Amorphous Layer Research Articles

Shaping single crystalline BaTiO3 nanostructures by focused neon or helium ion milling

The realization of perovskite oxide nanostructures with controlled shape and dimensions remains a challenge. Here, we investigate the use of helium and neon focused ion beam (FIB) milling in an ion microscope to fabricate BaTiO3 nanopillars of sub-500 nm in diameter starting from BaTiO3 (001) single crystals. Irradiation of BaTiO3 with He ions induces the formation of nanobubbles inside the material, eventually leading to surface swelling and blistering. Ne-FIB is shown to be suitable for milling without inducing surface swelling. The resulting structures are defect-free single crystal nanopillars, which are enveloped, on the top and lateral sidewalls, by a point defect-rich crystalline region and an outer Ne-rich amorphous layer. The amorphous layer can be selectively etched by dipping in diluted HF. The geometry and beam-induced damage of the milled nanopillars depend strongly on the patterning parameters and can be well controlled. Ne ion milling is shown to be an effective method to rapidly prototype BaTiO3 crystalline nanostructures.

Core–Double-Shell TiO2@Fe3O4@C Microspheres with Enhanced Cycling Performance as Anode Materials for Lithium-Ion Batteries

Due to the volume expansion effect during charge and discharge processes, the application of transition metal oxide anode materials in lithium-ion batteries is limited. Composite materials and carbon coating are often considered feasible improvement methods. In this study, three types of TiO2@Fe3O4@C microspheres with a core–double-shell structure, namely TFCS (TiO2@Fe3O4@C with 0.0119 g PVP), TFCM (TiO2@Fe3O4@C with 0.0238 g PVP), and TFCL (TiO2@Fe3O4@C with 0.0476 g PVP), were prepared using PVP (polyvinylpyrrolidone) as the carbon source through homogeneous precipitation and high-temperature carbonization methods. After 500 cycles at a current density of 2 C, the specific capacities of these three microspheres are all higher than that of TiO2@Fe2O3 with significantly improved cycling stability. Among them, TFCM exhibits the highest specific capacity of 328.3 mAh·g−1, which was attributed to the amorphous carbon layer effectively mitigating the capacity decay caused by the volume expansion of iron oxide during charge and discharge processes. Additionally, the carbon coating layer enhances the electrical conductivity of the TiO2@Fe3O4@C materials, thereby improving their rate performance. Within the range of 100 to 1600 mA·g−1, the capacity retention rates for TiO2@Fe2O3, TFCS, TFCM, and TFCL are 27.2%, 35.2%, 35.9%, and 36.9%, respectively. This study provides insights into the development of new lithium-ion battery anode materials based on Ti and Fe oxides with the abundance and environmental friendliness of iron, titanium, and carbon resources in TiO2@Fe3O4@C microsphere anode materials, making this strategy potentially applicable.

Effects of TMAl predose time on the quality of submicron-thick GaN on Si

Submicron-thick (∼350 nm) gallium nitride (GaN) thin films with lower dislocation densities are grown on silicon (Si) substrate by metal organic chemical vapour deposition (MOCVD). Prior to the growth, a trimethylalluminum (TMAl) predose is performed. The effects of different TMAl predose time on the surface morphology and crystalline quality of submicron-thick GaN are investigated in this study. With prolonged TMAl predose time, the surface becomes rougher, while the screw dislocation densities both for GaN and aluminum nitride (AlN) are reduced. The edge dislocation densities tend to decrease first then increase again when the TMAl predose time is elongated from 90 s over 135 s–180 s. From the high resolution transmission electron microscopy (HRTEM), we found the thickness of amorphous layer between Si and AlN decreases with the increase of TMAl predose time. Such an amorphous layer should play an important role in the surface morphology and crystalline quality of submicron-thick GaN. A possible mechanism has also been proposed to elucidate the effects of TMAl predose time.

