Thin Samples Research Articles

Disorder induced band gap lowering in kesterite type Cu2ZnSnSe4 and Ag2ZnSnSe4: a first-principles and special quasirandom structures investigation

Quaternary chalcogenides, i.e. Cu2ZnSnS4, crystallising in the kesterite crystal structure have already been demonstrated as potential building blocks of thin film solar cells, containing only abundant elements and exhibiting power conversion efficiencies of about 14.9% so far. However, due to the potential presence of several structurally similar polymorphs, the unequivocal identification of their ground state crystal structures required the application of more elaborate neutron diffraction experiments. One particular complication arose from the later identified Cu–Zn disorder, present in virtually all thin film samples. Subsequently, it has been shown experimentally that this unavoidable Cu–Zn disorder leads to a band gap lowering in the respective samples. Additional theoretical investigations, mostly based on Monte-Carlo methods, tried to understand the atomistic origin of this disorder induced band gap lowering. Here, we present theoretical results from first-principles calculations based on density functional theory for the disorder induced band gap lowering in kesterite Cu2ZnSnSe4 and Ag2ZnSnSe4, where the Cu–Zn and Ag–Zn disorder is modelled via a supercell approach and special quasirandom structures. Results of subsequent analyses of structural, electronic, and optical properties are discussed with respect to available experimental results, and will provide additional insight and knowledge towards the atomistic origin of the observed disorder induced band gap lowering in kesterite type materials.

A new framework for soft x-ray transient gratings

The capability to use extreme ultraviolet (EUV) light for generating transient gratings (TGs) has enabled the study of thermoelastic and magnetic dynamics at the nanoscale, in thin solid samples and surfaces, without the need of specially modifying them. However, the current mirror-based setup for generating EUV TG limits both its extension to the soft x-ray photon energy range and the attainment of few femtosecond time-resolution. Here we propose to overcome these limitations with an alternative experimental scheme based on diffractive optical elements that has become feasible with the current technology. In addition, some aspects of the discussed setup may facilitate the implementation of the EUV TG approach at table-top high-harmonic generation sources.

Structural, electronic and superconducting properties of room temperature deposited VN[formula omitted] thin films

In recent years, vanadium mononitride (VN) thin films have emerged for their multifaceted functionalities e.g. as electrodes in battery and supercapacitors, as catalysts for hydrogen and oxygen evolution reactions, as superconductors for hot-electron bolometer detectors. In this study, we investigate the structural, electronic and superconducting properties of polycrystalline VNx thin films synthesized at room temperature using a reactive dc magnetron sputtering. The structural evolution of VNx samples with increase in partial N2 gas flow (RN2) during the reactive sputtering and corresponding change in the oxidation states were systematically studied. At a first glance, no visible changes appear in the lattice parameters within RN2= 5–50% samples. Despite this, only RN2 = 5 and 10% samples exhibit superconductivity. Probing the electronic structure around the V L-edges and O, N K-edge again did not reflect any minimal changes in RN2 = 5–100% samples. Across the V K-edge, the oxidation state was also found to be similar. However, the ambiguity was resolved from the Fourier transformed EXAFS spectra immediately revealing presence of a higher number of cationic vacancies. These vacancies drive the VNx system towards poor metals exhibiting dρ/dT = negative in the temperature dependent resistivity. This is in sharp contrast to the previous reports so far exhibiting positive slopes evident for metals. The present work insights on several ambiguities observed for the first time in the V-N system. The work further emphasizes the need to perform a similar study on epitaxially grown VNx thin film samples with reduced defects.

