Journal of Alloys and Compounds 647 (2015) 906e910

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Li2Se:Te as a neutron scintillator

Hongliang Shi, Mao-Hua Du*, David J. Singh
Materials Science & Technology Division and Center for Radiation Detection Materials and Systems, Oak Ridge National Laboratory, Oak Ridge, TN 37831,
USA

a r t i c l e i n f o a b s t r a c t

Article history: We show that Li2Se:Te is a potential neutron scintillator material based on density functional calcula-
Received 2 May 2015 tions. Li2Se exhibits a number of properties favorable for efficient neutron detection, such as a high Li
Received in revised form concentration for neutron absorption, a small effective atomic mass and a low density for reduced
12 June 2015
sensitivity to background gamma rays, and a small band gap for a high light yield. Our calculations show
Accepted 21 June 2015
Available online 23 June 2015
that Te doping should lead to the formation of deep acceptor complex VLieTeSe, which can facilitate
efficient light emission, similar to the emission activation in Te doped ZnSe.
© 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
Keywords:
Li2Se
(http://creativecommons.org/licenses/by/4.0/).
Neutron scintillator
Density functional theory
Dopants
Defects

1. Introduction
Neutron detection is an important technology that can be
applied to diverse areas including nonproliferation of special nu-
clear materials, homeland security, and various research instru-
mentation especially for detectors in neutron scattering
experiments. 3He gas detectors are very effective for thermal
neutron detection. However, the worldwide supply shortage of 3He
has increased interest in developing alternatives. 63 Li has a signifi-
cant thermal neutron capture cross-section of 940 b and thus many
Li-containing inorganic compounds (such as LiI:Eu [1], Cs2LiYCl6;
Ce [2], Li glass:Ce [3], and ZnS:AgeLiF [4]) have been developed as
neutron scintillators. Neutron detection has been demonstrated by
coupling these scintillators with photosensors (either photo-
multiplier tubes or photodiodes). However, new materials with
improved neutron detection efficiency are still highly desirable. For
efficient neutron detection, a high Li concentration in the neutron
scintillator is needed. A small effective atomic number and a low
density are desirable for reducing the sensitivity of the neutron
scintillator to background gamma rays. A smaller band gap is also
important for obtaining a larger number of excited electronehole
pairs and potentially a higher light yield.
Previously developed Li-based solid-state neutron detector
* Corresponding author.
E-mail address: mhdu@ornl.gov (M.-H. Du).
materials are mostly halides such as LiI and Cs2LiYCl6. Here we
propose a Li chalcogenide, Li2Se, as a new neutron scintillator
material. We studied Te-doped Li2Se because Li2Se has a relatively
small band gap, which may lead to a high light yield, and because
Te-doped ZnSe is a known gamma-ray scintillator [5], the activation
mechanism [6] of which may also apply to Te-doped Li2Se.
Li2Se has an anti-fluorite structure (space group Fm3m) as
shown in Fig. 1. Each Li is four-fold coordinated while each Se is
eight-fold coordinated. Li2Se has a high Li concentration of
3.70
1022 cm3, which should result in efficient neutron ab-
sorption. For comparison, LiI and Cs2LiYCl6 have Li concentrations
of 1.84
1022 cm3 and 3.47
1021 cm3, respectively. Li2Se has a
density of 2.87 g/cm3, much lower than those of LiI and Cs2LiYCl6,
which are 4.13 g/cm3 and 3.33 g/cm3, respectively. The effective
atomic number (Zeff) of Li2Se is 32.17, much smaller than those of LiI
and Cs2LiYCl6, which are 52.02 and 43.50, respectively. [The effec-
P
tive atomic number is given by Zeff ¼ ðai Zin Þ1=n , where Zi is the
atomic number of the ith atomic speciesi in the compound, ai is the
fraction of the total electron number which belongs to atoms with
atomic number Zi, and n is 2.94 (fitted to photoelectric absorption)
[7]]. Low-atomic-number, low-density scintillators are less sensi-
tive to the high-energy gamma rays, which should be of benefit to
neutron-gamma discrimination.
Although there is no experimentally measured Li2Se band gap
available, a previous density functional theory (DFT) calculation
using Engel and Vosko (EV) functional [8] estimated an indirect
band gap of 4.08 eV [9]. This is much smaller than those of LiI and

