Computational Study of Structural and Electronic Properties of Lead-Free CsMI3 Perovskites (M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba)

Debmalya Ray, Catherine Clark, Hung Q. Pham, Joshua Borycz, Russell J. Holmes, Eray Aydil, Laura Gagliardi

Research output: Contribution to journalArticle

Abstract

Electronic structure calculations of five crystallography-imitated structures of CsMI3 perovskites with M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba were performed. The formation energy of different perovskite phases, their relative stability, and structural and electronic properties were explored. The sensitivity of the calculations to the choice of the density functional was investigated, and the predictions were compared with experimental results. The outcome of this study is that Mg and Ba perovskites are unlikely to form in the cubic, tetragonal, or orthorhombic phases because they have positive formation energies. Although Ca and Sr perovskites have negative formation energies with respect to the metal-iodide precursors, they exhibit wide band gaps and high hygroscopicity, making these unlikely candidates for applications in photovoltaic devices. Our results suggest that the performance of a local density functional with a nonseparable gradient approximation (NGA) is similar to that of hybrid functionals in terms of band gap predictions, when M in CsMI3 is a p-block element (Pb, Sn, and Ge). However, local density functionals with NGA predictions for the band gap are similar to other local functionals with a generalized gradient approximation (PBE, PBEsol, and PBE-D3) and are worse than those of HSE06, when M is an s-block element (Mg, Ca, Sr, and Ba).

Original languageEnglish (US)
Pages (from-to)7838-7848
Number of pages11
JournalJournal of Physical Chemistry C
Volume122
Issue number14
DOIs
StatePublished - Apr 12 2018

Fingerprint

energy of formation
perovskites
functionals
Electronic properties
Structural properties
Energy gap
Lead
gradients
predictions
approximation
electronics
hygroscopicity
Crystallography
Iodides
Perovskite
iodides
crystallography
Electronic structure
Metals
electronic structure

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Computational Study of Structural and Electronic Properties of Lead-Free CsMI3 Perovskites (M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba). / Ray, Debmalya; Clark, Catherine; Pham, Hung Q.; Borycz, Joshua; Holmes, Russell J.; Aydil, Eray; Gagliardi, Laura.

In: Journal of Physical Chemistry C, Vol. 122, No. 14, 12.04.2018, p. 7838-7848.

Research output: Contribution to journalArticle

Ray, Debmalya ; Clark, Catherine ; Pham, Hung Q. ; Borycz, Joshua ; Holmes, Russell J. ; Aydil, Eray ; Gagliardi, Laura. / Computational Study of Structural and Electronic Properties of Lead-Free CsMI3 Perovskites (M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba). In: Journal of Physical Chemistry C. 2018 ; Vol. 122, No. 14. pp. 7838-7848.
@article{c96c7a03c2c743e39c75083b28ee4914,
title = "Computational Study of Structural and Electronic Properties of Lead-Free CsMI3 Perovskites (M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba)",
abstract = "Electronic structure calculations of five crystallography-imitated structures of CsMI3 perovskites with M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba were performed. The formation energy of different perovskite phases, their relative stability, and structural and electronic properties were explored. The sensitivity of the calculations to the choice of the density functional was investigated, and the predictions were compared with experimental results. The outcome of this study is that Mg and Ba perovskites are unlikely to form in the cubic, tetragonal, or orthorhombic phases because they have positive formation energies. Although Ca and Sr perovskites have negative formation energies with respect to the metal-iodide precursors, they exhibit wide band gaps and high hygroscopicity, making these unlikely candidates for applications in photovoltaic devices. Our results suggest that the performance of a local density functional with a nonseparable gradient approximation (NGA) is similar to that of hybrid functionals in terms of band gap predictions, when M in CsMI3 is a p-block element (Pb, Sn, and Ge). However, local density functionals with NGA predictions for the band gap are similar to other local functionals with a generalized gradient approximation (PBE, PBEsol, and PBE-D3) and are worse than those of HSE06, when M is an s-block element (Mg, Ca, Sr, and Ba).",
author = "Debmalya Ray and Catherine Clark and Pham, {Hung Q.} and Joshua Borycz and Holmes, {Russell J.} and Eray Aydil and Laura Gagliardi",
year = "2018",
month = "4",
day = "12",
doi = "10.1021/acs.jpcc.8b00226",
language = "English (US)",
volume = "122",
pages = "7838--7848",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Computational Study of Structural and Electronic Properties of Lead-Free CsMI3 Perovskites (M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba)

AU - Ray, Debmalya

AU - Clark, Catherine

AU - Pham, Hung Q.

AU - Borycz, Joshua

AU - Holmes, Russell J.

AU - Aydil, Eray

AU - Gagliardi, Laura

PY - 2018/4/12

Y1 - 2018/4/12

N2 - Electronic structure calculations of five crystallography-imitated structures of CsMI3 perovskites with M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba were performed. The formation energy of different perovskite phases, their relative stability, and structural and electronic properties were explored. The sensitivity of the calculations to the choice of the density functional was investigated, and the predictions were compared with experimental results. The outcome of this study is that Mg and Ba perovskites are unlikely to form in the cubic, tetragonal, or orthorhombic phases because they have positive formation energies. Although Ca and Sr perovskites have negative formation energies with respect to the metal-iodide precursors, they exhibit wide band gaps and high hygroscopicity, making these unlikely candidates for applications in photovoltaic devices. Our results suggest that the performance of a local density functional with a nonseparable gradient approximation (NGA) is similar to that of hybrid functionals in terms of band gap predictions, when M in CsMI3 is a p-block element (Pb, Sn, and Ge). However, local density functionals with NGA predictions for the band gap are similar to other local functionals with a generalized gradient approximation (PBE, PBEsol, and PBE-D3) and are worse than those of HSE06, when M is an s-block element (Mg, Ca, Sr, and Ba).

AB - Electronic structure calculations of five crystallography-imitated structures of CsMI3 perovskites with M = Ge, Sn, Pb, Mg, Ca, Sr, and Ba were performed. The formation energy of different perovskite phases, their relative stability, and structural and electronic properties were explored. The sensitivity of the calculations to the choice of the density functional was investigated, and the predictions were compared with experimental results. The outcome of this study is that Mg and Ba perovskites are unlikely to form in the cubic, tetragonal, or orthorhombic phases because they have positive formation energies. Although Ca and Sr perovskites have negative formation energies with respect to the metal-iodide precursors, they exhibit wide band gaps and high hygroscopicity, making these unlikely candidates for applications in photovoltaic devices. Our results suggest that the performance of a local density functional with a nonseparable gradient approximation (NGA) is similar to that of hybrid functionals in terms of band gap predictions, when M in CsMI3 is a p-block element (Pb, Sn, and Ge). However, local density functionals with NGA predictions for the band gap are similar to other local functionals with a generalized gradient approximation (PBE, PBEsol, and PBE-D3) and are worse than those of HSE06, when M is an s-block element (Mg, Ca, Sr, and Ba).

UR - http://www.scopus.com/inward/record.url?scp=85045382877&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85045382877&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.8b00226

DO - 10.1021/acs.jpcc.8b00226

M3 - Article

VL - 122

SP - 7838

EP - 7848

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 14

ER -