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.

    1. [1]

      Chung D. Y, Hogan T, Brazis P, Rocci-Lane M, Kannewurf C, Bastea M, Uher C, Kanatzidis M. G. CsBi4Te6: a high-performance thermoelectric material for low-temperature applications[J]. Science, 2000, 287:  1024-1027. doi: 10.1126/science.287.5455.1024 doi: 10.1126/science.287.5455.1024

    2. [2]

      Lin Z. S, Chen L, Wang L. M, Zhao J. T, Wu L. M. A promising mid-temperature thermoelectric material candidate: Pb/Sn-codoped In4PbxSnySe3[J]. Adv. Mater, 2013, 25:  4800-4806. doi: 10.1002/adma.v25.34 doi: 10.1002/adma.v25.34

    3. [3]

      Yu P, Wu L. M, Chen L. PbMnIn2S5: synthesis, structure, and properties[J]. Inorg. Chem, 2013, 52:  724-728. doi: 10.1021/ic3018584 doi: 10.1021/ic3018584

    4. [4]

      Poudeu P. F. P, Takas N, Anglin C, Eastwood J, Rivera A. FexPb4-xSb4Se10: a new class of ferromagnetic semiconductors with quasi 1D {Fe2Se10} ladders[J]. J. Am. Chem. Soc, 2010, 132:  5751-5760. doi: 10.1021/ja910545e doi: 10.1021/ja910545e

    5. [5]

      (a) Wu X. T, Chen L.Vol. Eds. Structure-property Relationships in Non-linear Optical Crystals. I. The UV-Vis Region. In Struct. Bonding (Berlin); Mingos D. M. P.Series Ed.; Springer: New York, 2012, Vol. 144. (b) Wu, X. T.; Chen, L. Vol. Eds. Structure-property Relationships in Nonlinear Optical Crystals. II. The IR Region. In Struct. Bonding (Berlin); Mingos, D. M. P., Series Ed.; Springer: New York, 2012, Vol. 145.

    6. [6]

      Chung I, Kanatzidis M. G. Metal chalcogenides: a rich source of nonlinear optical materials[J]. Chem. Mater, 2014, 26:  849-869. doi: 10.1021/cm401737s doi: 10.1021/cm401737s

    7. [7]

      (a) Jayaraman A, Narayanamurti V, Kasper H. M, Chin M. A, Maines R. G.Pressure-dependence of energy-gap in some I-III-VI2 compound semiconductors. Phys. Rev. B, 1976, 14: 3516-3519. (b) Harasaki, A.; Kato, K. New data on the nonlinear optical constant, phase-matching, and optical damage of AgGaS2. Jpn. J. Appl. Phys, 1997, 36: 700-703. (c) Catella, G. C.; Shiozawa, L. R.; Hietanen, J. R.; Eckardt, R. C.; Route, R. K.; Feigelson, R. S.; Cooper, D. G.; Marquardt, C. L. Mid-IR absorption in AgGaSe2 optical parametric oscillator crystals. Appl. Opt, 1993, 32: 3948-3951.

    8. [8]

      (a) Lin X. S, Zhang G, Ye N.Growth and characterization of BaGa4S7: a new crystal for mid-IR nonlinear optics. Cryst. Growth Des, 2009, 9: 1186-1189. (b) Yao, J. Y.; Mei, D. J.; Bai, L.; Lin, Z. S.; Yin, W. L.; Fu, P. Z.; Wu, Y. C. BaGa4Se7: a new congruent-melting IR nonlinear optical material. Inorg. Chem, 2010, 49: 9212-9216.

    9. [9]

      Chen M. C, Wu L. M, Lin H, Zhou L. J, Chen L. Disconnection enhances the second harmonic generation response: synthesis and characterization of Ba23Ga8Sb2S38[J]. J. Am. Chem. Soc, 2012, 134:  6058-6060. doi: 10.1021/ja300249n doi: 10.1021/ja300249n

    10. [10]

      Lin H, Zhou L. J, Chen L. Sulfides with strong nonlinear optical activity and thermochromism: ACd4Ga5S12 (A = K, Rb, Cs)[J]. Chem. Mater, 2012, 24:  3406-3414. doi: 10.1021/cm301550a doi: 10.1021/cm301550a

    11. [11]

      Chen M. C, Li L. H, Chen Y. B, Chen L. In-phase alignments of asymmetric building units in Ln4GaSbS9 (Ln = Pr, Nd, Sm, Gd-Ho) and their strong nonlinear optical responses in middle IR[J]. J. Am. Chem. Soc, 2011, 133:  4617-4624. doi: 10.1021/ja1111095 doi: 10.1021/ja1111095

    12. [12]

      Li Y. Y, Liu P. F, Hu L, Chen L, Lin H, Zhou L. J, Wu L. M. Strong IR NLO material Ba4MGa4Se10Cl2: highly improved laser damage threshold via dual ion substitution synergy[J]. Adv. Opt. Mater, 2015, 3:  957-966. doi: 10.1002/adom.201500038 doi: 10.1002/adom.201500038

    13. [13]

