High-resolution X-ray Diffraction Methods Research Articles

Status of X-ray Acoustooptics at the Institute of Microelectronics Technology Russian Academy of Sciences

The electrical measurement method, scanning electron microscopy method and high-resolution X-ray diffraction method have been used to investigate the process of the surface acoustic wave (SAW) propagation in a LiNbO3 ferroelectric crystal. Measurement of the amplitude-frequency response provides information on the losses in the acoustoelectronic device during the process of the SAW propagation. The scanning electron microscopy method permits to visualize the SAW on the surface of piezoelectric crystals in the real-time mode and to observe diffraction phenomena in acoustic beam. The X-ray diffraction method is sensitive to the crystal lattice distortions by surface acoustic wave and allows determining the SAW amplitudes.

Growth Twins and Premartensite Microstructure in Epitaxial Ni-Mn-Ga Films

Magnetic shape memory alloys have been examined intensively due to their multifunctionality and multitude of physical phenomena. For both areas, epitaxial films are promising since the absence of grain boundaries is beneficial for applications in microsystems and they also allow to understand the influence of a reduced dimension on the physical effects. Despite many efforts on epitaxial films, two particular aspects remain open. First, it is not clear how to keep epitaxial growth up to high film thickness, which is required for most microsystems. Second, it is unknown how the microstructure of premartensite, a precursor state during the martensitic transformation, manifests in films and differs from that in bulk.Here, we focus on micrometer-thick austenitic Ni-Mn-Ga films and explain two distinct microstructural features by combining high-resolution electron microscopy and X-ray diffraction methods. First, we identify pyramid-shaped defects, which originate from {1 1 1} growth twinning and cause the breakdown of epitaxial growth. We show that a sufficiently thick Cr buffer layer prevents this breakdown and allows epitaxial growth up to a thickness of at least 4 µm. Second, premartensite exhibits a hierarchical microstructure in epitaxial films. The reduced dimension of films results in variant selection and regions with distinct premartensite variants, unlike its microstructure in bulk.

Emission Variation of InAs Quantum Dots within (Al)GaInAs Quantum Wells in AlGaAs/GaAs Structures vs Quantum Well Compositions

The parameters of quantum dots (QDs) of InAs inserted in Al0.30Ga0.70As/GaAs hetero structures with additional cap/buffer AlGaInAs quantum wells (QWs) of different compositions have been investigated by photoluminescence, transmission electron microscopy and high-resolution X-ray diffraction methods. QD structures with the buffer layers: In0.15Ga0.85As (#1) or In0.25Ga0.75As (#2) and covering (cap) layers: Al0.10In0.15Ga0.75As (#1) or Al0.40In0.15Ga0.45As (#2), are compared. Structure #1 is characterized by a higher density of QDs, high QD emission intensity and a smaller full width at half maximum of the PL bands, compared to #2. The dependence of the intensity of QD emission against temperatures of 10–500 K has been studied. Significant thermal quenching of the PL intensity was revealed in #1 compared to #2. HR-XRD investigation has confirmed that QD structures are of perfect crystalline quality with sharp QW interfaces and a high number of Pendellösung peaks were detected. To fit the HR-XRD scans, the X′Pert Epitaxy software has been applied. The peculiarities of the QD emission and the parameters of the HR-XRD scans are compared, as well as the advances of the QD structures studied are discussed.

Structure and electrical behavior of silicon nanowires prepared by MACE process

We report on the structure and electrical characteristics of silicon nanowire arrays prepared by metal assisted chemical etching (MACE) method, investigated by cross-sectional scanning electron microscopy (SEM) and high resolution X-ray diffraction (HR-XRD) methods. SEM micrographs show arrays of merged parallel nanowires, with lengths of 700 nm and 1000 nm, resulted after 1.5 min and 5 min etching time, respectively. X-ray reciprocal space maps (RSMs) around Si (004) reciprocal lattice point indicate the presence of 0D structural defects rather than of extended defects. The photoluminescence spectra exhibit emission bands at 1.70 eV and 1.61 eV, with intensity significantly higher in the case of longer wires and associated with the more defected surface. The transient photoluminescence spectroscopy reveals average lifetime of 60 ôs and 111 ôs for the two SiNW arrays, which correlate with a larger density of defects states in the latest case. The I-V characteristics of the nanowires, show a memristive behavior with the applied voltage sweep rate in the range 5–0.32V/s. We attribute this behavior to trap states which control the carrier concentration, and model this effect using an equivalent circuit. Photogeneration processes under excitation wavelengths in visible domain, 405 nm - 650 nm, and under light intensity in the range 20–100 mW/cm2 provided a further insight into the trap states.

