Synthesis, Crystal Structure, and Optical Property of Zero-dimensional Quaternary Thioborate: Ba9B3GaS15

Jin-Qiu WANG Peng-Fei LIU Yan-Yan LI Li-Ming WU

Citation:  WANG Jin-Qiu, LIU Peng-Fei, LI Yan-Yan, WU Li-Ming. Synthesis, Crystal Structure, and Optical Property of Zero-dimensional Quaternary Thioborate: Ba9B3GaS15[J]. Chinese Journal of Structural Chemistry, 2016, 35(12): 1860-1867. doi: 10.14102/j.cnki.0254-5861.2011-1236 shu

Synthesis, Crystal Structure, and Optical Property of Zero-dimensional Quaternary Thioborate: Ba9B3GaS15

English

  • Chalcogenides attract intensive attention because of their diverse structures and interesting properties, such as thermoelectric property[1, 2], magnetic property[3, 4], infrared nonlinear optical (NLO) property[5, 6] and so forth. Among chalcogenides, distorted GaS4 tetrahedra are thought as one type of the microscopic NLO-active units, and numerous compounds containing GaS4 tetrahedra have been discovered, such as AgGaQ2 (Q = S, Se)[7], BaGa4Q7 (Q = S, Se)[8], Ba23Ga8Sb2S38 [9], ACd4Ga5S12 (A = K, Rb, Cs)[10], Ln4GaSbS9 (Ln = Pr, Nd, Sm, Gd-Ho)[11], Ba4MGa4Se10Cl2 [12], (M = Zn, Cd, Mn) and Ba2Ga8MS16 (M = Si, Ge)[13], which exhibit very strong second harmonic generation (SHG) responses in middle IR.

    On the other hand, thioborates play an important role in nonlinear optical field due to their wide transparency, large nonlinear coefficients and high damage thresholds[14]. Besides, the building unit of [BS3]3- trigonal plane with the π-conjugated electrons delocalized on the plane, which has strong polarization and tends to create noncentrosymmetric structure, is another superiority of thioborates, e.g., Ba3(BS3)(SbS3)[14]. However, the reported chalcogenides containing boron, like AEB2S4 (AE = Ca, Sr, Ba)[15], Sr4.2Ba2.8B4S13 [16], Ba3(BS3)1.5(MS3)0.5 (M = Sb, Bi)[14] and Ba3(BQ3)(SbQ3) (Q = S, Se)[14], are still rare. Surprisingly, there is no thioborate compound containing the typical NLO-active GaS4 tetrahedra. Therefore, we combine GaS4 tetrahedra with BS3 units into a single-crystal structure in order to construct a new noncentrosymmetric structure which may have remarkable NLO property in the AE/B/Ga/S (AE = alkali-earth metals) system.

    Herein, the first thioborate compound Ba9B3GaS15 of AE/B/Ga/S (AE = alkali-earth metals) system has been discovered. The 0D structure is built up by discrete [BS3]3- trigonal planes and isolated [GaS4]5- tetrahedra with Ba2+ and isolated S2- filled among them. The synthesis, single crystal and electronic structures, as well as optical band gap are reported.

    The following elements were used as obtained and stored in the Ar-filled glovebox, and all manipulations were performed in the glovebox. Ba rod (99.99%) was purchased from Alfa Aesar China (Tianjin) Co., Ltd. Ga and S (99.99%) were purchased from Sinopharm Chemical Reagent Co., Ltd. Amorphous boron powder (95~97%) was purchased from Dan Dong Chemical Industry. The title compound was synthesized in a 7:3:1:13 molar ratio of Ba, B, Ga, and S with a total weight of 400 mg. The mixture was loaded into a graphite crucible and sealed in an evacuated fused-silica tube under 10-3 Pa atmosphere. And the samples were heated to 920 ℃ within 35 h and kept there for 100 h, then cooled to 300 ℃ at a rate of 5 ℃/h before switching off the furnace. The bulk light-red crystals were picked for single-crystal structure studies which yielded a refined formula of Ba9B3GaS15. Pure phase of the title compound was tried to synthesize by the stoichiometric mixture of Ba, B, Ga, and S in a 9:3:1:15 molar ratio. The title compound (about 90%) together with small amounts of BaS and some unknown amorphous substances was obtained. Pure phased products were obtained by hand-picking crystals and confirmed by the X-ray diffraction (XRD) analysis (Fig. 1).

