Highly visible-light-active sulfur and carbon co-doped TiO2 (SC-TiO2) heterogeneous photocatalysts prepared by underwater discharge plasma.

To promptly and simply create highly crystalline S/C co-doped TiO2 (SC-TiO2) photocatalysts at room temperature and atmospheric pressure, we suggest a novel plasma-assisted sol-gel synthesis method. This method is a simultaneous synthetic process, in which an underwater plasma undergoes continuous reactions to generate high-energy atomic and molecular species that enable TiO2 to achieve crystallinity, a large surface area, and a heterogeneous structure within a few minutes. In particular, it was demonstrated that the heterogeneously structured TiO2 was formed by doping that sulfur and carbon replace O or Ti atoms in the TiO2 lattice depending on the composition of the synthesis solution during underwater plasma treatment. The resultant SC-TiO2 photocatalysts had narrowed bandgap energies and extended optical absorption scope into the visible range by inducing the intermediate states within bandgap due to generation of oxygen vacancies on the surface of TiO2 through synthesis, crystallization, and doping. Correspondingly, SC-TiO2 showed a significant degradation efficiency ([k] = 6.91 h-1) of tetracycline (TC, antibiotics) under solar light irradiation, up to approximately 4 times higher compared to commercial TiO2 ([k] = 1.68 h-1), resulting in great water purification. Therefore, we anticipate that this underwater discharge plasma system will prove to be an advantageous technique for producing heterostructural TiO2 photocatalysts with superior photocatalytic efficiency for environmental applications.

Reinforcing Synaptic Plasticity of Defect-Tolerant States in Alloyed 2D Artificial Transistors.

While two-dimensional (2D) materials possess the desirable future of neuromorphic computing platforms, unstable charging and de-trapping processes, which are inherited from uncontrollable states, such as the interface trap between nanocrystals and dielectric layers, can deteriorate the synaptic plasticity in field-effect transistors. Here, we report a facile and effective strategy to promote artificial synaptic devices by providing physical doping in 2D transition-metal dichalcogenide nanomaterials. Our experiments demonstrate that the introduction of niobium (Nb) into 2D WSe2 nanomaterials produces charge trap levels in the band gap and retards the decay of the trapped charges, thereby accelerating the artificial synaptic plasticity by encouraging improved short-/long-term plasticity, increased multilevel states, lower power consumption, and better symmetry and asymmetry ratios. Density functional theory calculations also proved that the addition of Nb to 2D WSe2 generates defect tolerance levels, thereby governing the charging and de-trapping mechanisms of the synaptic devices. Physically doped electronic synapses are expected to be a promising strategy for the development of bioinspired artificial electronic devices.

Environmentally Stable and Reconfigurable Ultralow-Power Two-Dimensional Tellurene Synaptic Transistor for Neuromorphic Edge Computing.

While neuromorphic computing can define a new era for next-generation computing architecture, the introduction of an efficient synaptic transistor for neuromorphic edge computing still remains a challenge. Here, we envision an atomically thin 2D Te synaptic device capable of achieving a desirable neuromorphic edge computing design. The hydrothermally grown 2D Te nanosheet synaptic transistor apparently mimicked the biological synaptic nature, exhibiting 100 effective multilevel states, a low power consumption of ∼110 fJ, excellent linearity, and short-/long-term plasticity. Furthermore, the 2D Te synaptic device achieved reconfigurable MNIST recognition accuracy characteristics of 88.2%, even after harmful detergent environment infection. We believe that this work serves as a guide for developing futuristic neuromorphic edge computing.

Visualizing Line Defects in non-van der Waals Bi2O2Se Using Raman Spectroscopy.

Atomic-layered materials, such as high-quality bismuth oxychalcogenides, which are composed of oppositely charged alternate layers grown using chemical vapor deposition, have attracted considerable attention. Their physical properties are well-suited for high-speed, low-power-consumption optoelectronic devices, and the rapid determination of their crystallographic characteristics is crucial for scalability and integration. In this study, we introduce how the crystallographic structure and quality of such materials can be projected through Raman spectroscopy analysis. Frequency modes at ∼55, ∼78, ∼360, and ∼434 cm-1 were detected, bearing out theoretical calculations from the literature. The low-frequency modes positioned at 55 and 78 cm-1 were activated by structural defects, such as grain boundaries and O-rich edges in the Bi2O2Se crystals, accompanied by sensitivity to the excitation energy. Furthermore, the line defects at ∼55 cm-1 exhibited a strong 2-fold polarization dependence, similar to graphene/graphite edges. Our results can help illuminate the mechanism for activating the Raman-active mode from the infrared active mode by defects, as well as the electronic structures of these two-dimensional layered materials. We also suggest that the nanoscale width line defects in Bi2O2Se can be visualized using Raman spectroscopy.