Application of X-ray diffraction and reflectometry methods for analysis of damaged layers on polar faces of ZnO after surface chemical-mechanical treatment

ZnO single crystals are used for the fabrication of laser targets for high-energy electron irradiated UV laser cathode-ray tubes and homoepitaxial substrates for lasers. The technology of ZnO based UV LEDs imposes strict requirements to surface quality. Chemical-mechanical polishing delivers good surface quality but it is known that polishing of ZnO polar faces may yield different results. Surface-sensitive high-resolution X-ray diffraction (HRXRD) and X-ray reflectometry (XRR) methods have been used for studying the structure of (0001) and (000–1) polar faces of ZnO after chemical-mechanical polishing. Two double-sided polished (0001) ZnO substrates have been cut out from different hydrothermally grown ingots. The damage and density depth profiles for the Zn and O faces of the specimens have been retrieved from the X-ray diffraction curves and the specular reflection curves, respectively. Intensity distributions in the vicinity of the [0002] and [0000] reciprocal lattice sites have been taken on a D8 Discover X-ray diffractometer (Bruker-AXS, Germany) in a triple-crystal setup. For separating the coherent and incoherent scattering components, the intensity profiles have been analyzed along sections perpendicular to the diffraction vector and located at different distances from the reciprocal lattice sites. The HRXRD and XRR data have been compared with atomic force microscopy (AFM) data. The HRXRD method has revealed damaged layers at both faces of the specimens, with the layer thicknesses differing for the Zn and O faces, i.e., 5–7 nm for the Zn face and 10–11 nm for the O face. The XRR method has shown that both faces are sufficiently smooth. These results have been confirmed by AFM (RMS roughness ~ 0.23 ± 0.07 nm). However, the concentration of electrons in the superficial layers has been found to change. The layer thickness proves to be greater for the O face. We have hypothesized that the phenomena observed are caused by the difference in the chemical interaction of the Zn and O faces with the polishing agents.

Application of X-ray diffraction and reflectometry methods for analysis of damaged layers on polar faces of ZnO after surface chemical-mechanical treatment

ZnO single crystals are used for the fabrication of laser targets for high-energy electron irradiated UV laser cathode-ray tubes and homoepitaxial substrates for lasers. The technology of ZnO based UV LEDs imposes strict requirements to surface quality. Chemical-mechanical polishing delivers good surface quality but it is known that polishing of ZnO polar faces may yield different results. Surface-sensitive high-resolution X-ray diffraction (HRXRD) and X-ray reflectometry (XRR) methods have been used for studying the structure of (0001) and (000–1) polar faces of ZnO after chemical-mechanical polishing. Two double-sided polished (0001) ZnO substrates have been cut out from different hydrothermally grown ingots. The damage and density depth profiles for the Zn and O faces of the specimens have been retrieved from the X-ray diffraction curves and the specular reflection curves, respectively. Intensity distributions in the vicinity of the [0002] and [0000] reciprocal lattice sites have been taken on a D8 Discover X-ray diffractometer (Bruker-AXS, Germany) in a triple-crystal setup. For separating the coherent and incoherent scattering components, the intensity profiles have been analyzed along sections perpendicular to the diffraction vector and located at different distances from the reciprocal lattice sites. The HRXRD and XRR data have been compared with atomic force microscopy (AFM) data. The HRXRD method has revealed damaged layers at both faces of the specimens, with the layer thicknesses differing for the Zn and O faces, i.e., 5–7 nm for the Zn face and 10–11 nm for the O face. The XRR method has shown that both faces are sufficiently smooth. These results have been confirmed by AFM (RMS roughness ~ 0.23 ± 0.07 nm). However, the concentration of electrons in the superficial layers has been found to change. The layer thickness proves to be greater for the O face. We have hypothesized that the phenomena observed are caused by the difference in the chemical interaction of the Zn and O faces with the polishing agents.