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 H. Shi et al. / Journal of Alloys and Compounds 647 (2015) 906e910
Fig. 1. Structure of Li2Se.
Cs2LiYCl6, i.e., 6.1 eV [10] and 7.5 eV [11], respectively. We confirm a
value lower than the halide scintillators using both modified Becke-
Johnson and hybrid functional calculations. The calculated band
gap of Li2Se is close to that of ZnS (3.80 eV) [12], which is the light-
emitting component of the well-known ZnSeLiF neutron scintil-
lator. In a ZnSeLiF neutron scintillator, LiF particles, which absorb
neutrons, are mixed with particles of ZnS:Ag, which is a high-light-
yield scintillator due to its small band gap. The problem of ZnSeLiF
is that its polycrystalline form requires the use of complicated de-
vice architectures to avoid loss of photons due to light scattering at
grain boundaries [4,13]. In contrast, a Li2Se neutron scintillator can
combine neutron absorption and light emission in one low-gap
single-crystal material. Thus, Li2Se neutron scintillators should
have the small-band-gap advantage of ZnSeLiF while avoiding the
light-scattering problem of polycrystalline ZnSeLiF.
In light of many favorable properties of Li2Se for neutron
detection, i.e., a small band gap, a high Li concentration, a small
effective atomic mass and a low density, we performed DFT cal-
culations to further study the electron structure, Te doping, and the
associated activation mechanism for Li2Se. The results show that
Li2Se:Te is potentially a high-light-yield neutron scintillator, which
can be activated by TeSeeVLi complexes.
2. Computational methods
Electronic structure and defect/dopant calculations were per-
formed based on the hybrid density functional method as imple-
mented in the Vienna ab initio simulation package [14,15]. We used
Heyd-Scuseria-Ernzerhof (HSE) functionals [16,17], which have a
25% Hartree-Fock exchange. The screening parameter of the
nonlocal Fock exchange in the HSE calculations was set at 0.2 Å1
(the HSE06 functional) [16]. The hybrid density functional methods
have been shown to improve results on the band gap, defects, and
the charge localization in semiconductors [18e22]. The electro-
neion interactions were described using projector augmented
wave potentials [23]. The valence wavefunctions were expanded on
a plane-wave basis with a cutoff energy of 550 eV. A 96-atom cubic
supercell and a 2
2
2 k-point mesh were used in defect and
dopant calculations. All atoms were relaxed to minimize the
Feynman-Hellmann forces to at least below 0.05 eV/Å.
The band gap and the refractive index were also calculated using
Tran-Blaha modified Becke-Johnson potential functional (TB-mBJ).
907
The TB-mBJ is a recently developed functional that has been shown
to give good band gaps and optical properties for many semi-
conductors and insulators but requires much lower computational
cost compared to HSE calculations [24e26]. The TB-mBJ calcula-
tions were performed using the general linearized augmented
plane-wave (LAPW) method as implemented in the WIEN2K code
[27]. We used highly converged zone samplings and basis sets,
including local orbitals to treat the semicore levels, including the Li
1s state and the chalcogen semicore s and d levels. We used LAPW
sphere radii of 2.4 bohr (a.u., 0.529177 Å), 2.2 bohr, and 2.0 bohr for
Te, Se and Li, respectively, with the basis set convergence parameter
Rminkmax ¼ 9 (Rmin is the Li sphere radius and kmax is the planewave
sector cut-off).
Defect formation energies are given by:
X    
ref
DH ¼ ðED  Eh Þ  ni mi þ mi þ q εVBM þ εf ; (1)
i
where ED and Eh are the total energies of the defect-containing and
the host (i.e. defect-free) supercells. Formation of a defect involves
exchange of atoms with their respective chemical reservoirs. The
second term in Eq. (1) represents the change in energy due to such
exchange of atoms, where ni is the difference in the number of
atoms for the ith atomic species between the defect-containing and
defect-free supercells. mi is the chemical potential for the ith atomic
ref
species relative to mi , which is the chemical potential for the
elemental bulk form. The third term in Eq. (1) represents the
change in energy due to exchange of electrons with its reser-
voir.εVBM is the energy of the valence band maximum (VBM) and εf
is the Fermi energy relative to the VBM. Corrections to the defect
formation energy due to the image charge and the potential
alignment (between the host and a charged defect supercell)
[28,29] were applied.
The chemical potentials of Li and Se satisfy the condition of
2mLi þ mSe ¼ DHf ðLi2 SeÞ; (2)
where DHf(Li2Se) is the enthalpy of formation for Li2Se. The
calculated DHf(Li2Se) is 3.90 eV, compared to the experimentally
measured value of 4.41 eV [30]. To avoid precipitation of
elemental Li and Se during crystal growth, the following conditions
should also be met: mLi  0 and mSe  0. In the case of Te doping, the
Te chemical potential (referenced to the chemical potential of bulk
elemental Te) is constrained by
2mLi þ mTe  DHf ðLi2 TeÞ and mTe  0 (3)
for not forming Li2Te and elemental Te, respectively. Here,
DHf(Li2Te) is the enthalpy of formation for Li2Te, calculated to
be 3.20 eV.
The transition level of a defect, ε(q/q0 ), corresponding to a
change in its charge state between q and q0 , is given by the Fermi
level, at which the formation energies, DH(q) and DH(q0 ), for charge
states q and q0 are equal to each other:
εðq=q0 Þ ¼ ½DHðqÞ  DHðq0 Þ=ðq0  qÞ: (4)
The spineorbit coupling (SOC) was used in electronic structure
calculations but not in total energy calculations for defects and
dopants because its effect is likely canceled out when evaluating
the total energy difference in Eq. (1). However, εVBM in Eq. (1) was
determined by the calculation that included the SOC. The experi-
mental lattice constant of 6.0014 Å was used for all calculations
[31].
908 H. Shi et al. / Journal of Alloys and Compounds 647 (2015) 906e910

