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Title: The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver–Bismuth Halide Compositions

Abstract

Replacing lead in halide perovskites is of great interest due to concerns about stability and toxicity. Recently, lead free double perovskites in which the unit cell is doubled and two divalent lead cations are substituted by a combination of mono- and trivalent cations have been synthesized as bulk single crystals and as thin films. In this report, we investigate stability and optical properties of all-inorganic cesium silver(I) bismuth(III) chloride and bromide nanocrystals with the double perovskite crystal structure. The cube-shaped nanocrystals are monodisperse in size with typical side lengths of 8 to 15 nm. The absorption spectrum of the nanocrystals presents a sharp peak, which we assign to a direct bismuth s-p transition and not to a quantum confined excitonic transition. Using this spectroscopic handle combined with high-resolution transmission electron microscopy (TEM) based elemental analysis, we conduct stoichiometric studies at the single nanocrystal level as well as decomposition assays in solution and observe that Ag+ diffusion and coalescence is one of the pathways by which this material degrades. Drying the nanocrystals leads to self-assembly into ordered nanocrystal solids, and these exhibit less degradation than nanocrystals in solution. Our results show that Cs 2AgBiX 6 (X = Cl, Br) nanocrystals aremore » a useful model system to study structure-function relationships in the search for stable nontoxic halide perovskites.« less

Authors:
ORCiD logo [1];  [1];  [2];  [1]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; China Scholarship Council; National Science Foundation (NSF)
OSTI Identifier:
1532323
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 18; Journal Issue: 6; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Lead-free halide perovskites; double perovskites; cesium silver bismuth halides; perovskite nanocrystals

Citation Formats

Bekenstein, Yehonadav, Dahl, Jakob C., Huang, Jianmei, Osowiecki, Wojciech T., Swabeck, Joseph K., Chan, Emory M., Yang, Peidong, and Alivisatos, A. Paul. The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver–Bismuth Halide Compositions. United States: N. p., 2018. Web. doi:10.1021/acs.nanolett.8b00560.
Bekenstein, Yehonadav, Dahl, Jakob C., Huang, Jianmei, Osowiecki, Wojciech T., Swabeck, Joseph K., Chan, Emory M., Yang, Peidong, & Alivisatos, A. Paul. The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver–Bismuth Halide Compositions. United States. doi:10.1021/acs.nanolett.8b00560.
Bekenstein, Yehonadav, Dahl, Jakob C., Huang, Jianmei, Osowiecki, Wojciech T., Swabeck, Joseph K., Chan, Emory M., Yang, Peidong, and Alivisatos, A. Paul. Wed . "The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver–Bismuth Halide Compositions". United States. doi:10.1021/acs.nanolett.8b00560. https://www.osti.gov/servlets/purl/1532323.
@article{osti_1532323,
title = {The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver–Bismuth Halide Compositions},
author = {Bekenstein, Yehonadav and Dahl, Jakob C. and Huang, Jianmei and Osowiecki, Wojciech T. and Swabeck, Joseph K. and Chan, Emory M. and Yang, Peidong and Alivisatos, A. Paul},
abstractNote = {Replacing lead in halide perovskites is of great interest due to concerns about stability and toxicity. Recently, lead free double perovskites in which the unit cell is doubled and two divalent lead cations are substituted by a combination of mono- and trivalent cations have been synthesized as bulk single crystals and as thin films. In this report, we investigate stability and optical properties of all-inorganic cesium silver(I) bismuth(III) chloride and bromide nanocrystals with the double perovskite crystal structure. The cube-shaped nanocrystals are monodisperse in size with typical side lengths of 8 to 15 nm. The absorption spectrum of the nanocrystals presents a sharp peak, which we assign to a direct bismuth s-p transition and not to a quantum confined excitonic transition. Using this spectroscopic handle combined with high-resolution transmission electron microscopy (TEM) based elemental analysis, we conduct stoichiometric studies at the single nanocrystal level as well as decomposition assays in solution and observe that Ag+ diffusion and coalescence is one of the pathways by which this material degrades. Drying the nanocrystals leads to self-assembly into ordered nanocrystal solids, and these exhibit less degradation than nanocrystals in solution. Our results show that Cs2AgBiX6 (X = Cl, Br) nanocrystals are a useful model system to study structure-function relationships in the search for stable nontoxic halide perovskites.},
doi = {10.1021/acs.nanolett.8b00560},
journal = {Nano Letters},
issn = {1530-6984},
number = 6,
volume = 18,
place = {United States},
year = {2018},
month = {5}
}

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