Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal-metal and metal-chalcogenide interactions. Herein, we present Ir6In32S21, a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P31m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of -4.95(5) eV, conduction band minimum of -3.47(5) eV, and a photoresponse shift of the Fermi level by ∼0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir6In32S21 make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the average hole effective masses near the VBM (1.19me) are substantially smaller than the average electron masses near the CBM (2.51me), an unusual feature for most semiconductors. The crystal and electronic structure of Ir6In32S21, along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes.
Bibliographical noteFunding Information:
This work was supported by the National Science Foundation (NSF) grant DMR-1708254 (synthesis and structural characterization). PYSA and KP measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. Single crystal diffraction data was performed at the IMSERC facility at Northwestern University, which has received support from the So and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the State of Illinois; and International Institute for Nanotechnology (IIN). This research used resources of the Advanced Photon Source (APS), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The work for DFT calculations carried out by J. E. P., J. H., and C. W. was supported by the U.S. Department of Energy, Office of Science Basic Energy Sciences grant DE-SC0014520. The NLO measurements were supported by AFOSR Grant FA9550-19-1-0243 (V. G., M. G. K.). We also acknowledge QUEST, a supercomputer facility at Northwestern University and resources of the National Energy Research Scientic Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. R. Z. and V. G. acknowledge support from the NSF grant number DMR-1807768 and NSF-MRSEC Penn State Center for Nanoscale Science, grant number DMR-1420620. We thank Dr Kyle M. McCall and Tyler J. Slade for insightful discussions.
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