Fig. 4. Band gaps of Li2Se1xTex as a function of x calculated using PBE functionals.

Fig. 2. Band structure of Li2Se calculated using HSE functionals including the SOC. Note that the PBE band gaps are underestimated but the trend is correct.

those of LiI and Cs2LiYCl6. However, for efficient light emission, an

Fig. 3. Refractive indexes (n) of Li2Se and Li2Te calculated using TB-mBJ functionals.
effective activator is required. LiI and Cs2LiYCl6 are activated by
Eu2þ and Ce3þ, respectively, both of which insert an electron
trapping (5d) and a hole trapping (4f) levels inside the host band
gaps. The small band gap of Li2Se makes it unlikely to accommodate
both the 5d and 4f levels of a rare-earth dopant. On the other hand,
it is known that ZnSe, a gamma ray scintillator, has a band gap of
2.82 eV and can be activated by Te due to the formation of VZneTeSe
complexes [6]. The luminescence in ZnSe:Te was explained by the
recombination between a hole trapped by VZneTeSe (a deep
acceptor) and an electron trapped at a shallow donor near VZneTeSe.
In light of this, we studied TeSe, VLi, and their complex, VLieTeSe, in
Li2Se.
Te is isovalent to Se in Li2Se. Our calculations cannot identify a
TeSe-induced localized state in the band gap but the states near the
VBM have strong Te-5p component. We changed the supercell size
with one Te in each supercell to study the variation of the band gap
as a function of Te concentration. The results in Fig. 4 show that the
band gap does not decrease linearly with the Te concentration but
drop sharply with a few percent of Te doping. Meanwhile the

