Synthesis, structure, and properties of Li2In2MQ 6 (M = Si, Ge; Q = S, Se): A new series of IR nonlinear optical materials

Article abstract of DOI:10.1021/ic300373z

The four isostructural compounds Li₂In₂MQ₆ (M = Si, Ge; Q = S, Se) have been synthesized for the first time. They crystallize in the noncentrosymmetric monoclinic space group Cc with the three-dimensional framework composed of corner-sharing LiQ₄, InQ ₄, and MQ₄ tetrahedra. The second-harmonic-generation signal intensities of the two sulfides and two selenides were close to those of AgGaS₂ and AgGaSe₂, respectively, when probed with a laser with 2090 nm as the fundamental wavelength. They possess large band gaps of 3.61(2) eV for Li₂In₂SiS₆, 3.45(2) eV for Li₂In₂GeS₆, 2.54(2) eV for Li ₂In₂SiSe₆, and 2.30(2) eV for Li ₂In₂GeSe₆, respectively. Moreover, these four compounds all melt congruently at relatively low temperatures, which makes it feasible to grow bulk crystals needed for practical application by the Bridgman-Stockbarger method.

Full text of DOI:10.1021/ic300373z

Article
pubs.acs.org/IC
Synthesis, Structure, and Properties of Li In MQ (M = Si, Ge; Q = S,
2
2
6
Se): A New Series of IR Nonlinear Optical Materials
Wenlong Yin,†,‡,§ Kai Feng,†,‡,§ Wenyu Hao,†,‡,§ Jiyong Yao,* and Yicheng Wu
,†,‡
†,‡
†
‡
Center for Crystal Research and Development and Key Laboratory of Functional Crystals and Laser Technology, Technical
Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China
§
Graduate University of the Chinese Academy of Sciences, Beijing 100049, People's Republic of China
S Supporting Information
*
ABSTRACT: The four isostructural compounds Li In MQ (M = Si, Ge; Q = S,
2
2
6
Se) have been synthesized for the first time. They crystallize in the
noncentrosymmetric monoclinic space group Cc with the three-dimensional
framework composed of corner-sharing LiQ , InQ , and MQ tetrahedra. The
4
4
4
second-harmonic-generation signal intensities of the two sulfides and two
selenides were close to those of AgGaS and AgGaSe , respectively, when probed
2
2
with a laser with 2090 nm as the fundamental wavelength. They possess large
band gaps of 3.61(2) eV for Li In SiS , 3.45(2) eV for Li In GeS , 2.54(2) eV for
2
2
6
2
2
6
Li In SiSe , and 2.30(2) eV for Li In GeSe , respectively. Moreover, these four
2
2
6
2
2
6
compounds all melt congruently at relatively low temperatures, which makes it
feasible to grow bulk crystals needed for practical application by the Bridgman−
Stockbarger method.
INTRODUCTION
achieving a large macroscopic NLO response if they are aligned
in a cooperative manner. In this way, compounds with a strong
NLO response and large band gap could be obtained.
■
Nowadays, frequency conversion through mid and far IR
nonlinear optical (NLO) crystals is an important way to
generate mid and far IR laser sources, which have many
important civil and military applications including atmospheric
monitoring, laser radar, and laser guidance. As a result of their
large NLO coefficient and wide transparent range in the IR
Besides optical properties, the easiness of obtaining bulk
crystals is another important factor that influences the potential
for practical application for IR NLO materials because bulk
crystals are needed for the thorough evaluation and practical
application of IR NLO materials. Nowadays, almost all bulk
crystals of chalcogenides are grown by the Bridgman−
Stockbarger method in sealed ampules, which indicates that
the material needs to exhibit congruent-melting behavior. Thus,
compounds exhibiting large NLO response, large band gaps,
and congruent-melting behavior are of great importance
because of their potential for practical application. Recently,
we reported our discovery of the low-melting-point, low-
lithium-content, new IR NLO material LiGaGe Se in the Li/
1
,2
range, the chalcopyrite-type AgGaQ (Q = S, Se) and
2
3
ZnGeP2 crystals have been the practically used IR NLO
materials since the 1970s. However, they possess serious
drawbacks of one or another in their properties. For example,
AgGaQ2 (Q = S, Se) has a low laser-damage threshold,
AgGaSe is not phase-matchable at 1 μm, and ZnGeP exhibits
2
2
strong two-photon absorption of the conventional 1 μm
Nd:YAG) or 1.55 μm (Yb:YAG) laser-pumping sources.
Thus, the search for new IR NLO materials with better overall
properties has been very active in recent years.
4
(
2
6
5
−17
Ga/Ge/Q (Q = S, Se, Te) system, which exhibits a second-
harmonic-generation (SHG) response at 2 μm that is
approximately half that of the benchmark material AgGaSe2
and melts congruently at the rather low temperature of 710 °C.
Detailed investigations on the growth technique and thorough
evaluation of these crystals are in process.
Among all of the requirements for a good IR NLO material,
increasing the laser-damage threshold and avoiding the two-
photon absorption problem of the conventional near-IR laser-
pumping sources are probably the two most demanding ones.
An effective way of achieving these goals is to enlarge the band
gap of the IR NLO material. The inclusion of alkali or alkaline-
earth metals in synthesizing new IR NLO materials is
conducive to increasing the band gaps of compounds. Thus,
recently, extensive research has focused on alkali- or alkaline-
earth metals containing chalcogenides with a high content of
In LiGaGe Se , the microscopic NLO-active unit is the (Ga/
2
6
Ge)Se tetrahedron. Considering that the heavier group III
4
element, In, will increase the NLO response and birefractive
index owing to the larger polarization of the electrons, we
extend our exploration to the Li/In/M/Q (M = Si, Ge; Q = S,
Se, Te) system and successfully obtained another new series of
5
−12
microscopic NLO-active units,
such as GaQ4 tetrahe-
1
8,19
dra.
The inclusion of an alkali or alkaline-earth metal will
increase the band gap, and a dense arrangement of the
microscopic NLO-active units will increase the possibility of
Received: February 19, 2012
Published: May 4, 2012
©
2012 American Chemical Society
5839
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Inorganic Chemistry
Article
Figure 1. Powder XRD patterns of Li In MQ (M = Si, Ge; Q = S, Se). The peaks marked with asterisks in Li In SiS and Li In GeS are due to very
2
2
6
2
2
6
2
2
6
small amounts of In S .
2
3
IR NLO materials with the desired optical and thermal
properties, Li In MQ (M = Si, Ge; Q = S, Se). Interestingly,
temperature by switching off the furnace. Many block-shaped crystals
with the color of light yellow were found in the ampules. The crystals
are stable in air.
2
2
6
these series of compounds possess different stoichiometries and
structures from LiGaGe Se . The two sulfides possess similar
Li In MSe (M = Si, Ge). The mixtures of LiInSe (1 mmol) and
2
2
6
2
2
6
MSe (M = Si, Ge; 0.5 mmol) were heated to 1123 K in 12 h, left for
2
NLO response as benchmark material AgGaS and larger band
2
4
8 h, cooled to 473 K at a rate of 4 K/h, and finally cooled to room
gaps than AgGaS , while the two selenides possess similar NLO
2
temperature by switching off the furnace. Many orange block-shaped
crystals were found in the ampules. The crystals are stable in air.
The block-shaped crystals were manually selected for structure
characterization and determined as Li In MQ (M = Si, Ge; Q = S,
response as benchmark material AgGaSe and larger band gaps
2
than AgGaSe . Moreover, all the four compounds in this series
2
exhibit congruent-melting behavior. In this paper, we report the
synthesis, structure, and optical and thermal physical properties
of the Li In MQ (M = Si, Ge; Q = S, Se) compounds.
2
2
6
Se). Analyses of the crystals with an energy-dispersive-X-ray (EDX)-
equipped Hitachi S-4800 scanning electron microscope showed the
presence of In, M (Si, Ge), and Q (S, Se) in the approximate ratio of
2
2
6
2
:1:6 (Li is undetectable in EDX).
Polycrystalline samples of Li In MQ
synthesized by solid-state reaction techniques. The mixtures of Li
MQ , and In (M = Si, Ge; Q = S, Se) in the molar ratio of 1:1:1
were heated to 973 K in 15 h and kept at that temperature for 72 h,
and then the furnace was turned off.
EXPERIMENTAL SECTION
■
2
2
6
(M = Si, Ge; Q = S, Se) were
Q,
Syntheses. Li was purchased from Alfa Aesar China (Tianjin) Co.,
Ltd., with a purity of 98%, while In, Si, Ge, S, and Se were purchased
from Sinopharm Chemical Reagent Co., Ltd., with purities of 4 N. All
of the above chemicals were used without further purification.
