Reversible Photochromic Phenomenon of Plasmonic Metal/Semiconductor Heterostructures via Photoinduced Electron Storage.

The transfer and migration process of the photogenerated charge carriers in plasmonic metal/semiconductor heterostructures not only affects their photocatalytic performance but also triggers some captivating phenomena. Here, a reversible photochromic behavior is observed on the Au/CdS heterostructures when they are investigated as photocatalysts for hydrogen production. The photochromism takes place upon excitation of the CdS component, in which the photogenerated holes are rapidly consumed by ethanol, while the electrons are transferred and stored on the Au cores, resulting in the blue shift of their localized surface plasmon resonance. The colloidal solution can restore its initial color after pumping with air, and the photochromic behavior can be cycled five times without obvious degradation. The finding represents great progress toward the photochromic mechanism of metal/semiconductor heterostructures and also reveals the importance of understanding the dynamic process of the photogenerated charge carriers in these heterostructures.

Copper-Nanoparticle-Decorated Hydrothermal Carbonaceous Carbon-Polydimethylsiloxane Nanocomposites: Unveiling Potential in Simultaneous Light-Driven Interfacial Water Evaporation and Power Generation.

This study introduces a hydrothermal synthesis method that uses glucose and Cu2+ ions to create a Cu-nanoparticle (NP)-decorated hydrothermal carbonaceous carbon hybrid material (Cu-HTCC). Glucose serves both as a reducing agent, efficiently transforming Cu2+ ions into elemental Cu nanostructures, and as a precursor for HTCC microstructures. An enhanced plasmon-induced electric field resulting from Cu NPs supported on microstructure matrices, coupled with a distinctive localized π-electronic configuration in the hybrid material, as confirmed by X-ray photoelectron spectroscopic analysis, lead to the heightened optical absorption in the visible-near-infrared range. Consequently, flexible nanocomposites of Cu-HTCC/PDMS and Cu-HTCC@PDMS (PDMS = polydimethylsiloxane) are designed as 2 and 3D structures, respectively, that exhibit broad-spectrum solar absorption. These composites promise efficient photo-assisted thermoelectric power generation and water evaporation, demonstrating commendable mechanical stability and flexibility. Notably, the Cu-HTCC@PDMS composite sponge simultaneously exhibits commendable efficiency in both water evaporation (1.47 kg m-2 h-1) and power generation (32.1 mV) under 1 sunlight illumination. These findings unveil new possibilities for innovative photothermal functional materials in diverse solar-driven applications.

Tunable Contacts of Bi2 O2 Se Nanosheets MSM Photodetectors by Metal-Assisted Transfer Approach for Self-Powered Near-Infrared Photodetection.

Owing to the Fermi pinning effect arose in the metal electrodes deposition process, metal-semiconductor contact is always independent on the work function, which challenges the next-generation optoelectronic devices. In this work, a metal-assisted transfer approach is developed to transfer Bi2 O2 Se nanosheets onto the pre-deposited metal electrodes, benefiting to the tunable metal-semiconductor contact. The success in Bi2 O2 Se nanosheets transfer is contributed to the stronger van der Waals adhesion of metal electrodes than that of growth substrates. With the pre-deposited asymmetric electrodes, the self-powered near-infrared photodetectors are realized, demonstrating low dark current of 0.04 pA, high Ilight /Idark ratio of 380, fast rise and decay times of 4 and 6 ms, respectively, under the illumination of 1310 nm laser. By pre-depositing the metal electrodes on polyimide and glass, high-performance flexible and omnidirectional self-powered near-infrared photodetectors are achieved successfully. This study opens up new opportunities for low-dimensional semiconductors in next-generation high-performance optoelectronic devices.

Novel Al/CoFe/p-Si and Al/NiFe/p-Si MS-type photodiode for sensing.

