Grazing Incidence X-ray Diffraction Research Articles

Investigating the in-vitro bioactivity, biodegradability and drug release behavior of the newly developed PES/HA/WS biocompatible nanocomposites as bone graft substitute

The nucleation of carbonate-containing apatite on the biomaterials surface is regarded as a significant stage in bone healing process. In this regard, composites contained hydroxyapatite (Ca10(PO4)6(OH)2, HA), wollastonite (CaSiO3, WS) and polyethersulfone (PES) were synthesized via a simple solvent casting technique. The in-vitro bioactivity of the prepared composite films with different weight ratios of HA and WS was studied by placing the samples in the simulated body fluid (SBF) for 21 days. The results indicated that the the surface of composites containing 2 wt% HA and 4 wt% WS was completely covered by a thick bone-like apatite layer, which was characterized by Grazing incidence X-ray diffraction, attenuated total reflectance–Fourier transform infrared spectrometer, field emission electron microscopy and energy dispersive X-ray analyzer (EDX). The degradation study of the samples showed that the concentration of inorganic particles could not influence the degradability of the polymeric matrix, where all samples expressed similar dexamethasone (DEX) release behavior. Moreover, the in-vitro cytotoxicity results indicated the significant cyto-compatibility of all specimens. Therefore, these findings revealed that the prepared composite films composed of PES, HA, WS and DEX could be regarded as promising bioactive candidates with low degradation rate for bone tissue engineering applications.

Interactions of Brominated Flame Retardants with Membrane Models of Dehalogenating Bacteria: Langmuir Monolayer and Grazing Incidence X-ray Diffraction Studies.

Brominated flame retardants (BFRs) are small organic molecules containing several bromine substituents added to plastics to limit their flammability. BFRs can constitute up to 30% of the weight of some plastics, which is why they are produced in large quantities. Along with plastic waste and microplastic particles, BFRs end up in the soil and can easily leach causing contamination. As polyhalogenated molecules, multiple BFRs were classified as persistent organic pollutants (POPs), meaning that their biodegradation in the soils is especially challenging. However, some anaerobic bacteria as Dehaloccocoides can dehalogenate BFRs, which is important in the bioremediation of contaminated soils. BFRs are hydrophobic, can accumulate in plasma membranes, and disturb their function. On the other hand, limited membrane accumulation is necessary for BFR dehalogenation. To study the BFR-membrane interaction, we created membrane models of soil dehalogenating bacteria and tested their interactions with seven legacy and novel BFRs most common in soils. Phospholipid Langmuir monolayers with appropriate composition were used as membrane models. These membranes were doped in the selected BFRs, and the incorporation of BFR molecules into the phospholipid matrix and also the effects of BFR presence on membrane physical properties and morphology were studied. It turned out that the seven BFRs differed significantly in their membrane affinity. For some, the incorporation was very limited, and others incorporated effectively and could affect membrane properties, while one of the tested molecules induced the formation of bilayer domains in the membranes. Thus, Langmuir monolayers can be effectively used for pretesting BFR membrane activity.

Synthesis of multiple layers of alternating ZnO and TiO2 using atomic layer deposition and their optical characterization

We report the optical characterization of bi-layer and quadri-layers of TiO2/ZnO transparent oxide films having a net thickness of 100 nm. The atomic layer deposition (ALD) was used to grow these multiple-layered films. We examined their optical properties to understand the impact of the number of layers. The grazing incidence X-ray diffraction (GIXRD) was used to assess the microstructure of the films, which showed that the ZnO layers were polycrystalline, while the TiO2 layers were (X-ray) amorphous. The optical transmission and reflection spectra of the investigated films were recorded in the range of 150–2500 nm at room temperature. The refractive index (n), extinction coefficient (k), real and imaginary parts of the dielectric constant, optical conductivity, and loss factor agree well with those of other amorphous oxides. It was established that the indirect allowed optical transitions are favorable and the optical gap (Eg) increases from 3.03 eV to 3.14 eV as the number of layers increases. The contribution of polarizability (ξ) and electrical susceptibility (χe) to the dielectric constant was also discussed. The relation between the relative density (D) and the porosity (Pro) with the crystalline quality, layer thickness, and the number of layers was also estimated. The results obtained from the study of TiO2/ZnO multilayer films indicate that multilayer thin films improve the quality of film crystallinity and optical properties with the increase of the layers numbers, and could guide the development of potential applications.

Unveiling Enhanced PEC Water Oxidation: Morphology Tuning and Interfacial Phase Change in α-Fe2O3@K-OMS-2 Branched Core-Shell Nanoarrays.

A simple fabrication method that involves two steps of hydrothermal reaction has been demonstrated for the growth of α-Fe2O3@K-OMS-2 branched core-shell nanoarrays. Different reactant concentrations in the shell-forming step led to different morphologies in the resultant composites, denoted as 0.25 OC, 0.5 OC, and 1.0 OC. Both 0.25 OC and 0.5 OC formed perfect branched core-shell structures, with 0.5 OC possessing longer branches, which were observed by SEM and TEM. The core K-OMS-2 and shell α-Fe2O3 were confirmed by grazing incidence X-ray diffraction (GIXRD), EDS mapping, and atomic alignment from high-resolution STEM images. Further investigation with high-resolution HAADF-STEM, EELS, and XPS indicated the existence of an ultrathin layer of Mn3O4 sandwiched at the interface. All composite materials offered greatly enhanced photocurrent density at 1.23 VRHE, compared to the pristine Fe2O3 photoanode (0.33 mA/cm2), and sample 0.5 OC showed the highest photocurrent density of 2.81 mA/cm2. Photoelectrochemical (PEC) performance was evaluated for the samples by conducting linear sweep voltammetry (LSV), applied bias photo-to-current efficiency (ABPE), electrochemical impedance spectroscopy (EIS), incident-photo-to-current efficiency (IPCE), transient photocurrent responses, and stability tests. The charge separation and transfer efficiencies, together with the electrochemically active surface area, were also investigated. The significant enhancement in sample 0.5 OC is ascribed to the synergetic effect brought by the longer branches in the core-shell structure, the conductive K-OMS-2 core, and the formation of the Mn3O4 thin layer formed between the core and shell.

Enhancing ferroelectricity in HfAlOx-based ferroelectric tunnel junctions: A comparative study of MFS and MFIS structures with ultrathin interfacial layers

This study explores the potential advantages of metal–ferroelectric–insulator–semiconductor (MFIS) structures compared with established metal–ferroelectric–semiconductor (MFS) and metal–ferroelectric–metal structures in the context of nonvolatile memory devices. Despite the superior performance of MFS structures in terms of electric field maintenance, switching speed, and power consumption, the presence of interface-related issues between the ferroelectric material and the semiconductor may degrade device performance. We propose an MFIS structure incorporating ultrathin interfacial layers (ILs) of SiO2, HfO2, and ZrO2 to address these issues. These insulator layers enhance device endurance by reducing physical stress and trap density at the interface, thereby improving electrical performance and long-term stability. Moreover, the presence of an IL reduces charge leakage between the ferroelectric layer and semiconductor, contributing to the resolution of the sneak path current problem. An additional feature of MFIS devices is their self-rectifying behavior, simplifying circuit design and manufacturing processes by eliminating the need for an external rectification circuit, consequently reducing costs. Through a series of experiments, this study evaluates the performance of the MFIS structure, investigates the ferroelectric properties of HfAlOx-based FTJs, and examines the conduction mechanism of the MFIS structure. By comparing the o-phase of MFS, SiO2, HfO2, and ZrO2 devices via grazing incidence X-ray diffraction (GIXRD) and using the positive-up-negative-down method to extract polarization and coercive voltage, we provide a comprehensive investigation of the impact of ultrathin ILs on ferroelectric properties. This research aims to offer valuable insights into the advancement of memory device technologies, presenting the MFIS structure as a promising platform for next-generation memory technologies. Further sections will elaborate on the experimental setup, methodology, and detailed study findings.

