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Title: Rb4Ag2BiBr9: A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability

Abstract

Replacement of the toxic heavy element lead in metal halide perovskites has been attracting a great interest because the high toxicity and poor air stability are two of the major barriers for their widespread utilization. Recently, mixed-cation double perovskite halides, also known as elpasolites, were proposed as an alternative lead-free candidate for the design of nontoxic perovskite solar cells. Herein, we report a new nontoxic and air stable lead-free all-inorganic semiconductor Rb4Ag2BiBr9 prepared using the mixed-cation approach; however, Rb4Ag2BiBr9 adopts a new structure type (Pearson’s code oP32) featuring BiBr6 octahedra and AgBr5 square pyramids that share common edges and corners to form a unique 2D layered non-perovskite structure. Rb4Ag2BiBr9 is also demonstrated to be thermally stable with the measured onset decomposition temperature of To = 520 °C. Optical absorption measurements and density functional theory calculations suggest a nearly direct band gap for Rb4Ag2BiBr9. Room temperature photoluminescence (PL) measurements show a broadband weak emission. Furthermore, temperature-dependent and power-dependent PL measurements show a strong competition between multiple emission centers and suggest the coexistence of defect-bound excitons and self-trapped excitons in Rb4Ag2BiBr9.

Authors:
 [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Oklahoma, Norman, OK (United States)
  2. East China Normal Univ., Shanghai (China); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. East China Normal Univ., Shanghai (China)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1507861
Grant/Contract Number:  
AC05-00OR22725; AR18-008; 61574059; 61722402; 15SG20; CHE-1726630; CHE-0130835
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 7; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sharma, Manila, Yangui, Aymen, Whiteside, Vincent R., Sellers, Ian R., Han, Dan, Chen, Shiyou, Du, Mao -Hua, and Saparov, Bayrammurad. Rb4Ag2BiBr9: A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.8b03623.
Sharma, Manila, Yangui, Aymen, Whiteside, Vincent R., Sellers, Ian R., Han, Dan, Chen, Shiyou, Du, Mao -Hua, & Saparov, Bayrammurad. Rb4Ag2BiBr9: A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability. United States. doi:10.1021/acs.inorgchem.8b03623.
Sharma, Manila, Yangui, Aymen, Whiteside, Vincent R., Sellers, Ian R., Han, Dan, Chen, Shiyou, Du, Mao -Hua, and Saparov, Bayrammurad. Fri . "Rb4Ag2BiBr9: A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability". United States. doi:10.1021/acs.inorgchem.8b03623. https://www.osti.gov/servlets/purl/1507861.
@article{osti_1507861,
title = {Rb4Ag2BiBr9: A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability},
author = {Sharma, Manila and Yangui, Aymen and Whiteside, Vincent R. and Sellers, Ian R. and Han, Dan and Chen, Shiyou and Du, Mao -Hua and Saparov, Bayrammurad},
abstractNote = {Replacement of the toxic heavy element lead in metal halide perovskites has been attracting a great interest because the high toxicity and poor air stability are two of the major barriers for their widespread utilization. Recently, mixed-cation double perovskite halides, also known as elpasolites, were proposed as an alternative lead-free candidate for the design of nontoxic perovskite solar cells. Herein, we report a new nontoxic and air stable lead-free all-inorganic semiconductor Rb4Ag2BiBr9 prepared using the mixed-cation approach; however, Rb4Ag2BiBr9 adopts a new structure type (Pearson’s code oP32) featuring BiBr6 octahedra and AgBr5 square pyramids that share common edges and corners to form a unique 2D layered non-perovskite structure. Rb4Ag2BiBr9 is also demonstrated to be thermally stable with the measured onset decomposition temperature of To = 520 °C. Optical absorption measurements and density functional theory calculations suggest a nearly direct band gap for Rb4Ag2BiBr9. Room temperature photoluminescence (PL) measurements show a broadband weak emission. Furthermore, temperature-dependent and power-dependent PL measurements show a strong competition between multiple emission centers and suggest the coexistence of defect-bound excitons and self-trapped excitons in Rb4Ag2BiBr9.},
doi = {10.1021/acs.inorgchem.8b03623},
journal = {Inorganic Chemistry},
number = 7,
volume = 58,
place = {United States},
year = {2019},
month = {2}
}

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Works referencing / citing this record:

CSD 1871838: Experimental Crystal Structure Determination
dataset, January 2019

  • Sharma, Manila; Yangui, Aymen; Whiteside, Vincent R.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20tswj

(CH 3 NH 3 )AuX 4 ⋅H 2 O (X=Cl, Br) and (CH 3 NH 3 )AuCl 4 : Low‐Band Gap Lead‐Free Layered Gold Halide Perovskite Materials
journal, July 2019

  • Worley, Chris; Yangui, Aymen; Roccanova, Rachel
  • Chemistry – A European Journal, Vol. 25, Issue 42
  • DOI: 10.1002/chem.201901112

(CH 3 NH 3 )AuX 4 ⋅H 2 O (X=Cl, Br) and (CH 3 NH 3 )AuCl 4 : Low‐Band Gap Lead‐Free Layered Gold Halide Perovskite Materials
journal, July 2019

  • Worley, Chris; Yangui, Aymen; Roccanova, Rachel
  • Chemistry – A European Journal, Vol. 25, Issue 42
  • DOI: 10.1002/chem.201901112