Synthesis and spectroscopic characterization of P-doped Na{sub 4}Si{sub 4}
- Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616 (United States)
- Department of Chemical Engineering and Materials Science, University of California, One Shields Avenue, Davis, CA 95616 (United States)
- NMR Facility, University of California, One Shields Avenue, Davis, CA 95616 (United States)
Na{sub 4}Si{sub 4} is a Zintl salt composed of Na{sup +} cations and Si{sub 4}{sup 4-} tetrahedral anions and is a unique solid-state precursor to clathrate structures and nanomaterials. In order to provide opportunities for the synthesis of complex materials, phosphorus was explored as a possible substituent for silicon. Phosphorus doped sodium silicides Na{sub 4}Si{sub 4-x}P{sub x} (x{<=}0.04) were prepared by reaction of Na with the mechanically alloyed Si{sub 4-x}:P{sub x} (x=0.04, 0.08, 0.12) mixture in a sealed Nb tube at 650 {sup o}C for 3 days. Energy dispersive X-ray spectroscopy confirms the presence of P in all products. Powder X-ray diffraction patterns are consistent with the retention of the Na{sub 4}Si{sub 4} crystal structure. As the amount of P increases, a new peak in the diffraction pattern that can be assigned to black phosphorus is apparent above the background. Raman and solid-state NMR provide information on phosphorus substitution in the Na{sub 4}Si{sub 4} structure. Raman spectroscopy shows a shift of the most intense band assigned to the Si{sub 4}{sup 4-} {nu}{sub 1} (A{sub 1}) mode from 486.4 to 484.0 cm{sup -1} with increasing P, consistent with P replacement of Si. Differential nuclear spin-lattice relaxation for the Si sites determined via {sup 29}Si solid-state NMR provides direct evidence for Si-P bonding in the (Si{sub 1-x}P{sub x}){sup 4-} tetrahedron. The {sup 23}Na NMR shows additional Na...P interactions and the {sup 31}P NMR shows two P sites, consistent with P presence in both of the crystallographic sites in the (Si{sub 4}){sup 4-} tetrahedron. - Graphical abstract: P-doped Na{sub 4}Si{sub 4} has been prepared and Raman spectroscopy and {sup 29}Si, {sup 23}Na, and {sup 31}P multinuclear NMR show that P dopes into both crystallographic sites for Si. Display Omitted
- OSTI ID:
- 21494106
- Journal Information:
- Journal of Solid State Chemistry, Vol. 183, Issue 11; Other Information: DOI: 10.1016/j.jssc.2010.07.051; PII: S0022-4596(10)00335-X; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANIONS
CATIONS
CLATHRATES
CRYSTAL STRUCTURE
CRYSTALLOGRAPHY
DOPED MATERIALS
NANOSTRUCTURES
NUCLEAR MAGNETIC RESONANCE
PHOSPHORUS
RAMAN SPECTROSCOPY
SILICON
SODIUM IONS
SODIUM SILICIDES
SPIN-LATTICE RELAXATION
SYNTHESIS
X-RAY DIFFRACTION
X-RAY SPECTROSCOPY
ALKALI METAL COMPOUNDS
CHARGED PARTICLES
COHERENT SCATTERING
DIFFRACTION
ELEMENTS
IONS
LASER SPECTROSCOPY
MAGNETIC RESONANCE
MATERIALS
NONMETALS
RELAXATION
RESONANCE
SCATTERING
SEMIMETALS
SILICIDES
SILICON COMPOUNDS
SODIUM COMPOUNDS
SPECTROSCOPY