Title: Viability of Lead-Free Perovskites with Mixed Chalcogen and Halogen Anions for Photovoltaic Applications

Abstract

We assess the viability for photovoltaic applications of proposed Pb-free perovskites with mixed chalcogen and halogen anions, AB(Ch,X)₃ (A = Cs or Ba; B = Sb or Bi; Ch = chalcogen; X = halogen), by examining critical issues such as the structural, electronic/optical properties, and stability through the combination of density-functional theory calculations and solid state reactions. The calculations show that these quaternary Pb-free perovskites are thermodynamically unstable--they are prone to decompose into ternary and/or binary secondary phases or form phases with nonperovskite structures. Solid-state synthesis efforts confirm the theoretically predicted difficulty for preparing these compounds; all attempted reactions do not form the desired perovskite phases with mixed chalcogen and halogen anions under conditions examined. Instead, they form separate binary and ternary compounds. Despite earlier predictions of promising characteristics for these prospective perovskites for photovoltaics, our results suggest that, due to their instability, the Pb-free perovskites with mixed chalcogen and halogen anions may be challenging to form under equilibrium synthetic conditions.

Authors:

Hong, Feng ^[1]; Saparov, Bayrammurad ^[2]; Meng, Weiwei ^[3]; Xiao, Zewen ^[4]; Mitzi, David B. ^[2]; Yan, Yanfa ^[4]

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+ Show Author Affiliations

1. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC); Shanghai Univ., Shanghai (China). Dept. of Physics
2. Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science, and Dept. of Chemistry
3. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC); Wuhan Univ., Wuhan (China). School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Inst. for Advanced Studies
4. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC)

Publication Date:

2016-03-09

Research Org.:

Duke Univ., Durham, NC (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:

1559761

Grant/Contract Number:  

EE0006712

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Physical Chemistry. C

Additional Journal Information:

Journal Volume: 120; Journal Issue: 12; Journal ID: ISSN 1932-7447

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY