Schottky Barrier Research Articles

Schottky-Barrier-Free Plasmonic Photocatalysts for Solar-Driven Ammonia Synthesis

Ammonia is not only an indispensable feedstock to produce essential industrial chemicals like fertilizers, but it is also a potential hydrogen energy carrier owing to its high energy density and hydrogen capacity. Currently, most ammonia required for humans comes from the Haber–Bosch process, which contributes more than 90% of the annual global ammonia output. However, the harsh reaction conditions of this process result in serious energy and environmental issues. According to the relevant statistics, the ammonia industry consumes about 2% of the total energy and generates about 1.6% of the total CO2 emission annually in the world.It is therefore crucial to develop a green and sustainable strategy for ammonia synthesis. Among various alternative technologies of the Haber–Bosch process, artificial photosynthesis has attracted wide research interests and has been regarded as a promising, environmentally friendly, and energy-saving process. Photocatalytic ammonia synthesis can utilize renewable solar energy to drive the reaction and operate under mild conditions, which possesses the benefits of the simple reaction system, low cost, and safety. Although numerous photocatalysts have been explored over the past several decades, their activity and efficiency have still been low and far from the practical application requirements. It is therefore a huge challenge to design efficient photocatalysts for ammonia synthesis.Localized surface plasmon resonance (LSPR) has recently drawn enormous attention. LSPR can not only endow plasmonic nanomaterials with large absorption cross-sections and intense local field enhancement but also generate energetic hot electrons and hot holes. Owing to the appealing features of LSPR, plasmonic photocatalysis has shown great potential in ammonia synthesis. Plasmonic photocatalysts are usually composed of noble metals and wide bandgap semiconductors. However, the Schottky barrier will form at the metal–semiconductor interface in such hybrid structures due to the mismatch of the band structures between plasmonic metals and semiconductors. Hence, a large portion of the hot electrons cannot cross the Schottky barrier and get lost in the metal through the recombination with the holes. To overcome the drawbacks caused by the Schottky barrier, it is strongly desirable to develop a new type of plasmonic semiconductor photocatalysts, i.e., Schottky-barrier-free plasmonic photocatalyst.The Schottky-barrier-free plasmonic photocatalysts are usually degenerately doped semiconductors containing lattice oxygen vacancies. They possess high free electron densities and strong plasmon resonance because of the high-level doping, which results in abundant hot charge carriers upon plasmon excitation. Moreover, they also have appropriate surface sites that can adsorb reactant molecules and activate them. The photogenerated plasmonic hot charge carriers can get trapped at the defect sites and thereafter drive redox reactions. Compared with traditional metal–semiconductor hybrid plasmonic photocatalysts, Schottky-barrier-free plasmonic photocatalysts enable hot charge carriers to be transported nearly freely in the material, resulting in high charge utilization and photocatalytic efficiency.We have demonstrated the synthesis of Schottky-barrier-free plasmonic MoO3−x nanospheres (NSs) with remarkably high oxygen vacancy (OV) contents by aerosol-spray. The MoO3−x NSs can achieve efficient ammonia photosynthesis through a “killing two birds with one stone” mechanism. On the one hand, the OVs can serve as chemisorption sites for N2 molecules and participate in their activation. On the other hand, the introduction of OVs generates a large number of free electrons near the conduction band, which induces a broad absorption band from the visible to the NIR region owing to the plasmon resonance. The Schottky-barrier-free nature of this plasmonic semiconductor allows free transportation of the plasmonic hot charge carriers, while the defect states introduced by the OVs can effectively trap the hot electrons to prevent rapid electron–hole recombination. As expected, the as-prepared material exhibits a superior ammonia production rate, with the highest apparent quantum efficiency (AQE) of 1.24% at 808 nm and an appreciable solar-to-ammonia conversion efficiency (SACE) of 0.057% for NH3 production. Besides MoO3−x , WO3−x is also an excellent candidate for Schottky-barrier-free plasmonic photocatalysts. We have synthesized square WO3−x nanoplates hydrothermally. The WO3-x nanoplates possess regular morphology, wide light absorption, and great ammonia production performance. Furthermore, by introducing doping elements (Mo, V, Fe, Bi) into WO3−x nanoplates, the N2 activation and dissociation can be improved by refining the defect states. The Mo-doped WO3−x nanoplates exhibit the highest ammonia production rate of 145.50 μmol g−1 h−1 with SACE of 0.011% since the Mo species can promote the chemisorption and polarization of N2 molecules and significantly reduce the reaction barrier. Notably, Mo-doped WO3−x nanoplates are a dual-function photocatalyst that can oxidize water to hydrogen peroxide in a stoichiometric ratio while synthesizing ammonia. Figure 1

