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Title: Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si

Abstract

The trends in electronic band structure are investigated in the cubic ABX3 halide perovskites fo rA=Cs;B=Pb,Sn, Ge, Si; andX=I, Br, Cl. The gaps are found to decrease from Pb to Sn and from Ge to Si, but increase from Sn to Ge. The trend is explained in terms of the atomic levels of the group-IV element and the atomic sizes which changes the amount of hybridization with X-p and hence the valence bandwidth. Along the same series spin-orbit coupling also decreases and this tends to increase the gap because of the smaller splitting of the conduction band minimum. Both effects compensate each other to a certain degree. The trend with halogens is to reduce the gap from Cl to I, i.e., with decreasing electronegativity. The part of the tolerance factor in avoiding octahedron rotations and octahedron edge sharing is discussed. The Ge containing compounds have tolerance factor t>1 and hence do not show the series of octahedral rotation distortions and the existence of edge-sharing octahedral phases known for Pb and Sn-based compounds, but rather a rhombohedral distortion. CsGeI3 is found to have a suitable gap for photovoltaics both in its cubic (high-temperature) and rhombohedral (low-temperature) phases. The structural stability ofmore » the materials in the different phases is also discussed. We find the rhombohedral phase to have lower total energy and slightly larger gaps but to present a less significant distortion of the bandstructure than the edge-sharing octahedral phases, such as the yellow phase in CsSnI3. The corresponding silicon based compounds have not yet been synthesized and therefore our estimates are less certain but indicate a small gap for cubic CsSiI3 and CsSiBr3of about 0.2±0.2 eV and 0.8±0.6 eV for CsSiCl3. The intrinsic stability of the Si compounds is discussed.« less

Authors:
 [1]; ORCiD logo [1]
  1. Case Western Reserve Univ., Cleveland, OH (United States)
Publication Date:
Research Org.:
Case Western Reserve Univ., Cleveland, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1591890
Alternate Identifier(s):
OSTI ID: 1254217
Grant/Contract Number:  
SC0008933
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 93; Journal Issue: 19; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; halide perovskite; band structure

Citation Formats

Huang, Ling-yi, and Lambrecht, Walter R. L. Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si. United States: N. p., 2016. Web. doi:10.1103/PhysRevB.93.195211.
Huang, Ling-yi, & Lambrecht, Walter R. L. Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si. United States. doi:10.1103/PhysRevB.93.195211.
Huang, Ling-yi, and Lambrecht, Walter R. L. Mon . "Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si". United States. doi:10.1103/PhysRevB.93.195211. https://www.osti.gov/servlets/purl/1591890.
@article{osti_1591890,
title = {Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si},
author = {Huang, Ling-yi and Lambrecht, Walter R. L.},
abstractNote = {The trends in electronic band structure are investigated in the cubic ABX3 halide perovskites fo rA=Cs;B=Pb,Sn, Ge, Si; andX=I, Br, Cl. The gaps are found to decrease from Pb to Sn and from Ge to Si, but increase from Sn to Ge. The trend is explained in terms of the atomic levels of the group-IV element and the atomic sizes which changes the amount of hybridization with X-p and hence the valence bandwidth. Along the same series spin-orbit coupling also decreases and this tends to increase the gap because of the smaller splitting of the conduction band minimum. Both effects compensate each other to a certain degree. The trend with halogens is to reduce the gap from Cl to I, i.e., with decreasing electronegativity. The part of the tolerance factor in avoiding octahedron rotations and octahedron edge sharing is discussed. The Ge containing compounds have tolerance factor t>1 and hence do not show the series of octahedral rotation distortions and the existence of edge-sharing octahedral phases known for Pb and Sn-based compounds, but rather a rhombohedral distortion. CsGeI3 is found to have a suitable gap for photovoltaics both in its cubic (high-temperature) and rhombohedral (low-temperature) phases. The structural stability of the materials in the different phases is also discussed. We find the rhombohedral phase to have lower total energy and slightly larger gaps but to present a less significant distortion of the bandstructure than the edge-sharing octahedral phases, such as the yellow phase in CsSnI3. The corresponding silicon based compounds have not yet been synthesized and therefore our estimates are less certain but indicate a small gap for cubic CsSiI3 and CsSiBr3of about 0.2±0.2 eV and 0.8±0.6 eV for CsSiCl3. The intrinsic stability of the Si compounds is discussed.},
doi = {10.1103/PhysRevB.93.195211},
journal = {Physical Review B},
number = 19,
volume = 93,
place = {United States},
year = {2016},
month = {5}
}

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