In-situ thermal phase transition and structural investigation of ferroelectric tetragonal barium titanate nanopowders with pseudo-cubic phase

Optimization and miniaturization of existing electronic devices require the development of advanced nanostructured materials with high phase and structural purity. Over the past decade, barium titanate (BaTiO3) has attracted considerable attention due to its outstanding ferroelectric and dielectric properties. The present study involved the investigation of the phase transition and structural stability of tetragonal BaTiO3 nanopowders with pseudo-cubic phase using an in-situ high resolution and high temperature X-ray diffraction method. Under ambient conditions, the coexistence the tetragonal and cubic phases with weight fractions of 75.7% and 24.3%, respectively, was determined in BaTiO3. In the temperature range of 25 °C-300 °C, phase boundaries of BaTiO3 (180 nm in size) exhibiting several phases were detected. The phase transformation behavior, relative crystal phase content, lattice parameters, crystallite size, and tetragonality of the BaTiO3 nanopowders were established by the Rietveld refinement method at the onset temperature from 25 °C to 300 °C. Up to 150 °C, the nanopowders exhibited a complete transition of the cubic phase. Additionally, a complete tetragonal to cubic transformation was accomplished by a decrease of tetragonality at 125 °C and an increase in the crystallite size at 300 °C.

CMT Joining of AA6061-T6 and AA6082-T6 and Examining Mechanical Properties and Microstructural Characterization

Nowadays, CMT is used for joining dissimilar thickness of dissimilar metals for achieving higher mechanical strength by using properties of both the metals. Joining of dissimilar aluminium alloys with dissimilar thickness by using gas metal arc welding with cold metal transfer (GMAW-CMT) process, is the primary objective of this work. CMT butt joining of 6061-T6 (3.18 mm) and 6082-T6 (2 mm) aluminium alloys was carried out by using ER4043 (Al–5%Si) wire. Mechanical properties and microstructural characterization were carried out for the weld bead. Microstructural examination at different weld zones is studied using optical microscope and field emission scanning electron microscope (FESEM). Macro-structural images were captured to study the weld bead geometry in relation to heat input. Mechanical properties were examined by Vicker’s microhardness and tensile test (with reinforcement, that is, the actual profile of the bead and without reinforcement, that is, the profile of bead are flattened to the surface of the plate). The residual stresses were measured using high-resolution X-ray diffraction (HR-XRD) method. Results showed significant changes in mechanical properties when heat input was in the range of 120–130 J/mm. Removal of reinforcement height improved almost 7–11% of tensile strength. Compressive residual stresses were experienced in the weldment. Comparatively cold metal transfer (CMT) showed better residual stress results than metal inert gas (MIG) welding at the same heat input.

Peculiarities of Structure and Morphology of Copper-Cerium Nanopowders Produced by Laser Ablation

Copper-cerium nanopowders CuOx–CeO2 (mass ratio Cu:Ce = 6:100) are prepared by mixing the dispersions of the copper and cerium oxides produced by the method of pulse laser ablation (PLA) in liquid, followed by drying. The initial dispersions of copper oxides were prepared by the method of PLA of a metal copper target in distilled water or 1% hydrogen peroxide solution, and those of cerium oxide – by PLA of metal cerium in distilled water. It is shown that ablation of copper in water and water solution of peroxide is followed by the formation of copper oxide particles of different morphologies and compositions (structure). It is established that no crystal phases of copper oxides are formed in the copper-cerium nanopowders produced from separate dispersions. Given this approach to forming copper-cerium nanoparticles, the oxidized copper is distributed in the form of a thin layer on the CeO2 surface, which is demonstrated by the results of investigation of these particles by the methods of high-resolution transmission electron microscopy and X-ray diffraction. The formation of a Cu–O–Ce interface at the interphase boundary gives rise to the formation of defects on the CeO2 surface, which is confirmed by the Raman spectroscopy. An investigation of the composition and electronic structure of the surface of CuOx nanoparticles and CuOx–CeO2 nanopowders performed by the method of X-ray photoelectronic spectroscopy reveals the presence of copper in the form of a combination of Cu (I) and Cu (II) with the prevailing contribution from a single-valence state for CuOx–CeO2 nanopowders, which could have resulted from the interaction between CuOx and CeO2 particles.

