CdS-based Schottky junctions for efficient visible light photocatalytic hydrogen evolution.

Heterojunctions photocatalysts play a crucial role in achieving high solar-hydrogen conversion efficiency. In this work, we mainly focus on the charge transfer dynamics and pathways for sulfides-based Schottky junctions in the photocatalytic water splitting process to clarify the mechanism of heterostructures photocatalysis. Sulfides-based Schottky junctions (CdS/CoP and CdS/1T-MoS2) were successfully constructed for photocatalytic water splitting. Because of the higher work function of CdS than that of CoP and 1T-MoS2, the direction of the built-in electric field is from CoP or 1T-MoS2 to semiconductor. Therefore, CoP and 1T-MoS2 can act as electrons acceptors to accelerate the transfer of photo-generated electron on the surface of CdS, thus improving the charge utilization efficiency. Meanwhile, CoP and 1T-MoS2 as active sites can also promote the water dissociation and lower the H+ reduction overpotential, thus contributing to the excellent photocatalytic hydrogen production activity (23.59 mmol·h-1·g-1 and 1195.8 mol·h-1·g-1 for CdS/CoP and CdS/1T-MoS2).

Constructing Built-In Electric Fields with Semiconductor Junctions and Schottky Junctions Based on Mo-MXene/Mo-Metal Sulfides for Electromagnetic Response.

The exploration of novel multivariate heterostructures has emerged as a pivotal strategy for developing high-performance electromagnetic wave (EMW) absorption materials. However, the loss mechanism in traditional heterostructures is relatively simple, guided by empirical observations, and is not monotonous. In this work, we presented a novel semiconductor-semiconductor-metal heterostructure system, Mo-MXene/Mo-metal sulfides (metal = Sn, Fe, Mn, Co, Ni, Zn, and Cu), including semiconductor junctions and Mott-Schottky junctions. By skillfully combining these distinct functional components (Mo-MXene, MoS2, metal sulfides), we can engineer a multiple heterogeneous interface with superior absorption capabilities, broad effective absorption bandwidths, and ultrathin matching thickness. The successful establishment of semiconductor-semiconductor-metal heterostructures gives rise to a built-in electric field that intensifies electron transfer, as confirmed by density functional theory, which collaborates with multiple dielectric polarization mechanisms to substantially amplify EMW absorption. We detailed a successful synthesis of a series of Mo-MXene/Mo-metal sulfides featuring both semiconductor-semiconductor and semiconductor-metal interfaces. The achievements were most pronounced in Mo-MXene/Mo-Sn sulfide, which achieved remarkable reflection loss values of - 70.6 dB at a matching thickness of only 1.885 mm. Radar cross-section calculations indicate that these MXene/Mo-metal sulfides have tremendous potential in practical military stealth technology. This work marks a departure from conventional component design limitations and presents a novel pathway for the creation of advanced MXene-based composites with potent EMW absorption capabilities.

Band Engineering versus Catalysis: Enhancing the Self-Propulsion of Light-Powered MXene-Derived Metal-TiO2 Micromotors To Degrade Polymer Chains.

Light-powered micro- and nanomotors based on photocatalytic semiconductors convert light into mechanical energy, allowing self-propulsion and various functions. Despite recent progress, the ongoing quest to enhance their speed remains crucial, as it holds the potential for further accelerating mass transfer-limited chemical reactions and physical processes. This study focuses on multilayered MXene-derived metal-TiO2 micromotors with different metal materials to investigate the impact of electronic properties of the metal-semiconductor junction, such as energy band bending and built-in electric field, on self-propulsion. By asymmetrically depositing Au or Ag layers on thermally annealed Ti3C2Tx MXene microparticles using sputtering, Janus structures are formed with Schottky junctions at the metal-semiconductor interface. Under UV light irradiation, Au-TiO2 micromotors show higher self-propulsion velocities due to the stronger built-in electric field, enabling efficient photogenerated charge carrier separation within the semiconductor and higher hole accumulation beneath the Au layer. On the contrary, in 0.1 wt % H2O2, Ag-TiO2 micromotors reach higher velocities both in the presence and absence of UV light irradiation, owing to the superior catalytic properties of Ag in H2O2 decomposition. Due to the widespread use of plastics and polymers, and the consequent occurrence of nano/microplastics and polymeric waste in water, Au-TiO2 micromotors were applied in water remediation to break down polyethylene glycol (PEG) chains, which were used as a model for polymeric pollutants in water. These findings reveal the interplay between electronic properties and catalytic activity in metal-semiconductor junctions, offering insights into the future design of powerful light-driven micro- and nanomotors with promising implications for water treatment and photocatalysis applications.

