Materials 2013, 6(1), 18-46; doi:10.3390/ma6010018
Article

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

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Received: 17 October 2012; in revised form: 20 November 2012 / Accepted: 3 December 2012 / Published: 20 December 2012
(This article belongs to the Special Issue NMR in Materials Science)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract: 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.
Keywords: silicon; nanoparticles; 29Si NMR; solid-state NMR; surface characterization
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MDPI and ACS Style

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.

AMA Style

Faulkner RA, DiVerdi JA, Yang Y, Kobayashi T, Maciel GE. The Surface of Nanoparticle Silicon as Studied by Solid-State NMR. Materials. 2013; 6(1):18-46.

Chicago/Turabian Style

Faulkner, Rebecca A.; DiVerdi, Joseph A.; Yang, Yuan; Kobayashi, Takeshi; Maciel, Gary E. 2013. "The Surface of Nanoparticle Silicon as Studied by Solid-State NMR." Materials 6, no. 1: 18-46.

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