF software package. The phase
purity of the sample was proved by comparing the XRD pattern with that in the PDF2
database (ICDD, USA, release 2016). The scanning electron microscopy (SEM, JEOL JSM-
6390 LA) study was performed to observe the particle morphology. The distribution of

2
 ACCEPTED MANUSCRIPT
magnesium, phosphorus and oxygen was determined by the energy dispersion X-ray (EDX)
analysis with a JED 2300 analyzer.
The room temperature photoluminescence (PL) and photoluminescence excitation (PLE)
spectra were recorded on a Varian Cary Eclipse fluorescence spectrometer coupled to a
personal computer with Varian software and supplied with a flash 75 kW Xenon lamp as
excitation source (pulse length τ=2µs, pulse frequency ν=80 Hz, wavelength resolution 0.5
nm; PMT Hamamatsu R928). The measurements were carried out in a pulse excitation mode

PT
with a delay time of 100µs. The decay kinetics of excited LiMgPO4 states was recorded using
a nanosecond optical pulse generator NLS-UV-40 (InTech, Russia) with τ = 1.2 ns and

RI
TCSPC Counter Module TCC2 (Edinburgh Instruments Ltd) with a cooled detector H10720-
01 (Hamamatsu). The diffuse reflectance spectrum was obtained with a Shimadzu UV-2401

SC
PC UV-VIS spectrophotometer using BaSO4 as a reference. The TSL curve was measured
with a homemade TL reader at a speed of β = 4 K/s in the range of T=300-600 K [35]. The

U
TSL signal was registered with a photomultiplier FEU-130 (Gran Company, Russia). Samples
of LiMgPO4 were irradiated with X-ray radiation (Rh-anode, U = 30 kV, I = 1-40 µA) with a
AN
dose of 2 Gy.
All the calculations in this work were carried out with the Vienna Ab initio Simulation
M

Package (VASP) and projector-augmented wave (PAW) potentials for modeling the core–
electron interactions [36-38]. For ideal LiMgPO4, the calculations were performed with a 28-
D

atom supercell of olivine structure, whereas a much larger supercell of 112 atoms was used to
minimize the interaction of oxygen vacancies in defective LiMgPO4. For defectless LiMgPO4,
TE

we used two different approximations for the exchange correlation functional, LDA and
GGA, where the Perdew-Burke-Ernzerhof (PBE) method [39] was adopted for GGA, while
EP

all the calculations for LiMgPO4 with oxygen vacancy were performed with the GGA method.
The plane-wave cutoff energy was chosen to be 500 eV, and the Brillouin zone was sampled
C

by using 8x8x8 and 4x4x4 Г-centered Monkhorst-Pack k-points grids [40] for small and large
AC

supercells, respectively. For all cases, we performed the structure optimization where both
lattice parameters and atomic positions were relaxed with a convergence criterion for the total
energy and interatomic forces set to 10-5 eV and 0.02 eV/Å, respectively. To predict a
favorable position for a single oxygen vacancy, we simulated a removal of a neutral oxygen
atom from nonequivalent O1, O2 or O3 sites, which we denote as F0 (O1), F0 (O2) and F0
(O3). The concentration of oxygen vacancies in the chosen supercell is ~1.5%. The most
energetically favorable vacancy site was determined from the total energy of relaxed supercell
with a defect. To study the frequency-dependent optical properties, we calculated the complex
dielectric function ε(ω) = ε1(ω) + iε2(ω), which describes the optical response to

3
 ACCEPTED MANUSCRIPT
electromagnetic field. The imaginary part ɛ2(ω) representing the optical absorption was
calculated by summing all possible direct interband transitions from occupied to empty states.

3. Results and discussion

Fig. 1 demonstrates an XRD pattern for polycrystalline LiMgPO4 which agrees well
with the standard data from ICDD (0-084-0342). No impurities were detected and all the
reflections can be well indexed in the olivine-type orthorhombic structure with the space

PT
group Pnma and lattice parameters a = 10.125(3) Å, b = 5.897(2) Å, c = 4.682(2) Å,
V=279.6(1) Å3. The powder comprises particles of irregular shape having a broad size

RI
distribution (Fig.2).
3.1. UV-vis spectroscopy

SC
Since, no experimental or theoretical studies of the bandgap in LiMgPO4 have been
performed, an accurate determination of the band gap (Eg) is very important for the

U
interpretation of processes in optical materials. The diffuse-reflectance (DR) spectroscopy is
the most widely used technique for measuring Eg in bulk specimens [41]. The UV-vis
AN
spectrum of diffuse reflection for LiMgPO4 is presented in Fig. 3. For the experimental
determination of Eg in bulk specimens, the DR spectra are generally converted into pseudo-
M

absorption spectra F(R) using the Kubelka–Munk transformation [42]: F(R)=(1-R)2/2R=K/S

(1), where K and S are the absorption and scattering coefficients, respectively, and R is the
D

reflectance. The obtained spectrum is shown in Fig.3 (inset). A characteristic feature of the
spectrum is the presence of two distinct steps. As seen from Fig.3, the first stage of absorption
TE

begins at a wavelength of λ≈320 nm, and the second stage at λ≈240 nm. The band gap
energies were deduced from the F(R) data using the well-known Tauc relation: [F(R)*hν]1/n =
EP

f(hν) (2), where n = 1/2, 3/2, 2 and 3 for the direct allowed, direct forbidden, indirect allowed
and indirect forbidden transitions, respectively, and hν is the photon energy [43]. Assuming a
C

direct band gap according to ab initio calculations [44, this work], we used n = 1/2 in Eq. (2)
AC

as shown in Fig.4. Two values of the energy, 5.5 eV (Eg1) and 4.4 eV (Eg2) were determined
from the plot. In accordance with the detailed refinement of the LiMgPO4 structure carried out
in [14], oxygen in LiMgPO4 occupies three non-equivalent structural positions. Our ab initio
calculations (given below) showed that the density of states for all oxygen atoms is the same,
and the charge transfer process, associated with oxygen ions located in three different regular
positions, should have similar energy characteristics. The calculations carried out in Ref. [44]
revealed that the insulating gap (Eg) occurs between the occupied O 2p and vacant P 3p states
forming the conduction band (CB). From the UV-Vis data we obtained a gap value of 5.5 eV
(Fig.4). A close value of the fundamental optical gap (5.75 eV) was determined by the authors

