Antimony germanides

Antimony germanides or antimonide germanides are compounds containing germanium and antimony along with one or more metals. Bonding is only partially ionic, and can be considered as a Zintl phase, rather than antimonide ions with germanide ions. There are often covalent bonds between the antimony, reducing its apparent valence.[1][2]

Some of the compounds have varying ratios of antimony and germanium. For example at 600 °C Gd5Sb3 and Gd5Ge3 can form a solid solution.[3]

Gold does not form a ternary compound,[4] and neither does gallium[5] or bismuth.[6]

Germanium containing antimonides have been investigated for use in thermoelectric materials.[7]

Production

Antimonide germanide compounds can be made by heating a mixture of the powdered elements together at 600° or higher. Tantalum is used as the crucible material, as it does not react. Oxygen must be excluded to stop oxides from forming.[3]

Related compounds include substitution of germanium with other elements from group 13 or 14: SiSb, SnSb, PbSb, AlSb, GaSb, and InSb. Replacing antimony with other pnictides can form related compounds such as phosphidosilicates, arsenidosilicates, phosphidogermanates, arsenidogermanates, phosphidostannates, arsenidostannates, phosphidoplumbates, and arsenidoplumbates.[1]

List

formula system space group unit cell volume density comment ref
TiGeSb tetragonal P4/nmm a = 3.7022 c = 8.214 Z = 2 112.58 [8]
Fe3Ge2Sb hexagonal P6/mmm a = 8.9070 c = 7.9217 [9]
FeGe1−𝑥⁢Sb𝑥 x<0.05 hexagonal P6/mmm [10]
FeGe1−𝑥⁢Sb𝑥 0.1<x<0.2 hexagonal P63/mmm [10]
Ti0.5Fe6Ge5Sb hexagonal P6/mmm a=8.845 c=7.9785 Z=3 [11]
Cr0.8Fe5.3Ge5.2Sb0.8 hexagonal P6/mmm a=8.850 c=8.025 Z=3 [11]
Mn1.8Fe4.6Ge4.9Sb1.1 hexagonal P6/mmm a=8.910 c=7.9665 Z=3 [11]
CoGexSb1-x hexagonal P63/mmm Ge and Sb disordered [12]
Co3Ge2Sb hexagonal P6/mmm a = 8.913 c = 7.6312 Z = 6 [12]
Cu6GeSb hexagonal P63/mmc a=4.16, c=7.47 [13][14]
Ge2GaSb cubic gallium antimonide and germanium forma solid solution [15]
Y5Sb2Ge2 [16]
ZrGeSb [17]
ZrGe0.211Sb1.78 orthorhombic Pnma a = 7.304 b = 3.9513 c = 9.576 Z=4 276.35 7.763 [18]
NbGeSb tetragonal P4/nmm a=3.75 c=8.30 [19]
ZnIn18GeSb20 [7]
La5Ge3Sb hexagonal P63/mcm a=9.156 c=7.231 Z=2 525.0 [20]
