Grazing Incidence X-ray Diffraction Research Articles

Exploring radiation damage in (Hf0.2Zr0.2Ta0.2Ti0.2Nb0.2)C high-entropy carbide ceramic: Integrating experimental and atomistic investigations

This study investigates the intricate mechanisms that govern irradiation damage in high-entropy ceramic materials. Specifically, we synthesized (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy carbide ceramics (HECC) with a single-phase rock-salt structure using spark plasma sintering. These ceramics were then subjected to irradiation with 1.08 MeV C ions, resulting in a dose of 7.2 dpa (dpa: displacements per atom) at both room temperature (RT) and 500 °C. To understand the resulting damage structure, we analyzed bulk irradiated HECC samples using Grazing Incidence X-ray Diffraction (GIXRD) and Transmission Electron Microscope (TEM) at both irradiation temperatures. GIXRD analysis revealed an average tensile strain out-of-plane of 0.16% for RT irradiation and 0.14% for irradiation at 500 °C. In addition, TEM analysis identified a buried damaged band, approximately 970 nm thick, under both irradiation temperatures. By employing the bright field TEM imaging technique under kinematic two-beam conditions, dislocation loops of both a/3 〈111〉{111} and a/2 〈110〉{110} types within the damaged band were observed. Furthermore, our analysis indicated an increase in the average size of the total dislocation loops within the band from 1.2 nm to 1.4 nm as the density decreased. Importantly, no amorphization, precipitates, or voids were detected in the damaged band under both irradiation temperatures. Density functional theory (DFT) simulations indicated that carbon predominantly resides in 〈110〉 split interstitial sites causing lattice expansion, while vacancies, particularly Nb, induced compression along the c-axis. Carbon atoms tend to bond when collectively present in the <110> split interstitial sites, contributing to the formation of interstitial loops.

Characterization of MoS2 films via simultaneous grazing incidence X-ray diffraction and grazing incidence X-ray fluorescence (GIXRD/GIXRF)

Physical vapor deposited (PVD) molybdenum disulfide (nominal composition MoS2) is employed as a thin film solid lubricant for extreme environments where liquid lubricants are not viable. The tribological properties of MoS2 are highly dependent on morphological attributes such as film thickness, orientation, crystallinity, film density, and stoichiometry. These structural characteristics are controlled by tuning the PVD process parameters, yet undesirable alterations in the structure often occur due to process variations between deposition runs. Nondestructive film diagnostics can enable improved yield and serve as a means of tuning a deposition process, thus enabling quality control and materials exploration. Grazing incidence X-ray diffraction (GIXRD) for MoS2 film characterization provides valuable information about film density and grain orientation (texture). However, the determination of film stoichiometry can only be indirectly inferred via GIXRD. The combination of density and microstructure via GIXRD with chemical composition via grazing incidence X-ray fluorescence (GIXRF) enables the isolation and decoupling of film density, composition, and microstructure and their ultimate impact on film layer thickness, thereby improving coating thickness predictions via X-ray fluorescence. We have augmented an existing GIXRD instrument with an additional X-ray detector for the simultaneous measurement of energy-dispersive X-ray fluorescence spectra during the GIXRD analysis. This combined GIXRD/GIXRF analysis has proven synergetic for correlating chemical composition to the structural aspects of MoS2 films provided by GIXRD. We present the usefulness of the combined diagnostic technique via exemplar MoS2 film samples and provide a discussion regarding data extraction techniques of grazing angle series measurements.

Two-step process for the fabrication of direct FLG\\MoS2 heterostructures

MoS2 has proven its efficacy in flexible electronics, transistor devices, and various biological and chemical applications. However, it is still challenging to achieve large-area MoS2 monolayers with desired material quality and electrical properties to fulfill the requirement for practical applications. Moreover, the main strategy for the preparation of a 2D heterostructure it is based on the sequential stacking of the layered materials using wet or dry transfer methods which introduces many defects. This paper presents an economically viable and straightforward two-step methodology to obtain MoS2 thin films, encompassing magnetron sputtering deposition of Mo and subsequent annealing in a sulfur-rich environment. This approach successfully yielded MoS2 thin films on Si\\SiO2 substrates. Additionally, heterostructures consisting of few layer graphene (FLG) and MoS2 were directly obtained using the same method. The utilization of grazing incidence X-ray diffraction verified the formation of the hexagonal MoS2 phase, a finding further confirmed by Raman spectroscopy. X-ray photoelectron spectroscopy (XPS) investigations revealed the successful sulfurization process, with surface-bound oxides forming only subsequent to air exposure. Comprehensive assessment involving X-ray reflectivity, atomic force microscopy and XPS collectively inferred the fabrication of thin films comprised of a small number of MoS2 layers covering the entire substrate. Electrical assessments exhibited an electrical hysteresis, demonstrating its potential for memristor applications. Overall, this study outlines a cost-effective fabrication method for producing nanoscale MoS2 thin films with excellent properties, avoiding the use of toxic gases such as H2S. These findings contribute to the potential development of cutting-edge applications.