CoFe and NiFe are used in the construction of Si-based MS-type photodiodes. Thin film layers are sputtered onto the p-Si surface where Al metal contacts are deposited by thermal evaporation technique. Film characteristics of the layers are investigated in terms of crystalline structure and surface morphology. Their electrical and optical properties are investigated by dark and illuminated current-voltage measurements. When these two diodes are compared, Al/NiFe/p-Si shows better rectification properties than Al/CoFe/p-Si diode. It has also a high barrier height where these values for both diodes increase with illumination. According to current-voltage analysis, the existence of an interlayer causes a deviation in diode ideality. In addition, the response to bias voltage and derivation of electrical parameters, the light sensitivity of diodes are evaluated by current-voltage measurements under different illumination intensities and also transient photosensitive characteristics.

Studies of carrier transport mechanism in NiO/Ag/NiO transparent conducting electrode/ZnO metal-semiconductor-metal photodetectors.

Oxide/metal/oxide multilayers as a transparent conducting electrode (TCE) have been developed to replace metals due to their high transparency and low sheet resistance. Nickel oxide (NiO) film with a high work function was used as an oxide to form NiO/Ag/NiO (NAN) TCE, therefore a high barrier height between NAN/zinc oxide (ZnO) interface. In the study, NAN TCE was deposited on ZnO surface to fabricate metal-semiconductor-metal (MSM) photodetectors (PDs) and study its carrier transport mechanism. The NAN TCE has a low sheet resistance of 6.5 Ω/sq. and transmittance more than 40% in a 300-1000 nm wavelength range. Such issues result in the figure-of-merit is higher (2.3 × 10-4Ω-1) than that (2.5 × 10-7Ω-1) of pure single NiO thin film. As compared to the conventional Au/ZnO MSM-PDs, the NAN/ZnO MSM-PDs demonstrates a lower leakage current as a result of Ni atoms diffusing into ZnO and passivating the defects. Due to the high work function of NiO, the NAN/ZnO interface exhibits a barrier height as high as 0.91 eV. The Au/ZnO MSM-PDs reveals only one carrier conduction of ohmic due to the electrons tunnel form Au into ZnO through the surface defects. In contrast, two distinct carrier transport mechanisms were observed in the NAN/ZnO MSM-PDs. At low-voltage forV⩽0.64 V, ohmic conduction dominates and the electrons inject from NAN to ZnO, trapped by the defect states of ZnO. At high-voltage for V⩾0.64 V, the trapped electrons acquire enough energy and emit from trap to conduction band, entering Poole-Frankel emission transport.

Light-Induced Dynamic Activation of Copper/Silicon Interface for Highly Selective Carbon Dioxide Reduction.

Numerous studies have shown a fact that phase transformation and/or reconstruction are likely to occur and play crucial roles in electrochemical scenarios. Nevertheless, a decisive factor behind the diverse photoelectrochemical activity and selectivity of various copper/silicon photoelectrodes is still largely debated and missing in the community, especially the possibly dynamic behaviors of metal catalyst/semiconductor interface. Herein, through in situ X-ray absorption spectroscopy and transmission electron microscope, a model system of Cu nanocrystals with well-defined facets on black p-type silicon (BSi) is unprecedentedly demonstrated to reveal the dynamic phase transformation of forming irreversible silicide at Cu nanocrystal-BSi interface during photoelectrocatalysis, which is validated to originate from the atomic interdiffusion between Cu and Si driven by light-induced dynamic activation process. Significantly, the adaptive junction at Cu-Si interface is activated by an expansion of interatomic Cu-Cu distance for CO2 electroreduction, which efficiently restricts the C-C coupling pathway but strengthens the bonding with key intermediate of *CHO for CH4 yield, resulting in a remarkable 16-fold improvement in the product ratio of CH4/C2 products and an intriguing selectivity switch. This work offers new insights into dynamic structural transformations of metal/semiconductor junction and design of highly efficient catalysts toward photosynthesis.

