Optical Materials 89 (2019) 329–333

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Effect of the amounts of Li+ additive on the luminescence properties of T

LiBaPO4:Eu phosphor
Daniela A. Horaa, Ariosvaldo J.S. Silvaa, Patresio A.M. Nascimentoa, David V. Sampaiob,
Benjamin J.A. Moultonb, Ronaldo S. Silvaa, Marcos V. dos S. Rezendea,∗
a
Grupo de Nanomateriais Funcionais (GNF), Departamento de Física, Universidade Federal de Sergipe, 49100-000, São Cristóvão, SE, Brazil
b
Departamento de Física, Universidade Federal de São Carlos, 13565-905, São Cristóvão, SP, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Eu-doped LiBaPO4 phosphors were synthesized by sol–gel route using PVA as the chelating agent. The structure
Optical materials and photoluminescence (PL) properties of the as-prepared LiBaPO4 phosphors were investigated by X-ray dif-
Defects fraction (XRD), X-ray absorption spectroscopy (XAS) and PL spectroscopy. The samples presented single hex-
Luminescence agonal phase and the incorporation of the excess Li did not affect the crystal structure. The luminescence
Europium
properties of the Eu-doped LiBaPO4 phosphors strongly depend on the Li concentration. It is possible that the Li
excess contributes to the Eu3+→Eu2+ reduction and enhances the Eu2+ stabilization in the LiBaPO4 structure.

1. Introduction
Phosphate-based compounds of the ABPO4 (A = alkaline metal,
B = alkaline earth metal) composition have become an important class
of luminescent materials due to their hydrolytic, thermal and chemical
stability and their rigid tetrahedral network matrix [1–6]. In general,
LiBaPO4 phosphors exhibit excellent luminescence properties when
doped with rare earth ions, such as Ce [7], Tb [8], Dy [9] or Sm
[10,11]. LiBaPO4 has many applications, especially for use in diodes,
because when it is doped with Eu because it emits white light
[10,12,13]. LiBaPO4 has a hexagonal unit cell with a P63 space group.
The unit cell is comprised of a PO4 tetrahedron that is connected with
LiO4 tetrahedra through corner sharing which builds a tridymite-like
skeleton. In this structure, there are three Ba2+ sites, two 9-coordinated
and one 6-coordinated. Due to its ionic size and valence state, the Eu
dopant is expected to replace the Ba2+sites [13].
Sample preparation and dopant concentration are important factors
which control the luminescent properties of ceramics. A series of works
have related an improved Eu emission when the samples are co-doped
with Li+ ions [14–18]. For example, Gou et al. [19] report that PL is
enhanced in KSrPO4:Dy when it is Li co-doped. Recently, we reported a
sensitivity of the Eu emission when Li was deficient or in excess of the
stoichiometric LiAl5O8 phosphors [20]. Below we have extended these
findings to the LiBaPO4:Eu phosphors to further investigate the effect of
excess Li on the luminescence properties.
In this paper, Eu-doped LiBaPO4 doped with various concentrations
of Li ions was synthesized via sol-gel route. The structure and lumi-
nescent characteristics of LiBaPO4:Eu3+ phosphors were investigated
using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and
photoluminescence (PL) measurements to investigate the effect of Li
excess on the photoluminescence and XEOL spectra of Eu-doped
LiBaPO4 phosphors.
2. Experimental
Sol-gel route using PVA was employed to prepare Eu-doped LiBaPO4
phosphors. Lithium nitrate LiNO3 (Sigma-Aldrich), barium nitrate Ba
(NO3)2 (Sigma-Aldrich), ammonium phosphate dibasic (NH4)2HPO4,
and Eu(NO3)3 (Sigma-Aldrich, 99.99%) were used as the raw materials.
First, stoichiometric concentrations were dissolved in distilled water
(20 ml). Then, 10 ml of 0.1 g/ml aqueous PVA (Proquímios) solution
was slowly added to the solution while continuously stirring and
heating at ∼100 °C. The solution became a gel after stirring for about
6 h. Second, the gel was transferred to alumina crucibles and calcined in
air for 2 h at 1000 °C. Eu3+ concentration was fixed at 1 mol% while
different amounts of Li+ were added to produce a series of samples with
the composition range LixBa0.99PO4:Eu, where x = 1.0, 1.05, 1.10 and
1.15. X-ray powder-diffraction data were collected over the 2θ range
20–60° with Co Kα radiation (λ = 1.79 Å; 40 kV, 40 mA) on a Rigaku
RINT 2000/PC diffractometer.
Photoluminescence excitation and emission spectra were performed
at room temperature to characterize the photoluminescence properties.

