Polaron hopping in olivine phosphates studied by nuclear resonant scattering

Valence fluctuations of Fe²⁺ and Fe³⁺ were studied in a solid solution of Li_xFePO₄ by nuclear resonant forward scattering of synchrotron x rays while the sample was heated in a diamond-anvil pressure cell. The spectra acquired at different temperatures and pressures were analyzed for the frequencies of valence changes using the Blume-Tjon model of a system with a fluctuating Hamil- tonian. These frequencies were analyzed to obtain activation energies and an activation volume for polaron hopping. There was a large suppression of hopping frequency with pressure, giving an anomalously large activation volume. This large, positive value is typical of ion diffusion, which indicates correlated motions of polarons, and Li⁺ ions that alter the dynamics of both.

In a parallel study of Na_xFePO₄, the interplay between sodium ordering and electron mobility was investigated using a combination of synchrotron x-ray diffraction and nuclear resonant scattering. Conventional Mossbauer spectra were collected while the sample was heated in a resistive furnace. An analysis of the temperature evolution of the spectral shapes was used to identify the onset of fast electron hopping and determine the polaron hopping rate. Synchrotron x-ray diffraction measurements were carried out in the same temperature range. Reitveld analysis of the diffraction patterns was used to determine the temperature of sodium redistribution on the lattice. The diffraction analysis also provides new information about the phase stability of the system. The temperature evolution of the iron site occupancies from the Mossbauer measurements, combined with the synchrotron diffraction results give strong evidence for a relationship between the onset of fast electron dynamics and the redistribution of sodium in the lattice.

Measurements of activation barriers for polaron hopping gave fundamental insights about the correlation between electronic carriers and mobile ions. This work established that polaron-ion interactions can alter the local dynamics of electron and ion transport. These types of coupled processes may be common in many materials used for battery electrodes, and new details concerning the influence of polaron-ion interactions on the charge dynamics are relevant to optimizing their electrochemical performance.

The microstructure of hydrogenated microcrystalline silicon thin films studied by small-angle x-ray scattering

The microstructures of hydrogenated microcrystalline silicon (tic-Si: H) thin films, prepared by plasma-enhanced chemical vapor deposition (PECVD), hot wire CVD(HWCVD) and plasma assisted HWCVD (PE-HWCVD), have been analyzed by the small angle x-ray scattering(SAXS) measurement. The SAXS data show that the microstructures of the μ c-Si: H films display different characteristics for different deposition techniques. For films deposited by PECVD, the volume fraction of micro-voids and mean size are smaller than those in HWCVD sample. Aided by suitable ion-bombardment, PE-HWCVD samples show a more compact structure than the HWCVD sample. The microstructure parameters of the μ c-Si: H thin films deposited by two-steps HWCVD and PE-HWCVD with Ar ions are evidently improved. The result of 45° tilting SAXS measurement indicates that the distribution of micro-voids in the film is anisotropic. The Fouriertransform infrared spectra confirm the SAXS data.

DETERMINATION OF SURFACE-ROUGHNESS OF INP (001) WAFERS BY X-RAY-SCATTERING

The surface roughness of polished InP (001) wafers were examined by x-ray reflectivity and crystal truncation rod (CTR) measurements. The root-mean-square roughness and the lateral correlation scale were obtained by both methods. The scattering intensities in the scans transverse to the specular reflection rod were found to contain two components. A simple surface model of surface faceting is proposed to explain the experimental data. The sensitivities of the two methods to the surface structure and the role of the resolution functions in the CTR measurements are discussed.

X-RAY-SCATTERING FROM A ROUGH-SURFACE AND DAMAGED LAYER OF POLISHED WAFERS

Theoretical and experimental investigations were performed to show the application of x-ray crystal truncation rod scattering combined with x-ray reflectivity in the measurements of surface roughness and near-surface damage of mechanochemically polished wafers. By fitting the measured crystal truncation rod curves it has been shown that polished wafers are divided into three parts -irregular steps on the surface, a damaged thin layer beneath the surface and a perfect bulk. The results show that the root mean square of the surface roughness of mechanochemically polished Fe-doped and/or S-doped InP wafers is one to two atom layers, and that the lateral correlation length of the surface roughness is about 3000-7500 Angstrom. The thickness of the damaged region is found to be about 1000 atom layers.

