Enhancing Performance of Ultraviolet C Photodetectors Through Single-Domain Epitaxy of Monoclinic ß-Ga2 O3 Films and Tailored Anti-Reflection Coating.

Implementing high-performance ultraviolet C photodetectors (UVC PDs) based on ß-Ga2 O3 films is challenging owing to the anisotropic crystal symmetry between the epitaxial films and substrates. In this study, highly enhanced state-of-the-art photoelectrical performance is achieved using single-domain epitaxy of monoclinic ß-Ga2 O3 films on a hexagonal sapphire substrate. Unlike 3D ß-Ga2 O3 films with twin domains, 2D ß-Ga2 O3 films exhibit a single domain with a smooth surface and low concentration of point defects, which enable efficient charge separation by suppressing boundary-induced recombination. Furthermore, a tailored anti-reflection coating (ARC) is adopted as a light-absorbing medium to improve charge generation. The tailored nanostructure, which features a gradient refractive index, not only substantially reduces the reflection, but also suppresses the surface leakage current as a passivation layer. This study provides fundamental insights into the single-domain epitaxy of ß-Ga2 O3 films and the application of ARC for the development of high-performance UVC PDs.

Controlled Band Offsets in Ultrathin Hematite for Enhancing the Photoelectrochemical Water Splitting Performance of Heterostructured Photoanodes.

Formation of type II heterojunctions is a promising strategy to enhance the photoelectrochemical performance of water-splitting photoanodes, which has been tremendously studied. However, there have been few studies focusing on the formation of type II heterojunctions depending on the thickness of the overlayer. Here, enhanced photoelectrochemical activities of a Fe2O3 film deposited-BiVO4/WO3 heterostructure with different thicknesses of the Fe2O3 layer have been investigated. The Fe2O3 (10 nm)/BiVO4/WO3 heterojunction photoanode shows a much higher photocurrent density compared to the Fe2O3 (100 nm)/BiVO4/WO3 photoanode. The Fe2O3 (10 nm)/BiVO4/WO3 trilayer heterojunction anodes have sequential type II junctions, while a thick Fe2O3 overlayer forms an inverse type II junction between Fe2O3 and BiVO4. Furthermore, the incident-photon-to-current efficiency measured under back-illumination is higher than those measured under front-illumination, demonstrating the importance of the illumination sequence for light absorption and charge transfer and transport. This study shows that the thickness of the oxide overlayer influences the energy band alignment and can be a strategy to improve solar water splitting performance. Based on our findings, we propose a photoanode design strategy for efficient photoelectrochemical water splitting.

Boosting Unassisted Alkaline Solar Water Splitting Using Silicon Photocathode with TiO2 Nanorods Decorated by Edge-Rich MoS2 Nanoplates.

To construct a highly efficient photoelectrochemical tandem device with silicon photocathode operating in alkaline conditions, it is desirable to develop stable and active catalysts which enable the photocathode to reliably perform under an alkaline environment. With nanostructured passivation layer and edge-exposed transition metal disulfides, silicon photocathode provides new opportunities for achieving unbiased alkaline solar water splitting. Here, the TiO2 nanorod arrays decorated by edge-rich MoS2 nanoplates are elaborately synthesized and deposited on p-Si. The vertically aligned TiO2 nanorods fully stabilize the Si surface and improve anti-reflectance. Moreover, MoS2 nanoplates with exposed edge sites provide catalytically active regions resulting in the kinetically favored hydrogen evolution under an alkaline environment. Interfacial energy band bending between p-Si and catalyst layers facilitates the transport of photogenerated electrons under steady-state illumination. Consequently, the MoS2 nanoplates/TiO2 nanorods/p-Si photocathode exhibits significantly improved photoelectrochemical-hydrogen evolution reaction (PEC-HER) performance in alkaline media with a high photocurrent density of 10 mA cm-2 at 0 V versus RHE and high stability. By integrating rationally designed photocathode with earth-abundant Fe60 (NiCo)30 Cr10 anode and perovskite/Si tandem photovoltaic cell, an unassisted alkaline solar water splitting is accomplished with a current density of 5.4 mA cm-2 corresponding to 6.6% solar-to-hydrogen efficiency, which is the highest among p-Si photocathodes.