Towards wake-up free ferroelectrics and scaling: Al-doped HZO and its crystallographic texture

Ferroelectric (FE) hafnium zirconium oxide (HZO) is an excellent candidate for data storage applications. However, it has some reliability limitations such as imprint and retention. Herein, we explore Al doping of HZO to overcome these limitations. FE behavior is tuned by the aluminum (Al) concentrations in the films and by annealing temperature. A correlation is done between electrical behavior, crystallographic texture, and FE phases determined by grazing-incidence X-ray diffraction (GIXRD) measurements. Reduced coercive field (2Ec) values and wake-up free HZO-based ferroelectrics are explored. We show the tunability of remanent polarization (2Pr) and 2Ec with respect to Al-doping concentration and anneal temperature, hence crystallographic texture.

UV/Ozone-Treated and Sol-Gel-Processed Y2O3 Insulators Prepared Using Gelation-Delaying Precursors.

In this study, a Y2O3 insulator was fabricated via the sol-gel process and the effect of precursors and annealing processes on its electrical performance was studied. Yttrium(III) acetate hydrate, yttrium(III) nitrate tetrahydrate, yttrium isopropoxide oxide, and yttrium(III) tris (isopropoxide) were used as precursors, and UV/ozone treatment and high-temperature annealing were performed to obtain Y2O3 films from the precursors. The structure and surface morphologies of the films were characterized via grazing-incidence X-ray diffraction and scanning probe microscopy. Chemical component analysis was performed via X-ray spectroscopy. Electrical insulator characteristics were analyzed based on current density versus electrical field data and frequency-dependent dielectric constants. The Y2O3 films fabricated using the acetate precursor and subjected to the UV/ozone treatment showed a uniform and flat surface morphology with the lowest number of oxygen vacancy defects and unwanted byproducts. The corresponding fabricated capacitors showed the lowest current density (Jg) value of 10-8 A/cm2 at 1 MV/cm and a stable dielectric constant in a frequency range of 20 Hz-100 KHz. At 20 Hz, the dielectric constant was 12.28, which decreased to 10.5 at 105 Hz. The results indicate that high-quality, high-k insulators can be fabricated for flexible electronics using suitable precursors and the suggested low-temperature fabrication methods.

Enhancement of remnant polarization in ferroelectric HfO2 thin films induced by mechanical uniaxial tensile strain after the crystallization process

The effect of strain on the ferroelectricity of HfO2 thin films after crystallization was investigated by applying uniaxial mechanical strains to Au/HfO2/TiN metal–ferroelectric–metal (MFM) capacitors. The remnant polarization (2P r) of MFM capacitors increased when tensile strain was applied during polarization switching. This phenomenon should not be attributed to phase transformation from the non-ferroelectric to the ferroelectric phase, taking account of the fast relaxation of 2P r after removal of the mechanical strain and the fact that the crystal structure of HfO2 thin films evaluated by grazing incidence X-ray diffraction measurement was not changed by the tensile strain.

Oxygen plasma treatment WO3 nanorods for Improvement H2S gas sensing

Herein, the oxygen (O2) plasma has been used to post-treat tungsten oxide (WO3) nanorods to improve the sensing performance of the H2S gas sensor. The reactive DC magnetron sputtering process with the glancing-angle deposition (GLAD) technique was used to prepare the WO3 nanorods. After deposition, the WO3 nanorod thin films were treated with O2 plasma at different treatment power from 100 – 200 W. The physical structure of as-deposition and treated WO3 nanorod thin films was investigated crystal structure and morphology by grazing incident X-ray diffraction (GIXRD), field-emission scanning electron microscope (FE-SEM), and high-resolution transmission electron microscope (HRTEM). The result indicated that the WO3 nanorod structure transformed to the monoclinic polycrystalline phase. FE-SEM and HRTEM observed slight changes in the shape of the WO3 nanorods. The H2S sensing properties were measured at 10 ppm at 150 – 350°C operating temperatures. At an operating temperature of 200 °C, the response to H2S of O2 plasma treated WO3 nanorods is increased by a factor of 5 – 15, and the maximum response to H2S is 15. The results showed that the O2 plasma treatment process improved the sensing response of the WO3 nanorods.