Use of plasma process diagnostic sensors for the monitoring of in situ dry cleaning of plasma enhanced chemical vapor deposition chamber

A potential source of particle contamination due to poorly maintained PECVD chamber condition forces to perform in situ dry cleaning also actively employed before the wet-cleaning chamber maintenance period. In this paper, we demonstrate the use of plasma process diagnostic sensors, optical emission spectroscope, and quadrupole mass spectrometer for in situ plasma monitoring of the dry-cleaning step. It is worthwhile to know the thin film residue on the chamber’s inner wall, but it is difficult to collect the deposited thin film sample from the wall since the preparation of the sample from the equipment is impossible. To alleviate the concern, we prepared silicon wafer samples mounted on the chamber sidewall over the prolonged exposure of the SiO2 deposition process, and the collected sensory data were investigated under the dry-cleaning condition. The residue film obtained through the experiment was characterized by Fourier transform infrared, x-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy. We found a useful insight into the chamber dry-cleaning end point detection application through residual gas analysis, and the results contribute to process engineers setting up the in situ dry-cleaning recipe to make sure that subsequent deposition can be consistently maintained.

Automated Whole Slide Imaging for Label-Free Histology Using Photon Absorption Remote Sensing Microscopy.

Pathologists rely on histochemical stains to impart contrast in thin translucent tissue samples, revealing tissue features necessary for identifying pathological conditions. However, the chemical labeling process is destructive and often irreversible or challenging to undo, imposing practical limits on the number of stains that can be applied to the same tissue section. Here we present an automated label-free whole slide scanner using a PARS microscope designed for imaging thin, transmissible samples. Peak SNR and in-focus acquisitions are achieved across entire tissue sections using the scattering signal from the PARS detection beam to measure the optimal focal plane. Whole slide images (WSI) are seamlessly stitched together using a custom contrast leveling algorithm. Identical tissue sections are subsequently H&E stained and brightfield imaged. The one-to-one WSIs from both modalities are visually and quantitatively compared. PARS WSIs are presented at standard 40x magnification in malignant human breast and skin samples. We show correspondence of subcellular diagnostic details in both PARS and H&E WSIs and demonstrate virtual H&E staining of an entire PARS WSI. The one-to-one WSI from both modalities show quantitative similarity in nuclear features and structural information. PARS WSIs are compatible with existing digital pathology tools, and samples remain suitable for histochemical, immunohistochemical, and other staining techniques. This work is a critical advance for integrating label-free optical methods into standard histopathology workflows.

Velocimetry of GHz elastic surface waves in quartz and fused silica based on full-field imaging of pump–probe reflectometry

This study reports an imaging method for gigahertz surface acoustic waves in transparent layers using infrared subpicosecond laser pulses in the ablation regime and an optical pump–probe technique. The reflectivity modulations due to the photoelastic effect of generated multimodal surface acoustic waves were imaged by an sCMOS camera illuminated by the time-delayed, frequency-doubled probe pulses. Moving the delay time between 6.0nsto11.5ns, image stacks of wave field propagation were created.Two representative samples were investigated: wafers of isotropic fused silica and anisotropic x-cut quartz. Rayleigh (SAW) and longitudinal dominant high-velocity pseudo-surface acoustic wave (HVPSAW) modes could be observed and tracked along a circular grid around the excitation center, allowing the extraction of angular profiles of the propagation velocity. In quartz, the folding of a PSAW was observed. A finite element simulation was developed to predict the measurement results. The simulation and measurement were in good agreement with a relative error of 2% to 5%.These results show the potential for fast and full-field imaging of laser-generated ultrasonic surface wave modes, which can be utilized for the characterization of thin transparent samples such as semiconductor wafers or optical crystals in the gigahertz frequency range.

Spin flop transitions and complex magnetic behaviour in CoMoO4 powders and [formula omitted]-CoMoO4 thin films

