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SrCdGeS and SrCdGeSe: Promising Infrared Nonlinear Optical Materials with Congruent-Melting Behaviour Yunwei Dou, Ying Chen, Zhuang Li, Abishek K. Iyer, Bin Kang, Wenlong Yin, Jiyong Yao, and Arthur Mar Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01649 • Publication Date (Web): 07 Jan 2019 Downloaded from http://pubs.acs.org on January 9, 2019
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Crystal Growth & Design
1
SrCdGeS4 and SrCdGeSe4: Promising Infrared Nonlinear Optical Materials with Congruent-Melting Behaviour
Yunwei Dou,† Ying Chen,† Zhuang Li,‡ Abishek K. Iyer,§ Bin Kang,† Wenlong Yin,†,§,* Jiyong Yao,‡ and Arthur Mar§,* †
Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900
People’s Republic of China ‡
Centre for Crystal Research and Development, Technical Institute of Physics and Chemistry,
Chinese Academy of Sciences, Beijing 100190, People’s Republic of China §
Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2
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2 Abstract The quaternary chalcogenides SrCdGeS4 and SrCdGeSe4 were prepared by hightemperature reactions in the form of single crystals (at 1223 and 1123 K, respectively) or microcrystalline samples (at 1023 K). They adopt noncentrosymmetric structures (orthorhombic, space group Ama2, Z = 4; a = 10.3352(14) Å, b = 10.2335(14) Å, c = 6.4408(9) Å for SrCdGeS4; a = 10.8245(8) Å, b = 10.6912(8) Å, c = 6.6792(5) Å for SrCdGeSe4) consisting of anionic [CdGeCh4]2– layers separated by Sr2+ cations. Although the structure is closely related to the BaZnSiSe4-type, the substitution of Cd for Zn is accompanied by a significant displacement away from an ideal tetrahedral site toward a trigonal pyramidal geometry. Relationships to other similar structures are also elucidated. Large optical band gaps of 2.6 eV for SrCdGeS4 and 1.9 eV for SrCdGeSe4 were deduced from the absorption edges, consistent with the light yellow and red colours, respectively, of crystals of these compounds. Nonlinear optical measurements on powder samples indicated that these compounds show intense second harmonic generation signals (2 AgGaS2 for SrCdGeS4 and 5 AgGaS2 for SrCdGeSe4) and type-I phase-matching behaviour using 2090 nm as the fundamental laser wavelength. They also melt congruently at relatively low temperatures (958 ºC for SrCdGeS4 and 851 ºC for SrCdGeSe4).
Keywords: Chalcogenides; Infrared nonlinear optical materials; Crystal structure; Electronic structure; Optical properties
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Crystal Growth & Design
3 Introduction Infrared lasers are crucial for various chemical, medical, industrial, and military applications, but the commercially available nonlinear optical (NLO) materials that can generate coherent and tunable light in the infrared region are currently limited to a few benchmark materials (AgGaS2, AgGaSe2, ZnGeP2), which suffer from limitations of low laser damage threshold and non-type-I phase matchability at desired wavelengths.1 Given their more covalent bonding character, smaller band gaps, and greater polarizability relative to oxides, metal sulfides and selenides inherently satisfy many of the key criteria for a good IR NLO material, namely large second harmonic generation (SHG) coefficients, high IR transmittance, and wide transparency range.2–5 Other practical requirements (high laser damage threshold, type-I phase matchability) are more difficult to anticipate, and the need to easily grow large single crystals favours compounds that melt congruently. Finally, despite many design strategies to incorporate asymmetric building blocks, there is never any guarantee that they will align appropriately in the crystal structure, although initial attempts in applying machine learning approaches to discover noncentrosymmetric structures appear enticing.6 Systematic investigation of the remaining vast uncharted territory of metal chalcogenides is still essential. Among the many metal chalcogenides that have been explored so far as candidates for IR NLO materials, one of the largest and most promising families contains tetrahedral MCh4 groups centred by main-group (typically group-13 or 14 elements) or d10 transition metal cations (Cu and Zn triad elements), as found in the benchmark materials AgGaS2 and AgGaSe2 themselves. They include ternary compounds such as Cd4GeS6,7 although quaternary compounds in combination with other monovalent or divalent cations are even more numerous, such as
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4 Na2ZnGe2S6,8 Pb5Ga6ZnS15,9 and Ba5CdGa6Se15.10 This brief listing is not exhaustive and many others can be found in reviews.3,4,11 In pursuit of these quaternary chalcogenides, we have been investigating the Ba–M–Tt– Ch (M = Zn, Cd, Hg; Tt = Si, Ge, Sn; Ch = S, Se) system within which the noncentrosymmetric compounds BaZnSiSe4 and BaZnGeSe4 were recently identified.12 Both of these compounds show good attributes for an IR NLO material, with BaZnGeSe4 exhibiting an SHG response as strong as that of AgGaS2 over similar particle sizes. We hypothesize that substitution of Cd for Zn would increase bond polarizability and may improve the SHG response, but at the expense of decreasing the band gap. However, substitution of Sr for Ba may offset this effect and maintain an appropriate band gap to ensure acceptable laser damage thresholds. We report here the synthesis and characterization of the quaternary chalcogenides SrCdGeS4 and SrCdGeSe4, and evaluate their potential as IR NLO materials.
