Lattice Parameter Measurements Research Articles

Growth Phenomena and Bandgap Shift in Melt‐Grown β‐(InxGa1−x)2O3 Alloys

β‐Ga2O3 is an emerging ultra‐wide bandgap semiconductor with great promise for power electronics and optoelectronics. Alloys in the In2O3‐Ga2O3 system are interesting for optoelectronic applications, particularly where bandgap tuning is desirable. Herein, β‐(InxGa1–x)2O3 alloys with target compositions x = 0.025 or 0.10 are grown from the melt using the Czochralski and vertical gradient freeze techniques. Growth with 10 mol% In yields only small, needle‐like crystals, while 2.5 mol% In allows growth of centimeter‐sized single crystals. A substantial degree of indium segregation is unveiled by spatial measurements of lattice parameters and the bandgap. The bandgap decreases by a maximum of 0.28 eV in the case of the highest In content crystals. Z‐contrast transmission electron microscopy confirms a solely octahedral coordination of In in the β‐Ga2O3 lattice. With indium concentrations higher than 2.5 mol%, samples contain micron‐scale voids that impart a dark coloration. All measured crystals are electrically conductive, with carrier concentrations varying 1016–1017 cm−3 depending upon the location of the sample in the growth. Lastly, a unique luminescence with unknown origin centered around 2.0 eV is revealed by photoluminescence spectroscopy.

Tuning the structural, optical, and dielectric properties of europium-doped barium titanate ceramics

This study explores the optical and dielectric properties of pure and europium-doped barium titanate ceramics with formula Ba1−3x/2EuxTiO3 (x=0,0.005,0.015and0.025\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$x=0,0.005, 0.015\ ext{ and }0.025$$\\end{document}). The materials were synthesized using the solid-state reaction method. The influence of Eu + 3 ion incorporation on the crystal structure was examined using XRD, which indicated the formation of a cubic phase. Lattice parameter measurements showed excellent agreement with various theoretical models for predicting the lattice constant, with an average error of only 0.20%. UV–visible spectroscopy analysis is utilized to investigate optical characteristics, revealing a decrease in the optical band gap from 2.65 to 2.77 eV post-Eu doping, which is notably lower than the bulk barium titanate value of 3.2 eV. Materials with smaller band gaps are more suited for optoelectronic applications like photodetectors and light-emitting diodes (LEDs). The dielectric response of europium-doped barium titanate was studied across a frequency range of 1 kHz to 2 MHz and a temperature range of 77 to 300 K, showing remarkable stability. The frequency-dependent dielectric analysis revealed that the dielectric constant initially increased with increasing doping concentration, but decreased at higher concentrations. These results suggest that europium-doped barium titanate holds significant promise for future electronic device applications due to its enhanced optical and dielectric properties.

X-Ray Diffraction and Structural Study of Ba1−xAExTiO3 Ceramics (AE: Ca, Mg and Sr for x=0,0.02,0.04,0.06 and 0.08)

By examining the X-ray powder diffraction data, the microstructure of the BaTiO3 ceramic modified by alkaline earth (AE) metals was characterized. Following profile fitting, the X-ray powder diffraction data of the powder mixtures were analyzed to estimate and evaluate the structural changes of the single-phase AE-modified BaTiO3. Each compound, as well as several polymorphic versions of the same compound, had a unique diffraction pattern, which was a coded representation of the crystal structure. The sole requirement for deciphering this data was the generation of exact data in order to enable phase identification, measurements of lattice parameters, atomic positions, etc. This work compares the various structural characteristics of void species nanostructure using X-ray diffraction with respect to the first sharp diffraction peak (FSDP) of different samples. Various parameters were computed using general expression and a comparison was presented in this paper.

Automatic center identification of electron diffraction with multi-scale transformer networks

Selected area electron diffraction (SAED) is a widely used technique for characterizing the structure and measuring lattice parameters of materials. An autonomous analytic method has become an urgent demand for the large-scale SAED data produced from in-situ experiments. In this work, we realize the automatic processing for center identification with a proposed deep segmentation model named the multi-scale Transformer (MS-Trans) network. This algorithm enables robust segmentation of the central spots by combining a novel gated axial-attention module and multi-scale feature fusion. The proposed MS-Trans model shows high precision and robustness, enabling autonomous processing of SAED patterns without any prior knowledge. The application on in-situ SAED data of the oxidation process of FeNi alloy demonstrates its capability of implementing autonomous quantitative processing.© 2017 Elsevier Inc. All rights reserved.

