Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy
Abstract
The dynamically flexible lattices in lead-halide perovskites may play important roles in extending carrier recombination lifetime in 3D perovskite solar-cell absorbers and in exciton self-trapping in 2D perovskite white-light phosphors. Here, two-dimensional infrared (2D IR) spectroscopy was applied to study a recently reported Pb-I-SCN layered perovskite. The Pb-ISCN perovskite was spin-coated on a SiO2 surface as a thin film, with a thickness of ~100 nm, where the S12CN– anions were isotopically diluted with the ratio of S12CN:S13CN=5:95 or 1:99 to avoid vibrational coupling and excitation transfer between adjacent SCN– anions. The minor S12CN– component was the principal vibrational probe that reported on the structural evolution through 2D IR spectroscopy. Spectral diffusion was observed with a time constant of 4.1 ± 0.3 ps. Spectral diffusion arises from small structural changes that result in sampling of frequencies within the distribution of frequencies that comprise the inhomogeneously broadened absorption spectrum of the in the Pb-I-SCN layered perovskite. These transitions among discrete local structures are distinct from oscillatory phonon motions of the lattice. To accurately evaluate the structural dynamics through measurement of spectral diffusion, the vibrational coupling between adjacent SCN– anions had to be carefully treated. Although the inorganic layers of typical 2D perovskitesmore »
- Authors:
-
[1];
[3];
[2];
[2]
- Stanford Univ., CA (United States); Univ. of Colorado, Boulder, CO (United States)
- Stanford Univ., CA (United States)
- Stanford Univ., CA (United States); National Institute for Materials Science (NIMS), Tsukuba (Japan)
- Publication Date:
- Research Org.:
- Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR)
- OSTI Identifier:
- 1788259
- Grant/Contract Number:
- FG02-84ER13251; FG03-84ER13251; FA9550-16-1-0104
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 31; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 14 SOLAR ENERGY; Anions; Lattices; Oscillation; Infrared light; Perovskites
Citation Formats
Nishida, Jun, Breen, John P., Lindquist, Kurt P., Umeyama, Daiki, Karunadasa, Hemamala I., and Fayer, Michael D. Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b03787.
Nishida, Jun, Breen, John P., Lindquist, Kurt P., Umeyama, Daiki, Karunadasa, Hemamala I., & Fayer, Michael D. Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy. United States. https://doi.org/10.1021/jacs.8b03787
Nishida, Jun, Breen, John P., Lindquist, Kurt P., Umeyama, Daiki, Karunadasa, Hemamala I., and Fayer, Michael D. Thu .
"Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy". United States. https://doi.org/10.1021/jacs.8b03787. https://www.osti.gov/servlets/purl/1788259.
@article{osti_1788259,
title = {Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy},
author = {Nishida, Jun and Breen, John P. and Lindquist, Kurt P. and Umeyama, Daiki and Karunadasa, Hemamala I. and Fayer, Michael D.},
abstractNote = {The dynamically flexible lattices in lead-halide perovskites may play important roles in extending carrier recombination lifetime in 3D perovskite solar-cell absorbers and in exciton self-trapping in 2D perovskite white-light phosphors. Here, two-dimensional infrared (2D IR) spectroscopy was applied to study a recently reported Pb-I-SCN layered perovskite. The Pb-ISCN perovskite was spin-coated on a SiO2 surface as a thin film, with a thickness of ~100 nm, where the S12CN– anions were isotopically diluted with the ratio of S12CN:S13CN=5:95 or 1:99 to avoid vibrational coupling and excitation transfer between adjacent SCN– anions. The minor S12CN– component was the principal vibrational probe that reported on the structural evolution through 2D IR spectroscopy. Spectral diffusion was observed with a time constant of 4.1 ± 0.3 ps. Spectral diffusion arises from small structural changes that result in sampling of frequencies within the distribution of frequencies that comprise the inhomogeneously broadened absorption spectrum of the in the Pb-I-SCN layered perovskite. These transitions among discrete local structures are distinct from oscillatory phonon motions of the lattice. To accurately evaluate the structural dynamics through measurement of spectral diffusion, the vibrational coupling between adjacent SCN– anions had to be carefully treated. Although the inorganic layers of typical 2D perovskites are structurally isolated from each other, the 2D IR data demonstrated that the layers of the Pb-I-SCN perovskite are vibrationally coupled. When both S12CN– and S13CN– were pumped simultaneously, cross-peaks between S12CN and S13CN vibrations and an oscillating 2D band shape of the S12CN– vibration were observed. Both observables demonstrate vibrational coupling between the closest SCN– anions, which reside in different inorganic layers. The thin films and the isotopic dilution produced exceedingly small vibrational echo signal fields; measurements were made possible using the near-Brewster’s angle reflection pump-probe geometry.},
doi = {10.1021/jacs.8b03787},
journal = {Journal of the American Chemical Society},
number = 31,
volume = 140,
place = {United States},
year = {Thu Jul 19 00:00:00 EDT 2018},
month = {Thu Jul 19 00:00:00 EDT 2018}
}
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