∗
Corresponding author. Tel.: +55 79 3194 6809.
E-mail address: mvsrezende@gmail.com (M.V.d.S. Rezende).

https://doi.org/10.1016/j.optmat.2019.01.044
Received 5 October 2018; Received in revised form 19 December 2018; Accepted 9 January 2019
Available online 06 February 2019
0925-3467/ © 2019 Elsevier B.V. All rights reserved.
D.A. Hora et al. Optical Materials 89 (2019) 329–333

Fig. 2. Emission spectra of the Eu-doped LixBaPO4 phosphors under excitation

Fig. 1. XRD patterns of Eu-doped LiBaPO4 phosphors with different contents of at 393 nm.
excess Li+. Standard JCPDS pattern of LiBaPO4 phosphors is also given for
reference.

A FP-8600 spectroflurometer system (JASCO) equipped with a 150 W

xenon discharge lamp as the excitation source was used. XAS experi-
ments were recorded at the X-ray Absorption and Fluorescence
Spectroscopy (XAFS2) beamline at the Brazilian Synchrotron Light
Source (LNLS). An optical fiber and a Hamamatsu R928 photomultiplier
were used to recorded the total X-ray excited optical luminescence
(XEOL) spectra. XEOL emission spectra were measured simultaneously
with the XAS spectra an optical fiber and an Ocean Optics QE 65000
spectrometer.

3. Results and discussions

XRD pattern of the Eu-doped LiBaPO4 samples with different con-

tents of Li+ are shown in Fig. 1. All the samples were found to be
crystalline and belong to the barium orthophosphate-type structure of
LiBaPO4 matched with the JCPDS file No. 14–0270 and no secondary
phases were found. The diffractograms show no evidence for structural
changes as a result of the excess Li in the LiBaPO4 orthophospate
structure. The absence of other oxide phases indicates that a complete
substitution of dopant ions into LiBaPO4 structure was achieved. Pre-
vious atomistic simulations revealed that the Eu dopant prefers to be
incorporated into the Ba sites with charge compensation by LiBa´ anti-
site [21]. Based on the peak width the crystallite sizes (D) of all the
samples were calculated from Scherrer's equation [22]. The average
crystalline size varies from 24 nm to 30 nm when the Li+ concentration
increases.
Fig. 2 shows the emission spectra for Eu-doped LixBaPO4 (x = 1.00,
1.05, 1.10 and 1.15) phosphors under excitation of 393 nm. As can be
seen, all spectra exhibit emission lines at 578, 592, 616, 655, and
703 nm, which are assigned to the 5D0-7FJ (J = 1–4) transitions of Eu3+
ions. The electric dipole transition 5D0-7F2 at 616 nm was observed to
be more intense than the magnetic dipole transition 5D0-7F1 at 592 nm.
This indicates that Eu ions are located in a low symmetry site. Com-
puter simulations show that the low symmetry site is enhanced due to
the LiBa´ anti-site nearby which was created to charge compensate the
defect [21]. The spectra also exhibit a broad band centered at 466 nm
which is attributed to the electric-dipole-allowed 4f65d1-4f7 transition
of the Eu2+ ions. Thus, even when synthesized in open atmosphere,
both Eu valence states are stabilized in LixBaPO4. Note that the relative
intensity between Eu3+ and Eu2+ emission change when the Li con-
centration change. This behavior can be better seen in Fig. 3 in which is
presented the integrated area of the PL emission spectra as function of
Fig. 3. PL integrate area of Eu2+ and Eu3+ peaks as a function of the Li con-
centration.
Li concentration.
As can be seen, the Eu2+ intensity increases (Eu3+ decreases) when
the Li concentration increases. This could indicate that the excess Li
influences the reduction Eu3+→Eu2+. In the literature several factors
are reported to affect the Eu reduction (e.g. particle sizes, reducing
agents, etc.). The Li excess may improve the crystallization by de-
creasing the number of surface defects and may increase the hole
concentration which reduces the internal reflection loss [23]. These
effects may also contribute to improve the Eu2+ emission.
Fig. 4 shows the excitation spectra of the phosphors monitored at
616 nm (Fig. 4a), the 5D0-7F2 Eu3+ transition, and at 464 nm (Fig. 4b),
the d-f Eu2+ transition. Note that the samples with Li excess did not
display a significant difference in the peak positions; however, there
were significant changes in the intensities. At 464 nm (Fig. 4a), the
spectra presented two broad band centered at 275 nm and 377 nm due
to the 4f-5d Eu2+ transitions. These excitation bands agree with the
literature values for of Eu2+ ions [8,12,13]. On the other hand, when
the excitation was monitored at 616 nm (Fig. 4a), the spectra consisted
of two broad bands, ranging from 220 to 320 nm, and several lines from
320 to 470 nm. The first absorption band, centered at 227 nm, is as-
signed to the charge transfer (CT) transition between Eu3+ and O2−
ions. The second band at 275 nm, is centered in the same position of
Eu2+ excitation observed in Fig. 4a. Thus, we suggest that this band is a

