Abstract
The thermal phonon transport is a key matter for heat managing in materials science which is crucial for device miniaturization and power density increase. Herein, we report the synthesis, structure and characterization of a new compound, Cs2Ge3Ga6Se14, with a unique anisotropic structure simultaneously containing Ge3+ and Ge2+ that adopt (Ge1)3+2Se6 dimer or (Ge2)2+Se6 octahedron, respectively. The thermal conductivity was measured to be 0.57–0.48 W m−1 K−1 from 323 to 773 K, the lowest value among all the known Ge containing compounds, approaching its glass limit according to the Cahill’s formulation. More importantly, we discover for the first time that the vibration uncoupling of Ge with different valence states hinders the effective thermal energy transport between the (Ge1)3+2Se6 dimer and (Ge2)2+Se6 octahedron, and consequently lowers the thermal conductivity. In addition, we propose a structure factor fi = sin(180 − β) × dGe−Q/li (i = A, B), with which a structure map of the Cs2Ge3M6Q14 family is given.
摘要
热管理是电子器件小型化和功率密度提高的关键, 因此研究材料热输运性质及声子传输机制具有非常重要的意义. 本文报道了一例含多价态锗(Ge3+, Ge2+)的新型硒化物, Cs2Ge3Ga6Se14. 单晶结构衍射数据表明, 化合物中不同价态锗分别采用(Ge3+)2Se6二聚体或(Ge2+)Se6八面体的配位模式, 323–773 K范围内, 其热导率测试值为0.57–0.48 W m−1 K−1, 该值是目前已知含锗固体材料中的最低值, 接近其玻璃态极限值. 更重要的是, 我们发现由于不同价态锗离子振动模式之间存在弱耦合性, 使得热振动能量无法在两种结构单元之间有效传递, 从而降低了化合物热导率. 这种机制在材料热导率研究领域尚属首次发现. 本文还通过结构因子fi=sin(180−β)× dGe−O/li (i=A, B)的大小, 给出了Cs2Ge3M6Q14家族的晶体结构分布规律.
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References
Xu X, Chen J, Li B. Phonon thermal conduction in novel 2D materials. J Phys-Condens Matter, 2016, 28: 483001–483021
Ummadisingu A, Steier L, Seo JY, et al. The effect of illumination on the formation of metal halide perovskite films. Nature, 2017, 545: 208–212
Island JO, Molina-Mendoza AJ, Barawi M, et al. Electronics and optoelectronics of quasi-1D layered transition metal trichalcogenides. 2D Mater, 2017, 4: 022003
Chung DY, Hogan T, Brazis P, et al. CsBi4Te6: a high-performance thermoelectric material for low-temperature applications. Science, 2000, 287: 1024–1027
Hsu KF, Loo S, Guo F, et al. Cubic AgPbmSbTe2+m: bulk thermoelectric materials with high figure of merit. Science, 2004, 303: 818–821
Tan G, Shi F, Hao S, et al. Codoping in SnTe: enhancement of thermoelectric performance through synergy of resonance levels and band convergence. J Am Chem Soc, 2015, 137: 5100–5112
Soni A, Shen Y, Yin M, et al. Interface driven energy filtering of thermoelectric power in spark plasma sintered Bi2Te2.7Se0.3 nanoplatelet composites. Nano Lett, 2012, 12: 4305–4310
Zhou C, Lee YK, Cha J, et al. Defect engineering for high-performance n-type PbSe thermoelectrics. J Am Chem Soc, 2018, 140: 9282–9290
Li Z, Xiao C, Zhu H, et al. Defect chemistry for thermoelectric materials. J Am Chem Soc, 2016, 138: 14810–14819
Biswas K, He J, Blum ID, et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature, 2012, 489: 414–418
Zhao LD, Dravid VP, Kanatzidis MG. The panoscopic approach to high performance thermoelectrics. Energy Environ Sci, 2014, 7: 251–268
Chen YK, Chen MC, Zhou LJ, et al. Syntheses, structures, and nonlinear optical properties of quaternary chalcogenides: Pb4Ga4GeQ12 (Q = S, Se). Inorg Chem, 2013, 52: 8334–8341
Li G, Wu K, Liu Q, et al. Na2ZnGe2S6: A new infrared nonlinear optical material with good balance between large second-harmonic generation response and high laser damage threshold. J Am Chem Soc, 2016, 138: 7422–7428
Mei D, Yin W, Feng K, et al. LiGaGe2Se6: A new IR nonlinear optical material with low melting point. Inorg Chem, 2012, 51: 1035–1040
Li GM, Liu Q, Wu K, et al. Na2CdGe2Q6 (Q = S, Se): two metal-mixed chalcogenides with phase-matching abilities and large second-harmonic generation responses. Dalton Trans, 2017, 46: 2778–2784
Feng K, Wang W, He R, et al. K2FeGe3Se8: A new antiferromagnetic iron selenide. Inorg Chem, 2013, 52: 2022–2028
Lin Z, Li C, Kang L, et al. SnGa2GeS6: synthesis, structure, linear and nonlinear optical properties. Dalton Trans, 2015, 44: 7404–7410
Aitken JA, Larson P, Mahanti SD, et al. Li2PbGeS4 and Li2EuGeS4: Polar chalcopyrites with a severe tetragonal compression. Chem Mater, 2001, 13: 4714–4721
