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Title: Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices

Abstract

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH 3NH 3PbI 3) are game-changing semiconductors for solar cells and light-emitting devices owing to their defect tolerance and exceptionally long carrier lifetimes and diffusion lengths. Determining whether the dynamically disordered organic cations with large dipole moment benefit the optoelectronic properties of CH 3NH 3PbI 3 has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the inorganic sublattice. The resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that the induced atomic motions of the organic cations do not alter the absorption or the photoluminescence response of CH 3NH 3PbI 3, beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH 3NH 3PbI 3 mainly derive from the inorganic lead-halide framework.

Authors:
ORCiD logo [1];  [1];  [2];  [1]; ORCiD logo [3];  [4];  [1];  [5];  [1]; ORCiD logo [2];  [1];  [3]; ORCiD logo [6]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  2. Northern Illinois Univ., DeKalb, IL (United States). Dept. of Chemistry and Biochemistry
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  5. Northwestern Univ., Evanston, IL (United States). Dept. of Physics and Astronomy
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States); Northern Illinois Univ., DeKalb, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); ANL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)
OSTI Identifier:
1494797
Grant/Contract Number:  
AC02-06CH11357; SC0012541; DMR-1806152
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; atomistic models; infrared spectroscopy; ultrafast photonics

Citation Formats

Guo, Peijun, Mannodi-Kanakkithodi, Arun, Gong, Jue, Xia, Yi, Stoumpos, Constantinos C., Cao, Duyen H., Diroll, Benjamin T., Ketterson, John B., Wiederrecht, Gary P., Xu, Tao, Chan, Maria K. Y., Kanatzidis, Mercouri G., and Schaller, Richard D. Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices. United States: N. p., 2019. Web. doi:10.1038/s41467-019-08363-2.
Guo, Peijun, Mannodi-Kanakkithodi, Arun, Gong, Jue, Xia, Yi, Stoumpos, Constantinos C., Cao, Duyen H., Diroll, Benjamin T., Ketterson, John B., Wiederrecht, Gary P., Xu, Tao, Chan, Maria K. Y., Kanatzidis, Mercouri G., & Schaller, Richard D. Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices. United States. doi:10.1038/s41467-019-08363-2.
Guo, Peijun, Mannodi-Kanakkithodi, Arun, Gong, Jue, Xia, Yi, Stoumpos, Constantinos C., Cao, Duyen H., Diroll, Benjamin T., Ketterson, John B., Wiederrecht, Gary P., Xu, Tao, Chan, Maria K. Y., Kanatzidis, Mercouri G., and Schaller, Richard D. Tue . "Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices". United States. doi:10.1038/s41467-019-08363-2. https://www.osti.gov/servlets/purl/1494797.
@article{osti_1494797,
title = {Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices},
author = {Guo, Peijun and Mannodi-Kanakkithodi, Arun and Gong, Jue and Xia, Yi and Stoumpos, Constantinos C. and Cao, Duyen H. and Diroll, Benjamin T. and Ketterson, John B. and Wiederrecht, Gary P. and Xu, Tao and Chan, Maria K. Y. and Kanatzidis, Mercouri G. and Schaller, Richard D.},
abstractNote = {Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH3NH3PbI3) are game-changing semiconductors for solar cells and light-emitting devices owing to their defect tolerance and exceptionally long carrier lifetimes and diffusion lengths. Determining whether the dynamically disordered organic cations with large dipole moment benefit the optoelectronic properties of CH3NH3PbI3 has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the inorganic sublattice. The resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that the induced atomic motions of the organic cations do not alter the absorption or the photoluminescence response of CH3NH3PbI3, beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH3NH3PbI3 mainly derive from the inorganic lead-halide framework.},
doi = {10.1038/s41467-019-08363-2},
journal = {Nature Communications},
issn = {2041-1723},
number = ,
volume = 10,
place = {United States},
year = {2019},
month = {1}
}

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Cited by: 4 works
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Figures / Tables:

Figure 1 Figure 1: Static and infrared pump electronic-probe (IPEP) measurements of CH3NH3PbI3. a Static, temperature-dependent absorbance around the bandgap. b Static, temperature-dependent absorbance around the N-H-as vibrational modes. c ΔOD spectral map measured with on-resonance infrared pump (centered at 3120 cm−1) at 10 K. The dashed line shows the wavelength atmore » which the kinetics are extracted (Fig. 2b). d Red: dependence of the magnitude of the strongest bleach signal on the center wavenumber of the pump pulse with a fixed fluence (measured at 10 K). Blue: spectral profile of the pump pulse centered at 3120 cm−1. Black: static absorbance of CH3NH3PbI3 (in arbitrary units) at 80 K« less

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