La6Ge2.8Sb13.2 orthorhombic Immm a = 4.3034 b = 10.851 c = 27.073 Z=2 1272.6 Metallic; columns of trigonal prisms [21][22]
La12Ge6.6Sb21 orthorhombic Immm a=4.3165 b=15.205 c=34.443 Z=2 [23]
Ce2GeSb3 orthorhombic Cmmm Sb ZigZag chain [24][1]
Ce3GeSb [24]
Ce5Ge3Sb2 [24]
Ce6Ge5Sb12 orthorhombic Immm a=4.2972 b=10.740 c=26.791 Z=2 1236.4 Metallic; columns of trigonal prisms [21]
Ce12Ge5.2Sb26.8 C222 a=8.6075 b=21.5154 c=26.8227 4967.4 7.117 [25]
Pr6Ge5Sb12 orthorhombic Immm a=4.2574 b=10.677 c=26.626 Z=2 1213.1 Metallic; columns of trigonal prisms [21]
Pr12Ge6.48Sb21 orthorhombic Immm a=4.2578 b=114.9777 c=33.938 Z=2 2164.3 7.240 [23]
Nd6Ge3.61Sb12.4 orthorhombic Immm a = 4.2310 b = 10.6362 c = 26.526 Z=2 1197.8 Metallic; columns of trigonal prisms [21][22]
Sm6Ge5Sb12 orthorhombic Immm a=4.1932 b=10.537 c=26.350 Z=2 1164.5 Metallic; columns of trigonal prisms [21]
Gd4Ge1.97Sb1.03 cubic I43d a=9.0111 [26]
Gd5Ge0.9Sb3.1 orthorhombic Cmce a = 12.241, b = 8.025, c = 8.039 Z=4 8.539 light grey [3]
Gd2Ge3.28Sb0.65 orthorhombic Cmcm a = 4.0198, b = 30.373, c = 4.1340 Z=4 8.440 grey [3]
Gd6Ge4.3Sb11.7 orthorhombic Immm a = 4.1509 b = 10.4438 c = 26.2400 Z=2 1136.7 Metallic; columns of trigonal prisms [21][22]
Gd8Ge13.29Sb1.72 orthorhombic Cmcm a = 4.02832 b =30.4101 c = 4.14426 Z=1 507.68 7.953 [26]
Gd1.02 Sc0.98Ge0.9Sb0.1 tetragonal I4/mmm a=4.2730 c=15.658 ferromagnetic < 333K [27]
Gd1.02 Sc0.98Ge0.5Sb0.5 tetragonal I4/mmm a=4.3277 c=15.904 ferromagnetic < 170K [27]
Gd1.02 Sc0.98Ge0.2Sb0.8 tetragonal P4/nmm a=4.3192 c=8.1461 [27]
Tb6Ge5Sb12 orthorhombic Immm a=4.1305 b=10.393 c=26.139 Z=2 1122.1 Metallic; columns of trigonal prisms [21]
Dy6Ge5Sb12 orthorhombic Immm a=4.103 b=10.345 c=26.014 Z=2 1104.2 Metallic; columns of trigonal prisms [21]
Dy5Sb2Ge2 orthorhombic Cmca [16]
Ho5Sb2Ge2 orthorhombic Cmca [16]
Er5Sb2Ge2 orthorhombic Cmca [16]
Tm5Sb2Ge2 orthorhombic Cmca [16]
Yb8Ge3Sb5 tetragonal I4/mmm a=15.8965 c=6.8206 Z=4 1723.6 8.520 metallic silver; 1∞(Ge3)4-; negative thermal expansion under 15 K [28][29][30]
CaYb4Al2Sb5.8Ge0.2 orthorhombic [2]
CaYb4Al2Sb5.5Ge0.5 orthorhombic P1m1 a=13.9770 b=4.4203 c=11.9985 741.30 [2]
CaYb4Al2Sb5.3Ge0.7 orthorhombic [2]
HfGe0.205Sb1.795 orthorhombic Pnma a=7.312 b=3.943 c=9.488 Z=4 273.5 10.002 [18]
Hf3Cu2Ge3.58Sb1.42 tetragonal P4/nmm a = 3.8023 c = 24.575 Z=2 355.3 10.241 [31]