Gate-controlled gas sensor utilizing 1D-2D hybrid nanowires network.

Novel gas sensors that work at room temperature are attracting attention due to their low energy consumption and stability in the presence of toxic gases. However, the development of sensing characteristics at room temperature is still a primary challenge. Diverse reaction pathways and low adsorption energy for gas molecules are required to fabricate a gas sensor that works at room temperature with high sensitivity, selectivity, and efficiency. Therefore, we enhanced the gas sensing performance at room temperature by constructing hybridized nanostructure of 1D-2D hybrid of SnSe2 layers and SnO2 nanowire networks and by controlling the back-gate bias (Vg = 1.5 V). The response time was dramatically reduced by lowering the energy barrier for the adsorption on the reactive sites, which are controlled by the back gate. Consequently, we believe that this research could contribute to improving the performance of gas sensors that work at room temperature.

High removal efficiency of industrial toxic compounds through stable catalytic reactivity in water treatment system.

We identified optimal conditions for the disposal of high concentration of organic contaminants within a short time using a hybrid advanced oxidation process (AOP) combining various oxidizing agents. Plasma-treated water (PTW) containing many active species, that play dominant roles in the degradation of organic substances like hydroxyl radicals, atomic oxygen, ozone, and hydrogen peroxide, was used in this study as a strategy to improve degradation performance without the use of expensive chemical reagents like hydrogen peroxide. In particular, the optimal decomposition conditions using PTW, which were combined with 10 mg/h ozone, 2 g/L iron oxide, and 4 W UV light, demonstrated excellent removal abilities of a high concentration of reactive black 5 (RB5; 100 mg/L, >99%, [k] = 4.15 h-1) and tetracycline (TC; 10 mg/L, >96.5%, [k] = 3.35 h-1) for 25 min, approximately 1.5 times higher than that without PTW (RB5; 100 mg/L, 94%, [k] = 2.80 h-1). These results confirmed that the production of strong reactive hydroxyl radicals from the decomposition process, as well as various reactive species included in PTW efficiently attacked pollutant substances, resulting in a higher removal rate. This suggests that a water treatment system with this optimal condition based on complex AOP systems using PTW could be useful in critical environmental and biomedical applications.

Accelerated Learning in Wide-Band-Gap AlN Artificial Photonic Synaptic Devices: Impact on Suppressed Shallow Trap Level.

Artificial synaptic platforms are promising for next-generation semiconductor computing devices; however, state-of-the-art optoelectronic approaches remain challenging, owing to their unstable charge trap states and limited integration. We demonstrate wide-band-gap (WBG) III-V materials for photoelectronic neural networks. Our experimental analysis shows that the enhanced crystallinity of WBG synapses promotes better synaptic characteristics, such as effective multilevel states, a wider dynamic range, and linearity, allowing the better power consumption, training, and recognition accuracy of artificial neural networks. Furthermore, light-frequency-dependent memory characteristics suggest that artificial optoelectronic synapses with improved crystallinity support the transition from short-term potentiation to long-term potentiation, implying a clear emulation of the psychological multistorage model. This is attributed to the charge trapping in deep-level states and suppresses fast decay and nonradiative recombination in shallow traps. We believe that the fingerprints of these WBG synaptic characteristics provide an effective strategy for establishing an artificial optoelectronic synaptic architecture for innovative neuromorphic computing.

In Situ Visualization of Localized Surface Plasmon Resonance-Driven Hot Hole Flux.

Nonradiative surface plasmon decay produces highly energetic electron-hole pairs with desirable characteristics, but the measurement and harvesting of nonequilibrium hot holes remain challenging due to ultrashort lifetime and diffusion length. Here, the direct observation of LSPR-driven hot holes created in a Au nanoprism/p-GaN platform using photoconductive atomic force microscopy (pc-AFM) is demonstrated. Significant enhancement of photocurrent in the plasmonic platforms under light irradiation is revealed, providing direct evidence of plasmonic hot hole generation. Experimental and numerical analysis verify that a confined |E|-field surrounding a single Au nanoprism spurs resonant coupling between localized surface plasmon resonance (LSPR) and surface charges, thus boosting hot hole generation. Furthermore, geometrical and size dependence on the extraction of LSPR-driven hot holes suggests an optimized pathway for their efficient utilization. The direct visualization of hot hole flow at the nanoscale provides significant opportunities for harnessing the underlying nature and potential of plasmonic hot holes.

