Does femtosecond time-resolved second-harmonic generation probe electron temperatures at surfaces?

Femtosecond pump-probe second-harmonic generation (SHG) and transient linear reflectivity measurements were carried out on polycrystalline Cu, Ag and Au in air to analyze whether the electron temperature affects Fresnel factors or nonlinear susceptibilities, or both. Sensitivity to electron temperatures was attained by using photon energies near the interband transition threshold. We find that the nonlinear susceptibility carries the electron temperature dependence in case of Ag and Au, while for Cu the dependence is in the Fresnel factors. This contrasting behavior emphasizes that SHG is not a priori sensitive to electron dynamics at surfaces or interfaces, notwithstanding its cause.Comment: 11 pages, 4 figure

Investigation of the Si(111) Surface in UHV: Oxidation and the Effect of Surface Phosphorus

We have studied the initial stages of oxidation, the segregation of phosphorus, and the effect of phosphorus on oxidation of the Si(111) 7 x 7 surface using optical second-harmonic generation. We have also observed a (..sqrt..3 x ..sqrt..3)R30/sup 0/ LEED pattern for P on Si(111)

Studies of surfaces using optical second-harmonic generation

The experiments reported in this thesis demonstrate the use of second-harmonic generation (SHG) and sum-frequency generation (SFG) in reflection from surfaces to study various surface properties. The experiments firmly establish SHG as a viable new surface probe that complements existing surface probes in ultrahigh vacuum environments and is in many ways unique for studying interfaces between dense media. Surface structural symmetry can be revealed through the anisotropy in the SH signal from the surface as the sample is rotated about its normal. The form of this anisotropy is derived in theory and verified with an experiment on the Si(100) and (111) surfaces. The SHG and SFG signals from molecules adsorbed on noninteracting substrates have a direct relationship to the number, average orientation, and spectroscopic properties of the molecules. The SH intensity was used to measure the isotherm for adsorption of p-nitrobenzoic acid from ethanolic solution to fused silica. Experiments performed on a strongly-interacting well-characterized Rh(111) surface in ultrahigh vacuum establish the sensitivity of the SH probe in corroboration with other surface probes. For the first time, the SH coverage-dependence was fit by theory in a quantitative way for the case of O-atom adsorption. The sensitivity of SH to adsorption at different sites was established for CO on top- and bridge-sites. SHG was shown to be surface specific in that the SHG from alkali metal surfaces originates from the first two monolayers. SH sensitivity to the adsorption of catalytically-important hydrocarbons and to chemical processes such as benzene dehydrogenation was also demonstrated. 122 references, 27 figures, 2 tables