Alexey Zozulya

Structural Evolution of Colloidal Crystal Films in the Process of Melting Revealed by Bragg Peak Analysis

In situ X-ray diffraction studies of structural evolution of colloidal crystal films formed by polystyrene spherical particles upon incremental heating are reported. The Bragg peak parameters, such as peak position, integrated intensity, and radial and azimuthal widths were analyzed as a function of temperature. A quantitative study of colloidal crystal lattice distortions and mosaic spread as a function of temperature was carried out using Williamson-Hall plots based on mosaic block model. The temperature dependence of the diameter of polystyrene particles was obtained from the analysis of Bragg peaks, and the form factor contribution extracted from the diffraction patterns. Four stages of structural evolution in a colloidal crystal upon heating were identified. Based on this analysis, a model of the heating and melting process in the colloidal crystal film is suggested.

Versatile atomic force microscopy setup combined with micro-focused X-ray beam

Micro-focused X-ray beams produced by third generation synchrotron sources offer new perspective of studying strains and processes at nanoscale. Atomic force microscope setup combined with a micro-focused synchrotron beam allows precise positioning and nanomanipulation of nanostructures under illumination. In this paper, we report on integration of a portable commercial atomic force microscope setup into a hard X-ray synchrotron beamline. Details of design, sample alignment procedure, and performance of the setup are presented.

Quantifying Angular Correlations between the Atomic Lattice and the Superlattice of Nanocrystals Assembled with Directional Linking

We show that the combination of X-ray scattering with a nanofocused beam and X-ray cross correlation analysis is an efficient way for the full structural characterization of mesocrystalline nanoparticle assemblies with a single experiment. We analyze several hundred diffraction patterns at individual sample locations, that is, individual grains, to obtain a meaningful statistical distribution of the superlattice and atomic lattice ordering. Simultaneous small- and wide-angle X-ray scattering of the same sample location allows us to determine the structure and orientation of the superlattice as well as the angular correlation of the first two Bragg peaks of the atomic lattices, their orientation with respect to the superlattice, and the average orientational misfit due to local structural disorder. This experiment is particularly advantageous for synthetic mesocrystals made by the simultaneous self-assembly of nanocrystals and surface-functionalization with conductive ligands. While the structural characterization of such materials has been challenging so far, the present method now allows correlating the mesocrystalline structure with optoelectronic properties.

Colloidal crystallite suspensions studied by high pressure small angle x-ray scattering

We report on high pressure small angle x-ray scattering on suspensions of colloidal crystallites in water. The crystallites made out of charge-stabilized poly-acrylate particles exhibit a complex pressure dependence which is based on the specific pressure properties of the suspending medium water. The dominant effect is a compression of the crystallites caused by the compression of the water. In addition, we find indications that also the electrostatic properties of the system, i.e. the particle charge and the dissociation of ions, might play a role for the pressure dependence of the samples. The data further suggest that crystallites in a metastable state induced by shear-induced melting can relax to a similar structural state upon the application of pressure and dilution with water. X-ray cross correlation analysis of the two-dimensional scattering patterns indicates a pressure-dependent increase of the orientational order of the crystallites correlated with growth of these in the suspension. This study underlines the potential of pressure as a very relevant parameter to understand colloidal crystallite systems in aqueous suspension.

Double hexagonal close-packed structure revealed in a single colloidal crystal grain by Bragg rod analysis

A coherent X-ray diffraction study of a single colloidal crystal grain composed of silica spheres is reported. The diffraction data contain Bragg peaks and additional features in the form of Bragg rods, which are related to the stacking of the hexagonally close-packed layers. The profile of the Bragg rod shows distinct intensity modulations which, under the specific experimental conditions used here, are directly related to the stacking sequence of the layers. Using a model for the scattered intensity along the Bragg rod for an exact stacking sequence of a finite number of hexagonally close-packed layers, it is found that a double hexagonal close-packed stacking sequence is present in the colloidal crystal grain. This analysis method opens up ways to obtain crucial structural information from finite-sized crystalline samples by employing advanced third-generation X-ray sources.

Revealing Three-Dimensional Structure of an Individual Colloidal Crystal Grain by Coherent X-Ray Diffractive Imaging

We present results of a coherent x-ray diffractive imaging experiment performed on a single colloidal crystal grain. The full three-dimensional (3D) reciprocal space map measured by an azimuthal rotational scan contained several orders of Bragg reflections together with the coherent interference signal between them. Applying the iterative phase retrieval approach, the 3D structure of the crystal grain was reconstructed and positions of individual colloidal particles were resolved. As a result, an exact stacking sequence of hexagonal close-packed layers including planar and linear defects were identified.

