Raman microprobe studies of long crystalline Si nanowires reveal for the first time the evolution of phonon confinement with wire diameter. The Raman band at similar to 520 cm(-1) in bulk Si is found to downshift and asymmetrically broaden to lower frequency with decreasing wire diameter (D) over bar, in good agreement with a phenomenological model first proposed by Richter et al. An adjustable parameter (alpha) is added to the theory that defines the width of the Gaussian phonon confinement function. We find that this parameter is not sensitive to diameter over the range 4-25 nm.
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