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Abstract Anionic redox allows the direct formation of O─O bonds from lattice oxygens and provides higher catalytic in the oxygen evolution reaction (OER) than does the conventional metal ion mechanism. While previous theories have predicted and experiments have suggested the possible O─O bond, it has not yet been directly observed in the OER process. In this study, operando soft X‐ray absorption spectroscopy (sXAS) at the O K‐edge and the operando Raman spectra is performed on layered double CoFe hydroxides (LDHs) after intercalation with [Cr(C2O4)3]3−, and revealed a three‐step oxidation process, staring from Co2+ to Co3+, further to Co4+ (3d6L), and ultimately leading to the formation of O─O bonds and O2 evolution above a threshold voltage (1.4 V). In contrast, a gradual oxidation of Fe is observed in CoFe LDHs. The OER activity exhibits a significant enhancement, with the overpotential decreasing from 300 to 248 mV at 10 mA cm−2, following the intercalation of [Cr(C2O4)3]3− into CoFe LDHs, underscoring a crucial role of anionic redox in facilitating water splitting.

Abstract Integrating two-dimensional (2D) layered materials with wide bandgap β-Ga2O3 has unveiled impressive opportunities for exploring novel physics and device concepts. This study presents the epitaxial growth of 2D β-In2Se3/3D β-Ga2O3 heterostructures on c-Sapphire substrates by plasma-assisted molecular beam epitaxy. Firstly, we employed a temperature-dependent two-step growth process to deposit Ga2O3 and obtained a phase-pure $$(\overline{2 }01)$$ ( 2 ¯ 01 ) β-Ga2O3 film on c-Sapphire. Interestingly, the in-situ reflective high-energy electron diffraction (RHEED) patterns observed from this heterostructure revealed the in-plane ‘b’ lattice constant of β-Ga2O3 ~ 3.038Å. In the next stage, for the first time, 2D In2Se3 layers were epitaxially realized on 3D β-Ga2O3 under varying substrate temperatures (Tsub) and Se/In flux ratios (RVI/III). The deposited layers exhibited (00l) oriented β-In2Se3 on $$(\overline{2 }01)$$ ( 2 ¯ 01 ) β-Ga2O3/c-Sapphire with the epitaxial relationship of $$[11\overline{2 }0]$$ [ 11 2 ¯ 0 ] β-In2Se3 || [010] β-Ga2O3 and $$[10\overline{1 }0]$$ [ 10 1 ¯ 0 ] β-In2Se3 || [102] β-Ga2O3 as observed from the RHEED patterns. Also, the in-plane ‘a’ lattice constant of β-In2Se3 was determined to be ~ 4.027Å. The single-phase β-In2Se3 layers with improved structural and surface quality were achieved at a Tsub ~ 280 °C and RVI/III ~ 18. The microstructural and detailed elemental analysis further confirmed the epitaxy of 2D layered β-In2Se3 on 3D β-Ga2O3, a consequence of the quasi-van der Waals epitaxy. Furthermore, the β-Ga2O3 with an optical bandgap (Eg) of ~ 5.04 eV (deep ultraviolet) when integrated with 2D β-In2Se3, Eg ~ 1.43eV (near infra-red) can reveal potential applications in the optoelectronic field.

In this work, vanadium pentoxide (V2O5) and titanium-modified V2O5 thin films were synthesized using the sol-gel spin coating route. The effect of Ti-doping concentration on the electrochromic optical properties and atomic/electronic structures of V2O5 smart thin films is examined. As the doping concentration of Ti increases, the surface roughness of the films is reduced. The structure of the films is analyzed using X-ray diffraction (XRD) and Raman spectroscopy, while the electrochromic modulation of atomic and electronic structures is elucidated through Raman and X-ray absorption spectroscopy (XAS) conducted during lithiation and delithiation. The XRD patterns demonstrate that an increase in Ti concentration leads to a more amorphous structure of the films and a shift of the main diffraction peak to a lower angle, attributable to the enlarged spacing between the stacking layers resulting from the incorporation of Ti ions. Soft X-ray absorption spectroscopy (XAS) and in situ hard XAS of the V L-edge, the O K-edge, and the V K-edge revealed a reduction in the charge state of V and local atomic structural symmetry modification upon lithated coloration and delithiated bleaching process. The critical insights provided by in situ XAS provides reveal that a small amount of Ti has the ability to modify the interlayer distance and local atomic structure of V2O5, thereby improving its electrochromic switching rate and stability when utilized in smart windows.

