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Our analysis shows that the frequency of the MA torsional modes in the crystal structures may be the result of two opposite effects, associated to the interactions between the cation and the inorganic cage

The Raman Spectrum of the CH3NH3PbI3 Hybrid Perovskite: Interplay of Theory and Experiment.

JOURNAL OF PHYSICAL CHEMISTRY LETTERS, no. 2 (2014): 279-284

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DFT calculationsRaman spectroscopyhybrid lead-halide perovskitessolar cells

Abstract

We report the low-frequency resonant Raman spectrum of methylammonium lead-iodide, a prototypical perovskite for solar cells applications, on mesoporous Al2O3. The measured spectrum assignment is assisted by DFT simulations of the Raman spectra of suitable periodic and model systems. The bands at 62 and 94 cm(-1) are assigned respectively...More

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Introduction

Hybrid lead−halide perovskites are revolutionizing the photovoltaic landscape, having been claimed as “the big thing in photovoltaics”.1 From their first application in 2009 by Kojima et al as solar cells sensitizers,[2] photovoltaic devices based on these materials showed a fast and continuous increase in their performance,[2−14] with recent top efficiency exceeding 15%.
The authors report a combined experimental and theoretical Raman vibrational analysis of MAPbI3 in the low-frequency region, where the bands associated to the vibrations of the interacting inorganic/organic constituents are expected.

Highlights

Hybrid lead−halide perovskites are revolutionizing the photovoltaic landscape, having been claimed as “the big thing in photovoltaics”.1. From their first application in 2009 by Kojima et al as solar cells sensitizers,[2] photovoltaic devices based on these materials showed a fast and continuous increase in their performance,[2−14] with recent top efficiency exceeding 15%
The assignment of the Raman spectrum of MAPbI3 is supported by first-principles DFT calculations[38,39] carried out on extended periodic systems and, for interpretative purposes, on simplified models. While this type of analyses have been applied to perovskites, especially in relation to their ferroelectric properties,[40−47] to the best of our knowledge this is the first report on the Raman spectrum of the prototypical MAPbI3 perovskite, along with the first DFT simulation of the vibrational spectra of hybrid perovskites
Since the three models differ mainly in the orientation of the organic cations, the fact that the region around the experimental band at 119 cm−1 is differently described in the three simulated structures suggests that this is probably associated with the MA libration modes
The fact that the Raman spectra calculated on the different models are quite different in the 100−150 cm−1 region suggests that the band at 119 cm−1 is probably associated to the motion of the organic cations
Our analysis shows that the frequency of the MA torsional modes in the crystal structures may be the result of two opposite effects, associated to the interactions between the cation and the inorganic cage

Results

Since the three models differ mainly in the orientation of the organic cations, the fact that the region around the experimental band at 119 cm−1 is differently described in the three simulated structures suggests that this is probably associated with the MA libration modes.
The fact that the Raman spectra calculated on the different models are quite different in the 100−150 cm−1 region suggests that the band at 119 cm−1 is probably associated to the motion of the organic cations.
The theoretical spectra calculated for the three investigated structures do not show any normal mode, neither Raman active or inactive, in the range 200−280 cm−1, though the results could be sensitive to both DFT functional and anharmonic effects, as the authors will explain below.
The large torsional frequencies difference predicted for the two tetragonal structures compared to those calculated for the orthorhombic structure may seem surprising at first glance, but it is not totally unexpected considering the large distribution of torsional frequencies reported in the literature for MA-based compounds.[27,33−35] comparing the theoretical spectra of Figure 1, the authors observe that the Raman intensity predicted for the torsional modes increases with the structural disorder, in the order tet-1 > tet-2 > ortho.
The calculated vibrational frequency of the torsional mode of the isolated MA cation at its optimized structure is predicted at 309 cm−1 by LDA (278 cm−1 when optimized by the same method used for periodic simulations in a large supercell) in good agreement with previous results.[36,37] This mode is predicted to be Raman inactive, consistent with the C3v symmetry of the isolated MA cation.
It is not unreasonable to speculate that a combination of DFT functional and anharmonic effects could down-shift the calculated torsional modes for the tetragonal structures to ∼250 cm−1, as in the experimental Raman spectrum.

Conclusion

The torsional mode frequency calculated in the harmonic approximation by LDA for the isolated MA cations at their crystal structures geometries are strongly blue-shifted, by more than 150 cm−1.
On the basis of electronic structure calculations, the authors have elucidated how the interactions between the organic cations and the inorganic counterpart may affect the vibrational frequency and the Raman broad and intensity of unresolved the MA band at torsional 200−340 mode cm−1 in is

Tables

Table1: Vibrational Frequencies (ω) and Raman Intensities

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Funding

We thank FP7-NMP-2013 project 604032 “MESO” for financial support

Reference

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Claudio Quarti

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Giulia Grancini

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Edoardo Mosconi

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Paola Bruno

James M Ball

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Michael M Lee

Henry J Snaith

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Annamaria Petrozza

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