2
Q
2 3
2
The binary starting materials Li Q (Q = S, Se) were prepared by the
Powder X-ray diffraction (XRD) analyses of the resultant powder
samples were performed at room temperature in the angular range of
2θ = 10−70° with a scan step width of 0.02° and a fixed counting time
of 0.1 s/step using an automated Bruker D8 X-ray diffractometer
equipped with a diffracted monochromator set for Cu Kα (λ = 1.5418
Å) radiation. The experimental powder XRD patterns were found to
be in agreement with the calculated pattern on the basis of the single-
2
stoichiometric reactions of Li with Q (S, Se) in liquid NH at 194 K,
3
while In S , In Se , GeS , GeSe , SiS , and SiSe were synthesized by
2
3
2
3
2
2
2
2
the stoichiometric reactions of elements at high temperatures in sealed
−3
silica tubes evacuated to 10 Pa. The ternary LiInQ (Q = S, Se) were
2
synthesized by the stoichiometric reactions of the binary chalcogenides
−
3
at high temperatures in sealed silica tubes evacuated to 10 Pa.
During the crystal growth and synthesis of the polycrystalline
samples of Li In MQ (M = Si, Ge; Q = S, Se), all reactants were
crystal crystallographic data of Li
Figure 1).
In MQ (M = Si, Ge; Q = S, Se;
2 6
2
2
2
6
ground, loaded into 12-mm-i.d. fused-silica tubes under an Ar
Structure Determination. The single-crystal XRD measurements
were performed on a Bruker SMART APEX II diffractometer at
296(2) K using Mo Kα radiation (λ = 0.71073 Å) and integrated with
the SAINT program. The program XPREP was used for face-
indexed absorption corrections.
atmosphere in a glovebox, then moved to a high-vacuum line, and
−3
flame-sealed under a high vacuum of 10 Pa. The tubes were then
placed in computer-controlled furnaces and heated according to the
heating profiles detailed below.
2
0
21
Li In MS (M = Si, Ge). The mixtures of LiInS (1 mmol) and MS
M = Si, Ge; 0.5 mmol) were heated to 1173 K in 15 h, left for 48 h,
cooled to 593 K at a rate of 3 K/h, and finally cooled to room
The structure was solved with direct methods implemented in the
program SHELXS and refined with the least-squares program SHELXL
of the SHELXTL.PC suite of programs. The program STRUCTURE
2
2
6
2
2
(
2
1
5
840
dx.doi.org/10.1021/ic300373z | Inorg. Chem. 2012, 51, 5839−5843

Inorganic Chemistry
Article
22
TIDY was then employed to standardize the atomic coordinates.
Additional experimental details are given in Table 1, and selected
metrical data are given in Table 2. Further information can be found in
the Supporting Information.
with a Q-switched Ho:Tm:Cr:YAG laser. The particle sizes of the
sieved samples are 80−100 μm. Microcrystalline AgGaS and AgGaSe
2
2
of similar particle size served as references for the two sulfides and two
selenides, respectively.
RESULTS AND DISCUSSION
Structure. The four compounds Li In MQ (M = Si, Ge; Q
S, Se) are isostructural. They belong to the Cd GeS
4 6
24
Table 1. Crystal Data and Structure Refinements for
■
=
Li In MQ (M = Si, Ge; Q = S, Se)
2
2
6
2
2
6
Li In SiS
Li In GeS
Li In SiSe
Li In GeSe
6
2
2
6
2
2
6
2
2
6
2
2
structure type and crystallize in the noncentrosymmetric
space group Cc of the monoclinic system. In the asymmetric
unit, there are two crystallographically independent Li atoms,
two independent In atoms, one M (Si, Ge) atom, and six Q (S,
Se) atoms. All of the atoms are at general positions with 100%
occupancy, and there is no detectable disorder among Li, In, or
M (Si, Ge) atoms in the structure, although the possibility of
such disorder cannot be completely ruled out. Because there
are no Q−Q (Q = S, Se) bonds in the structures, the oxidation
states of 1+, 3+, 4+, and 2− can be assigned to Li, In, M (Si,
Ge), and Q (S, Se), respectively.
