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Materials 2013, 6(1), 18-46;

The Surface of Nanoparticle Silicon as Studied by Solid-State NMR

Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA
Current Address: Colorado School of Mines, Golden, CO 80401, USA.
Current Address: Ames Laboratory, Iowa State University, Ames, IA 50011, USA.
Authors to whom correspondence should be addressed.
Received: 17 October 2012 / Revised: 20 November 2012 / Accepted: 3 December 2012 / Published: 20 December 2012
(This article belongs to the Special Issue NMR in Materials Science)
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The surface structure and adjacent interior of commercially available silicon nanopowder (np-Si) was studied using multinuclear, solid-state NMR spectroscopy. The results are consistent with an overall picture in which the bulk of the np-Si interior consists of highly ordered (“crystalline”) silicon atoms, each bound tetrahedrally to four other silicon atoms. From a combination of 1H, 29Si and 2H magic-angle-spinning (MAS) NMR results and quantum mechanical 29Si chemical shift calculations, silicon atoms on the surface of “as-received” np-Si were found to exist in a variety of chemical structures, with apparent populations in the order (a) (Si–O–)3Si–H > (b) (Si–O–)3SiOH > (c) (HO–)nSi(Si)m(–OSi)4−mn ≈ (d) (Si–O–)2Si(H)OH > (e) (Si–O–)2Si(–OH)2 > (f) (Si–O–)4Si, where Si stands for a surface silicon atom and Si represents another silicon atom that is attached to Si by either a SiSi bond or a Si–O–Si linkage. The relative populations of each of these structures can be modified by chemical treatment, including with O2 gas at elevated temperature. A deliberately oxidized sample displays an increased population of (Si–O–)3Si–H, as well as (Si–O–)3SiOH sites. Considerable heterogeneity of some surface structures was observed. A combination of 1H and 2H MAS experiments provide evidence for a substantial population of silanol (Si–OH) moieties, some of which are not readily H-exchangeable, along with the dominant Si–H sites, on the surface of “as-received” np-Si; the silanol moieties are enhanced by deliberate oxidation. An extension of the DEPTH background suppression method is also demonstrated that permits measurement of the T2 relaxation parameter simultaneously with background suppression. View Full-Text
Keywords: silicon; nanoparticles; 29Si NMR; solid-state NMR; surface characterization silicon; nanoparticles; 29Si NMR; solid-state NMR; surface characterization

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Faulkner, R.A.; DiVerdi, J.A.; Yang, Y.; Kobayashi, T.; Maciel, G.E. The Surface of Nanoparticle Silicon as Studied by Solid-State NMR. Materials 2013, 6, 18-46.

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