Semiquantum versus quantum methods for grazing-incidence fast-atom diffraction: Influence of the wave-packet size

Semiquantum versus quantum methods for grazing-incidence fast-atom diffraction: Influence of the wave-packet size

Effect of substrate temperature on growth mechanism and properties of PEALD-MgO dielectric films for amorphous-IGZO TFTs

Magnesium oxide (MgO) films have been prepared by plasma enhanced atomic layer deposition with bis(cyclopentadienyl)magnesium precursor and oxygen plasma reactant at substrate temperature between 150 °C and 450 °C. The structural, morphological, optical, and chemical properties of the prepared MgO films were studied by spectroscopic ellipsometer, grazing incidence X-ray diffraction (GIXRD), field emission scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS). The electrical property of MgO film was obtained by performing capacitance-voltage measurement on the Al/MgO/Si structures. The experiment result shows that growth rate of MgO film decreases with the deposition temperature increased. GIXRD analysis presented that MgO films are cubic with predominantly (220) crystal orientation. XPS analysis shows that ratio of Mg/O is highest in MgO film prepared at 350 °C. To illustrate the possible applications of MgO film as a gate dielectric in thin film transistor (TFT), indium‑gallium‑zinc oxide (IGZO) was used as channel layer. The optimized IGZO/MgO TFT showed an electron mobility of 1.63 cm2/Vs, an on/off current ratio of 106, and a subthreshold swing of 0.50 V/decade at a low operation voltage of −0.11 V.

The subtle usage of NH4BF4: Facile and economical fabrication of Ti black surface for enhanced optical absorption performance

The Ti black surface has been widely used in aerospace and photocatalysis for many years. However, the preparation technique for the Ti black surface has several disadvantages, such as a complex process, high cost and safety concerns. In this study, a new chemical immersion method using the mixed aqueous solution of 0.715 mol/L NH4BF4 and 0.004 mol/L HF was proposed to prepare a uniform Ti black surface, which is very facile, economical and efficient. Due to the etching of HF, the light-trapping nanostructure was formed on Ti surface. Grazing incidence X-ray diffraction (GIXRD) and X-ray photoelectron spectroscopy (XPS) observations indicated that the black surface was covered by the film mainly composed of TiOx, Ti(OH)x, and TiH2. The diffuse reflectance spectra demonstrated that the black surface exhibited great optical absorption performance with the maximum reflectance of 7.6 % to the UV–visible light and 35.3 % to the near-infrared light. The as-fabricated TiOx film with narrower bandgap could be contributed to the doping of Ti3+ and F− ions. The presence of F− ions in the film prevented the Ti3+ ions in the bulk of TiOx from being oxidized. The combined contribution of light-trapping nanostructure and TiOx film enhanced the optical absorption performance of Ti surface.

Effect of Annealing on Stress, Microstructure, and Interfaces of NiV/B4C Multilayers

The functionality and reliability of nanoscale multilayer devices and components are influenced by changes in stress and microstructure throughout fabrication, processing, and operation. NiV/B4C multilayers with a d-spacing of 3 nm were prepared by magnetron sputtering, and two groups of annealing experiments were performed. The stress, microstructure, and interface changes in NiV/B4C after annealing were investigated by grazing-incidence X-ray reflectometry (GIXR), grazing-incidence X-ray diffraction (GIXRD), X-ray diffuse scattering, and grazing-incidence small-angle X-ray scattering (GISAXS). The temperature dependence experiments revealed a gradual shift in the multilayer stress from compression to tension during annealing from 70 °C to 340 °C, with the stress approaching near-zero levels between 70 °C and 140 °C. The time-dependent experiments indicated that most of the stress changes occurred within the initial 10 min, which showed that prolonged annealing was unnecessary. Combining the X-ray diffraction and X-ray scattering measurements, it was found that the changes in the thickness, interface roughness, and lateral correlation length, primarily due to crystallization, drove the changes in stress and microstructure.