Strong Negative Thermal Expansion in a Low-Cost and Facile Oxide of Cu2P2O7.

Negative thermal expansion (NTE) behaviors have been observed in various types of compounds. The achievement in the merits of promising low-cost and facile NTE oxides remains challenging. In the present work, a simple and low-cost Cu2P2O7 has been found to exhibit the strongest NTE among the oxides (αV ∼ -27.69 × 10-6 K-1, 5-375 K). The complex NTE mechanism has been investigated by the combined methods of high-resolution synchrotron X-ray diffraction, neutron powder diffraction, X-ray pair distribution function, extended X-ray absorption fine structure spectroscopy, and density functional theory calculations. Interesting, the direct experimental evidence reveals that the coupling twist and rotation of PO4 and CuO5 polyhedra are the inherent factors for the NTE nature of Cu2P2O7, which is triggered by the transverse vibrations of oxygen atoms. The present new NTE material of Cu2P2O7 also has been verified for the practical application.

Analysis of mechanical behaviour of L-arginine hydrobromide monohydrate (LAHBr) single crystal grown by unidirectional growth technique

A single crystal of L-arginine Hydrobromide Monohydrate (LAHBr) with excellent crystalline perfection was grown by a modified way of unidirectional technique. The criteria behind this modified version were to reduce the temperature gradient of the solution which will enhance the quality of the single crystal. The formation of the crystal was confirmed by calculating lattice parameters from powder x-ray diffraction technique. The quality of the single crystal was analyzed by high-resolution x-ray diffraction which suggests that single crystal was free from grain boundaries and have the value full width half maxima is 9.36 arc second. Owing to high crystallinity, the single crystal was further underwent mechanical analysis using nanoindentation technique. Its structural, as well as physical transformation have been assessed by laser and shock damage threshold techniques. The presence of surface defects was examined by scanning electron microscope (SEM) and it is in tune with the high resolution x-ray diffraction method.

Physical Operating Principles of Palladium–Barium Cathodes of Microwave Devices

High-resolution X-ray diffraction method (XRD) is used to determine sizes and crystallographic orientation of the nanocrystallites of the Pd and Pd5Ba phases in palladium–barium cathode. Electron spectroscopy for chemical analysis (ESCA) is used to study Ba and Pd chemical states in cathode material and determine the phase composition including dissolved microimpurities in the phases. The comparison of the XRD and ESCA data makes it possible to reveal effects related to the formation of the BaO crystallites in the cathode material, which are responsible for the emission properties. Electron-energy loss spectroscopy is used to determine the concentration of oxygen vacancies in the BaO crystallites that are formed in the cathode material due to activation. An original crystallite model of the working palladium–barium cathodes that is based on the results of this work may serve as an alternative to the known film model and makes it possible to optimize technology of cathode fabrication and activation.

Finely tunable morphology controlled synthesis of spinel-cobalt oxide nanostructures and their electrocatalytic applications

Herein, we synthesize four morphologies of spinel-Co3O4 nanostructures, including rice-, dumbbell sheet-, nanoboxes-, and nanosheets spheres using a hydrothermal strategy. The surface morphology and size of the Co3O4 nanostructures are characterized by field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction(XRD), and electrochemical methods. Among the other Co3O4 nanostructures, nanosheets spheres- like morphology display a significantly enhanced electrochemical oxidation of sulfite (SO32−) in terms of higher anodic current density (1.50 mA cm−2) and low onset oxidation potential (∼1.10 V vs RHE). The Co3O4 nanosheets spheres offer a large surface area, and numerous active sites for accessing numerous sulfite molecules for efficient and enhanced electrocatalytic responses. Further, the Co3O4 nanosheets spheres based electrode display a low Rp value, and high durability when compared to other nanostructured electrodes. Thus, the Co3O4 nanostructured materials are versatile candidates, and offer a new optimism for use in various electrochemical technological applications.