Magnetic measurements were made on α-CoMoO4 powder and β-CoMoO4 thin film samples. α-CoMoO4 powder showed antiferromagnetic ordering below 13 K and two sharp spin flop transitions with complete magnetic saturation after the second transition (>5 T). A magnetic phase diagram for α-CoMoO4 was constructed, revealing three low-temperature magnetic phases: an antiferromagnetic phase at low field, an intermediate spin-flop phase, and a paramagnetic phase at high field. Two well-defined magnetisation plateaus were observed either side of the spin-flop phase: the first occurred with a moment per Co ion of 1/3 of spin saturation (where Co moments are completely aligned to the applied magnetic field), whereas the second occurred at a moment per Co ion matching calculations for spin saturation (3 μB per Co). No geometric origin for this factor of 1/3 could be found. Hysteresis was observed around the first spin-flop transition, indicating the presence of spin canting or magnetic domains under an applied field. The first successful fabrication of CoMoO4 thin films was achieved via RF magnetron sputtering, yielding β phase films which remain in the β phase upon cooling. The β-CoMoO4 thin films demonstrated antiferromagnetic ordering below 10 K. While two spin-flop transitions are seen in the β phase films (with a hysteresis around the first), spin saturation is not reached in fields up to 6 T, suggesting the existence of a third spin reorientation at higher field. A magnetic phase diagram was also constructed for the β-CoMoO4 film, which demonstrated the same three low-temperature magnetic phases, though with lower critical fields and transition temperatures. Comparisons with isostructural Ni and Mn molybdates showed that the key differences in the α and β phases arise from the different coordination of the Mo tetramers, indicating differences in magnetic properties in both phases arise from variations in the inter-tetramer exchange coupling.

Nitrogen-Doped Carbon Nanothin Film as a Buffer Layer between Anodic Graphite and Solid Electrolyte Interphase for Lithium-Ion Batteries.

Lithium-ion batteries are essential batteries for electric vehicle drive systems. Such batteries must provide stable performance over a long period of time. Therefore, the degradation or aging of the battery capacity must be improved. In the case of the current graphite anodes, graphite coated with an amorphous layer is used. It is known that the amorphous layer can reduce the irreversible capacity loss caused by the solid electrolyte interphase (SEI) layer. The amorphous carbon layers reduce the initial capacity due to higher electrical resistance. In this study, we aim to develop a buffer layer using nitrogen-containing graphene that would prevent the increase in electrical resistance while maintaining the amorphous structure. Coatings with different film thicknesses were prepared by using the solution plasma method. The thinnest sample was oven sintered to optimize the structure, especially the surface and interface of the layer. The battery capacity from charge-discharge experiments and the resistance change of each part from electrochemical impedance measurements were evaluated. The results showed that the coating layer increased the electrical resistance of the graphite anode. On the other hand, the resistance of the SEI layer was reduced by the coating layer. It can be predicted that the addition of the coating layer will increase the total charge transfer resistance (R ct) of the cell but will also improve the period average capacity in the long run. To be used as a practical material, the film thickness would need to be further reduced, and the balance between the loss of charge transfer resistance and the gain of SEI layer resistance would need to be further optimized.

Terahertz time-domain transmission spectroscopy of water and hydrogel thin films: Extraction of optical parameters and application to agarose gel characterization

Terahertz time-domain spectroscopy (THz-TDS) is an emerging optical technique that has potential applications in the characterization of (bio)materials. However, the complicated extraction of optical parameters from multi-layered and optically thin samples is a barrier towards its acceptance by applied scientists. Therefore, the aim of this work is to provide a straightforward approach for the extraction of the THz absorption coefficient and index of refraction profiles of aqueous thin films in a window-sample-window configuration, which is ubiquitous in many laboratories (i.e., sample in a cuvette). A numerical approach-based methodology that accounts for multiple layers, Fabry–Pérot effect, and sample thickness is elaborated which involves an optical interference model based on a tri-layer structure and a simple thickness estimation technique. This method was validated on water samples where a good agreement was found with the THz optical parameters of water reported in the literature, while the use of a commercial software resulted in erroneous optical parameters estimates when used without due regard to its limitations. A case study was then performed to demonstrate the ability of the proposed method to characterize agarose hydrogels with varying degree of sulfation. It was demonstrated that THz-TDS can provide insight into the hydration state of the agarose hydrogels, including the relative number of the hydrogen bonds between the hydroxyl moieties of water and the polysaccharide network which is perturbed by the presence of sulfate. The trend in the index of refraction profiles suggested microstructural differences between the agarose hydrogels, which were confirmed by visualizing the agarose network morphology using cryo-SEM imaging.