References

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  2. 1 2 3 4 Lim, Sung-Ji; Nam, Gnu; Shin, Seungeun; Ahn, Kyunghan; Lee, Yunho; You, Tae-Soo (6 May 2019). "Anionic Doping and Cationic Site Preference in CaYb 4 Al 2 Sb 6– x Ge x ( x = 0.2, 0.5, 0.7): Origin of the Enhanced Seebeck Coefficient and the Structural Transformation". Inorganic Chemistry. 58 (9): 5827–5836. doi:10.1021/acs.inorgchem.9b00181. PMID 30985118.
  3. 1 2 3 4 Department of Inorganic Chemistry, Ivan Franko National University of Lviv; Dankevych, Roman; Tokaychuk, Yaroslav; Department of Inorganic Chemistry, Ivan Franko National University of Lviv (2022). "The ternary system Gd–Ge–Sb at 600°C" (PDF). Chemistry of Metals and Alloys. 15 (1/2): 12–16. doi:10.30970/cma15.0423.
  4. ↑ Wang, J.; Leinenbach, C.; Roth, M. (October 2009). "Thermodynamic description of the Au–Ge–Sb ternary system". Journal of Alloys and Compounds. 485 (1–2): 577–582. doi:10.1016/j.jallcom.2009.06.030.
  5. ↑ Manasijević, Dragan; Minić, Duško; Balanović, Ljubiša; Premović, Milena; Gorgievski, Milan (February 2019). "Experimental Investigation and Thermodynamic Extrapolation of the Ga-Ge-Sb Phase Diagram". Journal of Phase Equilibria and Diffusion. 40 (1): 34–44. Bibcode:2019JPED...40...34M. doi:10.1007/s11669-018-0685-5.
  6. ↑ Premović, Milena; Minić, Duško; Ćosović, Vladan; Manasijević, Dragan; Živković, Dragana (October 2014). "Experimental Investigation and Thermodynamic Calculations of the Bi-Ge-Sb Phase Diagram". Metallurgical and Materials Transactions A. 45 (11): 4829–4841. Bibcode:2014MMTA...45.4829P. doi:10.1007/s11661-014-2445-4.
  7. 1 2 Kim, Donghun; Kurosaki, Ken; Ohishi, Yuji; Muta, Hiroaki; Yamanaka, Shinsuke (2012). "Reduction in Lattice Thermal Conductivity of InSb by Formation of the ZnIn18GeSb20 Alloy". Materials Transactions. 53 (11): 1976–1980. doi:10.2320/matertrans.M2012176. ISSN 1345-9678.
  8. ↑ Lam, Robert; Mar, Arthur (15 September 2009). "Titanium germanium antimonide, TiGeSb". Acta Crystallographica Section E: Structure Reports Online. 65 (9): i68. doi:10.1107/S1600536809031559. PMC 2969891. PMID 21577387.
  9. ↑ Gibson, Quinn D.; Daou, Ramzy; Zanella, Marco; Alaria, Jonathan; Rosseinsky, Matthew J. (2023-07-05). "Magnetic, electronic, and thermal properties of buckled kagome Fe 3 Ge 2 Sb". Physical Review B. 108 (3) 035102. doi:10.1103/PhysRevB.108.035102. ISSN 2469-9950.
  10. 1 2 Huang, Jiale; Shang, Chenglin; Qin, Jianfei; Pan, Feihao; Shi, Bingxian; Wang, Jinchen; Liu, Juanjuan; Xu, Daye; Zhang, Hongxia; Wang, Hongliang; Hao, Lijie; Bao, Wei; Cheng, Peng (2023-11-28). "FeGe 1 − x Sb x : A series of kagome metals with noncollinear antiferromagnetism". Physical Review B. 108 (18) 184431. doi:10.1103/PhysRevB.108.184431. hdl:2031/98d09f5c-e3ec-492e-a886-b966488b1724. ISSN 2469-9950.
  11. 1 2 3 Mills, Allison M.; Anderson, Erica J.; Mar, Arthur (June 2001). "Structures of the quaternary iron germanium antimonides R1−x(R,Fe)6Ge4(Ge,Sb)2 (R=Ti, Cr, Mn), filled derivatives of FeGe1−xSbx". Journal of Alloys and Compounds. 322 (1–2): 103–112. doi:10.1016/S0925-8388(01)01020-9.
