Maximizing Photoelectrochemical Performance in Metal-Oxide Hybrid Composites via Amorphous Exsolution-A New Exsolution Mechanism for Heterogeneous Catalysis.

Exsolution generates metal nanoparticles anchored within crystalline oxide supports, ensuring efficient exposure, uniform dispersion, and strong nanoparticle-perovskite interactions. Increased doping level in the perovskite is essential for further enhancing performance in renewable energy applications; however, this is constrained by limited surface exsolution, structural instability, and sluggish charge transfer. Here, hybrid composites are fabricated by vacuum-annealing a solution containing SrTiO3 photoanode and Co cocatalyst precursors for photoelectrochemical water-splitting. In situ transmission electron microscopy identifies uniform, high-density Co particles exsolving from amorphous SrTiO3 films, followed by film-crystallization at elevated temperatures. This unique process extracts entire Co dopants with complete structural stability, even at Co doping levels exceeding 30%, and upon air exposure, the Co particles embedded in the film oxidize to CoO, forming a Schottky junction at the interface. These conditions maximize photoelectrochemical activity and stability, surpassing those achieved by Co post-deposition and Co exsolution from crystalline oxides. Theoretical calculations demonstrate in the amorphous state, dopant─O bonds become weaker while Ti─O bonds remain strong, promoting selective exsolution. As expected from the calculations, nearly all of the 30% Fe dopants exsolve from SrTiO3 in an H2 environment, despite the strong Fe─O bond's low exsolution tendency. These analyses unravel the mechanisms driving the amorphous exsolution.

High Performance, Stable, and Flexible Piezoelectric Nanogenerator Based on GaN:Mg Nanowires Directly Grown on Tungsten Foil.

Rapid development of micro-electromechanical systems increases the need for flexible and durable piezoelectric nanogenerators (f-PNG) with high output power density. In this study, a high-performance, flexible, and highly stable f-PNG is prepared by directly growing the Mg-doped semi-insulating GaN nanowires (NWs) on a 30-µm-thick tungsten foil using vapor-liquid-solid growth mechanism. The direct growth of NWs on metal foil extends the overall lifetime of the f-PNG. The semi-insulating GaN NWs significantly enhance the piezoelectric performance of the f-PNG by reducing free electron density. Additionally, the direct integration of NWs on the tungsten foil improves the conductivity, resulting in current enhancement (2.5 mA) with an output power density of 13 mW cm-2 . The piezoelectric performance of the f-PNG is investigated under several bending angles, actuation frequencies, continuous vibrations, and airflow velocities. The maximum output voltage exhibited by the f-PNG is 20 V at a bending angle of 155°. The f-PNG is connected to the backside of an index finger to monitor finger bending behavior by changing the current density. Depending on its flexibility and sensitivity, the f-PNG can be used as a health-monitoring sensor to be mounted on joints (fingers, hands, elbows, and knees) to monitor their repeated bending and relaxation.

Enhanced stability of piezoelectric nanogenerator based on GaN/V2O5 core-shell nanowires with capacitive contact.

Enhanced stability of a piezoelectric nanogenerator (PNG) was demonstrated using c- and m-axis GaN/V2O5 core-shell nanowires (NWs) by analyzing the capacitive coupling of the PNG's output. The NW array grown on GaN thin film was embedded in polydimethylsiloxane (PDMS) matrix, following which the matrix was transferred to an indium (In)-coated PET substrate for achieving superior flexibility of the PNG. The stability of the PNG was enhanced by holding the NW PDMS composite with a PDMS polymer as a bonding material on the PET substrate. The inserted PDMS layer improved the lifetime of the PNG, however, because of the insulating nature of PDMS, the piezoelectric output of GaN NWs was coupled capacitively to In contact on PET substrate and it resulted in a slight degradation of piezoelectric output due to the voltage drop across the bottom capacitive contact. The maximum piezoelectric current was 64 nA and output voltage was 11.9 V from the PNG with c-axis NWs. While the PNG with direct bottom contact exhibited 57% output reduction after 72 000 operation cycles, the PNG with capacitive contact did not show any degradation in stability even after 150 000 cycles.

Type-II ZnO/ZnS core-shell nanowires: Earth-abundant photoanode for solar-driven photoelectrochemical water splitting.

