A synergetic cocatalyst for conversion of carbon dioxide, sunlight, and water into methanol.

The conversion of CO2 into liquid fuels, using only sunlight and water, offers a promising path to carbon neutrality. An outstanding challenge is to achieve high efficiency and product selectivity. Here, we introduce a wireless photocatalytic architecture for conversion of CO2 and water into methanol and oxygen. The catalytic material consists of semiconducting nanowires decorated with core-shell nanoparticles, with a copper-rhodium core and a chromium oxide shell. The Rh/CrOOH interface provides a unidirectional channel for proton reduction, enabling hydrogen spillover at the core-shell interface. The vectorial transfer of protons, electrons, and hydrogen atoms allows for switching the mechanism of CO2 reduction from a proton-coupled electron transfer pathway in aqueous solution to hydrogenation of CO2 with a solar-to-methanol efficiency of 0.22%. The reported findings demonstrate a highly efficient, stable, and scalable wireless system for synthesis of methanol from CO2 that could provide a viable path toward carbon neutrality and environmental sustainability.

Topological Dirac-vortex microcavity laser for robust on-chip optoelectronics.

Dirac-vortex microcavity laser based on InAs/InGaAs quantum dots have been experimentally realized on silicon substrate. The topological laser features a large spectral range and high robustness against variations such as cavity size.

Concentrated Solar Light Photoelectrochemical Water Splitting for Stable and High-Yield Hydrogen Production.

Photoelectrochemical water splitting is a promising technique for converting solar energy into low-cost and eco-friendly H2 fuel. However, the production rate of H2 is limited by the insufficient number of photogenerated charge carriers in the conventional photoelectrodes under 1 sun (100 mW cm-2) light. Concentrated solar light irradiation can overcome the issue of low yield, but it leads to a new challenge of stability because the accelerated reaction alters the surface chemical composition of photoelectrodes. Here, it is demonstrated that loading Pt nanoparticles (NPs) on single crystalline GaN nanowires (NWs) grown on n+-p Si photoelectrode operates efficiently and stably under concentrated solar light. Although a large number of Pt NPs detach during the initial reaction due to H2 gas bubbling, some Pt NPs which have an epitaxial relation with GaN NWs remain stably anchored. In addition, the stability of the photoelectrode further improves by redepositing Pt NPs on the reacted Pt/GaN surface, which results in maintaining onset potential >0.5 V versus reversible hydrogen electrode and photocurrent density >60 mA cm-2 for over 1500 h. The heterointerface between Pt cocatalysts and single crystalline GaN nanostructures shows great potential in designing an efficient and stable photoelectrode for high-yield solar to H2 conversion.

Water-promoted selective photocatalytic methane oxidation for methanol production.

Converting relatively inert methane into active chemical fuels such as methanol with high selectivity through an energy-saving strategy has remained a grand challenge. Photocatalytic technology consuming solar energy is an appealing alternative for methane reforming. However, the low efficiency and the undesirable formation of low-value products, such as carbon dioxide and ethane, limit the commercial application of photocatalytic technology. Herein, we find a facile and practical water-promoted pathway for photocatalytic methane reforming into methanol, enabling methanol production from methane and oxygen with a high selectivity (>93%) and production rate (21.4 µmol cm-2 h-1 or 45.5 mmol g-1 h-1) on metallic Ag nanoparticle-loaded InGaN nanowires (Ag/InGaN). The experimental XPS and theoretical PDOS analyses reveal that water molecules adsorbed on Ag nanoparticles (AgNPs) can promote the electron transfer from InGaN to AgNPs, which enables the formation of partial Ag species with a lower oxidation state in AgNPs. Through the in situ IR spectrum and the reaction pathway simulation studies, these newly formed Ag species induced by water adsorption were demonstrated to be responsible for the highly selective methanol production due to the effective formation of a C-O bond and the optimal desorption of the formed methanol from the surface indium site of the InGaN photocatalyst. This unique water promotion effect leads to a 55-fold higher catalytic rate and 9-fold higher selectivity for methanol production compared to photocatalytic methane reforming without water addition. This finding offers a new pathway for achieving clean solar fuels by photocatalysis-based methane reforming.

