Structural and surface characterizations of 2D ß-In2Se3/3D ß-Ga2O3 heterostructures grown on c-Sapphire substrates by molecular beam epitaxy.

Integrating two-dimensional (2D) layered materials with wide bandgap ß-Ga2O3 has unveiled impressive opportunities for exploring novel physics and device concepts. This study presents the epitaxial growth of 2D ß-In2Se3/3D ß-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 ( 2 ¯ 01 ) ß-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 ß-Ga2O3 ~ 3.038Å. In the next stage, for the first time, 2D In2Se3 layers were epitaxially realized on 3D ß-Ga2O3 under varying substrate temperatures (Tsub) and Se/In flux ratios (RVI/III). The deposited layers exhibited (00l) oriented ß-In2Se3 on ( 2 ¯ 01 ) ß-Ga2O3/c-Sapphire with the epitaxial relationship of [ 11 2 ¯ 0 ] ß-In2Se3 || [010] ß-Ga2O3 and [ 10 1 ¯ 0 ] ß-In2Se3 || [102] ß-Ga2O3 as observed from the RHEED patterns. Also, the in-plane 'a' lattice constant of ß-In2Se3 was determined to be ~ 4.027Å. The single-phase ß-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 ß-In2Se3 on 3D ß-Ga2O3, a consequence of the quasi-van der Waals epitaxy. Furthermore, the ß-Ga2O3 with an optical bandgap (Eg) of ~ 5.04 eV (deep ultraviolet) when integrated with 2D ß-In2Se3, Eg ~ 1.43eV (near infra-red) can reveal potential applications in the optoelectronic field.

Nanotribological Characteristics of the Al Content of AlxGa1-xN Epitaxial Films.

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.

Self-Trapped, Thermally Equilibrated Delayed Fluorescence Enables Low-Reabsorption Luminescent Solar Concentrators Based on Gold-Doped Silver Nanoclusters.

Reabsorption-free luminescent solar concentrators (LSCs) are crucial ingredients for photovoltaic windows. Atomically precise metal nanoclusters (NCs) with large Stokes-shifted photoluminescence (PL) hold great promise for applications in LSCs. However, a fundamental understanding of the PL mechanism, particularly on the excited-state interaction and exciton kinetics, is still lacking. Herein, we studied the exciton-phonon coupling and singlet/triplet exciton dynamics for gold-doped silver NCs in a solid matrix. Following photoexcitation, the excitons can be self-trapped via strong exciton-phonon coupling. Subsequently, rapid thermal equilibration between the singlet and triplet states occurs due to the coexistence of small energy splitting and spin-orbit coupling. Finally, broadband delayed fluorescence with a large Stokes shift can be generated, namely, self-trapped, thermally equilibrated delayed fluorescence (ST-TEDF). Benefiting from superior ST-TEDF, we demonstrated efficient LSCs with minimized reabsorption.

Effects of Oxygen Pressure on the Microstructures and Nanomechanical Properties of Samarium-Doped BiFeO3 Thin Films.

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.

Ferroelectricity and Oxide Reliability of Stacked Hafnium-Zirconium Oxide Devices.

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.

Effect of Ag-Decorated BiVO4 on Photoelectrochemical Water Splitting: An X-ray Absorption Spectroscopic Investigation.

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.

In Situ/Operando Soft X-ray Spectroscopic Identification of a Co4+ Intermediate in the Oxygen Evolution Reaction of Defective Co3O4 Nanosheets.

Defect engineering is an important means of improving the electrochemical performance of the Co3O4 electrocatalyst in the oxygen evolution reaction (OER). In this study, operando soft X-ray absorption spectroscopy (SXAS) is used to explore the electronic structure of Co3O4 under OER for the first time. The defect-rich Co3O4 (D-Co3O4) has a Co2.45+ state with Co2+ at both octahedral (Oh) and tetrahedral (Td) sites and Co3+ at Oh, whereas Co3O4 has Co2.6+ with Co2+ and Co3+ at Td and Oh sites, respectively. SXAS reveals that upon increasing the voltage, the Co2+ in D-Co3O4 is converted to low-spin Co3+, some of which is further converted to low-spin Co4+; most Co2+ in Co3O4 is converted to Co3+ but rarely to Co4+. When the voltage is switched off, Co4+ intermediates quickly disappear. These findings reveal Co(Oh) in D-Co3O4 can be rapidly converted to active low-spin Co4+ under operando conditions, which cannot be observed by ex situ XAS.

Solid Phase Epitaxy of Single Phase Two-Dimensional Layered InSe Grown by MBE.

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, ß-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 Effect of Heavy Fe-Doping on 3D Growth Mode and Fe Diffusion in GaN for High Power HEMT Application.

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.

Pressure induced structural phase crossover of a GaSe epilayer grown under screw dislocation driven mode and its phase recovery.

Hydrostatically pressurized studies using diamond anvil cells on the structural phase transition of the free-standing screw-dislocation-driven (SDD) GaSe thin film synthesized by molecular beam epitaxy have been demonstrated via in-situ angle-dispersive synchrotron X-ray diffraction and Raman spectroscopy. The early pressure-driven hexagonal-to-rock salt transition at approximately ~ 20 GPa as well as the outstandingly structural-phase memory after depressurization in the SDD-GaSe film was recognized, attributed to the screw dislocation-assisted mechanism. Note that, the reversible pressure-induced structural transition was not evidenced from the GaSe bulk, which has a layer-by-layer stacking structure. In addition, a remarkable 1.7 times higher in bulk modulus of the SDD-GaSe film in comparison to bulk counterpart was observed, which was mainly contributed by its four times higher in the incompressibility along c-axis. This is well-correlated to the slower shifting slopes of out-of-plane phonon-vibration modes in the SDD-GaSe film, especially at low-pressure range (< 5 GPa). As a final point, we recommend that the intense density of screw dislocation cores in the SDD-GaSe lattice structure plays a crucial role in these novel phenomena.

High Hole Concentration and Diffusion Suppression of Heavily Mg-Doped p-GaN for Application in Enhanced-Mode GaN HEMT.

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.

Utilizing host-guest interaction enables the simultaneous enhancement of the quantum yield and Stokes shift in organosilane-functionalized, nitrogen-containing carbon dots for laminated luminescent solar concentrators.

Solar energy can be harvested using luminescent solar concentrators (LSCs) incorporated with edge-mounted solar cells without sacrificing their see-through visibility, thus facilitating the development of solar windows. Eco-friendly carbon dots (CDs) are promising alternatives to heavy-metal-containing quantum dots in LSC applications. Unfortunately, their solid-state quantum yield (QY) at high optical density (required by laminated LSCs) is still low (<30%) and the Stokes shift is only moderate (<100 nm). Here, we studied the host-guest interaction between aminosilane-functionalized, nitrogen-containing CDs (Si-NCDs) and a silica matrix for preparing efficient laminated LSCs. We found that a sol-gel-derived silica matrix with vacuum treatment can efficiently suppress the direct nonradiative transition of the absorbing states and selectively enhance the long-wavelength-emitting surface states. Therefore, the formed Si-NCDs@silica composites simultaneously exhibited high QYs (>60%) and large Stokes shifts (>200 nm) even at a high loading content (∼10 wt%), while still exhibiting high optical transparency. Moreover, unlike conventional QY reduction upon increasing the excitation wavelengths, such high QY values can be maintained over all excitation wavelengths in the absorption region. Benefiting from these photophysical properties, efficient laminated LSCs were simply prepared, yielding a high optical efficiency of ∼4.4%.

Substrate-induced strain in 2D layered GaSe materials grown by molecular beam epitaxy.

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 [Formula: see text] 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.

Visible-Transparent Luminescent Solar Concentrators Based on Carbon Nanodots in the Siloxane Matrix with Ultrahigh Quantum Yields and Optical Transparency at High-Loading Contents.

Visible-transparent luminescent solar concentrators (VT-LSCs) can be integrated with solar cells for designing solar glasses. Recently, rare-earth complexes, semiconductor nanocrystals, and carbon nanodots (CNDs) have been applied in developing VT-LSCs. However, several challenges still existed, such as quantum yields (QYs) at high-loading contents, scattering/reabsorption losses, and stability. Here, highly luminescent and visible-transparent composites based on organosilane-functionalized CNDs (Si-CNDs) cross-linked in the siloxane matrix were prepared. The composites with a high-loading content (∼10 wt %) possess ultrahigh QYs of ∼94% due to surface passivation, cross-linking-enhanced emission, and negligible inter-CND energy transfer. Moreover, they still appear exceptionally transparent and, thus, are suitable for VT-LSCs. Eco-friendly VT-LSCs without colored tinting were fabricated, yielding high internal and external quantum efficiencies of ∼66% and ∼3.9%. Our demonstration would pave a bright way for the utilization of eco-friendly VT-LSCs in solar glasses.

Screw-Dislocation-Driven Growth Mode in Two Dimensional GaSe on GaAs(001) Substrates Grown by Molecular Beam Epitaxy.

Regardless of the dissimilarity in the crystal symmetry, the two-dimensional GaSe materials grown on GaAs(001) substrates by molecular beam epitaxy reveal a screw-dislocation-driven growth mechanism. The spiral-pyramidal structure of GaSe multi-layers was typically observed with the majority in ε-phase. Comprehensive investigations on temperature-dependent photoluminescence, Raman scattering, and X-ray diffraction indicated that the structure has been suffered an amount of strain, resulted from the screw-dislocation-driven growth mechanism as well as the stacking disorders between monolayer at the boundaries of the GaSe nanoflakes. In addition, Raman spectra under various wavelength laser excitations explored that the common ε-phase of 2D GaSe grown directly on GaAs can be transformed into the ß-phase by introducing a Se-pretreatment period at the initial growth process. This work provides an understanding of molecular beam epitaxy growth of 2D materials on three-dimensional substrates and paves the way to realize future electronic and optoelectronic heterogeneous integrated technology as well as second harmonic generation applications.

Coordination-induced emission enhancement in gold-nanoclusters with solid-state quantum yields up to 40% for eco-friendly, low-reabsorption nano-phosphors.

Colloidal quantum dots (CQDs) have gained much attention as light-emitting materials for light-conversion nano-phosphors and luminescent solar concentrators. Unfortunately, those CQDs involve toxic heavy metals and frequently need to be synthesized in the hazardous organic solvent. In addition, they suffer from severe solid-state aggregation-induced self-quenching and reabsorption losses. To address these issues, here we prepare Zn-coordinated glutathione-stabilized gold-nanocluster (Zn-GSH-AuNCs) assemblies without involving heavy metals and organic solvent. Unlike GSH-AuNCs dispersed in an aqueous solution with poor photoluminescence quantum yields (PL-QYs, typically ~1%), those Zn-GSH-AuNCs powders hold high solid-state PL-QYs up to 40 ± 5% in the aggregated state. Such Zn-induced coordination-enhanced emission (CEE) is attributed to the combined effects of suppressed non-radiative relaxation and enhanced charge-transfer interaction. In addition, they also exhibit a large Stokes shift, thus mitigating both aggregation-induced self-quenching and reabsorption losses. Motivated by these photophysical properties, we demonstrated white-light emission from all non-toxic, aqueous-synthesis nano-materials.

Greener Luminescent Solar Concentrators with High Loading Contents Based on in Situ Cross-Linked Carbon Nanodots for Enhancing Solar Energy Harvesting and Resisting Concentration-Induced Quenching.

A luminescent solar concentrator (LSC) is composed of loaded luminophores and a waveguide that can be employed to harvest and concentrate both direct and diffused sunlight for promising applications in solar windows. Thus far, most of efficient LSCs still relied on the heavy-metal-containing colloidal quantum dots (CQDs) dispersed into a polymer matrix with a very low loading (typically <1 wt %). Such low-loading constraint is required to mitigate the concentration-induced quenching (CIQ) and maintain high optical quality and film uniformity, but this would strongly reduce the light-absorbing efficiency. To address all issues, greener LSCs with high loading concentration were prepared by in situ cross-linking organosilane-functionalized carbon nanodots (Si-CNDs), and their photophysical properties relevant to LSC operation were studied. The PL emission is stable and does not suffer from the severe CIQ effect for cross-linked Si-CNDs even with 25 wt % loadings, thus exhibiting high solid-state quantum yields (QYs) up to 45 ± 5% after the calibration of the reabsorption losses. Furthermore, such LSCs can still hold high optical quality and film uniformity, leading to low scattering losses and high internal quantum efficiency of ∼22%. However, the reabsorption losses need to be further addressed to realize large-area LSCs based on earth-abundant, cost-effective CNDs.

