TY - JOUR
T1 - Direct Observation of Bandgap Oscillations Induced by Optical Phonons in Hybrid Lead Iodide Perovskites
AU - Guo, Peijun
AU - Xia, Yi
AU - Gong, Jue
AU - Cao, Duyen H.
AU - Li, Xiaotong
AU - Li, Xun
AU - Zhang, Qi
AU - Stoumpos, Constantinos C.
AU - Kirschner, Matthew S.
AU - Wen, Haidan
AU - Prakapenka, Vitali B.
AU - Ketterson, John B.
AU - Martinson, Alex B.F.
AU - Xu, Tao
AU - Kanatzidis, Mercouri G.
AU - Chan, Maria K.Y.
AU - Schaller, Richard D.
N1 - Funding Information:
This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE‐AC02‐06CH11357. Work at Northwestern was supported by grant SC0012541 from the U.S. Department of Energy, Office of Science (sample preparation and structural characterization). T.X. acknowledges the financial support from National Science Foundation (DMR‐1806152). Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. Work by A.B.F.M. and D.H.C. was supported by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE‐SC0001059. GeoSoilEnviroCARS was supported by the National Science Foundation – Earth Sciences (EAR – 1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR‐1531583). Q.Z. and H.W. acknowledge the support by the U.S. Department of Energy, Office of Science, under Contract No. DE‐SC0012509. The authors thank Nicholas Holtgrewe for help with the Raman measurements and Pierre Darancet for discussions.
Funding Information:
This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. Work at Northwestern was supported by grant SC0012541 from the U.S. Department of Energy, Office of Science (sample preparation and structural characterization). T.X. acknowledges the financial support from National Science Foundation (DMR-1806152). Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. Work by A.B.F.M. and D.H.C. was supported by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0001059. GeoSoilEnviroCARS was supported by the National Science Foundation ? Earth Sciences (EAR ? 1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). Q.Z. and H.W. acknowledge the support by the U.S. Department of Energy, Office of Science, under Contract No. DE-SC0012509. The authors thank Nicholas Holtgrewe for help with the Raman measurements and Pierre Darancet for discussions.
Publisher Copyright:
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/5/1
Y1 - 2020/5/1
N2 - Hybrid organic–inorganic perovskites such as methylammonium lead iodide have emerged as promising semiconductors for energy-relevant applications. The interactions between charge carriers and lattice vibrations, giving rise to polarons, have been invoked to explain some of their extraordinary optoelectronic properties. Here, time-resolved optical spectroscopy is performed, with off-resonant pumping and electronic probing, to examine several representative lead iodide perovskites. The temporal oscillations of electronic bandgaps induced by coherent lattice vibrations are reported, which is attributed to antiphase octahedral rotations that dominate in the examined 3D and 2D hybrid perovskites. The off-resonant pumping scheme permits a simplified observation of changes in the bandgap owing to the Ag vibrational mode, which is qualitatively different from vibrational modes of other symmetries and without increased complexity of photogenerated electronic charges. The work demonstrates a strong correlation between the lead–iodide octahedral framework and electronic transitions, and provides further insights into the manipulation of coherent optical phonons and related properties in hybrid perovskites on ultrafast timescales.
AB - Hybrid organic–inorganic perovskites such as methylammonium lead iodide have emerged as promising semiconductors for energy-relevant applications. The interactions between charge carriers and lattice vibrations, giving rise to polarons, have been invoked to explain some of their extraordinary optoelectronic properties. Here, time-resolved optical spectroscopy is performed, with off-resonant pumping and electronic probing, to examine several representative lead iodide perovskites. The temporal oscillations of electronic bandgaps induced by coherent lattice vibrations are reported, which is attributed to antiphase octahedral rotations that dominate in the examined 3D and 2D hybrid perovskites. The off-resonant pumping scheme permits a simplified observation of changes in the bandgap owing to the Ag vibrational mode, which is qualitatively different from vibrational modes of other symmetries and without increased complexity of photogenerated electronic charges. The work demonstrates a strong correlation between the lead–iodide octahedral framework and electronic transitions, and provides further insights into the manipulation of coherent optical phonons and related properties in hybrid perovskites on ultrafast timescales.
KW - Raman scattering
KW - coherent optical phonons
KW - electron–phonon coupling
KW - hybrid perovskites
KW - transient optical spectroscopy
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U2 - 10.1002/adfm.201907982
DO - 10.1002/adfm.201907982
M3 - Article
AN - SCOPUS:85082963230
SN - 1616-301X
VL - 30
JO - Advanced Functional Materials
JF - Advanced Functional Materials
IS - 22
M1 - 1907982
ER -