Achieving atomically ordered GaN/AlN quantum heterostructures: The role of surface polarity.

Interface engineering in heterostructures at the atomic scale has been a central research focus of nanoscale and quantum material science. Despite its paramount importance, the achievement of atomically ordered heterointerfaces has been severely limited by the strong diffusive feature of interfacial atoms in heterostructures. In this work, we first report a strong dependence of interfacial diffusion on the surface polarity. Near-perfect quantum interfaces can be readily synthesized on the semipolar plane instead of the conventional c-plane of GaN/AlN heterostructures. The chemical bonding configurations on the semipolar plane can significantly suppress the cation substitution process as evidenced by first-principles calculations, which leads to an atomically sharp interface. Moreover, the surface polarity of GaN/AlN can be readily controlled by varying the strain relaxation process in core-shell nanostructures. The obtained extremely confined, interdiffusion-free ultrathin GaN quantum wells exhibit a high internal quantum efficiency of ~75%. Deep ultraviolet light-emitting diodes are fabricated utilizing a scalable and robust method and the electroluminescence emission is nearly free of the quantum-confined Stark effect, which is significant for ultrastable device operation. The presented work shows a vital path for achieving atomically ordered quantum heterostructures for III-nitrides as well as other polar materials such as III-arsenides, perovskites, etc.

Graph-Collaborated Auto-Encoder Hashing for Multiview Binary Clustering.

Unsupervised hashing methods have attracted widespread attention with the explosive growth of large-scale data, which can greatly reduce storage and computation by learning compact binary codes. Existing unsupervised hashing methods attempt to exploit the valuable information from samples, which fails to take the local geometric structure of unlabeled samples into consideration. Moreover, hashing based on auto-encoders aims to minimize the reconstruction loss between the input data and binary codes, which ignores the potential consistency and complementarity of multiple sources data. To address the above issues, we propose a hashing algorithm based on auto-encoders for multiview binary clustering, which dynamically learns affinity graphs with low-rank constraints and adopts collaboratively learning between auto-encoders and affinity graphs to learn a unified binary code, called graph-collaborated auto-encoder (GCAE) hashing for multiview binary clustering. Specifically, we propose a multiview affinity graphs' learning model with low-rank constraint, which can mine the underlying geometric information from multiview data. Then, we design an encoder-decoder paradigm to collaborate the multiple affinity graphs, which can learn a unified binary code effectively. Notably, we impose the decorrelation and code balance constraints on binary codes to reduce the quantization errors. Finally, we use an alternating iterative optimization scheme to obtain the multiview clustering results. Extensive experimental results on five public datasets are provided to reveal the effectiveness of the algorithm and its superior performance over other state-of-the-art alternatives.

Oxynitrides enabled photoelectrochemical water splitting with over 3,000 hrs stable operation in practical two-electrode configuration.

Solar photoelectrochemical reactions have been considered one of the most promising paths for sustainable energy production. To date, however, there has been no demonstration of semiconductor photoelectrodes with long-term stable operation in a two-electrode configuration, which is required for any practical application. Herein, we demonstrate the stable operation of a photocathode comprising Si and GaN, the two most produced semiconductors in the world, for 3,000 hrs without any performance degradation in two-electrode configurations. Measurements in both three- and two-electrode configurations suggest that surfaces of the GaN nanowires on Si photocathode transform in situ into Ga-O-N that drastically enhances hydrogen evolution and remains stable for 3,000 hrs. First principles calculations further revealed that the in-situ Ga-O-N species exhibit atomic-scale surface metallization. This study overcomes the conventional dilemma between efficiency and stability imposed by extrinsic cocatalysts, offering a path for practical application of photoelectrochemical devices and systems for clean energy.

Ultrathin Nitride Ferroic Memory with Large ON/OFF Ratios for Analog In-Memory Computing.

