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journal articleΒ·2026-02-06Open access

Origin of ferroelectricity in germanium-based inorganic halide perovskites

Lingyao Zhang, Chang Liu, Rui Chen, Musen Li, Xiaoxuan Ma, Xiangyang Kong, David J. Singh, Gian-Marco Rignanese, Wei Ren

Physical Review BΒ· Volume 113Β· Issue 6
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Source abstract

Abstract

Compared to 𝐴⁒𝐡⁒O3 oxide perovskites, intrinsic ferroelectricity is less studied in 𝐴⁒𝐡⁒𝑋3 (𝑋=Cl, Br, I) halide perovskites. Nonetheless, it presents unique opportunities, such as achieving ferroelectric photovoltaics with band gaps suitable for the solar spectrum. In this work, we focus on the CsGe⁒𝑋3 halide perovskites as prototypes for investigating the origin of their ferroelectricity and its relationship with other properties. We find that the presence of stereochemically lone pairs on the perovskite 𝐡-site is the primary driving force for ferroelectricity, causing off-center displacements of the Ge ions and enhanced covalency with the halide ligands. This contrasts with the behavior of typical ferroelectric oxide perovskites. Our calculations confirm that halide perovskites are intrinsic modest band gap semiconductors. In particular, CsGeI3 exhibits a very favorable band gap of 1.6 eV for photovoltaic applications. Our findings provide valuable insights into the mechanism underlying high-temperature ferroelectricity in halide perovskites with potential optoelectronic applications.
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Research context

Electronic materials

OpenAlex topics: Perovskite Materials and Applications Β· Solid-state spectroscopy and crystallography Β· Photorefractive and Nonlinear Optics

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Shanghai University

UniversitΓ© catholique de Louvain

China Electronic Product Reliability and Environmental Testing Research Institute

Shanghai Jiao Tong University

University of Missouri

Funding

National Natural Science Foundation of China Β· Science and Technology Commission of Shanghai Municipality Β· China Scholarship Council Β· Shanghai Super Postdoctoral Incentive Program

References (77)

