CsSnI 3: Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. High hole mobility and phase-transitions

In Chung, Jung Hwan Song, Jino Im, John Androulakis, Christos D. Malliakas, Hao Li, Arthur J Freeman, John T. Kenney, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

328 Citations (Scopus)

Abstract

CsSnI 3 is an unusual perovskite that undergoes complex displacive and reconstructive phase transitions and exhibits near-infrared emission at room temperature. Experimental and theoretical studies of CsSnI 3 have been limited by the lack of detailed crystal structure characterization and chemical instability. Here we describe the synthesis of pure polymorphic crystals, the preparation of large crack-/bubble-free ingots, the refined single-crystal structures, and temperature-dependent charge transport and optical properties of CsSnI 3, coupled with ab initio first-principles density functional theory (DFT) calculations. In situ temperature-dependent single-crystal and synchrotron powder X-ray diffraction studies reveal the origin of polymorphous phase transitions of CsSnI 3. The black orthorhombic form of CsSnI 3 demonstrates one of the largest volumetric thermal expansion coefficients for inorganic solids. Electrical conductivity, Hall effect, and thermopower measurements on it show p-type metallic behavior with low carrier density, despite the optical band gap of 1.3 eV. Hall effect measurements of the black orthorhombic perovskite phase of CsSnI 3 indicate that it is a p-type direct band gap semiconductor with carrier concentration at room temperature of ∼ 10 17 cm -3 and a hole mobility of ∼585 cm 2 V -1 s -1. The hole mobility is one of the highest observed among p-type semiconductors with comparable band gaps. Its powders exhibit a strong room-temperature near-IR emission spectrum at 950 nm. Remarkably, the values of the electrical conductivity and photoluminescence intensity increase with heat treatment. The DFT calculations show that the screened-exchange local density approximation-derived band gap agrees well with the experimentally measured band gap. Calculations of the formation energy of defects strongly suggest that the electrical and light emission properties possibly result from Sn defects in the crystal structure, which arise intrinsically. Thus, although stoichiometric CsSnI 3 is a semiconductor, the material is prone to intrinsic defects associated with Sn vacancies. This creates highly mobile holes which cause the materials to appear metallic.

Original languageEnglish
Pages (from-to)8579-8587
Number of pages9
JournalJournal of the American Chemical Society
Volume134
Issue number20
DOIs
Publication statusPublished - May 23 2012

Fingerprint

Electric Conductivity
Semiconductors
Hole mobility
Phase Transition
Photoluminescence
Phase transitions
Metals
Semiconductor materials
Infrared radiation
Energy gap
Temperature
Crystal structure
Hall effect
Powders
Perovskite
Defects
Density functional theory
Carrier concentration
Hot Temperature
Single crystals

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

CsSnI 3 : Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. High hole mobility and phase-transitions. / Chung, In; Song, Jung Hwan; Im, Jino; Androulakis, John; Malliakas, Christos D.; Li, Hao; Freeman, Arthur J; Kenney, John T.; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 134, No. 20, 23.05.2012, p. 8579-8587.

Research output: Contribution to journalArticle

@article{e4e230cb861e4434b586018394a3c743,
title = "CsSnI 3: Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. High hole mobility and phase-transitions",
abstract = "CsSnI 3 is an unusual perovskite that undergoes complex displacive and reconstructive phase transitions and exhibits near-infrared emission at room temperature. Experimental and theoretical studies of CsSnI 3 have been limited by the lack of detailed crystal structure characterization and chemical instability. Here we describe the synthesis of pure polymorphic crystals, the preparation of large crack-/bubble-free ingots, the refined single-crystal structures, and temperature-dependent charge transport and optical properties of CsSnI 3, coupled with ab initio first-principles density functional theory (DFT) calculations. In situ temperature-dependent single-crystal and synchrotron powder X-ray diffraction studies reveal the origin of polymorphous phase transitions of CsSnI 3. The black orthorhombic form of CsSnI 3 demonstrates one of the largest volumetric thermal expansion coefficients for inorganic solids. Electrical conductivity, Hall effect, and thermopower measurements on it show p-type metallic behavior with low carrier density, despite the optical band gap of 1.3 eV. Hall effect measurements of the black orthorhombic perovskite phase of CsSnI 3 indicate that it is a p-type direct band gap semiconductor with carrier concentration at room temperature of ∼ 10 17 cm -3 and a hole mobility of ∼585 cm 2 V -1 s -1. The hole mobility is one of the highest observed among p-type semiconductors with comparable band gaps. Its powders exhibit a strong room-temperature near-IR emission spectrum at 950 nm. Remarkably, the values of the electrical conductivity and photoluminescence intensity increase with heat treatment. The DFT calculations show that the screened-exchange local density approximation-derived band gap agrees well with the experimentally measured band gap. Calculations of the formation energy of defects strongly suggest that the electrical and light emission properties possibly result from Sn defects in the crystal structure, which arise intrinsically. Thus, although stoichiometric CsSnI 3 is a semiconductor, the material is prone to intrinsic defects associated with Sn vacancies. This creates highly mobile holes which cause the materials to appear metallic.",
author = "In Chung and Song, {Jung Hwan} and Jino Im and John Androulakis and Malliakas, {Christos D.} and Hao Li and Freeman, {Arthur J} and Kenney, {John T.} and Kanatzidis, {Mercouri G}",
year = "2012",
month = "5",
day = "23",
doi = "10.1021/ja301539s",
language = "English",
volume = "134",
pages = "8579--8587",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "20",

}

TY - JOUR

T1 - CsSnI 3

T2 - Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. High hole mobility and phase-transitions

AU - Chung, In

AU - Song, Jung Hwan

AU - Im, Jino

AU - Androulakis, John

AU - Malliakas, Christos D.