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D.A. Hora et al.
Fig. 4. Excitation spectra of the Eu-doped LixBaPO4 samples monitored at (a)
464 nm, due to d-f Eu2+ transition and at (b) 616 nm, due to the 5D0-7F2 Eu3+
transition.
result of Eu2+ → Eu3+ energy transfer, due to Eu2+ excitation that
transfer its energy to Eu3+ which finally emits the light. The narrow
lines observed at 362, 382, 394, 415 and 464 nm correspond to the
transitions from the 7F0 ground state to the 5D4, 5GJ, 5L6, 5D3 and 5D2
excited levels, respectively.
In order to see the effect of Li+ addiction on the Eu emission under
high-energy excitation, X-ray excited optical luminescence (XEOL)
emission spectra excited at the Eu LIII-edge (6977 eV) were obtained
(Fig. 5). It can be observed that the XEOL emission spectra exhibit a
similar profile, Eu3+ and Eu2+ emission peaks, as the photo-
luminescence (PL) spectra (Fig. 3). An increase of Eu2+ emission with
the decrease of Eu3+ emission is clearly observed when the XEOL and
PL emission spectra are compared. In the XEOL emission spectra, the
Eu2+ emission is more intense than Eu3+ emission peaks for all com-
positions. This indicates that the high-energy excitation contributes to
further reduce the Eu, although it is not clear if this reduction is tran-
sient (due to the measurement) or a permanent effect. Besides, the
XEOL Eu2+ emission is clearly formed by two bands centered at ap-
proximately 420 and 480 nm. This indicates that there are two non-
symmetric Eu2+ sites. The splitting of the 5d-excitation level of Eu2+ is
caused by the strong influence of the crystal field. Each non-equivalent
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Optical Materials 89 (2019) 329–333
Fig. 5. XEOL emission spectra of the Eu-doped LixBaPO4 phosphors excited at
6977 eV.
Eu2+ sites has its own local symmetry that, consequently, has a dif-
ferent crystal field splitting generating different emission peaks asso-
ciated with their respective 4f5d-4f transitions. Moreover, the Eu2+
emission bands change with the Li+ amount. This is probably due to the
excess Li that may change the local symmetry of Eu2+ sites, and con-
sequently, also affects the crystal field splitting of the 4f5d-4f transi-
tions.
The XAS and XEOL spectra of Eu-doped LiBaPO4 were measured to
confirm the Eu reduction (Fig. 6). The XAS spectra are dominated by
their white lines at about 6977 eV which is assigned to the Eu3+ spe-
cies. It is important to highlight that all XANES spectra are similar,
indicating that the Li+ content did not affect the Eu valence stabilized
in the samples. Results carried on XEOL area spectra show that the
samples luminescence increases as a function of the excitation energy
(Fig. 6). A positive edge jump, similar to the XANES spectra is observed.
According to the phenomenological theory of XEOL [24], this means
that, after the absorption process occurs, relaxation results through the
recombination of the charge carrier pairs, which directly excite the Eu
ions and then it decays producing the XEOL emission spectra.
In order to prove the presence of Eu2+ species observed in the PL
and XEOL emission spectra, the derivative of the absorption curves was
calculated for all samples (Fig. 7). The maxima in the derivative curves
can be assigned to the absorption edges of the chemical species. The
spectra show two maxima at ∼6973 and ∼6978 eV, associated with
the Eu2+ and Eu3+ species, respectively. The Eu2+ and Eu3+ species
can be easily distinguished because their absorption edges are quite
different.
One explanation of how the two valence states of Eu are accom-
modated inside the LiBaPO4 structure, may be based on model where
their incorporation is balanced by the formation of charge compensa-