A core-shell structure, formed in a nanostructured photoanode, is an effective strategy to achieve high solar-to-hydrogen conversion efficiency. In this study, we present a facile and simple synthesis of a unique vertically aligned ZnO/ZnS core-shell heterostructure nanowires (NWs) on a Si substrate. Well-aligned ZnO NWs were grown on Si (100) substrates on a low-temperature ZnO buffer layer by metal-organic chemical vapor deposition. The ZnO NWs were then coated with various thicknesses of ZnS shell layers using atomic layer deposition. The structural characterizations exhibit the well-developed ZnO/ZnS core-shell NWs heterostructure. The as-prepared ZnO/ZnS core-shell NWs was applied as photoanode for photoelectrochemical (PEC) water splitting. This unique ZnO/ZnS core-shell NWs photoanode shows photocurrent density of 1.21 mA cm-2, which is 8.5 times higher than bare ZnO NWs. The PEC performance and the applied-bias-photon-to-current conversion efficiency of ZnO/ZnS core-shell NWs photoanode are further improved with the optimized ZnS shell. The type-II band alignment of the heterostructure photoanode is the key factor for their excellent PEC performance. Importantly, this type of core-shell NWs heterostructure provides useful insights into novel electrode design and fabrication based on earth abundant materials for low-cost solar fuel generation.

Enhanced photoelectrochemical stability of GaN photoelectrodes by Al2O3 surface passivation layer.

Photoelectrochemical (PEC) water splitting is one of the most promising hydrogen production methods because of its high efficiency, renewable resources and harmless by-products. Gallium nitride (GaN) is suitable for PEC water splitting because it has excellent stability in electrolyte and band gap energy which straddles the redox potential of water (Vredox = 1.23 V). These characteristics allow this material to split water stably without external bias. However, the stability of GaN is still not sufficient for practical applications. In this study, we investigated the properties of GaN photoelectrodes with aluminum oxide (Al2O3) thin film as a protection layer for increasing stability. In a long-term stability test, Al2O3-coated GaN showed more stable photocurrent than that of bare GaN. The total hydrogen production amount was also improved in Al2O3-coated samples than bare GaN. These results indicate that the Al2O3 protection layer significantly enhances stability and hydrogen production.

Solar-Powered AEM Electrolyzer via PGM-Free (Oxy)hydroxide Anode with Solar to Hydrogen Conversion Efficiency of 12.44.

Water electrolyzers powered by renewable energy are emerging as clean and sustainable technology for producing hydrogen without carbon emissions. Specifically, anion exchange membrane (AEM) electrolyzers utilizing non-platinum group metal (non-PGM) catalysts have garnered attention as a cost-effective method for hydrogen production, especially when integrated with solar cells. Nonetheless, the progress of such integrated systems is hindered by inadequate water electrolysis efficiency, primarily caused by poor oxygen evolution reaction (OER) electrodes. To address this issue, a NiFeCo─OOH has developed as an OER electrocatalyst and successfully demonstrated its efficacy in an AEM electrolyzer, which is powered by renewable electricity and integrated with a silicon solar cell.

Enhanced luminous efficacy in phosphor-converted white vertical light-emitting diodes using low index layer.

We demonstrated improved luminous efficacy for GaN-based vertical light emitting diodes (VLEDs) employing a low index layer composed of silicon dioxide (SiO(2)) on the top surface. Three-dimensional ðnite-difference time-domain simulations for the fabricated VLED chip show that the penetration ratio of the emitted/reflected light into the VLED chip decreased by approximately 20% compared to a normal VLED chip. This result is in good agreement with an empirical study stating that white VLEDs having a SiO(2) layer exhibit an 8.1% higher luminous efficacy than white VLEDs with no layer at an injection current of 350 mA. Photons penetrating into the VLED chip, which become extinct in the VLED chip, are reflected from the SiO(2) layer due to the index contrast between the SiO(2) layer and epoxy resin containing phosphor, with no degradation of the light-extraction efficiency of the VLED chip. As such, this structure can contribute to the enhancement of the luminous efficacy of VLEDs.

Improvement in crystal quality and optical properties of n-type GaN employing nano-scale SiO2 patterned n-type GaN substrate.

n-type GaN epitaxial layers were regrown on the patterned n-type GaN substrate (PNS) with different size of silicon dioxide (SiO2) nano dots to improve the crystal quality and optical properties. PNS with SiO2 nano dots promotes epitaxial lateral overgrowth (ELOG) for defect reduction and also acts as a light scattering point. Transmission electron microscopy (TEM) analysis suggested that PNS with SiO2 nano dots have superior crystalline properties. Hall measurements indicated that incrementing values in electron mobility were clear indication of reduction in threading dislocation and it was confirmed by TEM analysis. Photoluminescence (PL) intensity was enhanced by 2.0 times and 3.1 times for 1-step and 2-step PNS, respectively.

High-efficiency GaN-based vertical light-emitting diodes with periodic beveled rod-shaped structures.

The periodic beveled micro-rods (BMRs) were constructed on the emission surface of GaN-based vertical light-emitting diodes (VLEDs) in order to improve the light-extraction efficiency. It was experimentally demonstrated that the light output power of the VLEDs with a periodic BMR (BMR-VLED) were enhanced about 15.6%, compared with that of the VLEDs with randomly textured surface (RT-VLED) at an injection current of 350 mA. This finding indicates that the photons emitted from the active layer were well out-coupled at an n-GaN surface having a periodic BMR structure, resulting in an increase in the probability of escaping from the VLED structure.

Surface Engineering of Cu2O Photocathodes via Facile Graphene Oxide Decoration for Improved Photoelectrochemical Water Splitting.

Copper oxide (Cu2O) has attracted significant interest as an efficient photocathode for photoelectrochemical (PEC) water splitting owing to its abundance, suitable band gap, and band-edge potential. Nevertheless, a high charge recombination rate restricts its practical photoconversion efficiency and reduces the PEC water-splitting performance. To address this challenge, we present the facile electrodeposition of graphene oxide (GO) on the Cu2O photocathode surface. To determine the effect of varying GO weight percentages on PEC performance, varying amounts of GO were deposited on the Cu2O photocathode surface. The optimally deposited GO-Cu2O photocathode exhibited a photocurrent density of -0.39 to -1.20 mA/cm2, which was three times that of a photocathode composed of pristine Cu2O. The surface decoration of Cu2O with GO reduced charge recombination and improved the PEC water-splitting performance. These composites can be utilized in strategies designed to address the challenges associated with low-efficiency Cu2O photocathodes. The physicochemical properties of the prepared samples were comprehensively characterized by field-emission scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, Raman spectroscopy, UV-visible spectroscopy, and X-ray photoelectron spectroscopy. We believe that this research will pave the way for developing efficient Cu2O-based photocathodes for PEC water splitting.

Nanostructured Au Electrode with 100 h Stability for Solar-Driven Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide.

Solar-to-chemical energy conversion is a potential alternative to fossil fuels. A promising approach is the electrochemical (EC) reduction of CO2 to value-added chemicals, particularly hydrocarbons. Here, we report on the selective EC reduction of CO2 to CO on a porous Au nanostructure (pAu) cathode in 0.1 M KHCO3. The pAu cathode anodized at 2.6 V exhibited maximum Faradaic efficiency (FE) for conversion of CO2 to CO (up to 100% at -0.75 V vs reversible hydrogen electrode (RHE)). Furthermore, commercial Si photovoltaic cells were combined with EC systems (PV-EC) consisting of pAu cathodes and IrO2 anodes. The triple-junction cell and EC system resulted in a solar-to-CO conversion efficiency (SCE) of 5.3% under 1 sun illumination and was operated for 100 h. This study provides a PV-EC CO2 reduction system for CO production and indicates the potential of the PV-EC system for the EC reduction of CO2 to value-added chemicals.

Interface-engineered Z-scheme of BiVO4/g-C3N4 photoanode for boosted photoelectrochemical water splitting and organic contaminant elimination under solar light.

Although n-type bismuth vanadate (BiVO4) is regarded as an attractive solar-light-active photoanode, its short carrier-diffusion length, sluggish oxidation kinetics, low electronic conductivity, and high recombination rate are the major intrinsic shortcomings that limit its practical application. To this end, the rational design of a solar-light-active, metal-free BiVO4-based Z-scheme heterojunction photoanode is of great significance for achieving effective charge-separation features and maximum light utilization as well as boosting redox activity for efficient environmental treatment and photoelectrochemical water splitting. Herein, we propose a facile approach for the decoration of metal-free graphitic carbon nitride (g-C3N4) nanosheets on BiVO4 to form a Z-scheme BiVO4/g-C3N4 photoanode with boosted photoelectrochemical (PEC) water splitting and rapid photoelectrocatalytic degradation of methyl orange (MO) dye under simulated solar light. The successful preparation of the Z-scheme BiVO4/g-C3N4 photoanode was confirmed by comprehensive structural, morphological, and optical analyses. Compared with the moderate photocurrent density of bare BiVO4 (0.39 mA cm-2), the Z-scheme BiVO4/g-C3N4 photoanode yields a notable photocurrent density of 1.14 mA cm-2 at 1.23 V vs. RHE (≈3-fold higher) with the promising long-term stability of 5 h without any significant photo-corrosion. Moreover, the PEC dye-degradation studies revealed that the Z-scheme BiVO4/g-C3N4 photoanode successfully degraded MO (≈90%) in 75 min, signifying a 30% improvement over bare BiVO4. This research paves the way for rational interface engineering of solar-light-active BiVO4-based noble-metal-free Z-schemes for eco-friendly PEC water splitting and water remediation.

