Nanostructured Gallium Nitride Membrane at Wafer Scale for Photo(Electro)catalytic Polluted Water Remediation.

Photo(electro)catalysis methods have drawn significant attention for efficient, energy-saving, and environmental-friendly organic contaminant degradation in wastewater. However, conventional oxide-based powder photocatalysts are limited to UV-light absorption and are unfavorable in the subsequent postseparation process. In this paper, a large-area crystalline-semiconductor nitride membrane with a distinct nanoporous surface is fabricated, which can be scaled up to a full wafer and easily retrieved after photodegradation. The unique nanoporous surface enhances broadband light absorption, provides abundant reactive sites, and promotes the dye-molecule reaction with adsorbed hydroxyl radicals on the surface. The superior electric contact between the nickel bottom layer and nitride membrane facilitates swift charge carrier transportation. In laboratory tests, the nanostructure membrane can degrade 93% of the dye in 6 h under illumination with a small applied bias (0.5 V vs Ag/AgCl). Furthermore, a 2 inch diameter wafer-scale membrane is deployed in a rooftop test under natural sunlight. The membrane operates stably for seven cycles (over 50 h) with an outstanding dye degradation efficiency (>92%) and satisfied average total organic carbon removal rate (≈50%) in each cycle. This demonstration thus opens the pathway toward the production of nanostructured semiconductor layers for large-scale and practical wastewater treatment using natural sunlight.

Chlorine-Infused Wide-Band Gap p-CuSCN/n-GaN Heterojunction Ultraviolet-Light Photodetectors.

Copper thiocyanate (CuSCN) is a p-type semiconductor that exhibits hole-transport and wide-band gap (∼3.9 eV) characteristics. However, the conductivity of CuSCN is not sufficiently high, which limits its potential application in optoelectronic devices. Herein, CuSCN thin films were exposed to chlorine using a dry etching system to enhance their electrical properties, yielding a maximum hole concentration of 3 × 1018 cm-3. The p-type CuSCN layer was then deposited onto an n-type gallium nitride (GaN) layer to form a prototypical ultraviolet-based photodetector. X-ray photoelectron spectroscopy further demonstrated the interface electronic structures of the heterojunction, confirming a favorable alignment for holes and electrons transport. The ensuing p-CuSCN/n-GaN heterojunction photodetector exhibited a turn-on voltage of 2.3 V, a responsivity of 1.35 A/W at -1 V, and an external quantum efficiency of 5.14 × 102% under illumination with ultraviolet light (peak wavelength of 330 nm). The work opens a new pathway for making a plethora of hybrid optoelectronic devices of inorganic and organic nature by using p-type CuSCN as the hole injection layer.

Lattice Orientation Heredity in the Transformation of 2D Epitaxial Films.

The ability to control lattice orientation is often an essential requirement in the growth of both 2D van der Waals (vdW) layered and nonlayered thin films. Here, a unique and universal phenomenon termed "lattice orientation heredity" (LOH) is reported. LOH enables product films (including 2D-layered materials) to inherit the lattice orientation from reactant films in a chemical conversion process, excluding the requirement on the substrate lattice order. The process universality is demonstrated by investigating the lattice transformations in the carbonization, nitridation, and sulfurization of epitaxial MoO2 , ZnO, and In2 O3 thin films. Their resultant compounds all inherit the mono-oriented crystal feature from their precursor oxides, including 2D vdW-layered semiconductors (e.g., MoS2 ), metallic films (e.g., MXene-like Mo2 C and MoN), wide-bandgap semiconductors (e.g., hexagonal ZnS), and ferroelectric semiconductors (e.g., In2 S3 ). Using LOH-grown MoN as a seeding layer, mono-oriented GaN is achieved on an amorphous quartz substrate. The LOH process presents a universal strategy capable of growing epitaxial thin films (including 2D vdW-layered materials) not only on single-crystalline but also on noncrystalline substrates.

Engineering Band-Type Alignment in CsPbBr3 Perovskite-Based Artificial Multiple Quantum Wells.

Semiconductor heterostructures of multiple quantum wells (MQWs) have major applications in optoelectronics. However, for halide perovskites-the leading class of emerging semiconductors-building a variety of bandgap alignments (i.e., band-types) in MQWs is not yet realized owing to the limitations of the current set of used barrier materials. Here, artificial perovskite-based MQWs using 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole), tris-(8-hydroxyquinoline)aluminum, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline as quantum barrier materials are introduced. The structures of three different five-stacked perovskite-based MQWs each exhibiting a different band offset with CsPbBr3 in the conduction and valence bands, resulting in a variety of MQW band alignments, i.e., type-I or type-II structures, are shown. Transient absorption spectroscopy reveals the disparity in charge carrier dynamics between type-I and type-II MQWs. Photodiodes of each type of perovskite artificial MQWs show entirely different carrier behaviors and photoresponse characteristics. Compared with bulk perovskite devices, type-II MQW photodiodes demonstrate a more than tenfold increase in the rectification ratio. The findings open new opportunities for producing halide-perovskite-based quantum devices by bandgap engineering using simple quantum barrier considerations.

