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ARTICLE

Infrared Nonlinear Optical Properties of Lithium-containing

Dalton Transactions Accepted Manuscript


Diamond-like Semiconductors Li2ZnGeSe4 and Li2ZnSnSe4
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a b a a
Jian-Han Zhang, Daniel J. Clark, Jacilynn A. Brant, Charles W. Sinagra III, Yong Soo
Received 00th January 20xx, b,c b a
Kim, Joon I. Jang and Jennifer A. Aitken
Accepted 00th January 20xx
Two new lithium-containing diamond-like semiconductors, Li 2 ZnGeSe4 and Li 2ZnSnSe4 , have
DOI: 10.1039/x0xx00000x been prepared by high-temperature, solid-state synthesis. Single crystal X-ray diffraction
www.rsc.org/ reveals that both compounds adopt the wurtz-kesterite structure type, crystallizing in the
noncentrosymmetric space group Pn. X-ray powder diffraction coupled with Rietveld
refinement indicates the high degree of phase purity in which the materials are prepared.
Both compounds display optical bandgaps around 1.8 eV, wide optical transparency windows
from 0.7 to 25 μm and type-I phase matched second harmonic generation (SHG) starting at
2500 nm and persisting deeper into the infrared. Using the Kurtz powder method, the second-
(2)
order nonlinear optical coefficient, χ , was estimated to be 19 and 23 pm/V, for Li 2 ZnGeSe4
and Li 2ZnSnSe4 respectively. Using a 1064 nm incident laser beam with a pulse width (τ) of 30
2
ps both compounds exhibit a laser damage threshold of 0.3 GW/cm , which is higher than
that of the AgGaSe 2 reference material measured under identical conditions. Differential
thermal analysis shows that the title compounds are stable up to 684 and 736 °C, respectively.
These properties collectively demonstrate that Li 2 ZnGeSe4 and Li 2 ZnSnSe4 have great potential
for applications in tunable laser systems, especially in the infrared and even up to the
terahertz regime. Electronic structure calculations using a plane-wave pseudopotential
method within density functional theory provide insight regarding the nature of the bandgap
and bonding.

Introduction On the other hand, chalcogenide semiconductors are more


Nonlinear optical (NLO) materials are used to shift the promising in the IR region because of their relatively wide
coherent monochromatic light of lasers to other desirable optical transparency windows and large SHG coefficients. The
wavelengths for applications in the military, medical, large majority of commercially available IR NLO crystals such as
2 3
commercial and industrial sectors. In the past decades, AgGaS2 and AgGaSe2 belong to the I-III-VI2 family of diamond-
significant advances have been made in the discovery of new like semiconductors (DLSs). Unfortunately, each of these
and useful NLO crystals for the visible and ultraviolet regions, benchmark materials suffers from drawbacks such as difficultly
1
such as β-BaB2O4, LiB3O5, KH2PO4 and KTiOPO4. However, in crystal growth as well as low laser damage thresholds (LDTs)
4
these crystals, which have relatively low second harmonic and multiphoton effects that greatly limit practical use.
generation (SHG) efficiencies, are not suitable in the infrared Considering the important applications of IR NLO materials,
5
(IR) region mainly because of inadequate optical transparency. such as target acquisition, IR countermeasure systems, stand-
6
off detection of drugs and explosives, noninvasive medical
7
monitoring and diagnosis of diseases such as cystic fibrosis
a. 8
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA and high-precision laser surgery, the exploration and
152282, USA.
b.
Department of Physics, Applied Physics and Astronomy, Binghamton University, development of new IR NLO materials are of broad scientific
c.
Binghamton, NY 13902 USA. and technological importance.
Department of Physics and Energy Harvest-Storage Research Center, University of
Ulsan, 680-749 South Korea.
In order for a material to exhibit second-order optical
†Electronic Supplementary Information (ESI) available: X-ray crystallographic files nonlinearity, the crystal structure must be
in CIF format; atomic coordinates and equivalent isotropic displacement noncentrosymmetric (NCS). Recently, the strategy of targeting
parameters; important bond lengths and angles; bond orders and bond valences;
unit cell parameters from XRPD with Rietveld refinement; state energies of the LCB acentric building units for the assembly of NCS materials has
and HVB; calculated bond valence and bond order; anionic framework structure given rise to many successful discoveries of interesting IR NLO
figure; simulated, as-synthesized, and after DTA XRPD patterns; SHG particle-size (2)
dependence phase matching ability with various wavelengths. CSD reference
materials. For example, Ba7Sn5S15 has a deff of 19.5 pm/V (χ
9
numbers 424284-424288. =39 pm/V) and is phase matchable (PM) at 2.05 μm. Further,

This journal is © The Royal Society of Chemistry 2015 Dalton Tran., 2015, 00, 1-3 | 1
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ARTICLE Journal Name
DOI: 10.1039/C5DT01635E

the congruent melters, BaGa2GeS6 and BaGa2GeSe6, exhibit


PM SHG responses at 2.05 μm with deff values of 26.3 and 43.7
(2) 10
pm/V (χ =52.6 and 87.4 pm/V), respectively. Ba8Sn4S15
shows a strong second-order NLO response and a high LDT of
2 11
122.1 MW/cm (λ=1064 nm; τ=8 ns), and Li2Ga2GeS6 features
12
a larger LDT in comparison to Ba2SbGeS10. However, the
approach of targeting acentric building units is often inhibited
by centrosymmetric contenders and presents limited
opportunities for systematic investigations of structure-

