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Title: Chemical and Structural Diversity of Hybrid Layered Double Perovskite Halides

Abstract

Hybrid halide double perovskites are a class of compounds attracting growing interest due to their richness of structure and property. Two-dimensional (2D) derivatives of hybrid double perovskites are formed by the incorporation of organic spacer cations into three-dimensional (3D) double perovskites. Here, we report a series of seven new layered double perovskite halides with propylammonium (PA), octylammonium (OCA), and 1,4-butyldiammonium (BDA) cations. The general formulas of the compounds are AmMIMIIIX8 (single-layered Ruddlesden–Popper type with m = 4 and A = PA or OCA, and single-layered Dion–Jacobson type with m = 2 and A = BDA, MI = Ag, MIII= In or Bi, X = Cl or Br) and PA2CsMIMIIIBr7 (bilayered, with MI = Ag, MIII = In or Bi). These families of compounds demonstrate significant versatility, with tunable layer thickness, the ability to vary the interlayer spacing, and the ability to selectively tune the band gap by varying the MI and MIII cations along with the halide anions. The band gap of the single-layered materials varies from 2.41 eV for PA4AgBiBr8 to 3.96 eV for PA4AgInCl8. Photoluminescent emission spectra of the layered double perovskites at low-temperature (100 K) are reported, and density functional theory electronic structure calculations are presented tomore » understand the nature of the band gap evolution. The development of new structural and compositions in layered double perovskite halides enhances the understanding of structure–property relations in this important family.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Univ. of Crete (Greece)
  3. National Univ. of Singapore (Singapore); Univ. of California, Santa Barbara, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1599729
Grant/Contract Number:  
SC0012541; DMR-1720256
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 48; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mao, Lingling, Teicher, Samuel M. L., Stoumpos, Constantinos C., Kennard, Rhys M., DeCrescent, Ryan A., Wu, Guang, Schuller, Jon A., Chabinyc, Michael L., Cheetham, Anthony K., and Seshadri, Ram. Chemical and Structural Diversity of Hybrid Layered Double Perovskite Halides. United States: N. p., 2019. Web. https://doi.org/10.1021/jacs.9b09945.
Mao, Lingling, Teicher, Samuel M. L., Stoumpos, Constantinos C., Kennard, Rhys M., DeCrescent, Ryan A., Wu, Guang, Schuller, Jon A., Chabinyc, Michael L., Cheetham, Anthony K., & Seshadri, Ram. Chemical and Structural Diversity of Hybrid Layered Double Perovskite Halides. United States. https://doi.org/10.1021/jacs.9b09945
Mao, Lingling, Teicher, Samuel M. L., Stoumpos, Constantinos C., Kennard, Rhys M., DeCrescent, Ryan A., Wu, Guang, Schuller, Jon A., Chabinyc, Michael L., Cheetham, Anthony K., and Seshadri, Ram. Thu . "Chemical and Structural Diversity of Hybrid Layered Double Perovskite Halides". United States. https://doi.org/10.1021/jacs.9b09945. https://www.osti.gov/servlets/purl/1599729.
@article{osti_1599729,
title = {Chemical and Structural Diversity of Hybrid Layered Double Perovskite Halides},
author = {Mao, Lingling and Teicher, Samuel M. L. and Stoumpos, Constantinos C. and Kennard, Rhys M. and DeCrescent, Ryan A. and Wu, Guang and Schuller, Jon A. and Chabinyc, Michael L. and Cheetham, Anthony K. and Seshadri, Ram},
abstractNote = {Hybrid halide double perovskites are a class of compounds attracting growing interest due to their richness of structure and property. Two-dimensional (2D) derivatives of hybrid double perovskites are formed by the incorporation of organic spacer cations into three-dimensional (3D) double perovskites. Here, we report a series of seven new layered double perovskite halides with propylammonium (PA), octylammonium (OCA), and 1,4-butyldiammonium (BDA) cations. The general formulas of the compounds are AmMIMIIIX8 (single-layered Ruddlesden–Popper type with m = 4 and A = PA or OCA, and single-layered Dion–Jacobson type with m = 2 and A = BDA, MI = Ag, MIII= In or Bi, X = Cl or Br) and PA2CsMIMIIIBr7 (bilayered, with MI = Ag, MIII = In or Bi). These families of compounds demonstrate significant versatility, with tunable layer thickness, the ability to vary the interlayer spacing, and the ability to selectively tune the band gap by varying the MI and MIII cations along with the halide anions. The band gap of the single-layered materials varies from 2.41 eV for PA4AgBiBr8 to 3.96 eV for PA4AgInCl8. Photoluminescent emission spectra of the layered double perovskites at low-temperature (100 K) are reported, and density functional theory electronic structure calculations are presented to understand the nature of the band gap evolution. The development of new structural and compositions in layered double perovskite halides enhances the understanding of structure–property relations in this important family.},
doi = {10.1021/jacs.9b09945},
journal = {Journal of the American Chemical Society},
number = 48,
volume = 141,
place = {United States},
year = {2019},
month = {11}
}

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