Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics
Source abstract
Abstract
High Resolution Image Download MS PowerPoint Slide Lattice dynamics are critical to photovoltaic material performance, governing dynamic disorder, hot-carrier cooling, charge-carrier recombination, and transport. Soft metal-halide perovskites exhibit particularly intriguing dynamics, with Raman spectra exhibiting an unusually broad low-frequency response whose origin is still much debated. Here, we utilize ultra-low frequency Raman and infrared terahertz time-domain spectroscopies to provide a systematic examination of the vibrational response for a wide range of metal-halide semiconductors: FAPbI 3, MAPbI x Br 3– x, CsPbBr 3, PbI 2, Cs 2 AgBiBr 6, Cu 2 AgBiI 6, and AgI. We rule out extrinsic defects, octahedral tilting, cation lone pairs, and “liquid-like” Boson peaks as causes of the debated central Raman peak. Instead, we propose that the central Raman response results from an interplay of the significant broadening of Raman-active, low-energy phonon modes that are strongly amplified by a population component from Bose–Einstein statistics toward low frequency. These findings elucidate the complexities of light interactions with low-energy lattice vibrations in soft metal-halide semiconductors emerging for photovoltaic applications.
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Research context
OpenAlex topics: Perovskite Materials and Applications · Optical properties and cooling technologies in crystalline materials · Chalcogenide Semiconductor Thin Films
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Physics, Clarendon Laboratory, University of Oxford, Parks Road, Oxford OX1 3PU, United Kingdom
Department of Physics, King’s College London, London WC2R 2LS, United Kingdom
Department of Chemistry and Applied Biosciences, Institute of Inorganic Chemistry, ETH Zürich, Zürich 8093, Switzerland
Empa-Swiss Federal Laboratories for Materials Science and Technology, Dübendorf 8600, Switzerland
Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU), Butenandtstr. 11, 81377 Munich, Germany
Key Lab of Artificial Micro- and Nano-Structures of Ministry of Education of China, School of Physics and Technology, Wuhan University, Wuhan 430072, Hubei, China
Institute for Advanced Study, Technical University of Munich, Lichtenbergstrasse 2a, D-85748 Garching, Germany
Funding
Engineering and Physical Sciences Research Council · Institute for Advanced Study, Technische Universit?t M?nchen · Deutsche Forschungsgemeinschaft · University of Oxford
References (85)
Show source-provided references
1. Kittel C. · Introduction to Solid State Physics · 2005 · 692
2. 10.1002/adma.20180248610.1002/adma.201802486 ↗
3. 10.1002/pip.355710.1002/pip.3557 ↗
4. 10.1088/0953-8984/13/32/31210.1088/0953-8984/13/32/312 ↗
5. 10.1103/PhysRev.171.93510.1103/PhysRev.171.935 ↗
6. 10.1021/cr050140x10.1021/cr050140x ↗
7. 10.1039/D3NA00319A10.1039/D3NA00319A ↗
8. 10.1021/acs.nanolett.8b0427610.1021/acs.nanolett.8b04276 ↗
9. 10.1021/acs.jpclett.8b0281110.1021/acs.jpclett.8b02811 ↗
10. 10.1126/sciadv.aaw745310.1126/sciadv.aaw7453 ↗
11. 10.1038/s41427-022-00394-410.1038/s41427-022-00394-4 ↗
12. 10.1126/sciadv.170146910.1126/sciadv.1701469 ↗
13. 10.1126/science.aaf957010.1126/science.aaf9570 ↗
14. 10.1002/aenm.20170028610.1002/aenm.201700286 ↗
15. 10.1103/PhysRevB.94.22030110.1103/PhysRevB.94.220301 ↗
16. 10.1002/admi.20180175810.1002/admi.201801758 ↗
17. 10.1039/D2MA00071G10.1039/D2MA00071G ↗
18. 10.1103/PhysRevLett.118.13600110.1103/PhysRevLett.118.136001 ↗