    Figure 1

    Figure 1.  Experimental and simulated X-ray diffraction patterns of Ba9B3GaS15

    The single crystal diffraction data were collected by a Mercury CCD diffractometer equipped with graphite-monochromated MoΚα radiation (λ = 0.71073 Å) at 293 K. The data were corrected for Lorentz and polarization factors. And the structure was solved by direct methods and refined by full-matrix least-squares fitting on F2 using the SHELX-97[17]. The structure was solved and refined successfully in the centrosymmetric Pbca space group. No missed symmetry elements were found after using the PLATON[18] program to check the final refined crystal structure. The final R values were converged to R = 0.0362 and wR = 0.1053 (w = 1/[σ2(Fo 2) + (0.1301P)2 + 0.0000P], where P = (Fo2 + 2Fc 2)/3), (Δρ) max = 5.039, (Δρ) min = -5.409 e/Å3, and S = 1.034 with a charge-balanced formula of (Ba2+)9(B3+)3(Ga3+) (S2-)15, which agreed well with the EDX results (Table 2). Some selected bond distances and bond angles are listed in Table 1. The crystals are stable in air.

    Table 1

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) of Ba9B3GaS15
    DownLoad: CSV
    BondDist.BondDist.BondDist.B(1)–S(2)1.82(2)B(2)–S(15)1.83(2)Ga–S(8)2.277(3)Angle(°)Angle(°)Angle(°)S(2)–B(1)–S(7)116.7(6)S(9)–B(2)–S(15)122.7(7)S(6)–Ga–S(11)104.8(2)S(1)–B(2)–S(15)120.4(7)S(6)–Ga–S(8)111.4(2)S(11)–Ga–S(14)116.7(2)
    B(1)–S(7)1.84(2)B(3)–S(5)1.79(2)Ga–S(11)2.218(3)
    B(1)–S(10)1.81(2)B(3)–S(12)1.83(2)Ga–S(14)2.202(3)
    B(2)–S(1)1.81(2)B(3)–S(13)1.82(2)
    B(2)–S(9)1.82(2)Ga–S(6)2.250(3)
    S(2)–B(1)–S(10)119.0(6)S(5)–B(3)–S(12)119.9(7)S(6)–Ga–S(14)107.4(2)
    S(7)–B(1)–S(10)123.9(7)S(5)–B(3)–S(13)121.9(8)S(8)–Ga–S(11)107.62)
    S(1)–B(2)–S(9)116.7(7)S(12)–B(3)–S(13)118.1(8)S(8)–Ga–S(14)108.9(2)

    Table 2

    Table 2.  EDX Data of Ba9B3GaS15
    DownLoad: CSV
    Point-1Point-2ElementWeight%Atomic%FormulaElementWeight%Atomic%FormulaSK27.2460.3115.18SK33.1266.7918.45Point-3Point-4ElementWeight%Atomic%FormulaElementWeight%Atomic%FormulaSK27.3159.7515.22SK25.8757.9114.41Point-5ElementWeight%Atomic%FormulaAverage formula:Ba8.63Ga1.35S15.83SK28.5161.3715.89Total100
    GaK4.144.211.06GaK3.753.480.96
    BaL68.6335.488.93BaL63.1329.728.21
    Total100Total100
    GaK6.296.331.61GaK6.66.791.69
    BaL66.433.928.64BaL67.5335.298.79
    Total100Total100
    GaK5.565.51.42
    BaL65.9333.138.58

    The powder X-ray diffraction data pattern was recorded at room temperature on a Rigaku MiniFlex II diffractometer by using CuKα radiation (λ = 1.5406 Å). The scanning range was 10~70° in 2θ with a step size of 0.02°. As shown in Fig. 1, the experimental XRD pattern was in good agreement with the simulated one based on the single-crystal crystallographic data.

    The semi-quantitative energy dispersive X-ray spectra (EDX, Oxford INCA) were measured on a field emission scanning electron microscope (FESEM, JSM6700F). The EDX results confirmed the presence of Ba, Ga, and S in an approximate molar ratio about 8.63:1.35:15.83 (Fig. 2, Table 2). The EDX results are in accordance with the single-crystal diffraction data.

    Figure 2

    Figure 2.  EDX spectrum of Ba9B3GaS15

    The IR spectrum was measured by a Nicolet Magana 750 FT-IR spectrophotometer in the range of 2.5 ~ 25 μm. Polycrystalline samples of Ba9B3GaS15 were ground with KBr and pressed into transparent pellets for measurement.