Microscopic evidence of strong interactions between chemical vapor deposited 2D MoS2 film and SiO2 growth template.

Two-dimensional MoS2 film can grow on oxide substrates including Al2O3 and SiO2. However, it cannot grow usually on non-oxide substrates such as a bare Si wafer using chemical vapor deposition. To address this issue, we prepared as-synthesized and transferred MoS2 (AS-MoS2 and TR-MoS2) films on SiO2/Si substrates and studied the effect of the SiO2 layer on the atomic and electronic structure of the MoS2 films using spherical aberration-corrected scanning transition electron microscopy (STEM) and electron energy loss spectroscopy (EELS). The interlayer distance between MoS2 layers film showed a change at the AS-MoS2/SiO2 interface, which is attributed to the formation of S-O chemical bonding at the interface, whereas the TR-MoS2/SiO2 interface showed only van der Waals interactions. Through STEM and EELS studies, we confirmed that there exists a bonding state in addition to the van der Waals force, which is the dominant interaction between MoS2 and SiO2. The formation of S-O bonding at the AS-MoS2/SiO2 interface layer suggests that the sulfur atoms at the termination layer in the MoS2 films are bonded to the oxygen atoms of the SiO2 layer during chemical vapor deposition. Our results indicate that the S-O bonding feature promotes the growth of MoS2 thin films on oxide growth templates.

Correction: Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

Correction for 'Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces' by Woonbae Sohn et al., Nanoscale, 2021, 13, 708-715, DOI: 10.1039/D0NR07545K.

Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

A quasi-two-dimensional electron gas (2DEG) evolved at the LaAlO3 (LAO)/SrTiO3 (STO) interface has attracted significant attention, because the insertion of perovskite titanates can tune the 2DEG conductivity. However, this depends on the Ti-O-Ti bonding angle and structural symmetry. In this study, we controlled the octahedral tilt of the LAO/CaTiO3 (CTO) interface by heterostructuring it with CTO grown on STO substrates of various thicknesses. The 2DEG was maintained when the thickness of CTO was below the critical thickness of 5 unit cells (uc); however, it was suppressed when the CTO thickness was above the critical thickness. High-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) combined with integrated differential phase contrast (iDPC) STEM imaging was used to visualize the TiO6 octahedral tilt propagation and symmetry of the 5 uc and 24 uc CTO films. The symmetry of the 5 uc CTO film resembled that of the STO substrate, whereas the octahedral tilt propagated in the 24 uc CTO film due to the structural relaxation. These results show that the interface engineering of the octahedral tilt can enable or suppress the formation of the 2DEG in perovskite oxides.

Unraveling the Origin and Mechanism of Nanofilament Formation in Polycrystalline SrTiO3 Resistive Switching Memories.

Three central themes in the study of the phenomenon of resistive switching are the nature of the conducting phase, why it forms, and how it forms. In this study, the answers to all three questions are provided by performing switching experiments in situ in a transmission electron microscope on thin films of the model system polycrystalline SrTiO3 . On the basis of high-resolution transmission electron microscopy, electron-energy-loss spectroscopy and in situ current-voltage measurements, the conducting phase is identified to be SrTi11 O20 . This phase is only observed at specific grain boundaries, and a Ruddlesden-Popper phase, Sr3 Ti2 O7 , is typically observed adjacent to the conducting phase. These results allow not only the proposal that filament formation in this system has a thermodynamic origin-it is driven by electrochemical polarization and the local oxygen activity in the film decreasing below a critical value-but also the deduction of a phase diagram for strongly reduced SrTiO3 . Furthermore, why many conducting filaments are nucleated at one electrode but only one filament wins the race to the opposite electrode is also explained. The work thus provides detailed insights into the origin and mechanisms of filament generation and rupture.