3. Results and discussion

Fig. 2 shows the band structure of Li2Se calculated using HSE

functionals including the SOC. Li2Se has an indirect band gap with
the valence band maximum (VBM) at G point and the conduction
band minimum (CBM) at X point. The band gap calculated using
HSE with and without the SOC are 3.72 eV and 3.85 eV, respectively.
Using TB-mBJ with the SOC, the band gap is calculated to be 4.03 eV,
in good agreement with our HSE result and a previous result ob-
tained by using EV functionals without the SOC (4.08 eV). The
refractive index of Li2Se and Li2Te were calculated using TB-mBJ
functional and is shown in Fig. 3. The refractive index near 2 is
not high and should allow reasonably simple device architecture to
couple the Li2Se scintillator with a photosensor. The refractive in-
dex of Li2Te (Fig. 3) is not much higher than that of Li2Se, which
suggests that heavy Te hoping of Li2Se (discussed below) should not
change the refractive index significantly.
The calculated band gap of Li2Se (3.72 eV) is significantly smaller
than many other Li-based inorganic neutron scintillator materials,
such as LiI (6.1 eV) and Cs2LiYCl6 (7.5 eV). This result suggests that
the light yield of Li2Se has the potential to be much higher than Fig. 5. Spin-orbit splitting of the VBM states in Li2Se1xTex as a function of x calculated
using PBE functionals.
 H. Shi et al. / Journal of Alloys and Compounds 647 (2015) 906e910
spineorbit splitting of the VBM states increases with the Te con-
centration as shown in Fig. 5. These results are similar to those
observed in ZnSe1xTex at the Se-rich side of the alloy [32]. The
steep drop of the band gap with a few percent of Te doping in-
dicates that it is likely that TeSe introduces a localized level slightly
above the VBM, which nevertheless cannot be identified in our
calculations due to the small supercells we used. Such Te-induced
localized level could result in the trapping of excitons and the
associated exciton emission, in analogy to Te in ZnSe [33,6].
Note that the Perdew-Burke-Ernzerhof (PBE) [34] functionals
were used to calculate the band gaps and the spineorbit splitting in
Li2Se1xTex (Figs. 4 and 5). The PBE calculation is known to un-
derestimate band gaps of semiconductors, but it generally can
produce other electronic structure features correctly, such as the
band gap variation in alloys. Also, when calculating band gaps in
Li2Se1xTex with different x, the Te dopants were arranged peri-
odically in the crystal lattice. Although we did not simulate a
random alloy, the model systems we used suffice to show the trend
of the band gap.
Although TeSe may introduce a localized level slightly above the
VBM, which leads to exciton trapping and emission, such exciton
emission likely suffers from thermal quenching due to the shal-
lowness of the Te level. For efficient emission at room temperature,
it is desirable to trap carriers at deep centers. We studied the Li
vacancy (VLi) in Li2Se and found that it is a shallow single-electron
acceptor. We then replaced a Te atom adjacent to the Li vacancy
forming VLieTeSe. HSE calculations show that VLieTeSe is a deep
acceptor, which induces a (0/) thermodynamic transition level at
εtherm
VLi TeSe ð0=Þ ¼ EVBM þ 0.49 eV (calculated using Eq. (4)). Fig. 6
shows the partial charge density of the hole localized on TeSe
with an adjacent VLi. The hole trapped at the deep center of VLieTeSe
can be recombined with an electron trapped at a nearby donor
defect similar to the donor-acceptor-pair (DAP) recombination
involving VZneTeSe and a shallow donor in ZnSe:Te [6]. A bound
exciton may also be formed at a deep acceptor leading to
luminescence.
Fig. 6. Isosurface of partial charge densities of the localized hole state at (VLieTeSe)0.
The charge density of the isosurface is 0.006 e/bohr [3]. The red, green, and yellow balls
represent Li, Se, and Te atoms, respectively. The Te and the three Se atoms surrounding
the Li vacancy are labeled. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
909
The emission energy due to VLieTeSe can be determined by
ECBMeεopt VLi TeSe ð0=ÞeDBe. Following the Franck-Condon principle,
opt
εVLi TeSe ð0=Þ can be calculated using Eq. (4) by fixing the structures
of both (VLieTeSe)0 and (VLieTeSe) as the relaxed (VLieTeSe)0
structure. (Note that when calculating εtherm VLi TeSe ð0=Þ, both (VLie-
TeSe)0 and (VLieTeSe) were relaxed.) This yields
opt
εVLi TeSe ð0=Þ ¼ EVBM þ 0.87 eV and the emission energy of
2.85 eVeDBe. DBe is the electron binding energy for the shallow
donor (in the case of DAP recombination) or for the bound exciton
(in the case of bound-exciton emission). DBe should be relatively
opt
small compared to εVLi TeSe ð0=Þ, which involves a deep hole.
We further calculated the formation energy of (VLieTeSe) using
Eq. (1), which yields DH[(VLiTeSe)] ¼ 0.78 eV þ mLimTeεf. We
take the Te-rich limit, which corresponds to the maximum mTe
allowed by Eq. (3). At the Li-rich limit (mLi ¼ 0), we find

Te ¼ 3.20 eV and DH[(VLiTeSe) ] ¼ 3.98 eVεf. At the Li-poor
mmax
limit (mLi ¼ 1.95 eV), we find mmax Te ¼ 0 and DH
[(VLiTeSe)] ¼ 2.73 eVεf. A Li-poor growth condition (low mLi) and
a high εf (εmaxf
¼ εg ¼ 3:72 eV) should reduce the formation energy
of (VLieTeSe). However, a Li-poor condition promotes the forma-
tion of Li vacancies (which are acceptor defects) and suppresses the
formation of Se vacancies (which are donor defects), resulting in a
low εf. Therefore, mLi should be optimized during the growth to
minimize the term mLiεf in DH[(VLiTeSe)]. In addition, electron
donors such as Br may be introduced under a Li-poor condition to
lead to a high εf and a low mLi, which promote the formation of
(VLieTeSe).
4. Conclusion
We show that Li2Se:Te is a potential neutron scintillator mate-
rial. Li2Se has a high Li concentration, a small effective atomic mass,
a low density, and a small band gap. These properties should lead to
efficient neutron absorption, low sensitivity to background gamma
rays, and potentially high light yields. Hybrid density functional
calculations show that Te doping of Li2Se leads to the formation of
VLieTeSe complexes, which introduce deep acceptor levels. The
deep defect levels facilitate charge carrier localization and the
subsequent radiative recombination similar to the emission acti-
vation mechanism in Te doped ZnSe.
Acknowledgments
Initial electronic structure calculations with the modified Becke-
Johnson potential were supported by the ORNL LDRD fund. The
remainder of the work including optical and defect calculations was
supported by the Department of Energy, Office of Science, Basic
Energy Sciences, Materials Sciences and Engineering Division.
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