4
 ACCEPTED MANUSCRIPT
of [45] for another phosphate KMg4(PO4)3. The absorbance band at 4.36 eV can be due to the
existence of defects in LiMgPO4. It is known that for MgO, whose absorption spectrum is
also stepped [46-47], a large number of defects including single oxygen and magnesium
vacancies, divacancies, as well as surface low-coordinated and impurity or substitutional
atoms have been described [48].
3.2. Ab initio calculations
For the interpretation of the observed optical properties, we were the first to carry out

PT
ab initio calculations of oxygen vacancies in LiMgPO4 (F-centers), which are the most
extensively studied intrinsic defects in the wide-gap oxides. We compared the total formation

RI
energies of neutral oxygen vacancy F0 in three non-equivalent positions and predicted the
most energy preferable site. The dielectric function was calculated for defectless LiMgPO4

SC
and F0: LiMgPO4 to establish the vacancy effect on the optical properties.
At first, we compared the crystal parameters and band gap calculated for LiMgPO4

U
using two different approximations for exchange correlation functional. It was found that
LDA underestimates the equilibrium volume VR and lattice parameters (VR = 264.88 Å3,
AN
a=9.9502 Å, b=5.7815 Å, c=4.6044 Å), whereas GGA slightly overestimates them (VR =
285.67 Å3, a=10.1946 Å, b=5.9381 Å, c=4.7189 Å) in comparison with our experimental
M

data. The both functionals predict very close values of the band gap, Eg = 5.52 eV (LDA) and
5.53 eV (GGA). So, all subsequent results were obtained using DFT-GGA, which provides a
D

better agreement with the experimental structure.

The calculated total density of states TDOS for LiMgPO4 in the optimized structure is
TE

shown in Fig.5a. The valence band (VB) from −8 eV to −4 eV is composed mainly of the P
3s3p states, whereas the O 2p states are located in the energy region between −4 eV and 0 eV
EP

with pronounced peaks at −2 eV and −0.5 eV. The Mg 3s3p and Li 2s states give much
smaller contributions to the TDOS compared with the P 3s3p and O 2p states. The insulating
C

gap (Eg =5.53 eV) corresponds to the direct transitions at the Г-point between the highest
occupied O 2p and lowest vacant P, Mg and Li states, which form the bottom of the
AC

conduction band (CB).

To determine the preferable location of oxygen vacancy, we performed a geometry
optimization for three 111-atom supercell configurations, in which oxygen atom was removed
from nonequivalent O1, O2 or O3 sites. The most preferable location is found to be the F0
(O1) defect, however, the energy difference between the other oxygen sites is small (0.13 eV
and 0.34 eV, respectively) and the F0 (O2) and F0 (O3) defects are also possible. The neutral
oxygen vacancy in LiMgPO4 results in the appearance of a highly localized defect level in the
middle of the band gap (Fig.5), which is occupied by two defect electrons. The position of the

5
 ACCEPTED MANUSCRIPT
defect level with respect to VB, calculated with GGA, is almost equal (~1.3 eV) for F0 (O1),
F0 (O2) and F0 (O3). The obvious difference in the nonequivalent oxygen vacancies is only
the presence of a TDOS peak near the top of the valence band for F0 (O1). Thus, electrons
from this defect level may transfer to the vacant states at the VB top and change the optical
spectra of LiMgPO4.
To study the influence of neutral oxygen vacancy on the optical properties, we
compared the imaginary part of the dielectric function ε2(ω) for defectless LiMgPO4 and F0:

PT
LiMgPO4 (Fig.6). We considered F0 (O1) as the most energy preferable oxygen vacancy,
because the positions of different defect levels are similar. The non-diagonal elements of

RI
ε2(ω) were obtained negligible. Three diagonal components of the imaginary part of the
dielectric function ε2(ω) for LiMgPO4 are shown in Fig.6a as a function of photon energy for

SC
the electric field parallel to the crystallographic axes. The most pronounced changes in ε2(ω)
with electric field direction variation occur from 5 to 7 eV and for energies > 9 eV. In the

U
energy interval from 7 to 9 eV, where the curve slope determines the optical gap, the
spectrum depends weakly on the crystallographic direction.
AN
The oxygen vacancy (F0: LiMgPO4) results in appearance of low-intensity peaks at 5-
6 eV, i.e. below the absorption edge in defectless LiMgPO4 (Fig.6b). Their positions and
M

intensities depend on the polarization of photon energies up to 6 eV. Isotropic optical

properties should be expected from 7 eV to 9 eV, whereas conspicuous anisotropy exists at
D

higher energies.
The dielectric function ε2(ω) averaged over crystallographic directions for LiMgPO4
TE

and F0:LiMgPO4 is shown in Fig.6c, where the insert displays the absorption edges for the
both curves up to 8 eV. Since ε2(ω) represents optical absorption, we can conclude that a
EP

pronounced absorption in defectless LiMgPO4 begins at ~6 eV and reaches a maximum at 9

