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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 Fe

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 LaAlO

The use of chemoresistive gas sensors based on metal oxides has expanded to various fields such as medical diagnosis and air quality systems as well as gas leakage detectors with the development of the Internet of Things. Accordingly, sensitivity, selectivity, power consumption, and reproducibility become important factors in the development of gas sensors. Herein, we developed a facile method to fabricate a gas sensor based on porous Au-incorporated tungsten trioxide (WO3) thin films for highly sensitive and selective NO2 sensing. The mixed solution of ammonium tetrathiotungstate [(NH4)2WS4] and gold chloride (AuCl3) was transformed to Au-incorporated WO3 thin films through the spin-coating and annealing process. The gas sensors based on the Au-incorporated WO3 thin films exhibited improved sensitivity, selectivity, and response time upon exposure to NO2 with a significantly low theoretical detection limit of 28 ppt at 150 ℃ compared to gas sensors based on the pristine WO3 thin film. The high sensing properties are attributed to the porous structure and catalytic effects of Au nanoparticles. In addition to these remarkable NO2 sensing properties, the facile and cost-effective fabrication process enlarges the potential of the Au-incorporated WO3 thin films for practical and commercial gas sensing applications.

Although there is considerable interest in BiFeO3 owing to its versatile physical properties, which make it suitable for a wide range of applications, its high leakage current is a significant limi...

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 TiO

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.

α-Ga2O3 of the corundum structure and the large bandgap of 5.3 eV has attracted great interest because it can be grown on a sapphire (α-Al2O3) substrate with the same crystal structure. However, the lattice mismatch (4.3%) between α-Ga2O3 and the sapphire substrate induces a high density of threading dislocations, which act as breakdown leakage paths and lead to deterioration of the crystallinity and electrical properties of the α-Ga2O3 films grown directly on the substrate. Herein, to circumvent this issue compositionally graded α-(AlxGa1-x)2O3 layers are adopted to reduce threading dislocations for a high quality of epitaxial α-Ga2O3 films. The evolution of strain relaxation and the inclination of threading dislocations in graded α-(AlxGa1-x)2O3 layers are confirmed by reciprocal space mapping (RSM) and transmission electron microscopy (TEM). Through RSM and TEM studies, we confirmed that compressive strain enhances the inclination of dislocations and therefore, the dislocations merge and annihilate in the graded α-(AlxGa1-x)2O3 layers. The calculated density of threading dislocations in an α-Ga2O33 films with a graded α-(AlxGa1-x)2O3 buffer layer is reduced by 64.9% compared with that of an α-Ga2O3 films deposited directly grown on a bare sapphire substrate. Furthermore, a fabricated lateral-structure Schottky diode reveals enhanced breakdown voltages and forward current density due to the improved crystalline quality by using the graded α-(AlxGa1-x)2O3 buffer layer. This study provides an attractive approach for obtaining high-quality epitaxial α-Ga2O3 thin films for high voltage power devices.

Additional file 1: Figure S1. Raman spectra of the MoS2 thin film on the SiO2/Si substrate. Lateral growth of multilayer MoS2 film has been successful. The two characteristic Raman vibration modes E12g and A1g are labelled. Figure S2. TEM images of MoS2 film on SiO2/Si. (a) Low magnification, (b), (c) HRTEM images of AS-MoS2 film. (d) Low magnification, (e), (f) HRTEM images of TR-MoS2 film. Figure S3. (a) Position in which interlayer distance values are measured in AS-MoS2 films and (b) position in which interlayer distance values are measured in TR-MoS2 films. Figure S4. XPS spectra of MoS2 films. XPS core level spectra of (a) Mo 3d, (b) S 2p of AS-MoS2 film and (c) Mo 3d, (d) S 2p of TR-MoS2 films.

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.

A Li0.27K0.72Ni0.6Co0.2Mn0.2O2 (LKNCM) cathode for potassium-ion batteries (PIBs) was obtained from LiNi0.6Co0.2Mn0.2O2 (NCM622) via ion exchange. In-situ X-ray diffraction and high-resolution transmission electron microscopy analyses showed the morphological and structural changes that occur during K+-ion insertion. Particularly, the primary particles became porous, and the (003) interlayer distance expanded from 4.76 to 6.50 A, providing a potassiation/depotassiation framework. Inductively coupled plasma-optical emission spectroscopy revealed that 0.72 mol of K+ ions were inserted into the Li-extracted NCM622 cathode per formula unit, indicating that the amounts of extracted Li+ and inserted K+ were similar. The developed LKNCM cathode exhibited a theoretical capacity of 160.79 mAh g−1 and an initial discharge capacity of 106.95 mAh g−1 with an average potential of 3.1 V vs. K/K+. These results demonstrate that ion exchange enables layered NCM cathodes for lithium-ion batteries to be applied as cathodes for PIBs.

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.

Vertically ordered hematite nanotubes decorated with Au nanoparticles are synthesized by a facile electrochemical anodization method and self-agglomeration of Au films. Au decoration significantly enhances the response of hematite nanotubes to acetone at 350 °C and the response to acetone is 2.4 times higher than the response to ethanol, the counterpart target gas. The Au nanoparticles decorated hematite nanotubes exhibit unprecedentedly high and selective responses to acetone at 350 °C with 50% relative humidity condition (calibrated at room temperature, 25 °C). The enhanced gas sensing properties in a humid condition were attributed to the spillover effect by Au nanoparticles and high porosity of hematite nanotubes with a large surface-to-volume ratio. These results indicate that Au nanoparticles decorated hematite nanotubes are promising for use in high quality sensor materials for breath analyzers to diagnose diabetes mellitus.

