Sustainable All-Day Thermoelectric Power Generation From the Hot Sun and Cold Universe.

Energy conversion from the environment into electricity is the most direct and effective electricity source to sustainably power off-grid electronics, once the electricity requirement exceeds the capability of traditional centralized power supply systems. Normally photovoltaic cells have enabled distributed power generation during the day, but do not work at night. Thus, efficient electricity generation technologies for a sustainable all-day power supply with no necessity for energy storage remain a challenge. Herein, an innovative all-day power generation strategy is reported, which self-adaptively integrates the diurnal photothermal and nocturnal radiative cooling processes into the thermoelectric generator (TEG) via the spectrally dynamic modulated coating, to continuously harvest the energy from the hot sun and the cold universe for power generation. Synergistic with the optimized latent heat phase change material, the electricity generation performance of the TEG is dramatically enhanced, with a maximum power density exceeding 1000 mW m-2 during the daytime and up to 25 mW m-2 during the nighttime, corresponding to an improvement of 123.1% and 249.1%, compared with the conventional strategy. This work maximizes the utilization of ambient energy resources to provide an environmentally friendly and uninterrupted power generation strategy. This opens up new possibilities for sustained power generation both daytime and nighttime.

Multifield-Modulated Spintronic Terahertz Emitter Based on a Vanadium Dioxide Phase Transition.

The efficient generation and active modulation of terahertz (THz) waves are strongly required for the development of various THz applications such as THz imaging/spectroscopy and THz communication. In addition, due to the increasing degree of integration for the THz optoelectronic devices, miniaturizing the complex THz system into a compact unit is also important and necessary. Today, integrating the THz source with the modulator to develop a powerful, easy-to-adjust, and scalable or on-chip THz emitter is still a challenge. As a new type of THz emitter, a spintronic THz emitter has attracted a great deal of attention due to its advantages of high efficiency, ultrawide band, low cost, and easy integration. In this study, we have proposed a multifield-modulated spintronic THz emitter based on the VO2/Ni/Pt multilayer film structure with a wide band region of 0-3 THz. Because of the pronounced phase transition of the integrated VO2 layer, the fabricated THz emitter can be efficiently modulated via thermal or electric stimuli with a modulation depth of about one order of magnitude; the modulation depths under thermal stimulation and electrical stimulation were 91.8% and 97.3%, respectively. It is believed that this multifield modulated spintronic THz emitter will provide various possibilities for the integration of next-generation on-chip THz sources and THz modulators.

Redox Gating for Colossal Carrier Modulation and Unique Phase Control.

Redox gating, a novel approach distinct from conventional electrolyte gating, combines reversible redox functionalities with common ionic electrolyte moieties to engineer charge transport, enabling power-efficient electronic phase control. This study achieves a colossal sheet carrier density modulation beyond 1016 cm-2, sustainable over thousands of cycles, all within the sub-volt regime for functional oxide thin films. The key advantage of this method lies in the controlled injection of a large quantity of carriers from the electrolyte into the channel material without the deleterious effects associated with traditional electrolyte gating processes such as the production of ionic defects or intercalated species. The redox gating approach offers a simple and practical means of decoupling electrical and structural phase transitions, enabling the isostructural metal-insulator transition and improved device endurance. The versatility of redox gating extends across multiple materials, irrespective of their crystallinity, crystallographic orientation, or carrier type (n- or p-type). This inclusivity encompasses functional heterostructures and low-dimensional quantum materials composed of sustainable elements, highlighting the broad applicability and potential of the technique in electronic devices.

Liquid-Metal-Assisted Synthesis of Patterned GaN Thin Films for High-Performance UV Photodetectors Array.

GaN's outstanding physical characteristics allow for a wide range of applications in numerous industries. Although individual GaN-based ultraviolet (UV) photodetectors are the subject of in-depth research in recent decades, the demand for photodetectors array is rising as a result of advances in optoelectronic integration technology. However, as a prerequisite for constructing GaN-based photodetectors array, large-area, patterned synthesis of GaN thin films remains a certain challenge. This work presents a facile technique for pattern growing high-quality GaN thin films for the assembly of an array of high-performance UV photodetectors. This technique uses UV lithography, which is not only very compatible with common semiconductor manufacturing techniques, but also enables precise patterning modification. A typical detector has impressive photo-response performance under 365 nm irradiation, with an extremely low dark current of 40 pA, a high Ilight /Idark ratio over 105 , a high responsivity of 4.23 AW-1 , and a decent specific detectivity of 1.76 × 1012 Jones. Additional optoelectronic studies demonstrate the strong homogeneity and repeatability of the photodetectors array, enabling it to serve as a reliable UV image sensor with enough spatial resolution. These outcomes highlight the proposed patterning technique's enormous potential.

Quantum imaging of the reconfigurable VO2 synaptic electronics for neuromorphic computing.

Neuromorphic computing has shown remarkable capabilities in silicon-based artificial intelligence, which can be optimized by using Mott materials for functional synaptic connections. However, the research efforts focus on two-terminal artificial synapses and envisioned the networks controlled by silicon-based circuits, which is difficult to develop and integrate. Here, we propose a dynamic network with laser-controlled conducting filaments based on electric field-induced local insulator-metal transition of vanadium dioxide. Quantum sensing is used to realize conductivity-sensitive imaging of conducting filament. We find that the location of filament formation is manipulated by focused laser, which is applicable to simulate the dynamical synaptic connections between the neurons. The ability to process signals with both long-term and short-term potentiation is further demonstrated with ~60 times on/off ratio while switching the pathways. This study opens the door to the development of dynamic network structures depending on easily controlled conduction pathways, mimicking the biological nervous systems.

Continuous Photothermal and Radiative Cooling Energy Harvesting by VO2 Smart Coatings with Switchable Broadband Infrared Emission.

Extensive use of renewable and clean energy is one of the promising ways to solve energy/environmental problems and promote the sustainable development of our society. As inexhaustible energy sources, the photothermal (PT) and radiative cooling (RC) energy from the sun and outer space have recently attracted tremendous interest. However, these two kinds of energy utilization have distinctly opposite spectral properties, especially in the infrared range, making it extremely difficult to integrate these two energy harvesting modes within a fixed device for continuous energy collection. Thus, in the current study, we have proposed a spectrally self-adaptive broadband absorber/emitter (SSBA/E) based on vanadium dioxide (VO2), a typical phase transition material, to achieve continuous energy harvesting via collecting solar thermal energy in PT mode during the day and obtaining cool energy in wide-band RC mode at night. Experimental results show that owing to the phase transition property of the VO2 layer, these two energy collection modes can be adaptively switched. Specifically, the VO2-based device shows a broadband infrared emissivity modulation from 0.21 to 0.75 and low critical temperatures (58.4 and 49.2 °C) during the phase transition, leading to continuous energy harvesting with high efficiency. Due to the broadband infrared emission, the RC maximum power of the SSBA/E device was estimated to be 58 W m-2. The proposed VO2 smart coatings are also applicable for many other applications such as thermal management of spacecraft, infrared camouflage, or adaptive optical devices.

Multiphysical Field Modulated VO2 Device for Information Encryption.

In the information explosion society, information security is highly demanded in the practical application, which raised a surge of interest in designing secure and reliable information transmission channels based on the inherent properties of emerging devices. Here, an innovative strategy to achieve the data encryption and reading during the data confidential transmission based on VO2 device is proposed. Owing to the specific insulator-to-metal transition property of VO2 , the phase transitions between the insulator and metallic states are modulated by the combination of electric field, temperature, and light radiation. These external stimulus-induced phase diagram is directly associated with the defined VO2 device, which are applicable for control the "0" or "1" electrical logic state for the information encryption. A prototype device is fabricated on an epitaxial VO2 film, which displayed a unique data encryption function with excellent stability. The current study not only demonstrated a multiphysical field-modulated VO2 device for information encryption, but also supplied some clues for functional devices applications in other correlated oxide materials.

Ultrahigh Effective Diffusion in Oxide by Engineering the Interfacial Transporter Channels.

Mass storage and removal in solids always play a vital role in technological applications such as modern batteries and neuronal computations. However, they were kinetically limited by the slow diffusional process in the lattice, which made it challenging to fabricate applicable conductors with high electronic and ionic conductivities at room temperature. Here, we proposed an acid solution/WO3/ITO sandwich structure and achieved ultrafast H transport in the WO3 layer by interfacial job-sharing diffusion, which means the spatially separated transport of the H+ and e- in different layers. From the color change of WO3, the effective diffusion coefficient (Deff) was estimated, dramatically increasing ≤106 times and overwhelming values from previous reports. The experiments and simulations also revealed the universality of extending this approach to other atoms and oxides, which could stimulate systematic studies of ultrafast mixed conductors in the future.

Fabrication of a VO2-Based Tunable Metasurface by Electric-Field Scanning Probe Lithography with Precise Depth Control.

Vanadium dioxide (VO2) is widely employed in developing tunable optoelectronic devices due to its significant changes in optical and electric properties upon phase transition. To fabricate the VO2-based functional devices down to the micro/nanoscale, a high-resolution processing technique is in demand. Scanning probe lithography (SPL) on the basis of a tip-induced electric field provides a promising approach for prototyping. Here, we demonstrated a precise VO2 etching strategy by direct writing on a VO2 film with a negative tip bias and subsequent sonication removal of the written area. The effects of bias voltage, sonication, and thermal treatment as well as the mechanical difference between the tip-modulated area and the pristine VO2 film were investigated systematically. The results show that VO2 can be etched layer by layer via alternately repeating tip modulation and sonication, and arbitrary patterns can be written. Based on this route, we designed a kind of metasurface by arranging VO2-gold nanoblocks with different sizes and heights for spectrally selective tunable reflectivity in near- and mid-infrared. This electric-field SPL method demonstrates the prominent advantages of high resolution down to several tens of nanometers, quasi-3D patterning, and resist-free maskless direct writing, which should be applicable for prototyping other micro/nanodevices.

Enhanced Pd/a-WO3 /VO2 Hydrogen Gas Sensor Based on VO2 Phase Transition Layer.

The utilization of clean hydrogen energy is becoming more feasible for the sustainable development of this society. Considering the safety issues in the hydrogen production, storage, and utilization, a sensitive hydrogen sensor for reliable detection is essential and highly important. Though various gas sensor devices are developed based on tin oxide, tungsten trioxide, or other oxides, the relatively high working temperature, unsatisfactory response time, and detection limitation still affect the extensive applications. In the current study, an amorphous tungsten trioxide (a-WO3 ) layer is deposited on a phase-change vanadium dioxide film to fabricate a phase transition controlled Pd/a-WO3 /VO2 hydrogen sensor for hydrogen detection. Results show that both the response time and sensitivity of the hydrogen sensor are improved greatly if increasing the working temperature over the transition temperature of VO2 . Theoretical calculations also reveal that the charge transfer at VO2 /a-WO3 interface becomes more pronounced once the VO2 layer transforms to the metal state, which will affect the migration barrier of H atoms in a-WO3 layer and thus improve the sensor performance. The current study not only realizes a hydrogen sensor with ultrahigh performance based on VO2 layer, but also provides some clues for designing other gas sensors with phase-change material.

Enhanced Contrast of WO3-Based Smart Windows by Continuous Li-Ion Insertion and Metal Electroplating.

The electrochromic WO3 smart window based on an aqueous electrolyte shows an excellent liquid/solid interface and thus can achieve a fast electrochromic response, while the aqueous electrolyte has a limited electrochemical window, which probably induces the H+ reduction and degrades the practical application. Here, we propose a strategy to modify the traditional Li+ acidic aqueous electrolyte by adding some selective inert metal ions, which not only improve the electrochromic performance but also avoid the possible production of hydrogen bubbles due to the broadened electrochemical window. Furthermore, reversible electroplating of inert metal ions will occur, leading to an enhanced optical transmission change of up to 77.5% at 500 nm and 70.4% at 700 nm. This combination of Li-ion insertion and metal electroplating in the ESW device makes it superior to all of the previous reports. The device also demonstrates high stability and high electrochromic efficiency after 1000 cycles. The current study not only emphasizes the rational design for aqueous electrolytes but also demonstrates a practical way to realize an excellent electrochromic window for practical applications.

Self-adaptive integration of photothermal and radiative cooling for continuous energy harvesting from the sun and outer space.

The sun (∼6,000 K) and outer space (∼3 K) are two significant renewable thermodynamic resources for human beings on Earth. The solar thermal conversion by photothermal (PT) and harvesting the coldness of outer space by radiative cooling (RC) have already attracted tremendous interest. However, most of the PT and RC approaches are static and monofunctional, which can only provide heating or cooling respectively under sunlight or darkness. Herein, a spectrally self-adaptive absorber/emitter (SSA/E) with strong solar absorption and switchable emissivity within the atmospheric window (i.e., 8 to 13 µm) was developed for the dynamic combination of PT and RC, corresponding to continuously efficient energy harvesting from the sun and rejecting energy to the universe. The as-fabricated SSA/E not only can be heated to ∼170 °C above ambient temperature under sunshine but also be cooled to 20 °C below ambient temperature, and thermal modeling captures the high energy harvesting efficiency of the SSA/E, enabling new technological capabilities.

Facile Removal of Bulk Oxygen Vacancy Defects in Metal Oxides Driven by Hydrogen-Dopant Evaporation.

Oxygen vacancy is a common defect in metal oxides that causes appreciable damage to material properties and performance. Removing bulk defects of oxygen vacancy (VO) typically needs harsh conditions such as high-temperature annealing. Supported by first-principles simulations, we propose an effective strategy of removing VO bulk defects in metal oxides by evaporating hydrogen dopants. The hydrogen dopants not only lower the migration barrier of VO but also push VO away due to their repulsive interaction. The coevaporation mechanism was supported by a neural networks potential-based molecular dynamics simulation, which shows that the migration of hydrogen dopants from inside to surface at 400 K promotes the migration of VO as well. Our proof-of-concept study suggests an alternative and efficient way of modulating oxygen vacancies in metal oxides via reversible hydrogen doping.

Photoassisted Electron-Ion Synergic Doping Induced Phase Transition of n-VO2/p-GaN Thin-Film Heterojunction.

As a typical correlated metal oxide, vanadium dioxide (VO2) shows specific metal-insulator transition (MIT) properties and demonstrates great potential applications in ultrafast optoelectronic switch, resistive memory, and neuromorphic devices. Effective control of the MIT process is essential for improving the device performance. In the current study, we have first proposed a photoassisted ion-doping method to modulate the phase transition of the VO2 layer based on the photovoltaic effect and electron-ion synergic doping in acid solution. Experimental results show that, for the prepared n-VO2/p-GaN nanojunction, this photoassisted strategy can effectively dope the n-VO2 layer by H+, Al3+, or Mg2+ ions under light radiation and trigger consecutive insulator-metal-insulator transitions. If combined with standard lithography or electron beam etching processes, selective doping with nanoscale size area can also be achieved. This photoassisted doping method not only shows a facile route for MIT modulation via a doping route under ambient conditions but also supplies some clues for photosensitive detection in the future.

Atomic Origin for Hydrogenation Promoted Bulk Oxygen Vacancies Removal in Vanadium Dioxide.

Oxygen vacancies (VO), a common type of point defect in metal oxides materials, play important roles in the physical and chemical properties. To obtain stoichiometric oxide crystal, the pre-existing VO is always removed via careful post-annealing treatment at high temperature in an air or oxygen atmosphere. However, the annealing conditions are difficult to control, and the removal of VO in the bulk phase is restrained because of the high energy barrier of VO migration. Here, we selected VO2 crystal film as the model system and developed an alternative annealing treatment aided by controllable hydrogen doping, which can realize effective removal of VO defects in the VO2-δ crystal at a lower temperature. This finding is attributed to the hydrogenation accelerated oxygen vacancies recovery in the VO2-δ crystal. Theoretical calculations revealed that the H-doping-induced electrons are prone to accumulate around the oxygen defects in the VO2-δ film, which facilitates the diffusion of VO and thus makes it easier to be removed. The methodology is expected to be applied to other metal oxides for oxygen-related point defects control.

A Hydrogenated Metal Oxide with Full Solar Spectrum Absorption for Highly Efficient Photothermal Water Evaporation.

Searching for cost-effective photothermal material that can harvest the full solar spectrum is critically important for solar-driven water evaporation. Metal oxides are cheap materials but cannot cover the full solar spectrum. Here we prepared a hydrogenated metal oxide (H1.68MoO3) material, in which H-doping causes the insulator-to-metal phase transition of the originally semiconductive MoO3. It offers a blackbody-like solar absorption of ≥95% over the entire visible-to-near-infrared solar spectrum, owing to its unusual quasi-metallic energy band, and high solar-to-heat conversion rate due to quick relaxation of excited electrons. Using a self-floating H1.68MoO3/airlaid paper photothermal film, we achieved a stable and high water vapor generation rate of 1.37 kg m-2 h-1, a superb solar-to-vapor efficiency of 84.8% under 1 sun illumination, and daily production of 12.4 L of sanitary water/m2 from seawater under natural sunlight. This thus opens a new avenue of designing cost-effective photothermal materials based on metal oxides.