    The UV-Vis diffuse reflectance was recorded at room temperature using a PerkinElmer Lambda 900 UV-Vis spectrophotometer in the range of 0.19~ 2.5 μm. BaSO4 was used as a reference. The absorption spectrum was calculated from the diffuse reflection spectrum according to the Kubelka-Munk function: α/S = (1 - R)2/2R, where α, S and R are the absorption coefficient, scattering coefficient, and reflectance, respectively[19].

    The electronic structure of Ba9B3GaS15 was calculated by density functional theory (DFT) implemented in the Vienna ab-initio simulation package code (VASP)[20]. The generalized gradient approximation (GGA)[21] and projector augmented wave (PAW)[22] were chosen as exchange-correlation potential and ionic cores, respectively. The mesh cutoff energy of 500 eV was set for the selfconsistent filed convergence. Ba 5s25p66s2, B 2s22p1, Ga 4s24p1, and S 3s23p4 were treated as valence electrons. The reciprocal space was sampled with 0.05 Å-1 spacing in the Monkhorst-Pack scheme for structure optimization, while denser k-point grids with 0.02 Å-1 spacing were adopted for property calculation. A mesh cutoff energy of 500 eV was used to determine the self-consistent charge density. All geometries were relaxed until the Hellmann- Feynman force on atoms was less than 0.01 eV/Å and the total energy change was lower than 1.0×10-5 eV.

    The compound Ba9B3GaS15 crystallizes in a new structure type in orthorhombic space group of Pbca (No. 61) with a = 8.4759(8), b = 22.266(2), c = 31.426(3) Å, V = 5931(2) Å3, and Z = 8. There are 9 crystallographically independent Ba atoms, 3 B atoms, 1 Ga and 15 S atoms. All atoms are at the Wyckoff 8c sites. The occupancies of all atoms are 100%.

    The compound Ba9B3GaS15 features a zerodimensional structure containing discrete [BS3]3- trigonal planes and isolated [GaS4]5- tetrahedra with Ba2+ and isolated S2- filled among them (Fig. 3(a)). As shown in Fig. 3(b) to (c) , each boron atom linked with three sulfide atoms forms a trigonal plane with the bond lengths ranging from 1.79(2) to 1.84(2) Å. These bond lengths are comparable to those in BaB2S4 [15] and Sr4.2Ba2.8B4S13 [16]. From the B-S distances and S-B-S angles, we can conclude that these discrete [BS3]3- trigonal planes are distorted and polarized but the overall polarities are canceled because of the inversion center symmetry operation. The distorted [GaS4]5- tetrahedra have Ga-S distances ranging from 2.202(3) to 2.277(3) Å (Fig. 3(d)), which are in accordance with those of 2.21~2.32 Å in Ba23Ga8Sb2S38 [9]. Ba atoms are 7- or 8-fold coordination with the Ba-S bond lengths falling in the 3.282(2) to 3.576(2) Å range, which are comparable to 3.007~3.674 Å in Ba5Ga2S8 [23].

    Figure 3

    Figure 3.  Structure of Ba9B3GaS15 (a), and the coordination environment of B (1) atom (b), B (2) atom (c), B (3) atom (d), and Ga atom (e) in Ba9B3GaS15

    Both of the building units of [BS3]3- trigonal planes and [GaS4]5- tetrahedra in the structure are distorted, which are likely to form a NCS structure. However, due to the inversion center symmetry operation, the overall polarity disappears. By changing the ratio of [BS3]3- and [GaS4]5-, the center of symmetry is possible to vanish and a new NCS structure tends to be created. Further exploration is worthwhile.

    The infrared spectra result (Fig. 4) of Ba9B3GaS15 indicates strong absorption bands from 800 to 900 cm-1 and weak absorption band near 450 cm-1, which are respectively attributed to the E and the A1 asymmetrical stretching modes of [BS3]3- units[24, 25]. The infrared spectra prove the presence of lighter element boron. Compounds Na3BS3 and Ba7B4S13 have similar absorption bands[26, 27].

    Figure 4

    Figure 4.  Infrared transmission spectra of [BS3]3- units in Ba9B3GaS15

    As shown in Fig. 5, the optical band gap of Ba9B3GaS15 is measured to be approximately 3.15 eV, which is consistent with its light-red color.