In situ X-ray crystallographic study of the structural evolution of colloidal crystals upon heating

The results of a real-time X-ray crystallographic study of the melting transition of polystyrene colloidal crystals during heating are presented.

Ptychographic X-Ray Imaging of Colloidal Crystals

Ptychographic coherent X-ray imaging is applied to obtain a projection of the electron density of colloidal crystals, which are promising nanoscale materials for optoelectronic applications and important model systems. Using the incident X-ray wavefield reconstructed by mixed states approach, a high resolution and high contrast image of the colloidal crystal structure is obtained by ptychography. The reconstructed colloidal crystal reveals domain structure with an average domain size of about 2 µm. Comparison of the domains formed by the basic close-packed structures, allows us to conclude on the absence of pure hexagonal close-packed domains and confirms the presence of random hexagonal close-packed layers with predominantly face-centered cubic structure within the analyzed part of the colloidal crystal film. The ptychography reconstruction shows that the final structure is complicated and may contain partial dislocations leading to a variation of the stacking sequence in the lateral direction. As such in this work, X-ray ptychography is extended to high resolution imaging of crystalline samples.

Ferroelectric domain wall dynamics characterized with X-ray photon correlation spectroscopy

Significance The dynamics in many complex systems is essentially heterogeneous and involves a series of discrete events—in particular, local structural changes. The nature and scale of these changes may vary greatly, ranging from rearrangements of atomic positions during phase transitions to displacements of tectonic plates during earthquakes. In this work, we introduce X-ray photon correlation spectroscopy (XPCS) as a powerful tool for investigating heterogeneous dynamics of interfaces. We observe the motion of ferroelectric domain walls by means of XPCS and obtain the information about nanoscale changes, which is inaccessible for other techniques. Further experiments can provide important insights into the mechanisms of unusual properties of materials such as anomalously large piezoelectric response in relaxor-based ferroelectrics and magnetoelectric coupling in multiferroics. Technologically important properties of ferroic materials are determined by their intricate response to external stimuli. This response is driven by distortions of the crystal structure and/or by domain wall motion. Experimental separation of these two mechanisms is a challenging problem which has not been solved so far. Here, we apply X-ray photon correlation spectroscopy (XPCS) to extract the contribution of domain wall dynamics to the overall response. Furthermore, we show how to distinguish the dynamics related to the passing of domain walls through the periodic (Peierls) potential of the crystal lattice and through the random potential caused by lattice defects (pinning centers). The approach involves the statistical analysis of correlations between X-ray speckle patterns produced by the interference of coherent synchrotron X-rays scattered from different nanosize volumes of the crystal and identification of Poisson-type contribution to the statistics. We find such a contribution in the thermally driven response of the monoclinic phase of a ferroelectric PbZr0.55Ti0.45O3 crystal and calculate the number of domain wall jumps in the studied microvolume.

Structural Changes in a Single GaN Nanowire under Applied Voltage Bias

GaN nanowires (NWs) are promising building blocks for future optoelectronic devices and nanoelectronics. They exhibit stronger piezoelectric properties than bulk GaN. This phenomena may be crucial for applications of NWs and makes their study highly important. We report on an investigation of the structure evolution of a single GaN NW under an applied voltage bias along polar [0001] crystallographic direction until its mechanical break. The structural changes were investigated using coherent X-ray Bragg diffraction. The three-dimensional (3D) intensity distributions of the NWs without metal contacts, with contacts, and under applied voltage bias in opposite polar directions were analyzed. Coherent X-ray Bragg diffraction revealed the presence of significant bending of the NWs already after metal contacts deposition, which was increased at applied voltage bias. Employing analytical simulations based on elasticity theory and a finite element method (FEM) approach, we developed a 3D model of the NW bending under applied voltage. From this model and our experimental data, we determined the piezoelectric constant of the GaN NW to be about 7.7 pm/V in [0001] crystallographic direction. The ultimate tensile strength of the GaN NW was obtained to be about 1.22 GPa. Our work demonstrates the power of in operando X-ray structural studies of single NWs for their effective design and implementation with desired functional properties.