Modification induced by 120 MeV Ag ion irradiation in ZnS

We report the structural, morphological, and optical properties of ZnS thin films before and after swift heavy ion (SHI) irradiation of 120 MeV Ag ions. These films were deposited by the spin coating method on the glass substrate and irradiated at various ion fluencies from 1 × 1011 to 1 × 1013 ions/cm2. The Grazing Incidence X-ray diffraction (GIXRD), Scanning electron microscopy (SEM), UV–visible transmittance, Photoluminescence (PL), and Raman Spectroscopy were used to characterize these ZnS thin films. The GIXRD patterns show a mixed phase of cubic and hexagonal structure after the ion irradiation. The crystallite sizes of pure and irradiated films are significantly modified. Raman spectroscopy shows a slight increase in the intensity of the 3LO mode of ZnS on irradiation. The SEM image shows nanoflake-like structures in pristine, and the irradiated thin films depict various morphologies (rod, platy, and sphere-like). UV–visible shows a cut-off wavelength at 339 nm and the spectra are blue-shifted with the increase in ion fluence. The Tauc plots reveal the increase in the band gap. The intensity of PL decreases with ion irradiation. Hence the analytical results show that the structural and optical properties of ZnS thin films are altered on swift heavy ion irradiation which may have potential applications in optoelectronic applications.

Aggregation induced strong photoluminescence at room temperature in large-area C8BTBT thin films

Study of optical properties of 2,7-dioctyl[1]benzothieno[2,3-b]benzothiophene (C8BTBT) is promising for applications in low-cost and flexible optoelectronic devices. Here, we systematically investigated the thickness dependent structural and photophysical properties of large-area C8BTBT films. The large-area C8BTBT thin films of different thickness below 80 nm were prepared by off-centre spin coating method. Grazing incidence X-ray diffraction measurements confirm the highly crystalline nature of the thin films and reveal that crystal coherence length increases with increase of film thickness. The film morphology and its thickness were studied using atomic force microscopy. Further, optical absorption and emission behaviors of the thin films were analyzed. The results show strong ultraviolet (UV) emissions at room temperature. The photoluminescence behaviour of higher-thickness films differs from that of lower-thickness films. The thickness dependent UV emission spectra are explained in terms of defects and aggregation behavior of C8BTBT thin films. We determine the impact of thickness and aggregation (J- and H-type) on emission behaviors of the C8BTBT thin films. Our findings open a new avenue for the future optimization and prospective applications in photonics based on two-dimensional organic semiconductors.

Transistors with ferroelectric ZrXAl1−XOY crystallized by ZnO growth for multi-level memory and neuromorphic computing

Ferroelectric (FE) field-effect transistors are interesting for their non-destructive readout characteristic and energy efficiency but are difficult to integrate on silicon platforms. Here, FE ZrXAl1−XOY (ZAO) is demonstrated by compressive strain in contact with ZnO. The metal-ferroelectric-semiconductor-metal capacitor exhibits a substantial remnant polarization of 15.2 µC cm−2, along with a bowknot-like anti-clockwise hysteresis in the capacitance curves. The FE-ZAO gated ZnO thin-film transistor presents a large memory window (3.84 V), low subthreshold swing (55 mV dec−1), high ION/IOFF ratio (≈108), and low off-state current (≈1 pA). The grazing incidence X-ray diffraction and scanning transmission electron microscopy analyses reveal the ferroelectric rhombohedral phase (space group R3m) in the nanocrystal ZAO, containing an angle of ≈71.7° between the [111] and [11-1] directions with d111-spacing of 3.037 Å and d11-1-spacing of 2.927 Å. Finally, the memory and neuromorphic applications are analyzed by demonstrating multi-level memory and synaptic weight performance with a high learning accuracy of 91.82%.

Effect of titanium interlayer configurations on residual stresses and performance of titanium/titanium nitride multilayer coatings

Multilayer coatings provide an effective measure to control and optimise of residual stresses, enhance coating adhesion, fracture toughness, wear and corrosion resistance of coating system. In this study, we designed and produced bi-layer and four-layer titanium/titanium nitride magnetron sputtered coating configurations by altering the position of the interlayer. The in-plane residual stresses in different coating configurations are measured by multiple peak grazing incidence X-ray diffraction techniques. Subsequently, the effect of different compressive residual stresses on adhesion, mechanical properties, wear and corrosion resistance of coatings are investigated. Results show that the position of interlayer in multilayer coating configuration has a great impact on relaxation of residual stresses. The residual stresses are relieved by 26% and 46% by lowering the position of titanium interlayer from 800 nm at the top to 1000 nm and 1200 nm, respectively. The nanoindentation hardness is decreased by 11% and 13%, respectively. The wear rate of multilayer coating having interlayer position at 800 and 1000 nm from the top is ≈ 23% lower compared to bilayer however it is increased by ≈ 50% when interlayer coatings position changed to 1200 nm from the top. The interposition of interlayer in multilayer coating configurations decreased the corrosion current density by ≈ 50%. All multilayer coatings including higher residual stresses show better adhesion to the substrate compared to bilayer coatings which shows severe delamination.