  12. 1 2 Mills, Allison M; Lam, Robert; Mar, Arthur (1998-11-01). "Ternary cobalt germanium pnictides CoGe x Pn 1- x ( Pn = P, As, Sb) and the structure of Co 3 Ge 2 Sb, an intermetallic compound with stuffed Sb 2 pairs". Canadian Journal of Chemistry. 76 (11): 1588–1594. doi:10.1139/v98-142. ISSN 0008-4042.
  13. ↑ Premović, Milena; Du, Yong; Minić, Duško; Zhang, Cong; Manasijević, Dragan; Balanović, Ljubiša; Marković, Ivana (December 2017). "Experimental investigation and thermodynamic calculation of the Cu-Ge-Sb system". Journal of Alloys and Compounds. 726: 820–832. doi:10.1016/j.jallcom.2017.08.051.
  14. ↑ Lenz, Jürgen; Schubert, Konrad (1971-11-01). "Über einige Leerstellen- und Stapelvarianten der Beta-Messing Strukturfamilie". International Journal of Materials Research. 62 (11): 810–816. Bibcode:1971IJMR...62..810L. doi:10.1515/ijmr-1971-621110. ISSN 2195-8556.
  15. ↑ DUWEZ, POL; WILLENS, R. H.; KLEMENT, JR, W. (14 June 1960). "Metastable Solid Solutions in the Gallium Antimonide-Germanium Pseudo-binary System" (PDF). Journal of Applied Physics. 31 (8): 1500. Bibcode:1960JAP....31.1500D. doi:10.1063/1.1735872. Archived from the original (PDF) on 2017-09-22.
  16. 1 2 3 4 5 Kozlov, A.Yu.; Pavlyuk, V.V.; Davydov, V.M. (February 2004). "The crystal structure of the new ternary compounds RE5Sb2X2 (RE—Y, Tb, Dy, Ho, Er, Tm; X—Si or Ge)". Intermetallics. 12 (2): 151–155. doi:10.1016/j.intermet.2003.09.010.
  17. ↑ Ozyar, U.F.; Deligoz, E.; Colakoglu, K. (February 2015). "Systematic study on the anisotropic elastic properties of tetragonal XYSb (X = Ti, Zr, Hf; Y = Si, Ge) compounds". Solid State Sciences. 40: 92–100. Bibcode:2015SSSci..40...92O. doi:10.1016/j.solidstatesciences.2015.01.001.
  18. 1 2 Soheilnia, Navid; Assoud, Abdeljalil; Kleinke, Holger (2003-11-01). "MA δ Sb 2- δ (M = Zr, Hf; A = Si, Ge): A New Series of Ternary Antimonides and Not "β-ZrSb 2 "". Inorganic Chemistry. 42 (22): 7319–7325. doi:10.1021/ic0347440. ISSN 0020-1669. PMID 14577804.
  19. ↑ Guo, Lei; Zhao, Weiyao; Ding, Ning; Shi, Xin-Yao; Xu, Meng; Chen, Lei; Gao, Guan-Yin; Dong, Shuai; Zheng, Ren-Kui (2020-10-14). "Magnetotransport properties of square-net compounds of NbSiSb and NbGeSb single crystals". Journal of Physics: Condensed Matter. 32 (43): 435701. arXiv:2007.15437. Bibcode:2020JPCM...32Q5701G. doi:10.1088/1361-648X/aba385. ISSN 0953-8984. PMID 32634789.
  20. ↑ Guloy, Arnold M.; Corbett, John D. (August 1993). "The lanthanum-germanium system. Nineteen isostructural interstitial compounds of the La5Ge3 host". Inorganic Chemistry. 32 (16): 3532–3540. doi:10.1021/ic00068a025. ISSN 0020-1669.
  21. 1 2 3 4 5 6 7 8 Deakin, Laura; Lam, Robert; Mar, Arthur (2001-02-01). "Rare-Earth Germanium Antimonides RE 6 Ge 5 - x Sb 11+ x ( RE = La−Nd, Sm, Gd−Dy). II. Magnetic and Transport Properties". Inorganic Chemistry. 40 (5): 960–965. doi:10.1021/ic0014078. ISSN 0020-1669.