Dalton Transactions Accepted Manuscript


property and composition-property relationships.
Our methodology, which provides an avenue for systematic
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investigations, is to target DLSs. The formulae of all quaternary


DLSs, for example I2-II-IV-VI4, can be easily predicted using
13
valence electron rules and Pauling’s rules. The ions chosen to Figure 1. Optical images of Li2ZnGeSe4 and Li2ZnSnSe4. The
reside in these compounds must adopt tetrahedral geometry. crystal sizes are in the range of 0.1-0.5 mm.
Based on either a cubic or hexagonal closest packed array of
anions, the structures are inherently NCS with all tetrahedra were then placed into a programmable furnace and heated to 190
pointing in a single direction. The highly polar structures and °C in 2 hours, held at 190 °C for 10 h, and then heated up to 700 °C
significant degree of covalent bonding in these materials lead in 5 hours, held at 700 °C for 100 hour and slowly cooled to 350 °C
to sizable SHG responses. Our approach to target quaternary in 100 h. The samples were then radiatively cooled to room
DLSs, a logical progression from the benchmark I-III-VI2 ternary temperature by switching off the furnace. The reaction vessels were
DLSs, increases the diversity of elements employed and opened under ambient conditions. As observed using an optical
provides greater opportunities for the deliberate modification microscope, Li2ZnGeSe4 was prepared as orange-red rod-like
of physical properties. We have previously reported strong polycrystals and Li2ZnSnSe4 was obtained as orange-red irregular
second-order optical nonlinearity for Cu2CdSnS4, α/β- polyhedral-shaped crystals (Figure 1). The optical images of both
14 15 16
Cu2ZnSiS4, Li2CdGeS4 and Li2MnGeS4 with the latter two samples were taken directly under the optical microscope using a
2
compounds exhibiting exceptional LDTs, ~5 GW/cm with digital camera. Both materials are air-stable.
2
saturable absorption and 16 GW/cm , respectively. Here we
report the synthesis, crystal structures and physicochemical Single crystal structure determination
characterization of two new lithium-containing quaternary
DLSs, Li2ZnGeSe4 and Li2ZnSnSe4, with LDTs higher than that of Single crystal X-ray diffraction data were collected using a Bruker
AgGaSe2. These new compounds show type-I PM SHG and SMART Apex 2 CCD single crystal X-ray diffractometer employing
excellent optical transparency over a wide range of graphite monochromatized Mo-Kα radiation (λ = 0.71073 Å) and
wavelengths, far into the IR region. operating with a tube power of 50 kV and 30 mA. Data were
collected for 40 s/frame at room temperature. The program
17 18
SAINT was used to integrate the data and SADABS was
Experimental section employed to perform the multiscan-type absorption correction.
Reagents Based on the systematic absences, two space groups were
considered, Pn and P2/n; however, all DLSs possess NCS structures
All of the chemicals were of analytical purity from commercial due to the alignment of all tetrahedra along one crystallographic
sources and used without further purification: (1) lithium direction; therefore, Pn was selected. The structures of Li2ZnGeSe4
metal (rod, 99.9%, Sigma-Aldrich); (2) zinc powder (99.9%, and Li2ZnSnSe4 were solved by direct methods and refined by the
Cerac); (3) germanium pieces (99.999%, Strem) were ground 2
full-matrix least-squares fitting on F by SHELX-97.
19
Atomic
by a diamonite mortar and pestle into a powder prior to use; displacement parameters of all atoms were anisotropically refined
(4) tin powder (99.99%, Cerac); and (5) selenium powder except for Li(1) and Li(2) in Li2ZnGeSe4 which were refined
(99.99%, Strem). isotropically. The Flack parameter of 0.15(6) for
Li2ZnGeSe4 indicates the existence of a small extent of racemic
Synthesis of Li2ZnGeSe4 and Li2ZnSnSe4 twinning for the crystal. The Flack parameter of 0.073(9) for
Li2ZnGeSe4 and Li2ZnSnSe4 were prepared via traditional high- Li2ZnSnSe4 is close to zero, which indicates that the absolute
temperature, solid-state reactions. The starting materials were structure is correct. Both structures were checked for additional
20
weighed in stoichiometric amounts of Li (0.0138 g), Zn (0.0654 g), symmetry using PLATON. Crystallographic data and structural
Ge (0.0726g) and Se (0.3156 g) for Li2ZnGeSe4 and Li (0.0132 g), Zn refinements for both compounds are summarized in Table 1.
(0.0628 g), Sn (0.1140g) and Se (0.3030 g) for Li2ZnSnSe4 in an Atomic coordinates and equivalent isotropic displacement
argon-filled glove box. The reactants were placed into graphite parameters are listed in Table S1. Selected bond distances and
tubes inside 12 mm o.d. fused-silica tubes. The tubes were sealed angles are listed in Table S2.
–3
under a pressure of approximately 10 mbar. The sealed tubes