High-Throughput Computational Screening of All-MXene Metal-Semiconductor Junctions for Schottky-Barrier-Free Contacts with Weak Fermi-Level Pinning.

Van der Waals (vdW) metal-semiconductor junctions (MSJs) exhibit huge potential to reduce the contact resistance and suppress the Fermi-level pinning (FLP) for improving the device performance, but they are limited by optional (2D) metals with a wide range of work functions. Here a new class of vdW MSJs entirely composed of atomically thin MXenes is reported. Using high-throughput first-principles calculations, highly stable 80 metals and 13 semiconductors are screened from 2256 MXene structures. The selected MXenes cover a broad range of work functions (1.8-7.4 eV) and bandgaps (0.8-3 eV), providing a versatile material platform for constructing all-MXene vdW MSJs. The contact type of 1040 all-MXene vdW MSJs based on Schottky barrier heights (SBHs) is identified. Unlike conventional 2D vdW MSJs, the formation of all-MXene vdW MSJs leads to interfacial polarization, which is responsible for the FLP and deviation of SBHs from the prediction of Schottky-Mott rule. Based on a set of screening criteria, six Schottky-barrier-free MSJs with weak FLP and high carrier tunneling probability (>50%) are identified. This work offers a new way to realize vdW contacts for the development of high-performance electronic and optoelectronic devices.

Multipod Bi(Cu2-xS)n Nanocrystals formed by Dynamic Cation-Ligand Complexation and Their Use as Anodes for Potassium-Ion Batteries.

We report the formation of an intermediate lamellar Cu-thiolate complex, and tuning its relative stability using alkylphosphonic acids are crucial to enabling controlled heteronucleation to form Bi(Cu2-xS)n heterostructures with a tunable number of Cu2-xS stems on a Bi core. The denticity of the phosphonic acid group, concentration, and chain length of alkylphosphonic acids are critical factors determining the stability of the Cu-thiolate complex. Increasing the stability of the Cu-thiolate results in single Cu2-xS stem formation, and decreased stability of the Cu-thiolate complex increases the degree of heteronucleation to form multiple Cu2-xS stems on the Bi core. Spatially separated multiple Cu2-xS stems transform into a support network to hold a fragmented Bi core when used as an anode in a K-ion battery, leading to a more stable cycling performance showing a specific capacity of ∼170 mAh·g-1 after 200 cycles compared to ∼111 mAh·g-1 for Bi-Cu2-xS single-stem heterostructures.

Construction of Spatially Separated Gold Nanocrystal/Cuprous Oxide Architecture for Plasmon-Driven CO2 Reduction.

Plasmonic hot electrons have shown great potential in photocatalysis, but little is known about the hot hole-driven chemical reactions due to the lack of desired plasmonic metal/p-type semiconductor architectures. Herein, we describe a general and robust strategy for the site-selective growth of a p-type semiconductor, Cu2O on Au nanocrystals (NCs), to produce diverse spatially separated Au/Cu2O heterostructures. The preferential growth of Cu2O on the tips/ends/edges of Au NCs is directed by the sparse coverage of the surfactant molecules at the high-curvature sites of Au NCs. The obtained dumbbell-shaped nanostructures serve as the ideal platforms for probing the hot-hole-mediated CO2 reduction reaction. Benefiting from the hot-hole injection, a new reaction pathway is unlocked, and the C2 product activity and selectivity are significantly improved. This study demonstrates the genuine superiority of the dumbbell-shaped nanostructures in photocatalysis, offering a new unique avenue to explore the underlying mechanism of hot-hole-mediated chemical reactions.

Recent Advances of Constructing Metal/Semiconductor Catalysts Designing for Photocatalytic CO2 Hydrogenation.