eV. As seen from TDOS for LiMgPO4 (Fig. 5), the charge transfer transitions from the
C

topmost occupied O2p states in VB to the vacant states in CB are responsible for ε2(ω)
between 6 eV and 10 eV. The oxygen vacancy results in a low-intensity peak at ~5.3 eV and
AC

the absorption edge corresponds to ~ 4.3 eV. According to the density of state for F0:
LiMgPO4 (Fig.5b-d), we can attribute the low energy peak in ε2(ω) to the oxygen defect state
in the bandgap. For the neutral oxygen vacancy, two electrons occupy this level and their
transitions to the vacant states in CB are responsible for this peak.
3.3. Photoluminescence
There is no available data on the optical properties and in particular luminescent
properties of undoped LiMgPO4. We found that the PL spectra of LiMgPO4 have a rather
complicated shape. The PL spectrum recorded at λex=210 nm is shown in Fig. 7. Two groups

6
 ACCEPTED MANUSCRIPT
of signals can be readily distinguished in the spectrum. The first group containing at least four
well-resolved emission lines is located in the ultraviolet region at 363, 378, 387, and 393 nm.
We found that the intensity of the emission lines depends non-monotonically on the excitation
wavelength, although their positions remain unchanged. The PL spectra obtained in the
scanning range from 210 nm to 480 nm are given in the Supplementary Material. The changes
observed in the emission spectra when the excitation wavelength is varied (Fig. S1) are
nontrivial and require adequate interpretation. At present, we can not give an exhaustive

PT
explanation of the obtained results. Additional experimental and theoretical efforts are needed
to solve this problem.

RI
Note that wide band gap semiconductors, e.g. ZnO, ZnS etc., have received
considerable attention due to their promising applications as UV light sources (nanolasers)

SC
[49]. So, materials demonstrating well-resolved UV spectra at room temperature are of
particular importance. In addition to these narrow lines, there is a separate broad line centered

U
at 448 nm in the blue region of the PL spectrum of LiMgPO4. It has much lower intensity
compared to the signals observed in the UV region. It is interesting that a very close line is
AN
often observed in the emission spectra of many phosphates. So, in CaZr4(PO4)6 [50] there is a
single emission band at ~460 nm. The luminescence was suggested to originate from the
M

charge transfer from the central zirconium ion to the oxygen ligand, while in Sr9Ga(PO4)7 the
emission spectrum shows bright blue luminescence at 435 nm. In the latter case the
D

luminescence originates from the self-activation center of the octahedral GaO groups [51].
Fig. 8 shows that the luminescent signal in LiMgPO4 centered at 448 nm consists of several
TE

lines. Additionally, we found a wide emission band consisting of overlapping peaks in the
near infrared region (Fig. 8) with a center at about 730 nm. These multicolor emissions may
EP

indicate the presence of various defect states within the band gap, and each color is due to a
certain electronic transition. A similar emission spectrum (UV−visible−NIR) was described
C

for colloidal nanocrystals of ZnS in Ref. [52].

The most notable feature of the emission spectrum (Fig. 7) is a zone with a fine
AC

structure in the UV region. The authors of Ref. [48] concluded that the emission band at short
wavelengths in ZnS with a similar fine structure is due to transitions arising from energy
states of vacancy and interstitial defects. As in our case, the full width at half maximum for
the peaks in ZnS is ~ 5÷10 nm [48]. It should be noted that the majority of works dealing with
luminescence in ZnS provide no evidence of fine structure of the UV emission band [53-56].
Apparently, the detection of fine structure calls for sufficient power of the radiation source, a
high spectral resolution of the measurement system as well as a high quality of samples [57].

7
 ACCEPTED MANUSCRIPT
The excitation spectra recorded at λem corresponding to all detected photoluminescent
signals are shown in Fig. 9. Since LiMgPO4 is a wide-band material, the excitation peaks
should be due to the transitions of electrons from the valence band and defect states within the
band gap either to the excited states or the conduction band. The room-temperature excitation
spectra recorded in the scanning range from 200 nm to 350 nm show an excitation band with a
long-wavelength edge at ≈225 nm. This value agrees with the boundary of the high-energy
adsorption band in the UV-visible measurements (5.5 eV), which is a long-wavelength edge

PT
of fundamental absorption, and as well as with the results of our ab initio calculations. These
spectra demonstrate that the states in the conduction band are involved in the excitation of all

RI
PL signals, and each of them has its own additional source of excitation. So, the emission line
centered at 448 nm can be associated with the individual peak at 328 nm on the excitation

SC
spectrum, and the lines with maxima at 363 nm, 378 nm and 392 nm – with peaks at 265 nm,
277 nm, and 288 nm, respectively. The much lower intensity of the individual peaks in

U
comparison with the high-energy band probably reflects transitions with participation of
different states in the forbidden band. The probability of such transitions is lower than the
AN
charge transfer from the valence to the conduction band.
In order to determine the excited states lifetime, which is an important parameter of
M

luminescence, we measured the PL spectrum at λex=280 nm using a nanosecond optical pulse

generator. It was expected to observe a PL spectrum containing a narrow peak with a
D

maximum near 390 nm; however, the obtained spectrum appeared to be a wide band centered
at 410 nm (Fig. 10, inset). The decay profile for λem=410 nm is shown in Fig. 10. The decay
TE

curve was found to be biexponential and was fitted using the following formula: I=A0+ A1
exp−t/ τ1+ A2 exp−t/τ2 (3), where A0, A1, A2 are scalar quantities obtained from the curve fitting,
EP

t is the time, and τ1, τ2 are decay time values for exponential components. The Table in Fig.
10 summarizes the decay constants. The PL spectrum recorded under nanosecond excitation
C

conditions reflects the short-lived excited states (τ≈16 ns), which are not manifested in the
spectrum shown in Fig. 7. However, the noticeable short-wave shoulder of the emission band
AC