Dual-Site Activation Coupling with a Schottky Junction Boosts the Electrochemiluminescence of Carbon Nitride.

Robust electrochemiluminescence (ECL) of carbon nitride (CN) requires efficient electron-hole recombination and the suppression of electrode passivation. In this work, Au nanoparticles and single atoms (AuSA+NP ) loaded on CN serve as dual active sites that significantly accelerate charge transfer and activate peroxydisulfate. Meanwhile, the well-established Schottky junctions between Au NPs and CN act as electron sinks, effectively trapping over-injected electrons to prevent electrode passivation. As a result, the porous CN modified with AuSA+NP exhibits an enhanced and stable ECL emission, with a minimal relative standard deviation of 0.24 %. Furthermore, the designed ECL biosensor based on AuSA+NP -CN shows a remarkable performance in detecting organophosphorus pesticides. This innovative strategy has the potential to offer new insights into strong and stable ECL emission for practical applications.

Controllable resistive switching behaviors in heteroepitaxial LaNiO3/Nb:SrTiO3Schottky junctions through oxygen vacancies engineering.

Perovskite oxide-based memristors have been extensively investigated for the application of non-volatile memories, and the oxygen vacancies associated with Schottky barrier changing are considered as the origin of the memristive behaviors. However, due to the difference of device fabrication progress, various resistive switching (RS) behaviors have been observed even in one device, deteriorating the stability and reproducibility of devices. Precisely controlling the oxygen vacancies distribution and shedding light on the behind physic mechanism of these RS behaviors, are highly desired to help improve the performance and stability of such Schottky junction-based memristors. In this work, the epitaxial LaNiO3(LNO)/Nb:SrTiO3(NSTO) is adopted to explore the influence of oxygen vacancy profiles on these abundant RS phenomena. It demonstrates that the migration of oxygen vacancy in LNO films plays a key role in memristive behaviors. When the effect of oxygen vacancies at the LNO/NSTO interface is negligible, improving the oxygen vacancies concentration in LNO film could facilitate resistance on/off ratio of HRS and LRS, and the corresponding conducting mechanisms attributes to the thermionic emission and tunneling-assisted thermionic emission, respectively. Moreover, it is found that reasonably increasing the oxygen vacancies at LNO/NSTO interface makes trap-assisted tunneling possible, also providing an effective way to improve the performance of the device. The results in this work have clearly elucidated the relationship between oxygen vacancy profile and RS behaviors, and give physical insights into the strategies for improving the device performance of Schottky junction-based memristors.

Synthesis of the Ni2P-Co Mott-Schottky Junction as an Electrocatalyst to Boost Sulfur Conversion Kinetics and Application in Separator Modification in Li-S Batteries.

To overcome the shuttling effect and sluggish conversion kinetics of polysulfides, a large number of catalysts have been designed for lithium-sulfur (Li-S) batteries. Herein, a Mott-Schottky junction catalyst composed of Co nanoparticles and Ni2P was designed to improve polysulfide kinetics. Our investigations reveal the rearrangement of charges at the Schottky junction interface and the construction of the built-in electric field are crucial for lowering the activation energy of the dissolved Li2Sn reduction and Li2S nucleation reaction. Furthermore, a series of experimental and electrochemical tests were performed to demonstrate that the Schottky catalytic effect enhanced the synergistic catalytic effect. With a Ni2P-Co@CNT catalyst, the battery exhibits an initial specific capacity of 874 mAh g-1 at a rate of 4.0 C, and the decay rate per cycle is 0.049% in 700 cycles. Meanwhile, the battery shows 0.118% decay rate per cycle at 0.5 C in 100 cycles at a high sulfur loading of 10 mg cm-2. The Schottky heterojunction structure proposed here has been shown to have a good catalytic effect on the reduction of Li2Sn and nucleation of Li2S, which provides a profound guidance for efficient and rational catalyst design.