Toward Large-Scale Ga2O3 Membranes via Quasi-Van Der Waals Epitaxy on Epitaxial Graphene Layers.

Epitaxial growth using graphene (GR), weakly bonded by van der Waals force, is a subject of interest for fabricating technologically important semiconductor membranes. Such membranes can potentially offer effective cooling and dimensional scale-down for high voltage power devices and deep ultraviolet optoelectronics at a fraction of the bulk-device cost. Here, we report on a large-area ß-Ga2O3 nanomembrane spontaneous-exfoliation (1 cm × 1 cm) from layers of compressive-strained epitaxial graphene (EG) grown on SiC, and demonstrated high-responsivity flexible solar-blind photodetectors. The EG was favorably influenced by lattice arrangement of SiC, and thus enabled ß-Ga2O3 direct-epitaxy on the EG. The ß-Ga2O3 layer was spontaneously exfoliated at the interface of GR owing to its low interfacial toughness by controlling the energy release rate through electroplated Ni layers. The use of GR templates contributes to the seamless exfoliation of the nanomembranes, and the technique is relevant to eventual nanomembrane-based integrated device technology.

Quantifying the Transverse-Electric-Dominant 260 nm Emission from Molecular Beam Epitaxy-Grown GaN-Quantum-Disks Embedded in AlN Nanowires: A Comprehensive Optical and Morphological Characterization.

There has been a relentless pursuit of transverse electric (TE)-dominant deep ultraviolet (UV) optoelectronic devices for efficient surface emitters to replace the environmentally unfriendly mercury lamps. To date, the use of the ternary AlGaN alloy inevitably has led to transverse magnetic (TM)-dominant emission, an approach that is facing a roadblock. Here, we take an entirely different approach of utilizing a binary GaN compound semiconductor in conjunction with ultrathin quantum disks (QDisks) embedded in AlN nanowires (NWs). The growth of GaN QDisks is realized on a scalable and low-cost Si substrate using plasma-assisted molecular beam epitaxy as a highly controllable monolayer growth platform. We estimated an internal quantum efficiency of ∼81% in a wavelength regime of ∼260 nm for these nanostructures. Additionally, strain mapping obtained by high-angle annular dark-field scanning transmission electron microscopy is studied in conjunction with the TE and TM modes of the carrier recombination. Moreover, for the first time, we quantify the TE and TM modes of the PL emitted by GaN QDisks for deep-UV emitters. We observed nearly pure TE-polarized photoluminescence emission at a polarization angle of ∼5°. This work proposes highly quantum-confined ultrathin GaN QDisks as a promising candidate for deep-UV vertical emitters.

Titanium Carbide MXene Nucleation Layer for Epitaxial Growth of High-Quality GaN Nanowires on Amorphous Substrates.

Growing III-nitride nanowires on 2D materials is advantageous, as it effectively decouples the underlying growth substrate from the properties of the nanowires. As a relatively new family of 2D materials, MXenes are promising candidates as III-nitride nanowire nucleation layers capable of providing simultaneous transparency and conductivity. In this work, we demonstrate the direct epitaxial growth of GaN nanowires on Ti3C2 MXene films. The MXene films consist of nanoflakes spray coated onto an amorphous silica substrate. We observed an epitaxial relationship between the GaN nanowires and the MXene nanoflakes due to the compatibility between the triangular lattice of Ti3C2 MXene and the hexagonal structure of wurtzite GaN. The GaN nanowires on MXene show good material quality and partial transparency at visible wavelengths. Nanoscale electrical characterization using conductive atomic force microscopy reveals a Schottky barrier height of ∼330 meV between the GaN nanowire and the Ti3C2 MXene film. Our work highlights the potential of using MXene as a transparent and conductive preorienting nucleation layer for high-quality GaN growth on amorphous substrates.

Improved solar hydrogen production by engineered doping of InGaN/GaN axial heterojunctions.