fw
463.97
23
508.47
23
745.37
23
789.87
23
T (°C)
a (Å)
12.0741(11)
7.0221(5)
12.0802(9)
110.060(5)
962.09(13)
Cc
12.165(2)
12.6210(4)
7.3788(3)
12.5800(4)
109.704(2)
1102.95(7)
Cc
12.7226(4)
7.4527(4)
12.6698(5)
109.826(4)
1130.12(8)
Cc
b (Å)
7.0840(14)
12.131(2)
110.26(3)
980.7(3)
Cc
c (Å)
β (deg)
V (Å3)
space group
Z
4
4
4
4
3
ρ (g/cm )
3.203
3.444
4.489
4.642
c
μ (cm−1)
6.139
8.906
24.021
25.946
The structure of Li In SiS is illustrated in Figure 2. The LiS ,
a
2
2
6
4
R(F)
0.0098
0.0215
0.0221
0.0338
InS , and SiS tetrahedra are connected to each other via
2
o
b
4
4
R (F )
w
0.0231
0.0501
0.0534
0.0791
a
2
2
b
2
2
R(F) = ∑||F | − |F ||/∑|F | for F > 2σ(F ). R (F ) = {∑[w(F
o
c
o
o
o
w
o
o
2
2
4
1/2
−1
2
2
2
−
F ) ]/∑wF } for all data. w = σ (F ) + (zP) , where P =
c
o
o
2 2
(
max(F ,0) + 2 F )/3; z = 0.01 for Li In SiS and 0.04 for the other
o
c
2
2
6
three.
Table 2. Selected Interatomic Distances (Å) for Li In MQ
2
2
6
(M = Si, Ge; Q = S, Se)
Li In SiS
Li In GeS
Li In SiSe
Li In GeSe
2 2
2
2
6
2
2
6
2
2
6
6
Li1−Q1
Li1−Q2
Li1−Q4
Li1−Q5
Li2−Q1
Li2−Q2
Li2−Q3
Li2−Q6
In1−Q1
In1−Q2
In1−Q3
In1−Q5
In2−Q1
In2−Q2
In2−Q4
In2−Q6
M−Q3
2.510(4)
2.493(4)
2.716(6)
2.513(4)
2.494(4)
2.508(5)
2.518(5)
2.566(5)
2.522(9)
2.549(9)
2.66(1)
2.64(1)
2.61(1)
2.86(2)
2.64(1)
2.63(1)
2.64(1)
2.62(1)
2.66(1)
2.66(2)
2.64(2)
2.86(3)
2.69(2)
2.66(2)
2.65(2)
2.69(2)
2.65(3)
2.584(1)
2.592(1)
2.614(1)
2.599(1)
2.591(1)
2.597(1)
2.612(1)
2.594(1)
2.323(1)
2.314(1)
2.331(1)
2.323(1)
2.522(9)
2.523(9)
2.544(9)
2.520(9)
2.548(9)
2.459(1)
2.468(1)
2.498(1)
2.471(1)
2.466(1)
2.480(1)
2.488(2)
2.467(1)
2.4564(5)
2.4630(6)
2.5032(5)
2.4750(5)
2.4685(5)
2.4733(5)
2.4918(6)
2.4708(5)
2.1072(7)
2.1040(7)
2.1199(7)
2.1166(7)
2.5776(8)
2.5843(7)
2.6194(7)
2.6014(7)
2.5892(8)
2.5931(8)
2.6097(7)
2.5931(7)
2.251(2)
2.239(2)
2.257(2)
2.255(2)
Figure 2. Unit cell of the Li In SiS structure.
2
2
6
corner-sharing to generate a three-dimensional framework. In
comparison, another compound in the quaternary Li/M/M′/Q
(
M = Si, Ge; M′ = Al, Ga, In; Q = S, Se, Te) system, namely,
LiGaGe Se , has some differences with Li In MQ (M = Si, Ge;
2
6
2
2
6
2.1801(1)
2.184(1)
2.197(1)
2.188(1)
Q = S, Se) in the structure. LiGaGe Se crystallizes in the
2
6
M−Q4
M−Q5
M−Q6
orthorhombic space group Fdd2 with the asymmetric unit
containing one crystallographically independent Li atom at the
Wyckoff position 16b with 50% occupancy, one independent
Ga atom at the Wyckoff position 8a, one independent Ge atom
at the Wyckoff position 16b, and three independent Se atoms at
Diffuse-Reflectance Spectroscopy. A Cary 1E UV−visible
spectrophotometer with a diffuse-reflectance accessory was used to
the Wyckoff position 16b, leading to LiGaGe
Se stoichiometry.
2 6
measure the spectra of Li In MQ (M = Si, Ge; Q = S, Se) over the
range 200 nm (6.2 eV) to 1800 nm (0.69 eV).
