Semiconducting properties and phase-matching nonlinear optical response of the one-dimensional selenophosphates ANb2PSe10 (A = K, Rb, and Cs)

Jonathan C. Syrigos, Daniel J. Clark, Felix O. Saouma, Samantha M. Clarke, Lei Fang, Joon I. Jang, Mercouri G Kanatzidis

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Abstract

The new compounds ANb2PSe10, where A = K, Rb and Cs, form from polyselenophosphate flux reactions and crystallize in the noncentrosymmetric space group Pc. They feature infinite one-dimensional 1/-[Nb2PSe10-] chains separated by alkali cations. The chains consist of [Nb2(Se2)2]4+ clusters bridged by a diselenide and a [PSe4]3- group. The chains pack differently depending on which alkali cation is present in the lattice. As a result, the analogs are not isostructural with respect to each other, and each has a different unit cell. The reaction chemistry involving a multitude of reaction conditions and their respective products is discussed. Other products from these reactions include NbSe3 and Nb2Se9 in both crystalline and microfibrous morphologies. The ANb2PSe10 compounds are stable to oxidation in ambient air but decompose when heated above 350 °C. Their band gaps were measured to be 1.1-1.2 eV and the resistivity of the K analog at room temperature was measured at 4.5 ω·cm. Nonlinear optical second harmonic generation measurements were done on the Rb analog yielding a χ2 of ∼7 pm/V and showing phase matching behavior.

Original languageEnglish
Pages (from-to)255-265
Number of pages11
JournalChemistry of Materials
Volume27
Issue number1
DOIs
Publication statusPublished - Jan 13 2015

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Phase matching
Alkalies
Cations
Positive ions
Harmonic generation
Energy gap
Fluxes
Crystalline materials
Oxidation
Air
Temperature
selenophosphate

ASJC Scopus subject areas

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

Cite this

Semiconducting properties and phase-matching nonlinear optical response of the one-dimensional selenophosphates ANb2PSe10 (A = K, Rb, and Cs). / Syrigos, Jonathan C.; Clark, Daniel J.; Saouma, Felix O.; Clarke, Samantha M.; Fang, Lei; Jang, Joon I.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 27, No. 1, 13.01.2015, p. 255-265.

Research output: Contribution to journalArticle

Syrigos, Jonathan C. ; Clark, Daniel J. ; Saouma, Felix O. ; Clarke, Samantha M. ; Fang, Lei ; Jang, Joon I. ; Kanatzidis, Mercouri G. / Semiconducting properties and phase-matching nonlinear optical response of the one-dimensional selenophosphates ANb2PSe10 (A = K, Rb, and Cs). In: Chemistry of Materials. 2015 ; Vol. 27, No. 1. pp. 255-265.
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