McGuire MA, Scheidemantel TJ, Badding JV, et al. Tl2AXTe4 (A = Cd, Hg, Mn; X = Ge, Sn): Crystal structure, electronic structure, and thermoelectric properties. Chem Mater, 2005, 17: 6186–6191
Li G, Zhen N, Chu Y, et al. Li3Ge3Se6: the first ternary lithium germanium selenide with interesting ∞[Ge6Se12]n chains constructed by ethane-like [Ge2Se6]6− clusters. Dalton Trans, 2017, 46: 16399–16403
Wu K, Yang Z, Pan S. Na4MgM2Se6 (M = Si, Ge): The first non-centrosymmetric compounds with special ethane-like [M2Se6]6− units exhibiting large laser-damage thresholds. Inorg Chem, 2015, 54: 10108–10110
Cui Y, Assoud A, Kleinke H. Synthesis and structural and physical properties of new semiconducting quaternary tellurides: Ba4Ag3.95Ge2Te9 and Ba4Cu3.71Ge2Te9. Inorg Chem, 2009, 48: 5313–5319
Choudhury A, Strobel S, Martin BR, et al. Synthesis of a family of solids through the building-block approach: A case study with Ag+ substitution in the ternary Na-Ge-Se system ChemInform, 2007, 38
Choudhury A, Ghosh K, Grandjean F, et al. Structural, optical, and magnetic properties of Na8Eu2(Si2S6)2 and Na8Eu2(Ge2S6)2: Europium(II) quaternary chalcogenides that contain an ethane-like (Si2S6)6− or (Ge2S6)6− moiety. J Solid State Chem, 2015, 226: 74–80
Marking GA, Kanatzidis MG. The ethane-like [Ge2S6]6− and (Si2Se6)6− metals in Na8Pb2[Ge2S6]2, Na8Sn2[Ge2S6]2, and Na8Pb2[Si2Se6]2. J Alloys Compd, 1997, 259: 122–128
Wu X, Hu Y, Pan H, et al. Na9Sb(Ge2Q6)2 (Q = S, Se): two new antimony(III) quaternary chalcogenides with ethane-like [Ge2Q6]6− ligands. RSC Adv, 2016, 6: 99475–99481
Zhang CY, Zhou LJ, Chen L. Quaternary tellurides with different valent Ge centers: Cs2Ge3M6Te14 (M = Ga, In). Inorg Chem, 2012, 51: 7007–7009
Palchik O, Marking GM, Kanatzidis MG. Exploratory synthesis in molten salts: Role of flux basicity in the stabilization of the complex thiogermanates Cs4Pb4Ge5S16, K2PbGe2S6, and K4Sn3Ge3S14. Inorg Chem, 2005, 44: 4151–4153
Poling SA, Nelson CR, Sutherland JT, et al. Crystal structure of thiogermanic acid H4Ge4S10. Inorg Chem, 2003, 42: 7372–7374
Wu YY, Xiong L, Jia F, et al. Cs2Ge3In6Se14: A structure transformation driven by the size preference and its properties. Inorg Chem, 2018, 57: 4667–4672
Sheldrick GM. SHELXTL, version 5.1. Bruker-AXS: Madison, WI, 1998
Spek AL. Single-crystal structure validation with the program PLATON. J Appl Crystlogr, 2003, 36: 7–13
Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54: 11169–11186
Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865–3868
Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B, 1999, 59: 1758–1775
Blöchl PE. Projector augmented-wave method. Phys Rev B, 1994, 50: 17953–17979
Parliñski K. Software phonon, cracow (2001) as implemented in medeA 2.2. Materials Design, Angel Fire, New Mexico, 2005
Anderson MW, Gebbie-Rayet JT, Hill AR, et al. Predicting crystal growth via a unified kinetic three-dimensional partition model. Nature, 2017, 544: 456–459
Rak M, Izdebski M, Brozi A. Kinetic Monte Carlo study of crystal growth from solution. Comput Phys Commun, 2001, 138: 250–263
Cuppen HM, van Veenendaal E, van Suchtelen J, et al. A Monte Carlo study of dislocation growth and etching of crystals. J Cryst Growth, 2000, 219: 165–175
Wei L, Lv X, Yang Y, et al. Theoretical investigation on the microscopic mechanism oflattice thermal conductivity of ZnXP2 (X = Si, Ge, and Sn). Inorg Chem, 2019, 58: 4320–4327
Garg J, Bonini N, Marzari N. High thermal conductivity in short-period superlattices. Nano Lett, 2011, 11: 5135–5141
Shaabani L, Aminorroaya-Yamini S, Byrnes J, et al. Thermoelectric performance of Na-doped GeSe. ACS Omega, 2017, 2: 9192–9198
Ibáñez M, Zamani R, LaLonde A, et al. Cu2ZnGeSe4 nanocrystals: Synthesis and thermoelectric properties. J Am Chem Soc, 2012, 134: 4060–4063
Perez CJ, Bates VJ, Kauzlarich SM. Hydride synthesis and thermoelectric properties of type-I clathrate K8E8Ge38 (E = Al, Ga, In). Inorg Chem, 2019, 58: 1442–1450
Pavan Kumar V, Paradis-Fortin L, Lemoine P, et al. Designing a thermoelectric copper-rich sulfide from a natural mineral: Synthetic germanite Cu22Fe8Ge4S32. Inorg Chem, 2017, 56: 13376–13381