Lateral periodicity in highly-strained (GaIn)As/Ga(PAs) superlattices investigated by X-ray scattering techniques

In this work we investigate the lateral periodicity of symmetrically strained (GaIn)As/GaAs/Ga(PAs)/GaAs superlattices by means of X-ray scattering techniques. The multilayers were grown by metalorganic Vapour phase epitaxy on (001)GaAs substrates, which were intentionally off-oriented towards the [011]-direction. The substrate off-orientation and the strain distribution was found to affect the structural properties of the superlattices inducing the generation of laterally ordered macrosteps. Several high-resolution triple-crystal reciprocal space maps, which were recorded for different azimuth angles in the vicinity of the (004) Bragg diffraction and contour maps of the specular reflected beam collected in the vicinity of the (000) reciprocal lattice point, are reported and discussed. The reciprocal space maps clearly show a two-dimensional periodicity of the X-ray peak intensity distribution which can be ascribed to the superlattice periodicity in the direction of the surface normal and to a lateral periodicity in a crystallographic direction coinciding with the miscut orientation. The distribution and correlation of the vertical as well as of the lateral interface roughness was investigated by specular reflectivity and diffuse scattering measurements. Our results show that the morphology of the roughness is influenced by the off-orientation angle and can be described by a 2-dimensional waviness.

INPLANE X-RAY-SCATTERING OF EPITAXIAL STRUCTURES

A new approach for in-plane X-ray scattering from the cleavages of epitaxial films or superlattices, where the scattering vectors are parallel to the interfaces, is proposed. This method can be employed to determine directly the in-plane X-ray strains and other atomic registry along the interfaces of the epitaxial structures.

Effect of annealing on the deformation mechanism of a styrene/n-butyl acrylate copolymer latex film investigated by synchrotron small-angle X-ray scattering

The deformation mechanism of a styrene/n-butyl acrylate copolymer latex film subjected to uniaxial tensile stress was studied by small-angle X-ray scattering. The influence of annealing at 23, 60, 80, and 100 degrees C for 4 h on microscopic deformation processes was elucidated. It was demonstrated that the microscopic deformation mechanism of the latex films transformed gradually from nonaffine deformation behavior to affine deformation behavior with increasing annealing temperature.

Structural evolution of tensile deformed high-density polyethylene at elevated temperatures: Scanning synchrotron small- and wide-angle X-ray scattering studies

The structural evolution of an ice-quenched high-density polyethylene (HDPE) subjected to uniaxial tensile deformation at elevated temperatures was examined as a function of the imposed strains by means of combined synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques. The data show that when stretching an isotropic sample with the spherulitic structure, intralamellar slipping of crystalline blocks was activated at small deformations, followed by a stress-induced fragmentation and recrystallization process yielding lamellar crystallites with their normal parallel to the stretching direction. Stretching of an isothermally crystallized HDPE sample at 120 degrees C exhibited changes of the SAXS diagram with strain similar to that observed for quenched HDPE elongated at room temperature, implying that the thermal stability of the crystal blocks composing the lamellae is only dependent on the crystallization temperature.

DEFORMATION OF SOFT COLLOIDAL CRYSTALLINE STRUCTURE - THEORETICAL CONSIDERATIONS AND EXPERIMENTAL EVIDENCES BY SYNCHROTRON SMALL-ANGLE X-RAY SCATTERING ON TENSILE STRETCHED POLYMERIC LATEX FILM

Films obtained via drying a polymeric latex dispersion are normally colloidal crystalline where latex particles are packed into a face centered cubic (fcc) structure. Different from conventional atomic crystallites or hard sphere colloidal crystallites, the crystalline structure of these films is normally deformable due to the low glass transition temperature of the latex particles. Upon tensile deformation, depending on the drawing direction with respect to the normal of specific crystallographic plane, one observes different crystalline structural changes. Three typical situations where crystallographic c-axis, body diagonal or face diagonal of the fcc structure of the colloidal crystallites being parallel to the stretching direction were investigated.