(Fig. 10, inset) apparently reflects the contribution from the peak expected at 390 nm. The
results of the band decomposition are given in the Supplementary Material. The coexistence
of excited states with different lifetimes can be considered as a further evidence of the
complexity of electronic structure of LiMgPO4 and the presence of numerous defects.
There is another interpretation of the observed well-resolved UV part of the emission
spectra. It can reflect the exciton properties near the band edge that is typical of many wide-
gap semiconductors, for example, free or donor-trapped excitons in ZnO [58-59], excitons in
MgO [60], phosphates [61] etc. It should be noted, however, that the fine structure of the UV

8
 ACCEPTED MANUSCRIPT
part of the emission spectra caused by excitons is usually observed at low temperatures [53],
whereas in our case the luminescence spectra are obtained at room temperature. To gain an
insight into the origin of luminescence in LiMgPO4 and to draw conclusions about its
connection with defects, it is necessary to have detailed information on the energies of
possible optical transitions and radiative recombination of free excitons, ionized bound
excitons, and neutral bound excitons. Note that for such a familiar object as ZnO, a clear
picture is a result of 70 year research in this field [62], while for LiMgPO4 such studies have

PT
not been conducted to date. Based on the above data it can be assumed that energy transfer to
intrinsic or defect-related luminescence centers may take place in LiMgPO4. That is why

RI
LiMgPO4 is attractive matrix for dosimetric materials.
3.4. Thermoluminescence

SC
We studied the thermoluminescence (TL) of undoped LiMgPO4. In TL, light emission
occurs when energy stored on crystal defects is released on heating of irradiated material. A

U
plot of the intensity of emitted light as a function of temperature gives a TL glow curve. Its
position, shape and intensity reflect the properties of the trapping states. Therefore, analyzing
AN
the TL curves, additional data on the defect structure of undoped LiMgPO4 can be obtained. A
TL curve of LiMgPO4 exposed to 2 Gy X-ray irradiation is shown in Fig.11. The TL glow
M

curve was deconvoluted and the obtained curves can be seen in Fig.11. They were described
by the general order kinetics [63], and the calculated activation energy E, frequency factor S
D

and the order of kinetics b are presented in Table 1 for the most intensive peaks.
From Fig.11 it is seen that the TL glow curve consists of overlapping peaks in
TE

temperature range 300-600 K. There are three rather intense peaks at 365, 410 and 570 K and
two peaks with a lower intensity at ~460 and 480 K, which are difficult to separate. Note that
EP

the TL glow curves shown in Fig.11 are similar to those obtained in [64-65] for single-
crystals grown by the micro pulling down (MPD) technique. Insignificant differences are
C

observed in the positions of the peaks at ~365 and 410 K and in the variation of the intensities
in favor of the higher temperature peak.
AC

As shown by the experimental data, irradiated LiMgPO4 has sufficiently large light
sums, but the TL peaks are located at too low temperatures, which does not allow one to
consider the undoped phosphate as a material for TL dosimetry and for dosimetry based on
the optically stimulated luminescence effect (OSL) [66-67]. The results of our work evidently
show that there is a large number of various defects in LiMgPO4 that serve as traps during
irradiation. These intrinsic defects are capable of storing energy that provides the dosimetric
application of LiMgPO4. The introduction of dopants significantly improves the dosimetric
characteristics and makes LiMgPO4 the most suitable material for determining the dose

9
 ACCEPTED MANUSCRIPT
equivalents in mixed gamma-neutron radiation. Tb and B doped LiMgPO4 was proposed as a
new sensitive OSL phosphor for the first time in Ref. [16]. Since then, a number of works
appeared providing a convincing evidence that doped LiMgPO4 can compete with anion-
deficient corundum used in TLD-500 and Al2O3:C detectors [19-20, 68] in both TL and OSL
methods of dosimetry [69-71].
3.5. Proposed model
A schematic model of different relaxation processes in irradiated and photoexcited

PT
LiMgPO4 can be proposed from our theoretical and experimental data (Fig. 12). For this
purpose, we summarize the main results. 1. The width of the band gap is 5.5 eV (Figs. 4, 5a);

RI
2. There are oxygen defect states in the bandgap near the top of the valence band. They are
located at 4.3 eV from the bottom of the conduction band (Figs. 5-6). 3. There is a set of at

SC
least 5 levels in the forbidden band (Fig. 12), which can serve as traps during irradiation. The
activation energies of these levels are within 0.7 -1 eV range. 4. The emission spectrum of

U
LiMgPO4 consists of three broad bands with a complex structure, which are centered at 3.3
eV in the UV region, 2.8 eV in the visible region and 1.7 eV in the near-IR region (Figs. 7, 8).
AN
All these signals have a unified source of excitation - the interband electron transition
VB→CB.
M

Fig. 12 (right) shows a scheme of thermoluminescence in LiMgPO4. The electron-hole

pairs formed by irradiation are captured by traps (oxygen vacancies or other defects). Their
D

positions are shown in the scheme. As a result of subsequent heating, the release of trapped
electrons and holes and their radiative recombination take place. The left part of the scheme is
TE

related to the photoluminescence process in UV-Vis –NIR regions. We show that the main
source of excitation is the VB→CB interband electron transition. The UV part of the emission
EP

spectra is due to transitions involving a number of levels near the bottom of the conduction
band and the top of the valence band. These levels are created by the neutral and charged (not
C

considered in this article) oxygen vacancies. To understand the origin of the Vis and NIR
signals, we can assume the existence of additional deep levels. For reliable explanation of
AC

these features of intrinsic luminescence in LiMgPO4, further theoretical and experimental

studies are required.