2 | Dalton Trans.., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
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22
interface. The crystal structures of Li2ZnGeSe4 and Li2ZnSnSe4
Table 1. Crystallographic data and structure refinement details
obtained from the single crystal X-ray data sets were used as
for Li2ZnGeSe4 and Li2ZnSnSe4.
starting structure models. The backgrounds were fitted with a
23
shifted Chebyschev polynomial, and the peak shapes were
Formula Li2ZnGeSe4 Li2ZnSnSe4
modelled using Lorentzian terms, the Lorentzian isotropic
Formula weight 467.68 513.78 crystallite size broadening (LX) and Lorentizian isotropic strain
broadening (LY), within the type-3 profile function. Lattice
Space group Pn Pn
parameters, atomic coordinates and isotropic displacement
a (Å) 6.5515(1) 6.6848(1) parameters were also refined.

Dalton Transactions Accepted Manuscript


b (Å) 6.8589(1) 7.0303(1) Scanning electron microscopy and energy dispersive spectroscopy
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c (Å) 8.2427(1) 8.3234(1) (SEM/EDS)


Energy dispersive spectroscopy (EDS) was performed on a Hitachi S-
β (deg) 90.063(1) 90.050(1)
3400N scanning electron microscope (SEM) equipped with a Bruker
3
V (Å ) 370.394(9) 391.168(9) Quantax model 400 EDS using an XFlash® 5010 EDS detector with a
129 eV resolution. Data were collected at a working distance of
Z 2 2
10 mm and an accelerating voltage of 15 kV for 5 min live time.
-3
dc (g·cm ) 4.193 4.362
-1
Differential thermal analysis (DTA)
µ(Mo Kα) (mm ) 26.828 24.754
Differential thermal analysis (DTA) data were collected using a
F(000) 408 444 Shimatzu DTA-50 differential thermal analyzer. Data were recorded
Reflections collected / using the TA60-WS collection program. Calibration of the
unique 4672 / 1601 5006 / 1706 instrument was performed using a three-point calibration curve
Completeness to θ = based on the melting points of indium, zinc and gold metals.
27.14 99.6 % 99.8 % Approximately 10 mg of each sample was sealed in a carbon-
2 coated, fused-silica ampoule and flame-sealed under a vacuum of
GOF on F 1.149 0.901 -3
~10 mbar. The sample and the reference material, Al2O3, of
Flack factor 0.15(6) 0.073(9) comparable mass were heated at a rate of 10 °C /min from 25 °C to
0.0328, 0.0138, 1000 °C under a constant flow of nitrogen gas, held at the high
a
R1,wR2 [I>2σ(I)] 0.0802 0.0335 temperature for 1 min and cooled at a rate of 10 °C/min to 100 °C.
0.0335, 0.0139, The running of a second cycle resulted in severe attack of the fused-
a
R1, wR2 (all data) 0.0805 0.0336 silica ampoule and therefore only one cycle of data is reported
1.192, 0.499, here.
3
Peak and hole(e/A ) -1.196 -0.496
a UV-vis-NIR and FT-IR spectroscopy
R1 = ∑||Fo| -|Fc||/∑|Fo|,
2 2 2 2 2 1/2 The optical diffuse reflectance spectra of polycrystalline powder
wR2 = {∑w[(Fo) -(Fc) ] /∑w[(Fo) ] }
samples were measured at room temperature using a Varian Cary
5000 UV-vis-NIR spectrometer equipped with a Harrick Praying
X-ray powder diffraction (XRPD) and Rietveld refinement Mantis diffuse reflectance accessory. The samples were ground and
X-ray powder diffraction (XRPD) data were collected on a placed into a sample holder. Barium sulfate was used as a 100%
PANalytical X’Pert Pro MPD X-ray powder diffractometer using Cu- reflectance standard in the range of 0.19-2.5 μm. The measurement
–1
Kα radiation (λ = 1.541871 Å) and operating with a tube power of 45 was conducted at a scan rate of 600 nm·min . The absorption
kV and 40 mA. Data were collected from 5° to 145° 2θ with a step spectra were calculated from the reflectance spectra via the
size of 0.0083556° and scan rate of 0.010644°/s. The incident beam Kubelka−Munk equaaon.
optics were comprised of a 0.02 rad soller slit, a 1/4° divergent slit The IR data were measured by a Nicolet 380 FT-IR
and a 1/2° anti-scatter slit; whereas, the diffracted beam optics spectrophotometer equipped with an attenuated total reflectance
included a 0.02 rad soller slit, a 1/4° anti-scatter slit and a nickel (ATR) accessory. The IR spectra, comprised of 64 scans, were
-1 -1
filter. The samples were prepared for data collection by grinding collected over the range of 400 cm to 4000 cm . The OMNIC
with an agate mortar and pestle for twenty minutes, and then software was used for data collection and analysis. The instrument
placed into a backfilled sample holder. Phase identification was uses a diamond crystal in optical contact with the sample resulting
21
carried out using the X’Pert HighScore Plus software package in a sample penetration depth of ~2 μm, which is near the lower
along with the International Centre for Diffraction Data (ICDD) limit of the particle sizes for the studied samples. Therefore, the
powder diffraction file database. effect of thickness on the intensity of the measured spectra is
24
Rietveld refinements using the collected XRPD data were negligible.
carried out using the GSAS software package with the EXPGUI

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Second-order nonlinear optical (NLO) property measurements


Polycrystalline Li2ZnGeSe4 and Li2ZnSnSe4 were prepared for SHG
measurements by sieving into discrete particle size ranges of ~2–20
µm, 20–45 µm, 45–63 µm, 63–75 µm, 75–90 µm, 90–106 µm, 106–
125 µm and 125–150 µm to examine the PM behaviour. The
specific particle sizes were enclosed in quartz capillary tubes. All
capillary tubes were flame sealed to prevent exposure to air and
moisture during measurements. Each tube was loaded into a
homemade sample holder that was mounted on a Z-scan

Dalton Transactions Accepted Manuscript


translation stage. SHG data were collected as a function of particle
size using fundamental wavelengths from λ = 2100 – 3100 nm in
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steps of 200 nm in order to determine the onset wavelength of


phase matchability for the title compounds.
Broadband SHG experiments were conducted at room
temperature for the largest particle size range. The incident
wavelength was tuned from 1100-3700 nm in steps of 200 nm with Figure 2. Lonsdaleite structure (left) and the wurtz-kesterite
an input pulse energy of 15 μJ. The corresponding SHG range is λSHG structure of the new quaternary DLSs Li2Zn-IV-Se4, where IV is
= 550 – 1850 nm. The relative SHG signals, spectrally resolved in a Ge or Sn (right).
broad wavelength range, were precisely calibrated with the known
and measured efficiencies of all optical components. The SHG code. All calculations were performed using the structures of
efficiencies of the samples were compared to that of a ground Li2ZnGeSe4 and Li2ZnSnSe4 that were obtained from the room-
commercially-obtained, optical-quality single crystal of the temperature single-crystal X-ray diffraction data collections as
benchmark NLO material, AgGaSe2 (66 pm/V). The   values were reported herein, without volume or geometry optimization.
estimated using SHG responses in the long-wavelength range of λ =
3300 – 3700 nm where both of the compounds and the reference Results and discussion
are PM and the SHG responses becomes essentially static.
Additional details regarding the instrument setup can be found Single crystal structures
15
elsewhere.
LDTs were estimated for both compounds by measuring Li2ZnGeSe4 and Li2ZnSnSe4 crystallize in the monoclinic polar space
SHG responses using an incident laser with λ = 1064 nm and a group Pn with the wurtz-kesterite structure that can be considered
pulse width, τ, of 30 ps. The SHG response was measured as as a superstructure of lonsdaleite, the rare hexagonal diamond
28
the input laser intensity was varied over two orders of (Figure 2). The most common structure-type for quaternary DLSs
magnitude. It was confirmed that the thermal load on the derived from hexagonal diamond is the wurtzite-stannite (Pmn21)
samples by the laser pulses tuned below the bandgap was structure; however, the number of quaternary DLSs with the wurtz-
negligible due to its slow repetition rate of 50 Hz. kesterite structure has recently expanded. Thus far, Li2MnGeS4,
Li2CoSnS4, Li2ZnSnS4, Ag2ZnSiS4, Ag2FeSiS4, Li2FeGeS4, Li2FeSnS4, β-
Electronic structure calculations Cu2ZnSiS4 and Li2CoGeS4 have been reported with the wurtz-
16, 29
kesterite structure. Since the two title compounds are
Electronic band structure and density of states (DOS)
isostructural, only the structure of Li2ZnSnSe4 will be discussed in
calculations for Li2ZnGeSe4 and Li2ZnSnSe4 were performed
detail.
with the total-energy code CASTEP, which uses density
functional theory and the plane wave pseudopotential method
25
to solve the one-electron Kohn-Sham equations The Perdew-
Burke-Ernzerhof generalized gradient approximation (PBE-
26
GGA) was used to treat the exchange and correlation effects.
The interactions between the ionic cores and the electrons
27
were described by the norm-conserving pseudopotential.
The following orbital electrons were treated as valence
1 10 6 2 2 2 2 2
electrons: Li-2s , Zn-3d 3p 4s , Ge-4s 4p , Sn-5s 5p and Se-
2 4
4s 4p . The number of plane waves included in the basis set
was determined by a cutoff energy of 600 eV, and the
numerical integration of the Brillouin zone was performed Figure 3. (a) A representative Oak Ridge thermal ellipsoid plot
using a 4×4×3 Monkhorst-Pack k-point sampling for both (ORTEP) of the Se(1) anion coordination environment. The
compounds. The distance cut-off for Mulliken bond population thermal ellipsoids are drawn at 50% probability. (b) 3D
analysis was set as 3.5 Å. The other calculating parameters and tetrahedra view of Li2ZnSnSe4 with an ABAB cation ordering
convergence criteria were the default values of the CASTEP along a-axis.

