The laser-induced desorption/ionization of organic compounds from etched carbon and silicon substrate surfaces was investigated. Two different etching procedures were used. Silicon surfaces were etched either by galvanostatic anodization to produce porous silicon or by a hyperthermal (∼5 eV) F-atom beam to produce nonporous silicon. Atomic force microscopy (AFM) images showed that both etching procedures yielded surfaces with sub-micrometer structures. Highly oriented pyrolytic graphite was etched with hyperthermal O atoms. A 337 nm ultraviolet (UV) laser and a 3.28 μm infrared (IR) laser were used for desorption. Analytes were deposited on the substrates either from the liquid or the gas phase. Mass spectra were obtained provided that three conditions were fulfilled. First, sufficient laser light had to be absorbed. When the IR laser was employed, a thin physisorbed solvent layer was required for sufficient laser light absorption to occur. Though the required fluence of IR and UV light differed by a factor of about 20, the calculated maximum surface temperatures were similar, about 1000 K. The second requirement was that the substrate had a “rough” surface. The third requirement, for the observation of protonated analytes, was that the aqueous pKa-value of the analyte be larger than about 4. These observations support the conclusion that the desorption–ionization mechanisms of analytes from porous and nonporous surfaces are very similar or essentially the same.

The generation of ions from silicon substrates in surface-assisted laser desorption ionization (SALDI) has been studied using silicon substrates prepared and etched by a variety of different methods. The different substrates were compared with respect to their ability to generate peptide mass spectra using standard liquid sample deposition. The desorption/ionization processes were studied using gas-phase analyte deposition. Mass spectra were obtained from compounds with gas-phase basicities above 850 kJmol and with molecular weights up to 370 Da. UV, VIS, and IR lasers were used for desorption. Ionization efficiencies were measured as a function of laser fluence and accumulated laser irradiance dose. Solvent vapors were added to the ion source and shown to result in fundamental laser-induced chemical and physical changes to the substrate surfaces. It is demonstrated that both the chemical properties of the substrate surface and the presence of a highly disordered structure with a high concentration of "dangling bonds" or deep gap states are required for efficient ion generation. In particular, amorphous silicon is shown to be an excellent SALDI substrate with ionization efficiencies as high as 1%, while hydrogen-passivated amorphous silicon is SALDI inactive. Based on the results, a novel model for SALDI ion generation is proposed with the following reaction steps: (1) the adsorption of neutral analyte molecules on the SALDI surface with formation of a hydrogen bond to surface Si-OH groups, (2) the electronic excitation of the substrate to form free electron/hole pairs (their relaxation results in trapped positive charges in near-surface deep gap states, causing an increase in the acidity of the Si-OH groups and proton transfer to the analyte molecules), and (3) the thermally activated dissociation of the analyte ions from the surface via a "loose" transition state.

Porous GaP layers prepared by electrochemical anodization of (100)-oriented bulk material was found to exhibit blue and ultraviolet photoluminescence when excited by a KrF excimer laser. The energy position of the UV luminescence band (3.3 eV at 300 K) is explained on the basis of charge carrier confinement in crystalline quantum wires of about 25 Å in diameter. Additional evidence for quantum size effect in porous GaP was obtained by Raman scattering measurements.

The third-order optical nonlinearity χ(3) of porous silicon has been measured using the Z-scan technique. Intensity dependent absorption was observed and attributed to a resonant two photon absorption process. The real and imaginary parts of χ(3) have been measured at 665 nm and found to be 7.5×10−9 esu and −1.9×10−9 esu, respectively. This constitutes a significant enhancement over crystalline silicon. All optical switching based on nonlinear absorption is demonstrated.

CuxS nanocrystals (NC’s) are reported. The samples are prepared by a CdS-to-CuxS chemical conversion from the glasses originally containing CdS NC’s. A room-temperature linear absorption of the converted samples shows several well resolved peaks with spectral positions from red to blue. These spectral features are explained by size quantization within CuxS NC’s (∼4 nm radius) with different copper deficiency [x is in the range from 1.8 (digenite) to 2 (chalcosite)]. A strong bleaching of the samples with a 3-ns relaxation is observed in the pump–probe measurements. A high value of the third-order nonlinear susceptibility (∼10−7 esu) is derived from the nonlinear transmission spectra.