    Figure 5

    Figure 5.  UV-Vis diffuse reflection spectrum of Ba9B3GaS15

    The electronic band structure of Ba9B3GaS15 indicates the direct band gap of 2.24 eV (Fig. 6(a)), which is smaller than the experimental observation of 3.15 eV owning to the discontinuity of exchange-correlation potential that underestimates the band gaps in semiconductors and insulators[28]. The total and partial density of states (DOS) of Ba9B3GaS15 are shown in Fig. 6(b). It is found that the valence band (VB) ranging from -4 to -2.5 eV contains mainly B-2p, Ga-4p, and S-3p states. The top of the VB predominantly originates from S-3p states with minor Ba-5d and Ga-3d states. Above the Fermi level, the conduction band (CB) is dominated by B-2p and S-3p states mixed with a small amount of Ga-4s, Ga-4p, and Ba-5d states. Therefore, the electronic transitions of Ba9B3GaS15 are mainly from S-3p to B-2p states.

    Figure 6

    Figure 6.  (a) Calculated band structure of Ba9B3GaS15. (b) Total and partial density of states of Ba9B3GaS15

    In summary, the first thioborate compound Ba9B3GaS15 in AE/B/Ga/S (AE = alkali-earth metals) system with its own structure type has been discovered by conventional high-temperature solid-state reaction. Its 0D structure is built up by discrete [BS3]3- trigonal planes and isolated [GaS4]5-tetrahedra with Ba2+ and isolated S2- filled among them. Ba9B3GaS15 exhibits a larger optical band gap of 3.15 eV, which is in agreement with the calculated value. By changing the ratio of the distorted [BS3]3- and [GaS4]5- of the title compound, the center of symmetry is likely to be vanished and a new NCS structure with interesting NLO property may be created. Further efforts are going on.

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  • Figure 1  Experimental and simulated X-ray diffraction patterns of Ba9B3GaS15

    Figure 2  EDX spectrum of Ba9B3GaS15

    Figure 3  Structure of Ba9B3GaS15 (a), and the coordination environment of B (1) atom (b), B (2) atom (c), B (3) atom (d), and Ga atom (e) in Ba9B3GaS15

    Figure 4  Infrared transmission spectra of [BS3]3- units in Ba9B3GaS15

    Figure 5  UV-Vis diffuse reflection spectrum of Ba9B3GaS15

    Figure 6  (a) Calculated band structure of Ba9B3GaS15. (b) Total and partial density of states of Ba9B3GaS15

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) of Ba9B3GaS15

    BondDist.BondDist.BondDist.B(1)–S(2)1.82(2)B(2)–S(15)1.83(2)Ga–S(8)2.277(3)Angle(°)Angle(°)Angle(°)S(2)–B(1)–S(7)116.7(6)S(9)–B(2)–S(15)122.7(7)S(6)–Ga–S(11)104.8(2)S(1)–B(2)–S(15)120.4(7)S(6)–Ga–S(8)111.4(2)S(11)–Ga–S(14)116.7(2)
    B(1)–S(7)1.84(2)B(3)–S(5)1.79(2)Ga–S(11)2.218(3)
    B(1)–S(10)1.81(2)B(3)–S(12)1.83(2)Ga–S(14)2.202(3)
    B(2)–S(1)1.81(2)B(3)–S(13)1.82(2)
    B(2)–S(9)1.82(2)Ga–S(6)2.250(3)
    S(2)–B(1)–S(10)119.0(6)S(5)–B(3)–S(12)119.9(7)S(6)–Ga–S(14)107.4(2)
    S(7)–B(1)–S(10)123.9(7)S(5)–B(3)–S(13)121.9(8)S(8)–Ga–S(11)107.62)
    S(1)–B(2)–S(9)116.7(7)S(12)–B(3)–S(13)118.1(8)S(8)–Ga–S(14)108.9(2)
    下载: 导出CSV

    Table 2.  EDX Data of Ba9B3GaS15

    Point-1Point-2ElementWeight%Atomic%FormulaElementWeight%Atomic%FormulaSK27.2460.3115.18SK33.1266.7918.45Point-3Point-4ElementWeight%Atomic%FormulaElementWeight%Atomic%FormulaSK27.3159.7515.22SK25.8757.9114.41Point-5ElementWeight%Atomic%FormulaAverage formula:Ba8.63Ga1.35S15.83SK28.5161.3715.89Total100
    GaK4.144.211.06GaK3.753.480.96
    BaL68.6335.488.93BaL63.1329.728.21
    Total100Total100
    GaK6.296.331.61GaK6.66.791.69
    BaL66.433.928.64BaL67.5335.298.79
    Total100Total100
    GaK5.565.51.42
    BaL65.9333.138.58
    下载: 导出CSV
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