4. Conclusions
Recently, LiMgPO4 doped with rare-earth elements attracted much attention as a
material for dosimetric applications. To obtain a material with improved properties, the
information on the nature and energy of defects in pure and doped LiMgPO4 is of much

10
 ACCEPTED MANUSCRIPT
importance. In this work, we report the evidence of the defects in LiMgPO4 obtained by
optical methods and ab initio calculations.
Two distinct absorption steps at 5.5 and 4.4 eV were determined using UV-vis
spectroscopy. The former was attributed to the fundamental band gap in LiMgPO4 between
the highest occupied O 2p and lowest vacant P, Mg and Li states. The latter was assigned to
oxygen defect levels within the gap. The observed two-step absorbtion spectrum agrees with
the results of ab initio calculations, which evidently demonstrate that oxygen vacancies result

PT
in the appearance of an additional low-intensity peak in the imaginary parts of the dielectric
function ε2(ω).

RI
The most notable features of the photoluminescence spectrum are a zone with a fine
structure in the UV region, a separate rather broad line centered at 448 nm in the blue region

SC
and a wide emission band in the near infrared region with a center at 730 nm. These
multicolor emissions indicate the presence of various defect states within the band gap. We

U
observed the thermoluminescence (TL) for undoped LiMgPO4 with TL glow consisting of
five overlapping peaks with activation energies within 0.7 -1 eV range. TL with sufficiently
AN
large light sums shows that defects in LiMgPO4 serve as traps during irradiation.
Acknowledgements
M

This work was financially supported by the Russian Foundation for Basic Research
(Grant No. 18-08-00093 -a). A part of ab initio calculations was carried out in accordance
D

with AAAA-A16-116122810214-9 program.

TE

References
[1] A. K. Padhi, K. S. Nanjundaswamy, J. B. Goodenough, Phosphoolivines as positive-
EP

electrode materials for rechargeable lithium batteries, J. Electrochem Soc. 144 (1997) 1188-
1194.
C

[2] N. H. Kwon, H.Yin, T. Vavrova, J. H.-W. Lim, U. Steiner, B. Grobéty, K. M.Fromm,

Nanoparticle shapes of LiMnPO4, Li+ diffusion orientation and diffusion coefficients for high
AC

volumetric energy Li+ ion cathodes, J. Power Sources 342 (2017) 231-240.
[3] K. J. Kreder, A. Manthiram, Vanadium-substituted LiCoPO4 core with a monolithic
LiFePO4 shell for high-voltage lithium-ion batteries, ACS Energy Lett. 2 (2017) 64-69.
[4] C. A. Calderón, J. E. Thomas, G. Lener, D. E. Barraco, A. Visintin, J. Electrochemical
comparison of LiFePO4 synthesized by a solid-state method using either microwave heating
or a tube furnace, J. Appl. Electrochem. 47 (2017) 1179-1188.

11
 ACCEPTED MANUSCRIPT
[5] J. Ludwig, C. Marino, D. Haering, C. Stinner, H. A. Gasteiger, T. Nilges, Morphology-
controlled microwave-assisted solvothermal synthesis of high-performance LiCoPO4 as a
high-voltage cathode material for Li-ion batteries, J. Power Sources 342 (2017) 214-223.
[6] O. Arcelus, S. Nikolaev, J. Carrasco, I. Solovyev, Magnetism of NaFePO4 and related
polyanionic compounds, Phys. Chem. Chem. Phys. 20 (2018) 13497-13507.
[7] E. Fogh, R. Toft-Petersen, E. Ressouche, C. Niedermayer, S. L. Holm, M. Bartkowiak, O.
Prokhnenko, S. Sloth, F. W. Isaksen, D. Vaknin, N. B. Christensen, Magnetic order,

PT
hysteresis, and phase coexistence in magnetoelectric LiCoPO4, Phys. Rev. B 96 (2017)
104420.

RI
[8] B. B. Van Aken, J.- P. Rivera, H. Schmid, M. Fiebig, Observation of ferrotoroidic
domains, Nature 449 (2007) 702-705.

SC
[9] V. S. Hingwe, N. S. Bajaj, S. K. Omanwar, Eu3+ doped N-UV emitting LiSrPO4 phosphor
for W-LED application, Optik - Int, J. Light Electron. Opt. 130 (2017) 149-153.

U
[10] B. R. Verma, R.N. Baghel, A review on luminescence properties in Eu doped phosphate
phosphors, Int. J. Mater. Sci. 12 (2017) 483-489.
AN
[11] M. B. Amara, M. Vlasse, G.L. Flem, P. Hagenmuller, Structure of the low temperature
variety of calcium sodium orthophosphate NaCaPO4, Acta Crystallogr. C 39 (1983) 1483-
M

1485.
[12] R. D. Shannon, Revised effective ionic radii and systematic studies of interatomic
D

distances in halides and chalcogenides, Acta Crystallogr. A32 (1976) 751-767.

[13] B. Elouadi, L. Elammari, Crystal structures and ferroelectric properties of AIBIIPO4
TE

(AI - monovalent cation and BII - divalent cation), Ferroelectrics 107 (1990) 253-258.
[14] F. Hanic, M. Handlovic, K. Burdova, J. Majling, Crystal structure of lithium magnesium
EP

phosphate, LiMgPO4: crystal chemistry of the olivine-type compounds, J. Crystallogr.