Research on bubble free Si/SiC hydrophilic bonding approach for high quality Si-on-SiC fabrication

Abstract The electrical device fabricated by the Si-on-SiC substrate exhibits superior heat dissipation and minimal RF loss. However, a common challenge in hydrophilic direct bonding is the inevitable formation of bubbles at the Si/SiC interface, which compromises material utilization efficiency. To address this issue, a multi-bonding process was introduced in this research. Experimental findings revealed that this method effectively mitigated interfacial bubble formation, especially when incorporating a multi-step annealing-separating-bonding approach, yielding even more promising results. Ultimately, a bubble-free 3×3 cm2 Si-on-SiC substrate was fabricated. Material characterization techniques confirmed the high crystal quality and minimal surface roughness for the Si functional layer. Transmission electron microscopy further revealed the presence of an amorphous oxide layer (~3.5 nm) at the interface, devoid of any defects or nanovoids. It is believed that with the excellent physical properties, Si-on-SiC will have a broader application prospect in extreme environments.

Photoluminescence studies of the charge states of nitrogen vacancy centers in diamond after arsenic ion implantation and subsequent annealing

In this work, nitrogen vacancy (NV) centers of high nitrogen diamond implanted with arsenic ions were investigated by photoluminescence spectroscopy. The transition of the NV center charge state was discussed by the regularly changing laser excitation power and measurement temperature following high-temperature annealing. After high-temperature annealing, the amorphous layer generated by arsenic ion implantation is transformed into a graphitization layer, resulting in a decrease in the NV yield. The electric neutral NV (NV0) center and negatively charged NV (NV−) center are affected by both radiation recombination and Auger recombination with increasing laser power. Accompanied by the increasing measurement temperature, the intensities of NV centers gradually decreased and eventually quenched. In addition, the charge states of NV− and NV0 centers were undergoing a transition. The zero phonon line positions of NV centers were also red shift, it was attributed to the dominant role of electron–phonon interaction in the temperature-dependent displacement of diamond energy gaps. The full width at half maxima of NV center were broadened significantly at higher temperatures.

Corrosion Enhancement of PM Processed Magnesium by Turning Native Oxide on Mg Powders into Carbonates

In addition to its use as a lightweight material, pure magnesium is a promising candidate for prospective bioimplants considering its excellent biocompatible properties. Regardless of what Mg application is used, the ultimate goal is to improve magnesium's mechanical properties and degradation behaviour. Because of the high affinity for oxygen native oxide layer of gas-atomized powders is naturally formed in contact with the atmosphere. S/TEM investigation of the native oxide of the Mg powder particles revealed a nonhomogeneous nano-crystalline MgO layer. MgO is relatively soluble in water and does not provide sufficient corrosion protection. Among various surface treatment methods, conversion of the non-protective magnesium oxide to carbonate products is possible depending on the environmental conditions. This work used a simple experimental method using CO2 and water vapour to achieve surface carbonation of Mg powders. Two carbonated samples and pure magnesium were prepared by direct extrusion. The samples after carbonation retained good mechanical properties and the layer of carbonates had a significant impact on corrosion resistance. 1 day carbonation resulted in transformation of native oxide into amorphous layer and reduction of corrosion rate. Longer carbonation (10 days) revealed layer growth and transformation of native oxide to crystalline nesquehonite structure.

Elevated Water Oxidation by Cation Leaching Enabled Tunable Surface Reconstruction

Water electrolysis is one promising and eco‐friendly technique for energy storage, yet its overall efficiency is hindered by the sluggish kinetics of oxygen evolution reaction (OER). In response, developing strategies to boost OER catalyst performance is crucial. With the advances in characterization techniques, an extensive phenomenon of surface structure evolution into an active amorphous layer was uncovered. Surface reconstruction in a controlled fashion was then proposed as an emerging strategy to elevate water oxidation efficiency. In this work, Cr substitution induces the reconstruction of NiFexCr2‐xO4 during cyclic voltammetry (CV) conditioning by Cr leaching, which leads to a superior OER performance. The best‐performed NiFe0.25Cr1.75O4 shows a ~1500% current density promotion at overpotential η = 300 mV, which outperforms many advanced NiFe‐based OER catalysts. It is also found that their OER activities are mainly determined by Ni:Fe ratio rather than Fe content in all metal elements. Meanwhile, the turnover frequency (TOF) values based on redox peak and total mass were obtained and analysed, and their possible limitations in the case of NiFexCr2‐xO4 are discussed. Additionally, the high activity and durability were further verified in a membrane electrode assembly (MEA) cell, highlighting its potential for practical large‐scale and sustainable hydrogen gas generation.

Synergetic Catalytic Effect between Ni and Co in Bimetallic Phosphide Boosting Hydrogen Evolution Reaction.

The application of electrochemical hydrogen evolution reaction (HER) for renewable energy conversion contributes to the ultimate goal of a zero-carbon emission society. Metal phosphides have been considered as promising HER catalysts in the alkaline environment, which, unfortunately, is still limited owing to the weak adsorption of H* and easy dissolution during operation. Herein, a bimetallic NiCoP-2/NF phosphide is constructed on nickel foam (NF), requiring rather low overpotentials of 150 mV and 169 mV to meet the current densities of 500 and 1000 mA cm-2, respectively, and able to operate stably for 100 h without detectable activity decay. The excellent HER performance is obtained thanks to the synergetic catalytic effect between Ni and Co, among which Ni is introduced to enhance the intrinsic activity and Co increases the electrochemically active area. Meanwhile, the protection of the externally generated amorphous phosphorus oxide layer improves the stability of NiCoP/NF. An electrolyser using NiCoP-2/NF as both cathode and anode catalysts in an alkaline solution can produce hydrogen with low electric consumption (overpotential of 270 mV at 500 mA cm-2).

Enhancing cement hydration by core/shell PS@SiO2 nanoparticles

Nanoparticles are widely used in construction. Here, nano-SiO2 is employed, in a way that prevents agglomeration of the nanoparticles, as pozzolanic material to improve Portland cement hydration and to improve the properties of the concrete. To explore the effect of nano-SiO2 and core-shell PS@SiO2 on cement properties, spherical polystyrene particles were prepared by dispersion polymerization of styrene in polar solvents and characterized by FTIR and E-SEM. The core shells PS@SiO2 were synthesized by Stöber method. The results showed an amorphous nano-SiO2 layer can be deposited uniformly on polystyrene particles. This core/shell structure was reducing the aggregation of nano-SiO2 effectively. It was shown that PS@SiO2 particles improved the concrete performances compared to blended cement with nano-SiO2 due to the agglomeration affect. Highlights • Core/shell PS@SiO2 nanoparticles with a uniform coating layer were prepared. • As-prepared nanoparticles were characterized by a variety of advanced methods. • Nanoparticles accelerate hydration and lower the spatial weight of cement paste. • Core/shell nanoparticles improve cement hydration much better than nano-SiO2.

Amorphous nitrogen-doped carbon layers forming the interfacial channel for rapid charge transfer in ZnIn2S4/BiVO4 Z-scheme photocatalyst for enhancing organic pollutants degradation with simultaneous hydrogen evolution

Efficient photocatalytic hydrogen evolution from the organic wastewater represents an ideal solution for simultaneously addressing energy shortages and environmental pollution. However, the sluggish transport of photogenerated carriers at contact interface poses a key obstacle to enhancing photocatalytic activity. Here, ZnIn2S4/BiVO4@N-C (ZIS/BVO@N-C) Z-scheme photocatalysts were successfully constructed by a simple hydrothermal-impregnation method. ZIS/BVO@N-C-10% demonstrated outstanding photocatalytic performance, achieving a hydrogen evolution rate of 2695.68 μmol·g−1·h−1 and a degradation rate of 492.96 mmol·g−1·h−1 under visible light, surpassing those of ZIS (851.52 μmol·g−1·h−1 and 174.83 mmol·g−1·h−1) and ZIS/BVO-10% (1228.98 μmol·g−1·h−1 and 277.78 mmol·g−1·h−1). Characterization results and density functional theory (DFT) calculations revealed that the introduction of the N-C layer reduced interfacial impedance and enhanced the strength of interfacial electric field, overcoming the interfacial barrier and improving the photogenerated separation and migration efficiency at the interface, and ultimately enhancing the photocatalytic activity of ZIS/BVO@N-C. Based on experimental and characterization results, the photocatalytic mechanism of ZIS/BVO@N-C Z-scheme has been proposed. Furthermore, ZIS/BVO@N-C exhibited excellent stability, highlighting its potential for practical applications. This work also presents a new strategy for designing highly active Z-scheme photocatalysts for organic wastewater treatment and simultaneous hydrogen energy recovery.

