Crystal growth and characterization of the narrow-band-gap semiconductors OsPn2 (Pn = P, As, Sb)

Daniel E. Bugaris, Christos D. Malliakas, Daniel P. Shoemaker, Dat T. Do, Duck Young Chung, Subhendra D. Mahanti, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Using metal fluxes, crystals of the binary osmium dipnictides OsPn2 (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 threedimensional framework of corner- and edge-sharing OsPn6 octahedra, as well as [Pn24-] anions. Raman spectroscopy shows the presence of P-P single bonds, consistent with the presence of [Pn2-4] 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 Pn2 dimer are below the Fermi energy, and the corresponding antibonding states are above, consistent with a Pn-Pn 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.

Original languageEnglish
Pages (from-to)9959-9968
Number of pages10
JournalInorganic Chemistry
Volume53
Issue number18
DOIs
Publication statusPublished - Sep 15 2014

Fingerprint

Crystallization
Anions
narrowband
crystal growth
Osmium
Seebeck coefficient
Thermoelectric power
Optical band gaps
Fermi level
Dimers
Band structure
Relaxation time
anions
Density functional theory
Raman spectroscopy
Cations
n-type semiconductors
osmium
transport theory
Metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Bugaris, D. E., Malliakas, C. D., Shoemaker, D. P., Do, D. T., Chung, D. Y., Mahanti, S. D., & Kanatzidis, M. G. (2014). Crystal growth and characterization of the narrow-band-gap semiconductors OsPn2 (Pn = P, As, Sb). Inorganic Chemistry, 53(18), 9959-9968. https://doi.org/10.1021/ic501733z

Crystal growth and characterization of the narrow-band-gap semiconductors OsPn2 (Pn = P, As, Sb). / Bugaris, Daniel E.; Malliakas, Christos D.; Shoemaker, Daniel P.; Do, Dat T.; Chung, Duck Young; Mahanti, Subhendra D.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 53, No. 18, 15.09.2014, p. 9959-9968.

Research output: Contribution to journalArticle

Bugaris, DE, Malliakas, CD, Shoemaker, DP, Do, DT, Chung, DY, Mahanti, SD & Kanatzidis, MG 2014, 'Crystal growth and characterization of the narrow-band-gap semiconductors OsPn2 (Pn = P, As, Sb)', Inorganic Chemistry, vol. 53, no. 18, pp. 9959-9968. https://doi.org/10.1021/ic501733z
Bugaris DE, Malliakas CD, Shoemaker DP, Do DT, Chung DY, Mahanti SD et al. Crystal growth and characterization of the narrow-band-gap semiconductors OsPn2 (Pn = P, As, Sb). Inorganic Chemistry. 2014 Sep 15;53(18):9959-9968. https://doi.org/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 OsPn2 (Pn = P, As, Sb). In: Inorganic Chemistry. 2014 ; Vol. 53, No. 18. pp. 9959-9968.
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