Approaching the Intrinsic Threshold Breakdown Voltage and Ultrahigh Gain in a Graphite/InSe Schottky Photodetector.

Realizing both ultralow breakdown voltage and ultrahigh gain is one of the major challenges in the development of high-performance avalanche photodetector. Here, it is reported that an ultrahigh avalanche gain of 3 × 105 can be realized in the graphite/InSe Schottky photodetector at a breakdown voltage down to 5.5 V. Remarkably, the threshold breakdown voltage can be further reduced down to 1.8 V by raising the operating temperature, approaching the theoretical limit of 1.5 E g \[{{\cal E}_{\bf g}}\] /e, with E g ${{\cal E}_{\bf g}}$ the bandgap of semiconductor. A 2D impact ionization model is developed and it is uncovered that observation of high gain at low breakdown voltage arises from reduced dimensionality of electron-phonon scattering in the layered InSe flake. These findings open up a promising avenue for developing novel weak-light detectors with low energy consumption and high sensitivity.

Piezoelectricity across 2D Phase Boundaries.

Piezoelectricity in low-dimensional materials and metal-semiconductor junctions has attracted recent attention. Herein, a 2D in-plane metal-semiconductor junction made of multilayer 2H and 1T' phases of molybdenum(IV) telluride (MoTe2 ) is investigated. Strong piezoelectric response is observed using piezoresponse force microscopy at the 2H-1T' junction, despite that the multilayers of each individual phase are weakly piezoelectric. The experimental results and density functional theory calculations suggest that the amplified piezoelectric response observed at the junction is due to the charge transfer across the semiconducting and metallic junctions resulting in the formation of dipoles and excess charge density, allowing the engineering of piezoelectric response in atomically thin materials.

Ti3 C2 TX MXene Modified with ZnTCPP with Bacteria Capturing Capability and Enhanced Visible Light Photocatalytic Antibacterial Activity.

Light-assisted antibacterial therapy is a promising alternative to antibiotic therapy due to the high antibacterial efficacy without bacterial resistance. Recent research has mainly focused on the use of near-infrared light irradiation to kill bacteria by taking advantage of the synergistic effects rendered by hyperthermia and radical oxygen species. However, photocatalytic antibacterial therapy excited by visible light is more convenient and practical, especially for wounds. Herein, a visible light responsive organic-inorganic hybrid of ZnTCPP/Ti3 C2 TX is designed and fabricated to treat bacterial infection with antibacterial efficiency of 99.86% and 99.92% within 10 min against Staphylococcus aureus and Escherichia coli, respectively. The porphyrin-metal complex, ZnTCPP, is assembled on the surface of Ti3 C2 TX MXene to capture bacteria electrostatically and the Schottky junction formed between Ti3 C2 TX and ZnTCPP promotes visible light utilization, accelerates charge separation, and enhances the mobility of photogenerated charges, and finally increases the photocatalytic activity. As a result of the excellent bacteria capturing ability and photocatalytic antibacterial effects, ZnTCPP/Ti3 C2 TX exposed to visible light has excellent antibacterial properties in vitro and in vivo. Therefore, organic-inorganic materials that have been demonstrated to possess good biocompatibility and enhance wound healing have large potential in bio-photocatalysis, antibacterial therapy, as well as antibiotics-free treatment of wounds.

Implementation of Ambipolar Polysilicon Thin-Film Transistors with Nickel Silicide Schottky Junctions by Low-Thermal-Budget Microwave Annealing.

In this study, the efficient fabrication of nickel silicide (NiSix) Schottky barrier thin-film transistors (SB-TFTs) via microwave annealing (MWA) technology is proposed, and complementary metal-oxide-semiconductor (CMOS) inverters are implemented in a simplified process using ambipolar transistor properties. To validate the efficacy of the NiSix formation process by MWA, NiSix is also prepared via the conventional rapid thermal annealing (RTA) process. The Rs of the MWA NiSix decreases with increasing microwave power, and becomes saturated at 600 W, thus showing lower resistance than the 500 °C RTA NiSix. Further, SB-diodes formed on n-type and p-type bulk silicon are found to have optimal rectification characteristics at 600 W microwave power, and exhibit superior characteristics to the RTA SB-diodes. Evaluation of the electrical properties of NiSix SB-TFTs on excimer-laser-annealed (ELA) poly-Si substrates indicates that the MWA NiSix junction exhibits better ambipolar operation and transistor performance, along with improved stability. Furthermore, CMOS inverters, constructed using the ambipolar SB-TFTs, exhibit better voltage transfer characteristics, voltage gains, and dynamic inverting behavior by incorporating the MWA NiSix source-and-drain (S/D) junctions. Therefore, MWA is an effective process for silicide formation, and ambipolar SB-TFTs using MWA NiSix junctions provide a promising future for CMOS technology.