Effective use of adaptive slicing in binder jetting using Taguchi method and surface roughness measurement with image processing

PurposeThe use of additive manufacturing in many branches of industry is increasing significantly because of its many advantages, such as being able to produce complex parts that cannot be produced by classical methods, using fewer materials, easing the supply chain with on-site production, being able to produce with all kinds of materials and producing lighter parts. The binder jetting technique, one of the additive manufacturing methods researched within the scope of this work, is predicted to be the additive manufacturing method that will grow the most in the next decade, according to many economic reports. Although additive manufacturing methods have many advantages, they can be slower than classical manufacturing methods regarding production speed. For this reason, this study aims to increase the manufacturing speed in the binder jetting method.Design/methodology/approachAdaptive slicing and variable binder amount algorithm (VBAA) were used to increase manufacturing speed in binder jetting. Taguchi method was used to optimize the layer thickness and saturation ratio in VBAA. According to the Taguchi experimental design, 27 samples were produced in nine different conditions, three replicates each. The width of the samples in their raw form was measured. Afterward, the samples were sintered at 1,500 °C for 2 h. After sintering, surface roughness and density tests were performed. Therefore, the methods used have been proven to be successful. In addition, measurement possibilities with image processing were investigated to make surface roughness measurements more accessible and more economical.FindingsAs a result of the tests, the optimum printing condition was decided to be 180–250 µm for layer thickness and 50% for saturation. A separate test sample was then designed to implement adaptive slicing. This test sample was produced in three pieces: adaptive (180–250 µm), thin layer (180 µm) and thick layer (250 µm) with the determined parameters. The roughness values of the adaptive sliced sample and the thin layer sample were similar and better than the thick layer sample. A similar result was obtained using 12.31% fewer layers in the adaptive sample than in the thin layer sample.Originality/valueThe use of adaptive slicing in binder jetting has become more efficient. In this way, it will increase the use of adaptive slicing in binder jetting. In addition, a cheap and straightforward image processing method has been developed to calculate the surface roughness of the parts.

Characterizing oxidation, thickness, and composition of metallic glass thin films with combined electron probe microanalysis and X-ray photoelectron spectroscopy

Metallic glass thin films (MGTFs) are a recently developed class of alloy coatings with potential applications ranging from biomedical devices to electrical components. Their tribological performance in service conditions is dictated by MGTF bulk composition but can be limited by the native oxide surface that inevitably forms upon exposure to atmosphere. Surface oxidation, thickness, and composition of ZrCuNiAl MGTFs were characterized using a combination of X-ray photoelectron microscopy (XPS) and electron probe microanalysis (EPMA). MGTF samples with nominal thicknesses of 50, 500, and 1500 nm were sputtered onto Si and SiN wafer substrates within a high vacuum deposition chamber and their amorphicity was confirmed by X-ray diffraction. XPS depth profiling identified the thin film composition and showed that the surface oxide was dominated by a mixed layer of mostly ZrO2, a little oxidized Al, and some metallic Zr. EPMA X-ray intensities were acquired as a function of beam energy to excite characteristic X-rays from different depths of the MGTFs and reconstructed using open-source thin film analysis software BadgerFilm, to determine the composition and thickness of sample layers. EPMA results constrain the composition to be Zr54Cu29Al10Ni7 within 0.7 at. % variation and total thicknesses to be 49, 470, and 1546 nm. Using the oxide composition identified from XPS depth profiling as an input for BadgerFilm analysis, EPMA results indicate the surface oxidation layer on each of the thin film samples was 6.5 ± 1.1 nm thick and uniform across a 0.25 mm region of the film.