Nanostructured CuO with a thin g-C3N4 layer as a highly efficient photocathode for solar water splitting.

A g-C3N4/CuO nanostructure featuring improved photoelectrochemical properties was successfully prepared using a facile and cost-effective method involving electrodeposition and thermal oxidation. The improved photoelectrochemical properties were mainly ascribed to the increased surface area and improved charge transportation of the g-C3N4/CuO photocathode. This photocathode can be used in novel strategies for resolving problems associated with low-efficiency CuO photocathodes.

GaN Nanowire Growth Promoted by In-Ga-Au Alloy Catalyst with Emphasis on Agglomeration Temperature and In Composition.

The crystallographic orientation control of GaN nanowires (NWs) has been widely investigated by varying the V-III ratio. Here, we report the tuning of crystallographic orientation of GaN NWs by varying the composition of indium (In) in gallium-gold (Ga-Au) alloy catalyst using metal-organic chemical vapor deposition (MOCVD). The c-plane GaN thin film and sapphire substrate are used as growth templates. We found that the substrates of same orientation have a negligible influence on the orientation of the GaN NWs. The catalyst composition and the dimensions of alloy droplets determine the morphology of the NWs. The density of the NWs was controlled by tuning the droplet size of the alloy catalysts. With the constant V/III ratio, the crystallographic orientation of the GaN NWs was tuned from m- to c-axis by increasing the In composition inside alloy catalyst.

Fanless, porous graphene-copper composite heat sink for micro devices.

Thermal management in devices directly affects their performance, but it is difficult to apply conventional cooling methods such as the use of cooling liquids or fans to micro devices owing to the small size of micro devices. In this study, we attempted to solve this problem by employing a heat sink fabricated using copper with porous structures consisting of single-layer graphene on the surface and graphene oxide inside the pores. The porous copper/single-layer graphene/graphene oxide composite (p-Cu/G/rGO) had a porosity of approximately 35%, and the measured pore size was approximately 10 to 100 µm. The internal GO was reduced at a temperature of 1000 °C. On observing the heat distribution in the structure using a thermal imaging camera, we could observe that the p-Cu/G/rGO was conducting heat faster than the p-Cu, which was consistent with the simulation. Furthermore, the thermal resistance of p-Cu/G/rGO was lower than those of the p-Cu and pure Cu. When the p-Cu/G/rGO was fabricated into a heat sink to mount the light emitting diode (LED) chip, the measured temperature of the LED was 31.04 °C, which was less than the temperature of the pure Cu of 40.8 °C. After a week of being subjected to high power (1000 mA), the light intensity of p-Cu/G/rGO decreased to 95.24%. However, the pure Cu decreased significantly to 66.04%. The results of this study are expected to be applied to micro devices for their effective thermal management.

Nanoporous Ta3N5via electrochemical anodization followed by nitridation for solar water oxidation.

Nanoporous tantalum nitride (Ta3N5) is a promising visible-light-driven photoanode for photoelectrochemical (PEC) water splitting with a narrow band gap of approximately 2.0 eV. It can utilize a large portion of the solar spectrum up to 600 nm to improve the activity of photooxidation reactions because of enhanced light scattering and an overall increase of the surface area with high light absorption and carrier collection. Herein, we synthesized a new n-type nanoporous tantalum nitride film on Ta foil by electrochemical anodization with a fluorinated electrolyte. Post-annealing in a nitrogen/ammonia mixture gas environment then transformed amorphous TaOx to crystalline Ta3N5. Effects of annealing temperature on the microstructure, optical properties, and PEC properties of samples were then investigated under changeable stoichiometry of Ta and N elements in the Ta-based nitride film. Results showed that the film annealed at 1000 °C showed high crystallinity, high visible light absorption, and a highly conductive interlayer between the substrates, resulting in the highest photocurrent density (JSC) of ∼0.25 mA cm-2 at 1.23 VRHE in PEC water splitting. In addition, depending on the annealing temperature, it is possible to engineer band alignment in the nanoporous Ta3N5 layer, allowing a beneficial charge transfer process.

