Intrinsic Instability of the Hybrid Halide Perovskite Semiconductor CH3NH3PbI3

Yue Yu Zhang, Shiyou Chen, Peng Xu, Hongjun Xiang, Xin Gao Gong, Aron Walsh, Su Huai Wei

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

The organic-inorganic hybrid perovskite CH3NH3PbI3 has attracted significant interest for its high performance in converting solar light into electrical power with an efficiency exceeding 20%. Unfortunately, chemical stability is one major challenge in the development of CH3NH3PbI3 solar cells. It was commonly assumed that moisture or oxygen in the environment causes the poor stability of hybrid halide perovskites, however, here we show from the first-principles calculations that the room-temperature tetragonal phase of CH3NH3PbI3 is thermodynamically unstable with respect to the phase separation into CH3NH3I+PbI2, i.e., the disproportionation is exothermic, independent of the humidity or oxygen in the atmosphere. When the structure is distorted to the low-temperature orthorhombic phase, the energetic cost of separation increases, but remains small. Contributions from vibrational and configurational entropy at room temperature have been considered, but the instability of CH3NH3PbI3 is unchanged. When I is replaced by Br or Cl, Pb by Sn, or the organic cation CH3NH3 by inorganic Cs, the perovskites become more stable and do not phase-separate spontaneously. Our study highlights that the poor chemical stability is intrinsic to CH3NH3PbI3 and suggests that element-substitution may solve the chemical stability problem in hybrid halide perovskite solar cells.

Original languageEnglish
Article number036104
JournalChinese Physics Letters
Volume35
Issue number3
DOIs
Publication statusPublished - 2018 Mar

Fingerprint

halides
perovskites
solar cells
room temperature
oxygen
moisture
humidity
substitutes
entropy
costs
cations
atmospheres
causes

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)

Cite this

Zhang, Yue Yu ; Chen, Shiyou ; Xu, Peng ; Xiang, Hongjun ; Gong, Xin Gao ; Walsh, Aron ; Wei, Su Huai. / Intrinsic Instability of the Hybrid Halide Perovskite Semiconductor CH3NH3PbI3 In: Chinese Physics Letters. 2018 ; Vol. 35, No. 3.
@article{bc316a03c5364e0c91e55496493a9d05,
title = "Intrinsic Instability of the Hybrid Halide Perovskite Semiconductor CH3NH3PbI3 ∗",
abstract = "The organic-inorganic hybrid perovskite CH3NH3PbI3 has attracted significant interest for its high performance in converting solar light into electrical power with an efficiency exceeding 20{\%}. Unfortunately, chemical stability is one major challenge in the development of CH3NH3PbI3 solar cells. It was commonly assumed that moisture or oxygen in the environment causes the poor stability of hybrid halide perovskites, however, here we show from the first-principles calculations that the room-temperature tetragonal phase of CH3NH3PbI3 is thermodynamically unstable with respect to the phase separation into CH3NH3I+PbI2, i.e., the disproportionation is exothermic, independent of the humidity or oxygen in the atmosphere. When the structure is distorted to the low-temperature orthorhombic phase, the energetic cost of separation increases, but remains small. Contributions from vibrational and configurational entropy at room temperature have been considered, but the instability of CH3NH3PbI3 is unchanged. When I is replaced by Br or Cl, Pb by Sn, or the organic cation CH3NH3 by inorganic Cs, the perovskites become more stable and do not phase-separate spontaneously. Our study highlights that the poor chemical stability is intrinsic to CH3NH3PbI3 and suggests that element-substitution may solve the chemical stability problem in hybrid halide perovskite solar cells.",
author = "Zhang, {Yue Yu} and Shiyou Chen and Peng Xu and Hongjun Xiang and Gong, {Xin Gao} and Aron Walsh and Wei, {Su Huai}",
year = "2018",
month = "3",
doi = "10.1088/0256-307X/35/3/036104",
language = "English",
volume = "35",
journal = "Chinese Physics Letters",
issn = "0256-307X",
publisher = "IOP Publishing Ltd.",
number = "3",

}

Intrinsic Instability of the Hybrid Halide Perovskite Semiconductor CH3NH3PbI3 . / Zhang, Yue Yu; Chen, Shiyou; Xu, Peng; Xiang, Hongjun; Gong, Xin Gao; Walsh, Aron; Wei, Su Huai.

In: Chinese Physics Letters, Vol. 35, No. 3, 036104, 03.2018.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Intrinsic Instability of the Hybrid Halide Perovskite Semiconductor CH3NH3PbI3 ∗

AU - Zhang, Yue Yu

AU - Chen, Shiyou

AU - Xu, Peng

AU - Xiang, Hongjun

AU - Gong, Xin Gao

AU - Walsh, Aron

AU - Wei, Su Huai

PY - 2018/3

Y1 - 2018/3

N2 - The organic-inorganic hybrid perovskite CH3NH3PbI3 has attracted significant interest for its high performance in converting solar light into electrical power with an efficiency exceeding 20%. Unfortunately, chemical stability is one major challenge in the development of CH3NH3PbI3 solar cells. It was commonly assumed that moisture or oxygen in the environment causes the poor stability of hybrid halide perovskites, however, here we show from the first-principles calculations that the room-temperature tetragonal phase of CH3NH3PbI3 is thermodynamically unstable with respect to the phase separation into CH3NH3I+PbI2, i.e., the disproportionation is exothermic, independent of the humidity or oxygen in the atmosphere. When the structure is distorted to the low-temperature orthorhombic phase, the energetic cost of separation increases, but remains small. Contributions from vibrational and configurational entropy at room temperature have been considered, but the instability of CH3NH3PbI3 is unchanged. When I is replaced by Br or Cl, Pb by Sn, or the organic cation CH3NH3 by inorganic Cs, the perovskites become more stable and do not phase-separate spontaneously. Our study highlights that the poor chemical stability is intrinsic to CH3NH3PbI3 and suggests that element-substitution may solve the chemical stability problem in hybrid halide perovskite solar cells.

AB - The organic-inorganic hybrid perovskite CH3NH3PbI3 has attracted significant interest for its high performance in converting solar light into electrical power with an efficiency exceeding 20%. Unfortunately, chemical stability is one major challenge in the development of CH3NH3PbI3 solar cells. It was commonly assumed that moisture or oxygen in the environment causes the poor stability of hybrid halide perovskites, however, here we show from the first-principles calculations that the room-temperature tetragonal phase of CH3NH3PbI3 is thermodynamically unstable with respect to the phase separation into CH3NH3I+PbI2, i.e., the disproportionation is exothermic, independent of the humidity or oxygen in the atmosphere. When the structure is distorted to the low-temperature orthorhombic phase, the energetic cost of separation increases, but remains small. Contributions from vibrational and configurational entropy at room temperature have been considered, but the instability of CH3NH3PbI3 is unchanged. When I is replaced by Br or Cl, Pb by Sn, or the organic cation CH3NH3 by inorganic Cs, the perovskites become more stable and do not phase-separate spontaneously. Our study highlights that the poor chemical stability is intrinsic to CH3NH3PbI3 and suggests that element-substitution may solve the chemical stability problem in hybrid halide perovskite solar cells.

UR - http://www.scopus.com/inward/record.url?scp=85044192498&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85044192498&partnerID=8YFLogxK

U2 - 10.1088/0256-307X/35/3/036104

DO - 10.1088/0256-307X/35/3/036104

M3 - Article

AN - SCOPUS:85044192498

VL - 35

JO - Chinese Physics Letters

JF - Chinese Physics Letters

SN - 0256-307X

IS - 3

M1 - 036104

ER -