Raman scattering of TixV1‐xO2 thin films on (110) rutile TiO2 in the low and high temperature phase adjacent to the metal–insulator transition

AbstractVanadium dioxide (VO2) undergoes a reversible first‐order metal‐to‐insulator transition (MIT) from a high‐temperature metallic phase to a low‐temperature insulating phase at a critical temperature Tc of 68°C. The MIT is accompanied by a structural phase transition. In addition to the metallic high‐temperature rutile phase, several insulating phases may be involved depending on doping, interfacial stress, or external stimuli. Unambiguously identifying the crystal phases involved in the phase transition is of key interest from the point of view of application as well as fundamental science. We study the impact of Ti doping of VO2 thin films on (110) rutile TiO2 substrates. We conduct a careful analysis of structural properties by combining results of x‐ray diffraction, Raman spectroscopy, and transmission electron microscopy. The transition temperature Tc of the deposited thin films decreases with increasing Ti‐content. All our thin film samples undergo a structural phase transition from the monoclinic M1‐phase to the rutile R‐phase with increasing temperature without passing the intermediate monoclinic M2‐phase. A careful analysis of polarization and angle‐dependent Raman data reveals that, above Tc, the unit cell of the high‐temperature rutile TixV1‐xO2 phase is aligned with that of the rutile TiO2 substrate whereas, below Tc, 180°‐domains of the M1‐phase of TixV1‐xO2 are observed. The structural relationship between TiO2 substrate and the high respective low‐temperature phase of the TixV1‐xO2 determined by Raman spectroscopy is in excellent agreement with TEM results on these samples. Raman spectroscopy is a powerful tool for studying structural changes of VO2‐based samples in the vicinity of MIT.

Thickness-dependent topological domain textures of layered ferroelectric Bi2WO6 thin films

Topological polar structures are attracting attention as potential applications of next-generation high-density memories. We investigate how the ferroelectric domain evolves with film thickness in c-axis oriented epitaxial Bi2WO6 thin films grown on (LaAlO3)0.3(Sr2AlTaO6)0.7 substrates. In addition to the general thickness scaling effect on domain size, we find that 3- or 4-variant domains appear in a sample thicker than 120 nm, whereas ⟨100⟩-type domains compete with the ⟨110⟩ ones in thinner samples, resulting in a variety of nontrivial topological structures. By visualizing the spatial distribution of electric polarizations through angle-resolved piezoresponse force microscopy, we provide direct evidence for the spontaneous emergence of nontrivial topological polar structures. These results provide useful insights into the domain behavior of layered ferroelectric thin films.

Enhancing ferroelectric characterization at nanoscale: A comprehensive approach for data processing in spectroscopic piezoresponse force microscopy

Switching Spectroscopy Piezoresponse Force Microscopy (SSPFM) stands out as a powerful method for probing ferroelectric properties within materials subjected to incremental polarization induced by an external electric field. However, the dense data processing linked to this technique is a critical factor influencing the quality of obtained results. Furthermore, meticulous exploration of various artifacts, such as electrostatics, which may considerably influence the signal, is a key factor in obtaining quantitative results. In this paper, we present a global methodology for SSPFM data processing, accessible in open-source with a user-friendly Python application called PySSPFM. A ferroelectric thin film sample of potassium sodium niobate has been probed to illustrate the different aspects of our methodology. Our approach enables the reconstruction of hysteresis nano-loops by determining the PR as a function of applied electric field. These hysteresis loops are then fitted to extract characteristic parameters that serve as measures of the ferroelectric properties of the sample. Various artifact decorrelation methods are employed to enhance measurement accuracy, and additional material properties can be assessed. Performing this procedure on a grid of points across the surface of the sample enables the creation of spatial maps. Furthermore, different techniques have been proposed to facilitate post-treatment analysis, incorporating algorithms for machine learning (K-means), phase separation, and mapping cross correlation, among others. Additionally, PySSPFM enables a more in-depth investigation of the material by studying the nanomechanical properties during poling, through the measurement of the resonance properties of the cantilever–tip–sample surface system.