Epitaxial Growth of GaN Core and InGaN/GaN Multiple Quantum Well Core/Shell Nanowires on a Thermally Conductive Beryllium Oxide Substrate.

Beryllium oxide (BeO) belongs to a very unique material family that exhibits the divergent properties of high thermal conductivity and high electrical resistivity. BeO has the same crystal structure as GaN, and the absolute difference in the lattice constants is less than 17%. Here, the growth of GaN nanowires (NWs) on the polycrystalline BeO substrate is reported for the first time. The NWs are grown by a vapor-liquid-solid approach using a showerhead-based metal-organic chemical vapor deposition. The growth direction of NWs is along the m-axis on all planes of the substrate, and it is confirmed by transmission electron microscopy (TEM) and selected area electron diffraction (SAED) patterns. The vertical and tilted growth of NWs is due to the different planes of the substrate such as the m-plane, a-plane, and semipolar planes and is confirmed by X-ray diffraction. Subsequently, the GaN shell and InGaN/GaN multiple quantum wells (MQWs) are coaxially grown using a vapor-solid approach in the same reactor. A very high crystal quality is verified by TEM and SAED and is also confirmed by measuring the photoluminescence. The optical emission is tuned for the entire visible spectrum by increasing the indium incorporation in InGaN quantum wells. The conformal growth of InGaN/GaN MQW shells and the defect-free nature of the structure are confirmed from spatially resolved cathodoluminescence. This study will provide a platform for researchers to grow GaN NWs on the BeO substrate for a range of optical and electrical applications.

Lateral arrays of vertical ZnO nanowalls on a periodically polarity-inverted ZnO template.

Well aligned ZnO nanowall arrays with submicron pitch were grown on a periodically polarity-inverted ZnO template using a carbothermal reduction process. Under the conditions of a highly dense Au catalyst for increasing nucleation sites, ZnO nanowalls with a thickness of 126 +/- 10 nm, an average height of 3.4 microm, and a length of about 10 mm were formed on the template. The nanowalls were only grown on a Zn-polar surface due to a different growth mode with an O-polar surface. The results of x-ray diffraction and photoluminescence (PL) measurements revealed a single crystalline, vertical alignment on the template, and a large surface to volume ratio of the ZnO nanowalls.

Ultrafast carrier dynamics of conformally grown semi-polar (112[combining macron]2) GaN/InGaN multiple quantum well co-axial nanowires on m-axial GaN core nanowires.

The growth of semi-polar (112[combining macron]2) GaN/InGaN multiple-quantum-well (MQW) co-axial heterostructure shells around m-axial GaN core nanowires on a Si substrate using MOCVD is reported for the first time. The core GaN nanowire and GaN/InGaN MQW shells are grown in a two-step growth sequence of vapor-liquid-solid and vapor-solid growth modes. The luminescence and carrier dynamics of GaN/InGaN MQW coaxial nanowires are studied by photoluminescence, cathodoluminescence, and low temperature time-resolved photoluminescence (TRPL). The emission is tuned from 430 nm to 590 nm by increasing the InGaN QW thickness. The non-single exponential decay measured by low-temperature TRPL was attributed to the indium fluctuations in the InGaN QW. The ultrafast radiative lifetime was measured from 14 ps to 26 ps with different emission wavelengths at a very high internal quantum efficiency up to 68%. An ultrafast carrier lifetime was assigned to the growth of the InGaN QW on semi-polar (112[combining macron]2) growth facet and the improved carrier collection efficiency due to the radial growth of the GaN/InGaN MQW shells. Such an ultrafast carrier dynamics of NWs provides a meaningful active medium for high speed optoelectronic applications.

Stable and efficient transfer-printing including repair using a GaN-based microscale light-emitting diode array for deformable displays.

GaN-based microscale light-emitting diodes (µLEDs) are reported for assembly into deformable displays and repair systems. A stamp-imprinting method that enables large area assembly without spatial limitation is involved in the system, and a selective pick-up method is presented that includes a method for removing detected defective chips through micro-pulsed laser scanning. The photosensitive functional material, which is an accepted layer for the stable imprinting of chips, is determined by controlling the adhesion. In addition, selective pick-up and adhesion-controlled functional materials allow the implementation of defect-free displays through two pick-and-place cycles. Displays and related systems fabricated with this method can offer interesting optical and electrical properties.