With the development of the world economy and the rapid advancement of global industrialization, the demand for energy continues to grow. The significant consumption of fossil fuels, such as oil, coal, and natural gas, has led to excessive carbon dioxide emissions, causing global ecological problems. CO2 hydrogenation technology can convert CO2 into high-value chemicals and is considered one of the potential ways to solve the problem of CO2 emissions. Metal/semiconductor catalysts have shown good activity in carbon dioxide hydrogenation reactions and have attracted widespread attention. Therefore, we summarize the recent research on metal/semiconductor catalysts for photocatalytic CO2 hydrogenation from the design of catalysts to the structure of active sites and mechanistic investigations, and the internal mechanism of the enhanced activity is elaborated to give guidance for the design of highly active catalysts. Finally, based on a good understanding of the above issues, this review looks forward to the development of future CO2 hydrogenation catalysts.

Composition Dependent Electrical Transport in Si1-x Gex Nanosheets with Monolithic Single-Elementary Al Contacts.

Si1-x Gex is a key material in modern complementary metal-oxide-semiconductor and bipolar devices. However, despite considerable efforts in metal-silicide and -germanide compound material systems, reliability concerns have so far hindered the implementation of metal-Si1-x Gex junctions that are vital for diverse emerging "More than Moore" and quantum computing paradigms. In this respect, the systematic structural and electronic properties of Al-Si1-x Gex heterostructures, obtained from a thermally induced exchange between ultra-thin Si1-x Gex nanosheets and Al layers are reported. Remarkably, no intermetallic phases are found after the exchange process. Instead, abrupt, flat, and void-free junctions of high structural quality can be obtained. Interestingly, ultra-thin interfacial Si layers are formed between the metal and Si1-x Gex segments, explaining the morphologic stability. Integrated into omega-gated Schottky barrier transistors with the channel length being defined by the selective transformation of Si1-x Gex into single-elementary Al leads, a detailed analysis of the transport is conducted. In this respect, a report on a highly versatile platform with Si1-x Gex composition-dependent properties ranging from highly transparent contacts to distinct Schottky barriers is provided. Most notably, the presented abrupt, robust, and reliable metal-Si1-x Gex junctions can open up new device implementations for different types of emerging nanoelectronic, optoelectronic, and quantum devices.

Laser modification of Au-CuO-Au structures for improved electrical and electro-optical properties.

CuO nanomaterials are one of the metal-oxides that received extensive investigations in recent years due to their versatility for applications in high-performance nano-devices. Tailoring the device performance through the engineering of properties in the CuO nanomaterials thus attracted lots of effort. In this paper, we show that nanosecond (ns) laser irradiation is effective in improving the electrical and optoelectrical properties in the copper oxide nanowires (CuO NWs). We find that ns laser irradiation can achieve joining between CuO NWs and interdigital gold electrodes. Meanwhile, the concentration and type of point defects in CuO can be controlled by ns laser irradiation as well. An increase in the concentration of defect centers, together with a reduction in the potential energy barrier at the Au/CuO interfaces due to laser irradiation increases electrical conductivity and enhances photo-conductivity. We demonstrate that the enhanced electrical and photo-conductivity achieved through ns laser irradiation can be beneficial for applications such as resistive switching and photo-detection.

Plasmonic Near-Infrared Photoconductor Based on Hot Hole Collection in the Metal-Semiconductor-Metal Junction.

Harvesting energetic carriers from plasmonic resonance has been a hot topic in the field of photodetection in the last decade. By interfacing a plasmonic metal with a semiconductor, the photoelectric conversion mechanism, based on hot carrier emission, is capable of overcoming the band gap limitation imposed by the band-to-band transition of the semiconductor. To date, most of the existing studies focus on plasmonic structural engineering in a single metal-semiconductor (MS) junction system and their responsivities are still quite low in comparison to conventional semiconductor, material-based photodetection platforms. Herein, we propose a new architecture of metal-semiconductor-metal (MSM) junctions on a silicon platform to achieve efficient hot hole collection at infrared wavelengths with a photoconductance gain mechanism. The coplanar interdigitated MSM electrode's configuration forms a back-to-back Schottky diode and acts simultaneously as the plasmonic absorber/emitter, relying on the hot-spots enriched on the random Au/Si nanoholes structure. The hot hole-mediated photoelectric response was extended far beyond the cut-off wavelength of the silicon. The proposed MSM device with an interdigitated electrode design yields a very high photoconductive gain, leading to a photocurrent responsivity up to several A/W, which is found to be at least 1000 times higher than that of the existing hot carrier based photodetection strategies.

