Kirill S. Napolskii

High‐Resolution Transmission X‐ray Microscopy: A New Tool for Mesoscopic Materials

The whole is sometimes more than the sum of its parts. Certainly it is true for ordered mesoscopic materials, when the assembly of particles acquires properties which are not the intrinsic ones of the constituent particles. One of the best illustrative examples is the case of photonic crystals – attractive optical materials for controlling and manipulating the fl ow of light. Since the appearance of seminal papers in 1987 the number of research papers devoted to the subject, began to grow exponentially. [ 1–2 ] Three-dimensional photonic crystals offer additional features compared to 1D (gratings, multilayers) and 2D cases, possibly leading to new device concepts (e.g., for optical computing), but manufacturing problems are still far from being solved. While 2D structures could be created by techniques adapted from semiconductor industry, this is less obvious for the 3D case, and as an alternative self-assembly approaches are considered to have a great potential. [ 3 ] The effi ciency of the latter approach is demonstrated long ago by the very existence of prototypical photonic crystals – gem opals. In the case of photonic materials, the crystalline structure of individual subunits is practically of no relevance. The target design properties are not only defi ned by the average mesoscopic structure, but by its specifi c realization, including random or correlated defects (non-monodisperse subunits, vacancies, dislocations, stacking faults, etc.). The mesoscale can be probed by imaging-related or diffraction-related methods. The fi rst family of techniques was exclusively limited to surface imaging, namely to scanning electron microscopy and a replica-technique variety of transmission electron microscopy. [ 4–6 ]

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.

Magnetoplasmonic nanostructures based on nickel inverse opal slabs

Nanostructured nickel surfaces representing periodically arranged spherical voids in a nickel film are obtained by electrochemical deposition through a self-assembled opaline template. Excitation of surface plasmon-polaritons (SPPs) on the surface of the sample is experimentally observed as the Wood’s anomaly in the reflectance spectra. Transversal magneto-optical Kerr effect (TMOKE) spectra are measured at the different angles of incidence and azimuthal angles. The two- to-threefold enhancement of TMOKE caused by the excitation of mixed plasmons in two selected azimuthal configurations is observed.

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.

Determination of the real structure of artificial and natural opals on the basis of three-dimensional reconstructions of reciprocal space

The distribution of the scattering intensity in the reciprocal space for natural and artificial opals has been reconstructed from a set of small-angle X-ray diffraction patterns. The resulting three-dimensional intensity maps are used to analyze the defect structure of opals. The structure of artificial opals can be satisfactorily described in the Wilson probability model with the prevalence of layers in the fcc environment. The diffraction patterns observed for a natural opal confirm the presence of sufficiently long unequally occupied fcc domains.

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.