(Invited) Plasmon-Driven Nitrogen Photofixation

Ammonia is one of the most important chemicals as well as an efficient energy carrier. The nitrogen element is indispensable for nearly all living species on the earth. However, dinitrogen molecules that are abundant in the atmosphere cannot be used directly by living species. They need to be converted into ammonia or nitrate for use. Such conversion is known as nitrogen fixation. Because natural nitrogen fixation is insufficient for sustaining all population on the earth, the industrial Haber-Bosch process has been developed for producing ammonia from dinitrogen and dihydrogen. The process consumes a large amount of energy and generates a large amount of carbon dioxide. Photocatalytic nitrogen fixation can operate under mild conditions and uses solar energy and water. It offers an intriguing alternative approach for the conversion of atmospheric dinitrogen into ammonia.Plasmonic metal nanocrystals can effectively absorb light and efficiently generate hot charge carriers. Compared to traditional interband excitation in semiconductors, plasmon excitation offers a new approach for generating hot charge carriers, which can thereafter be utilized for various physical and chemical processes. The use of plasmonic hot charge carriers for photocatalysis has become a hot research topic in the recent years. Plasmonic hot charge carriers can not only enhance the reaction yield and selectivity, but also introduce new reaction pathways. Moreover, the plasmon resonance wavelengths of various nanoparticles can be synthetically adjusted over a broad range that surpasses the solar spectrum.We have demonstrated the powerfulness of localized plasmon resonance on driving photocatalytic reduction of atmospheric nitrogen, where plasmonic hot electrons play an essential role. First, Au nanoparticles are anchored on ultrathin titania nanosheets with oxygen vacancies. The oxygen vacancies chemisorb and activate nitrogen molecules, which are subsequently reduced to ammonia by plasmonic hot electrons generated from the Au nanoparticles. Our synthesized all-inorganic hybrid structures mimic the function of biological nitrogenase enzymes, where the plasmonic Au nanoparticles play the role of the Fe proteins and the titania nanosheets play the role of the MoFe proteins. Second, we have extended the biomimetic idea into another popular semiconductor. A plasmonic hybrid catalyst is produced by uniformly embedding Au nanoparticles in the mesopores of nitrogen-deficient hollow carbon nitride spheres. The carbon nitride spheres possess abundant nitrogen vacancies, which serve as the sites for nitrogen chemisorption and activation, and capture photoexcited electrons stemmed from the carbon nitride spheres and the plasmon resonance of the embedded Au nanoparticles for the efficient reduction of the adsorbed nitrogen molecules to ammonia. Third, when metal-semiconductor hybrid nanostructures are designed as photocatalysts for nitrogen fixation, the introduction of a Schottky barrier at the junction is unavoidable. This Schottky barrier will undoubtedly lower the utilization efficiency of plasmonic charge carriers because only plasmonic hot charge carriers with sufficient energies and appropriate momenta can overcome the barrier and inject into the semiconductor. In addition, noble metals are well-known to be expensive. We have synthesized different metal oxide nanoparticles that are degenerately doped and thus exhibit strong plasmon resonance and demonstrated Schottky-barrier-free plasmonic photocatalysts for nitrogen fixation. The excitation of the plasmon resonance in these metal oxide nanoparticles can efficiently generate hot charge carriers. Because of the abundance of defects in these degenerately doped semiconductor nanoparticles, the photogenerated hot charge carriers can rapidly migrate to the defect sites and get trapped there. In this way, the lifetime of the plasmonic hot charge carriers is Moreover, these metal oxide nanoparticles possess active sites for adsorbing and activating dinitrogen molecules. Therefore, they function in a “one-stone-two-birds” manner. As a result, a record-high solar-to-chemical energy conversion efficiency has been achieved.