Computing in the analog regime using nonlinear ferroelectric resistive memory arrays can potentially alleviate the energy constraints and complexity/footprint challenges imposed by digital von Neumann systems. Yet the current ferroelectric resistive memories suffer from either low ON/OFF ratios/imprint or limited compatibility with mainstream semiconductors. Here, for the first time, ferroelectric and analog resistive switching in an epitaxial nitride heterojunction comprising ultrathin (≈5 nm) nitride ferroelectrics, i.e., ScAlN, with potentiality to bridge the gap between performance and compatibility is demonstrated. High ON/OFF ratios (up to 105 ), high uniformity, good retention, (<20% variation after > 105  s) and cycling endurance (>104 ) are simultaneously demonstrated in a metal/oxide/nitride ferroelectric junction. It is further demonstrated that the memristor can provide programmability to enable multistate operation and linear analogue computing as well as image processing with high accuracy. Neural network simulations based on the weight update characteristics of the nitride memory yielded an image recognition accuracy of 92.9% (baseline 96.2%) on the images from Modified National Institute of Standards and Technology. The non-volatile multi-level programmability and analog computing capability provide first-hand and landmark evidence for constructing advanced memory/computing architectures based on emerging nitride ferroelectrics, and promote homo and hybrid integrated functional edge devices beyond silicon.

Ferroelectric Nitride Heterostructures on CMOS Compatible Molybdenum for Synaptic Memristors.

Achieving ferroelectricity in III-nitride (III-N) semiconductors by alloying with rare-earth elements, e.g., scandium, has presented a pivotal step toward next-generation electronic, acoustic, photonic, and quantum devices and systems. To date, however, the conventional growth of single-crystalline nitride semiconductors often requires the use of sapphire, Si, or SiC substrate, which has prevented their integration with the workhorse complementary metal oxide semiconductor (CMOS) technology. Herein, we demonstrate single-crystalline ferroelectric nitride semiconductors grown on CMOS compatible metal-molybdenum. Significantly, we find that a unique epitaxial relationship between wurtzite and body-centered cubic crystal structure can be well maintained, enabling the realization of single-crystalline wurtzite ferroelectric nitride semiconductors on polycrystalline molybdenum that was not previously possible. Robust and wake-up-free ferroelectricity has been measured, for the first time, in the epitaxially grown ScAlN directly on metal. We further propose and demonstrate a ferroelectric GaN/ScAlN heterostructure for synaptic memristor, which shows the capability of emulating the spike-time-dependent plasticity in a biological synapse. This work provides a viable path for the integration of III-N architectures with the mature CMOS technology and sheds light on the promising applications of ferroelectric nitride memristors in neuromorphic computing.

An Ultrahigh Efficiency Excitonic Micro-LED.

High efficiency micro-LEDs, with lateral dimensions as small as one micrometer, are desired for next-generation displays, virtual/augmented reality, and ultrahigh-speed optical interconnects. The efficiency of quantum well LEDs, however, is reduced to negligibly small values when scaled to such small dimensions. Here, we show such a fundamental challenge can be overcome by developing nanowire excitonic LEDs. Harnessing the large exciton oscillator strength of quantum-confined nanostructures, we demonstrate a submicron scale green-emitting LED having an external quantum efficiency and wall-plug efficiency of 25.2% and 20.7%, respectively, the highest values reported for any LEDs of this size to our knowledge. We established critical factors for achieving excitonic micro-LEDs, including the epitaxy of nanostructures to achieve strain relaxation, the utilization of semipolar planes to minimize polarization effects, and the formation of nanoscale quantum-confinement to enhance electron-hole wave function overlap. This work provides a viable path to break the efficiency bottleneck of nanoscale optoelectronics.

Solar-to-hydrogen efficiency of more than 9% in photocatalytic water splitting.

