Cs2Hg3S4

A low-dimensional direct bandgap semiconductor

Saiful M. Islam, S. Vanishri, Hao Li, Constantinos C. Stoumpos, John A. Peters, Maria Sebastian, Zhifu Liu, Shichao Wang, Alyssa S. Haynes, Jino Im, Arthur J Freeman, Bruce Wessels, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Cs2Hg3S4 was synthesized by slowly cooling a melted stoichiometric mixture of Hg and Cs2S4. Cs2Hg3S4 crystallizes in the Ibam spacegroup with a = 6.278(1) Å, b = 11.601(2) Å, and c = 14.431(3)Å; dcalc = 6.29 g/cm3. Its crystal structure consists of straight chains of [Hg3S4]n2n- that engage in side-by-side weak bonding interactions forming layers and are charge balanced by Cs+ cations. The thermal stability of this compound was investigated with differential thermal analysis and temperature dependent in situ synchrotron powder diffraction. The thermal expansion coefficients of the a, b, and c axes were assessed at 1.56 × 10-5, 2.79 × 10-5, and 3.04 × 10-5 K-1, respectively. Large single-crystals up to ∼5 cm in length and ∼1 cm in diameter were grown using a vertical Bridgman method. Electrical conductivity and photoconductivity measurements on naturally cleaved crystals of Cs2Hg3S4 gave resistivity ρ of ≥108 ω·cm and carrier mobility-lifetime (μδ) products of 4.2 × 10-4 and 5.82 × 10-5 cm2 V-1 for electrons and holes, respectively. Cs2Hg3S4 is a semiconductor with a bandgap Eg ∼ 2.8 eV and exhibits photoluminescence (PL) at low temperature. Electronic band structure calculations within the density functional theory (DFT) framework employing the nonlocal hybrid functional within Heyd-Scuseria-Ernzerhof (HSE) formalism indicate a direct bandgap of 2.81 eV at. The theoretical calculations show that the conduction band minimum has a highly dispersive and relatively isotropic mercury-based s-orbital-like character while the valence band maximum features a much less dispersive and more anisotropic sulfur orbital-based band.

Original languageEnglish
Pages (from-to)370-378
Number of pages9
JournalChemistry of Materials
Volume27
Issue number1
DOIs
Publication statusPublished - Jan 13 2015

Fingerprint

Energy gap
Semiconductor materials
Crystal growth from melt
Carrier mobility
Photoconductivity
Valence bands
Conduction bands
Synchrotrons
Mercury
Sulfur
Band structure
Differential thermal analysis
Thermal expansion
Density functional theory
Cations
Photoluminescence
Thermodynamic stability
Crystal structure
Positive ions
Single crystals

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Islam, S. M., Vanishri, S., Li, H., Stoumpos, C. C., Peters, J. A., Sebastian, M., ... Kanatzidis, M. G. (2015). Cs2Hg3S4: A low-dimensional direct bandgap semiconductor. Chemistry of Materials, 27(1), 370-378. https://doi.org/10.1021/cm504089r

Cs2Hg3S4 : A low-dimensional direct bandgap semiconductor. / Islam, Saiful M.; Vanishri, S.; Li, Hao; Stoumpos, Constantinos C.; Peters, John A.; Sebastian, Maria; Liu, Zhifu; Wang, Shichao; Haynes, Alyssa S.; Im, Jino; Freeman, Arthur J; Wessels, Bruce; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 27, No. 1, 13.01.2015, p. 370-378.

Research output: Contribution to journalArticle

Islam, SM, Vanishri, S, Li, H, Stoumpos, CC, Peters, JA, Sebastian, M, Liu, Z, Wang, S, Haynes, AS, Im, J, Freeman, AJ, Wessels, B & Kanatzidis, MG 2015, 'Cs2Hg3S4: A low-dimensional direct bandgap semiconductor', Chemistry of Materials, vol. 27, no. 1, pp. 370-378. https://doi.org/10.1021/cm504089r
Islam SM, Vanishri S, Li H, Stoumpos CC, Peters JA, Sebastian M et al. Cs2Hg3S4: A low-dimensional direct bandgap semiconductor. Chemistry of Materials. 2015 Jan 13;27(1):370-378. https://doi.org/10.1021/cm504089r
Islam, Saiful M. ; Vanishri, S. ; Li, Hao ; Stoumpos, Constantinos C. ; Peters, John A. ; Sebastian, Maria ; Liu, Zhifu ; Wang, Shichao ; Haynes, Alyssa S. ; Im, Jino ; Freeman, Arthur J ; Wessels, Bruce ; Kanatzidis, Mercouri G. / Cs2Hg3S4 : A low-dimensional direct bandgap semiconductor. In: Chemistry of Materials. 2015 ; Vol. 27, No. 1. pp. 370-378.
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