4 | Dalton Trans.., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
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The asymmetric unit of Li2ZnSnSe4 consists of eight


crystallographically independent atoms, one Zn, one Ge, two Li and
four Se atoms, all of which are tetrahedrally coordinated and reside
on general positions. As expected, Pauling’s electrostatic valency
13c 2+
principle is satisfied, as each Se anion is coordinated by one Zn ,
4+ +
one Sn and two Li cations, resulting in local charge neutrality
(Figure 3a). All of the metal-selenium bond distances and angles are
30 , 31
consistent with those observed in other DLSs. Each ZnSe4
tetrahedron is connected to four SnSe4 tetrahedra by corner-

Dalton Transactions Accepted Manuscript


sharing, whereas each SnSe4 unit is also connected to four ZnSe4
tetrahedra. The strict alternation of ZnS4 and SnS4 tetrahedra lead
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2-
to a 3D honeycomb anionic [ZnSnS4] network with Li cations
balancing the charge (Figure S1). The bond valence sum (BVS)
calculations give values of 1.08 and 1.14 for Li(1) and Li(2), 1.88 for
Zn(1) and 4.08 for Sn(1), which are consistent with the expected
32
valence states (table S5). Although the metrics of the unit cell
appear to be close to those of an orthorhombic structure, the
structure of the title compounds cannot be described by mmm
symmetry. The lower symmetry of the monoclinic structure, in
comparison to an orthorhombic structure such as wurtz-stannite
type, does not arise from lattice distortions, but rather from the
cation ordering arrangement.

Figure 5. UV–vis–NIR and FT-IR spectra of Li2ZnGeSe4 and


Li2ZnSnSe4. The red area denotes the important atmospheric
windows in mid-IR and far-IR regions for NLO application.
From the tetrahedral packing of Li2ZnSnSe4 viewed down
the b-axis (Figure 3b), one can see that the 3D structure is
composed a 2D stacking in an ABAB mode along the a-axis.
The A and B layers contain the same composition of LiSe4
(green), LiSe4 (green), SnSe4 (red) and ZnSe4 (blue) tetrahedra
from left to right, but with a 4.15(2) Å shift along the c-axis.
The alignment of the cations in the Li2ZnSnSe4 structure along
a single direction, the a-axis (Figure 3b), allows polarizations
associated with asymmetric tetrahedra to be constructive,
thus producing the large macroscopic dipole moment that is
favorable for a large SHG response.

X-ray powder diffraction (XRPD) and Rietveld refinement

XRPD of polycrystalline samples of Li2ZnGeSe4 and Li2ZnSnSe4 in


conjunction with Rietveld refinements allowed the structures, as
determined by single crystal X-ray diffraction, to be confirmed and
the phase purity to be assessed. The results are shown in Figure 4.
All diffraction peaks were indexed to the wurtz-kesterite (Pn)
structures. No additional structural models were added to the
refinements. The results of Rietveld refinements yielded excellent
2
refinement statistics, Rp = 0.0700, wRp = 0.1009, χ = 2.396 for
2
Li2ZnGeSe4 and Rp = 0.0576, wRp = 0.0809, χ = 3.398 for Li2ZnSnSe4,
which show that both of samples have been prepared with high
phase purity. The unit cell parameters attained from Rietveld
Figure 4. Rietveld refinement results for Li2ZnGeSe4 and refinements, which are listed in Table S3, are in good agreement
Li2ZnSnSe4 using XRPD data. with those obtained from single crystal X-ray diffraction.

This journal is © The Royal Society of Chemistry 2015 Dalton Trans., 2015, 00, 1-3 | 5
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ARTICLE Journal Name
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for Li2ZnGeSe4 is best fit using Tauc’s function for a direct


bandgap; therefore Li2ZnGeS4 is assigned a direct bandgap of
1.86 eV (667 nm). On the other hand Li2ZnSnSe4 is determined
to be an indirect bandgap semiconductor with Eg = 1.87 eV
(664 nm). These bandgaps agree well with the orange-red
colour of the compounds. Interestingly the bandgaps of these
new materials lie in the optimal range (1.8-2.0 eV) for use as
radiation detectors. Samples of Li2ZnGeSe4 and Li2ZnSnSe4
6
prepared using the enriched Li isotope could exhibit neutron

Dalton Transactions Accepted Manuscript


detection capabilities since lithium-6 is one of the few isotopes
35
with a high neutron capture cross-section.
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Differential thermal analysis (DTA)

DTA diagrams of both Li2ZnGeSe4 and Li2ZnSnSe4 were found


to have only one endothermic peak during heating and one
exothermic peak during cooling. As shown in Figure 7, upon
heating the endothermic peak for Li2ZnGeSe4 appears at
684 °C and upon cooling the exothermic peak occurs at 677 °C,
whereas the endothermic and exothermic peaks for Li2ZnSnSe4
arise at 736 °C and 716 °C, respectively. These events were
identified as the melting and recrystallization points,

Figure 6. Optical diffuse reflectance spectra converted to


absorption using the Kubelka-Munk equation for Li2ZnGeSe4 and
Li2ZnSnSe4 on both linear and log scales. The Urbach tail region
was identified from the log scale plot and the data at energies
above the Urbach tail were used to determine the bandgap. The
data for Li2ZnGeSe4 were best fit using Tauc’s function for
direct-gap semiconductors, while the data for Li2ZnSnSe4 were
better fit using the function for indirect-gap semiconductors.