Production of hydrogen fuel from sunlight and water, two of the most abundant natural resources on Earth, offers one of the most promising pathways for carbon neutrality1-3. Some solar hydrogen production approaches, for example, photoelectrochemical water splitting, often require corrosive electrolyte, limiting their performance stability and environmental sustainability1,3. Alternatively, clean hydrogen can be produced directly from sunlight and water by photocatalytic water splitting2,4,5. The solar-to-hydrogen (STH) efficiency of photocatalytic water splitting, however, has remained very low. Here we have developed a strategy to achieve a high STH efficiency of 9.2 per cent using pure water, concentrated solar light and an indium gallium nitride photocatalyst. The success of this strategy originates from the synergistic effects of promoting forward hydrogen-oxygen evolution and inhibiting the reverse hydrogen-oxygen recombination by operating at an optimal reaction temperature (about 70 degrees Celsius), which can be directly achieved by harvesting the previously wasted infrared light in sunlight. Moreover, this temperature-dependent strategy also leads to an STH efficiency of about 7 per cent from widely available tap water and sea water and an STH efficiency of 6.2 per cent in a large-scale photocatalytic water-splitting system with a natural solar light capacity of 257 watts. Our study offers a practical approach to produce hydrogen fuel efficiently from natural solar light and water, overcoming the efficiency bottleneck of solar hydrogen production.

Pt nanoclusters on GaN nanowires for solar-asssisted seawater hydrogen evolution.

Seawater electrolysis provides a viable method to produce clean hydrogen fuel. To date, however, the realization of high performance photocathodes for seawater hydrogen evolution reaction has remained challenging. Here, we introduce n+-p Si photocathodes with dramatically improved activity and stability for hydrogen evolution reaction in seawater, modified by Pt nanoclusters anchored on GaN nanowires. We find that Pt-Ga sites at the Pt/GaN interface promote the dissociation of water molecules and spilling H* over to neighboring Pt atoms for efficient H2 production. Pt/GaN/Si photocathodes achieve a current density of -10 mA/cm2 at 0.15 and 0.39 V vs. RHE and high applied bias photon-to-current efficiency of 1.7% and 7.9% in seawater (pH = 8.2) and phosphate-buffered seawater (pH = 7.4), respectively. We further demonstrate a record-high photocurrent density of ~169 mA/cm2 under concentrated solar light (9 suns). Moreover, Pt/GaN/Si can continuously produce H2 even under dark conditions by simply switching the electrical contact. This work provides valuable guidelines to design an efficient, stable, and energy-saving electrode for H2 generation by seawater splitting.

InGaN micro-light-emitting diodes monolithically grown on Si: achieving ultra-stable operation through polarization and strain engineering.

Micro or submicron scale light-emitting diodes (µLEDs) have been extensively studied recently as the next-generation display technology. It is desired that µLEDs exhibit high stability and efficiency, submicron pixel size, and potential monolithic integration with Si-based complementary metal-oxide-semiconductor (CMOS) electronics. Achieving such µLEDs, however, has remained a daunting challenge. The polar nature of III-nitrides causes severe wavelength/color instability with varying carrier concentrations in the active region. The etching-induced surface damages and poor material quality of high indium composition InGaN quantum wells (QWs) severely deteriorate the performance of µLEDs, particularly those emitting in the green/red wavelength. Here we report, for the first time, µLEDs grown directly on Si with submicron lateral dimensions. The µLEDs feature ultra-stable, bright green emission with negligible quantum-confined Stark effect (QCSE). Detailed elemental mapping and numerical calculations show that the QCSE is screened by introducing polarization doping in the active region, which consists of InGaN/AlGaN QWs surrounded by an AlGaN/GaN shell with a negative Al composition gradient along the c-axis. In comparison with conventional GaN barriers, AlGaN barriers are shown to effectively compensate for the tensile strain within the active region, which significantly reduces the strain distribution and results in enhanced indium incorporation without compromising the material quality. This study provides new insights and a viable path for the design, fabrication, and integration of high-performance µLEDs on Si for a broad range of applications in on-chip optical communication and emerging augmented reality/mixed reality devices, and so on.

Metal-Support Interaction-Promoted Photothermal Catalytic Methane Reforming into Liquid Fuels.