Tailoring of Interfacial Band Offsets by an Atomically Thin Polar Insulating Layer To Enhance the Water-Splitting Performance of Oxide Heterojunction Photoanodes.

An important factor in the performance of photoelectrochemical water splitting is the band edge alignment of the photoelectrodes for efficient transport and transfer of photogenerated carriers. Many studies for improving charge transfer ability between the electrode and the electrolyte have been reported, while research to improve charge transfer at the interface of the photoactive semiconductor and the conducting substrate is largely lacking. Here, we demonstrate that the water-splitting performance of an oxide heterostructured photoelectrode can be increased 6-fold by inserting an atomically thin polar LaAlO3 interlayer compared with that of an oxide heterostructure without an insertion to modify interfacial band offsets. The electrically lowered Schottky barrier is driven by the atomically thin layer, and the charge transfer resistance between the oxides is reduced by up to 2 orders of magnitude upon insertion of LaAlO3, a wide-gap (5.6 eV) insulator. We show that the critical thickness of the polar layer for enhancing the charge transfer is 3 unit cells. The dipole moment from the polar sheets of LaAlO3 introduces an internal electric field, which modifies the effective band offsets in the device. This work serves as a proof of concept that photoelectrochemical performance can be improved by manipulating the band offsets of the heterostructure interface, suggesting a new design strategy for heterostructured water-splitting photoelectrodes.

Efficient Water Splitting Cascade Photoanodes with Ligand-Engineered MnO Cocatalysts.

The band edge positions of semiconductors determine functionality in solar water splitting. While ligand exchange is known to enable modification of the band structure, its crucial role in water splitting efficiency is not yet fully understood. Here, ligand-engineered manganese oxide cocatalyst nanoparticles (MnO NPs) on bismuth vanadate (BiVO4) anodes are first demonstrated, and a remarkably enhanced photocurrent density of 6.25 mA cm-2 is achieved. It is close to 85% of the theoretical photocurrent density (≈7.5 mA cm-2) of BiVO4. Improved photoactivity is closely related to the substantial shifts in band edge energies that originate from both the induced dipole at the ligand/MnO interface and the intrinsic dipole of the ligand. Combined spectroscopic analysis and electrochemical study reveal the clear relationship between the surface modification and the band edge positions for water oxidation. The proposed concept has considerable potential to explore new, efficient solar water splitting systems.

Synthesis of Numerous Edge Sites in MoS2 via SiO2 Nanorods Platform for Highly Sensitive Gas Sensor.

The utilization of edge sites in two-dimensional materials including transition-metal dichalcogenides (TMDs) is an effective strategy to realize high-performance gas sensors because of their high catalytic activity. Herein, we demonstrate a facile strategy to synthesize the numerous edge sites of vertically aligned MoS2 and larger surface area via SiO2 nanorod (NRs) platforms for highly sensitive NO2 gas sensor. The SiO2 NRs encapsulated by MoS2 film with numerous edge sites and partially vertical-aligned regions synthesized using simple thermolysis process of [(NH4)2MoS4]. Especially, the vertically aligned MoS2 prepared on 500 nm thick SiO2 NRs (500MoS2) shows approximately 90 times higher gas-sensing response to 50 ppm NO2 at room temperature than the MoS2 film prepared on flat SiO2, and the theoretical detection limit is as low as ∼2.3 ppb. Additionally, it shows reliable operation with reversible response to NO2 gas without degradation at an operating temperature of 100 °C. The use of the proposed facile approach to synthesize vertically aligned TMDs using nanostructured platform can be extended for various TMD-based devices including sensors, water splitting catalysts, and batteries.

Facile synthesis of CsPbBr3/PbSe composite clusters.