Low Frequency Electronic Noise Characterization of Au-W/β-Ga2O3 Schottky Diodes

Ultra-wide bandgap (UWBG) semiconductors have attracted tremendous amount of interest for applications in high-power electronics and solar-blind UV photodetectors. In particular, β-Ga2O3 has attracted significant research attention in recent years due to its promising electrical and optical characteristics including a large bandgap, high breakdown electrical field, and large Baliga’s figure of merit compared to well-established wide-bandgap technologies such as GaN and SiC [1].Low frequency electronic noise, which is present in all electronic devices, can be used as a diagnostic tool for semiconductor material and device characterization. By studying the low frequency noise in semiconductor materials and devices, the physics associated with the noise properties of bulk and interface defects and traps can be investigated [2]. Measurement of low frequency noise is also crucial for evaluating material quality and device reliability.In this work, we investigate the forward-bias diode parameters and low-frequency electronic noise in Au-W/β-Ga2O3 Schottky barrier diodes. The Schottky contact is formed by depositing 20 nm of Tungsten (W) using dc sputtering followed by 340 nm of Gold (Au) using e-beam evaporation, and subsequent annealing [3].We first measure the I-V characteristics and extract important diode parameters, such as the Schottky barrier height, ideality factor, and series resistance from room temperature forward-bias current-voltage characteristics. The extracted Schottky barrier height for these devices is in the range 0.7-0.8 eV and the ideality factor is approximately 1.2.We next measure the low-frequency electronic noise in Au-W/β-Ga2O3 Schottky diodes at different forward bias voltages at room temperature. We find that the current noise spectral density exhibits 1/f-type behavior for all forward bias voltages at low frequency with an exponent ranging from 0.75 to 1.15, indicating that the low frequency noise of these devices is dominated by excess (flicker) noise. No Lorentzian-shaped generation-recombination (G-R) noise is observed. At low frequencies, the shot noise contribution is found to be negligible for the values of the current in our devices, and the total noise is 1/f-limited.We also investigate the dependence of the current noise spectral density on forward bias current, revealing different relationships in different current regimes. At low currents, the noise spectral density is found to scale approximately as the square of current, whereas at high currents, the noise spectral density begins to saturate. Such noise behavior can be attributed to different noise sources dominating in different current regimes. Furthermore, using the noise figure of merit adapted for ultra-wide bandgap semiconductor devices [4], we find that the Au-W/β-Ga2O3 devices have lower noise levels compared to other emerging UWBG materials and similar noise levels as well-established technologies such as GaN.These results provide important insights into the electronic noise properties of Au-W/β-Ga2O3 Schottky diodes and show that low frequency noise characterization is an important diagnostic tool for assessing the quality and reliability of gallium oxide based wide-bandgap materials and device technologies.

Engineering the PEM Water Electrolysis Anode for Better Interfacial Electrical Conductivity

In pursuing cost-effective green hydrogen production via proton exchange membrane water electrolysis (PEMWE), the high expense of the iridium (Ir)-based oxygen evolution reaction (OER) catalysts poses a significant challenge. To overcome this issue, researchers have focused on developing active OER catalysts and catalyst layers (CLs) with minimum uses of Ir. However, they frequently encountered performance problems at the single-cell level that originate not only from the kinetic polarization but also from the ohmic polarization. In this aspect, we have focused on identifying the reasons for the poor performance of low IrOx-loaded anodes, with loadings as low as 0.10 mg cm-2. We pinpoint the cause of the poor performance of the low loaded anodes to an electron transport problem within the native oxide on the Ti porous transport layer (PTL). Our analysis, grounded in the metal-insulator band model, reveals that the primary factors contributing to electron conductivity loss in the Ti oxide are the upward band bending induced by the Schottky contact with high work function IrOx and by the pinch-off effect from the extensive ionomer contact. Based on the above understanding, we propose an anode CL composed of a one-dimensional iridium catalyst, fabricated by electrospinning and calcination processes. Our nanofiber-based CL effectively mitigates the electron transport problem of the native Ti oxide. This improvement stems from the low work function of the Ir nanofiber catalyst and the highly porous structure that reduces the ionomer contact with the Ti oxide. Furthermore, the highly porous nature of the nanofiber-based CL enhances two-phase mass transport, facilitating the high current operation. These findings underscore the critical role of the CL/PTL interface of the PEMWE anode and present the necessity of a well-structured CL to achieve efficient and cost-effective water electrolysis.