FT-IR and UV-vis-NIR spectroscopy

The IR and UV-vis-NIR spectra of Li2ZnGeSe4 and Li2ZnGeSe4


indicate a broad transparency region of 0.7–25 μm for both
samples with high transmittance. These data suggest that high-
quality single crystals of these materials could potentially have
wider transparency windows than the typical clarity windows
of commercial AgGaS2 (0.53–12 μm), AgGaSe2 (0.9–16 μm) and
33
ZnGeP2 (0.64–12 μm). For the important atmospheric
transparency windows in the mid-IR (3−5 μm) and far IR
(8−14μm) regions, which are marked as red in Figure 5, both
compounds exhibit high transparency above 65%.
The UV-vis-NIR optical diffuse reflectance spectral data of both
materials are shown in Figure 6. The linear region in the log of
the absorption as a function of energy was used to fit the
Urbach tail and the nature of the bandgaps were determined Figure 7. Differential thermal analysis (DTA) curves of
by fitting both functions for direct and indirect bandgaps to Li2ZnGeSe4 and Li2ZnSnSe4. The black and red lines indicate the
34 heating and cooling, respectively.
the data at energies above the Urbach tail region. The data

6 | Dalton Trans.., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
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respectively. The XRPD patterns for the materials before and to the far-IR or even terahertz (THz) region, as evidenced by its
after DTA were compared to assess the reversibility of the relatively static behavior. This feature gives appeal to these
thermal events (Figure S2). It is observed that the diffraction materials for applications that require relatively long-wavelength
patterns of the DTA residues indicate that the major phase is generation.
still Li2ZnGeSe4 and Li2ZnSnSe4; however, there exist additional
peaks, some of which can be indexed to ZnSe, indicating a Second harmonic generation (SHG). Based on the fact that
partial decomposition. Li2ZnGeSe4 and Li2ZnSnSe4 are PM, the broadband SHG responses
were probed using the largest particle size,   125 –150 μm, with
Nonlinear optical (NLO) properties incident λ = 1100 – 3700 nm. Figure 8 shows the broadband SHG

Dalton Transactions Accepted Manuscript


response of Li2ZnGeSe4 and Li2ZnSnSe4 as well as that of a
15a
The naturally polar crystal structures of DLSs, in this case homemade microcrystalline sample of AgGaSe2 (MC), which was
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(2)
crystallizing in the Pn space group, prompted us to investigate the prepared by high-temperature, solid-state synthesis. Using the χ
value of 66 pm/V for AgGaSe2,3 the   values of both samples
b
macroscopic NLO properties of Li2ZnGeSe4 and Li2ZnSnSe4. To be
specific, the PM ability, second-order NLO coefficient, and LDT were were estimated in the wavelength range of λ = 3300 – 3700 nm,
determined. where both compounds and the reference are PM and the SHG
responses becomes essentially static. Using the Kurtz powder
39 (2)
Phase matchability. Phase matchability is one of the most critical method, the χ of these compounds can be calculated by
36
factors for the discovery of next-generation NLO materials. Our comparison with the reference for the PM case;
/
choice to pursue quaternary DLSs toward this goal has been quite  
 2 
   , 1
successful, considering that many of the DLSs that we have
 2 
where
 2  and
 2  are the SHG intensities of the sample and
14-16,37
investigated thus far clearly show PM behaviours except for
16
some Fe-containing compounds in which the response was reference, respectively. “Dips” in the SHG response common to all
seriously masked by absorption effects within our monitoring plots at λSHG = 1050 nm are due to linear absorption of the
range. Still, those compounds have good mid-IR/THz transparency, fundamental beam by the capillary tubes, but this does not affect
(2) (2)
implicating potential importance at longer wavelengths. In this the estimation of χ . The χ values of Li2ZnGeSe4 and Li2ZnSnSe4
work, the particle size dependence of the SHG responses were used were estimated to be 43.1 and 52.1 pm/V, respectively. While these
to determine the wavelengths at which Li2ZnGeSe4 and Li2ZnSnSe4 values are lower than that of AgGaSe2, they are higher than that of
are PM. A positive trend in the SHG response as a function of AgGaS2 and considerably exceed the values reported for the
40
increasing particle size indicates that a material is type-I PM at the commercially-available, lithium-containing DLSs such as LiInS2 and
40a,41
applied wavelength, while a decrease in the SHG intensity with LiInSe2 . Nevertheless, it should be noted that AgGaSe2 (MC)
increasing particle size is a characteristic of non-PM (type-I) exhibits a lower SHG response in comparison to AgGaSe2 (OQ), an
38
materials. As shown in Fig. S5, both Li2ZnGeSe4 and Li2ZnSnSe4 are optical quality AgGaSe2 reference that was obtained from a
type-I PM with an onset wavelength around 2500 nm in the IR commercial supplier and ground to a powder. The difference
region, and the phase matchability of both materials likely extends between the MC and OQ samples likely arises from crystal defects
(e.g., antisites, vacancies) within the powder that are minimized or
not present in the single crystal. Yet, an improvement in SHG
response may not always be observed when comparing a
microcrystalline sample to an optical quality single crystal.
(2)
Accordingly, we have assigned the upper limit of the χ in
comparison to AgGaSe2 (MC), as explained above, and a lower
(2)
bound on the χ values for Li2ZnGeSe4 and Li2ZnSnSe4 as 19 and 23
pm/V, respectively, from comparison to the AgGaSe2 (OQ)
reference. These lesser values still exceed those reported for
40 40a,41
LiInS2 and rival those obtained for LiInSe2. Additionally, both
the upper and lower bound values can be used for direct
14-
comparison with our previous results for other quaternary DLSs.
16,37
While the SHG responses of the title compounds are weaker
15 14
than those of Li2CdGeS4 and Cu2CdSnS4, both Li2ZnGeSe4 and
16 14
Li2ZnSnSe4 outperform Li2MnGeS4 and Cu2ZnSiS4, in terms of
(2)
SHG response. Yet, χ is not the sole predictor of potential
applications for a given material because other important factors
36
such as LDT are critical.
Figure 8. Broadband SHG response of Li2ZnGeSe4 and Li2ZnSnSe4
compared with the AgGaSe2 (MC) reference at λ = 1100–3700 Laser damage threshold (LDT). The LDTs were measured using an
nm.   is estimated in the long-wavelength regime where the incident laser with λ = 1064 nm and τ = 30 ps. Note that the
SHG response plateaus. fundamental Nd:YAG line can induce 2-photon absorption (2PA) in