Low-cost O2 plasma activation assisted direct bonding of β-Ga2O3 and Si substrates in air

This study presents a novel technique for directly bonding β-Ga2O3 and Si substrates using O2 plasma activation at room temperature. The activation process resulted in excellent surface hydrophilicity and roughness. Annealing in an N2 atmosphere revealed a bonding strength of 6.23 MPa, with partial fracture of the Si substrate. The bonding interface was observed by TEM and EDS. A distorted amorphous intermediate layer with a thickness of 100 nm and amorphous bubbles were observed in the bonding interface. In addition, the Ga, O, and Si elements were diffused and enriched, forming approximately 30 nm nodules at the bonding interface. This method offers a promising approach for integrating wide bandgap semiconductor materials in devices, bypassing the need for vacuum treatment.

Heterogeneous Ni-Boride/Phosphide Anchored Amorphous B-C Layer for Overall Water Electrocatalysis.

The rational design of efficient and economical bifunctional electrocatalysts remained a challenge for overall water electrolysis. In this work, the Ni-boride/ phosphide particles anchored amorphous B-doped carbon layer with hierarchical porous characteristics in Ni foam (Ni3P/Ni3B/B-C/NF) was fabricated for overall water splitting. The Boroncarbide (B4C) power was filled and fixed in the NF interspace through the electroplating and electroless plating, and then annealed in vacuum high temperature. The amorphous B-C layer derived from the B4 C not only speeded up the electron transport, but also cooperate with Ni-boride/phosphide to enhance the electrocatalytic activity for HER and OER synergistically. Furthermore, the hierarchical porous architecture of Ni3P/Ni3B/B-C/NF increased space utilization to load more active materials. The self-supported Ni3P/Ni3B/B-C/NF electrode possessed a low overpotential of 212 and 280 mV to deliver 100 mA cm-2 for HER and OER, respectively, and high stability for 48 h. In particular, the electrolyzer constituted with the Ni3P/Ni3B/B-C/NF bifunctional electrocatalyst only required a voltage of 1.59 V at 50 mA cm-2 for water electrocatalysis under alkaline medium, and demonstrated long-term stability for 48 h. This study provides a new technical path for the development of bifunctional of transition metal borides to promote the application of hydrogen production from water splitting.

Synthesis, characterisation and in vitro anticancer activity of conjugated protease inhibitor-silver nanoparticles (AgNPs-PI) against human breast MCF-7 and prostate PC-3 cancer cell lines.

The conjugated silver nanoparticles using biomolecules have attracted great attention of researchers because physical dimensions and surface chemistry play important roles in toxicity and biocompatibility of AgNPs. Hence, in the current study, synthesis of bio-conjugated AgNPs with protein protease inhibitor (PI) isolated from Streptomyces spp. is reported. UV-visible spectra of PI and AgNPs showed stronger peaks at 280 and 405nm, confirming the synthesis of conjugated AgNPs-PI. TEM and SEM images of AgNPs-PI showed spherical-shaped nanoparticles with a slight increase in particle size and thin amorphous layer around the surface of silver nanomaterial. Circular dichroism, FT-IR and fluorescence spectral studies confirmed AgNPs-PI conjugation. Conjugated AgNPs-PI showed excellent anticancer potential than AgNPs and protease inhibitor separately on human breast MCF-7 and prostate PC-3 cell lines. The findings revealed that surface modification of AgNPs with protein protease inhibitor stabilised the nanomaterial and increased its anticancer activity.

Analysis of the Structure of Heavy Ion Irradiated LaFeO3 Using Grazing Angle X-ray Absorption Spectroscopy.