In situ transmission electron microscopy of temperature-dependent carbon nanofiber and carbon nanotube growth from ethanol vapor

Carbon nanofibers (CNFs) and carbon nanotubes (CNTs), which have been known for decades, recently gained significant commercial interests for various applications. However, the controlled synthesis of CNF/CNT has been hindered by the lack of nanoscale experimental evidence on how the growth temperature affects the growth process under real growth environment. We report the in situ transmission electron microscopy (TEM) experiments to directly observe Ni catalyzed CNF/CNT growth from alcohol precursor at near atmospheric pressure using a homebuilt bubbler system for the introduction of ethanol vapor. Using real time imaging, we revealed the active state of the Ni catalyst during the temperature-dependent CNF/CNT growth (600–800 °C). We observed the formation of CNFs starting from 600 °C and CNTs were formed at higher temperatures. The lattice parameter measurements pointed to an expansion of the Ni lattice as the temperature was increased, which we attribute to increased carbon solubility. The as-grown CNFs and CNTs were further characterized by XPS, Raman spectroscopy, and EELS, that allowed to have a highly reliable overall view of the structure changes with temperature. Results revealed that the change in structure with temperature was caused by the combined effects of increased carbon solubility and graphitization of the walls of the growing nanostructure. This increased carbon solubility in turn affected carbon diffusion and could be the reason for the change in structure from CNF to CNT at high temperature. Using in situ TEM we clearly revealed the effect of growth temperature on the structural changes.

Thermal expansion of 4H and 6H SiC from 5 K to 340 K

The first thermal expansion measurements of the 4H and 6H polytypes of SiC below room temperature are reported. The measurements were carried out on single-crystal specimens using high-resolution capacitive-based dilatometry. For both polytypes, the thermal expansion coefficient is below 2.4 × 10−6 1/K near room temperature. No phase transitions are observed over the 5 K to 340 K temperature range of the measurements. The thermal expansion coefficient α of 4H SiC is slightly anisotropic for measurements parallel and perpendicular to the crystallographic c axis with α|| about 2.2 × 10−7 1/K larger than α⊥ near room temperature. For 6H SiC no discernible anisotropy is observed. The differences in anisotropy can be understood by considering the ratio of hexagonal to cubic bonds of each polytype. Narrow regions with negative thermal expansion that are within the limits of our resolution (∼1×10−8) are observed in the vicinity of 30 K for both specimens. Tabulated data, polynomial fits, fit parameters, and comparison to data based on lattice-parameter measurements are provided.

Remote plasma-enhanced chemical vapor deposition of GeSn on Si: Material and defect characterization

Germanium–tin (GeSn) alloys at sufficiently high Sn concentration, above several atomic percent, are the only group IV semiconductor exhibiting a direct bandgap and have generated much recent interest for optoelectronic applications into the mid-infrared region. Because the large lattice mismatch between GeSn and Si results in considerable strain for thin layers and a high defect density for thicker strain-relaxed layers, most reported GeSn growths incorporate a Ge buffer layer rather than depositing directly on Si substrates. Published reports of GeSn growth directly on Si utilize specialized precursors such as higher order germanes (Ge2H6, Ge3H8, or Ge4H10) or SnD4. In this paper, we report GeSn films with up to 10.6% Sn grown directly on Si substrates by remote plasma-enhanced chemical vapor deposition using GeH4 and SnCl4 precursors. These alloys have been characterized in detail using x-ray diffraction (XRD), transmission electron microscopy (TEM), and Rutherford backscattering spectrometry with channeling (RBS-C), as well as Raman spectroscopy (RS) and optical microscopy. The films studied are almost fully relaxed, with small residual strain observed, particularly in thinner films, and contain a high interface density of misfit dislocations that increases with Sn concentration. The defect density decreases toward the surface. Good agreement is found between the various characterization methods for the Sn content (XRD and RBS-C), lattice parameter measurement (XRD and TEM), and defect characterization (RBS-C, TEM, and RS). Such characterization of GeSn grown directly on Si substrates is essential to allow growth parameters to be optimized for the realization of the attractive optoelectronic properties of these alloys.