InGaN-based nanowires (NWs) have been investigated as efficient photoelectrochemical (PEC) water splitting devices. In this work, the InGaN/GaN NWs were grown by molecular beam epitaxy (MBE) having InGaN segments on top of GaN seeds. Three axial heterojunction structures were constructed with different doping types and levels, namely n-InGaN/n-GaN NWs, undoped (u)-InGaN/p-GaN NWs, and p-InGaN/p-GaN NWs. With the carrier concentrations estimated by Mott-Schottky measurements, a PC1D simulation further confirmed the band structures of the three heterojunctions. The u-InGaN/p-GaN and p-InGaN/p-GaN NWs exhibited optimized stability in pH 0 electrolytes for over 10 h with a photocurrent density of about -4.0 and -9.4 mA/cm2, respectively. However, the hydrogen and oxygen evolution rates of the Pt-treated u-InGaN/p-GaN NWs exhibited a less favorable stoichiometric ratio. On the other hand, the Pt-decorated p-InGaN/p-GaN NWs showed the best PEC performance, generating approximately 1000 µmol/cm2 hydrogen and 550 µmol/cm2 oxygen in 10 h. The band-engineered p-InGaN/p-GaN axial NWs-heterojunction demonstrated a great potential for highly efficient and durable photocathodes.

Direct Growth of Single Crystalline GaN Nanowires on Indium Tin Oxide-Coated Silica.

In this work, we demonstrated the direct growth of GaN nanowires on indium tin oxide (ITO)-coated fused silica substrate. The nanowires were grown catalyst-free using plasma-assisted molecular beam epitaxy (PA-MBE). The effect of growth condition on the morphology and quality of the nanowires is systematically investigated. Structural characterization indicates that the nanowires grow in the (0001) direction directly on top of the ITO layer perpendicular to the substrate plane. Optical characterization of the nanowires shows that yellow luminescence is absent from the nanowire's photoluminescence response, attributed to the low number of defects. Conductive atomic force microscopy (C-AFM) measurement on n-doped GaN nanowires shows good conductivity for individual nanowires, which confirms the potential of using this platform for novel device applications. By using a relatively low-temperature growth process, we were able to successfully grow high-quality single-crystal GaN material without the degradation of the underlying ITO layer.

Facile fabrication of ZnO nanowire memory device based on chemically-treated surface defects.

In this study, we demonstrate a transistor-type ZnO nanowire (NW) memory device based on the surface defect states of a rough ZnO NW, which is obtained by introducing facile H2O2 solution treatment. The surface defect states of the ZnO NW are validated by photoluminescence characterisation. A memory device based on the rough ZnO NW exhibits clearly separated bi-stable states (ON and OFF states). A significant current fluctuation does not exist during repetitive endurance cycling test. Stable memory retention characteristics are also achieved at a high temperature of 85 °C and at room temperature. The surface-treated ZnO NW device also exhibits dynamically well-responsive pulse switching under a sequential pulse test configuration, thereby indicating its potential practical memory applications. The simple chemical treatment strategy can be widely used for modulating the surface states of diverse low-dimensional materials.

Flexible InGaN nanowire membranes for enhanced solar water splitting.

III-Nitride nanowires (NWs) have recently emerged as potential photoelectrodes for efficient solar hydrogen generation. While InGaN NWs epitaxy over silicon is required for high crystalline quality and economic production, it leads to the formation of the notorious silicon nitride insulating interface as well as low electrical conductivity which both impede excess charge carrier dynamics and overall device performance. We tackle this issue by developing, for the first time, a substrate-free InGaN NWs membrane photoanodes, through liftoff and transfer techniques, where excess charge carriers are efficiently extracted from the InGaN NWs through a proper ohmic contact formed with a high electrical conductivity metal stack membrane. As a result, compared to conventional InGaN NWs on silicon, the fabricated free-standing flexible membranes showed a 10-fold increase in the generated photocurrent as well as a 0.8 V cathodic shift in the onset potential. Through electrochemical impedance spectroscopy, accompanied with TEM-based analysis, we further demonstrated the detailed enhancement within excess charge carrier dynamics of the photoanode membranes. This novel configuration in photoelectrodes demonstrates a novel pathway for enhancing the performance of III-nitrides photoelectrodes to accelerate their commercialization for solar water splitting.

Efficient Light Absorption by GaN Truncated Nanocones for High Performance Water Splitting Applications.