  22. 1 2 3 Lam, Robert; McDonald, Robert; Mar, Arthur (2001-02-01). "Rare-Earth Germanium Antimonides RE 6 Ge 5 - x Sb 11+ x ( RE = La−Nd, Sm, Gd−Dy). I. Syntheses and Structures". Inorganic Chemistry. 40 (5): 952–959. doi:10.1021/ic0009472. ISSN 0020-1669.
  23. 1 2 Bie, Haiying; Mar, Arthur (September 2009). "Ge Pairs and Sb Ribbons in Rare-Earth Germanium Antimonides RE 12 Ge 7− x Sb 21 ( RE =La–Pr)". Chemistry – an Asian Journal. 4 (9): 1465–1473. doi:10.1002/asia.200900063. ISSN 1861-4728. PMID 19554602.
  24. 1 2 3 Stetskiv, A.O.; Pavlyuk, V.V.; Bodak, O.I. (May 1998). "Interaction of the Components in the Ce-Ge-Sb System". Polish Journal of Chemistry. 72 (5): 956–958.
  25. ↑ Nasir, Navida; Grytsiv, Andriy; Rogl, Peter; Saccone, Adriana; Giester, Gerald (April 2009). "Phase equilibria in systems Ce–M–Sb (M=Si, Ge, Sn) and superstructure Ce12Ge9−xSb23+x (x=3.8±0.1)". Journal of Solid State Chemistry. 182 (4): 645–656. doi:10.1016/j.jssc.2008.12.009.
  26. 1 2 Liu, Hongrui; Liao, Changzhong; Zeng, Weijing; Yang, Tonghan; Zeng, Lingmin; He, Wei (June 2020). "Phase equilibria in the Gd-Ge-Sb system at 773 K and the magnetic properties of novel compound Gd8Ge13.29Sb1.72". Journal of Alloys and Compounds. 825 153841. doi:10.1016/j.jallcom.2020.153841.
  27. 1 2 3 Guillou, F; Pathak, A K; Hackett, T A; Paudyal, D; Mudryk, Y; Pecharsky, V K (2017-12-06). "Crystal, magnetic, calorimetric and electronic structure investigation of GdScGe 1– x Sb x compounds". Journal of Physics: Condensed Matter. 29 (48): 485802. doi:10.1088/1361-648X/aa93aa. ISSN 0953-8984. OSTI 1411177. PMID 29120868.
  28. ↑ Salvador, James R.; Bilc, Daniel; Mahanti, S. D.; Hogan, Tim; Guo, Fu; Kanatzidis, Mercouri G. (2004-04-01). "Yb 8 Ge 3 Sb 5 , a Metallic Mixed-Valent Zintl Phase Containing the Polymeric 1 ∞ [Ge 3 4- ] Anions". Journal of the American Chemical Society. 126 (14): 4474–4475. Bibcode:2004JAChS.126.4474S. doi:10.1021/ja0395487. ISSN 0002-7863. PMID 15070338.
  29. ↑ Margadonna, Serena; Prassides, Kosmas; Chondroudi, Maria; Salvador, James R.; Kanatzidis, Mercouri G. (2005). "Temperature-induced abrupt volume inflation in the mixed-valence ternary Zintl phase Yb8Ge3Sb5". Chemical Communications (46): 5754–5756. doi:10.1039/b511606f. ISSN 1359-7345. PMID 16307135.
  30. ↑ Kosaka, Masashi; Kasuya, Shunsuke; Michimura, Shinji; Iizuka, Ryosuke; Uwatoko, Yoshiya (2020-03-19). "Magnetic and Transport Properties of Rare Earth Zintl Compound Yb8Ge3Sb5". Proceedings of the International Conference on Strongly Correlated Electron Systems (SCES2019). Physical Society of Japan. doi:10.7566/JPSCP.30.011138. ISBN 978-4-89027-142-9.
  31. ↑ Guch, Mykhailo; Sankar, Cheriyedath Raj; Assoud, Abdeljalil; Kleinke, Holger (2010-12-14). "Crystal Structure and Physical Properties of the New Antimonide Hf 3 Cu 2 Ge 3.58 Sb 1.42". Chemistry of Materials. 22 (23): 6433–6437. doi:10.1021/cm102632a. ISSN 0897-4756.
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