Experimental Section Synthesis. Starting materials were Sr pieces (99%, Sigma-Aldrich), Cd shot (99.95%, Alfa-Aesar), CdSe powder (99.99%, Sinopharm), Ge ingot (99.9999%, Alfa-Aesar), S flakes (99.998%, Sigma-Aldrich), and Se powder (99.99%, Sigma-Aldrich). Single crystals were grown from reactions involving slow cooling from the melt. For SrCdGeS4, a mixture of Sr (61 mg, 0.70 mmol), Cd (79 mg, 0.70 mmol), Ge (51 mg, 0.70 mmol), and S (90 mg, 2.80 mmol) in a molar ratio of 1:1:1:4 was loaded into a fused-silica tube, which was evacuated and sealed. The tube was heated to 1223 K over 30 h, kept at that temperature for 96 h, and then slowly cooled to room temperature over 144 h. Light yellow (almost colourless) air-stable crystals were obtained. For SrCdGeSe4, a mixture of Sr (44 mg,
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Crystal Growth & Design
5 0.50 mmol), CdSe (96 mg, 0.50 mmol), Ge (36 mg, 0.50 mmol), and Se (118 mg, 1.50 mmol) in a molar ratio of 1:1:1:3 was loaded into a fused-silica tube which was evacuated and sealed. The tube was heated to 1123 K over 30 h, kept at that temperature for 72 h, and then slowly cooled to room temperature over 96 h. Red air-stable crystals were obtained. Energy-dispersive X-ray (EDX) analysis of these crystals, which were examined on a JEOL JSM-6010LA InTouchScope scanning electron microscope, revealed compositions of 15(2)% Sr, 15(2)% Cd, 10(2)% Ge, and 60(4)% Ch, close to expectations (14% Sr, 14% Cd, 14% Ge, 57% Ch (Ch = S, Se)). These crystals were chosen for structure determination. Crystals of both compounds remained visibly unchanged after exposure to air over several months. Polycrystalline samples were prepared from reactions of the same mixtures of starting materials as before. The tubes were heated to 1023 K in 24 h, kept at that temperature for 96 h, and then cooled by shutting off the furnace. The samples were reground and subjected to a repeated heat treatment. Powder X-ray diffraction (XRD) patterns were collected on an Inel diffractometer equipped with a curved position-sensitive detector (CPS 120) and a Cu K1 radiation source operated at 40 kV and 20 mA. These patterns agreed well with the ones simulated from the single-crystal structure determination (Figure 1). The initial discovery of these compounds involved the use of elemental components for the synthesis of SrCdGeS4 and a binary CdSe precusor for the synthesis of SrCdGeSe4. However, subsequent experiments in optimization revealed that both compounds can be prepared easily through either route, involving other combinations of elemental components or binary chalcogenides as starting materials, provided that the correct stoichiometric quantities are used. Structure Determination. Intensity data for SrCdGeS4 and SrCdGeSe4 were collected at room temperature on a Bruker PLATFORM diffractometer equipped with a SMART APEX II
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6 CCD detector and a graphite-monochromated Mo K radiation source, using scans at 6 (for SrCdGeSe4) or 8 (for SrCdGeS4) different angles with a frame width of 0.3º and an exposure time of 20 s per frame. Face-indexed numerical absorption corrections were applied. Structure solution and refinement were carried out with use of the SHELXTL (version 6.12) program package.13 The noncentrosymmetric orthorhombic space group Ama2 was chosen over other possibilities (A21am, Amam) on the basis of Laue symmetry, systematic absences, and intensity statistics, as well as the close similarity of the cell parameters to those of the chemically related compounds BaZnSiSe4 and BaZnGeSe4.12 Initial locations of all atoms were found by direct methods.
Atomic positions and labels were standardized with the program STRUCTURE
TIDY.14 The structure refinements for both compounds were straightforward. The Cd and Ge atoms were clearly distinguishable by their disparate distances to surrounding chalcogen atoms. The ordered distribution of these atoms was confirmed by refinements of occupancies in models that presumed site mixing. For example, these occupancies converged to 0.97(1) Cd / 0.03(1) Ge in the site at ¼, 0.17, 0.55 and –0.02(1) Cd / 1.02(1) Ge in the site at ¼, 0.28, 0.01 in SrCdGeS4, and similar results were obtained for SrCdGeSe4.
