Nanocrystalline Systems Research Articles

Nanocrystalline diamond: Effect of confinement, pressure, and heating on phonon modes

Micro- and nanocrystalline systems exhibit properties that differ markedly from bulk systems. Diamond, a prototypical system, demonstrates a broadening, shift, and emergence of Raman phonon modes that are believed to originate from finite-size effects. Such information should be useful in constraining confinement models developed to describe the state of these mesoscopic systems. For example, previous investigations have analyzed crystallite size and stresses in scientifically and technologically relevant environments, including chemical-vapor-deposition diamond films and diamond nanocomposites. We have experimentally measured the effect on the diamond Raman phonon modes due to confinement, pressure, and heating effects. At ambient pressure, we present Raman measurements for diamond crystallites ranging from 6 nm to 10 \ensuremath{\mu}m, which were synthesized by both static and dynamic techniques. The Raman spectra obtained from the statically synthesized samples exhibit a characteristic strong and narrow diamond band, while those dynamically synthesized exhibit both diamond and graphiticlike features. A redshift of the diamond Raman band is observed for decreasing particle size. However, the pressure dependence of the phonon is about the same as that for the bulk system up to 30 kbar for crystallite sizes between 6 and 10 nm. Our measurements also indicate that heating effects from the incident laser dramatically affect the measured Raman spectra. This result leads us to an explanation for discrepancies among previously published results. We show that crystallite size and stress information cannot be determined without compensating for heating effects. Lastly, the phonon confinement model is able to explain the shifts of the Raman modes with size.

Light-Induced Redox Reactions in Nanocrystalline Systems

A review with 156 refs. on interfacial electron transfer reactions in colloidal semiconductor solns. and thin films and their application for solar light energy conversion and photocatalytic water purifn. Some of the topics discussed include; optical and electronic properties of colloidal semiconductor particles, quantum size effects in the photoluminescence of colloidal semiconductors, light-induced charge sepn., dynamics of interfacial charge transfer processes, properties and prepn. of nanocryst. semiconductor electrodes, energetics and operations of the nanoporous solar cell.

Nanocrystalline solar cells

The quality of human life depends to a large degree on the availability of energy sources. The present worldwide energy consumption exceeds already the level of 6000 Gigawatt. It is expected to further increase sharply from the rising demand of energy in the developing countries. This implies enhanced depletion of fossil fuel reserves. leading to further aggravation of the environmental pollution exerting adverse effects on the well being of man kind. Adding the dangers arising from the accumulation of plutonium fission products from nuclear reactors, the quality of life on earth is threatened unless renewable energy resources can be developed in the near future. Photovoltaics is expected to make important contributions to identify environmentally friendly solutions of the energy problem. One attractive strategy discussed in this lecture is the development of systems that mimic natural photosynthesis in the conversion solar energy for the fixation of carbon dioxide. The task to be accomplished by these systems is to harvest sun light to produce electricity or drive an uphill chemical reaction, such as the cleavage of water into hydrogen and oxygen. The hydrogen can be subsequently employed to reduce carbon dioxide to produce fuels and chemical feed stocks. Learning from the concepts used by green plants we have developed a molecular photovoltaic device whose overall efficiency for solar energy conversion to electricity has already attained 10%.. The system is based on the sensitization of nanocrystalline films by transition metal charge transfer sensitizers. In analogy to photosynthesis, the new chemical solar cell achieves the separation of light absorption and charge carrier transport. Extraordinary yields for the conversion of incident photons into electric current are obtained, exceeding 90% for transition metal complexes within the wavelength range of their absorption band. Conventional photovoltaic cells for solar energy conversion into electricity are solid state devices do not economically compete for base load utility electricity production. The low cost and ease of production of the new nanocrystalline cell should be benefit large scale applications in particular in underdeveloped or developing countries. These regions of the earth benefit from generous sun shine rendering the availability of a cheap solar cell technology important in view of improving the quality of life and preserving natural resources. Quite aside from its intrinsic merits as a photovoltaic device, the nanocrystalline films development opens up a whole number of additional avenues for energy storage ranging from intercalation batteries to the formation of chemical fuels. These nanocrystalline systems will undoubtedly promote the acceptance of renewable energy technologies, not least by setting new standards of convenience and economy.