Clean and renewable photocatalytic technology for methane reforming into high-value liquid fuels, such as methanol, is a promising strategy for commercial industrial applications. However, poor charge separation, sluggish methane activation, and excessive oxidation collectively inhibit the production of methanol from photocatalytic methane reforming. Herein, we have developed enhanced metal-support interactions between a GaN nanowire photocatalyst and a Cu nanoparticle (CuNP) cocatalyst via p-doping in GaN. CuNP-loaded p-type GaN (Cu/p-GaN) with enhanced metal-support interaction has 3.5-fold higher activity (12.8 mmol g-1 h-1, higher than previous reports) for methanol production in photothermal catalytic methane reforming with oxygen as an oxidant and sunlight as the sole energy source than CuNP-loaded intrinsic GaN (Cu/i-GaN) or n-type GaN (Cu/n-GaN). In-situ IR measurements indicate that enhanced metal-support interaction significantly promotes activation of methane and formation of methanol. Combining with X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) simulations demonstrate that this enhanced metal-support interaction in Cu/p-GaN greatly improves electron transfer from p-GaN photocatalysts to the 3d states of CuNP cocatalysts through the interface between them. Catalytic pathway simulations further reveal that the enhanced metal-support interaction in Cu/p-GaN also desirably decreases the reaction energy of rate-determining methanol desorption, which decreases the excessive oxidation of the produced methanol and accelerates the regeneration of surface catalytic sites. These studies and findings offer critical insights into the design and development of metal nanoparticle-loaded photocatalysts for photocatalysis-based methane reforming into methanol.

Tunable green syngas generation from CO2 and H2O with sunlight as the only energy input.

The carbon-neutral synthesis of syngas from CO2 and H2O powered by solar energy holds grand promise for solving critical issues such as global warming and the energy crisis. Here we report photochemical reduction of CO2 with H2O into syngas using core/shell Au@Cr2O3 dual cocatalyst-decorated multistacked InGaN/GaN nanowires (NWs) with sunlight as the only energy input. First-principle density functional theory calculations revealed that Au and Cr2O3 are synergetic in deforming the linear CO2 molecule to a bent state with an O-C-O angle of 116.5°, thus significantly reducing the energy barrier of CO2RR compared with that over a single component of Au or Cr2O3. Hydrogen evolution reaction was promoted by the same cocatalyst simultaneously. By combining the cooperative catalytic properties of Au@Cr2O3 with the distinguished optoelectronic virtues of the multistacked InGaN NW semiconductor, the developed photocatalyst demonstrated high syngas activity of 1.08 mol/gcat/h with widely tunable H2/CO ratios between 1.6 and 9.2 under concentrated solar light illumination. Nearly stoichiometric oxygen was evolved from water splitting at a rate of 0.57 mol/gcat/h, and isotopic testing confirmed that syngas originated from CO2RR. The solar-to-syngas energy efficiency approached 0.89% during overall CO2 reduction coupled with water splitting. The work paves a way for carbon-neutral synthesis of syngas with the sole inputs of CO2, H2O, and solar light.

Self-Rolled-Up Aluminum Nitride-Based 3D Architectures Enabled by Record-High Differential Stress.

Aluminum nitride (AlN) continues to kindle considerable interest in various microelectromechanical system (MEMS)-related fields because of its superior optical, mechanical, thermal, and piezoelectric properties. In this study, we use magnetron sputtering to tailor intrinsic stress in AlN thin films from highly compressive (-1200 MPa) to highly tensile (+700 MPa), with a differential stress of 1900 MPa. By monolithically combining the compressive and tensile ultrathin AlN bilayer membranes (20-60 nm) during deposition, perfectly curved three-dimensional (3D) architectures are spontaneously formed upon dry-releasing from the substrate via a 3D MEMS approach: the complementary metal-oxide-semiconductor (CMOS)-compatible strain-induced self-rolled-up membrane (S-RuM) method. The thermal stability of the AlN 3D architectures is examined, and the curvature of S-RuM microtubes and helical structures as a function of the cumulative membrane thickness and stress are characterized experimentally and simulated using a finite-element physiomechanic method. By combining AlN with various materials such as metal (Cu) and silicon nitride (SiNx), AlN-based hybrid S-RuM microtubes with diameters as small as ∼6 µm are demonstrated with a near-unity yield (∼99%). Compared with other stressed thin films for S-RuMs, including PECVD SiNx, magnetron-sputtered AlN-based S-RuMs show better structural controllability and versatility, probably due to the high Young's modulus and stress uniformity. This work establishes the sputtered AlN thin film as a superior stress-configurable S-RuM shell material for high-performance applications in miniaturizing and integrating electronic components beyond those based on other materials such as SiNx. In addition, for the first time, a single-crystal Al1-xScxN/AlN bilayer grown by molecular beam epitaxy is successfully rolled-up with the diameter varying from ∼9 to 14 µm, paving the way for 3D tubular Al1-xScxN piezoelectric devices.