The Liquid Jet Endstation for Hard X-ray Scattering and Spectroscopy at the Linac Coherent Light Source

The ability to study chemical dynamics on ultrafast timescales has greatly advanced with the introduction of X-ray free electron lasers (XFELs) providing short pulses of intense X-rays tailored to probe atomic structure and electronic configuration. Fully exploiting the full potential of XFELs requires specialized experimental endstations along with the development of techniques and methods to successfully carry out experiments. The liquid jet endstation (LJE) at the Linac Coherent Light Source (LCLS) has been developed to study photochemistry and biochemistry in solution systems using a combination of X-ray solution scattering (XSS), X-ray absorption spectroscopy (XAS), and X-ray emission spectroscopy (XES). The pump–probe setup utilizes an optical laser to excite the sample, which is subsequently probed by a hard X-ray pulse to resolve structural and electronic dynamics at their intrinsic femtosecond timescales. The LJE ensures reliable sample delivery to the X-ray interaction point via various liquid jets, enabling rapid replenishment of thin samples with millimolar concentrations and low sample volumes at the 120 Hz repetition rate of the LCLS beam. This paper provides a detailed description of the LJE design and of the techniques it enables, with an emphasis on the diagnostics required for real-time monitoring of the liquid jet and on the spatiotemporal overlap methods used to optimize the signal. Additionally, various scientific examples are discussed, highlighting the versatility of the LJE.

Precise determination of oxygen content in SmBa2Cu3O7-δ thin film samples using x-ray diffraction

Abstract The superconducting properties of SmBa2Cu3O7-δ (SmBCO) thin films are predominantly influenced by the oxygen deficiency δ. Yet, the established methods to determine δ such as iodometric titration or thermogravimetry cannot be applied to thin films due to their very small volume.
Therefore, an alternative way to determine δ for SmBCO thin film samples using X-ray diffraction (XRD) is presented. Main point of this analysis is the structural relationship between the a, b and c lattice parameters and δ. A linear relationship between c and δ is found in SmBCO powder samples for both the orthorhombic and tetragonal phases.
Furthermore, an attempt is made to quantify the chemical composition using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). This attempt was inconclusive because of drastically changing ion yields due to δ influencing the valence state of the analyzed ions.
The found crystal structural relationship gathered from the powder samples is applied to thin film samples. Thereby, it becomes clear that thermal strain is affecting the crystal structure of the thin films. A simple correction model is used to correct for thermal strain and a good match between powder, literature and thin film data is achieved and thus a non-destructive way for the determination of δ using XRD.


X-ray Photoelectron Spectroscopy Analysis of Nafion-Containing Samples: Pitfalls, Protocols, and Perceptions of Physicochemical Properties.

X-ray photoelectron spectroscopy (XPS) is one of the most common techniques used to analyze the surface composition of catalysts and support materials used in polymer electrolyte membrane (PEM) fuel cells and electrolyzers, providing important insights for further improvement of their properties. Characterization of catalyst layers (CLs) is more challenging, which can be at least partially attributed to the instability of ionomer materials such as Nafion during measurements. This work explores the stability of Nafion during XPS measurements, illuminating and addressing Nafion degradation concerns. The extent of Nafion damage as a function of XPS instrumentation, measurement conditions, and sample properties was evaluated across multiple instruments. Results revealed that significant Nafion damage to the ion-conducting sulfonic acid species (>50% loss in sulfur signal) may occur in a relatively short time frame (tens of minutes) depending on the exact nature of the sample and XPS instrument. This motivated the development and validation of a multipoint XPS data acquisition protocol that minimizes Nafion damage, resulting in reliable data acquisition by avoiding significant artifacts from Nafion instability. The developed protocol was then used to analyze both thin film ionomer samples and Pt/C-based CLs. Comparison of PEM fuel cell CLs to Nafion thin films revealed several changes in Nafion spectral features attributed to charge transfer due to interaction with conductive catalyst and support species. This study provides a method to reliably characterize ionomer-containing samples, facilitating fundamental studies of the catalyst-ionomer interface and more applied investigations of structure-processing-performance correlations in PEM fuel cell and electrolyzer CLs.