AlGaInAs capping layer impact on emission and structure of AlGaAs/GaAs quantum wells with InAs quantum dots

Three types of GaAs/Al0.30Ga0.70As quantum wells (QWs) with InAs quantum dots (QDs) cavered by the different capping layers: GaAs (#1), Al0.30Ga0.70As (#2) and Al0.1Ga0.75In0.15As (#3), have been investigated. The photoluminescence (PL), its temperature dependence and high resolution X-ray diffraction (HR-XRD) methods were applied. It is revealed that QD emission in the structure #3 is characterized by the lower PL peak energy, highest PL intensity and smaller half widths of PL bands, in comparison with the QD emissions in #1 and #2. PL temperature dependences have been studied that revealing the QD material composition in #3 is closer to InAs than those in #1 and #2.HR-XRD scan fitting permits to understand the process of strain relaxation in studied structures at high QW growth temperatures. This process in the structures #1 and #2 was connected with material composition varying the QDs and capping layers due to Ga/In atom intermixing that leads to the QD emission shift into the higher energy range and PL intensity decreasing. Meanwhile in the structure #3 with Al0.1Ga0.75In0.15As capping, the strain relaxation manifests itself by InAs QD height decreasing without changing the InAs QD material composition. The advantages of Al0.1Ga0.75In0.15As capping layer used and its impact on the emission of InAs QDs have been discussed.

Emission and HR-XRD study of MBE structures with InAs quantum dots and AlGaInAs strain reducing layers

GaAs/Al0.30Ga0.70As quantum wells (QWs) with InAs quantum dot (QD) arrays covered by the different capping layers: Al0.30Ga0.70As or Al0.1Ga0.75In0.15As, have been investigated by means of the photoluminescence (PL) and high resolution X-ray diffraction (HR-XRD) methods. It is revealed that the QD emission in the structure with Al0.1Ga0.75In0.15As capping is characterized by the lower PL energy, higher PL intensity of ground state emission and smaller its full width at half maximum (FWHM) in comparison with ground state QD emission at Al0.30Ga0.70As capping. The analysis of PL and HR-XRD scans has shown that the strain relaxation at high QW growth temperatures in the structure with Al0.30Ga0.70As capping was connected with changing significantly the material compositions of the QDs and capping layer. As a result the QD emission shifts into the higher energy range, the PL intensity decreases and the FWHMs of PL bands increase. In contrary, in the structure with Al0.1Ga0.75In0.15As capping the strain relaxation manifests itself by decreasing the InAs QD heights without changing the InAs QD material composition. The advantage of Al0.1Ga0.75In0.15As capping has been discussed.

Structure determination and crystal chemistry of large repeat mixed-layer hexaferrites.

Hexaferrites are an important class of magnetic oxides with applications in data storage and electronics. Their crystal structures are highly modular, consisting of Fe- or Ba-rich close-packed blocks that can be stacked in different sequences to form a multitude of unique structures, producing large anisotropic unit cells with lattice parameters typically >100 Å along the stacking axis. This has limited atomic-resolution structure solutions to relatively simple examples such as Ba2Zn2Fe12O22, whilst longer stacking sequences have been modelled only in terms of block sequences, with no refinement of individual atomic coordinates or occupancies. This paper describes the growth of a series of complex hexaferrite crystals, their atomic-level structure solution by high-resolution synchrotron X-ray diffraction, electron diffraction and imaging methods, and their physical characterization by magnetometry. The structures include a new hexaferrite stacking sequence, with the longest lattice parameter of any hexaferrite with a fully determined structure.

Direct growth of type II InAs/GaSb superlattice MWIR photodetector on GaAs substrate

We report on the direct growth and characterization of type-II InAs/GaSb superlattice (T2SL) MWIR photodetector structure grown on a GaAs substrate by molecular beam epitaxy. The designed photodetector structure contains 140 period of 8.0 ML InAs/8.3 ML GaSb p-i-n SL structure with a 50% cutoff wavelength of 3.78 μm. We achieved a peak specific detectivity (D∗) and differential resistance area product at zero bias (R0A) of 1.3 × 1012 cm Hz½ W−1 and 104 Ω cm2 at 80 K, respectively. The obtained D∗ value is the best value reported up to now for a T2SL MWIR p-i-n photodetector grown on a GaAs substrate. The crystalline quality and the uniformity of the grown structure were verified by high resolution X-ray diffraction method by measuring three different spots on grown structure on a full 4 inch SI GaAs substrate.