The nanotribological properties of aluminum gallium nitride (AlxGa1−xN) epitaxial films grown on low-temperature-grown GaN/AlN/Si substrates were investigated using a nanoscratch system. It was confirmed that the Al compositions played an important role, which was directly influencing the strength of the bonding forces and the shear resistance. It was verified that the measured friction coefficient (μ) values of the AlxGa1−xN films from the Al compositions (where x = 0.065, 0.085, and 0.137) were in the range of 0.8, 0.5, and 0.3, respectively, for Fn = 2000 μN and 0.12, 0.9, and 0.7, respectively, for Fn = 4000 μN. The values of μ were found to decrease with the increases in the Al compositions. We concluded that the Al composition played an important role in the reconstruction of the crystallites, which induced the transition phenomenon of brittleness to ductility in the AlxGa1−xN system.

In this study, samarium (Sm-10at%)-doped BiFeO3 (SmBFO) thin films were grown on platinum-coated glass substrates using pulsed laser deposition (PLD) to unveil the correlation between the microstructures and nanomechanical properties of the films. The PLD-derived SmBFO thin films were prepared under various oxygen partial pressures (PO2) of 10, 30, and 50 mTorr at a substrate temperature of 600 °C. The scanning electron microscopy analyses revealed a surface morphology consisting of densely packed grains, although the size distribution varied with the PO2. X-ray diffraction results indicate that all SmBFO thin films are textured and preferentially oriented along the (110) crystallographic orientation. The crystallite sizes of the obtained SmBFO thin films calculated from the Scherrer and (Williamson–Hall) equations increased from 20 (33) nm to 25 (52) nm with increasing PO2. In addition, the nanomechanical properties (the hardness and Young’s modulus) of the SmBFO thin films were measured by using nanoindentation. The relationship between the hardness and crystalline size of SmBFO thin films appears to closely follow the Hall–Petch equation. In addition, the PO2 dependence of the film microstructure, the crystallite size, the hardness, and Young’s modulus of SmBFO thin films are discussed.

In this work, we investigate that the capping layer (CL) engineering of aluminum oxide (AlOx) on the dopant-free hafnium oxide (HfOx) and the hafnium zirconium oxide (HfZrOx) ferroelectric metal-ferroelectric-metal (MFM) capacitors. The AlOx CL featuring large bandgap and excellent thermal stability offers a stable interface favorable for ferroelectric phase transition. Therefore, the ferroelectric polarization and high-temperature leakage current of HfZrOx MFM capacitor can be largely improved due to the combination of zirconium doping and AlOx capping effect. From the analysis of interface thermodynamic stability and leakage current mechanism, the AlOx CL effectively alleviates interface defect traps between electrode and ferroelectric HfZrOx, which lowers high-temperature leakage current, reduces ferroelectric domains pinning, enhances ferroelectric polarization, and stabilizes the long-term endurance cycling.

In this work, we investigate the ferroelectricity of stacked zirconium oxide and hafnium oxide (stacked HfZrO) with different thickness ratios under metal gate stress and simultaneously evaluate the electrical reliability of stacked ferroelectric films. Based on experimental results, we find that the stacked HfZrO films not only exhibited excellent ferroelectricity but also demonstrated a high performance on reliability. The optimized condition of the 45% Zr proportion exhibited a robust ferroelectric polarization value of 32.57 μC/cm2, and a polarization current with a peak value of 159.98 μA. Besides this, the ferroelectric stacked HfZrO also demonstrated good reliability with a ten-year lifetime under >−2 V constant voltage stress. Therefore, the appropriate modulation of zirconium proportion in stacked HfZrO showed great promise for integrating in high-performance ferroelectric memory.

A two-dimensional (2D) material known as indium selenide (InSe) is widely considered a promising layered semiconductor with potential applications in electronics and optoelectronics. However, the single phase of InSe is still a challenge due to the close formation energy of InSe and In2Se3. In this study, we demonstrate a novel growth method for 2D InSe with an indium precursor layer by molecular beam epitaxy. Indium pre-deposited on substrate at room temperature followed by growth of InSe at 550°C can overcome the problem of stoichiometry control and can be applied on amorphous substrate with high quality. According to Raman scattering spectra, X-ray diffraction, and high-resolution transmission electron microscopy results, we find that 2D InSe phase can be facile formed under both indium-rich and -poor conditions. The pre-deposited indium precursor effectively induces replacement with subsequent Se and In atoms to form the InSe phase while suppressing the In2Se3 phase. Additionally, this single phase InSe is stable in the atmosphere, exhibiting superior electronic properties even after over 100 days exposure. Recently, this method has been successfully applied to a flexible substrate, such as aluminum foil, resulting in reliable InSe quality. Our results demonstrate an innovative and forward-looking approach to developing 2D InSe material.

Abstract Two-dimensional (2D) layered GaSe films were grown on GaAs (001), GaN/Sapphire, and Mica substrates by molecular beam epitaxy (MBE). The in situ reflective high-energy electron diffraction monitoring reveals randomly in-plane orientations of nucleated GaSe layers grown on hexagonal GaN/Sapphire and Mica substrates, whereas single-orientation GaSe domain is predominant in the GaSe/GaAs (001) sample. Strong red-shifts in the frequency of in-plane $${E}_{2g}^{2}$$ E2g2 vibration modes and bound exciton emissions observed from Raman scattering and photoluminescence spectra in all samples are attributed to the unintentionally biaxial in-plane tensile strains, induced by the dissimilarity of symmetrical surface structure between the 2D-GaSe layers and the substrates during the epitaxial growth. The results in this study provide an important understanding of the MBE-growth process of 2D-GaSe on 2D/3D hybrid-heterostructures and pave the way in strain engineering and optical manipulation of 2D layered GaSe materials for novel optoelectronic integrated technologies.

Bismuth vanadate (BiVO4) has attracted substantial attention on account of its usefulness in producing hydrogen by photoelectrochemical (PEC) water splitting. The exploitation of BiVO4 for this purpose is yet limited by severe charge recombination in the bulk of BiVO4, which is caused by the short diffusion length of the photoexcited charge carriers and inefficient charge separation. Enormous effort has been made to improve the photocurrent density and solar-to-hydrogen conversion efficiency of BiVO4. This study demonstrates that modulating the composition of the electrode and the electronic configuration of BiVO4 by decoration with silver nanoparticles (Ag NPs) is effective in not only enhancing the charge carrier concentration but also suppressing charge recombination in the solar water splitting process. Decoration with a small number of Ag NPs significantly enhances the photocurrent density of BiVO4 to an extent that increases with the concentration of the Ag NPs. At 0.5% Ag NPs, the photocurrent density approaches 4.1 mA cm−2 at 1.23 V versus a reversible hydrogen electrode (RHE) under solar simulated light illumination; this value is much higher than the 2.3 mA cm−2 of pure BiVO4 under the same conditions. X-ray absorption spectroscopy (XAS) is utilized to investigate the electronic structure of pure BiVO4 and its modification by decoration with Ag NPs. Analytical results indicate that increased distortion of the VO4 tetrahedra alters the V 3d–O 2p hybridized states. Additionally, as the Ag concentration increases, the oxygen vacancy defects that act as recombination centers in BiVO4 are reduced. In situ XAS, which is conducted under dark and solar illumination conditions, reveals that the significantly enhanced PEC performance is attributable to the synergy of modulated atomic/electronic structures and the localized surface plasmon resonance effect of the Ag nanoparticles.

Single-phase two-dimensional (2D) indium monoselenide (γ-InSe) film is successfully grown via solid phase epitaxy in the molecular beam epitaxy (MBE) system. Having high electron mobility and high photoresponsivity, ultrathin 2D γ-InSe semiconductors are attractive for future field-effect transistor and optoelectronic devices. However, growing single-phase γ-InSe film is a challenge due to the polymorphic nature of indium selenide (γ-InSe, α-In2Se3, β-In2Se3, γ-In2Se3, etc.). In this work, the 2D α-In2Se3 film was first grown on a sapphire substrate by MBE. Then, the high In/Se ratio sources were deposited on the α-In2Se3 surface, and an γ-InSe crystal emerged via solid-phase epitaxy. After 50 min of deposition, the initially 2D α-In2Se3 phase was also transformed into a 2D γ-InSe crystal. The phase transition from 2D α-In2Se3 to γ-InSe was confirmed by Raman, XRD, and TEM analysis. The structural ordering of 2D γ-InSe film was characterized by synchrotron-based grazing-incidence wide-angle X-ray scattering (GIWAXS).

