Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics

Vincent J.Y. Lim; Marcello Righetto; Siyu Yan; Jay B. Patel; Thomas Siday; Benjamin Putland; Kyle M. McCall; Maximilian T. Sirtl; Yuliia Kominko; Jiali Peng; Qianqian Lin; Thomas Bein; Maksym Kovalenko; Henry J. Snaith; Michael B. Johnston; Laura M. Herz

doi:10.1021/acsenergylett.4c01473

Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics

Vincent J.Y. Lim, Marcello Righetto, Siyu Yan, Jay B. Patel, Thomas Siday, Benjamin Putland, Kyle M. McCall, Maximilian T. Sirtl, Yuliia Kominko, Jiali Peng, Qianqian Lin, Thomas Bein, Maksym Kovalenko, Henry J. Snaith, Michael B. Johnston, Laura M. Herz^*

^*Corresponding author for this work

Physics

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

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: FAPbI₃, MAPbI_xBr_3-x, CsPbBr₃, PbI₂, Cs₂AgBiBr₆, Cu₂AgBiI₆, 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.

Original language	English
Pages (from-to)	4127-4135
Number of pages	9
Journal	ACS Energy Letters
Volume	9
Issue number	8
Early online date	29 Jul 2024
DOIs	https://doi.org/10.1021/acsenergylett.4c01473
Publication status	Published - 9 Aug 2024

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Lim, V. J. Y., Righetto, M., Yan, S., Patel, J. B., Siday, T., Putland, B., McCall, K. M., Sirtl, M. T., Kominko, Y., Peng, J., Lin, Q., Bein, T., Kovalenko, M., Snaith, H. J., Johnston, M. B., & Herz, L. M. (2024). Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics. ACS Energy Letters, 9(8), 4127-4135. https://doi.org/10.1021/acsenergylett.4c01473

@article{b07fb8ed518948b4ad953e1ac1ccc5be,

title = "Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics",

abstract = "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: FAPbI3, MAPbIxBr3-x, CsPbBr3, PbI2, Cs2AgBiBr6, Cu2AgBiI6, 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.",

author = "Lim, {Vincent J.Y.} and Marcello Righetto and Siyu Yan and Patel, {Jay B.} and Thomas Siday and Benjamin Putland and McCall, {Kyle M.} and Sirtl, {Maximilian T.} and Yuliia Kominko and Jiali Peng and Qianqian Lin and Thomas Bein and Maksym Kovalenko and Snaith, {Henry J.} and Johnston, {Michael B.} and Herz, {Laura M.}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

month = aug,

day = "9",

doi = "10.1021/acsenergylett.4c01473",

language = "English",

volume = "9",

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journal = "ACS Energy Letters",

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Lim, VJY, Righetto, M, Yan, S, Patel, JB, Siday, T, Putland, B, McCall, KM, Sirtl, MT, Kominko, Y, Peng, J, Lin, Q, Bein, T, Kovalenko, M, Snaith, HJ, Johnston, MB & Herz, LM 2024, 'Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics', ACS Energy Letters, vol. 9, no. 8, pp. 4127-4135. https://doi.org/10.1021/acsenergylett.4c01473

TY - JOUR

T1 - Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics

AU - Lim, Vincent J.Y.

AU - Righetto, Marcello

AU - Yan, Siyu

AU - Patel, Jay B.

AU - Siday, Thomas

AU - Putland, Benjamin

AU - McCall, Kyle M.

AU - Sirtl, Maximilian T.

AU - Kominko, Yuliia

AU - Peng, Jiali

AU - Lin, Qianqian

AU - Bein, Thomas

AU - Kovalenko, Maksym

AU - Snaith, Henry J.

AU - Johnston, Michael B.

AU - Herz, Laura M.

PY - 2024/8/9

Y1 - 2024/8/9

N2 - 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: FAPbI3, MAPbIxBr3-x, CsPbBr3, PbI2, Cs2AgBiBr6, Cu2AgBiI6, 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.

AB - 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: FAPbI3, MAPbIxBr3-x, CsPbBr3, PbI2, Cs2AgBiBr6, Cu2AgBiI6, 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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U2 - 10.1021/acsenergylett.4c01473

DO - 10.1021/acsenergylett.4c01473

M3 - Article

AN - SCOPUS:85201052781

SN - 2380-8195

VL - 9

SP - 4127

EP - 4135

JO - ACS Energy Letters

JF - ACS Energy Letters

IS - 8

ER -

Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics

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