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of 2.13 eV with both the CBMin and VBMax occurring at the G point.
The magnitude of the bandgap is overestimated in these two cases
but accurate bandgap values are not expected based on DFT
calculations using the PBE-GGA functional. The type of transition
(i.e. direct or indirect) predicted by the calculations also differs from
experiment and this may be due to the fact that there are other
transitions of very similar energy near the G point in both band
structures. Furthermore, the optical diffuse reflectance data are
obtained at room temperature, while the calculations are carried

Dalton Transactions Accepted Manuscript


out for athermal conditions for perfect structures with no defects.
Here the qualitative analysis of the density of states (DOS) is of
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more relevance.
The right-hand side of Figure 10 shows the calculated total DOS
(TDOS) and partial DOS (PDOS) of the title materials. It is commonly
expected that selenides will have smaller bandgaps than the
corresponding sulfides; however the magnitude of the decrease is
difficult to predict without the use of electronic structure
2- 2-
calculations. The Se anion has a greater crystal radius than S
leading to larger sized unit cells and higher energy p-orbitals that
result in significantly narrower bandgap energies. In the case of the
42
popular Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) the difference

Figure 9. I-dependent SHG to determine the 2PA coefficients


and the LDTs.

both samples and the reference. In the absence of 2PA and


damage, the SHG intensity is expected to follow a squared power
law. However, in the presence of 2PA, the power law is modified to



  
 ;
  , 2
1  

where I is the input laser intensity,  is the 2PA coefficient and d is
the particle size. The I-dependent SHG and LDT fits are shown in Fig.
9 where the solid black trace indicates a squared power
dependence in the absence of 2PA and the solid red trace is the
modified squared law expressed in Equation (2). The LDT value of
2
Li2ZnGeSe4 and Li2ZnSnSe4 is ~0.3 GW/cm , which is comparable to
2
the commercial AgGaS2 (0.3-0.4 GW/cm ) and better than that of
2 15
AgGaSe2 (~0.2 GW/cm ) measured under the same conditions. Yet
this improvement over commercial materials is not as dramatic as
that discovered for the wide-gap Li2CdGeS4 and Li2MnGeS4
15,16
materials.

Electronic structure calculations

The calculated electronic band structures of Li2ZnGeSe4 and


Li2ZnSnSe4 along the high symmetry points of the first Brillouin zone
are plotted on the left-hand side of Figure 10. The state energies of
the conduction band minimum (CBMin) and valence band maximum
(VBMax) at each k point are listed in Table S5. According to these
calculations, Li2ZnGeSe4 is an indirect gap semiconductor with a
bandgap of 2.21 eV; the CBMin is at the Y point and the VBMax is at Figure 10. The electronic band structures, TDOS and PDOS of
the G point. On the other hand, Li2ZnSnSe4 shows a direct bandgap Li2ZnGeSe4 and Li2ZnSnSe4.