Evaluation of Strain in 3C-SiC/Si Epiwafers from X-Ray Diffraction Measurements

X-Ray diffraction measurements of lattice parameter were performed for (111) and (100) oriented 3C-SiC/Si epiwafers. Strain of 3C-SiC epilayer and Si substrate were estimated and the result was compared with routine wafer deformation measurements. An unexpected discrepancy was observed between XRD and curvature measurements for (100) oriented samples.

Effect of prior [formula omitted] phase on precipitation kinetics of O-phase in advanced Ti2AlNb alloy

To study the influence of prior α2 phase on O-phase formation kinetics in β matrix, different isothermal heat treatments were performed at 876 and 780 °C using an advanced Ti2AlNb alloy with varying fraction of α2 phase. The kinetics of phase transformations was followed by electric resistivity measurements coupled to multi-scale microstructure characterization using scanning and transmission electron microscopy, energy dispersive X-ray spectrometry (EDS) and quantitative X-ray diffraction. It is revealed that the effect of α2 phase on the formation of O-phase depends on transformation temperature: while at 876 °C prior α2 precipitates lead to significantly slower formation of O-phase, as compared to α2 free alloy, the kinetics of O-phase formation is faster at 780 °C in the presence of α2 phase. Using EDS data as well as accurate measurements of lattice parameter of β phase, the diffusion character of O-phase formation in β matrix with and without prior α2 is shown for 876 °C while at 780 °C the diffusionless character of the O-phase formation is revealed for the beginning of the transformation followed by the partitioning of the alloying elements for prolonged treatment durations.

Lattice parameters of austenite and martensite during transformation for Fe–18Ni alloy investigated through in-situ neutron diffraction

Martensitic transformation is accompanied by the generation of microscale and macroscale internal stresses during cooling below the martensitic transformation start temperature. These internal stresses have been determined through X-ray or neutron diffraction, but the reported results are not consistent, probably because the measured lattice parameter is influenced not only by the internal stress but also by several factors, including solute elements and crystal defects. Therefore, in-situ neutron diffraction combined with dilatometry measurements during martensitic transformation and subsequent cyclic tempering were performed for an Fe–18Ni alloy. The phase strains calculated by lattice parameter variations show that a hydrostatic compressive strain in austenite and a tensile strain in martensite arose as the martensitic transformation progressed during continuous cooling or isothermal holding. However, the phase stresses of austenite and martensite estimated from these strains failed to hold stress balance law when dense crystal defects involved in the processes. After these crystal defects were removed by appropriate tempering, the stress balance law held well. Meanwhile, the phase stresses of austenite and martensite were changed to opposite, revealing their true identity. Furthermore, the lattice parameter of quenched full martensite and the specimen diameter were both decreased by tempering, demonstrating that there is a direct correlation among lattice parameter, specimen volume and dislocation density. As a result, various crystal defects in austenite and martensite, introduced by plastic accommodation, were suggested to affect their lattice parameters and then their phase stresses.

Nanoscale mapping of point defect concentrations with 4D-STEM

Vacancies are missing atoms in a crystalline material, and occur both at equilibrium (varying with temperature) and out of equilibrium such as when crystalline materials are damaged with radiation or corrosion. While we know of their importance, particularly regarding diffusive mechanisms, it is not straightforward to experimentally measure their concentration or to visualize them directly. Traditionally, measurements such as positron annihilation spectroscopy and to some degree X-ray diffraction can measure average concentrations, but generally lack the ability to visualize or quantify a heterogenous concentration of vacancies that can occur at the level of individual defects and microstructural features. Here, we present a method to map vacancy concentrations and their distribution using local lattice parameter measurements with a high-resolution electron microscope. Our method utilizes a Au thin film as a model to demonstrate the method via four-dimensional scanning transmission electron microscopy (4D-STEM) by correlating the differences between changes in lattice parameter and the volumetric thermal expansion during in situ heating experiments. The vacancy mapping methodology is also applied to non-equilibrium defects accumulated in pure Al via knock-on electron beam irradiation. Our method demonstrates the ability to map point defect concentrations in heterogeneous systems in situ with nanometer spatial resolution. The result is a technique that can provide direct measurements of vacancy concentrations at the level of individual defects in studies of materials in and out of equilibrium.

