Publications

Light induced electron transfer (ET) from nanosize semiconductors of MoS2 to organic electron acceptors such as 2,2′-bipyridine (bpy) and methyl substituted 4,4′,5,5′-tetramethyl-2,2′-bipyridine (tmb) was studied by static and time resolved photoluminescence spectroscopy. The kinetics of ET were varied by changing the nanocluster size (the band gap), the electron acceptor, and the polarity of the solvent. MoS2 is an especially interesting semiconductor material as it is an indirect semiconductor in bulk form, and has a layered covalent bonding arrangement which is highly resistant to photocorrosion.

Highly crystalline nanoclusters of MoS{sub 2} were synthesized and their optical absorption and photoluminescence spectra were investigated. Key results include: (1) strong quantum confinement effects with decreasing size; (2) preservation of the quasiparticle (or excitonic) nature of the optical response for clusters down to {approximately} 2.5 nm in size which are only two unit cells thick; (3) demonstration that 3-D confinement produces energy shifts which are over an order of magnitude larger than those due to 1-D confinement; (4) observation of large increases in the spin-orbit splittings at the top of the valence band at the K and M points of the Brillouin zone with decreasing cluster size; and (5) observation of photoluminescence due to both direct and surface recombination. Application is to photocatalysts for solar fuel production and detoxification of chemical waste.

High quality crystalline, monodisperse nanometer-size semiconductor clusters were successfully grown using an inverse micellar synthesis process and their optical and structural properties were studied. Among the materials studied were PbS, FeS{sub 2}, MoS{sub 2}, CdS and related compounds. The results demonstrated strong electronic quantum confinement effects and broad tailorability of the bandgaps with decreasing cluster size, features that are important for the potential use of these materials as photocatalysts for solar fuel production and solar detoxification. The highlights of the work are included in an Executive Summary.

This research has produced a variety of monodisperse, nanometer-size clusters (nanoclusters for short), characterized their size and crystal structure and developed a scientific understanding of the size dependence of their physical properties. Of specific interest were the influence of quantum electronic confinement on the optical properties, magnetic properties, and dielectric properties. These properties were chosen both for their potential practical impact on various applications identified in the National Critical Technologies list (e.g., catalysis, information storage, sensors, environmental remediation, ...) as well as for their importance to the fundamental science of clusters. An Executive Summary provides a description of the major highlights.

Since both FeS2 and MoS2 are optically opaque and have bandgaps in the near IR, photochemical applications of these materials are non-existent. It is however demonstrated in the study that nanosize FeS2 and MoS2 have bandgaps that can be adjusted to the visible and even UV region of the spectrum by control of the cluster size. Discussed are measurements of size, structure, optical absorbance and photoemission for these new materials. Also, briefly outlines are synthetic procedures and novel methods for chemical processing of these nanoclusters.

We report a real-time, two-dimensional light scattering study of the evolution of structure of a two component nonionic micelle system undergoing phase separation. The micelles act like molecular slug-a-beds whose domain growth is pathetically lathargic (i.e. slower than the cube root of time prediction for simple binary fluids). In fact, the growth kinetics can be empirically described as a stretched exponential approach to a pinned domain size. Although the kinetics are not yet understood, this anomalous behavior may be due to the ability of the spherical micelles to reorganize into more complex structures.

We report formation of several small colloidal metal catatlysts in inverted micelle (oil-continuous) systems. These materials have demonstrated catalytic activity in situ (i.e. unsupported). The range of solvents possible in this process is large, including all saturated hydrocarbons, cyclic hydrocarbons (e.g. cyclohexane) and aromatics (e.g. toluene, xylene). Three classes of micelle system were investigated, nonionic, anionic, and cationic. Nonionic types allow precise size control but in general do not act as strong stabilizing agents at high temperatures. Cationics can be chosen to provide this permanent stability, providing both charge and steric stabilization. Metal systems formed include Rh, Ni, NiB, MoO{sub 2}, Pd, Au and Ag and alloys. Selected examples are given. 4 figs.