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Title: Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb)

Abstract

Using metal fluxes, crystals of the binary osmium dipnictides OsPn(2) (Pn = P, As, Sb) have been grown for the first time. Single-crystal X-ray diffraction confirms that these compounds crystallize in the marcasite structure type with orthorhombic space group Pnnm. The structure is a three-dimensional framework of corner- and edge-sharing OsPn(6) octahedra, as well as [Pn(2)(-4)] anions. Raman spectroscopy shows the presence of PP single bonds, consistent with the presence of [Pn(2)(-4)] anions and formally Os4+ cations. Optical-band-gap and high-temperature electrical resistivity measurements indicate that these materials are narrow-band-gap semiconductors. The experimentally determined Seebeck coefficients reveal that nominally undoped OsP2 and OsSb2 are n-type semiconductors, whereas OsAs2 is p-type. Electronic band structure using density functional theory calculations shows that these compounds are indirect narrow-band-gap semiconductors. The bonding p orbitals associated with the Pn(2) dimer are below the Fermi energy, and the corresponding antibonding states are above, consistent with a PnPn single bond. Thermopower calculations using Boltzmann transport theory and constant relaxation time approximation show that these materials are potentially good thermoelectrics, in agreement with experiment.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Revolutionary Materials for Solid State Energy Conversion (RMSSEC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1356360
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 53; Journal Issue: 18; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Bugaris, Daniel E., Malliakas, Christos D., Shoemaker, Daniel P., Do, Dat T., Chung, Duck Young, Mahanti, Subhendra D., and Kanatzidis, Mercouri G. Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb). United States: N. p., 2014. Web. doi:10.1021/ic501733z.
Bugaris, Daniel E., Malliakas, Christos D., Shoemaker, Daniel P., Do, Dat T., Chung, Duck Young, Mahanti, Subhendra D., & Kanatzidis, Mercouri G. Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb). United States. doi:10.1021/ic501733z.
Bugaris, Daniel E., Malliakas, Christos D., Shoemaker, Daniel P., Do, Dat T., Chung, Duck Young, Mahanti, Subhendra D., and Kanatzidis, Mercouri G. Mon . "Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb)". United States. doi:10.1021/ic501733z.
@article{osti_1356360,
title = {Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb)},
author = {Bugaris, Daniel E. and Malliakas, Christos D. and Shoemaker, Daniel P. and Do, Dat T. and Chung, Duck Young and Mahanti, Subhendra D. and Kanatzidis, Mercouri G.},
abstractNote = {Using metal fluxes, crystals of the binary osmium dipnictides OsPn(2) (Pn = P, As, Sb) have been grown for the first time. Single-crystal X-ray diffraction confirms that these compounds crystallize in the marcasite structure type with orthorhombic space group Pnnm. The structure is a three-dimensional framework of corner- and edge-sharing OsPn(6) octahedra, as well as [Pn(2)(-4)] anions. Raman spectroscopy shows the presence of PP single bonds, consistent with the presence of [Pn(2)(-4)] anions and formally Os4+ cations. Optical-band-gap and high-temperature electrical resistivity measurements indicate that these materials are narrow-band-gap semiconductors. The experimentally determined Seebeck coefficients reveal that nominally undoped OsP2 and OsSb2 are n-type semiconductors, whereas OsAs2 is p-type. Electronic band structure using density functional theory calculations shows that these compounds are indirect narrow-band-gap semiconductors. The bonding p orbitals associated with the Pn(2) dimer are below the Fermi energy, and the corresponding antibonding states are above, consistent with a PnPn single bond. Thermopower calculations using Boltzmann transport theory and constant relaxation time approximation show that these materials are potentially good thermoelectrics, in agreement with experiment.},
doi = {10.1021/ic501733z},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 18,
volume = 53,
place = {United States},
year = {2014},
month = {9}
}