High-k Dielectrics-Based Electric Field Engineering in β-Ga2O3 Power Diodes

We present β-Ga2O3 high-voltage Schottky barrier diodes (SBD) incorporating advanced electric field engineering approaches through the use of high-permittivity dielectrics. We present two approaches: 1) the lateral dielectric superjunction SBD, where the electric field within the drift layer is modified from triangular to rectangular profile, enhancing the breakdown voltage and enabling the use of higher drift layer doping to reduce on-resistance, and 2) the vertical high-k RESURF trench SBD, which leverages the reduced surface electric field effect (RESURF) to reduce the electric field at the metal-semiconductor junction and reverse leakage currents.A superjunction-like structure uses charge balance to push the VBR-Ron-sp trade-off beyond the material’s unipolar figure of merit. The lack of p-type doping in β-Ga2O3 makes the realization of such structures very difficult. However, field flattening can be achieved in β-Ga2O3 drift layers using a high permittivity material with appropriate choice of dielectric constant, device aspect ratio and semiconductor/dielectric width. An analytical model is discussed to highlight the device design strategy and experimental demonstration is reported in the lateral geometry. 500 nm of Si-doped Ga2O3 epitaxial layer with a sheet charge of 1.6×1013 cm-2 is grown using metal organic vapor phase epitaxy (MOVPE). Trenches with three different fin widths (WFin = 2, 5, 10 µm) were made and high-k dielectric BaTiO3 (BTO) with dielectric constant of 220 is deposited on the sample. A low specific on resistance of 1.65 mΩ-cm2 is observed for LAC = 5µm due to the high charge density epitaxial lateral Fins. For the SBD with LAC = 5µm and WFin = 5µm, a high average electric field of ~3 MV/cm (VBR/ LAC) is estimated across the entire length of the device. A very high Baliga's figure of merit (BFOM) of 1.35 GW/cm2 is observed for the RESURF SBD with LAC=5µm and WFin=2µm (VBR=1.49 kV and Ron-sp=1.65 mΩ-cm2), surpassing SiC unipolar FOM when considering just the conducting area.While superjunction-like structures effectively flatten the electric field inside the drift layer, high electric fields at the metal/semiconductor junction results in increased leakage current at large reverse bias, particularly in the case of vertical Schottky Barrier Diodes (SBDs). To circumvent this challenge, we present the approach of β-Ga2O3 Vertical Trench Schottky Barrier Diode (SBD) with a high-permittivity dielectric RESURF. The incorporation of a trench geometry, coupled with the high-permittivity dielectric RESURF, effectively reduces the surface electric field at the metal-semiconductor junction. This reduction facilitates the use of a lower work-function anode contact, further diminishing the turn-on voltage. The use of high-k dielectric also significantly reduces the dielectric leakage contribution to the overall reverse leakage of the diode. Large-area SBDs with areas of 1mm2 and 4mm2 exhibit pulsed forward current of 6A/20A and a catastrophic breakdown voltage of 1.74kV/1.4kV, surpassing other β-Ga2O3-based large-area power diodes, while small-area SBDs (200×200 µm2) do not exhibit catastrophic breakdown until 3kV. The large-area SBDs also demonstrate lower capacitance, stored charge, and stored energy compared to commercial SiC SBDs, indicating potential for superior switching performance. The combination of lower stored charge and a low forward voltage drop results in an excellent trade-off between conduction and switching power loss, yielding a QCVF figure of merit comparable to commercial bare die SiC SBDs. We demonstrate the potential of high permittivity dielectrics-based extreme field engineering to push the performance limits of β-Ga2O3 diodes for next-generation power electronics.We acknowledge funding from AFOSR MURI program (Dr. Ali Sayir) and Coherent/II-VI foundation.

Au – MoS2 nanoflowers sensors on interdigitated electrode for monitoring human respiration

Abstract Respiratory humidity sensors are essential for monitoring breath conditions in a variety of applications such as respiratory disease diagnosis, sleep apnea screening, and personalized medicine. With the increasing prevalence of respiratory diseases, such as asthma, chronic obstructive pulmonary disease (COPD), and sleep apnea, they have become essential tools for healthcare professionals, researchers and individuals. However, existing humidity sensors often suffer from poor sensitivity, slow response, and limited flexibility. In this paper, we report a novel Au – MoS2 respiratory humidity sensor that exhibits high resistivity, fast response, and excellent flexibility. The sensor is fabricated by drop casting a thin layer of Au decorated MoS2 on copper interdigitated electrodes (fabricated using copper clad PCB). The increase in the intensity of the peak was observed in Au – MoS2 hybrids in comparison to MoS2 analyzed using micro–Raman Spectroscopy. Using scanning electron microscopy (SEM), the morphology of MoS2 was observed, confirming its flower like structure. The Au nanoparticles were detected on the edges of MoS2, confirmed by transmission electron microscope (TEM).
The interfacial electronic interaction suggests that there is the formation of Schottky barrier between Au and MoS2 as confirmed by X–Ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The improved electronic interaction results in better sensing properties. The high dielectric constant and excellent surface-to-volume ratio of the MoS2 layer make it extremely sensitive to humidity; the Au nanoparticles offer good electrical conductivity and mechanical flexibility in its place. The study tested a respiratory sensor in a simulated environment, finding it more responsive to breathing and quick to return to rest. This suggests potential for the Au-MoS2 sensor in tracking breath states due to its sensitivity and adaptability, promising applications across various fields.