Effects of UV-ozone treatment on the performance of deep-ultraviolet photodetectors based on ZnGa2O4 epilayers

ZnGa2O4 epilayers have been grown on sapphire using the metalorganic chemical vapor deposition system. However, there is a trade-off between high conductivity and large defect density (oxygen vacancies) with the growth time of the growth of ZnGa2O4 epilayers. The ultraviolet (UV)-ozone treatment on the ZnGa2O4 epilayer at 100 ° C was proposed to reduce the number of oxygen vacancies in ZnGa2O4. The effect of UV-ozone treatment on the performance of ZnGa2O4 metal-semiconductor-metal (MSM) photodetector (PD) was evaluated. X-ray photoelectron spectroscopy analysis showed a decrease in the number of oxygen vacancies after UV-ozone treatment of ZnGa2O4. The measured lattice parameter near the surface around 10 nm of untreated ZnGa2O4 was 8.3434 ± 0.0120 A˙ and increased slightly to 8.3775 ± 0.0083 A˙ after UV-ozone treatment due to the decrease in oxygen vacancies. The dark current (at 5 V) of ZnGa2O4 PD was significantly reduced from 251 to 20.2 pA before and after UV-ozone treatment; it resulted in a substantial one-order enhancement in the on/off ratio of the PDs from 2.7 × 105 and 2.15 × 106 after the UV-ozone treatment. Furthermore, the rejection ratio also improved between 240 and 470 nm from 35 to 84 after UV-ozone treatment. The relationship between photocurrent and light intensity and the improvement in raising and falling time also showed the reduced density of trap states by UV-ozone treatment. This indicates that UV-ozone treatment can enhance the characteristics of ZnGa2O4 PDs for UV sensing applications.

Alloying Effects on the Stability of D022 γ”-Ni3M (M: Nb, Ta, V) Precipitates at Elevated Temperatures in Alloy 718 Type Ni-Based Alloys

The effects of alloying elements, M (M = Nb, Ta, and V), on the stability of D022 γ”-Ni3M precipitates at elevated temperatures were investigated in Ni-22Cr-based ternary and quaternary alloys using heat-treated diffusion-multiple and bulk samples with discrete chemical compositions, with a final goal to improve the precipitate stability and the temperature capability of the Alloy-718-type Ni-based superalloys. Our microstructural characterization indicated that a complete replacement of Nb with Ta stabilized the γ” precipitates at temperatures up to 800 °C. A partial replacement of Ta with V was found to stabilize the precipitates even at 900 °C. Differential scanning calorimetry and high-temperature X-ray diffraction experiments demonstrated that the D0a-Ni3M structure was stable at elevated temperatures in the Ni-Cr-Ta ternary system. Lattice parameter measurements at room temperature suggested that a partial replacement of Ta with V decreased the lattice misfit between the fcc γ matrix and the γ” precipitate phases along the a- and c-axes of the tetragonal γ” crystal structure. The improved γ” precipitate stability was discussed in terms of the chemical driving force, misfit strain, and diffusion kinetics viewpoints.

Compositional analysis of oxide-embedded III–V nanostructures

Nanowire growth enables creation of embedded heterostructures, where one material is completely surrounded by another. Through materials-selective post-growth oxidation it is also possible to combine amorphous oxides and crystalline, e.g. III–V materials. Such oxide-embedded structures pose a challenge for compositional characterization through transmission electron microscopy since the materials will overlap in projection. Furthermore, materials electrically isolated by an embedding oxide are more sensitive to electron beam-induced alterations. Methods that can directly isolate the embedded material, preferably at reduced electron doses, will be required in this situation. Here, we analyse the performance of two such techniques—local lattice parameter measurements from high resolution micrographs and bulk plasmon energy measurements from electron energy loss spectra—by applying them to analyse InP-AlInP segments embedded in amorphous aluminium oxide. We demonstrate the complementarity of the two methods, which show an overall excellent agreement. However, in regions with residual strain, which we analyse through molecular dynamics simulations, the two techniques diverge from the true value in opposite directions.