The absolute configurations in these
noncentrosymmetric structures were established by refining a Flack parameter. No additional symmetry was revealed by the ADDSYM routine in the PLATON suite of programs.15 Table 1 lists crystal data and further details, Table 2 lists positional and equivalent isotropic displacement parameters, and Table 3 lists selected interatomic distances. Diffuse Reflectance Spectroscopy. Optical diffuse reflectance spectra for SrCdGeS4 and SrCdGeSe4 were measured from 350 nm (3.54 eV) to 2000 nm (0.62 eV) on a Cary 5000 UV-vis-NIR spectrophotometer equipped with a diffuse reflectance accessory, with a compacted pellet of BaSO4 used as a 100% reflectance standard. These reflectance spectra were converted
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Crystal Growth & Design
7 to optical absorption spectra using the Kubelka-Munk function, F(R) = /S = (1–R)2/2R, where is the Kubelka–Munk absorption coefficient, S is the scattering coefficient, and R is the reflectance.16 Second-Harmonic Generation Measurements. Optical second-harmonic generation (SHG) signals were measured on SrCdGeS4 and SrCdGeSe4 using the Kurtz-Perry method.17 Light with a fundamental wavelength of 2090 nm was generated by a Q-switched Ho:Tm:Cr:YAG laser. The samples were ground and sieved with particle sizes in the ranges of 20–41, 41–74, 74–105, 105–150, and 150–200 m. Microcrystalline AgGaS2 with particle sizes over similar ranges served as the reference. Thermal Analysis. Differential scanning calorimetry (DSC) was performed on a Labsys TG-DTA16 (SETARAM) thermal analyzer and calibrated with Al2O3. Powder samples of SrCdGeS4 and SrCdGeSe4 (about 15 mg each) were sealed within small fused-silica tubes which were evacuated to 10–3 Pa. The heating and cooling rates were 20 K/min. Electronic Structure Calculations. Tight-binding linear muffin tin orbital electronic structure calculations were performed on SrCdGeS4 and SrCdGeSe4 within the local density and atomic spheres approximation with use of the Stuttgart TB-LMTO-ASA program (version 4.7).18 The basis sets consisted of Sr 5s/5p/4d/4f, Cd 5s/5p/4d/4f, Ge 4s/4p/4d, S 3s/3p/3d, and Se 4s/4p/4d orbitals, with the Sr 5p/4f, Cd 4f, Ge 4d, S 3d, and Se 4d orbitals being downfolded. Integrations in reciprocal space were carried out with an improved tetrahedron method over 108 irreducible k points within the first Brillouin zone. Bonding interactions were evaluated through an energy-resolved visualization as quantified by crystal orbital Hamilton populations (COHP).19
Results and Discussion
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8 Within the systems AE–M–Tt–Ch (AE = alkaline-earth metal; M = Zn, Cd, Hg; Tt = Si, Ge, Sn; Ch = S, Se), the previously known quaternary phases were BaCdGeS4,20 BaMSnS4 (M = Zn, Cd, Hg),21–24 and Ba3CdSn2S8 BaCdSnSe4
26
23,25
among the sulfides, and BaZnTtSe4 (Tt = Si, Ge)12 and
among the selenides. It is surprising that these compounds have been limited so
far to Ba-containing ones, with the most prevalent composition being AEMTtCh4.
The
quaternary chalcogenides SrCdGeS4 and SrCdGeSe4 prepared here are the first Sr-containing members in these systems. SrCdGeS4 and SrCdGeSe4 adopt a noncentrosymmetric orthorhombic structure in space group Ama2. Anionic layers [CdGeCh4]2– lie parallel to the bc-plane and separated by Sr2+ cations along the stacking a-direction (Figure 2a). The layers are built up by connecting Cd- and Ge-centred polyhedra through corner- and edge-sharing (Figure 2b).
There is a clear
differentiation between the longer distances of the surrounding Ch atoms to the Cd atoms (2.452(2)–2.663(2) Å in SrCdGeS4, 2.566(1)–2.778(2) Å in SrCdGeSe4) and the shorter distances to the Ge atoms (2.188(2)–2.235(2) Å in SrCdGeS4, 2.327(2)–2.381(2) Å in SrCdGeSe4). Although both Cd and Ge atoms are four-coordinate, the geometry around the Cd atoms is better described as trigonal pyramidal whereas that around the Ge atoms is tetrahedral. The bond angles around the Cd atoms between the apical and any of three basal Ch atoms are greatly contracted (94.46(5)–99.72(7)º in SrCdGeS4, 95.02(3)–98.95(5)º in SrCdGeSe4); in fact, the coordination geometry around the Cd atoms could equally well be described as 3+1, with the longest bond to the apical Ch atom. In contrast, the bond angles around the Ge atoms are closer to the ideal tetrahedral values (104.68(9)–117.14(6)º in SrCdGeS4, 104.67(6)–117.07(4)º in SrCdGeSe4).
The Sr atoms are eight-coordinate in what could be described as tetragonal
antiprismatic or bicapped trigonal prismatic geometry, greatly distorted, of course (Figure 2c).
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Crystal Growth & Design
9 The structures of the quaternary chalcogenides AEMTtCh4 (AE = Sr, Ba; M = Zn, Cd, Hg; Tt = Si, Ge, Sn; Ch = S, Se) are all closely related but there are subtle differences between them. It is interesting that all of them crystallize in noncentrosymmetric orthorhombic space groups with similar cell parameters which could be doubled and with a polar twofold axis along the cdirection (Table 4).
To draw structural relationships clearly, a good starting point is the
BaZnSiSe4-type structure, which crystallizes in space group Ama2 (Figure 3a).12 Here, onedimensional chains of edge-sharing tetrahedra are centred alternately by M and Tt atoms, which are almost collinear and aligned parallel to the polar c-axis. SrCdGeS4 and SrCdGeSe4 also crystallize in space group Ama2 with similar cell parameters and positions of all atoms as in BaZnSiSe4 and BaZnGeSe4, with one important difference: The M atoms are strongly displaced to one side of the chain so that they link with a chalcogen atom of an adjacent chain, forming a two-dimensional layer (Figure 3b). The shift in atomic position is quite drastic; for example, the Zn atom in BaZnSiSe4 is located at ¼, 0.246, 0.514 but the Cd atom in SrCdGeS4 is located at ¼, 0.169, 0.554, with a considerable difference in the y-coordinate.
