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.

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.

No abstract

Starting with Co‐salt‐loaded inverse micelles, which form if the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) is dissolved in a selective solvent like toluene and CoCl2 is added to the solution, monomicellar arrays of such micelles exhibiting a significant hexagonal order can be prepared on top of various substrates with tailored intermicellar distances and structure heights. In order to remove the polymer matrix and to finally obtain arrays of pure Co nanoparticles, the micelles are first exposed to an oxygen plasma, followed by a treatment in a hydrogen plasma. Applying in‐situ X‐ray photoelectron spectroscopy, it is demonstrated that: 1) The oxygen plasma completely removes the polymer, though conserving the original order of the micellar array. Furthermore, the resulting nanoparticles are entirely oxidized with a chemical shift of the Co 2p3/2 line pointing to the formation of Co3O4. 2) By the subsequent hydrogen plasma treatment the nanoparticles are fully reduced to metallic Co. 3) By exposing the pure Co nanoparticles for 100 s to various oxygen partial pressures p, a stepwise oxidation is observed with a still metallic Co core surrounded by an oxide shell. The data allow the extraction of the thickness of the oxide shell as a function of the total exposure to oxygen (p × time), thus giving the opportunity to control the ferromagnetic–antiferromagnetic composition of an exchange‐biased magnetic system.