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Reactive surface of mesoporous nanocrystalline silicon was used to synthesise noble metal nanoparticles via in situ reduction of the precursor salt solutions. The synthetic methodology for metal nanoparticle formation was systematically developed, and reaction conditions of metal salts reduction were optimised to prepare nanoparticles of controlled size distribution in the order 5–10 nm inside the mesoporous silicon template. CO oxidation was used as a test reaction for the synthesised Pt/porous silicon catalysts. Sharp reaction light-off was observed at about 120 °C on the optimised catalysts. The catalysts were shown to be stable in the extended steady-state runs and in the catalysts re-use experiments. Metal nanoparticles were shown to be stable to sintering at elevated temperatures up to 1000 °C. However, after thermal treatment on air, Pt nanoparticles were covered by a SiOx layer and were less active in CO oxidation.

Reactive surface of mesoporous nanocrystalline silicon was used to synthesise noble metal nanoparticles via in situ reduction of the precursor salt solutions. The synthetic methodology for metal nanoparticle formation was systematically developed, and reaction conditions of metal salts reduction were optimised to prepare nanoparticles of controlled size distribution in the order 5–10 nm inside the mesoporous silicon template. CO oxidation was used as a test reaction for the synthesised Pt/porous silicon catalysts. Sharp reaction light-off was observed at about 120 °C on the optimised catalysts. The catalysts were shown to be stable in the extended steady-state runs and in the catalysts re-use experiments. Metal nanoparticles were shown to be stable to sintering at elevated temperatures up to 1000 °C. However, after thermal treatment on air, Pt nanoparticles were covered by a SiOx layer and were less active in CO oxidation.

The efficiency of singlet oxygen photosensitization by porous silicon is compared with that of a conventional dye photosensitizer tetraphenylporphine by means of singlet oxygen-mediated photooxidation of α-terpinene. Based on photoluminescence measurements it was concluded that the efficiency of porous silicon as a sensitizer is much lower than that of the conventional organic dye. The main reasons for this are the low quantum yield of long living photoinduced electronic excitations (excitones) confined in silicon nanocrystals and deactivation of singlet oxygen by H-terminated internal surface of porous silicon powder. Efficient quenching of excitons in porous silicon by 1,3-diphenylisobenzofuran via the direct energy transfer was demonstrated. This process is believed to be responsible for photobleaching of 1,3-diphenylisobenzofuran at its millimolar concentrations.

The longitudinal acoustic velocity for 1 GHz waves propagating along the 100 direction in p++ porous silicon layers has been measured using an acoustic wave transmission technique. The velocities obtained are significantly higher than those previously observed for p+ samples. The porosity dependence is measured to be VL = 8.43(l – P)0.58 km/s, where VL is longitudinal velocity and P is porosity. The low value of the exponent (0.58) is an indication of a relatively well-ordered pore structure. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

In this work we studied the reduction of metal salts and their mixtures on extended hydrogen-terminated porous silicon surfaces. For these experiments we employed salts of Au, Ag, Pt and their mixtures. We show that the size and shape of resulting metal and metal alloy nanoparticles depends on the pore morphology. This has been confirmed by transmission electron microscopy measurements and plasmon resonance experiments. Finally we demonstrate catalytic activity of formed Pt nanoparticles in PSi matrix via monitoring the conversion of carbon monoxide.

In this Letter we demonstrate that hydrogen-terminated porous silicon (PSi) layers and powders can serve as highly efficient reductive templates for noble metal salts. The reduction results in metal nanoparticle (NP) formation in the pores of PSi. Gold NP formation has been monitored in-situ by measuring the plasmon resonance response. Pt NPs, formed in the PSi matrix, were investigated by transmission electron microscopy and energy-dispersive X-ray analysis. Furthermore, hybrid Pt/PSi nanocomposites exhibit a high catalytic activity for CO oxidation.

Silicon nanoparticles of three types (oxide-terminated silicon nanospheres, micron-sized hydrogen-terminated porous silicon grains and micron-size oxide-terminated porous silicon grains) were incorporated into silica aerogels at the gel preparation stage. Samples with a wide range of concentrations were prepared, resulting in aerogels that were translucent (but weakly coloured) through to completely opaque for visible light over sample thicknesses of several millimetres. The photoluminescence of these composite materials and of silica aerogel without silicon inclusions was studied in vacuum and in the presence of molecular oxygen in order to determine whether there is any evidence for non-radiative energy transfer from the silicon triplet exciton state to molecular oxygen adsorbed at the silicon surface. No sensitivity to oxygen was observed from the nanoparticles which had partially H-terminated surfaces before incorporation, and so we conclude that the silicon surface has become substantially oxidised. Finally, the FTIR and Raman scattering spectra of the composites were studied in order to establish the presence of crystalline silicon; by taking the ratio of intensities of the silicon and aerogel Raman bands, we were able to obtain a quantitative measure of the silicon nanoparticle concentration independent of the degree of optical attenuation.

Periodic solid state structures exhibit transmission stop bands for waves of certain frequencies. We report the realization and direct measurement of acoustic band gaps in porous silicon multilayer structures which exhibit similar to 50 dB stop bands for longitudinal acoustic waves in the gigahertz range. Furthermore, realization of an acoustic microcavity structure in porous silicon is demonstrated.

We present a method for the formation of noble metal nanoparticle ensembles in nanostructured silicon. The key idea is based on the unique property of the large reduction potential of extended internal hydrogen-terminated porous silicon surfaces. The process of metal nanoparticle formation in porous silicon was experimentally traced using their optical plasmon resonance response. We also demonstrate that bimetallic compounds can be formed in porous silicon and that their composition can be controlled using this technique. Experimental results were found to contradict partially with considerations based on Mie theory.

Generation of singlet oxygen due to energy transfer from photoexcited silicon nanocrystals in D2O is demonstrated. It is shown that the singlet oxygen generation efficiency, i.e., the intensity of near-infrared emission from singlet oxygen gradually decreases when Si nanocrystals are continuously irradiated in O2-saturated D2O. The mechanism of the photodegradation of the photosensitizing efficiency is studied using photoluminescence and infrared absorption techniques. Experimental results suggest that the interaction of photogenerated singlet oxygen with the hydrogen-terminated surface of silicon nanocrystals results in photo-oxidation of silicon nanocrystals, and the surface oxides reduce the photosensitizing efficiency. It is also demonstrated that photo-oxidation of porous silicon in O2-saturated water results in a strong enhancement of the photoluminescence quantum yield of porous Si.

The dissolution rate of porous silicon layers was measured in-situ during etching by HF and NaOH solutions. Cellular models were applied to the structure of the pSi from which the expected rates of change of porosity with time were calculated. Experimental results indicate that the nanostructure of porous silicon may be best modeled as an open-cell foam. This is in contrast to the honeycomb model often used which is not supported by the experimental data.