APPLIED PHYSICS LETTERS 92, 201908 共2008兲

Near optical isotropy in noncubic SrI2: Density functional calculations

D. J. Singha兲
Materials Science and Technology Division and Center for Radiation Detection Materials and Systems, Oak
Ridge National Laboratory, Oak Ridge, Tennessee 37831-6114, USA
共Received 24 March 2008; accepted 1 May 2008; published online 22 May 2008兲
We report calculations of the electronic structure and optical properties of orthorhombic SrI2. These
were done using the Engel–Vosko generalized gradient approximation. We find that the dielectric
function and refractive indices are almost isotropic in this noncubic material. This suggests that low
cost nonconventional routes for producing SrI2-based scintillators may be practical and, in
particular, that ceramic processing may be used. © 2008 American Institute of Physics.
关DOI: 10.1063/1.2936079兴

There has been renewed interest in the use of scintilla-
tors for high resolution spectroscopic gamma ray detection
over the past several years. This has been stimulated largely
by the discovery of highly proportional, high light output
scintillation in hexagonal LaBr3 : Ce3+, leading to energy
resolutions of ⬃3% at 662 keV.1 One issue impeding wide-
spread application of this material has been the difficulty of
finding low cost methods for growing high quality crystalline
material. Problems include cracking and interaction with the
crucible. Very recently, Cherepy et al. showed that SrI2 : Eu2+
crystals with high Eu contents can have performance rivaling
or exceeding that of LaBr3 : Ce3+ both in terms of light yield
and proportionality.5 In fact, SrI2 : Eu2+ and the related mate-
rials CaI2 : Eu2+ and BaI2 : Eu2+ were known scintillators
whose application had been impeded by crystal growth is-
sues, especially the difficulty in growing high quality large
single crystals2–5 and which were solved via Bridgman
growth in the recent work of Cherepy et al. for SrI2 : Eu2+.
Nonetheless, many applications such as large area detection
would benefit from the availability of a scintillator detector
that combines large size, flexible shape, low cost, and high
energy resolution—a combination that is nearly impossible
to achieve with current Bridgman growth techniques.
Here, we show that despite its essentially orthorhombic
crystal structure, space group Pbca,6–9 the optical constants
of SrI2 are almost isotropic over a wide energy range. The
implication is that regardless of its noncubic crystal struc-
ture, it may be possible to make SrI2 : Eu2+ in a transparent
ceramic form bypassing Bridgman growth.
The calculations reported here were performed within
density functional theory using the Engel–Vosko exchange-
correlation functional10 although we did local density ap-
proximation 共LDA兲 calculations as well. The Engel–Vosko
generalized gradient approximation 共GGA兲 functional was
designed to reproduce as much as possible the exact
exchange-correlation potential rather than the total energy,
and as a result gives significantly improved results10–12 for
the band gap and related optical properties as compared with
the LDA and standard GGA functionals such as those of
Perdew et al.13 The calculations were done with the general
potential linearized augmented planewave 共LAPW兲14
method, as implemented in the WIEN2K code15 and are based
on the experimental orthorhombic Pbca crystal structure as
a兲
Electronic mail: singhdj@ornl.gov.
obtained by Hodorowicz and Eick.9 Well converged basis
sets and zone samplings were employed, with LAPW sphere
radii of 3.0 bohrs for both the Sr and I atoms. The optical
dielectric function and refractive indices were obtained using
the WIEN2K optical package, which is based on the calcula-
tion of electric dipole transitions.
The structure of SrI2 is depicted in Fig. 1. As may be
seen, this structure is essentially orthorhombic and cannot be
regarded as a small distortion of a cubic structure. The struc-
ture contains 24 atoms per unit cell, with eight equivalent Sr
atoms, and two inequivalent sets of eight I atoms, denoted as
I1 and I2, respectively. Interesting, though perhaps not sur-
prisingly considering the practically identical ionic radii16 of
Sr2+ and Eu2+, EuI2 can be made in the same structure with
almost the same lattice parameters 共denoted as EuI2-II; there
is also a monoclinic form that can be made兲6,8 and is ex-
pected to form a solid solution with SrI2 over the entire com-
position range.17
The calculated electronic density of states 共DOS兲 and I
projections are shown in Fig. 2. The calculated band gap is
4.5 eV. This compares with a LDA value of 3.7 eV. As ex-
pected, the gap is of charge transfer character between I
p-derived valence bands and metal-derived conduction
bands. Interestingly, the projections show a significant
chemical difference between the I1 and I2 sites. Halide struc-
tures involve a balance between optimizing the Coulomb po-
tential and satisfying constraints imposed by ionic radii and
anion overlap.17 In this compound, the result is a sevenfold
coordination of Sr by I: three on I1 sites and four on I2 sites.
FIG. 1. 共Color online兲 Orthorhombic structure of SrI2 viewed along the c
axis 共left兲 and a axis 共right兲. Sr is shown as large green spheres, and Sr as
small blue spheres. Note the clearly noncubic structure.