Inorganic Chiral Hybrid Nanostructures for Tailored Chiroptics and Chirality-Dependent Photocatalysis.

Inorganic chiral hybrid nanostructures that embed chirality within distinct material compositions can create novel chiral properties and functionalities absent from achiral nanostructures; however, they remain largely unexplored. We report, for the first time, a class of chiral plasmonic metal-semiconductor core-shell nanostructures that employ structurally chiral nanoparticles as chirality inducing templates to grow functional shell materials, which allowed us to independently control material parameters such as core geometry and shell thickness, as well as handedness of the system. We experimentally and theoretically achieved enhanced and tunable chiroptical activity of the heterostructures as a result of the core-shell strong coupling effect. As a proof-of-concept demonstration, we demonstrate that the chiral hybrid nanostructures can drive chirality-dependent photocatalytic hydrogen generation under circularly polarized light. This study enables rational design and functionalization of chiral hybrid nanomaterials towards enhanced chiral light-matter interactions and chiral device applications.

Toward Unusual-High Hole Mobility of p-Channel Field-Effect-Transistors.

The relative low hole mobility of p-channel building block device challenges the continued miniaturization of modern electronic chips. Metal-semiconductor junction is always an efficient strategy to control the carrier concentration of channel semiconductor, benefiting the carrier mobility regulation of building block device. In this work, complementary metal oxide semiconductor (CMOS)-compatible metals are selected to deposit on the surface of the important p-channel building block of GaSb nanowire field-effect-transistors (NWFETs), demonstrating the efficient strategy of hole mobility enhancement by metal-semiconductor junction. When deposited with lower work function metal of Al, the peak hole mobility of GaSb NWFET can be enhanced to as high as ≈3372 cm2 V-1 s-1 , showing three times than the un-deposited one. The as-studied metal-semiconductor junction is also efficient for the hole mobility enhancement of other p-channel devices, such as GaAs NWFET, GaAs film FET, and WSe2 FET. With the enhanced mobility, the as-constructed CMOS inverter shows good invert characteristics, showing a relatively high gain of ≈18.1. All results may be regarded as important advances to the next-generation electronics.

Two-step CVD synthesis of NiTe2-MoS2vertical junctions with improved MoS2transistors performance.

The primary challenge for widespread applications of two-dimensional electronics is to achieve satisfactory electrical contacts due to the difficulties in inevitable physical damages and selectively doping during traditional metal integration process. The two-dimensional (2D) metal-semiconductor junctions have attracted captivated attention for potential applications in future atomically thin electronics as perfect candidates for achieving reliable electrical contacts. Here we demonstrate the van der Waals epitaxial growth of 2D NiTe2-MoS2 metal-semiconductor vertical junctions which the upper NiTe2 selectively nucleate at the edge of underlying MoS2. Optical microscopy (OM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning transmission electron microscope (STEM) studies confirm that NiTe2-MoS2 metal-semiconductor vertical junctions are successfully synthesized. Electrical properties of the NiTe2-contacted MoS2 field-effect transistors (FETs) show higher field-effect mobilities (µFE) than those with deposited Cr/Au contacts. This study demonstrates an effective pathway to improved MoS2 transistors performance with metal-semiconductor junctions.

Status and prospects of Ohmic contacts on two-dimensional semiconductors.