Constructing electrostatic self-assembled ultrathin porous red 2D g-C3N4/Fe2N Schottky catalyst for high-efficiency tetracycline removal in photo-Fenton-like processes.

The traditional heterogeneous photo-Fenton reaction was mainly restricted by the fewer surface-active sites, low Fe3+/Fe2+ transformation and H2O2 activation efficiency of catalyst. This work designed and fabricated the efficient photo-Fenton Schottky catalysts via a facile electrostatic self-assembly of metallic Fe2N nanoparticles scattering on the surface of red g-C3N4 (ultrathin porous oxygen-doped 2D g-C3N4 nanosheets). The porous morphology and exceptional electrical structure of red g-C3N4 endowed more active sites and facilitated the photoexcited charge separation. Benefitting from the Schottky effect and unique dimensional coupling structure, the strong visible light absorption and fast spatial charge transfer were realized in the Schottky junction system. More strikingly, Fe2N as an efficient co-catalyst was in favor of the trap and export of e-, leading to the Fe3+/Fe2+ transformation and H2O2 activation during the photo-Fenton process. Accordingly, the as-prepared catalysts revealed outstanding activity in photo-Fenton like degradation of tetracycline (TC) although under 5 W white LED light irradiation. Furthermore, the reasonable degradation pathway of TC and corresponding toxicity of the intermediates, as well as the photo-Fenton catalytic mechanism were interpreted and discussed in detail. This study would be a great aid in the development of various Schottky catalysts for heterogeneous photo-Fenton-based environmental remediation systems.

Boosting Electrochemical Water Oxidation on NiFe (oxy) Hydroxides by Constructing Schottky Junction toward Water Electrolysis under Industrial Conditions.

The practical deployment of promising NiFe-based oxygen evolution reaction (OER) electrocatalysts is heavily limited due to the constrain in both stability and activity under industrial conditions. Herein, a 3D free-standing NiFe(oxy)hydroxide-based electrode with Schottky junction is constructed, in which NiFe(oxy)hydroxide (NiFe(OH)x ) nanosheets are chemically assembled on the top of metal-like Ni3 S2 scaffold that are in situ formed on commercial Ni mesh. Such an assembly enhances the binding strength of each components, promotes the charge transfer across the interfaces, and modulates the electronic and nanostructural features of NiFe(OH)x . Consequently, the electrode delivers current densities of as high as 500 and 1000 mA cm-2 for OER at overpotentials of only 248 and 270 mV with long-term stability in 1 m KOH. When it was paired with a NiMo hydrogen evolution cathode in a practical two-electrode system, a current density of 1000 mA cm-2 is achieved at a low cell voltage of ≈1.61 V at 80 °C in 30% KOH without losing performance for at least 1500 h. This is the best performance reported thus far for alkaline water electrolysis under industrial conditions, demonstrating its great potential for practical applications.

Semiconductor Gas Sensor for Triethylamine Detection.

With the demanding detection of unique toxic gas, semiconductor gas sensors have attracted tremendous attention due to their intriguing features, such as, high sensitivity, online detection, portability, ease of use, and low cost. Triethylamine, a typical gas of volatile organic compounds, is an important raw material for industrial development, but it is also a hazard to human health. This review presents a concise compilation of the advances in triethylamine detection based on chemiresistive sensors. Specifically, the testing system and sensing parameters are described in detail. Besides, the sensing mechanism with characterizing tactics is analyzed. The research status based on various chemiresistive sensors is also surveyed. Finally, the conclusion and challenges, as well as some perspectives toward this area, are presented.

ZnO Structures with Surface Nanoscale Interfaces Formed by Au, Fe2O3, or Cu2O Modifier Nanoparticles: Characterization and Gas Sensing Properties.

