Controlling the interparticle spacing of Au-salt loaded micelles and Au nanoparticles on flat surfaces.

The self-organization of diblock copolymers into micellar structures in an appropriate solvent allows the deposition of well ordered arrays of pure metal and alloy nanoparticles on flat surfaces with narrow distributions in particle size and interparticle spacing. Here we investigated the influence of the materials (substrate and polymer) and deposition parameters (temperature and emersion velocity) on the deposition of metal salt loaded micelles by dip-coating from solution and on the order and inter-particle spacing of the micellar deposits and thus of the metal nanoparticle arrays resulting after plasma removal of the polymer shell. For identical substrate and polymer, variation of the process parameters temperature and emersion velocity enables the controlled modification of the interparticle distance within a certain length regime. Moreover, also the degree of hexagonal order of the final array depends sensitively on these parameters.

Alloy formation of supported gold nanoparticles at their transition from clusters to solids: does size matter?

Gold nanoclusters of a size approaching the molecular limit (<3 nm) were prepared on Si substrates in order to study alloy formation on the nanometer scale. For this purpose, indium atoms are deposited on top of the gold particles at room temperature and the formation of AuIn(2) is studied by x-ray photoelectron spectroscopy in situ. It is observed that the alloy formation takes place independent of whether the particles electronically are in an insulating molecular or in a metallic state. Most important, however, closed packed full-shell clusters containing 55 Au atoms are found to exhibit an outstanding stability against alloying despite a large negative heat of formation of the bulk Au-In system. Thus, Au(55) clusters may play a significant role in the design of nanoscaled devices where chemical inertness is of crucial importance.

A generalized technique of two-wavelength, nondiffuse holographic interferometry.

A generalized technique of two-wavelength, nondiffuse holographic interferometry is developed for use with transparent experimental media. It is shown that a single pair of nondiffuse transmission holograms recorded simultaneously at different wavelengths can be reconstructed so as to produce a large number of interferograms with widely varying sensitivities. For ease in interpretation, these interferograms can have either an infinite-fringe background or a multiple-fringe background with any desired fringe orientation and spacing.

Two-wavelength holographic interferometry for transparent media using a diffraction grating.

A new technique of two-wavelength nondiffuse holographic interferometry is demonstrated that is capable of producing interferograms of transparent media with high or low sensitivity. Incorporating an arrangement similar to Bryngdahl's longitudinally reversed shearing interferometer, the technique works by superposing the reconstructed true and/or conjugate images of two transmission image holograms of the test medium recorded at different wavelengths. Extensions of the technique allow one to record interferograms sensitive only to the optical dispersion of the test medium and to generate light beams with phase distributions equal to the sum or difference of the phases of the original object beams.

Chemically induced metal-to-insulator transition in Au55 clusters: effect of stabilizing ligands on the electronic properties of nanoparticles.

The cluster compound Au55(PPh3)12Cl6 has been reanalyzed by photoelectron spectroscopy giving direct evidence for a nonmetallic behavior of the individual Au clusters as long as their ligand shell remains intact. The exposure to x-rays during the measurements is found to partly decompose the shell by removal of the chlorine atoms, resulting in a metallic behavior of the clusters as demonstrated by a steplike intensity at the Fermi energy. These observations resolve a long-standing controversy about the metallic behavior of ligated Au clusters emphasizing, in addition, the influence of the local environment on the electronic properties of nanoscaled materials.

Oxidation-resistant gold-55 clusters.

Gold nanoparticles ranging in diameter from 1 to 8 nanometers were prepared on top of silicon wafers in order to study the size dependence of their oxidation behavior when exposed to atomic oxygen. X-ray photoelectron spectroscopy showed a maximum oxidation resistance for "magic-number" clusters containing 55 gold atoms. This inertness is not related to electron confinement leading to a size-induced metal-to-insulator transition, but rather seems to be linked to the closed-shell structure of such magic clusters. The result additionally suggests that gold-55 clusters may act as especially effective oxidation catalysts, such as for oxidizing carbon monoxide.