tion defects. In general, Eu3+ substitution might occur at the Li+, Ba2+
or P5+ sites, and therefore more than one possible mode of charge
compensation may be possible. Previous atomistic simulations [21] of
LiBaPO4 reveals that Eu3+ ions will enter the Ba sites causing the for-
mation of a LiBa´ anti-site or lithium vacancy, VLi´, to fulfill the charge
compensation requirements. These processes are described by equa-
tions (1) and (2) below, respectively. The set of defect reactions in-
vestigated are listed using Krӧger-Vink notation [25]. Atomistic simu-
lations also reveal that Eu substitution at P5+ sites tend to be more
energetically unfavorable because P5+ ions have a very different formal
oxidation state and electronegativity than Li+ and Ba2+ ions. More-
over, the fact that P5+ forms strong covalent bonds to oxygen compared
to the other cations also suggests that Eu substitution for P is un-
favorable. As shown in the PL and XEOL results, part of Eu3+ is
D.A. Hora et al.
Fig. 6. XAS (lines) and XEOL (circles) area curves of Eu-doped LiBaPO4 samples
with different contents of Li+ excited at Eu LIII-edge.
Fig. 7. XAS and XEOL area curves of Eu-doped LiBaPO4 samples with different
Li+ contents excited at Eu LIII-edge.
reduced, i.e., part of EuBa• defect became electron acceptors. At this
moment, LiBa´ anti-site or lithium vacancy, VLi´, will act as the electron
donor (e.g. equations (3) and (4)). Under thermal or X-ray stimulation,
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Optical Materials 89 (2019) 329–333
the negative charges in the charge compensation defects (LiBa´ or VLi´)
would be then transferred and captured by the EuBa• defects and reduce
Eu3+ to Eu2+ as shown in equation (5). The whole process can be
described by the following equations:
•
Eu2 O3 + Li2 O + 4BaBa → 2EuBa + 2Li′Ba + 4BaO (1)
•
Eu2 O3 + 2LiLi + 2BaBa → 2EuBa + 2V ′Li + 2BaO + Li2 O (2)
×
Li′Ba → LiBa + e′ (3)
V ′Li → VLi× + e′ (4)
• ×
EuBa + e′ → EuBa (5)
Based on the emission intensities of the sample, it is not possible to
determine the quantitative amounts of Eu2+ and Eu3+ ions due to the
fact that the two luminescence centers have their own characteristic
excitation wavelengths and probabilities. According to Laporte, Eu2+
has a spin forbidden transition with lifetime in the order of μs, whereas
Eu3+ has a forbidden transition with lifetime in the order of ms.
4. Conclusions
We have synthesized Eu-doped LiBaPO4 phosphors with different
amounts of excess Li by sol-gel route. Changes in the PL and XEOL
spectra of LiBaPO4:Eu were observed with the addition of Li+ ions such
that both Eu2+ and Eu3+ were formed. The PL and XEOL emission of all
samples are consisted of transition of Eu2+ and Eu3+ ions, suggesting
that Eu reduction is enhanced by excess Li. The addition of lithium
causes an increase in the Eu2+ and a decrease of the Eu3+ emission
bands. We have proposed a mechanism based on charge compensation
defects to explain how the two valence states of Eu ions are able to be
accommodated inside the LiBaPO4 structure.
Declaration of interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
The authors declare the following financial interests/personal re-
lationships which may be considered as potential competing interests:
Acknowledgments
The authors are grateful to FINEP (Brazilian Innovation Agency),
CAPES (Brazilian Federal Agency), CNPq (Brazilian National Council
for Scientific and Technological Development). BJAM and DVS would
also like to thank the São Paulo Research Foundation (FAPESP) for
funding this research through the CEPID grant #2013/07793-6 and
post-doctoral grants # 2016/15962-0 and 2016/18567-5.
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