Compositional engineering of interfacial charge transfer in van der Waals heterostructures of graphene and transition metal dichalcogenides.

Owing to their unique optical and electronic properties, vertical van der Waals heterostructures (vdWHs) have attracted considerable attention in optoelectronic applications, such as photodetection, light harvesting, and light-emitting diodes. To fully harness these properties, it is crucial to understand the interfacial charge transfer (CT) and recombination dynamics across vdWHs. However, the effects of interfacial energetics and defect states on interfacial CT and recombination processes in graphene-transition metal dichalcogenide (Gr-TMD) vdWHs remain debated. Here, we investigate the interfacial CT dynamics in Gr-TMD vdWHs with different chemical compositions (W, Mo, S, and Se) and tunable interfacial energetics. We demonstrate, using ultrafast terahertz spectroscopy, that while the photo-induced electron transfer direction is universal with graphene donating electrons to TMDs, its efficiency is chalcogen-dependent: the CT efficiency of S atom-based vdWHs is 3-5 times higher than that of Se-based vdWHs thanks to the lower Schottky barrier present in S-based vdWHs. In contrast, the electron back transfer process from TMD to Gr, which defines the charge separation time, is transition metal-dependent and dominated by the mid-gap defect level of TMDs: W transition metal-based vdWHs possess extremely long charge separation, well beyond 1ns, which is significantly longer than Mo-based vdWHs with only 10s of ps charge separation. This difference can be traced to the much deeper mid-gap defect reported in W-based TMDs compared to Mo-based ones, resulting in modified energetics for the back electron transfer from the trapped states to graphene. Our results shed light on the role of interfacial energetics and defects by tailoring chemical compositions of TMDs on the interfacial CT and recombination dynamics in Gr-TMD vdWHs, which is pivotal for optimizing optoelectronic devices, particularly in the field of photodetection.

Low Contact Resistance on Monolayer MoS2 Field-Effect Transistors Achieved by CMOS-Compatible Metal Contacts.

Contact engineering on monolayer layer (ML) semiconducting transition metal dichalcogenides (TMDs) is considered the most challenging problem toward using these materials as a transistor channel in future advanced technology nodes. The typically observed strong Fermi-level pinning induced in part by the reaction of the source/drain contact metal and the ML TMD frequently results in a large Schottky barrier height, which limits the electrical performance of ML TMD field-effect transistors (FETs). However, at a microscopic level, little is known about how interface defects or reaction sites impact the electrical performance of ML TMD FETs. In this work, we have performed statistically meaningful electrical measurements on at least 120 FETs combined with careful surface analysis to unveil contact resistance dependence on interface chemistry. In particular, we achieved a low contact resistance for ML MoS2 FETs with ultrahigh-vacuum (UHV, 3 × 10-11 mbar) deposited Ni contacts, ∼500 Ω·μm, which is 5 times lower than the contact resistance achieved when deposited under high-vacuum (HV, 3 × 10-6 mbar) conditions. These electrical results strongly correlate with our surface analysis observations. X-ray photoelectron spectroscopy (XPS) revealed significant bonding species between Ni and MoS2 under UHV conditions compared to that under HV. We also studied the Bi/MoS2 interface under UHV and HV deposition conditions. Different from the case of Ni, we do not observe a difference in contact resistance or interface chemistry between contacts deposited under UHV and HV. Finally, this article also explores the thermal stability and reliability of the two contact metals employed here.

Barrier height enhancement in β-Ga2O3 Schottky diodes using an oxygen-rich ultra-thin AlOx interfacial layer

Schottky barrier height (SBH) enhancement directly translates into increased breakdown voltage (VBR) of β-Ga2O3 Schottky barrier diodes (SBDs). In this work, ultra-thin (5, 10, and 15 Å) oxygen-rich AlOx interfacial layers (ILs), deposited using plasma-enhanced atomic layer deposition, are shown to enhance the SBH of post-metallization oxygen annealed Pt/AlOx/β-Ga2O3 SBDs by up to 0.8 eV resulting in a maximum VBR of nearly 500 V (2× gain) on 2–4 × 1016 cm−3 doped substrates, without compromising the specific on-resistance. The SBH and VBR enhancement is observed on (2¯ 01) as well as (001) surfaces. X-ray photoelectron spectroscopy (XPS) analysis shows that excess oxygen interstitial concentration in 5 Å AlOx films decreases (increases) with increasing thickness (oxygen anneal), making them more stoichiometric. The decreasing (increasing) trend in SBH and VBR with increasing IL thickness (oxygen anneal) is consistent with the XPS-derived O/Al ratio of the films and the formation of an AlOx/β-Ga2O3 interfacial dipole due to a difference in oxygen areal densities. The AlOx deposition can be easily integrated with field management methods such as field plates and guard rings that can further enhance β-Ga2O3 SBD performance.

