A method is presented for generating quasiregular arrays of nanometer-sized noble metal and metal oxide clusters on flat substrates by the use of a polymer template. The approach is of general applicability to other metals and various oxides. In the first step, polymeric micelles with a polar core were generated by dissolution of poly(styrene)-block-poly(2-vinylpyridine) in toluene. These micelles were used as nanocompartments that were loaded with a defined amount of a metal precursor. The metal ions can be reduced in such a way that exactly one elemental or oxidic particle is formed in each micelle, where each particle is of equal size. By dipping a flat substrate into a dilute solution, a monolayer of the micelles was obtained whereby the embedded equally large particles became arranged in a mesoscopic quasihexagonal two-dimensional (2-D) lattice. Exposure to an oxygen plasma allowed removal of the polymer completely, leaving the naked metal particles firmly attached to the substrate in the same quasihexagonal order as in the monomicellar film. A modified procedure in which the precursor salt was not reduced before the plasma treatment yielded clusters of identical size and in the same 2-D order. The size (height) of the clusters could be varied between 1 and 15 nm depending on the concentration of the metal salt. The interparticle distance could be varied between 30 and 140 nm by using block copolymers with different lengths of the blocks. Such lattices of Au particles have been used to bind streptavidin proteins in an ordered array.

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.

The preparation of hexagonally ordered metallic nanodots was studied in detail with emphasis on the chemical state of the resulting particles. To obtain these dots, in a first step micellar structures were formed from diblock copolymers in solution. The reverse micelles themselves are capable of ligating defined amounts of a metal salt within their cores, acting as nanoreactors. After transfer of the metal‐loaded reverse micelles onto a substrate, the polymer was removed by means of different plasmas (oxygen and/or hydrogen), which also allow the metal salt to be reduced to the metallic state. In this way, ordered arrays of metallic nanodots can be prepared on various substrates. By adjusting the appropriate parameters, the separation and the size of the dots can be varied and controlled. To determine their purity, chemical state, and surface cleanliness—all of which are crucial for subsequent experiments since nanoscale structures are intrinsically surface dominated—in‐situ X‐ray photoelectron spectroscopy (XPS) and ex‐situ transmission electron microscopy (TEM) were applied, also giving information on the formation of the nanodots.

Hexagonally ordered arrays of non‐close‐packed nanoscaled spherical polystyrene (PS) particles are prepared exhibiting precisely controlled diameters and interparticle distances. For this purpose, a newly developed isotropic plasma etching process is applied to extended monolayers of PS colloids (starting diameters <300 nm) deposited onto hydrophilic silicon. Accurate size, shape, and smoothness control of such particles is accomplished by etching at low temperatures (−150 °C) with small rates not usually available in standard reactive ion etching equipment. The applicability of such PS arrays as masks for subsequent pattern transfer is demonstrated by fabricating arrays of cylindrical nanopores into Si.

Depositing metal layers onto a self‐assembled monolayer (SAM) is achieved using a new technique. Au(111) bearing a 4,4′‐dithiodipyridine SAM is immersed into a PdII solution without potential control, causing PdII to adsorb on the surface by forming a complex with the pyridine species. The PdII ions are then electrochemically reduced to Pd0 (see Figure). Angle‐resolved X‐ray photoelectron spectroscopy measurements unequivocally show that the reduced Pd resides on top of the SAM.