Spectrosc. Res. 12 (1982) 99-127.
C

[15] A. Baran, S. Mahlik, M. Grinberg, P. Cai, S.I. Kim, H.J. Seo, Luminescence properties
of different Eu sites in LiMgPO4:Eu2+, Eu3+, J. Phys. Condens. Matter 26 (2014) 385401.
AC

[16] W. Gieszczyk, D. Kulig(Wróbel), P. Bilski, B. Marczewska, M. Kłosowski, Analysis of

TL and OSL kinetics in lithium magnesium phosphate crystals, Radiat. Measur. 106 (2017)
100–106.
[17] M. Gai, Z. Chen, Y. Fan, S.-Y. Yan, Y.-X. Xie, J. Wang, Y. Zhang, Synthesis of
LiMgPO4: Eu, Sm, B phosphors and investigation of their optically stimulated luminescence
properties, Radiat. Measur. 78 (2015) 48-52.
[18] B. Marczewska, P. Bilski, D. Wrobel, M. Kłosowski, Investigations of OSL properties
of LiMgPO4: Tb, B based dosimeters, Radiat. Measur. 90 (2016) 265-268.

12
 ACCEPTED MANUSCRIPT
[19] S. W. S. Makeover, M. S Akselrod, B. G. Markey, Pulsed optically stimulated
luminescence dosimetry using alpha-Al2O3: C, Radiat. Prot. Dosim. 65 (1996) 267–272.
[20] R. M. Abashev, A.I.Surdo, I.I.Milman, High-temperature thermoluminescence of anion-
deficient corundum and its connection with Ti impurity, Radiat. Meas.106 (2017) 161-165.
[21] S. V. Nikiforov, V. S. Kortov, A. N. Kiryakov, K. A. Petrovykh, Luminescence of
ultrafine magnesium oxide ceramics with deep traps, J. Phys.: Conf. Ser. 830 (2017) 012135.
[22] R. Halder, S.Bandyopadhyay, Synthesis and optical properties of anion deficient nano

PT
MgO, J. Alloys Compd. 693 (2017) 534-542.
[23] A.I. Popov, E.A. Kotomin, J. Maier, Analysis of self-trapped hole mobility in alkali

RI
halides and metal halides, Solid State Ionics 302 (2017) 3-6.
[24] N. Pathak, P. S. Ghosh, S. K. Gupta, S. Mukherjee, R. M. Kadam, A. Arya, An insight

SC
into the various defects-induced emission in MgAl2O4 and their tunability with phase
behavior: combined experimental and theoretical approach, J. Phys. Chem. C 120 (2016)

U
4016–4031.
[25] E. Erdem, Microwave power, temperature, atmospheric and light dependence of
AN
intrinsic defects in ZnO nanoparticles: A study of electron paramagnetic resonance (EPR)
spectroscopy, J. Alloys Compd. 605 (2014) 34-44.
M

[26] E. Giamello, A. Ferrero, S. Coluccia, A. Zecchina, Defect centers induced by

evaporation of alkali and alkaline-earth metals on magnesium oxide: an EPR study, Phys.
D

Chem. 95 (1991) 9385–9391.

[27] C. Freysoldt, B. Grabowski, T. Hickel, J. Neugebauer, G. Kresse, A. Janotti, C. G. Van
TE

de Walle, First-principles calculations for point defects in solids, Rev. Mod. Phys. 86 (2014)
253 – 305.
EP

[28] T. Yamamoto, T. Mizoguchi, First principles study on oxygen vacancy formation in

rock salt-type oxides MO (M: Mg, Ca, Sr and Ba), Ceram. Int. 39 (2013) S287-S292.
C

[29] G. Pacchioni, Quantum chemistry of oxide surfaces: from CO chemisorption to the

identification of the structure and nature of point defects on MgO, Surf. Rev. Lett. 7 (2000)
AC

277-306.
[30] J. Jupille and G. Thornton (eds.), Defects at Oxide Surfaces Springer International
Publishing Switzerland 2015, Springer Series in Surface Sciences 58, DOI 10.1007/978-3-
319-14367-5.
[31] L. Luo, Y. Jin, H. Pan, X. Zheng, L.Wu, R.You, W.Huang, Distribution and role of Li in
Li-doped MgO catalysts for oxidative coupling of methane, J. Catal. 346 (2017) 57-61.
[32] U. Simon, S. A.Villaseca, H. Shang, S. V. Levchenko, S. Arndt, J. D. Epping, O. Gçrke,
M. Scheffler, R. Schomcker, J. van Tol, A. Ozarowski, K.-P. Dinse, Li/MgO catalysts doped

13
 ACCEPTED MANUSCRIPT
with alio-valent ions. Part II: Local topology unraveled by EPR/NMR and DFT modeling,
ChemCatChem 9 (2017) 3597 –3610.
[33] S. Arndt, G. Laugel, S. Levchenko, R. Horn, M. Baerns, M. Scheffler, R. Schlögl,
R.Schomäcker, A Critical assessment of Li/MgO-based catalysts for the oxidative coupling of
methane, Cat. Rev.- Sci. Eng. 53 (2011) 424–514.
[34] N.S. Bajaj, C.B. Palan, S.K. Omanwar, Low temperature synthesis and improvement in
optical properties of MgO: Tb3+, Int. J. Mater. Sci. Eng. 3 (2015) 167-174.