Alpha particle detection based on low leakage and high-barrier vertical PtOx/β-Ga2O3 Schottky barrier diode

High-performance radiation detectors are essential in many sectors spanning medical diagnostics, nuclear control, and particle physics. Ultrawide bandgap semiconductor materials have become one of the most promising candidates due to their excellent performance. Here, based on β-Ga2O3, a Schottky diode-type alpha particle detector was demonstrated. In order to reduce the reverse leakage current of the large-area device, the metal-oxide electrode PtOx was introduced to form high-barrier contacts (1.83 eV) with Ga2O3. The device exhibits a low leakage current density of 63 pA/cm2 at −100 V and apparent energy spectra of 241Am generated alpha particles with an energy of 5.486 MeV at various reverse voltages from −40 to −120 V. The charge collection efficiency (CCE) and energy resolution of the device (at −120 V) are 31.7% and 15.3%, respectively. Meanwhile, the mechanism of interaction between alpha particles and β-Ga2O3 was analyzed, and a 45° oblique incidence was adopted to increase the deposited energy of alpha particles in the depletion region. Furthermore, the differences between actual CCE and theoretical CCE are investigated as guidance for further improving detector performance. This work reveals the great potential and good prospects of Ga2O3 as an economical, efficient, and radiation-resistant ionizing radiation detector.

The synergistic effect of Cl doping and Bi coupling to promote the carrier separation of BiOBr for efficient photocatalytic nitrogen reduction

Photocatalytic nitrogen reduction reaction (NRR) is a sustainable process for ammonia synthesis under mild conditions. However, photocatalytic NRR activity and are generally limited by inefficient carrier separation and transfer. Therefore, parallel engineering of bulk phase doping and surface coupling is critical to achieving the goal of efficient NRR. In this study, Cl doped BiOBr nanosheet assemblies (BiOBr/Cl) were constructed in delicately designed deep eutectic solvents (DESs), combined with ionothermal methods at low temperatures and Bi3+ exsolution reduction strategy at high temperatures. The unique liquid state and reducibility of DESs induce the reduction of Bi3+ and the in situ coupling of Bi quantum dots at the surface of BiOBr/Cl nanosheets along with the construction of Bi-BiOBr/Cl nanosheet assemblies. The experimental results show that Cl doping could reduce the exciton dissociation energy and promote its dissociation to free carriers. Bi quantum dots could form tightly coupled Schottky junction with BiOBr/Cl enabling the efficient and unidirectional transmission of photogenerated electrons from BiOBr/Cl to metal Bi. The formed electron deficient region at Schottky interface promotes the adsorption and activation of N2. The hierarchical structure of Bi-BiOBr/Cl nanosheet assembly benefits to providing more N2 adsorption active sites. The DFT calculation shows that the accumulation of high concentration of active hydrogen in Bi-BiOBr/Cl leads to a significant decrease of energy barrier of the first step hydrogenation of N2. Bi-BiOBr/Clis more inclined to adsorb nitrogen for NRR in comparison with H* for hydrogen production. The synergistic effect of Cl doping and Bi coupling result in a high NRR activity of Bi-BiOBr/Cl photocatalyst of 6.67 mmol·g−1·h−1, which was 11.3 times higher than that of initial BiOBr. This study provides a promising strategy for designing highly active NRR photocatalysts with high efficiency carrier dissociation and transport.

Achieving ultralow contact resistivity in Si via Te hyperdoping and millisecond post-metallization annealing

Achieving extremely low specific contact resistance (ρc) has become a critical challenge for nanoelectronics to achieve high device performance with increased miniaturization. In this work, we explore the use of Tellurium hyperdoping and millisecond-range post-metallization flash lamp annealing as a potential solution to overcome this bottleneck. The epitaxially-resolidified hyperdoped Si layers with tunable carrier densities approaching 1021 cm−3 are achieved, which consequently alters the band diagrams as simulated by COMSOL Multiphysics®. This results in a sufficiently narrow Schottky barrier, which enables electron tunneling and can ultimately achieve extremely low ρc on the order of 10−9 Ω·cm2 in an Au/Ti/Te-hyperdoped Si junction. This study introduces an alternative fabrication process for Schottky barrier engineering, providing a viable method for the realization of future miniaturized nanoelectronics devices with high carrier density and extremely low ρc.