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43 (2)
in bandgap is ~0.5 eV according to both experiment and theory. (Eg=2.05; χ =150 pm/V) AgGaSe2 has a lower hardness, lower
On the other hand, in the case of the title compound Li2ZnSnSe4 and thermal conductivity, lower LDT, much more severe anisotropic
(2)
the corresponding sulfide, Li2ZnSnS4, the bandgap is more thermal expansion and a χ value that is less than half that of ZGP;
significantly lowered, 2.87 eV versus 1.87 eV for the sulfide and however, AgGaSe2 surpasses ZnGeP2 in terms of its transparency
29
selenide, respectively. This variance likely arises from the window which extends significantly deeper in the IR giving rise to a
51
different origin of the states near the Fermi level in these electronic broader range of laser applications in the mid-IR. Likewise, the
(2)
structures. The bandgap in CZTS and CZTSe is defined by the title compounds have some attributes, besides χ , that make them
hybridization of Cu d and chalcogen p states that overwhelmingly more attractive than current materials. For example, the title
dominate the VBMax and the hybridization of S s and p states with compounds are type-I PM, with onset wavelengths around 2500

Dalton Transactions Accepted Manuscript


the s states of Sn at the CBMin. In contrast the VBMax in the title nm, and optically transparent over the wide range of 0.7–25 μm.
compounds has a modest contribution from the Li p states; instead, Additionally, Li2ZnGeSe4 and Li2ZnSnSe4 are biaxial, unlike AgGaS2
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Li s and p states predominantly contribute to states high in the and AgGaSe2 that are uniaxial, giving rise to a greater prospect of
conduction band, at energies greater than 4 eV, due to the highly phase matchability. Furthermore, while AgGaS2 and AgGaSe2 suffer
ionic bonding interaction with the anion. This is also evidenced in from severely divergent thermal expansion along the a- and c-axes
52,53
the Mulliken bond population analyses that show the bond orders with sign anisotropy, the title compounds have been easily
of Zn-Se, Ge-Se and Sn-Se as 1.19–1.50, 1.31–1.52 and 1.16–1.30, prepared as small (~0.5 mm) crystals; no cracking of reaction
2
respectively, significantly larger than those of the Li-Se bonds (-1.10 ampoules has been observed. Favourable LDTs of 0.3 GW/cm also
– -0.53), (Table S5). While the VBMax does show some Li p character add to the appeal of the title materials. It is interesting that, while
there also exist states of Zn p character that hybridize with the Se p AgGaSe2 has a larger NLO coefficient, Li2ZnGeSe4 and Li2ZnSnSe4
states. The states at the CBMin chiefly arise from the Sn/Ge s states outshine AgGaSe2 in terms of LDT. A deeper understanding of the
(2)
and Se p states; however there are also quite significant factors, besides bandgap, that determine the balance between χ
contributions from the Li and Zn s and p states. Figure 10 shows and LDT in these DLSs is needed to propel this research toward
that the Se p states dominate the whole Fermi level region and improved IR NLO materials.
overlap fully with Li p, Zn p, and Ge/Sn s and p orbitals. The great The results of our studies indicate that tuning the composition of
extent of orbital overlap leads to narrower bandgaps for the title quaternary DLSs can greatly change the physical properties such as
compounds. However, in pursuing lithium-containing I2-II-IV-VI4 bandgap energy and second-order optical nonlinearity which may
DLSs we aim to stabilize compounds with wider bandgaps than afford new functional materials. Our future research efforts will
those of the corresponding copper and silver-containing phases, continue to explore the structure-composition-property
giving rise to the possibility of greater LDTs. For example, the correlations in diamond-structured semiconductors so that we may
44
bandgap increase upon going from Cu2MnGeS4 (2.04 eV) to move toward knowledge-based optimization of physicochemical
Li2MnGeS4 (3.15 eV) is greater than 1 eV. When comparing properties with the goal of finding improved IR NLO materials.
45,46 47 46,48
CuInS2 (1.37-1.55 eV) to LiInS2 (3.59 eV) or CuInSe2 (0.98- Theoretical studies on these systems are warranted.
47
1.04 eV) to LiInSe2 (2.86 eV) the increase in bandgap is quite
dramatic, ~2 and ~1.8 eV respectively. However, in the case of the
title compounds the bandgap increase due to lithium incorporation Acknowledgements
is relatively small. Compared to the compounds Cu2ZnGeSe4 (1.29- This work was supported by the National Science Foundation of
49,50 42
1.52 eV) and Cu2ZnSnSe4 (~ 1eV) the bandgap energies of the United States under Grant No. DMR-1201729. Y.S.K. acknowledges
title compounds are only increased by ~0.2 and 0.7 eV for support from the Basic Science Research Program (2014-010369)
Li2ZnGeSe4 and Li2ZnSnSe4, respectively. In summary, we have and Priority Research Center Program (2009-0093818) through the
observed a significant decrease in bandgap upon going from S to Se NRF of Korea funded by the Ministry of Education. The authors
for the title phases and a relatively small increase in bandgap due to acknowledge Gooch and Housego (Ohio) for providing the optical-
the replacement of Cu with Li; all together this leads to relatively quality AgGaSe2 single crystal reference material. A special thanks
narrow gap materials with Eg = ~1.8 eV. Therefore, it is not to Gary Catella (Director of Technology) and Dr. Carl Brunetta for
surprising that Li2ZnGeSe4 and Li2ZnSnSe4 show only a modest useful discussions regarding practical NLO materials.
improvement in terms of LDT in comparison to AgGaSe2.

Notes and references


Conclusions
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