This displacement also
elongates the chains, reflected in the larger c-parameters of SrCdGeS4 and SrCdGeSe4 even though smaller Sr atoms have been substituted in place of Ba atoms. Given the significant displacement of the M atom and the altered connectivity of the polyhedra, it is useful to designate SrCdGeS4 as its own structure type, which is a distorted variant distinct from the BaZnSiS4-type structure. Lastly, the BaCdSnS4-type structure crystallizes in space group Fdd2 with all cell parameters doubled relative to the previous structures.22,23 This time, both M and Tt atoms within the ideal one-dimensional chains of edge-sharing tetrahedra are displaced to opposite sides, linking with chalcogen atoms of adjacent chains to form a more complex twodimensional layer lying parallel to the bc-plane (Figure 3c). The repeat distances are lengthened
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10 within this plane, as reflected in the doubled b- and c-parameters, and the stacking sequence of these layers has also changed, as reflected in the doubled a-parameter. In fact, the SrCdGeS4-type structure is most closely related to the BaHgSnS4-type structure.24 As summarized in a Bärnighausen tree,27 SrCdGeS4 (space group Ama2) transforms to BaHgSnS4 (space group Pnn2) through a klassengleiche reduction in symmetry of index 2 (Figure 4). The connectivities of the polyhedra are identical in both structures and there are only very small shifts in atomic positions. Among other symmetry elements, a mirror plane on which the M and Tt atoms lie in SrCdGeS4 has been lost on proceeding to BaHgSnS4, but these atoms are only displaced by less than 0.1 Å off the plane. Moreover, the Sr site (at 4a) in SrCdGeS4 splits into two separate Ba sites (at 2a and 2b) in BaHgSnS4, with a small shift of 0.2 Å of the second site off the ideal position. Relationships can be made to simpler ternary structures. The SrCdGeS4-type structure could be regarded as a quaternary derivative of the Sr2SnS4-type structure (adopted by only one other compound, Sr2GeSe4).28 Figure 5 shows the evolution of the chains in the selenides BaZnGeSe4 (BaZnSiSe4-type), SrCdGeSe4 (SrCdGeS4-type), and Sr2GeSe4 (Sr2SnS4-type). Replacement of Zn with Cd atoms results in a more asymmetric environment, but the covalent bonding network within the chains is retained. Replacement of Cd with highly electropositive Sr atoms, which participate in ionic bonding to the surrounding Se atoms, interrupts the covalent bonding network of the chains. As in other AEMTtCh4 compounds, SrCdGeS4 and SrCdGeSe4 conform to the chargebalanced formula (Sr2+)(Cd2+)(Ge4+)(Ch2–)4, in agreement with the calculated bond valence sums for each atom (Table 5). The valence-precise formulation implies the presence of a band gap. This expectation was confirmed by electronic structure calculations performed on SrCdGeS4 and
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Crystal Growth & Design
11 SrCdGeSe4. As seen in the density of states (DOS) curves, valence and conduction bands are separated by 2.1 eV in SrCdGeS4 and a narrower gap of 1.4 eV in SrCdGeSe4 (Figure 6). The atomic projections of the DOS reveal that the valence band (extending from –4.8 to 0 eV in both compounds) involves mixing of S 3p or Se 4p states with Cd 4s/4p and Ge 4p states, corresponding to strong covalent bonding interactions between Cd or Ge atoms and chalcogen atoms, as confirmed in the crystal orbital Hamilton population (COHP) curves. Most of the Srbased states are located in empty conduction bands well above the Fermi level, but they also contribute slightly to the valence band. As evaluated by the integrated COHP values (–ICOHP) (Table 6), Ge–Ch interactions are not only inherently the strongest but they also provide the greatest contribution to the covalent bonding stability of the structure. In fact, the magnitude of the band gap is ultimately controlled by the separation of bonding Ge–Ch interactions at the top of the valence band and antibonding Ge–Ch interactions at the bottom of the conduction band. This is an important result because it suggests that the concerns expressed in the introduction about Cd substitution leading to too small a band gap can be allayed. The band dispersion diagrams show that the band gap is indirect (from to Y) in SrCdGeS4 but direct in SrCdGeSe4 (from Y to Y) (Figure 7). However, given that the energy of the top of the valence band at Y is merely 0.05 eV lower than at , the gap is nearly a direct one in SrCdGeS4. The optical band gaps were measured experimentally from the UV-vis-NIR diffuse reflectance spectra, which were converted to absorption spectra (Figure 8).
Band gaps
extrapolated from the absorption edges were 2.6 eV for SrCdGeS4 and 1.9 eV for SrCdGeSe4, which are larger than the ones obtained from the band structure calculations above but consistent with the light yellow and red colours, respectively, of crystals of these compounds. These values can be compared with those of related quaternary chalcogenides (BaZnSiSe4, 2.7 eV;
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12 BaZnGeSe4, 2.5 eV; BaCdSnS4, 2.3 eV; BaCdSnSe4, 1.8 eV)12,23,26 and benchmark IR NLO materials (AgGaSe2, 1.8 eV; AgGaS2, 2.7 eV; ZnGeP2, 2.0 eV).1 The reasonably large band gaps found for SrCdGeS4 and SrCdGeSe4 thus portend well for their ability to withstand laserinduced damage, although this expectation will need to be confirmed separately. Optical SHG measurements were performed on SrCdGeS4 and SrCdGeSe4 using fundamental light with a wavelength of 2090 nm, and compared to AgGaS2 as a reference material. The SHG responses are impressively strong: over the same particle size range of 150– 200 m, SrCdGeS4 shows about twice the intensity and SrCdGeSe4 shows about five times the intensity as AgGaS2 (Figure 9a).