Achieving ultralow contact resistance and reducing residual hydrogen by surface doping

Indium gallium zinc oxide (IGZO)-based materials and devices hold a significant position in integrated circuit manufacturing industries, yet challenges persist in controlling residual hydrogen and managing high source/drain contact resistance. Our proposed hypothesis not only targets the control of residual hydrogen through out-diffusion but also offers an opportunity for surface doping of IGZO, promising a substantial reduction in contact resistance. Interestingly, a 30 s hydrogen plasma deposition resulted in a lower hydrogen concentration compared to the residual hydrogen in IGZO, leading to increased carrier density at the interface. The higher carrier density, coupled with metallization-induced band bending at the interface, significantly lowers the Schottky barrier height and density of states, thereby facilitating sophisticated electron transport between molybdenum and IGZO. To the best of our knowledge, this study represents the first substantial reduction in residual hydrogen from IGZO films (initially deposited at 1020 cm−3, reduced to 1019 cm−3), while achieving ultralow specific contact resistivity (2.47 × 10-9 Ω•cm2) and sheet resistance (177.67 Ω/□). Our hypothesis introduces a novel strategy to reduce contact resistance in electronic devices.

Demonstrating the β-Ga2O3 Schottky diodes for alpha radiation detection

Schottky barrier diodes were fabricated on (001) monoclinic β-Ga2O3 wafers with low doped epitaxial layers of 7.0 × 1015 cm−3. Circular Ni Schottky contacts with area 2 mm2 were deposited by electron beam evaporation. Devices were characterized electrically by performing forward and reverse current-voltage sweeps with a range of −100 V–2 V, as well as capacitance-voltage sweeps to −30 V. The breakdown voltage was also determined to be −180 V for the devices. Experiments measuring the electrical response from incident X-ray radiation was performed. A response time to X-ray radiation of less than 1 s was recorded and a decay time of approximately 2 s after removing X-ray source, which primarily attribute to X-ray switching on and off time. Energy spectra of alpha particles from a 0.9 μCi 241Am button source was collected at various voltage biases using devices with the lowest measured leakage current while reverse biased. The total count rate was observed to increase linearly with increasing device bias. The peak channel number was observed to increase with increasing bias with the best resolution of 9.5% at −100 V reverse bias.

Self-rectifying and forming-free resistive switching with Cu/BN/SiO2/Pt bilayer device

Selector-free 3D vertical crossbar with low power consumption is necessary for developing high-density memory devices. Sneaking current in these devices is the prime factor for their degradation as they lose power, and there are glitches in data retrieval. In this article, we have successfully illustrated a forming free and self-rectifying cell in a chemically synthesized 2D memristive device based on hexagonal Boron Nitride (h-BN) material. The device performs well with a Rectification Ratio (RR) > 102 with SiO2/BN bi-layer structure at ±1.3 V. The device performed over 20000 cycles at a pulse width of 10 μs. Also, the device endurance decays with a different pulse width of 100 μs and 1 ms. Schottky barrier formation and development of conductive filament of oxygen vacancies are the primary causes for the proposed device to show Rectifying Resistive Switching (RRS) and Bipolar Resistive Switching (BRS), respectively. The device also performs good stability with the temperature range from Room Temperature (RT) to 250 °C. The sneak path concern and thermal stability enable potential applications for neuromorphic computing and future memory technology.

Programmed electrochemical reconstruction of NiCoxMo4-xN5 for making Core-Shell shaped Schottky junction electrocatalyst

Electrochemical reconstruction (ECR) sets natural limit to exploring reactivity of pristine catalysts in the electrocatalytic reactions. The ECR phenomena need to be regulated to unveil intrinsic property of pristine catalysts. Herein, we introduced ‘sacrificial cation optimization’ method to control element-leaching phenomenon at NiMo4N5 surface during the ECR. Partial substitution of sacrificial Mo with Co enabled timely cessation of the ECR of NiCoxMo4-xN5 with forming stable oxyhydroxide outer shell. This controlled ECR generated classic Schottky junction (SJ) at the core–shell interface of NiCoxMo4-xN5 | Ni1-yCoyOOH. The in situ formed SJ remarkably enhanced electron transfer with nullifying the poor conductance of front-line oxyhydroxides. As a result, the core–shell SJ yielded the current density of 10 mA/cm2 at a low overpotential of 126 mV (without iR compensation). The in situ formation of core–shell SJ proposed a breakthrough in the research to regulate ECR process as well as produced a new type of electrode beyond the oxyhydroxides.