Studies on the Crystal Growth and Characterization of Large Size Sr:LCB Single Crystals

Extending the shortest second harmonic generation output wavelength of nonlinear optical crystals into the deep ultraviolet (UV) range is important for their application as frequency conversion devices for an advanced laser. The doping of ions with a large atomic number is believed to be an effective way to realize a shorter SHG output wavelength. In this work, large-sized Sr2+-doped La2CaB10O19 (Sr:LCB) crystals with nominal ratios of 10%, 15% and 30% were grown by the top-seeded solution growth method. The measured lattice parameters of the grown Sr:LCB are nearly the same as that of the LCB crystal, and the rocking curves reveal that the grown Sr:LCB crystals are of high quality. Sr: LCB crystals have a UV cut-off edge of 168 nm. The refractive index of the Sr:LCB crystals was measured, based on which the Sellmeier equations of the Sr:LCB crystals were fitted. The calculated shortest SHG output wavelength for Type I phase matching is 270.5 nm, which is 17.5 nm shorter than that of LCB crystals (288 nm). The characterization results demonstrate that Sr:LCB is a potential nonlinear optical crystal for the deep UV range.

Synthesis and oxidation behavior of Ti0.35Al0.65By (y = 1.7–2.4) coatings

The effect of B concentration on phase formation and oxidation resistance of (Ti0.35Al0.65)By coatings with y = 1.7, 2.0, 2.4 was investigated. Elemental B targets in radio frequency mode and a compound Ti0.4Al0.6 target in direct current mode were sputtered. The B concentration was varied systematically by adjusting the applied power to the respective magnetrons, while keeping the power supplied to the magnetron with the Ti0.4Al0.6 target constant. Measured lattice parameters and elastic properties are consistent with ab initio predictions. The oxidation resistance at 700 °C in air for up to 8 h was compared to a cathodic arc evaporated (Ti0.37Al0.63)0.49N0.51 coating with an Al/Ti ratio of 1.69 ± 0.20 which is very similar to 1.84 ± 0.40 for the boride coatings. Scanning transmission electron microscopy imaging revealed oxide scale thicknesses of 39 ± 7 and 101 ± 25 nm for (Ti0.35Al0.65)B2.0 and (Ti0.37Al0.63)0.49N0.51 after 8 h, respectively. Hence, the close to stoichiometric diboride outperforms the nitride coating. This behavior can be understood based on composition and structure analysis of the oxide scales: While the protective layer on the diboride is primarily composed of Al and O, the porous oxide layer on the nitride coating contains Ti, Al and O.

The influence of OH content on elastic constants of topaz [Al2SiO4(F,OH)2

Abstract Topaz, Al2SiO4(OH)xF(2–x), may play a significant role in transporting water and fluorine into the Earth’s interior at subduction zones. Seismological detection of topaz gives us insights into the transport mechanisms of water and fluorine but requires a thorough understanding of its elastic properties. The influence of OH content on elastic constants of topaz has not been fully understood, though experimental and theoretical studies have been done on topaz with various OH contents. We thus determined elastic constants of topaz for five natural single-crystal specimens with different OH contents (x = 0.28~0.72) via the sphere resonance method at an ambient condition. Our determined C11, C22, C44, C66, C12, C23, and C31 increase with OH content while C33 and C55 decrease. For the change in OH molar content from 0.0 to 1.0, relatively large changes (>3.0%) are seen in C33 [8.0(6)%], C55 [4.9(6)%], and C22 [3.1(7)%]. The OH content dependence of elastic constants is qualitatively similar to that of theoretically determined values except for C11. The theoretical value of C11 decreases as the OH molar content increases from 0.0 to 1.0, whereas the experimental value of C11 slightly increases. Our elastic constants are significantly higher (>3%) than theoretically determined values, especially in diagonal components (Cii). The theoretical lower values must be related to the used lattice parameters, which are systematically larger than the measured lattice parameters. The theoretical approach should be modified to reproduce measured lattice parameters and lead to the agreement of theoretical and experimental elastic constants. Our results provide a clue to a better understanding of the elasticity of topaz and a basis for the seismological detection of subducted oceanic sediments.