Crystallographic Effects of GaN Nanostructures in Photoelectrochemical Reaction.

Tuning the surface structure of the photoelectrode provides one of the most effective ways to address the critical challenges in artificial photosynthesis, such as efficiency, stability, and product selectivity, for which gallium nitride (GaN) nanowires have shown great promise. In the GaN wurtzite crystal structure, polar, semipolar, and nonpolar planes coexist and exhibit very different structural, electronic, and chemical properties. Here, through a comprehensive study of the photoelectrochemical performance of GaN photocathodes in the form of films and nanowires with controlled surface polarities we show that significant photoelectrochemical activity can be observed when the nonpolar surfaces are exposed in the electrolyte, whereas little or no activity is measured from the GaN polar c-plane surfaces. The atomic origin of this fundamental difference is further revealed through density functional theory calculations. This study provides guideline on crystal facet engineering of metal-nitride photo(electro)catalysts for a broad range of artificial photosynthesis chemical reactions.

Interfacial Modulated Lattice-Polarity-Controlled Epitaxy of III-Nitride Heterostructures on Si(111).

Monolithic integration of wurtzite III-nitrides with nonpolar silicon (Si), the two most-produced semiconductor materials, is essential and critical for a broad range of applications in electronics, optoelectronics, quantum photonics, and renewable energy. To date, however, it has remained challenging to achieve III-nitride heterostructures on Si with controlled lattice-polarity. Herein, we show that such critical challenges of III-nitrides on Si can be fundamentally addressed through a unique interfacial modulated lattice-polarity-controlled epitaxy (IMLPCE). It is discovered that the lattice-polarity of aluminum nitride (AlN) grown on Si(111) is primarily determined by the AlSiN interlayer: N-polar and Al-polar AlN can be achieved by suppressing and promoting the AlSiN interlayer formation, respectively. Furthermore, we develop a unique active-nitrogen-free in situ annealing process to mitigate the AlSiN layer formation at the GaN/AlN interface, which can eliminate the inverted domain formation commonly seen in N-polar GaN on AlN/Si. This study provides an alternative approach for controlling the lattice-polarity of III-nitrides on Si substrates and will enable their seamless integration with the mature Si-based device technology.

Scalable Synthesis of Monolayer Hexagonal Boron Nitride on Graphene with Giant Bandgap Renormalization.

Monolayer hexagonal boron nitride (hBN) has been widely considered a fundamental building block for 2D heterostructures and devices. However, the controlled and scalable synthesis of hBN and its 2D heterostructures has remained a daunting challenge. Here, an hBN/graphene (hBN/G) interface-mediated growth process for the controlled synthesis of high-quality monolayer hBN is proposed and further demonstrated. It is discovered that the in-plane hBN/G interface can be precisely controlled, enabling the scalable epitaxy of unidirectional monolayer hBN on graphene, which exhibits a uniform moiré superlattice consistent with single-domain hBN, aligned to the underlying graphene lattice. Furthermore, it is identified that the deep-ultraviolet emission at 6.12 eV stems from the 1s-exciton state of monolayer hBN with a giant renormalized direct bandgap on graphene. This work provides a viable path for the controlled synthesis of ultraclean, wafer-scale, atomically ordered 2D quantum materials, as well as the fabrication of 2D quantum electronic and optoelectronic devices.