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Title: Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed Goldschmidt Tolerance Factor and Impact on Exciton–Phonon Interaction

Abstract

The stability and formation of a perovskite structure is dictated by the Goldschmidt tolerance factor as a general geometric guideline. The tolerance factor has limited the choice of cations (A) in 3D lead iodide perovskites (APbI 3), an intriguing class of semiconductors for high-performance photovoltaics and optoelectronics. Here, we show the tolerance factor requirement is relaxed in 2D Ruddlesden-Popper (RP) perovskites, enabling the incorporation of a variety of larger cations beyond the methylammonium (MA), formamidinium, and cesium ions in the lead iodide perovskite cages for the first time. This is unequivocally confirmed with the single-crystal X-ray structure of newly synthesized guanidinium (GA)-based ($n$-C 6H 13NH 3) 2(GA)Pb 2I 7, which exhibits significantly enlarged and distorted perovskite cage containing sterically constrained GA cation. Structural comparison with ($n$-C 6H 13NH 3) 2(MA)Pb 2I 7 reveals that the structural stabilization originates from the mitigation of strain accumulation and self-adjustable strain-balancing in 2D RP structures. Furthermore, spectroscopic studies show a large A cation significantly influences carrier dynamics and exciton-phonon interactions through modulating the inorganic sublattice. These results enrich the diverse families of perovskite materials, provide new insights into the mechanistic role of A-site cations on their physical properties, and have implications to solar devicemore » studies using engineered perovskite thin films incorporating such large organic cations.« less

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [3];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Wisconsin, Milwaukee, WI (United States). Dept. of Chemistry
  2. Hunan Univ., Changsha (China). Key Laboratory for Micro-Nano Physics and Technology of Hunan Province, College of Materials Science and Engineering
  3. Department of Chemistry, Columbia University, New York, New York 10027, United States
  4. Columbia Univ., New York, NY (United States). Dept. of Chemistry
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1544598
Alternate Identifier(s):
OSTI ID: 1559863
Grant/Contract Number:  
SC0010692; FG02-09ER46664; SC0002162
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 5; Journal Issue: 8; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Fu, Yongping, Hautzinger, Matthew P., Luo, Ziyu, Wang, Feifan, Pan, Dongxu, Aristov, Michael M., Guzei, Ilia A., Pan, Anlian, Zhu, Xiaoyang, and Jin, Song. Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed Goldschmidt Tolerance Factor and Impact on Exciton–Phonon Interaction. United States: N. p., 2019. Web. doi:10.1021/acscentsci.9b00367.
Fu, Yongping, Hautzinger, Matthew P., Luo, Ziyu, Wang, Feifan, Pan, Dongxu, Aristov, Michael M., Guzei, Ilia A., Pan, Anlian, Zhu, Xiaoyang, & Jin, Song. Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed Goldschmidt Tolerance Factor and Impact on Exciton–Phonon Interaction. United States. doi:10.1021/acscentsci.9b00367.
Fu, Yongping, Hautzinger, Matthew P., Luo, Ziyu, Wang, Feifan, Pan, Dongxu, Aristov, Michael M., Guzei, Ilia A., Pan, Anlian, Zhu, Xiaoyang, and Jin, Song. Wed . "Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed Goldschmidt Tolerance Factor and Impact on Exciton–Phonon Interaction". United States. doi:10.1021/acscentsci.9b00367.
@article{osti_1544598,
title = {Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed Goldschmidt Tolerance Factor and Impact on Exciton–Phonon Interaction},
author = {Fu, Yongping and Hautzinger, Matthew P. and Luo, Ziyu and Wang, Feifan and Pan, Dongxu and Aristov, Michael M. and Guzei, Ilia A. and Pan, Anlian and Zhu, Xiaoyang and Jin, Song},
abstractNote = {The stability and formation of a perovskite structure is dictated by the Goldschmidt tolerance factor as a general geometric guideline. The tolerance factor has limited the choice of cations (A) in 3D lead iodide perovskites (APbI3), an intriguing class of semiconductors for high-performance photovoltaics and optoelectronics. Here, we show the tolerance factor requirement is relaxed in 2D Ruddlesden-Popper (RP) perovskites, enabling the incorporation of a variety of larger cations beyond the methylammonium (MA), formamidinium, and cesium ions in the lead iodide perovskite cages for the first time. This is unequivocally confirmed with the single-crystal X-ray structure of newly synthesized guanidinium (GA)-based ($n$-C6H13NH3)2(GA)Pb2I7, which exhibits significantly enlarged and distorted perovskite cage containing sterically constrained GA cation. Structural comparison with ($n$-C6H13NH3)2(MA)Pb2I7 reveals that the structural stabilization originates from the mitigation of strain accumulation and self-adjustable strain-balancing in 2D RP structures. Furthermore, spectroscopic studies show a large A cation significantly influences carrier dynamics and exciton-phonon interactions through modulating the inorganic sublattice. These results enrich the diverse families of perovskite materials, provide new insights into the mechanistic role of A-site cations on their physical properties, and have implications to solar device studies using engineered perovskite thin films incorporating such large organic cations.},
doi = {10.1021/acscentsci.9b00367},
journal = {ACS Central Science},
issn = {2374-7943},
number = 8,
volume = 5,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acscentsci.9b00367

Figures / Tables:

Figure 1 Figure 1: Crystal structures of APbI3 and 2D RP perovskites of (HA)2(A)Pb2I7. (a) The schematic crystal structure of 3D lead iodide perovskites APbI3, A = Cs, MA, or FA. (b) Goldschmidt tolerance factor of APbI3 perovskite with different A cations. The inset images depict the molecular structures of A cations.more » Large organic cations, such as dimethylammonium (DMA), ethylammonium (EA), guanidinium (GA), and acetamidinium (AA), do not support a 3D perovskite structure. (c) Photographs of yellow nonperovskite structures of APbI3 with various A cations. (d) Photographs of red 2D RP perovskites of (HA)2(A)Pb2I7 with various A cations. (e) The schematic crystal structure of 2D RP perovskites of (HA)2(A)Pb2I7, where HA is $n$-hexylammonium and A = MA, FA, DMA, EA, GA, and AA. (f) PXRD patterns of the (HA)2(A)Pb2I7 crystalline powder products prepared by antisolvent growth of APbI3 with excessive $n$-hexylammonium iodide, in comparison with the calculated PXRD pattern of (HA)2(MA)Pb2I7. (g) Absorption spectra of the suspension solutions of (HA)2(A)Pb2I7 with various cations.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.