PT
[35] I. I. Mil’man, E. V. Moiseikin, S. V. Nikiforov, S. V. Solov’ev, I. G. Revkov, E. N.
Litovchenko, The role of deep traps in luminescence of anion-defective α-Al2O3:C crystals,

RI
Phys. Solid State 50 (2008) 2076-2080.
[36] G. Kresse, J. Furthmuller, Efficiency of ab-initio total energy calculations for metals

SC
and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6 (1996) 15-50.
[37] G. Kresse, J. Furthmüller, Efficient iterative schemes for ab initio total-energy

U
calculations using a plane-wave basis set, Phys. Rev. B 54 (1996) 11169-11186.
[38] G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave
AN
method, Phys. Rev. B, 59 (1999) 1758-1775.
[39] J. P. Perdew, S. Burke, M. Ernzerhof, Generalized gradient approximation made simple,
M

Phys. Rev. Lett. 77 (1996) 3865-3868.

[40] H. J. Monkhorst, J. D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B
D

13 (1976) 5188-5192.
[41] Z. M. Gibbs, A. Lalonde, G. J. Snyder, Optical band gap and the Burstein-Moss effect in
TE

iodine doped PbTe using diffuse reflectance infrared Fourier trans- form spectroscopy, New J.
Phys. 15 (2013) 075020.
EP

[42] P. Kubelka, F. Munk, An article on optics of paint layers, Z. Tech. Phys. 12 (1931) 593–
603.
C

[43] J. Tauc, R. Grigorovici, A. Vancu, Optical properties and electronic structure of

amorphous germanium, Phys. Status Solidi 15 (1966) 627-637.
AC

[44] Yu. A. Barykina, N. I. Medvedeva, V. G. Zubkov, D. G. Kellerman, Luminescence of

VO43-centers in LiMgPO4 and LiMgVO4: Effect of [PO4]3-/[VO4]3- substitution on the
structure and optical properties, J. Alloys Compd. 709 (2017) 1-7.
[45] J. Chen, Y. Liu, L. Mei, H. Liu, M. Fang and Z. Huang, Crystal structure and
temperature-dependent luminescence characteristics of KMg4(PO4)3:Eu2+ phosphor for white
light-emitting diodes, Sci. Reports. 5 (2015) 9673.
[46] M. Sterrer, T. Berger, O. Diwald, and E. Knözinger, Energy transfer on the MgO
surface, monitored by UV-induced H2 chemisorption, J. Am. Chem. Soc. 125 (2003) 195-199.

14
 ACCEPTED MANUSCRIPT
[47] F. S. Stone, E. Garrone and A. Zecchina, Surface properties of alkaline earth oxides as
studied by UV-visible diffuse reflectance spectroscopy, Mater. Chem. Phys. 13 (1985) 33l-
346.
[48] E. Giamello, D. Murphy, L. Ravera, S. Coluccia and A. Zecchina, Surface colour
centres on magnesium oxide generated by magnesium and alkali-metal doping, J. Chem. Soc.
Faraday Trans. 90 (1994) 3167-3174.
[49] M. H. Huang, S. Mao, H. Feick, H. Q.Yan, Y. Y. Wu, H. Kind, E. Weber, R. Russo, P.

PT
D. Yang, Room-temperature ultraviolet nanowire nanolasers, Science, 292 (2001) 1897–1899.
[50] G. Ju, Y. Hu, L. Chen, Y. Jin, S. Zhang, F. Xue and H. Chen, Self-activated

RI
photoluminescence and persistent luminescence in CaZr4(PO4)6, Mater. Res. Bull. 83 (2016)
211–216.

SC
[51] F. Du, Y. Huang, S. Kim, and H. J. Seo, The self-activated luminescence properties of
blue-emitting Sr9Ga(PO4)7, Chem. Lett. 41 (2012) 15-17.

U
[52] D. Denzler, M. Olschewski, and K. Sattler, Luminescence studies of localized gap states
in colloidal ZnS nanocrystals, J. Appl. Phys. 84 (1998) 2841-2845.
AN
[53] Y. Li, Y. Wu, Transparent and luminescent ZnS ceramics consolidated by vacuum hot
pressing method, J. Am. Ceram. Soc. 98 (2015) 2972–2975.
M

[54] U. Das, Development of ZnS nanostructure based luminescent devices, Imp. J.

Interdiscip. Res. (IJIR) 2 (2016) 627-630.
D

[55] D. Wu and Z. Chen, ZnS quantum dots-based fluorescence spectroscopic technique for
the detection of quercetin, Luminescence 29 (2014) 307–313.
TE

[56] M. K. Sharma, P. Rohani, S. Liu, M. Kaus, and M. T. Swihart, Polymer and surfactant-
templated synthesis of hollow and porous ZnS nano- and microspheres in a spray pyrolysis
EP

reactor, Langmuir 31 (2015) 413−423.

[57] B. Liu, C. W. Cheng, R. Chen, Z. X. Shen, H. J. Fan, and H. D. Sun, Fine structure of
C

ultraviolet photoluminescence of tin oxide nanowires, J. Phys. Chem. C 114 (2010) 3407–
3410.
AC

[58] Ü. Özgür, Ya. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov, S. Doǧan, V. Avrutin, S.-J.
Cho, H. Morko¸ A comprehensive review of ZnO materials and devices, J. Appl. Phys. 98
(2005) 1-103.
[59] C. Ton-That, L. L. C. Lem, M. R. Phillips, F. Reisdorffer, J. Mevellec, T.-P. Nguyen, C.
Nenstiel, A. Hoffmann, Shallow carrier traps in hydrothermal ZnO crystals, New J. Phys. 16
(2014) 083040.
[60] F. Feldbach, 1. Kuusmannl, C. Zimmerer, Exitons and edge luminescence in MgO, J.
Lumines. 24/25 (1981) 433-436.