In this work, CsPbBr3 and PbSe nanocomposites were synthesized to protect perovskite material from self-enlargement during reaction. UV absorption and photoluminescence (PL) spectra indicate that the addition of Se into CsPbBr3 quantum dots modified the electronic structure of CsPbBr3, increasing the band gap from 2.38 to 2.48 eV as the Cs:Se ratio increased to 1:3. Thus, the emission color of CsPbBr3 perovskite quantum dots was modified from green to blue by increasing the Se ratio in composites. According to X-ray diffraction patterns, the structure of CsPbBr3 quantum dots changed from cubic to orthorhombic due to the introduction of PbSe at the surface. Transmission electron microscopy and X-ray photoemission spectroscopy confirmed that the atomic distribution in CsPbBr3/PbSe composite clusters is uniform and the composite materials were well formed. The PL intensity of a CsPbBr3/PbSe sample with a 1:1 Cs:Se ratio maintained 50% of its initial intensity after keeping the sample for 81 h in air, while the PL intensity of CsPbBr3 reduced to 20% of its initial intensity. Therefore, it is considered that low amounts of Se could improve the stability of CsPbBr3 quantum dots.

Decoration of metal oxide surface with {111} form Au nanoparticles using PEGylation.

The benefit of introducing gold nanoparticles is due to the plasmon relaxation process. The plasmon decay induces various phenomena such as near-field enhancement, hot electron injection, and resonance energy transfer. Shape-controlled octahedral gold nanoparticles can maximize the efficiency of these processes. For practical purposes, a high-coverage decoration method, comparable to physical vapor deposition on a metal oxide semiconductor nanostructure, is indispensable. However, the ligand exchange reaction to attach octahedral gold nanoparticles is limited in aqueous solution due to the inactivity of the gold (111) surface as a result of a densely-packed cetyltrimethylammonium bilayer structure. Herein, we report a controllable high-coverage surface decoration method of octahedral gold nanoparticles on the targeted semiconductor nanostructures via phase transfer by an organic medium with thiolated-polyethylene glycol. Our results deliver an innovative platform for future plasmonic gold nanoparticle applications.

p-p Heterojunction of Nickel Oxide-Decorated Cobalt Oxide Nanorods for Enhanced Sensitivity and Selectivity toward Volatile Organic Compounds.

The utilization of p-p isotype heterojunctions is an effective strategy to enhance the gas sensing properties of metal-oxide semiconductors, but most previous studies focused on p-n heterojunctions owing to their simple mechanism of formation of depletion layers. However, a proper choice of isotype semiconductors with appropriate energy bands can also contribute to the enhancement of the gas sensing performance. Herein, we report nickel oxide (NiO)-decorated cobalt oxide (Co3O4) nanorods (NRs) fabricated using the multiple-step glancing angle deposition method. The effective decoration of NiO on the entire surface of Co3O4 NRs enabled the formation of numerous p-p heterojunctions, and they exhibited a 16.78 times higher gas response to 50 ppm of C6H6 at 350 °C compared to that of bare Co3O4 NRs with the calculated detection limit of approximately 13.91 ppb. Apart from the p-p heterojunctions, increased active sites owing to the changes in the orientation of the exposed lattice surface and the catalytic effects of NiO also contributed to the enhanced gas sensing properties. The advantages of p-p heterojunctions for gas sensing applications demonstrated in this work will provide a new perspective of heterostructured metal-oxide nanostructures for sensitive and selective gas sensing.

Facile Solution Synthesis of Tungsten Trioxide Doped with Nanocrystalline Molybdenum Trioxide for Electrochromic Devices.