The high electron mobility transistor (HEMT) structures on Si (111) substrates were fabricated with heavily Fe-doped GaN buffer layers by metalorganic chemical vapor deposition (MOCVD). The heavy Fe concentrations employed for the purpose of highly insulating buffer resulted in Fe segregation and 3D island growth, which played the role of a nano-mask. The in situ reflectance measurements revealed a transition from 2D to 3D growth mode during the growth of a heavily Fe-doped GaN:Fe layer. The 3D growth mode of Fe nano-mask can effectively annihilate edge-type threading dislocations and improve transfer properties in the channel layer, and consequently decrease the vertical leakage current by one order of magnitude for the applied voltage of 1000 V. Moreover, the employment of GaN:C film on GaN:Fe buffer can further reduce the buffer leakage-current and effectively suppress Fe diffusion.

This investigation considers a method to ameliorate drain induced barrier lowing behavior in amorphous-indium-gallium-zinc-oxide thin-film transistors. The Vth is found to shift negatively when increasing the ID-VG measurement condition VD from 0.1 to 15 V. The current-voltage curves show that this degradation is caused by the effective channel length (Leff) being shorter than the mask channel length (L). Using the transmission line method to extract Leff, we discover that the degradation will be completely suppressed by an annealing treatment. As a result, the degradation mechanism of shorter channel length a-IGZO thin film transistors is due to oxygen-vacancies which are located between the channel and the source/drain junction.

The effect of Mg doping on the electrical and optical properties of the p-GaN/AlGaN structures on a Si substrate grown by metal organic chemical vapor deposition was investigated. The Hall measurement showed that the activation efficiency of the sample with a 450 sccm Cp2Mg flow rate reached a maximum value of 2.22%. No reversion of the hole concentration was observed due to the existence of stress in the designed sample structures. This is attributed to the higher Mg-to-Ga incorporation rate resulting from the restriction of self-compensation under compressive strain. In addition, by using an AlN interlayer (IL) at the interface of p-GaN/AlGaN, the activation rate can be further improved after the doping concentration reaches saturation, and the diffusion of Mg atoms can also be effectively suppressed. A high hole concentration of about 1.3 × 1018 cm−3 can be achieved in the p-GaN/AlN-IL/AlGaN structure.

A comprehensive lattice dynamical study is reported to emphasize the vibrational behavior of perfect/imperfect zinc-blende (zb) ZnSe, MnSe and Zn1−xMnxSe alloys. Low temperature far-infrared (FIR) reflectivity measurements performed on a series of molecular beam epitaxy grown Zn1−xMnxSe/GaAs (001) epilayers have a typical ‘intermediate-phonon-mode’ behavior. Besides perceiving ZnSe- and MnSe-like TO-phonon resonances, the study also revealed a weak Mn alloy-disorder mode below MnSe band. A classical effective-medium theory of multilayer optics is used to evaluate dielectric tensors of both epilayers and substrate for simulating reflectivity and transmission spectra of ultrathin epifilms and superlattices at near normal and/or oblique incidence. In the framework of a realistic rigid-ion model and exploiting an average t-matrix Greens function (ATM-GF) theory we appraised the vibrational properties of nitrogen and phosphorous doped Zn-Mn chalcogenides. Lattice relaxations around isolated NSe (PSe) defects in ZnSe and zb MnSe are evaluated by first principles bond-orbital model that helped construct perturbation models for simulating the localized vibrational modes (LVMs). Calculated shift of impurity modes for isotopic 14NSe (15NSe) defects in ZnSe offered a strong revelation of an inflexible defect–host interaction. By retaining force constant change parameter of 14NSe (15NSe) in heavily N-doped ZnSe, the ATM-GF theory predicted (a) three non-degenerate LVMs for the photoluminescence defect center V Se-Zn-14NSe (V Se-Zn-15NSe) of C s symmetry, and (b) six impurity modes for the second nearest-neighbor NSe-Zn-NSe pair defect of C 2v symmetry. From the range of simulated defect modes, we have ruled out the possibility of N-pairs and justified the presence of VSe-Zn-NSe complex centers – likely to be responsible for the observed large absorption bandwidth in highly N-doped ZnSe. High resolution measurements of FIR absorption and/or Raman scattering spectroscopy are needed to validate the accuracy of our theoretical conjectures.