Show source-provided references
1. M. E. Lines Β· 200110.1093/acprof:oso/9780198507789.001.0001 β†—
2. 10.1126/science.112956410.1126/science.1129564 β†—
3. V. M. Fridkin Β· 2012
4. 10.1038/nmat328210.1038/nmat3282 β†—
5. 10.1038/nnano.2009.45110.1038/nnano.2009.451 β†—
6. 10.1038/nature1262210.1038/nature12622 β†—
7. 10.1126/science.124398210.1126/science.1243982 β†—
8. 10.1038/nphoton.2014.13410.1038/nphoton.2014.134 β†—
9. 10.1039/C4TA01198H10.1039/C4TA01198H β†—
10. 10.1021/jacs.9b1134110.1021/jacs.9b11341 β†—
11. 10.1126/science.aai853510.1126/science.aai8535 β†—
12. 10.1038/s41563-018-0152-z10.1038/s41563-018-0152-z β†—
13. 10.1002/adma.20220541010.1002/adma.202205410 β†—
14. 10.1039/c9ee00884e10.1039/c9ee00884e β†—
15. 10.1038/s41563-019-0480-710.1038/s41563-019-0480-7 β†—
16. 10.1126/sciadv.abj588110.1126/sciadv.abj5881 β†—
17. 10.1021/acs.jpcc.2c0681810.1021/acs.jpcc.2c06818 β†—
18. 10.3891/acta.chem.scand.19-042110.3891/acta.chem.scand.19-0421 β†—
19. 10.1002/zaac.1987545021710.1002/zaac.19875450217 β†—
20. 10.1007/s00257005051510.1007/s002570050515 β†—
21. 10.1016/0038-1098(69)90406-210.1016/0038-1098(69)90406-2 β†—
22. 10.1103/PhysRevLett.74.406710.1103/PhysRevLett.74.4067 β†—
23. 10.1103/PhysRevB.72.05411410.1103/PhysRevB.72.054114 β†—
24. See Supplemental Material at http://link.aps.org/supplemental/10.1103/ytr2-c1zh for details on (i) Computational Method, (ii) Phonon Dispersions, and (iii) Band Structures of Ferroelectric Phases.
25. 10.1021/acs.jpclett.0c0240510.1021/acs.jpclett.0c02405 β†—
26. 10.1107/S002188980902806410.1107/S0021889809028064 β†—
27. 10.1103/PhysRevB.46.667110.1103/PhysRevB.46.6671 β†—
28. 10.1063/5.005903610.1063/5.0059036 β†—
29. 10.1021/acs.jpcc.1c0071810.1021/acs.jpcc.1c00718 β†—
30. 10.1021/jp202489s10.1021/jp202489s β†—
31. 10.1021/j100135a01410.1021/j100135a014 β†—
32. M. I. Aroyo Β· Bulg. Chem. Commun. Β· 2011 Β· 43 Β· 183
33. 10.1103/PhysRevB.55.1035510.1103/PhysRevB.55.10355 β†—
34. 10.1016/0927-0256(96)00008-010.1016/0927-0256(96)00008-0 β†—
35. 10.1103/PhysRevB.54.1116910.1103/PhysRevB.54.11169 β†—
36. 10.7566/JPSJ.92.01200110.7566/JPSJ.92.012001 β†—
37. 10.1103/PhysRevB.59.175810.1103/PhysRevB.59.1758 β†—
38. 10.1016/j.cpc.2013.12.02310.1016/j.cpc.2013.12.023 β†—
39. 10.1021/acs.jpcc.9b0468310.1021/acs.jpcc.9b04683 β†—
40. 10.1021/acs.jpcc.7b0106610.1021/acs.jpcc.7b01066 β†—
41. 10.1088/1361-648X/acd83110.1088/1361-648X/acd831 β†—
42. 10.1063/1.240466310.1063/1.2404663 β†—
43. 10.1039/D0CP03567J10.1039/D0CP03567J β†—
44. 10.1103/RevModPhys.84.141910.1103/RevModPhys.84.1419 β†—
45. 10.1107/S010876731001624710.1107/S0108767310016247 β†—
46. 10.1103/PhysRevMaterials.5.06380310.1103/PhysRevMaterials.5.063803 β†—
47. 10.1016/j.commt.2024.10000210.1016/j.commt.2024.100002 β†—
48. 10.1103/PhysRevB.75.11513110.1103/PhysRevB.75.115131 β†—
49. 10.1016/j.commatsci.2012.10.02810.1016/j.commatsci.2012.10.028 β†—
50. 10.1103/PhysRevLett.100.13640610.1103/PhysRevLett.100.136406 β†—
51. 10.1103/PhysRevLett.115.03640210.1103/PhysRevLett.115.036402 β†—
52. 10.1107/S002188980300321210.1107/S0021889803003212 β†—
53. 10.1016/j.cpc.2019.10704210.1016/j.cpc.2019.107042 β†—
54. 10.1016/j.cpc.2018.01.01210.1016/j.cpc.2018.01.012 β†—
55. 10.1103/PhysRevB.47.165110.1103/PhysRevB.47.1651 β†—
56. 10.1016/j.cpc.2021.10803310.1016/j.cpc.2021.108033 β†—
57. 10.1088/1361-648X/ab51ff10.1088/1361-648X/ab51ff β†—
58. 10.1063/1.514426110.1063/1.5144261 β†—
59. 10.1103/PhysRevB.96.03514310.1103/PhysRevB.96.035143 β†—
60. 10.1038/s41524-020-00360-010.1038/s41524-020-00360-0 β†—
61. 10.1103/PhysRevLett.72.361810.1103/PhysRevLett.72.3618 β†—
62. 10.1021/jacs.8b1068510.1021/jacs.8b10685 β†—
63. 10.1038/358136a010.1038/358136a0 β†—
64. 10.1038/s41524-022-00869-610.1038/s41524-022-00869-6 β†—
65. 10.1103/PhysRevLett.3.41210.1103/PhysRevLett.3.412 β†—
66. 10.1080/0001873600010122910.1080/00018736000101229 β†—
67. 10.1209/epl/i1996-00404-810.1209/epl/i1996-00404-8 β†—
68. 10.1038/ncomms452510.1038/ncomms4525 β†—
69. 10.1016/0031-9163(66)91127-910.1016/0031-9163(66)91127-9 β†—
70. 10.1039/c1cs15098g10.1039/c1cs15098g β†—
71. 10.1038/s41467-021-20955-510.1038/s41467-021-20955-5 β†—
72. 10.1021/acs.chemrev.6b0013610.1021/acs.chemrev.6b00136 β†—
73. 10.1007/BF0150752710.1007/BF01507527 β†—
74. 10.1107/S056773947600155110.1107/S0567739476001551 β†—
75. 10.1021/jacs.5b0102510.1021/jacs.5b01025 β†—
76. 10.1021/jacs.4c0067910.1021/jacs.4c00679 β†—
77. 10.1021/acs.inorgchem.5b0121310.1021/acs.inorgchem.5b01213 β†—