A facile, highly efficient approach to obtain molybdenum trioxide (MoO3)-doped tungsten trioxide (WO3) is reported. An annealing process was used to transform ammonium tetrathiotungstate [(NH4)2WS4] to WO3 in the presence of oxygen. Ammonium tetrathiomolybdate [(NH4)2MoS4] was used as a dopant to improve the film for use in an electrochromic (EC) cell. (NH4)2MoS4 at different concentrations (10, 20, 30, and 40 mM) was added to the (NH4)2WS4 precursor by sonication and the samples were annealed at 500 °C in air. Raman, X-ray diffraction, and X-ray photoelectron spectroscopy measurements confirmed that the (NH4)2WS4 precursor decomposed to WO3 and the (NH4)2MoS4-(NH4)2WS4 precursor was transformed to MoO3-doped WO3 after annealing at 500 °C. It is shown that the MoO3-doped WO3 film is more uniform and porous than pure WO3, confirming the doping quality and the privileges of the proposed method. The optimal MoO3-doped WO3 used as an EC layer exhibited a high coloration efficiency of 128.1 cm2/C, which is larger than that of pure WO3 (74.5 cm2/C). Therefore, MoO3-doped WO3 synthesized by the reported method is a promising candidate for high-efficiency and low-cost smart windows.

Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape-Controlled Au Nanoparticles.

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape-controlled Au NPs on bismuth vanadate (BiVO4 ) are studied, and a largely enhanced photoactivity of BiVO4 is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO4 achieves 2.4 mA cm-2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO4 . It is the highest value among the previously reported plasmonic Au NPs/BiVO4 . Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape-controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.

Toward High-Performance Hematite Nanotube Photoanodes: Charge-Transfer Engineering at Heterointerfaces.

Vertically ordered hematite nanotubes are considered to be promising photoactive materials for high-performance water-splitting photoanodes. However, the synthesis of hematite nanotubes directly on conducting substrates such as fluorine-doped tin oxide (FTO)/glass is difficult to be achieved because of the poor adhesion between hematite nanotubes and FTO/glass. Here, we report the synthesis of hematite nanotubes directly on FTO/glass substrate and high-performance photoelectrochemical properties of the nanotubes with NiFe cocatalysts. The hematite nanotubes are synthesized by a simple electrochemical anodization method. The adhesion of the hematite nanotubes to the FTO/glass substrate is drastically improved by dipping them in nonpolar cyclohexane prior to postannealing. Bare hematite nanotubes show a photocurrent density of 1.3 mA/cm(2) at 1.23 V vs a reversible hydrogen electrode, while hematite nanotubes with electrodeposited NiFe cocatalysts exhibit 2.1 mA/cm(2) at 1.23 V which is the highest photocurrent density reported for hematite nanotubes-based photoanodes for solar water splitting. Our work provides an efficient platform to obtain high-performance water-splitting photoanodes utilizing earth-abundant hematite and noble-metal-free cocatalysts.

Room Temperature Deposition of Crystalline Nanoporous ZnO Nanostructures for Direct Use as Flexible DSSC Photoanode.

A facile approach to fabricate dye-sensitized solar cells (DSSCs) is demonstrated by depositing (001) oriented zinc oxide (ZnO) nanostructures on both glass and flexible substrates at room temperature using pulsed laser deposition. Unique crystallographic characteristics of ZnO combined with highly non-equilibrium state of pulsed laser-induced ablated species enabled highly crystalline ZnO nanostructures without aid of any chemically induced additives or organic/inorganic impurities at room temperature. Film morphology as well as internal surface area is tailored by varying ambient oxygen pressure and deposition time. It is revealed that the optimization of these two experimental factors was essential for achieving structure providing large surface area as well as efficient charge collection. The DSSCs with optimized ZnO photoanodes showed overall efficiencies of 3.89 and 3.4 % on glass and polyethylene naphthalate substrates, respectively, under AM 1.5G light illumination. The high conversion efficiencies are attributed to elongated electron lifetime and enhanced electrolyte diffusion in the high crystalline ZnO nanostructures, verified by intensity-modulated voltage spectroscopy and electrochemical impedance measurements.