LiGaGe Se also has a three-dimensional framework built up
2
2
6
2
6
from corner-sharing LiSe , GaSe , and GeSe tetrahedra, but
4 4 4
Thermal Analysis. The thermal properties were investigated by
differential scanning calorimetry (DSC) analysis using a Labsys TG-
DTA16 (SETARAM) thermal analyzer (the calorimeter was calibrated
with Al O ). About 10 mg of each Li In MQ (M = Si, Ge; Q = S, Se)
the Li position is only half-occupied in LiGaGe Se .
2
6
Selected bond distances are listed in Table 2. For the two
sulfides, the Li−S distances range from 2.493(4) to 2.716(6) Å,
2
3
2
2
6
25
which are close to those in LiInS (2.392−2.750 Å); the In−S
2
sample was placed in sealed carbon-coated silica tubes evacuated to
−
3
distances of 2.4564(5)−2.5032(5) Å are comparable to the In−
10
Pa. The heating and cooling rates were 20 K/min.
26
S distances of 2.392−2.500 Å in Ba In S ; the Si−S distances
SHG Measurement. Optical SHG tests of Li In MQ (M = Si, Ge;
2
2 5
2
2
6
Q = S, Se) were performed on the powder samples by means of the
of 2.1040(7)−2.1199(7) Å are close to those in KBiSiS
4
23
27
Kurtz−Perry method. Fundamental 2090 nm light was generated
[2.094(1)−2.155(2) Å)];
the Ge−S distances of
5
841
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Inorganic Chemistry
Article
2
2
.1801(1)−2.197(1) Å are comparable to those of 2.180(2)−
2.54(2), and 2.30(2) eV, and consequently the absorption
edges are 343, 360, 490, and 540 nm for Li In SiS , Li In GeS ,
2
7
.239(2) Å in KBiGeS
and 2.208(1)−2.265(1) Å in
4
2
2
6
2
2
6
2
8
AgGaGeS4. As for the two selenides, the Li−Se distances of
Li In SiSe , and Li In GeSe , respectively, as deduced by a
2 2 6 2 2 6
32
2
2
.61(1)−2.86(3) Å are in good agreement with those of
straightforward extrapolation method. The band gaps of the
5
.64(3)−2.83(3) Å in LiGaGe Se ; the In−Se distances range
two sulfides are significantly larger than that of AgGaS (2.64
2
6
2
from 2.5776(8) to 2.6194(7) Å, which resemble those of 2.569
eV), while those of the two selenides are also obviously larger
2
9
Å in LiInSe2; the Si−Se distances of 2.239(2)−2.257(2) Å are
than that of AgGaSe (1.8 eV). Owing to this large band gap,
2
30
comparable to those of 2.224−2.328 Å in Ag In SiSe ; the
the Li In MQ (M = Si, Ge; Q = S, Se) compounds may
2
2
6
2
2
6
Ge−Se distances range from 2.314(1) to 2.331(1) Å, which are
in good agreement with those in Ag In GeSe (2.313−2.336
possess high laser-induced damage thresholds. Moreover, the
pumping sources can be conventional near-IR laser pumping
(Nd:YAG or Yb:YAG) or even the 800 nm Ti:sapphire laser
without two-photon absorption problems, as in the case of
2
2
6
3
1
Å).
Experimental Band Gaps. On the basis of the UV−
33
visible−near-IR diffuse-reflectance spectra of Li In MQ (M =
Si, Ge; Q = S, Se; Figure 3), the band gaps are 3.61(2), 3.45(2),
LiInS2.
Thermal Analysis. The DSC curves of Li In MQ (M = Si,
2
2
6
2
2
6
Ge; Q = S, Se) are shown in Figure 4. It shows that Li In MQ
2
2
6
(
M = Si, Ge; Q = S, Se) compounds melt congruently, with the
melting points being 858 °C, 780 °C, 801 °C, and 722 °C for
Li In SiS , Li In GeS , Li In SiSe , and Li In GeSe , respec-
2
2
6
2
2
6
2
2
6
2
2
6
tively. Owing to the congruent-melting behavior, bulk crystals
needed for thorough evaluation and practical application can be
grown by the Bridgman−Stockbarger technique. These melting
points are lower than those of traditional IR NLO materials
(
1025 °C for ZnGeP , 998 °C for AgGaS , and 860 °C for
2
2
AgGaSe ). The rather low melting points of Li In MQ (M =
2
2
2
6
Si, Ge; Q = S, Se) will favor crystal growth by the Bridgman−
Stockbarger technique.
