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X-Ray Absorption Spectroscopy from H-Passivated Porous Si and Oxidized Si Nanocrystals

Published online by Cambridge University Press:  15 February 2011

S. Schuppler
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
S. L. Friedman
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
M. A. Marcus
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
D. L. Adler
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
Y.-H. Xie
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
F. M. Ross
Affiliation:
National Center for Electron Microscopy, Lawrence Berkeley Laboratory, Berkeley, CA 94720
T. D. Harris
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
W. L. Brown
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
Y. J. Chabal
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
P. J. Szajowski
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
E. E. Chaban
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
L. E. Brus
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
P. H. Citrin
Affiliation:
AT&T Bell Laboratories, Murray Hill, NJ 07974
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Abstract

Quantum confinement in nanoscale Si structures is widely believed to be responsible for the visible luminescence observed from anodically etched porous silicon (por-Si), but little is known about the actual size or shape of these structures. Extended x-ray absorption fine structure data from a wide variety of por-Si samples show significantly reduced average Si coordination numbers due to the sizable contribution of surface-coordinated H. (The H/Si ratios, as large as 1.2, were independently confirmed by ir-absorption and α-recoil measurements.) The Si coordinations imply very large surface/volume ratios, enabling the average Si structures to be identified as crystalline particles (not wires) whose dimensions are typically <15 Å. Comparison of the size-dependent peak luminescence energies with those of oxidized Si nanocrystals, whose shapes are known, shows remarkable agreement. Furthermore, near-edge x-ray absorption fine structure measurements of the nanocrystals shows the outer oxide and interfacial suboxide layers to be constant over a wide range of nanocrystal sizes. The combination of these results effectively rules out surface species as being responsible for the observed visible luminescence in por-Si, and strongly supports quantum confinement as the dominant mechanism occurring in Si particles which are substantially smaller than previously reported or proposed.

Type
Research Article
Copyright
Copyright © Materials Research Society 1995

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