      Liu B. W, Zeng H. Y, Zhang M. J, Fan Y. H, Guo G. C, Huang J. S, Dong Z. C. Syntheses, structures, and nonlinear-optical properties of metal sulfides Ba2Ga8MS16 (M = Si, Ge)[J]. Inorg. Chem, 2015, 54:  976-981. doi: 10.1021/ic502362f doi: 10.1021/ic502362f

    14. [14]

      Li Y. Y, Li B. X, Zhang G, Zhou L. J, Lin H, Shen J. N, Zhang C. Y, Chen L, Wu L. M. Syntheses, characterization, and optical properties of centrosymmetric Ba3(BS3)1.5(MS3)0.5 and noncentrosymmetric Ba3(BQ3)(SbQ3)[J]. Inorg. Chem, 2015, 54:  4761-4767. doi: 10.1021/acs.inorgchem.5b00189 doi: 10.1021/acs.inorgchem.5b00189

    15. [15]

      (a) Sasaki, T.; Takizawa, H.; Takeda, T.; Endo, T. High-pressure synthesis of a new calcium thioborate, CaB2S4. Mater. Res. Bull. 2003, 38, 33−39. (b) Püttmann, C.; Hamann, W.; Krebs, B. Preparation and crystal structures of TlBS2 and SrB2S4-4 membered B2S2 rings in thioborates. Eur. J. Solid State Inorg. Chem. 1992, 29, 857−872. (c) Hammerschmidt, A.; Doch, M.; Wulff, M.; Krebs, B. BaB2S4: the first non-oxidic chalcogenoborate with boron in a trigonal-planar and tetrahedral coordination. Z. Anorg. Allg. Chem. 2002, 628, 2637−2640.

    16. [16]

      Hammerschmidt A, Koster C, Kuper J, Lindemann A, Krebs B. Novel alkaline earth metal chalcogenoborates: syntheses and crystal structures of Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se[J]. Z. Anorg. Allg. Chem, 2001, 627:  1253-1258. doi: 10.1002/(ISSN)1521-3749 doi: 10.1002/(ISSN)1521-3749

    17. [17]

      (a) Sheldrick, G. M. SHELXS97 Program for Solution of Crystal Structures, 1997.(b) Sheldrick G. M.Program for the refinement of crystal structures, 1997.

    18. [18]

      Spek A. L. J. Single-crystal structure validation with the program PLATON[J]. Appl. Crystallogr, 2003, 36:  7-13. doi: 10.1107/S0021889802022112 doi: 10.1107/S0021889802022112

    19. [19]

      Kortüm G, Lohr J. E.Reflectance Spectroscopy: Principles, Methods, Applications. Springer-Verlag: New York, 1969.

    20. [20]

      Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Phys. Rev. B, 1996, 54:  11169-11186. doi: 10.1103/PhysRevB.54.11169 doi: 10.1103/PhysRevB.54.11169

    21. [21]

      Blöchl P. E. Projector augmented-wave method[J]. Phys. Rev. B, 1994, 50:  17953-17979. doi: 10.1103/PhysRevB.50.17953 doi: 10.1103/PhysRevB.50.17953

    22. [22]

      Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Phys. Rev. B, 1999, 59:  1758-1775.  

    23. [23]

      Eisenmann B, Jakowski M, Schafer H. Ba5(GaS4)2: the 1st ortho-thiogallate(III)[J]. Z. Naturforsch. B, 1984, 39:  27-30.

    24. [24]

      Kim Y, Martin S. W, Ok K. M, Halasyamani P. S. Synthesis of the thioborate crystal ZnxBa2B2S5+x (x ≈ 0.2) for second order nonlinear optical applications[J]. Chem. Mater, 2005, 2005, 17:  2046-2051.  

    25. [25]

      Royle M, Cho J, Martin S. W. Raman spectroscopy studies of xNa2S-(1-x)B2S3 glasses and polycrystals[J]. J. Non-Cryst. Solids, 2001, 279:  97-109. doi: 10.1016/S0022-3093(00)00344-6 doi: 10.1016/S0022-3093(00)00344-6

    26. [26]

      Kuchinke J, Jansen C, Lindemann A, Krebs B. Syntheses and crystal structures of the novel ternary thioborates Na3BS3, K3BS3, and Rb3BS3[J]. Z. Anorg. Allg. Chem, 2001, 627:  896-902. doi: 10.1002/(ISSN)1521-3749 doi: 10.1002/(ISSN)1521-3749

    27. [27]

      Kim Y, Martin S. W. Synthesis and crystal structure of barium thioborate Ba7(BS3)4S[J]. Inorg. Chem, 2004, 43:  2773-2775. doi: 10.1021/ic035454m doi: 10.1021/ic035454m

    28. [28]

      (a) Godby, R. W.; Schlüter, M.; Sham, L. J. Trends in self-energy operators and their corresponding exchange-correlation potentials. Phys. Rev. B 1987, 36, 6497–6500; (b) Okoye, C. M. I. Theoretical study of the electronic structure, chemical bonding and optical properties of KNbO3 in the paraelectric cubic phase. J. Phys. Condens. Matter. 2003, 15, 5945–5958.

  • 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
  • 加载中
计量
  • PDF下载量:  0
  • 文章访问数:  4464
  • HTML全文浏览量:  74
文章相关
  • 收稿日期:  2016-04-08
  • 接受日期:  2016-05-06
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章