Si(111) islands on β-phase Si(111)√3 × √3R30°-Bi

β-phase √3 × √3R30°-bismuth (Bi) on silicon (Si)(111)7 × 7 surface has been exploited as a template for growing Si films. Two-dimensional Si islands with √3 × √3 reconstruction, parallel to that of Si(111)√3 × √3R30°-Bi, have been resolved by means of scanning tunneling microscopy, grazing-incidence X-ray diffraction (XRD) and low electron energy diffraction. Auger electron spectroscopy and scanning tunneling spectroscopy gave interesting electronic features on two-dimensional Si islands, with the evidence of a reduced band gap to ~0.55 eV, related to the presence of the underneath Bi layer, and atomic structural properties typical of Si(111). These experimental findings fully confirm the recently reported calculation based on the first-principles density functional theory, on the prediction of Si(111) growth on top of β-phase √3 × √3R30°-Bi/Si(111)7 × 7 reconstruction, shedding new light on silicon structures.

Investigation of the damage behavior in SiC without any additives irradiated with Si ions by GIXRD, Raman and TEM

The SPS-prepared SiC without any additives was irradiated with 15.9MeV Si ions at room temperature and 500 ℃. The damage behavior was investigated by Grazing incident X-ray diffraction (GIXRD) spectroscopy, Raman spectroscopy and transmission electron microscopy (TEM). GIXRD and Raman spectra show that the disorder of SiC increases and the lattice swelling occurs with the increase of irradiation at room temperature. High temperature irradiation was associated with the reduction of swelling and the recovery of disorder. TEM results indicate that at room temperature, with increasing dose, the material transitions from slight amorphization to complete amorphization. The amorphization dose is estimated to be around 1.2dpa. The combined effects of stacking faults, high-energy ions accompanied by higher electronic energy loss inducing displacement cascades, and cascade-induced annealing delay damage accumulation, leading to an increased critical dose for amorphization. Moreover, the transient thermal spikes due to higher electronic energy loss, leading to defect annealing and the formation of Frank loops at lower irradiation temperatures.

The impact of post-deposition annealing durations on the formation of Tb4O7 passivation layer on silicon substrate

In this study, we have effectively utilized radio frequency (RF) sputtering to sputter the Tb4O7 passivation layer on an n-type silicon (Si) substrate in an argon (Ar) ambient. Various characterization approaches were used to investigate the impact of varying annealing durations on structural, morphological, compositional, and optical properties. The grazing incidence X-ray diffraction (GIXRD) pattern confirmed that all investigated Tb4O7 passivation layers (as grown) and annealed at (15, 30, and 45 min) showed a crystalline structure, respectively. As observed, the sample annealed for 30 min attained the highest crystallinity, around 39.51 nm. Surface morphology analysis revealed different surface structures in response to different annealing durations when observed using the field emission scanning electron microscopy (FESEM) technique. Atomic force microscopy (AFM) was utilized to investigate the top surface of the examined samples, and a higher surface roughness of around 2.37 nm was obtained for the sample annealed for 30 min. The band gap energies (Eg) were estimated by applying the Kubelka-Munk (KM) approach for all the investigated samples, and the obtained values were within a range between (1.94–3.07 eV) earlier reported in the literature. Previous studies have shown that the Tb4O7 passivation layer deposited onto Si substrates using RF sputtering and then annealed for 5 min at 900 °C in an Ar atmosphere, resulted in the formation of a highly crystalline passivation layer. However, there is a lack of a clear explanation for the observation, and the authors mainly concentrated on the electrical properties of the Tb4O7 material. This inspired us to carry out this study to investigate the impact of various annealing durations on the formation of Tb4O7 passivation layers, focusing on their structure, composition, morphology, and optical properties.