Crystalline ceramics are candidate materials for the immobilization of radionuclides, particularly transuranics (such as U, Pu, and Am), arising from the nuclear fuel cycle. Due to the α-decay of transuranics and the associated recoil of the parent nucleus, crystalline materials may eventually be rendered amorphous through changes to the crystal lattice caused by these recoil events. Previous work has shown irradiation of titanate-based ceramics to change the local cation environment significantly, particularly in the case of Ti which was shown to change from 6- to 5-fold coordination. Here, this work expands the Ti-based study to investigate the behavior in Fe-based materials, using LaFeO3 as an example material. Irradiation was simulated by heavy ion implantation of the bulk LaFeO3 ceramic, with the resulting amorphous layer characterized with grazing angle X-ray absorption spectroscopy (GA-XAS). Insights into the Fe speciation changes exhibited by the amorphized surface layer were provided through quantitative analysis, including pre-edge analysis, and modeling of the extended X-ray absorption fine structure (EXAFS), of the GA-XAS data.

Surface topography and subsurface structure evolution in laser micro polishing of monocrystalline silicon

Ultra-smooth silicon surfaces, crucial in short-wave optics, can be marred by surface defects and subsurface damage incurred during machining, thereby affecting the imaging quality and transmission efficiency of optical components. Laser micro-polishing emerges as a versatile and efficient technique for ultra-precision polishing. This study aims to scrutinize the surface topography and subsurface structural evolution of monocrystalline silicon wafers during laser micro-polishing experimentally and to formulate an accessible evaluation model that incorporates multiple process parameters for optimal polishing results. As laser fluence escalates, the polishing process can be divided into six regimes: bulge, coalescence, smoothness, groove, ripple, and ablation. Each regime's crystal structure evolution is analyzed using Raman spectroscopy, demonstrating a close relationship with the surface expansion preceding the melting of monocrystalline silicon. Surface roughness diminishes from 6 nm to 0.7 nm, and an optimal crystalline quality devoid of an amorphous layer, residual stress, or significant subsurface damage is achieved. Amorphous silicon, 20 μm thick, is converted into monocrystalline silicon through recrystallization, and subsurface distortions and dislocations are rectified due to silicon atom redistribution. Moreover, a mapping relationship between multiple process parameters and surface polishing effects is established. A dimensionless fluence considering multiple parameters is derived, and a predictive model for process parameter optimization to secure optimal polishing results is proposed.

Strength and toughness of semicrystalline polymer fibers: Influence of molecular chain entanglement

The mechanical properties of oriented semicrystalline polymers fibers are mainly determined by the semicrystalline morphology in which lamellar crystals and disordered amorphous layers are in staggered arrangement. As a stress transmission channel, amorphous entanglement network can affect the strength and toughness of fiber together with crystalline phase. In this study, the relationship between mechanical properties and amorphous entanglement of oriented poly (l-lactic acid) fibers was clarified by studying the cyclic loading characteristics. Based on the Haward-Thakray model of semi-crystalline polymers, the energy contributions of the crystalline phase and the amorphous phase are separated. During the deformation of oriented fiber, the crystal will be broken under the action of tight entanglement network, and the entanglement network can transfer stress well without failure under the action of straight chain. Therefore, although the crystalline phase and the amorphous phase jointly bear the strength, the toughness and fracture behavior mainly affected by the entangled network of the amorphous phase.

Surface aspects of novel Bio-HEAs MAO-treated in a Ca-, P-, and Mg-rich electrolyte

This study evaluated the effect of alloying elements, applied voltage, and bioactive species (Ca, P, and Mg) enrichment during the micro-arc oxidation (MAO) treatment of novel high entropy alloys (HEAs) targeted for biomedical applications. The non-equiatomic TiZrNbTaMo (TaMo), TiZrNbTaMn (TaMn), and TiZrNbFeMo (FeMo) samples were submitted to MAO treatment at distinct voltages (100, 200, and 300 V), then their chemical, phase, and morphological aspects were evaluated by x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and scanning and transmission electron microscopy (SEM and TEM). Finally, the preliminary physicochemical behavior regarding contact angle and surface energy in distilled water at room temperature was evaluated. The results indicated that the alloying elements played a global role in the bulk’s phase composition, possessing distinct proportions of BCC and HCP phases. The MAO-treated surfaces depicted different mechanisms of anodic oxide growth and dielectric breakdown, forming the typical porous surface at distinct applied voltages. The bioactive species (Ca, P, and Mg) were gradually enriched in the oxide layer, composed of distinct nano-crystalline and amorphous layers that are typical of MAO-treated surfaces. As a result, roughness, contact angle and surface energy values of the MAO-treated samples were affected by the applied voltage and the bulk’s chemical composition, indicating potential for use in the biomedical field, especially as long-term implants and bone fixation devices.