Current Transport Mechanism in Palladium Schottky Contact on Si-Based Freestanding GaN.

In this study, the charge transport mechanism of Pd/Si-based FS-GaN Schottky diodes was investigated. A temperature-dependent current-voltage analysis revealed that the I-V characteristics of the diodes show a good rectifying behavior with a large ratio of 103-105 at the forward to reverse current at ±1 V. The interface states and non-interacting point defect complex between the Pd metal and FS-GaN crystals induced the inhomogeneity of the barrier height and large ideality factors. Furthermore, we revealed that the electronic conduction of the devices prefers the thermionic field emission (TFE) transport, not the thermionic emission (TE) model, over the entire measurement conditions. The investigation on deep level transient spectroscopy (DLTS) suggests that non-interacting point-defect-driven tunneling influences the charge transport. This investigation about charge transport paves the way to achieving next-generation optoelectronic applications using Si-based FS-GaN Schottky diodes.

Highly Efficient Excitonic Recombination of Non-polar ([Formula: see text]) GaN Nanocrystals for Visible Light Emitter by Hydride Vapour Phase Epitaxy.

While non-polar nanostructured-GaN crystals are considered as a prospective material for the realization of futuristic opto-electronic application, the formation of non-polar GaN nanocrystals (NCs) with highly efficient visible emission characteristics remain unquestionable up to now. Here, we report the oxygen-incorporated a-plane GaN NCs with highly visible illumination excitonic recombination characteristics. Epitaxially aligned a-plane NCs with average diameter of 100 nm were formed on r-plane sapphire substrates by hydride vapor phase epitaxy (HVPE), accompanied by the oxygen supply during the growth. X-ray photoemission spectroscopy measurements proved that the NCs exhibited Ga-O bonding in the materials, suggesting the formation of oxidized states in the bandgap. It was found that the NCs emitted the visible luminescence wavelength of 400‒500 nm and 680‒720 nm, which is attributed to the transition from oxygen-induced localized states. Furthermore, time-resolved photoluminescence studies revealed the significant suppression of the quantum confined Stark effect and highly efficient excitonic recombination within GaN NCs. Therefore, we believe that the HVPE non-polar GaN NCs can guide the simple and efficient way toward the nitride-based next-generation nano-photonic devices.

The Electrochemical Performances of n-Type Extended Lattice Spaced Si Negative Electrodes for Lithium-Ion Batteries.

The electrochemical performances of lithium-ion batteries with different lattice-spacing Si negative electrodes were investigated. To achieve a homogeneous distribution of impurities in the Si anodes, single crystalline Si wafers with As-dopant were ball-milled to form irregular and agglomerated micro-flakes with an average size of ~10 µm. The structural analysis proved that the As-doped Si negative materials retain the increased lattice constant, thus, keep the existence of the residual tensile stress of around 1.7 GPa compared with undoped Si anode. Electrochemical characterization showed that the As-doped Si anodes have lower discharge capacity, but Coulombic efficiency and capacity retention were improved in contrast with those of the undoped one. This improvement of electrochemical characteristics was attributed to the increased potential barrier on the side of Si anodes, inherited from the electronic and mechanical nature of Si materials doped with As. We believe that this study will guide us the way to optimize the electrochemical performances of LIBs with Si-based anodes.

First observation of electronic trap levels in freestanding GaN crystals extracted from Si substrates by hydride vapour phase epitaxy.