Cu-doped NiO thin film's structural, optical, and electrical properties and its negative absorption behaviour in the Infra-Red region

NiO undoped and Cu-doped thin films on FTO-coated glass (fluorine-doped tin oxide) are prepared by employing the sol-gel spin coating method. The Cu-doping effect was observed in all the characterized reports such as absorption, transmittance, field emission scanning electron microscope (FESEM), Grazing Incidence X-ray Diffraction (GIXRD), photoluminescence (PL), Raman spectra, current-voltage measurement (IV), and X-ray photoelectron spectroscopy (XPS). Enhancement in electrical conductivity due to Cu doping and IR illumination has been found. Band gap can also be tuned by varying doping concentrations. One new phenomenon called negative absorption (NA) has been found while investigating the optical properties in the infrared (IR) region for both undoped and Cu-doped NiO on the FTO substrate, which opens a new door for advanced research. The multifarious properties of NiO thin films offer various applications in many different fields.

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.

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.

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.

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.

Enhanced remnant polarization in ferroelectric Hf0.5Zr0.5O2 thin film capacitors through Mo top electrode by post-metallization annealing treatment

Zr-doped HfO2 (Hf0.5Zr0.5O2) ferroelectric thin films have garnered considerable attention due to their appealing attributes, including a large bandgap (>5 eV), low crystallization temperature, and compatibility with CMOS technology. In this study, we present the achievement of a substantial remnant polarization in ferroelectric Hf0.5Zr0.5O2 thin films, fabricated through atomic layer deposition, with Mo and TiN serving as the top and bottom electrodes, respectively. The Mo/Hf0.5Zr0.5O2/TiN capacitor exhibited commendable ferroelectric behavior and demonstrated high endurance within a thermal budget ranging from 400 to 500 °C. Leveraging the relatively low thermal expansion coefficient of the Mo top electrode facilitated the induction of in-plane tensile strain, fostering an increased formation of the ferroelectric orthorhombic phase within the Hf0.5Zr0.5O2 layer. Elevating the post-metallization annealing temperature to 500 °C yielded a substantial increase in 2Pr (≈54 μC/cm2) with excellent endurance exceeding 106 cycles. The influence of annealing temperature on the morphological and structural properties of Hf0.5Zr0.5O2 thin films was comprehensively analyzed through atomic force microscopy and grazing incidence X-ray diffraction analysis.

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 15.9 MeV Si ions at room temperature and 500 °C. 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 1.2 dpa. 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.

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.

Strain-drived giant flexoelectric field and its efficient modulation in (111) BiFeO3 films

Flexoelectric effect in ferroelectric epitaxy films has attracted significant attention due to its theoretical and application potentials. However, the origin and control of flexoelectric field is not yet fully understood. In this study, we investigated the surface structure of single-domain epitaxial BiFeO3 films with a (111) orientation using grazing incidence X-ray diffraction and X-ray reflection methods. We observed large strain gradient on the surface of the BiFeO3 films, which produces a giant flexoelectric field up to 82.55 MV/m at the surface of 15 nm thick BiFeO3 film. Additionally, we discovered the presence of a surface layer with lower electron density than that of the underlying BiFeO3 layer, which is related to the flexoelectric field. Moreover, with increased film thickness, we found the strain distribution along growth direction of the film is changed, thereby leads to the decreased flexoelectric field and increasing thickness of the surface layer respectively. These findings convinced the coupling between the strain state and surface structure, changing the thickness of the ferroelectric film and consequently the strain state is an efficient way to adjust the flexoelectric field and the surface structure.

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.