Andrey A. Eliseev

Complexes of Cu(II) with polyvinyl alcohol as precursors for the preparation of CuO/SiO2 nanocomposites

Abstractu2002Cupric oxide (CuO) nanoparticles have been prepared in amorphous SiO2 matrix using a novel variant of sol-gel technique. The method is based on the polycondensation of a silica source (sodium silicate) in the presence of an aqueous solution containing complex of Cu(II) with polyvinyl alcohol (CuPVA). After gelation, polymeric complexes containing several thousands Cu atoms each are incorporated into the silica network forming a precursor, which is then annealed in oxygen to get rid of organic components. The formation of CuO nanoparticles was confirmed by electron diffraction studies. The size of nanoparticles can be controlled by varying [Cu2+]/[PVA] ratio in the precursor. Thus prepared CuO/SiO2 nanocomposites are characterized by high specific surface area as measured by capillary adsorption of nitrogen, suggesting their possible use in catalysis.

Double stacking faults in convectively assembled crystals of colloidal spheres.

Using microradian X-ray diffraction, we investigated the crystal structure of convectively assembled colloidal photonic crystals over macroscopic (0.5 mm) distances. Through adaptation of Wilsons theory for X-ray diffraction, we show that certain types of line defects that are often observed in scanning electron microscopy images of the surface of these crystals are actually planar defects at 70.5 degrees angles with the substrate. The defects consist of two parallel hexagonal close-packed planes in otherwise face-centered cubic crystals. Our measurements indicate that these stacking faults cause at least 10% of stacking disorder, which has to be reduced to fabricate high-quality colloidal photonic crystals.

Fabrication of artificial opals by electric-field-assisted vertical deposition.

We present a new technique for large-scale fabrication of colloidal crystals with controllable quality and thickness. The method is based on vertical deposition in the presence of a DC electric field normal to the conducting substrate. The crystal structure and quality are quantitatively characterized by microradian X-ray diffraction, scanning electron microscopy, and optical reflectometry. Attraction between the charged colloidal spheres and the substrate promotes growth of thicker crystalline films, while the best-quality crystals are formed in the presence of repulsion. Highly ordered thick crystalline layers with a small amount of stacking faults and a low mosaic spread can be obtained by optimizing the growth conditions.

Controlled growth of metallic inverse opals by electrodeposition

The kinetics of nickel electrodeposition through a template of ordered polystyrene spheres is addressed experimentally and applied to prepare a series of metallic inverse opals with a non-integer number of layers. The observed layer-by-layer growth is discussed in terms of subsequently increasing disorder of the growth front. Reflection and transmission spectra of the samples demonstrate that the key optical features of these photonic crystals are most pronounced when the thickness does not essentially exceed two layers. The intensities and band positions can be additionally tuned by varying the height of the metal coating continuously, not discretely. These findings are confirmed semi-quantitatively by means of computational modeling of the spectra. Specific deposition current transients for in situ control of geometric parameters are discussed.

Long-range ordering in anodic alumina films: A microradian X-ray diffraction study

A quantitative analysis of long-range order in the self-organized porous structure of anodic alumina films has been performed on the basis of a microradian X-ray diffraction study. The structure is shown to possess orientational order over macroscopic distances larger than 1 mm. At the same time, the interpore positional order is only short-range and does not extend over more than � 10 interpore distances. These positional correlations are mostly lost gradually rather than at the domain boundaries, as suggested by the divergence of the peak width for the higher-order reflections. In the direction of the film growth the pores have a very long longitudinal self-correlation length of the order of tens of micrometres.

Origin of long-range orientational pore ordering in anodic films on aluminium

Porous anodic aluminium oxide has a long history of practical application for corrosion protection and coloring. In the last few decades a lot of hi-tech applications of this material have been found owing to the discovery of anodization conditions leading to the formation of highly ordered porous structures with a narrow pore size distribution. Here we show that in-plane orientation of the porous system in anodic films on aluminium is fully determined by the intrinsic crystallographic orientation of the Al substrate. The anisotropy of aluminium oxidation rates on a scalloped metal–oxide interface leads to reorientation of Al spikes in certain directions, which builds up an in-plane orientational order on a macroscopic scale restricted by a crystallite size. This is a unique example of the inheritance of the substrate crystal structure by an amorphous film through a size difference of three orders of magnitude.

Comparative Study of Structure and Permeability of Porous Oxide Films on Aluminum Obtained by Single- and Two-Step Anodization

A comparative study of the structure and transport properties of porous aluminum oxide films obtained by single- and two-step anodization was carried out. It is shown that the oxidation regime significantly affect the number of dead-ended channels, which results in more than twice the variation in membrane permeability. The effect is explained by multiple branching of channels on the initial stages of organization of the porous structure. Branching also occurs on later stages governing mass transport properties of porous anodic alumina films. A model describing transport properties of anodic aluminum oxide membranes based on pore branching on domain boundaries was suggested to fit experimental results of permeance of membranes obtained by both single- and two-step anodization.

Electric-Field-Assisted Self-Assembly of Colloidal Particles

A method for formation of photonic crystals has been proposed. The method is based on convective deposition of colloidal particles onto vertical substrates in the presence of a direct-current electric field directed perpendicular to the surface of the formed film and an alternating-current electric field applied parallel to the substrate plane. The structure and optical properties of the prepared colloidal crystals have been investigated using scanning electron microscopy, high resolution small-angle X-ray diffraction, and optical spectroscopy.

Longitudinal pore alignment in anodic alumina films grown on polycrystalline metal substrates

A quantitative analysis of longitudinal pore alignment in anodic alumina films grown on polycrystalline metal substrates was performed on the basis of small-angle X-ray diffraction mapping. The very high sensitivity of the diffraction pattern to the orientation of the anodic alumina film allowed the average pore alignment within the irradiated area to be determined, with an accuracy better than 0.1°. It is shown that pores deviate from the orientation orthogonal to the metal surface by a small angle that is constant within a single-crystal grain. Strong correlation between the longitudinal pore alignment within the anodic alumina film and the grain structure of the aluminium substrate indicates the important role of the crystallographic orientation of the metal in the pore growth process.

Nanomechanical humidity detection through porous alumina cantilevers

Summary We present here the behavior of the resonance frequency of porous anodic alumina cantilever arrays during water vapor adsorption and emphasize their possible use in the micromechanical sensing of humidity levels at least in the range of 10–22%. The sensitivity of porous anodic aluminium oxide cantilevers (Δf/Δm) and the humidity sensitivity equal about 56 Hz/pg and about 100 Hz/%, respectively. The approach presented here for the design of anodic alumina cantilever arrays by the combination of anodic oxidation and photolithography enables easy control over porosity, surface area, geometric and mechanical characteristics of the cantilever arrays for micromechanical sensing.