The electronic deep level states of defects embedded in freestanding GaN crystals exfoliated from Si substrates by hydride vapour phase epitaxy (HVPE) is investigated for the first time, using deep level transient spectroscopy (DLTS). The electron traps are positioned 0.24 eV (E1) and 1.06 eV (E2) below the conduction band edge, respectively. The capture cross sections of E1 and E2 are evaluated to be 1.65 × 10-17 cm2 and 1.76 × 10-14 cm2 and the corresponding trap densities are 1.07 × 1014 cm-3 and 2.19 × 1015 cm-3, respectively. The DLTS signal and concentration of the electronic deep levels are independent of the filling pulse width, and the depth toward the bottom of the sample, evidenced by the fact that they are correlated to noninteracting point defects. Furthermore, Photoluminescence (PL) measurement shows green luminescence, suggesting that unidentified point defects or complex, which affect the optical characterisitics, exhibit. Despite the Si-based materials, the freestanding GaN exhibits deep level characteristics comparable to those of conventional freestanding GaN, suggesting that it is a desirable material for use in the next generation optoelectronic devices with the large-scalibilityand low production costs.

Significant improvement of reverse leakage current characteristics of Si-based homoepitaxial InGaN/GaN blue light emitting diodes.

The nature of reverse leakage current characteristics in InGaN/GaN blue light emitting diodes (LEDs) on freestanding GaN crystals detached from a Si substrate is investigated for the first time, using temperature-dependent current-voltage (T-I-V) measurement. It is found that the Si-based homoepitaxial InGaN/GaN LEDs exhibit a significant suppression of the reverse leakage current without any additional processes. Their conduction mechanism can be divided into variable-range hopping and nearest neighbor hopping (NNH) around 360 K, which is enhanced by Poole-Frenkel emission. The analysis of T-I-V curves of the homoepitaxial LEDs yields an activation energy of carriers of 35 meV at -10 V, about 50% higher than that of the conventional ones (Ea = 21 meV at -10 V). This suggests that our homoepitaxial InGaN/GaN LEDs bears the high activation energy as well as low threading dislocation density (about 1 × 106/cm2), effectively suppressing the reverse leakage current. We expect that this study will shed a light on the high reliability and carrier tunneling characteristics of the homoepitaxial InGaN/GaN blue LEDs produced from a Si substrate and also envision a promising future for their successful adoption by LED community via cost-effective homoepitaxial fabrication of LEDs.

Investigation of Forward Tunneling Characteristics of InGaN/GaN Blue Light-Emitting Diodes on Freestanding GaN Detached from a Si Substrate.

We report forward tunneling characteristics of InGaN/GaN blue light emitting diodes (LEDs) on freestanding GaN detached from a Si substrate using temperature-dependent current⁻voltage (T-I-V) measurements. T-I-V analysis revealed that the conduction mechanism of InGaN/GaN LEDs using the homoepitaxial substrate can be distinguished by tunneling, diffusion and recombination current, and series resistance regimes. Their improved crystal quality, inherited from the nature of homoepitaxy, resulted in suppression of forward leakage current. It was also found that the tunneling via heavy holes in InGaN/GaN LEDs using the homoepitaxial substrate can be the main transport mechanism under low forward bias, consequentially leading to the improved forward leakage current characteristics.

Partial Edge Dislocations Comprised of Metallic Ga Bonds in Heteroepitaxial GaN.

We investigated the atomic structure of inclined threading edge dislocation (TED) typically observed in GaN grown on Si(111) through (scanning) transmission electron microscopy. Atomic observations verified that the inclined TED consisted of two partial dislocations. These results imply that the inclined TED possesses a Ga-Ga atomic configuration that is energetically unfavorable. However, the introduction of such structures is considered unavoidable because the TEDs should climb regularly to mediate the applied stress or the increasing surface due to the buffer layer. This Ga-Ga configuration is highly likely to form metallic bonds and appears to be the primary reason for the inferior efficacy of a GaN light-emitting diode grown on Si(111).

Electronic Transport Mechanism for Schottky Diodes Formed by Au/HVPE a-Plane GaN Templates Grown via In Situ GaN Nanodot Formation.

We investigate the electrical characteristics of Schottky contacts for an Au/hydride vapor phase epitaxy (HVPE) a-plane GaN template grown via in situ GaN nanodot formation. Although the Schottky diodes present excellent rectifying characteristics, their Schottky barrier height and ideality factor are highly dependent upon temperature variation. The relationship between the barrier height, ideality factor, and conventional Richardson plot reveals that the Schottky diodes exhibit an inhomogeneous barrier height, attributed to the interface states between the metal and a-plane GaN film and to point defects within the a-plane GaN layers grown via in situ nanodot formation. Also, we confirm that the current transport mechanism of HVPE a-plane GaN Schottky diodes grown via in situ nanodot formation prefers a thermionic field emission model rather than a thermionic emission (TE) one, implying that Poole⁻Frenkel emission dominates the conduction mechanism over the entire range of measured temperatures. The deep-level transient spectroscopy (DLTS) results prove the presence of noninteracting point-defect-assisted tunneling, which plays an important role in the transport mechanism. These electrical characteristics indicate that this method possesses a great throughput advantage for various applications, compared with Schottky contact to a-plane GaN grown using other methods. We expect that HVPE a-plane GaN Schottky diodes supported by in situ nanodot formation will open further opportunities for the development of nonpolar GaN-based high-performance devices.