Visible light-induced electronic structure modulation of Nb- and Ta-doped α-Fe2O3 nanorods for effective photoelectrochemical water splitting.

The photoelectrochemical (PEC) water splitting activity of Nb and Ta-doped hematite (α-Fe2O3) nanorods was investigated with reference to electronic structures by in situ synchrotron x-ray absorption spectroscopy (XAS). Current density-potential measurements demonstrate that the PEC activity of α-Fe2O3 nanorods depends strongly on the species and concentrations of dopants. The doping of α-Fe2O3 nanorods with a low level of Nb or Ta can improve their electrical conductivity and thereby facilitate charge transport and reduced electron-hole recombination therein. The photoconversion effects of Nb and Ta-doped α-Fe2O3 by in situ XAS in the dark and under illumination revealed opposite evolutions of the spectral intensities of the Fe L-edge and Nb/Ta L-edge, indicating that charge transfer and a conduction pathway are involved in the photoconversion. Analytic in situ XAS results reveal that the α-Fe2O3 that is doped with a low level of Nb has a greater photoconversion efficiency than that doped with Ta because Nb sites are more active than Ta sites in α-Fe2O3. The correlation between PEC activity and the electronic structure of Nb/Ta-doped α-Fe2O3 is examined in detail using in situ XAS and helps to elucidate the mechanism of PEC water splitting in terms of the electronic structure.

Operando X-ray spectroscopic observations of modulations of local atomic and electronic structures of color switching smart film.

Smart windows, which change color in response to external stimuli, are extensively studied owing to their potential technological applications in sensors and their ability to reduce the energy consumed by buildings. Most related studies focus on the optical properties of smart color switching films that can control the transmission of light and that of heat independently. This study examines the vanadium pentoxide thin film as a model system of a color switchable window. A gasochromic thin film of V2O5 is fabricated using sol-gel spin coating. In operando soft X-ray absorption spectroscopy (XAS) at the V L-edge is used to determine the evolutions of the electronic and atomic structures of V2O5 thin film under gasochromic color switching. Analysis of the V K-edge with respect to crystalline structural symmetry and valence requires many reference samples, whereas the V L-edge, which involves V 3d orbitals of various symmetries, can provide information about the atomic/electronic structures without many reference samples. A new gas reaction in situ cell was developed to collect the total-electron-yield XAS. The total-electron-yield signal can provide more accurate information about atomic and electronic structures than can the fluorescence-yield signal, which typically exerts a saturation effect. Analytical results reveal that the gasochromic reaction changes the charge state and causes a local atomic structural deformation of the film. The suggestion has been made that in the reaction, the central vanadium atom within the octahedron moves closer to the basal plane such that the apical V-O bond becomes more symmetrical than the film before gasochromic coloration. Unlike the cell that is used for hard XAS, and for which only cation sites can be studied, this in situ gas cell enables the real-time studies of atomic/electronic structures at gas-solid interfaces from viewpoints of both cation and anion sites.

Enhanced Conversion Efficiency of III-V Triple-junction Solar Cells with Graphene Quantum Dots.

Graphene has been used to synthesize graphene quantum dots (GQDs) via pulsed laser ablation. By depositing the synthesized GQDs on the surface of InGaP/InGaAs/Ge triple-junction solar cells, the short-circuit current, fill factor, and conversion efficiency were enhanced remarkably. As the GQD concentration is increased, the conversion efficiency in the solar cell increases accordingly. A conversion efficiency of 33.2% for InGaP/InGaAs/Ge triple-junction solar cells has been achieved at the GQD concentration of 1.2 mg/ml, corresponding to a 35% enhancement compared to the cell without GQDs. On the basis of time-resolved photoluminescence, external quantum efficiency, and work-function measurements, we suggest that the efficiency enhancement in the InGaP/InGaAs/Ge triple-junction solar cells is primarily caused by the carrier injection from GQDs to the InGaP top subcell.