Despite the importance of gallium nitride (GaN) nanostructures for photocatalytic activity, relatively little attention has been paid to their geometrical optimization on the basis of wave optics. In this study, we present GaN truncated nanocones to provide a strategy for improving solar water splitting efficiencies, compared to the efficiency provided by the conventional geometries (i.e., flat surface, cylindrical, and cone shapes). Computational results with a finite difference time domain (FDTD) method and a rigorous coupled-wave analysis (RCWA) reveal important aspects of truncated nanocones, which effectively concentrate light in the center of the nanostructures. The introduction of nanostructures is highly recommended to address the strong light reflection of photocatalytic materials and carrier lifetime issues. To fabricate the truncated nanocones at low cost and with large-area, a dry etching method was employed with thermally dewetted metal nanoparticles, which enables controllability of desired features on a wafer scale. Experimental results exhibit that the photocurrent density of truncated nanocones is improved about three times higher compared to that of planar GaN.

Contact resistance reduction of ZnO thin film transistors (TFTs) with saw-shaped electrode.

We report on a saw-shaped electrode architecture ZnO thin film transistor (TFT), which effectively increases the channel width. The contact line of the saw-shaped electrode is almost twice as long at the contact metal/ZnO channel junction. We experimentally observed an enhancement in the output drive current by 50% and a reduction in the contact resistance by over 50%, when compared to a typically shaped electrode ZnO TFT consuming the same chip area. This performance enhancement is attributed to the extension of the channel width. This technique can contribute to device performance enhancement, and in particular reduce the contact resistance, which is a serious challenge.

Direct Growth of III-Nitride Nanowire-Based Yellow Light-Emitting Diode on Amorphous Quartz Using Thin Ti Interlayer.

Consumer electronics have increasingly relied on ultra-thin glass screen due to its transparency, scalability, and cost. In particular, display technology relies on integrating light-emitting diodes with display panel as a source for backlighting. In this study, we undertook the challenge of integrating light emitters onto amorphous quartz by demonstrating the direct growth and fabrication of a III-nitride nanowire-based light-emitting diode. The proof-of-concept device exhibits a low turn-on voltage of 2.6 V, on an amorphous quartz substrate. We achieved ~ 40% transparency across the visible wavelength while maintaining electrical conductivity by employing a TiN/Ti interlayer on quartz as a translucent conducting layer. The nanowire-on-quartz LED emits a broad linewidth spectrum of light centered at true yellow color (~ 590 nm), an important wavelength bridging the green-gap in solid-state lighting technology, with significantly less strain and dislocations compared to conventional planar quantum well nitride structures. Our endeavor highlighted the feasibility of fabricating III-nitride optoelectronic device on a scalable amorphous substrate through facile growth and fabrication steps. For practical demonstration, we demonstrated tunable correlated color temperature white light, leveraging on the broadly tunable nanowire spectral characteristics across red-amber-yellow color regime.

III-nitride core-shell nanorod array on quartz substrates.

We report the fabrication of near-vertically elongated GaN nanorods on quartz substrates. To control the preferred orientation and length of individual GaN nanorods, we combined molecular beam epitaxy (MBE) with pulsed-mode metal-organic chemical vapor deposition (MOCVD). The MBE-grown buffer layer was composed of GaN nanograins exhibiting an ordered surface and preferred orientation along the surface normal direction. Position-controlled growth of the GaN nanorods was achieved by selective-area growth using MOCVD. Simultaneously, the GaN nanorods were elongated by the pulsed-mode growth. The microstructural and optical properties of both GaN nanorods and InGaN/GaN core-shell nanorods were then investigated. The nanorods were highly crystalline and the core-shell structures exhibited optical emission properties, indicating the feasibility of fabricating III-nitride nano-optoelectronic devices on amorphous substrates.

4 channel × 10 Gb/s bidirectional optical subassembly using silicon optical bench with precise passive optical alignment.

We demonstrate an advanced structure for optical interconnect consisting of 4 channel × 10 Gb/s bidirectional optical subassembly (BOSA) formed using silicon optical bench (SiOB) with tapered fiber guiding holes (TFGHs) for precise and passive optical alignment of vertical-cavity surface-emitting laser (VCSEL)-to-multi mode fiber (MMF) and MMF-to-photodiode (PD). The co-planar waveguide (CPW) transmission line (Tline) was formed on the backside of silicon substrate to reduce the insertion loss of electrical data signal. The 4 channel VCSEL and PD array are attached at the end of CPW Tline using a flip-chip bonder and solder pad. The 12-channel ribbon fiber is simply inserted into the TFGHs of SiOB and is passively aligned to the VCSEL and PD in which no additional coupling optics are required. The fabricated BOSA shows high coupling efficiency and good performance with the clearly open eye patterns and a very low bit error rate of less than 10-12 order at a data rate of 10 Gb/s with a PRBS pattern of 231-1.