19. 10.1103/PhysRevB.105.02430610.1103/PhysRevB.105.024306 ↗
20. 10.1021/jacs.2c0344310.1021/jacs.2c03443 ↗
21. 10.1038/s41467-019-12830-110.1038/s41467-019-12830-1 ↗
22. 10.1103/PhysRevMaterials.4.09240110.1103/PhysRevMaterials.4.092401 ↗
23. 10.1039/D1MA00288K10.1039/D1MA00288K ↗
24. 10.1063/1.499352410.1063/1.4993524 ↗
25. 10.1021/acs.jpclett.5b0222310.1021/acs.jpclett.5b02223 ↗
26. 10.1146/annurev.pc.27.100176.00234110.1146/annurev.pc.27.100176.002341 ↗
27. 10.1002/adma.20210793210.1002/adma.202107932 ↗
28. 10.1021/acs.jpcc.8b0466910.1021/acs.jpcc.8b04669 ↗
29. 10.1016/S0038-1098(97)00199-310.1016/S0038-1098(97)00199-3 ↗
30. 10.1103/PhysRevMaterials.7.04460210.1103/PhysRevMaterials.7.044602 ↗
31. 10.1088/0034-4885/31/1/30310.1088/0034-4885/31/1/303 ↗
32. 10.1038/s41467-021-26192-010.1038/s41467-021-26192-0 ↗
33. 10.1103/PhysRevB.62.1100610.1103/PhysRevB.62.11006 ↗
34. 10.1039/C5EE02925B10.1039/C5EE02925B ↗
35. 10.1021/acsenergylett.6b0038110.1021/acsenergylett.6b00381 ↗
36. 10.1021/jacs.6b0628710.1021/jacs.6b06287 ↗
37. 10.1557/mrs.2020.14210.1557/mrs.2020.142 ↗
38. 10.1063/5.000190810.1063/5.0001908 ↗
39. 10.1038/s41467-024-48581-x10.1038/s41467-024-48581-x ↗
40. 10.1021/acs.chemmater.6b0096810.1021/acs.chemmater.6b00968 ↗
41. 10.1039/C4SC02211D10.1039/C4SC02211D ↗
42. 10.1002/smll.20230356510.1002/smll.202303565 ↗
43. 10.1063/5.001276310.1063/5.0012763 ↗
44. 10.3390/app1115673310.3390/app11156733 ↗
45. 10.1021/acsami.8b0793710.1021/acsami.8b07937 ↗
46. 10.1103/PhysRevB.14.403010.1103/PhysRevB.14.4030 ↗
47. 10.1016/0038-1098(74)90698-X10.1016/0038-1098(74)90698-X ↗
48. 10.1039/C9MH00500E10.1039/C9MH00500E ↗
49. 10.1088/2752-5724/ace8aa10.1088/2752-5724/ace8aa ↗
50. 10.1557/mrc.2015.6910.1557/mrc.2015.69 ↗
51. 10.1016/0022-3093(94)90427-810.1016/0022-3093(94)90427-8 ↗
52. 10.1016/0038-1098(86)90854-910.1016/0038-1098(86)90854-9 ↗
53. 10.1557/PROC-407-21510.1557/PROC-407-215 ↗
54. 10.1103/PhysRevE.102.02250210.1103/PhysRevE.102.022502 ↗
55. 10.1038/nature0147510.1038/nature01475 ↗
56. 10.1088/0034-4885/65/8/20310.1088/0034-4885/65/8/203 ↗
57. 10.1103/PhysRevLett.25.22210.1103/PhysRevLett.25.222 ↗
58. 10.1103/PhysRevB.17.192810.1103/PhysRevB.17.1928 ↗
59. 10.1111/jace.1777110.1111/jace.17771 ↗
60. 10.1103/PhysRevLett.26.64210.1103/PhysRevLett.26.642 ↗
61. 10.1016/0038-1098(77)91183-810.1016/0038-1098(77)91183-8 ↗
62. 10.1088/0953-8984/15/9/30210.1088/0953-8984/15/9/302 ↗
63. 10.1088/1361-648X/ab808e10.1088/1361-648X/ab808e ↗
64. 10.1088/0022-3719/19/20/01210.1088/0022-3719/19/20/012 ↗
65. 10.1103/PhysRevB.66.05420510.1103/PhysRevB.66.054205 ↗
66. Surovtsev N. V. · 2004 · 1 · 2867
67. 10.1103/PhysRevB.48.602410.1103/PhysRevB.48.6024 ↗
68. 10.1103/PhysRevB.92.17430210.1103/PhysRevB.92.174302 ↗
69. 10.1039/C6CP03474H10.1039/C6CP03474H ↗
70. 10.1021/jz402589q10.1021/jz402589q ↗
71. 10.1039/C9CP06568G10.1039/C9CP06568G ↗
72. 10.1002/jrs.614110.1002/jrs.6141 ↗
73. 10.1021/acs.jpcc.5b0743210.1021/acs.jpcc.5b07432 ↗
74. 10.1039/C6MH00275G10.1039/C6MH00275G ↗
75. 10.1103/PhysRev.148.84510.1103/PhysRev.148.845 ↗
76. 10.1103/PhysRevLett.126.07740110.1103/PhysRevLett.126.077401 ↗
77. 10.1103/PhysRevB.59.677410.1103/PhysRevB.59.6774 ↗
78. 10.1103/PhysRevB.43.1204910.1103/PhysRevB.43.12049 ↗
79. 10.1103/PhysRevB.43.493910.1103/PhysRevB.43.4939 ↗
80. 10.1038/ncomms1175510.1038/ncomms11755 ↗
81. 10.1021/acsenergylett.9b0107310.1021/acsenergylett.9b01073 ↗
82. 10.1038/s42005-020-0313-710.1038/s42005-020-0313-7 ↗
83. 10.1038/s41563-021-00947-y10.1038/s41563-021-00947-y ↗
84. 10.1038/ncomms1608610.1038/ncomms16086 ↗
85. 10.1038/s41467-019-11087-y10.1038/s41467-019-11087-y ↗