SHG Measurement. With the use of a laser with 2090 nm
as the fundamental wavelength and with similar particle size,
the SHG signal intensities of the two sulfides were close to that
of AgGaS and those for the two selenides were similar to that
2
of AgGaSe , which indicate that the NLO responses of
2
Figure 3. Diffuse-reflectance spectra of Li In MQ (M = Si, Ge; Q = S,
Se).
Li In MQ (M = Si, Ge; Q = S, Se) compounds are sufficient
2
2
6
2
2
6
for application in IR nonlinear optics.
Figure 4. DSC curves of Li In MQ (M = Si, Ge; Q = S, Se).
2
2
6
5
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Article
(
14) Liao, J.-H.; Marking, G. M.; Hsu, K. F.; Matsushita, Y.; Ewbank,
CONCLUSION
A new series of IR NLO material Li In MQ (M = Si, Ge; Q =
S, Se) have been synthesized for the first time. They adopt the
■
M. D.; Borwick, R.; Cunningham, P.; Rosker, M. J.; Kanatzidis, M. G. J.
Am. Chem. Soc. 2003, 125, 9484−9493.
(
2
2
6
15) Guo, S. P.; Guo, G. C.; Wang, M. S.; Zou, J. P.; Xu, G.; Wang,
Cd GeS structure type and crystallize in the noncentrosym-
4
6
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metric space group Cc. The LiQ , InQ , and MQ (M = Si, Ge;
Q = S, Se) tetrahedra are connected to each other by corner-
sharing to generate a three-dimensional framework. Li In MQ
6
M = Si, Ge; Q = S, Se) exhibit SHG responses at 2 μm that are
approximately close to those of benchmark AgGaQ (Q = S,
4
4
4
2
2
(
(
18) Bai, L.; Lin, Z.; Wang, Z.; Chen, C.; Lee, M. H. J. Chem. Phys.
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(22) Gelato, L. M.; Parthe,
2
2
(
0
(
Se). Their large band gaps will be very beneficial to increase the
laser-damage threshold and avoid the two-photon absorption of
the conventional 1 μm (Nd:YAG) or 1.55 μm (Yb:YAG) laser
pumping. Moreover, the valuable property of congruent-
melting behavior for all of the four compounds makes it
feasible to grow bulk crystals needed for thorough evaluation
and practical application by the Bridgman−Stockbarger
method. Our preliminary experimental results indicated that
Li In MQ are promising IR NLO materials for practical
(
́
E. J. Appl. Crystallogr. 1987, 20, 139−143.
(23) Kurtz, S. K.; Perry, T. T. J. Appl. Phys. 1968, 39, 3798−3813.
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966−1968.
1
(
2
2
6
25) Kish, Z. Z.; Kanishcheva, A. S.; Mikhailov, Yu. N.; Lazarev, V. B.;
application. Further research is in progress.
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(
ASSOCIATED CONTENT
Supporting Information
Crystallographic file in CIF format for Li In MQ (M = Si, Ge;
■
*
S
1
51−159.
2
2
6
(27) Mei, D.; Lin, Z.; Bai, L.; Yao, J.; Fu, P.; Wu, Y. J. Solid State
Q = S, Se). This material is available free of charge via the
Internet at http://pubs.acs.org.
Chem. 2010, 183, 1640−1644.
(28) Pobedimskaia, E. A.; Alimova, L. L.; Belov, N. V.; Badikov, V. V.
Dokl. Akad. Nauk SSSR 1981, 257, 611−614.
(
29) Beister, H. J.; Ves, S.; Ho
Rev. B 1991, 43, 9635−9642.
30) Olekseyuk, I. D.; Sachanyuk, V. P.; Parasyuk, O. V. J. Alloys
̈
̈
nle, W.; Syassen, K.; Kuhn, G. Phys.
AUTHOR INFORMATION
Corresponding Author
E-mail: jyao@mail.ipc.ac.cn.
■
(
*
Compd. 2006, 414, 73−77.
(31) Krykhovets, O. V.; Sysa, L. V.; Olekseyuk, I. D.; Glowyak, T. J.
Alloys Compd. 1999, 287, 181−184.
Notes
The authors declare no competing financial interest.
(
32) Schevciw, O.; White, W. B. Mater. Res. Bull. 1983, 18, 1059−
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ACKNOWLEDGMENTS
■
(
This research was supported by the National Basic Research
Project of China (Grant 2010CB630701), National Natural
Science Foundation of China (Grant 51072203), and the
Scientific Research Foundation for the Returned Overseas
Chinese Scholars, State Education Ministry.
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