Zinc oxide rod structures are synthetized and subsequently modified with Au, Fe2O3, or Cu2O to form nanoscale interfaces at the rod surface. X-ray photoelectron spectroscopy corroborates the presence of Fe in the form of oxide-Fe2O3; Cu in the form of two oxides-CuO and Cu2O, with the major presence of Cu2O; and Au in three oxidation states-Au3+, Au+, and Au0, with the content of metallic Au being the highest among the other states. These structures are tested towards nitrogen dioxide, ethanol, acetone, carbon monoxide, and toluene, finding a remarkable increase in the response and sensitivity of the Au-modified ZnO films, especially towards nitrogen dioxide and ethanol. The results for the Au-modified ZnO films report about 47 times higher response to 10 ppm of nitrogen dioxide as compared to the non-modified structures with a sensitivity of 39.96% ppm-1 and a limit of detection of 26 ppb to this gas. These results are attributed to the cumulative effects of several factors, such as the presence of oxygen vacancies, the gas-sensing mechanism influenced by the nano-interfaces formed between ZnO and Au, and the catalytic nature of the Au nanoparticles.

Efficient Schottky Junction Construction in Metal-Organic Frameworks for Boosting H2 Production Activity.

Manipulation of the co-catalyst plays a vital role in charge separation and reactant activation to enhance the activity of metal-organic framework-based photocatalysts. However, clarifying and controlling co-catalyst related charge transfer process and parameters are still challenging. Herein, three parameters are proposed, V transfer (the electron transfer rate from MOF to co-catalyst), D transfer (the electron transfer distance from MOF to co-catalyst), and V consume (the electron consume rate from co-catalyst to the reactant), related to Pt on UiO-66-NH2 in a photocatalytic process. These parameters can be controlled by rational manipulation of the co-catalyst via three steps: i) Compositional design by partial substitution of Pt with Pd to form PtPd alloy, ii) location control by encapsulating the PtPd alloy into UiO-66-NH2 crystals, and iii) facet selection by exposing the encapsulated PtPd alloy (100) facets. As revealed by ultrafast transient absorption spectroscopy and first-principles simulations, the new Schottky junction (PtPd (100)@UiO-66-NH2) with higher V transfer and V consume exhibits enhanced electron-hole separation and H2O activation than the traditional Pt/UiO-66-NH2 junction, thereby leading to a significant enhancement in the photoactivity.

Schottky Junctions with Bi Cocatalyst for Taming Aqueous Phase N2 Reduction toward Enhanced Solar Ammonia Production.

Solar-powered N2 reduction in aqueous solution is becoming a research hotspot for ammonia production. Schottky junctions at the metal/semiconductor interface have been effective to build up a one-way channel for the delivery of photogenerated electrons toward photoredox reactions. However, their applications for enhancing the aqueous phase reduction of N2 to ammonia have been bottlenecked by the difficulty of N2 activation and the competing H2 evolution reaction (HER) at the metal surface. Herein, the application of Bi with low HER activity as a robust cocatalyst for constructing Schottky-junction photocatalysts toward N2 reduction to ammonia is reported. The introduction of Bi not only boosts the interfacial electron transfer from excited photocatalysts due to the built-in Schottky-junction effect at the Bi/semiconductor interface but also synchronously facilitates the on-site N2 adsorption and activation toward solar ammonia production. The unidirectional charge transfer to the active site of Bi significantly promotes the photocatalytic N2-to-ammonia conversion efficiency by 65 times for BiOBr. In addition, utilizing Bi to enhance the photocatalytic ammonia production can be extended to other semiconductor systems. This work is expected to unlock the promise of engineering Schottky junctions toward high-efficiency solar N2-to-ammonia conversion in aqueous phase.

Nanoburl Graphites.