More importantly, as indicated by the increase in SHG
intensity with particle sizes (Figure 9b), both compounds exhibit type-I phase matching in the infrared region, which is an essential criterion for an NLO material to be viable in a technological application.29 This achievement represents a marked improvement over the related compounds BaZnGeSe4 (1 AgGaS2 over all particle size ranges and type-I phase matchable),12 BaCdSnS4 (5 AgGaS2 at 38–55 m particle sizes but not type-I phase matchable),23 and BaCdSnSe4 (1.6 AgGaS2 at 38–55 m particle sizes but not type-I phase matchable).26 DSC measurements show that both compounds melt congruently, at 958 ºC for SrCdGeS4 and 851 ºC for SrCdGeSe4 (Figure 10). These melting points are similar to those of benchmark materials, 998 ºC for AgGaS2 and 860 ºC for AgGaSe2.1 The considerable effort which will be required to grow large single crystals of NLO materials is thus facilitated by the congruent melting behaviour and relatively low melting points of these new quaternary chalcogenides.
Conclusions
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Crystal Growth & Design
13 In the introduction, we had proposed that substitution of Sr for Ba and Cd for Zn in the previously known compound BaZnGeSe4 may improve SHG responses while maintaining a reasonably large band gap. This hypothesis was fulfilled by the characterization of the selenide SrCdGeSe4, as well as the corresponding sulfide SrCdGeS4. Both compounds satisfy many of the essential criteria for practical IR NLO materials: They show intense SHG signals (several times greater than AgGaS2), are type-I phase-matchable, have large and essentially direct band gaps, and melt congruently below 1000 ºC. The enhanced SHG behaviour can be traced not only to greater polarizability of Cd–Ch bonds, but also to the unexpected displacement of the Cd atoms away from ideal tetrahedral sites toward a trigonal pyramidal geometry in the crystal structure, leading to greater polarization along the c-direction. Because the magnitude of the band gap is influenced largely by Ge–Ch interactions, it should be possible to carry out further substitutions (perhaps Hg for Cd) to increase polarization without affecting the band gap. The closely related structures of compounds within the AEMTtCh4 series suggest that size factors play an important role in determining the structure type adopted; further work is in progress to prepare other members of this series.
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14 Table 1. Crystallographic Data for SrCdGeS4 and SrCdGeSe4 SrCdGeS4
SrCdGeSe4
fw (amu)
400.85
588.45
space group
Ama2 (no. 40)
Ama2 (no. 40)
a (Å)
10.3352(14)
10.8245(8)
b (Å)
10.2335(14)
10.6912(8)
c (Å)
6.4408(9)
6.6792(5)
V (Å3)
681.21(16)
772.96(10)
Z
4
4
T (K)
296(2)
296(2)
c (g cm–3)
3.908
5.057
crystal dimensions (mm)
0.06 0.04 0.02
0.04 0.04 0.04
(Mo K) (mm–1)
16.38
32.19
transmission factors
0.479–0.732
0.327–0.407
2 limits
7.48–66.49°
7.19–66.55°
data collected
–15 h 15, –15 k 15, –9 l 9
–16 h 16, –16 k 16, –10 l 10
no. of data collected
4937
5518
no. of unique data, including 1368 (Rint = 0.048) Fo2 < 0
1553 (Rint = 0.045)
no. of unique data, with Fo2 > 2(Fo2)
1219
1345
no. of variables
40
39
Flack parameter
0.004(9)
0.029(10)
R(F) for Fo2 > 2(Fo2) a
0.031
0.031
Rw(Fo2) b
0.057
0.064
goodness of fit
1.08
1.01
()max, ()min (e Å-3)
1.49, –1.48
2.03, –1.32
a
R(F) = ∑||Fo| – |Fc|| / ∑|Fo| for Fo2 > 2(Fo2).
b
Rw(Fo2) = [∑[w(Fo2 – Fc2)2] / ∑wFo4]1/2; w–1 = [σ2(Fo2) +
(Ap)2 + Bp], where p = [max(Fo2,0) + 2Fc2] / 3.
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Crystal Growth & Design
15 Table 2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for SrCdGeS4 and SrCdGeSe4 atom
Wyckoff position
x
y
z
Ueq (Å2) a
Sr
4a
0
0
0.00000(14)
0.01687(19)
Cd
4b
¼
0.16892(7)
0.55404(11)
0.0261(2)
Ge
4b
¼
0.28260(8)
0.01054(13)
0.01322(19)
S1
8c
0.57964(14)
0.22862(17)
0.3003(3)
0.0167(3)
S2
4b
¼
0.0962(2)
0.1913(3)
0.0147(4)
S3
4b
¼
0.4379(2)
0.2442(3)
0.0173(5)
Sr
4a
0
0
0.00000(17)
0.0194(2)
Cd
4b
¼
0.83319(10)
0.43856(13)
0.0302(2)
Ge
4b
¼
0.21985(11)
0.48770(17)
0.0151(2)
Se1
8c
0.57611(8)
0.26924(8)
0.20158(12)
0.01886(18)
Se2
4b
¼
0.41010(11)
0.30251(16)
0.0162(2)
Se3
4b
¼
0.06337(11)
0.24560(17)
0.0201(3)
SrCdGeS4
SrCdGeSe4
a
Ueq is defined as one-third of the trace of the orthogonalized Uij tensor.