AU - Li, Hao

AU - Freeman, Arthur J

AU - Kenney, John T.

AU - Kanatzidis, Mercouri G

PY - 2012/5/23

Y1 - 2012/5/23

N2 - CsSnI 3 is an unusual perovskite that undergoes complex displacive and reconstructive phase transitions and exhibits near-infrared emission at room temperature. Experimental and theoretical studies of CsSnI 3 have been limited by the lack of detailed crystal structure characterization and chemical instability. Here we describe the synthesis of pure polymorphic crystals, the preparation of large crack-/bubble-free ingots, the refined single-crystal structures, and temperature-dependent charge transport and optical properties of CsSnI 3, coupled with ab initio first-principles density functional theory (DFT) calculations. In situ temperature-dependent single-crystal and synchrotron powder X-ray diffraction studies reveal the origin of polymorphous phase transitions of CsSnI 3. The black orthorhombic form of CsSnI 3 demonstrates one of the largest volumetric thermal expansion coefficients for inorganic solids. Electrical conductivity, Hall effect, and thermopower measurements on it show p-type metallic behavior with low carrier density, despite the optical band gap of 1.3 eV. Hall effect measurements of the black orthorhombic perovskite phase of CsSnI 3 indicate that it is a p-type direct band gap semiconductor with carrier concentration at room temperature of ∼ 10 17 cm -3 and a hole mobility of ∼585 cm 2 V -1 s -1. The hole mobility is one of the highest observed among p-type semiconductors with comparable band gaps. Its powders exhibit a strong room-temperature near-IR emission spectrum at 950 nm. Remarkably, the values of the electrical conductivity and photoluminescence intensity increase with heat treatment. The DFT calculations show that the screened-exchange local density approximation-derived band gap agrees well with the experimentally measured band gap. Calculations of the formation energy of defects strongly suggest that the electrical and light emission properties possibly result from Sn defects in the crystal structure, which arise intrinsically. Thus, although stoichiometric CsSnI 3 is a semiconductor, the material is prone to intrinsic defects associated with Sn vacancies. This creates highly mobile holes which cause the materials to appear metallic.

AB - CsSnI 3 is an unusual perovskite that undergoes complex displacive and reconstructive phase transitions and exhibits near-infrared emission at room temperature. Experimental and theoretical studies of CsSnI 3 have been limited by the lack of detailed crystal structure characterization and chemical instability. Here we describe the synthesis of pure polymorphic crystals, the preparation of large crack-/bubble-free ingots, the refined single-crystal structures, and temperature-dependent charge transport and optical properties of CsSnI 3, coupled with ab initio first-principles density functional theory (DFT) calculations. In situ temperature-dependent single-crystal and synchrotron powder X-ray diffraction studies reveal the origin of polymorphous phase transitions of CsSnI 3. The black orthorhombic form of CsSnI 3 demonstrates one of the largest volumetric thermal expansion coefficients for inorganic solids. Electrical conductivity, Hall effect, and thermopower measurements on it show p-type metallic behavior with low carrier density, despite the optical band gap of 1.3 eV. Hall effect measurements of the black orthorhombic perovskite phase of CsSnI 3 indicate that it is a p-type direct band gap semiconductor with carrier concentration at room temperature of ∼ 10 17 cm -3 and a hole mobility of ∼585 cm 2 V -1 s -1. The hole mobility is one of the highest observed among p-type semiconductors with comparable band gaps. Its powders exhibit a strong room-temperature near-IR emission spectrum at 950 nm. Remarkably, the values of the electrical conductivity and photoluminescence intensity increase with heat treatment. The DFT calculations show that the screened-exchange local density approximation-derived band gap agrees well with the experimentally measured band gap. Calculations of the formation energy of defects strongly suggest that the electrical and light emission properties possibly result from Sn defects in the crystal structure, which arise intrinsically. Thus, although stoichiometric CsSnI 3 is a semiconductor, the material is prone to intrinsic defects associated with Sn vacancies. This creates highly mobile holes which cause the materials to appear metallic.

UR - http://www.scopus.com/inward/record.url?scp=84861414374&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84861414374&partnerID=8YFLogxK

U2 - 10.1021/ja301539s

DO - 10.1021/ja301539s

M3 - Article

C2 - 22578072

AN - SCOPUS:84861414374

VL - 134

SP - 8579

EP - 8587

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 20

ER -