Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites

Aurélien M A Leguy, Alejandro R Goñi, Jarvist M Frost, Jonathan Skelton, Federico Brivio, Xabier Rodríguez-Martínez, Oliver J Weber, Anuradha Pallipurath, M Isabel Alonso, Mariano Campoy-Quiles, Mark T Weller, Jenny Nelson, Aron Walsh, Piers R F Barnes

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Abstract

We present Raman and terahertz absorbance spectra of methylammonium lead halide single crystals (MAPbX3, X = I, Br, Cl) at temperatures between 80 and 370 K. These results show good agreement with density-functional-theory phonon calculations. Comparison of experimental spectra and calculated vibrational modes enables confident assignment of most of the vibrational features between 50 and 3500 cm(-1). Reorientation of the methylammonium cations, unlocked in their cavities at the orthorhombic-to-tetragonal phase transition, plays a key role in shaping the vibrational spectra of the different compounds. Calculations show that these dynamic effects split Raman peaks and create more structure than predicted from the independent harmonic modes. This explains the presence of extra peaks in the experimental spectra that have been a source of confusion in earlier studies. We discuss singular features, in particular the torsional vibration of the C-N axis, which is the only molecular mode that is strongly influenced by the size of the lattice. From analysis of the spectral linewidths, we find that MAPbI3 shows exceptionally short phonon lifetimes, which can be linked to low lattice thermal conductivity. We show that optical rather than acoustic phonon scattering is likely to prevail at room temperature in these materials.

Original languageEnglish
JournalPhysical Chemistry Chemical Physics
Issue number39
Early online date17 Jun 2016
DOIs
Publication statusPublished - 21 Oct 2016

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Vibrational spectra
perovskites
vibrational spectra
halides
disorders
life (durability)
Phonon scattering
Linewidth
Density functional theory
Cations
Raman scattering
torsional vibration
Thermal conductivity
Phase transitions
Acoustics
confusion
Single crystals
Temperature
retraining
vibration mode

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Leguy, A. M. A., Goñi, A. R., Frost, J. M., Skelton, J., Brivio, F., Rodríguez-Martínez, X., ... Barnes, P. R. F. (2016). Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites. Physical Chemistry Chemical Physics, (39). https://doi.org/10.1039/c6cp03474h

Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites. / Leguy, Aurélien M A; Goñi, Alejandro R; Frost, Jarvist M; Skelton, Jonathan; Brivio, Federico; Rodríguez-Martínez, Xabier; Weber, Oliver J; Pallipurath, Anuradha; Alonso, M Isabel; Campoy-Quiles, Mariano; Weller, Mark T; Nelson, Jenny; Walsh, Aron; Barnes, Piers R F.

In: Physical Chemistry Chemical Physics, No. 39, 21.10.2016.

Research output: Contribution to journalComment/debate

Leguy, AMA, Goñi, AR, Frost, JM, Skelton, J, Brivio, F, Rodríguez-Martínez, X, Weber, OJ, Pallipurath, A, Alonso, MI, Campoy-Quiles, M, Weller, MT, Nelson, J, Walsh, A & Barnes, PRF 2016, 'Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites', Physical Chemistry Chemical Physics, no. 39. https://doi.org/10.1039/c6cp03474h
Leguy, Aurélien M A ; Goñi, Alejandro R ; Frost, Jarvist M ; Skelton, Jonathan ; Brivio, Federico ; Rodríguez-Martínez, Xabier ; Weber, Oliver J ; Pallipurath, Anuradha ; Alonso, M Isabel ; Campoy-Quiles, Mariano ; Weller, Mark T ; Nelson, Jenny ; Walsh, Aron ; Barnes, Piers R F. / Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites. In: Physical Chemistry Chemical Physics. 2016 ; No. 39.
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abstract = "We present Raman and terahertz absorbance spectra of methylammonium lead halide single crystals (MAPbX3, X = I, Br, Cl) at temperatures between 80 and 370 K. These results show good agreement with density-functional-theory phonon calculations. Comparison of experimental spectra and calculated vibrational modes enables confident assignment of most of the vibrational features between 50 and 3500 cm(-1). Reorientation of the methylammonium cations, unlocked in their cavities at the orthorhombic-to-tetragonal phase transition, plays a key role in shaping the vibrational spectra of the different compounds. Calculations show that these dynamic effects split Raman peaks and create more structure than predicted from the independent harmonic modes. This explains the presence of extra peaks in the experimental spectra that have been a source of confusion in earlier studies. We discuss singular features, in particular the torsional vibration of the C-N axis, which is the only molecular mode that is strongly influenced by the size of the lattice. From analysis of the spectral linewidths, we find that MAPbI3 shows exceptionally short phonon lifetimes, which can be linked to low lattice thermal conductivity. We show that optical rather than acoustic phonon scattering is likely to prevail at room temperature in these materials.",
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T1 - Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites

AU - Leguy, Aurélien M A

AU - Goñi, Alejandro R

AU - Frost, Jarvist M

AU - Skelton, Jonathan

AU - Brivio, Federico

AU - Rodríguez-Martínez, Xabier

AU - Weber, Oliver J

AU - Pallipurath, Anuradha

AU - Alonso, M Isabel

AU - Campoy-Quiles, Mariano

AU - Weller, Mark T

AU - Nelson, Jenny

AU - Walsh, Aron

AU - Barnes, Piers R F

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N2 - We present Raman and terahertz absorbance spectra of methylammonium lead halide single crystals (MAPbX3, X = I, Br, Cl) at temperatures between 80 and 370 K. These results show good agreement with density-functional-theory phonon calculations. Comparison of experimental spectra and calculated vibrational modes enables confident assignment of most of the vibrational features between 50 and 3500 cm(-1). Reorientation of the methylammonium cations, unlocked in their cavities at the orthorhombic-to-tetragonal phase transition, plays a key role in shaping the vibrational spectra of the different compounds. Calculations show that these dynamic effects split Raman peaks and create more structure than predicted from the independent harmonic modes. This explains the presence of extra peaks in the experimental spectra that have been a source of confusion in earlier studies. We discuss singular features, in particular the torsional vibration of the C-N axis, which is the only molecular mode that is strongly influenced by the size of the lattice. From analysis of the spectral linewidths, we find that MAPbI3 shows exceptionally short phonon lifetimes, which can be linked to low lattice thermal conductivity. We show that optical rather than acoustic phonon scattering is likely to prevail at room temperature in these materials.

AB - We present Raman and terahertz absorbance spectra of methylammonium lead halide single crystals (MAPbX3, X = I, Br, Cl) at temperatures between 80 and 370 K. These results show good agreement with density-functional-theory phonon calculations. Comparison of experimental spectra and calculated vibrational modes enables confident assignment of most of the vibrational features between 50 and 3500 cm(-1). Reorientation of the methylammonium cations, unlocked in their cavities at the orthorhombic-to-tetragonal phase transition, plays a key role in shaping the vibrational spectra of the different compounds. Calculations show that these dynamic effects split Raman peaks and create more structure than predicted from the independent harmonic modes. This explains the presence of extra peaks in the experimental spectra that have been a source of confusion in earlier studies. We discuss singular features, in particular the torsional vibration of the C-N axis, which is the only molecular mode that is strongly influenced by the size of the lattice. From analysis of the spectral linewidths, we find that MAPbI3 shows exceptionally short phonon lifetimes, which can be linked to low lattice thermal conductivity. We show that optical rather than acoustic phonon scattering is likely to prevail at room temperature in these materials.

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