Electronic states of deep trap levels in a-plane GaN templates grown on r-plane sapphire by HVPE.

We report on the defect states incorporated in a-plane GaN crystals grown on r-plane sapphire substrates by hydride vapor phase epitaxy (HVPE), using deep level transient spectroscopy (DLTS). Two defect states were observed at 0.2 eV and 0.55 eV below the conduction band minimum with defect densities of 5 × 1012/cm3 and 4.7 × 1013/cm3, respectively. The size of capture cross section, non-linear relation of trap densities from the depth profile, filling pulse width, and PL measurements indicated that the electronic deep trap levels in a-plane GaN on r-plane sapphire by HVPE originated from non-interacting point defects such as NGa, complex defects involving Si, O, or C, and VGa-related centres. Even though the a-plane GaN templates were grown by HVPE with high growth rates, the electronic deep trap characteristics are comparable to those of a-plane GaN layers of high crystal quality grown by MOCVD. This study prove that the growth of a-plane GaN templates on r-plane sapphire by HVPE is a promising method to obtain a-plane GaN layers efficiently and economically without the degradation of electrical characteristics.

The investigation of in situ removal of Si substrates for freestanding GaN crystals by HVPE.

We investigate the etching of a Si substrate in the fabrication process of freestanding GaN crystal grown using a Si by HVPE. Followed by crystal growth, Si etching by vapor HCl at high temperature results in successful fabrication of the freestanding GaN. Due to the complicated vertical gas flows inside the reactor, careful design of the susceptor was implemented. The unintentional formation of Si x N y thin layer at the backside of the Si substrate after the epitaxial growth, which can cause the decreased etch rate and non-uniform etching of a Si substrate, was successfully prevented by N2 purging during and after the etching of a Si substrate. We believe that this study will guide us to achieve the growth of freestanding GaN over 8-inch diameters in the efficient and practical way.

Stress-engineered growth of homoepitaxial GaN crystals using hydride vapor phase epitaxy.

We report the growth of a 3.5 mm-thick bulk GaN layer using a stress-engineered homoepitaxy method without any external processes. We employ a gradient V/III ratio during the growth, which enables a 3.5 mm-thick bulk GaN layer with a smooth surface and high crystal quality to be obtained. For a constant V/III ratio of 10, the bulk GaN layer has a flat surface; however, microcracks emerge in the GaN layer. For a constant V/III ratio of 38, the bulk GaN layer has a rough surface, without microcracks. On the other hand, by decreasing the V/III ratio from 38 to 10, the structural properties of the GaN layers are successfully controlled. The higher V/III ratio in the initial growth stage leads to a rough surface, and reduced stress and dislocation density in the bulk GaN layers, while the lower V/III ratio in the second stage of the growth provides an opposite trend, confirmed by Raman spectroscopy and X-ray measurements. We expect that this study will offer a new opportunity to achieve the growth of high-crystallinity bulk GaN without ex situ and complicated processes.

The investigation of stress in freestanding GaN crystals grown from Si substrates by HVPE.

We investigate the stress evolution of 400 µm-thick freestanding GaN crystals grown from Si substrates by hydride vapour phase epitaxy (HVPE) and the in situ removal of Si substrates. The stress generated in growing GaN can be tuned by varying the thickness of the MOCVD AlGaN/AlN buffer layers. Micro Raman analysis shows the presence of slight tensile stress in the freestanding GaN crystals and no stress accumulation in HVPE GaN layers during the growth. Additionally, it is demonstrated that the residual tensile stress in HVPE GaN is caused only by elastic stress arising from the crystal quality difference between Ga- and N-face GaN. TEM analysis revealed that the dislocations in freestanding GaN crystals have high inclination angles that are attributed to the stress relaxation of the crystals. We believe that the understanding and characterization on the structural properties of the freestanding GaN crystals will help us to use these crystals for high-performance opto-electronic devices.