Nuss J, Wedig U, Xie W, et al. Phosphide-tetrahedrite Ag6Ge10P12: Thermoelectric performance of a long-forgotten silver-cluster compound. Chem Mater, 2017, 29: 6956–6965
Fu J, Su X, Zheng Y, et al. Thermoelectric properties of Ga/Ag codoped type-III Ba24Ge100 clathrates with in situ nanostructures. ACS Appl Mater Interfaces, 2015, 7: 19172–19178
Heinrich CP, Day TW, Zeier WG, et al. Effect of isovalent subs0titution on the thermoelectric properties of the Cu2ZnGeSe4−xSx series of solid solutions. J Am Chem Soc, 2014, 136: 442–448
Chen H, Chen YK, Lin H, et al. Quaternary layered semiconductor Ba2Cr4GeSe10: Synthesis, crystal structure, and thermoelectric properties. Inorg Chem, 2018, 57: 916–920
Kurosaki K, Kosuga A, Muta H, et al. Ag9TlTe5: A high-performance thermoelectric bulk material with extremely low thermal conductivity. Appl Phys Lett, 2005, 87: 061919
Wan CL, Pan W, Xu Q, et al. Effect of point defects on the thermal transport properties of (LaxGd1−x)2Zr2O7: Experiment and theoretical model. Phys Rev B, 2006, 74: 144109
Liu H, Shi X, Xu F, et al. Copper ion liquid-like thermoelectrics. Nat Mater, 2012, 11: 422–425
Ouyang T, Zhang X, Hu M. Thermal conductivity of ordered-disordered material: a case study of superionic Ag2Te. Nanotechnology, 2015, 26: 025702
Jiang B, Qiu P, Eikeland E, et al. Cu8GeSe6-based thermoelectric materials with an argyrodite structure. J Mater Chem C, 2017, 5: 943–952
Zhao LD, Lo SH, Zhang Y, et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature, 2014, 508: 373–377
Skoug EJ, Cain JD, Morelli DT. Structural effects on the lattice thermal conductivity of ternary antimony- and bismuth-containing chalcogenide semiconductors. Appl Phys Lett, 2010, 96: 181905
Cahill DG, Watson SK, Pohl RO. Lower limit to the thermal conductivity of disordered crystals. Phys Rev B, 1992, 46: 6131–6140
Acknowledgements
This research was supported by the National Natural Science Foundation of China (21975032 and 21571020), and the National Key Research and Development Program of China (2018YFA0702100). The room temperature ultrasonic pulse echo measurements were performed by Dr. Yu Xiao and Prof. Li-Dong Zhao from the School of Materials Science and Engineering, Beihang University, Beijing, China. Their great help was sincerely appreciated.
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Author contributions Chen L, Wu LM, and Ma N proposed the outline of the manuscript and wrote the paper. All authors discussed and revised the manuscript.
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Ni Ma received her BSc degree from the College of Science, Northeast Forestry University in 2015. Now, she is a PhD candidate under the supervision of Prof. Li-Ming Wu in the College of Chemistry, Beijing Normal University (BNU). Her research interest focuses on the syntheses of inorganic solid functional materials and their applications in energy conversion.
Ling Chen received her MSc from BNU in 1996 and PhD degree in Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS) in 1999, and carried out her postdoc research in Iowa State University, USA in 2000–2003. She joined the faculty of FJIRSM in 2003 as a full professor, and moved to BNU in 2015. Her research focuses on the exploration of solid-state compounds, and their nonlinear optical properties and thermoelectric properties.
Li-Ming Wu received his BSc and MSc degrees from BNU in 1993 and 1996, and PhD degree from Fuzhou University in 1999, and carried out his postdoctoral research in CAS (1999–2001) and Arizona State University, USA (2001–2004). Wu started his own research group as a full professor in 2004 in FJIRSM, CAS, and moved to BNU in 2015. His interests focus on the inorganic solid functional materials and theoretical chemistry of solids.
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Ma, N., Xiong, L., Chen, L. et al. Vibration uncoupling of germanium with different valence states lowers thermal conductivity of Cs2Ge3Ga6Se14. Sci. China Mater. 62, 1788–1797 (2019). https://doi.org/10.1007/s40843-019-1192-y
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DOI: https://doi.org/10.1007/s40843-019-1192-y