Surface-state origin for the blueshifted emission in anodically etched porous silicon carbide

Anodic etching of SiC yields a highly monodisperse distribution of nanometer dimension porous structures which extend to a significant depth. Cathodoluminescence (CL) studies of the porous layers yield luminescence peaks in the UV region, above the band gap energy of bulk SiC. Higher etching current densities produce porous silicon carbide (PSiC) with peak CL emission wavelengths deeper in the ultraviolet. Photoluminescence (PL) is also blueshifted in anodically etched PSiC, although not to the extent of the CL emission, suggesting that different emissive states are accessed in CL and PL. Raman investigations of the polar A1 LO mode, which couples strongly to the macroscopic electric field accompanying the LO phonon, were conducted in an attempt to discern whether quantum confinement effects could effectively explain the blueshifted emission. The principal feature of the Raman spectra was a significant low-frequency shoulder on the A1 LO mode, the magnitude of which correlates with the magnitude of the blueshift in PL and the intensity of the blueshifted CL emission. The shoulder was fit quantitatively with a model incorporating the effects of extraordinary LO modes and longitudinal and transverse Fröhlich modes. The Fröhlich mode widths derived from the fit are too wide to be due solely to Fröhlich modes and likely indicate the combined effects of diffuse scattering, broadening of spectral lines, and violation of the symmetry selection rules. The preponderance of the evidence, especially the inability to fit the low-frequency shoulder in the Raman spectra with a phonon confinement model, support an interpretation in which defect structures or surface states are responsible for the UV emission.