A critical challenge for the application of graphite is low strength, which originates from the easy cleavage of graphite (0002) planes. Inspired by the burl strengthening mechanism observed in tree trunks, nanodiamond particles converted into graphite onions are used as "nanoburls" embedded in graphite (0002) lattice planes to eliminate the graphite (0002) plane cleavage of bulk graphites prepared by spark plasma sintering from graphite powders. Covalent bonds are built between carbon atoms by sp3 hybridization at the interface between the graphite onions and flakes, which triggers an electron redistribution to form positive/negative charge domains within. Thus, pairs of pseudo-Schottky junctions are created by the hybridization, which further enhances the bonding between the graphite onions and flakes. With these bonding mechanisms, and with voids between the graphite powders filled in by the volume expansion associated with the change of nanodiamonds to the graphite onions, the loose compaction of graphite powder becomes consolidated at 1700 °C. The proposed nanoburl mechanism shows its potential and bestows the nanoburl graphites with strength five times that of conventional graphites prepared from graphite powders. The concept of nanoburl strengthening can be important in the microstructural design and property enhancement of other layered materials.

Bias Tunable Photocurrent in Metal-Insulator-Semiconductor Heterostructures with Photoresponse Enhanced by Carbon Nanotubes.

Metal-insulator-semiconductor-insulator-metal (MISIM) heterostructures, with rectifying current-voltage characteristics and photosensitivity in the visible and near-infrared spectra, are fabricated and studied. It is shown that the photocurrent can be enhanced by adding a multi-walled carbon nanotube film in the contact region to achieve a responsivity higher than 100   mA   W - 1 under incandescent light of 0.1   mW   cm - 2 . The optoelectrical characteristics of the MISIM heterostructures are investigated at lower and higher biases and are explained by a band model based on two asymmetric back-to-back Schottky barriers. The forward current of the heterojunctions is due to majority-carrier injection over the lower barrier, while the reverse current exhibits two different conduction regimes corresponding to the diffusion of thermal/photo generated carriers and majority-carrier tunneling through the higher Schottky barrier. The two conduction regimes in reverse bias generate two plateaus, over which the photocurrent increases linearly with the light intensity that endows the detector with bias-controlled photocurrent.

Self-generated carbon nanotubes for protecting active sites on bifunctional Co/CoOx schottky junctions to promote oxygen reduction/evolution reactions via efficient valence transition.

Protecting active species from aggregation and corrosion may be feasible to obtain stable catalytic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, bamboo-shaped N-doped carbon nanotubes (hollow BS-NCNTs as shells) are self-generated to in situ wrap the Co/CoOx schottky junctions (cores) to obtain the Co/CoOx@BS-NCNTs as bifunctional ORR/OER catalysts by using the Co-chelated melamine precursor. For ORR, Co/CoOx@BS-NCNTs (700 °C) exhibits more positive peak (0.822 V vs. RHE) and half-wave (0.842 V vs. RHE) potential than those of commercial Pt/C (10 wt%). Superior ORR activity is mainly attributed to the enriched coordination-unsaturated Co2+ (tetrahedral CoTd2+) in the CoOx wrapped in the tubular structure of BS-NCNTs featuring high electrical conductivity and active N species. Moreover, the π-π bonds of CNTs are activated by N substitution, which provides a stunning electron capture and transmission capability for enhancing ORR activity. For OER, Co/CoOx@BS-NCNTs (700 °C) obtains a smaller potential (1.590 V vs. RHE) than that of RuO2/C at 10 mA cm-2. The outstanding OER activity and durability of Co/CoOx@BS-NCNTs (700 °C) originates from strong interactions between C-skeleton and Co species, and efficient Co3+/Co4+ (Co4+OOH as active sites) transition protected by the externally-grown CNTs. Furthermore, abundant oxygen vacancies on CoOx surface can facilitate the adsorption of OH-/or OER-related intermediates to improve OER activity. Therefore, this study provides a promising strategy to develop NCNTs-wrapped Co species with high catalytic activity and stability for energy conversion.

Gate-Tunable Graphene-WSe2 Heterojunctions at the Schottky-Mott Limit.

Metal-semiconductor interfaces, known as Schottky junctions, have long been hindered by defects and impurities. Such imperfections dominate the electrical characteristics of the junction by pinning the metal Fermi energy. Here, a graphene-WSe2 p-type Schottky junction, which exhibits a lack of Fermi level pinning, is studied. The Schottky junction displays near-ideal diode characteristics with large gate tunability and small leakage currents. Using a gate electrostatically coupled to the WSe2 channel to tune the Schottky barrier height, the Schottky-Mott limit is probed in a single device. As a special manifestation of the tunable Schottky barrier, a diode with a dynamically controlled ideality factor is demonstrated.