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Page 16 of 38
16 Table 3. Interatomic Distances (Å) in SrCdGeS4 and SrCdGeSe4 SrCdGeS4
SrCdGeSe4
Sr–Ch2 (2)
3.0272(12)
3.1602(7)
Sr–Ch3 (2)
3.1297(13)
3.2362(8)
Sr–Ch1 (2)
3.1453(18)
3.2770(11)
Sr–Ch1 (2)
3.1692(18)
3.2828(10)
Cd–Ch2
2.452(2)
2.5662(13)
Cd–Ch1 (2)
2.5915(17)
2.6921(11)
Cd–Ch3
2.663(2)
2.7779(17)
Ge–Ch3
2.188(2)
2.3268(16)
Ge–Ch1 (2)
2.2240(16)
2.3658(11)
Ge–Ch2
2.663(2)
2.3806(16)
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Crystal Growth & Design
17 Table 4. Structures of Quaternary Chalcogenides AEMTtCh4 (AE = Sr, Ba; M = Zn, Cd, Hg; Tt = Si, Ge, Sn; Ch = S, Se) Compound
Structure type
Space group
a (Å)
b (Å)
c (Å)
Reference
SrCdGeS4
SrCdGeS4-type
Ama2
10.3352(14)
10.2335(14)
6.4408(9)
This work
SrCdGeSe4
SrCdGeS4-type
Ama2
10.8245(8)
10.6912(8)
6.6792(5)
This work
BaZnSiSe4
BaZnSiSe4-type
Ama2
11.3055(8)
11.2344(7)
6.1994(4)
12
BaZnGeSe4
BaZnSiSe4-type
Ama2
11.3255(6)
11.2527(6)
6.2917(3)
12
BaZnSnS4
BaCdSnS4-type
Fdd2
21.964
21.504
12.701
21
BaCdGeS4
BaCdSnS4-type
Fdd2
21.69
21.25
12.78
20
BaCdSnS4
BaCdSnS4-type
Fdd2
21.86(2)
21.69(1)
13.18(5)
22
BaCdSnS4
BaCdSnS4-type
Fdd2
21.566(13)
21.760(13)
13.110(8)
23
BaCdSnSe4
BaCdSnS4-type
Fdd2
22.381(14)
22.711(14)
13.588(9)
26
BaHgSnS4
BaHgSnS4-type
Pnn2
10.804
10.840
6.613
24
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18 Table 5. Bond Valence Sums in SrCdGeS4 and SrCdGeSe4 SrCdGeS4
SrCdGeSe4
Sr
1.94
1.98
Cd
1.90
1.91
Ge
4.03
3.90
Ch1
1.86
1.85
Ch2
2.22
2.17
Ch3
1.92
1.92
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Crystal Growth & Design
19 Table 6.
Integrated Crystal Orbital Hamilton Populations (–ICOHP) for SrCdGeS4 and
SrCdGeSe4 eV/bond
eV/cell
%
Sr–S
0.50
3.97
16.7
Cd–S
1.46
5.86
24.6
Ge–S
3.51
14.03
58.8
Sr–Se
0.50
3.99
18.6
Cd–Se
1.26
5.06
23.6
Ge–Se
3.09
12.37
57.7
SrCdGeS4
SrCdGeSe4
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Page 20 of 38
20 Figure Captions Figure 1.
Powder XRD patterns and SEM images of typical crystals (insets) for (a) SrCdGeS4 and (b) SrCdGeSe4.
Figure 2.
Structure of SrCdGeS4 and SrCdGeSe4 (a) viewed down the c-direction, (b) highlighting an anionic [CdGeCh4]2– layer, and (c) showing the coordination around Sr atoms.
Figure 3.
(a) One-dimensional chains of edge-sharing tetrahedra centred by M and Tt atoms in BaZnSiSe4-type structure. (b) M atoms are displaced to link with neighbouring chains, forming layers in SrCdGeS4-type structure. (c) M and Tt atoms are displaced to link with neighbouring chains, forming layers in BaCdSnS4-type structure.
Figure 4.
Group-subgroup relations between SrCdGeS4- and BaHgSnS4-type structures. The atomic positions for BaHgSnS4 have been transformed after interchanging the a and b axes in the orthorhombic unit cell as originally reported.24
Figure 5.
Linking of GeSe4 tetrahedra via (a) ZnSe4 tetrahedra in BaZnGeSe4, (b) CdSe4 trigonal pyramids in SrCdGeSe4, and (c) Sr atoms in Sr2GeSe4.
Figure 6.
Density of states (DOS) (left panel), atomic projections (middle panels), and crystal orbital Hamilton population (–COHP) curves (right panel) for (a) SrCdGeS4 and (b) SrCdGeSe4.
Figure 7.
Band dispersion diagrams for (a) SrCdGeS4 and (b) SrCdGeSe4.
Figure 8.
Optical absorption spectra, converted from the diffuse reflectance spectra, for SrCdGeS4 and SrCdGeSe4.
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Crystal Growth & Design
21 Figure 9.
SHG intensity at (a) particle sizes of 150–200 m and (b) different particle sizes for SrCdGeS4 and SrCdGeSe4, relative to AgGaS2, using fundamental light with wavelength of 2090 nm.
Figure 10. DSC curves for (a) SrCdGeS4 and (b) SrCdGeSe4.
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22
(a)
(b)
Figure 1. Powder XRD patterns and SEM images of typical crystals (insets) for (a) SrCdGeS4 and (b) SrCdGeSe4.