15
 ACCEPTED MANUSCRIPT
[61] V.V. Mikhailin, D.A. Spassky, V.N. Kolobanov, A.A. Meotishvili, D.G. Permenov, B.I.
Zadneprovski, Luminescence study of the LuBO3 and LuPO4 doped with RE, Radiat. Measur.
45 (2010) 307–310.
[62] C. Klingshirn, J. Fallert, H. Zhou, J. Sartor, C. Thiele, F. Maier-Flaig, D. Schneider, and
H. Kalt, 65 years of ZnO research – old and very recent results, Phys. Status Solidi B 247
(2010) 1424–1447.
[63] V. Pagonis, G. Kitis, C. Furetta. 2006, Numerical and Practical Exercises in

PT
Thermoluminescence. Springer Science & Business Media, 210 pages.
[64] D. Kulig (Wróbel), W. Gieszczyk, P. Bilski, B. Marczewska, M. Kłosowski,

RI
Thermoluminescence and optically stimulated luminescence studies on LiMgPO4 crystallized
by micro pulling down technique, Radiat. Measur. 85 (2016) 88–92.

SC
[65] B. Dhabekar, S. N. Menon, E. A. Raja, A. K. Bakshi, A.K. Singh, M.P. Chougaonkar,
Y.S. Mayya, LiMgPO4: Tb, B–A new sensitive OSL phosphor for dosimetry, Nucl. Instr.

U
Methods Phys. B 269 (2011) 1844–1848.
[66] Chen R., McKeever S.W.S. 1997 Theory of thermoluminescence and related
AN
phenomena Singapore: World Scientific, 559 pages.
[67] Yukihara E.G., McKeever S.W.S., 2011. Optically Stimulated Luminescence:
M

Fundamentals and Applications. John Wiley & Sons, 362 pages.

[68] E. G. Yukihara, S. W. McKeever, Optically stimulated luminescence (OSL) dosimetry
D

in medicine, Phys. Med. Biol. 53 (2008) R351.

[69] N. S. Bajaj, C. B. Palan, K. A. Koparkar , M. S. Kulkarni, S. K. Omanwar, Preliminary
TE

results on effect of boron co-doping on CW-OSL and TL properties of LiMgPO4: Tb, B, J.

Lumines. 175 (2016) 9–15.
EP

[70] S. N. Menon, A. K. Singh, B. Dhabekar, M.P. Chougaonkar and D. A. R. Babu, Effect

of UV in LiMgPO4:Tb, B phosphor, Int. J. Lumines. Applic. 4(II), (2014) 92-94.
C

[71] M. Kumar, B. Dhabekar, S. N. Menon, A. K. Bakshi, J. Udhayakumar, M. P.

AC

Chougaonkar and Y. S. Mayya, Beta response of LiMgPO4:Tb, B based OSL discs for
personnel monitoring applications, Radiat. Prot. Dosim. 155 (2013) 410-417.

16
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP

Fig. 1. The XRD pattern of LiMgPO4

C
AC

17
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M

Fig. 2. The SEM micrograph of LiMgPO4

D
TE
EP
C
AC

18
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP

Fig.3. The reflectance spectrum of LiMgPO4. Inset: the absorbance spectrum of LiMgPO4
C
AC

19
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
C EP
AC

Fig.4. Plots of (F(R)*hν)2 as a function of photon energy for the estimation of the
energy band gap in LiMgPO4

20
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Fig.5. The total density of states for LiMgPO4 and for F0 center in LiMgPO4: LiMgPO4 (a); single
EP

neutral oxygen vacancy in O1 (b), O2 (c) and O3 (d) sites. The Fermi level corresponds to zero
C
AC

21
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
C EP
AC

Fig.6. Three diagonal components of imaginary dielectric function ε2(ω) for electric
field parallel to the crystallographic axes in (a) LiMgPO4 and (b) F0:LiMgPO4. (c) The
dielectric function ε2(ω) averaged over crystallographic directions for LiMgPO4 and
F0:LiMgPO4. Insert shows the absorption edge up to 8 eV 22
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
C EP

Fig.7. The emission spectrum of LiMgPO4 recorded at λex=210 nm

AC

23
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
C EP

Fig.8. The emission spectrum of LiMgPO4 including NIR part recorded at λex=210 nm
AC

24
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
C EP

Fig. 9. The excitation spectra of LiMgPO4 recorded at different λ em

AC

25
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D

Fig. 10. The emission decay curve recorded for λem=410 nm at room temperature.
Inset: The emission band exited with λex=280 nm wavelength
TE
C EP
AC

26
 ACCEPTED MANUSCRIPT

PT
4
I, a.u.

RI
SC
2

U
AN
0
M

300 400 500 600

T, K
D
TE

Fig. 11. The TL glow curve of LiMgPO4 exposed to 2 Gy X-ray irradiation and the results of deconvolution
C EP
AC

27
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M

Fig. 12. Schematic models of UV-Vis-NIR luminescencse and thermoluminescencse in LiMgPO4

D
TE
C EP
AC

28
 ACCEPTED MANUSCRIPT
Table 1. Calculated parameters of the TL glow curves of LiMgPO4 exposed to a 2 Gy X-ray
irradiation
Tm, K 366 402
E, eV 0.70±0.03 1.03±0.03
b 1.42±0.06 1.67±0.06
S 1.1·109 2.5·1012

PT
RI
U SC
AN
M
D
TE
C EP
AC

29
 ACCEPTED MANUSCRIPT
• The two-step energy band gap in pure LiMgPO4 is observed.
• UV, blue and NIR luminescence in pure LiMgPO4 was demonstrated.
• The TL glow curve with a sufficiently large light sum was found.
• Ab initio calculations of the optical properties are performed.

PT
RI
U SC
AN
M
D
TE
EP
C
AC