Benzoquinone-Bridged Heterocyclic Zwitterions as Building Blocks for Molecular Semiconductors and Metals.

In pursuit of closed-shell building blocks for single-component organic semiconductors and metals, we have prepared benzoquino-bis-1,2,3-thiaselenazole QS, a heterocyclic selenium-based zwitterion with a small gap (λmax = 729 nm) between its highest occupied and lowest unoccupied molecular orbitals. In the solid state, QS exists in two crystalline phases and one nanocrystalline phase. The structures of the crystalline phases (space groups R3 c and P21/ c) have been determined by high-resolution powder X-ray diffraction methods at ambient and elevated pressures (0-15 GPa), and their crystal packing patterns have been compared with that of the related all-sulfur zwitterion benzoquino-bis-1,2,3-dithiazole QT (space group Cmc21). Structural differences between the S- and Se-based materials are interpreted in terms of local intermolecular S/Se···N'/O' secondary bonding interactions, the strength of which varies with the nature of the chalcogen (S vs Se). While the perfectly two-dimensional "brick-wall" packing pattern associated with the Cmc21 phase of QT is not found for QS, all three phases of QS are nonetheless small band gap semiconductors, with σRT ranging from 10-5 S cm-1 for the P21/ c phase to 10-3 S cm-1 for the R3 c phase. The bandwidths of the valence and conduction bands increase with applied pressure, leading to an increase in conductivity and a decrease in thermal activation energy Eact. For the R3 c phase, band gap closure to yield an organic molecular metal with a σRT of ∼102 S cm-1 occurs at 6 GPa. Band gaps estimated from density functional theory band structure calculations on the ambient- and high-pressure crystal structures of QT and QS correlate well with those obtained experimentally.

Lattice Parameters a-, c-, Strain-Stress Analysis and Thermal Expansion Coefficient of InGaN/GaN Solar Cell Structures Grown by MOCVD

Structural properties of InGaN/GaN solar cells (SCs) grown by metal organic chemical vapor deposition (MOCVD) technique are investigated by high resolution X-ray diffraction (HR-XRD) method. It is noticed that a- and c- lattice parameters of the structures showed small differences according to examined (hkl) planes. Fault percentage of the a- and c- lattice parameters are also calculated. It is seen that fault percentage is smaller than %2 for all samples. Investigations have been made for three different samples. Differences in crystal quality caused by growth conditions are seen in all three samples. At the same time, properties such as crystal size, strain and stress are determined. During determination of stress, two different methods including elastic constants, Young module and Poisson ratio are used. Results gained from these two methods are compared with each other. Thermal expansion coefficients of InGaN are calculated for (002), (004), (006) and (121) planes for 100 oC temperature difference (300-400 oC). It is seen that peak positions gained from HR-XRD are nearly the same with the ones in database. All the results obtained from calculations are given in tables in the following sections of this article. It can be seen that all these results are in accordance with previous works done by different authors and with the real values.

The crystal structure of compositionally homogeneous mixed ceria-zirconia oxides by high resolution X-ray and neutron diffraction methods

AbstractThe real/atomic structure of single phase homogeneous nanocrystalline Ce0.5Zr0.5O2±δoxides prepared by a modified Pechini route and Ni-loaded catalysts of methane dry reforming on their bases was studied by a combination of neutron diffraction, synchrotron X-ray diffraction, total X-ray scattering and X-ray absorption spectroscopy. The effects of sintering temperature and pretreatment in H2were elucidated. The structure of the mixed oxides corresponds to a tetragonal space group indicating a homogeneous distribution of Ce and Zr cations in the lattice. A pronounced disordering of the oxygen sublattice was revealed by neutron diffraction, supposedly due to incorporation of water into the structure when in contact with air promoted by the generation of anion vacancies in the lattice after reduction or calcination at high temperatures. However, such disordering has not resulted in any occupation of the oxygen interstitial positions in the bulk of the nanodomains.