In recent years, two-dimensional materials have received more and more attention in the development of semiconductor devices, and their practical applications in optoelectronic devices have also developed rapidly. However, there are still some factors that limit the performance of two-dimensional semiconductor material devices, and one of the most important is Ohmic contact. Here, we elaborate on a variety of approaches to achieve Ohmic contacts on two-dimensional materials and reveal their physical mechanisms. For the work function mismatch problem, we summarize the comparison of barrier heights between different metals and 2D semiconductors. We also examine different methods to solve the problem of Fermi level pinning. For the novel 2D metal-semiconductor contact methods, we analyse their effects on reducing contact resistance from two different perspectives: homojunction and heterojunction. Finally, the challenges of 2D semiconductors in achieving Ohmic contacts are outlined.

Evidence for a conducting surface ground state in high-quality single crystalline FeSi.

We report anomalous physical properties of high-quality single-crystalline FeSi over a wide temperature range of 1.8-400 K. The electrical resistivity ρ(T) can be described by activated behavior with an energy gap Δ = 57 meV between 150 and 67 K, below which the estimated energy gap is significantly smaller. The magneto-resistivity and Hall coefficient change sign in the vicinity of 67 K, suggesting a change of dominant charge carriers. At ∼19 K, ρ(T) undergoes a cross-over from semiconducting to metallic behavior which is very robust against external magnetic fields. The low-temperature metallic conductivity depends strongly on the width/thickness of the sample. In addition, no indication of a bulk-phase transition or onset of magnetic order is found down to 2 K from specific heat and magnetic susceptibility measurements. The measurements are consistent with one another and point to complex electronic transport behavior that apparently involves a conducting surface state in FeSi at low temperatures, suggesting the possibility that FeSi is a 3D topological insulator.

Sensitive Metal-Semiconductor Nanothermocouple Fabricated by FIB to Investigate Laser Beams with Nanometer Spatial Resolution.

The focused ion beam (FIB) technique was used to fabricate a nanothermocouple (with a 90 nm wide nanojunction) based on a metal-semiconductor (Pt-Si) structure, which showed a sensitivity up to 10 times larger (with Seebeck coefficient up to 140 µV/K) than typical metal-metal nanothermocouples. In contrast to the fabrication of nanothermocouples which requires a high-tech semiconductor manufacturing line with sophisticated fabrication techniques, environment, and advanced equipment, FIB systems are available in many research laboratories without the need for a high-tech environment, and the described processing is performed relatively quickly by a single operator. The linear response of the manufactured nanothermocouple enabled sensitive measurements even with small changes of temperature when heated with a stream of hot air. A nonlinear response of the nanothermocouple (up to 83.85 mV) was observed during the exposition to an argon-laser beam with a high optical power density (up to 17.4 Wcm-2), which was also used for the laser annealing of metal-semiconductor interfaces. The analysis of the results implies the application of such nanothermocouples, especially for the characterization of laser beams with nanometer spatial resolution. Improvements of the FIB processing should lead to an even higher Seebeck coefficient of the nanothermocouples; e.g., in case of the availability of other suitable metal sources (e.g., Cr).

Interfacial States Cause Equal Decay of Plasmons and Hot Electrons at Gold-Metal Oxide Interfaces.

We compare the decay of plasmons and "conventional" hot electrons within the same series of gold/metal oxide interfaces. We found an accelerated decay of hot electrons at gold-metal oxide interfaces with decreasing band gap of the oxide material. The decay is accelerated by the increased phase space for electron scattering caused by additional interfacial states. Since plasmons decay faster within the same series of gold-metal oxide interfaces, we propose plasmons are able to decay into the same interfacial states as hot electrons. The similarity of plasmon damping to conventional hot electron decay implies that many classical surface analysis techniques and theoretical concepts are transferable to plasmonic systems. Our results support the mechanism of direct decay of plasmons into interfacial hot electron pairs but the utility of these interfacial states for charge transfer reactions remains to be investigated.