0003-6951/2008/92共20兲/201908/3/$23.00 92, 201908-1 © 2008 American Institute of Physics

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 201908-2 D. J. Singh Appl. Phys. Lett. 92, 201908 共2008兲

FIG. 2. 共Color online兲 Calculated electronic density of states of SrI2 on a per FIG. 4. 共Color online兲 Wavelength dependent refractive index of SrI2 as
formula unit basis as obtained with the Engel–Vosko GGA. Projections onto obtained with the Engel–Vosko GGA.
the two inequivalent I LAPW spheres are also shown.
optical properties within the LDA. As mentioned, the crystal
The I1 sites are coordinated by three Sr atoms at an average structure is far from isotropic and, in fact, that the band
distance of 3.31 Å, while the I2 site has four Sr neighbors at structure is not isotropic either. However, optical properties
an average distance of 3.39 Å. Since the fourfold coordina- involve double integrals over valence and conduction bands,
tion is more favorable from the point of view of the Coulomb and apparently for SrI2, the anisotropies in the integrand can-
potential, the I2 DOS is centered at lower energy than the I1 cel in the integration.
site, which in contrast is largest near the valence band edge. The key requirements for fabrication of transparent ce-
We calculated the optical properties using the Engel– ramics are sinterability and optical isotropy. The requirement
Vosko electronic structure. The real and imaginary compo- for optical isotropy comes from the need to minimize light
nents of the dielectric tensor as a function of energy are scattering at grain boundaries with arbitrary orientation. The
shown in Fig. 3, while the anisotropic wavelength dependent soft lattices and low melting points of iodides are favorable
refractive index is given in Fig. 4. As may be seen, we obtain for sinterability. Generally, it is thought that complete isot-
the remarkable result that over a wide wavelength range the ropy is needed to produce fully transparent ceramic for op-
dielectric constant and refractive index are almost isotropic. tical applications. However, it should be noted that while
In particular, the xx and zz tensor components are practically high transparency is required for spectroscopic gamma de-
equal while the yy dielectric constant and refractive index tection using a scintillator, this is not an imaging application.
are only slightly larger. This difference amounts to less than As a result, weak scattering and image distortion are not as
2% in the dielectric constant and 1% in the refractive index detrimental as, for example, in a lens for an optical instru-
over the entire wavelength range shown. The values of the ment. This fact was discussed previously in the context of
refractive index at 435 nm, which is the midpoint of the monoclinic but also highly isotropic Lu2SiO5 : Ce3+ 共LSO兲
emission for SrI2 : Eu2+ 共Ref. 5兲, are nxx = nzz = 2.05 and nyy ceramic scintillators, which have high light output.18 As
= 2.07. While the precise values will be sensitive to the band noted in Ref. 18, for a scintillator application, scattering may
gap, the anisotropy is expected to be robust. To check this, be reduced by the use of larger grain sizes since image dis-
we also did calculations within the LDA, which as men- tortion is not an issue. Furthermore, we find almost complete
tioned has a smaller band gap. We find similarly isotropic isotropy between nxx and nzz. So in SrI2, texturing along the
b axis may be used to improve ceramic transparency.
To conclude, we find that despite its essentially noncubic
crystal structure, the optical constants of SrI2 are nearly iso-
tropic over a large wavelength range. Considering the very
high light output and excellent proportionality demonstrated
in SrI2 : Eu2+ crystals, the results suggest investigation of
SrI2 : Eu2+ ceramic as a low cost, high performance scintilla-
tor for spectroscopic gamma detection.
I am grateful for helpful discussions with L. A. Boatner
and M. H. Du. This work was supported by the Department
of Energy, Office of Non-Proliferation Research and
Development, NA-22.
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