Computational study of the performance of a solar dryer for improvement in the shelf life of the food materials.

In this study, the thermal and drying characteristics of a thin layer food sample were investigated. An indirect type, simple, efficient, and economically feasible solar dryer was fabricated and used for food preservation. However, a dynamic model of a fabricated solar dryer was also presented to gain a better insight into the drying and thermal actions. This model consists of thermal modeling of the drying chamber, solar collector, and solar-dried food sample. The law of conservation of energy was applied to evaluate the temperature at different sections of the solar dryer with respect to drying time. All listed model equations were solved in the MATLAB environment. This study helps to examine the influence of solar radiation on the collector plate temperature, drying chamber temperature, food sample temperature, and performance parameters such as thermal efficiency with respect to drying time. Model data was found in good agreement with experimental data within a 4% error. It is concluded that the drying of food material is affected by air temperature, the collector temperature, mode of heat transfer, and material characteristics such as dimension and mass of the food sample.

On the Effect of Interphase Boundary Energy Anisotropy on Morphologies: A New Type of Eutectic Grain Observed in a Three-Phase Eutectic System

Eutectic microstructures are dramatically affected by the anisotropy in interphase boundary energy. Depending on this anisotropy function, different eutectic grains may grow simultaneously at the same experimental conditions. In all reported quasi-isotropic and anisotropic two-phase and three-phase eutectic grains in thin samples, lamellar morphology is observed and the microstructure is essentially two dimensional (2D), since the interphase boundaries are perpendicular to the sample walls. Using the β(In)–In2Bi–γ(Sn) system and real-time solidification experiments in thin samples, we introduce a unique and new type of anisotropic three-phase eutectic grain, entitled here as “Laminated Matrix with Rods (LMR).” In this grain, due to the anisotropy in In2Bi/γ(Sn) interphase boundary, the evolving phases, and hence, the microstructures observed through the two glass plates of the thin sample are completely different, despite the strong confinement effect. During rotating directional solidification (RDS) experiments, the morphology or the aspect ratio of all phases changes periodically and drastically. Specifically, In2Bi, β(In), and γ(Sn) phases evolve from all being lamellar perpendicular to the sample walls to the matrix, elongated/trapezoidal rods, and a lamella parallel to the sample walls, respectively. Our experimental results show that these morphological transitions are due to change in the interphase boundary orientation with respect to the growth direction.Graphical abstract

Ferroelectric Organic-Inorganic Hybrid Ammonium Halogenobismuthate(III) for Piezoelectric Energy Harvesting.

Halogenobismuthate(III) compounds are of recent interest because of their low toxicity and distinct electrical properties. The utility of these materials as ferroelectrics for piezoelectric energy harvesters is still in its early stages. Herein, we report a hybrid ammonium halogenobismuthate(III) [BPBrDMA]2·[BiBr5], crystallizing in a ferroelectrically active polar noncentrosymmetric Pna21 space group. Its noncentrosymmetric structure was confirmed by the detection of the second harmonic generation response. The ferroelectric P-E hysteresis loop measurements on the thin film sample of [BPBrDMA]2·[BiBr5] gave a saturation polarization (Ps) of 5.72 μC cm-2. The piezoresponse force microscopy analysis confirmed its ferroelectric and piezoelectric nature, showing characteristic domain structures and signature hysteresis and butterfly loops. The piezoelectric energy harvesting attributes of [BPBrDMA]2·[BiBr5] were further probed on its polylactic acid (PLA) composites. The 15 wt % [BPBrDMA]2·[BiBr5]-PLA polymer composite resulted in a high output voltage of 26.2 V and power density of 15.47 μW cm-2. The energy harvested from this device was further utilized for charging a 10 μF capacitor within 3 min.