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Crystal Growth & Design
23
(a)
b Sr a Ch2
Ge Ch3 Cd
Ch1
(b) Ch3 Ch2 Ge Ch1
Ch1
Ch3
Cd
Ch2 c b
(c)
Ch1
Ch2
Ch1
Ch2 Sr Ch1
Ch1 Ch3
Ch3
Figure 2. Structure of SrCdGeS4 and SrCdGeSe4 (a) viewed down the c-direction, (b) highlighting an anionic [CdGeCh4]2– layer, and (c) showing the coordination around Sr atoms.
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Page 24 of 38
24 (a)
Tt
M
BaZnSiSe4-type (Ama2)
(b)
Tt
M
SrCdGeS4-type (Ama2)
(c)
Tt
M
BaCdSnS4-type (Fdd2)
Figure 3. (a) One-dimensional chains of edge-sharing tetrahedra centred by M and Tt atoms in BaZnSiSe4-type structure. (b) M atoms are displaced to link with neighbouring chains, forming layers in SrCdGeS4-type structure. (c) M and Tt atoms are displaced to link with neighbouring chains, forming layers in BaCdSnS4-type structure.
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Crystal Growth & Design
25
Ama2 SrCdGeS4
Sr: 4a ..2 0 0 0.000
Cd: 4b m.. ¼ 0.169 0.554
Ge: 4b m.. ¼ 0.283 0.011
Hg: 4c 1 0.247 0.173 0.567
Sn: 4c 1 0.257 0.287 0.030
S: 8c 1 0.580 0.229 0.300
S: 4b m.. ¼ 0.096 0.191
S: 4b m.. ¼ 0.438 0.244
S: 4c 1 0.257 0.097 0.226
S: 4c 1 0.250 0.448 0.269
a = 10.34 Å b = 10.23 Å c = 6.44 Å
k2
Pnn2 BaHgSnS4
Ba: 2a ..2 0 0 0.000
Ba: 2b ..2 ½ 0 0.027
S: 4c 1 0.583 0.223 0.297
S: 4c 1 0.924 0.236 0.306
a = 10.84 Å b = 10.80 Å c = 6.61 Å
Figure 4. Group-subgroup relations between SrCdGeS4- and BaHgSnS4-type structures. The atomic positions for BaHgSnS4 have been transformed after interchanging the a and b axes in the orthorhombic unit cell as originally reported.24
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26
(a)
(b)
(c)
Figure 5. Linking of GeSe4 tetrahedra via (a) ZnSe4 tetrahedra in BaZnGeSe4, (b) CdSe4 trigonal pyramids in SrCdGeSe4, and (c) Sr atoms in Sr2GeSe4.
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Crystal Growth & Design
27
(a)
(b)
Figure 6. Density of states (DOS) (left panel), atomic projections (middle panels), and crystal orbital Hamilton population (–COHP) curves (right panel) for (a) SrCdGeS4 and (b) SrCdGeSe4.
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28
(a)
(b)
Figure 7. Band dispersion diagrams for (a) SrCdGeS4 and (b) SrCdGeSe4.
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Crystal Growth & Design
29
Figure 8. Optical absorption spectra, converted from the diffuse reflectance spectra, for SrCdGeS4 and SrCdGeSe4.
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30
(a)
(b)
Figure 9. SHG intensity at (a) particle sizes of 150–200 m and (b) different particle sizes for SrCdGeS4 and SrCdGeSe4, relative to AgGaS2, using fundamental light with wavelength of 2090 nm.
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31
(a)
(b)
Figure 10. DSC curves for (a) SrCdGeS4 and (b) SrCdGeSe4.
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Page 32 of 38
32 Associated Content Accession Codes CCDC 1876032–1876033 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
[email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
Author Information Corresponding Authors * E-mail:
[email protected] (W.Y.). * E-mail:
[email protected] (A.M.). ORCID Wenlong Yin: 0000-0003-2660-0891 Arthur Mar: 0000-0003-0474-5918 Notes The authors declare no competing financial interest.
Acknowledgments This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC, through Discovery Grant RGPIN-2018-04294), the NSERC Collaborative Research and Training Experience Program (CREATE, through the Alberta/Technical University of Munich International Graduate School), the National Natural Science Foundation of China (through Grant No. 51402270), the Institute of Chemical Materials (through Grant No. 32203),
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33 and the Key Laboratory of Science and Technology on High Energy Laser at the China Academy of Engineering Physics.
Dedication This paper is dedicated to Professor Xin-Tao Wu in honour of his 80th birthday, the 55th anniversary of his independent career, and his contributions to the development of functional materials.
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34 References (1)
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Kanatzidis, M. G. Discovery-synthesis, design, and prediction of chalcogenide phases. Inorg. Chem. 2017, 56, 3158–3173.
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Guo, S.-P.; Chi, Y.; Guo, G.-C. Recent achievements on middle and far-infrared secondorder nonlinear optical materials. Coord. Chem. Rev. 2017, 335, 44–57.
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Liang, F.; Kang, L.; Lin, Z.; Wu, Y. Mid-infrared nonlinear optical materials based on metal chalcogenides: Structure–property relationship. Cryst. Growth Des. 2017, 17, 2254– 2289.
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Li, M.-Y.; Li, B.-X.; Lin, H.; Shi, Y.-F.; Ma, Z.; Wu, L.-M.; Wu, X.-T.; Zhu, Q.-L. Ternary mixed-metal Cd4GeS6: Remarkable nonlinear-optical properties based on a tetrahedralstacking framework. Inorg. Chem. 2018, 57, 8730–8734.