Tunable Hydrogen Doping of Metal Oxide Semiconductors with Acid-Metal Treatment at Ambient Conditions.

Hydrogen doping of metal oxide semiconductors is promising for manipulation of their properties toward various applications. Yet it is quite challenging because it requires harsh reaction conditions and expensive metal catalysts. Meanwhile, acids as a cheap source of protons have long been unappreciated. Here, we develop a sophisticated acid-metal treatment for tunable hydrogenation of metal oxides at ambient conditions. Using first-principles simulations, we first show that, with proper work function difference between the metal and metal oxide, H-diffusion into negatively charged metal oxide can be well controlled, resulting in tunable H-doping of metal oxides with quasi-metal characteristics. This has been verified by proof-of-concept experiments that achieved the controllable hydrogenation of WO3 using Cu and hydrochloric acid at ambient conditions. Further, H-doping of other metal oxides (TiO2/Nb2O5/MoO3) has been achieved by metal-acid treatment and induced a change in properties. Our work provides a promising way to tailor metal oxides via tunable H-doping.

Electron-Proton Co-doping-Induced Metal-Insulator Transition in VO2 Film via Surface Self-Assembled l-Ascorbic Acid Molecules.

Charge doping is an effective way to induce the metal-insulator transition (MIT) in correlated materials for many important utilizations, which is however practically limited by problem of low stability. An electron-proton co-doping mechanism is used to achieve pronounced phase modulation of monoclinic vanadium dioxide (VO2 ) at room temperature. Using l-ascorbic acid (AA) solution to treat VO2 , the ionized AA- species donate electrons to the adsorbed VO2 surface. Charges then electrostatically attract surrounding protons to penetrate, and eventually results in stable hydrogen-doped metallic VO2 . The variations of electronic structures, especially the electron occupancy of V 3d/O 2p hybrid orbitals, were examined by synchrotron characterizations and first-principle theoretical simulations. The adsorbed molecules protect hydrogen dopants from escaping out of lattice and thereby stabilize the metallic phase for VO2 .

Gate-controlled VO2 phase transition for high-performance smart windows.

Vanadium dioxide (VO2) is a promising material for developing energy-saving "smart windows," owing to its infrared thermochromism induced by metal-insulator transition (MIT). However, its practical application is greatly limited by its relatively high critical temperature (~68°C), low luminous transmittance (<60%), and poor solar energy regulation ability (<15%). Here, we developed a reversible and nonvolatile electric field control of the MIT of a monoclinic VO2 film. With a solid electrolyte layer assisting gating treatment, we modulated the insertion/extraction of hydrogen into/from the VO2 lattice at room temperature, causing tristate phase transitions that enable control of light transmittance. The dramatic increase in visible/infrared transmittance due to the phase transition from the metallic (lightly H-doped) to the insulating (heavily H-doped) phase results in an increased solar energy regulation ability up to 26.5%, while maintaining 70.8% visible luminous transmittance. These results break all previous records and exceed the theoretical limit for traditional VO2 smart windows, making them ready for energy-saving utilization.

Temperature-Controlled Asymmetric Transmission of Electromagnetic Waves.

Chiral materials can exhibit different levels of transmission for opposite propagation directions of the same electromagnetic wave. Here we demonstrate thermal switching of asymmetric transmission of linearly polarized terahertz waves. The effect is observed in a terahertz metamaterial containing 3D-chiral metallic inclusions and achiral vanadium dioxide inclusions. The chiral structure exhibits pronounced asymmetric transmission at room temperature when vanadium dioxide is in its insulator phase. As the metamaterial is heated, the insulator-to-metal phase transition of vanadium dioxide effectively renders the structure achiral and the transmission asymmetry vanishes. We demonstrate the effect numerically and experimentally, describe it analytically and explain the underlying physical mechanism based on simulated surface current distributions. Potential applications include directionally asymmetric active devices as well as intensity and polarization modulators for electromagnetic waves.