Low-high-low doped Ga2O3 Schottky barrier IMPATT diodes on various crystal orientations for terahertz applications

This article investigates low-high-low doped Ga2O3 Schottky barrier IMPATT diodes based on [100], [010], and [001] crystal orientations to promote oscillation power at the low-frequency band of terahertz regime. Simulation results demonstrate a conversion power of 4.88 MW/cm2 along [100] at its optimum frequency of 100 GHz, increasing by 0.73 times and 2.2 times compared to the [100] at 150 GHz and the [001] at 100 GHz, and exhibit the highest conversion efficiency of 6.83 % along [010] as indicated by the DC-RF conversion ability promoting 37 % and 30 % than that of [100] and [001] orientations, respectively. When considering a parasitic resistance of 1 × 10−5 Ω cm2, the optimal frequencies of along three orientations decrease to 90 GHz, 127 GHz, and 91 GHz, correspondingly, yielding the peak output power and total efficiency decrease by 0.3–0.4 times compared to those of the conversion characteristics.

Effects of contactless photoelectrochemical reaction on repair of etching damage in GaN SBD

This research investigates the reparative impact of photoelectrochemical (PEC) reactions on damage induced by inductively coupled plasma (ICP) etching in process of the Schottky barrier diodes (SBDs). After the PEC reaction repair, the reverse leakage current of the devices exhibited a significant reduction, typically ranging from 1 to 3 orders of magnitude. The ideality factor decreased from approximately 5 to 2, accompanied by a simultaneous decrease in series resistance. SBDs subjected to PEC processing displayed a notable decline in frequency dispersion. Quantitative analysis from capacitance-frequency measurements indicated that the PEC process effectively rectified the damage caused by dry etching on the GaN surface. The results of X-ray Photoelectron Spectroscopy (XPS) showed that the gallium oxide formed on a GaN surface by PEC treatment and the ratio of N/(Al + Ga) becomes larger, which indicates that fewer nitrogen vacancies (NV) after PEC repair process. The mechanism of the repair effects of PEC for the SBDs were discussed and analyzed. The observed improvements underscore the efficacy of PEC reactions in mitigating the adverse effects of etching, providing some inspirations for the enhancement of SBD performance in GaN-based devices.

TiO2 nanofilms for surface-enhanced Raman scattering analysis of urea

In this study, titanium dioxide (TiO2) nanofilms with nanoparticle structure were grown in situ on metallic aluminum (Al) sheets using a simple sol-hydrothermal method. Al sheets were chosen because they can form Schottky junctions with TiO2 during the calcination process, thus achieving a tight bonding between the nanoparticles and the solid substrate, which cannot be achieved with conventional glass substrates. The substrates synthesized with different contents of titanium butoxide [Ti(OBu)4] were investigated using 4-mercaptobenzoic acid as a probe molecule, and the results showed that the substrate with 9 % of the total volume of Ti(OBu)4 had the highest surface-enhanced Raman scattering (SERS) performance. As a low-cost SERS substrate that is simple to synthesize, it has excellent signal reproducibility, with a relative standard deviation of 4.51 % for the same substrate and 6.43 % for different batches of synthesized substrates. Meanwhile, the same batch of substrate can be stored at room temperature for at least 20 weeks and still maintain stable SERS signals. In addition, the synthetic substrate was used to quantitatively detect urea with a detection limit of 4.23 × 10−3 mol/L, which is comparable to the application of noble metal substrates. The feasibility of this method was verified in human urine, and the results were consistent with the clinical results, indicating that this method has great potential for clinical application.

Probing charge redistribution at the interface of self-assembled cyclo-P5 pentamers on Ag(111)

Phosphorus pentamers (cyclo-P5) are unstable in nature but can be synthesized at the Ag(111) surface. Unlike monolayer black phosphorous, little is known about their electronic properties when in contact with metal electrodes, although this is crucial for future applications. Here, we characterize the atomic structure of cyclo-P5 assembled on Ag(111) using atomic force microscopy with functionalized tips and density functional theory. Combining force and tunneling spectroscopy, we find that a strong charge transfer induces an inward dipole moment at the cyclo-P5/Ag interface as well as the formation of an interface state. We probe the image potential states by field-effect resonant tunneling and quantify the increase of the local change of work function of 0.46 eV at the cyclo-P5 assembly. Our experimental approach suggest that the cyclo-P5/Ag interface has the characteristic ingredients of a p-type semiconductor-metal Schottky junction with potential applications in field-effect transistors, diodes, or solar cells.