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35 (9)
Duan, R.-H.; Yu, J.-S.; Lin, H.; Zheng, Y.-J.; Zhao, H.-J.; Huang-Fu, S.-X.; Khan, M. A.; Chen, L.; Wu, L.-M. Pb5Ga6ZnS15: a noncentrosymmetric framework with chains of T2supertetrahedra. Dalton Trans. 2016, 45, 12288–12291.
(10) Yin, W.; Iyer, A. K.; Li, C.; Yao, J.; Mar, A. Ba5CdGa6Se15, a congruently-melting infrared nonlinear optical material with strong SHG response. J. Mater. Chem. C 2017, 5, 1057– 1063. (11) Chen, M.-M.; Xue, H.-G., Guo, S.-P. Multinary metal chalcogenides with tetrahedral structures for second-order nonlinear optical, photocatalytic, and photovoltaic applications. Coord. Chem. Rev. 2018, 368, 115–133. (12) Yin, W.; Iyer, A. K.; Li, C.; Yao, J.; Mar, A. Noncentrosymmetric chalcogenides BaZnSiSe4 and BaZnGeSe4 featuring one-dimensional structures. J. Alloys Compd. 2017, 708, 414–421. (13) Sheldrick, G. M. SHELXTL, version 6.12; Bruker AXS Inc.: Madison, WI, 2001. (14) Gelato, L. M.; Parthé, E. STRUCTURE TIDY – a computer program to standardize crystal structure data. J. Appl. Crystallogr. 1987, 20, 139–143. (15) Spek, A. L. Structure validation in chemical crystallograpy. Acta Crystallogr., Sect. D 2009, 65, 148–155. (16) Kortüm, G. Reflectance Spectroscopy; Springer: New York, 1969. (17) Kurtz, S. K.; Perry, T. T. A powder technique for the evaluation of nonlinear optical materials. J. Appl. Phys. 1968, 39, 3798–3813. (18) Tank, R.; Jepsen, O.; Burkhardt, A.; Andersen, O. K. TB-LMTO-ASA Program, version 4.7; Max Planck Institut für Festkörperforschung: Stuttgart, Germany, 1998.
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36 (19) Dronskowski, R.; Blöchl, P. E. Crystal orbital Hamilton populations (COHP). Energyresolved visualization of chemical bonding in solids based on density-functional calculations. J. Phys. Chem. 1993, 97, 8617–8624. (20) Teske, C. L. Zur Kenntnis von BaCdGeS4 mit einem Beitrag zur Kristallchemie von Verbindungen des Typs BaABS4. Z. Anorg. Allg. Chem. 1980, 468, 27–34. (21) Teske, C. L. Darstellung, Kristallstrukturdaten und Eigenschaften der quaternären Thiostannate(IV) BaZnSnS4 und BaMnSnS4. Z. Naturforsch. B 1980, 35, 509–510. (22) Teske, C. L. Darstellung und Kristallstruktur von Barium-Cadmium-Thiostannat(IV) BaCdSnS4. Z. Anorg. Allg. Chem. 1980, 460, 163–168. (23) Zhen, N.; Wu, K.; Wang, Y.; Li, Q.; Gao, W.; Hou, D.; Yang, Z.; Jiang, H.; Dong, Y.; Pan, S. BaCdSnS4 and Ba3CdSn2S8: syntheses, structures, and non-linear optical and photoluminescence properties. Dalton Trans. 2016, 45, 10681–10688. (24) Teske, C. L. Darstellung und Kristallstruktur von Barium-Quecksilber-Thiostannat(IV), BaHgSnS4. Z. Naturforsch. B 1980, 35, 7–11. (25) Teske, C. L. Darstellung und Kristallstruktur von Ba3CdSn2S8 mit einer Anmerkung über Ba6CdAg2Sn4S16. Z. Anorg. Allg. Chem. 1985, 522, 122–130. (26) Wu, K.; Su, X.; Yang, Z.; Pan, S. An investigation of new infrared nonlinear optical material: BaCdSnSe4, and three new related centrosymmetric compounds: Ba2SnSe4, Mg2GeSe4, and Ba2Ge2S6. Dalton Trans. 2015, 44, 19856–19864. (27) Müller, U. Symmetry Relationships between Crystal Structures; Oxford University Press: Oxford, U.K., 2013.
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37 (28) Pocha, R.; Tampier, M.; Hoffmann, R.-D.; Mosel, B. D.; Pöttgen, R.; Johrendt, D. Crystal structures and properties of the thiostannates Eu2SnS4 and Sr2SnS4 and the selenogermanate -Sr2GeSe4. Z. Anorg. Allg. Chem. 2003, 629, 1379–1384. (29) Zhang, W.; Yu, H.; Wu, H.; Halasyamani, P. S. Phase-matching in nonlinear optical compounds: A materials perspective. Chem. Mater. 2017, 29, 2655–2668.
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38 For Table of Contents Only
SrCdGeS4 and SrCdGeSe4:
Promising Infrared Nonlinear Optical Materials with
Congruent-Melting Behaviour Yunwei Dou, Ying Chen, Zhuang Li, Abishek K. Iyer, Bin Kang, Wenlong Yin, Jiyong Yao, and Arthur Mar
SrCdGeS4 and SrCdGeSe4, which adopt noncentrosymmetric orthorhombic structures, show strong SHG responses, are type-I phase-matchable, have large band gaps, and melt congruently.
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