A new heterogeneous nucleation mechanism of AM30 alloy refined by carbon inoculation

The AM30 alloy experiences remarkable grain refinement through carbon inoculation, resulting in a significant reduction of grain size from 623±21μm to 82 ± 2 μm. To delve into the influence of Mn on carbon inoculation in the presence of Ca, advanced techniques such as EDS, FIB, and TEM were utilized. This study reports the initial discovery of a unique duplex-phase particle characterized by an amorphous carbon layer coating on the Al8Mn5 phase. Notably, the amorphous layer exhibits a thickness of approximately 100nm. These distinctive duplex-phase particles are hypothesized to serve as effective nuclei for Mg grains. Supported by epitaxial growth theory and experimental data, these particles exhibit remarkable nucleation efficiency.

FeSiAl soft magnetic composite with double Al2O3 insulation layers for simultaneous high mechanical and magnetic properties

FeSiAl-based soft magnetic composites (SMCs), prepared from insulated FeSiAl powders, are widely applied in electronic devices. However, it is still challenging to achieve high magnetic and mechanical properties simultaneously due to the undesirable insulation layer. Here, double Al2O3 insulation layers are prepared for FeSiAl SMC. Atomic-scale characterizations reveal an in-situ epitaxial Al2O3 layer at FeSiAl surface under the catalysis of NaAlO2, and an outer amorphous Al2O3 layer by subsequent NaAlO2 hydrolysis. The above structure ensures effective insulation of FeSiAl powders and excellent magnetic properties of the FeSiAl/NaAlO2 SMC, with permeability of 101 and power loss of 128 mW/cm3 (50 mT, 100 kHz) respectively. Moreover, in-situ Al2O3/amorphous Al2O3 on FeSiAl matrix also leads to distinguished crush strength of 36.5 MPa for the core sample, which is ascribed to the enhanced adhesion at different interfaces as evidenced by similar local oxygen coordination and low strain distribution. This work provides a novel method to fabricate high-performance FeSiAl SMCs.

Dynamics of phase transformations in Si and Ge upon strong excitation with UV femtosecond laser pulses

Femtosecond laser processing of semiconductors has evolved into a mature, high-precision fabrication technique, enabling a wide range of applications. While initially most studies have employed pulses at near infrared wavelengths, the interest in using UV laser pulses is constantly increasing due to the different excitation conditions as a consequence of the much shorter optical penetration depth, leading to an improved resolution. In this context, fundamental studies on the temporal dynamics of phase transformations triggered by such pulses are necessary in order to comprehend and eventually control the complex phase transformation pathways. Here, we report a detailed time-resolved study on the phase transformation dynamics of crystalline silicon and germanium upon irradiation with single 400 nm, 100 fs laser pulses in the moderate and high excitation regime. To this end, we have employed fs-resolved optical microscopy with a probe wavelength of 800 nm to study the reflectivity evolution of the irradiated surface over a temporal window ranging from 100 fs up to 20 ns. At moderate excitation fluence, the data reveals the entire sequence of laser-induced processes, starting from the generation of a free-electron plasma, non-thermal melting, ablation onset and expansion of a semi-transparent ablation layer with sharp interfaces. At excitation with peak fluences more than 30 times the ablation threshold, an anomalous transient high-reflectivity state is observed, which might be indicative of a recoil pressure-induced liquid–liquid phase transition. Moreover, 70 nm-thick amorphous surface layers are formed in both materials after irradiation at moderate fluences. Overall, our results provide relevant information on both, transformation dynamics and final state of both materials for fs-pulse excitation in the near-UV wavelength range.