On the impact of lattice parameter accuracy of atomistic simulations on the microstructure of Ni–Ti shape memory alloys

Ni–Ti is a key shape-memory alloy (SMA) system for applications, being cheap and having good mechanical properties. Recently, atomistic simulations of Ni–Ti SMAs have been used with the purpose of revealing the nano-scale mechanisms that control superelasticity and the shape-memory effect (SME), which is crucial to guide alloying or processing strategies to improve materials performance. These atomistic simulations are based on molecular dynamics (MD) modelling that relies on (empirical) interatomic potentials (IAPs). These simulations must reproduce accurately the mechanism of martensitic transformation and the microstructure that it originates, since this controls both superelasticity and the SME. As demonstrated by the energy minimization theory of martensitic transformations (Ball and James (1987 Arch. Ration. Mech. Anal. 100 13–52)), the microstructure of martensite depends on the lattice parameters of the austenite and the martensite phases. Here, we compute the bounds of possible microstructural variations based on the experimental variations/uncertainties in the lattice parameter measurements. We show that both density functional theory and MD lattice parameters are typically outside the experimental range, and that seemingly small deviations from this range induce large deviations from the experimental bounds of the microstructural predictions, with notable cases where unphysical microstructures are predicted to form. Therefore, our work points to a strategy for benchmarking and selecting IAPs for atomistic modelling of SMAs, which is crucial to modelling the development of martensitic microstructures and their impact on the SME.

Irradiation temperature monitoring with SiC for RPV steel at low fluence

Accurate knowledge of the irradiation temperature is a key concern in irradiations of reactor pressure vessel (RPV) steel. We report results of passive temperature monitoring of RPV steel with SiC. Two un-instrumented capsules containing RPV steel blocks were irradiated in Belgian Reactor 2, at SCK CEN in Belgium. Because un-instrumented capsules were used, the irradiation conditions (gamma heating and irradiation temperature) were calculated. To have experimental verification of the irradiation conditions each capsule contained a passive silicon carbide (SiC) temperature monitor. After irradiation the resistivity and the radiation-induced swelling (lattice parameter) is measured using x-ray diffraction (XRD). These measurements were repeated after annealing treatments to determine the peak irradiation temperature. The best method to determine the peak irradiation temperature with the lowest uncertainty in this study was the resistivity technique. Although lattice parameter measurements could be improved by using material without preferential orientation. Tensile tests of the RPV blocks were compared to a large available database of RPV material with the proper sensitivity towards neutron fluence and irradiation temperature to find the irradiation temperature of the RPV steel. The data showed a discrepancy between the temperature obtained from SiC and the temperature obtained from tensile tests. The temperature differences were discussed and rationalized by finite element modelling with respect to uncertainties in the helium gap between the capsule and the RPV steel block. The aluminium holder accounted for the temperature difference and the use of a steel holder is recommended for future similar irradiations to minimize the temperature difference between SiC and tensile specimens . In-depth analysis showed that when the irradiation temperature dropped at the end of the irradiation for a considerable time, the SiC temperature monitor had a memory effect. In this case the post-irradiation resistivity analysis showed two peak irradiation temperatures with a region of constant resistivity between the two.

A machine learning approach to predict thermal expansion of complex oxides

Although it is of scientific and practical importance, the state-of-the-art of predicting the thermal expansion of oxides over broad temperature and composition ranges by physics-based atomistic simulations is currently limited to qualitative agreements. We present an emerging machine learning (ML) approach to accurately predict the thermal expansion of cubic oxides with a dataset consisting of experimentally measured lattice parameters while using the metal cation polyhedron and temperature as descriptors. High-fidelity ML models that can accurately predict temperature- and composition-dependent lattice parameters of cubic oxides with isotropic thermal expansions have been successfully trained. The ML-predicted thermal expansions of oxides not included in the training dataset have shown good agreement with available experiments. The limitations of the current approach and challenges to go beyond cubic oxides with isotropic thermal expansion are also briefly discussed.