Despite its abundant, nontoxicity and photochemical stability, titanium dioxide shows low solar water oxidation performance due to low photogenerated carrier transport and wide optical band gap, which results in substantially low photogenerated carrier density that impair the solar to hydrogen conversion efficiency. Herein, highly enhanced water oxidation performance of high-aspect-ratio TiO2 nanorods doped with dual heteroatoms, sulfur and nitrogen, for photoelectrochemical solar water oxidation is demonstrated. The codoped TiO2 NRs have shown enhanced optical absorption coefficient due to the induced impurities energy states near to the top of the valance band and result in a red shift in the optical absorption edges. Consequently, a 2.82 mAcm−2 photocurrent density at 1.23 V vs. RHE is obtained from the sulfur and nitrogen codoped TiO2 nanorods, and pristine TiO2 nanorods photoanode shows 0.7 mAcm−2. The applied bias photon-to-current conversion efficiency and external quantum efficiency of the codoped TiO2 nanorods are 1.49% and 97.0% at λ = 360 nm and 0.69% and 19.1% at λ = 370 nm for pristine TiO2 nanorods, respectively. Our study offers experimental and theoretical evidence for codoping of sulfur and nitrogen improve the optical and electrical properties of TiO2 for efficient photoelectrochemical solar water oxidation.

In this research, we investigate the effect of metal doping on the electrochromic (EC) performance of tungsten trioxide (WO3) films. These films were prepared by a novel method involving solution processing and thermal annealing. In this procedure, ammonium tetrathiotungstate ((NH4)2WS4) was dissolved in dimethylformamide at a high concentration ratio (200 mg mL−1) to obtain a homogeneous solution and then spin-coated onto the indium thin oxide (ITO) substrate for use as a working electrode. Subsequently, the film was annealed at the different temperatures (200, 300, 400, and 500 °C) to form a crystal structure of WO3. X-ray diffraction, Raman, and X-ray photoelectron spectroscopic results confirm the crystal formation of WO3. Moreover, in order to improve the electrochromic performance, different concentrations (10, 20, 30, and 40 mM) of different metal chlorides such as PtCl4, PdCl2, AuCl3, AgCl, CuCl2, NiCl2, NaCl, and KCl were added into the (NH4)2WS4 precursor and the mixture was coated on the ITO substrate and annealed at 500 °C. The results indicate that the performance of the Au-doped WO3 film was better than those with other dopants, likely as a result of the plasmonic effect. Therefore, the proposed method and Au-doped WO3 films are great candidates for the development of smart windows with high EC performance.

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 fa...

In this report, we present a new approach for the fabrication and application of Cs4PbBr6 microcrystals (Cs4PbBr6 MCs). The Cs4PbBr6 MCs are synthesized via an anti-solvent induced crystallization of PbBr2:CsBr directly in dimethylsulfoxide (DMSO) by introducing HBr (HBr, 48% aqueous solution). The ratio of HBr and DMSO plays a vital role in the formation of Cs4PbBr6. By controlling the HBr/DMSO ratio, pure Cs4PbBr6 or the CsPbBr3 phase can be obtained. The Cs4PbBr6 MCs were initially obtained by adding HBr to CsBr:PbBr2/DMSO. However, on increasing the amount of the added HBr, Cs4PbBr6 MCs were converted to CsPbBr3 MCs and the photoluminescence (PL) disappeared. It was also found that CsPbBr3 MCs can be transformed to Cs4PbBr6 MCs by simply adding DMSO to the dried CsPbBr3 MCs. The Cs4PbBr6 MCs exhibit a strong PL at 516 nm with a full width at half-maximum of 25 nm regardless of the crystal size (5–10 μm). On using Cs4PbBr6 MCs as a light converter in ultraviolet light emitting diodes, a PL intensity th...

Reduced graphene oxide (rGO) and MoS2, the most representative two-dimensional (2D) materials, are receiving significant attention for the fabrication of sensing devices owing to their high surface area, many abundant sites, and excellent mechanical flexibility. Herein, we demonstrated chemoresistive humidity sensors with fast response, excellent selectivity, and ultrahigh sensitivity based on 2D rGO and 2D MoS2 hybrid composites (RGMSs). The RGMSs were fabricated by simple ultrasonication without the addition of additives and additional heating. Compared to pristine rGO, the RGMS exhibited a 200 times higher response to humidity at room temperature. The significant enhancement in the sensing performance of the composite was attributed to electronic sensitization due to p–n heterojunction formation and porous structures between rGO and MoS2. The synergistic combination of rGO and MoS2 could be applied to construct a flexible humidity sensor. The sensing performance of an RGMS flexible device remains the same before and after bending; this indicates that the use of rGO and MoS2 is a viable new and simple strategy to realize a humidity sensor for use in wearable electronics.

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.

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.

Nanostructured bismuth (Bi) nanoflakes were designed and directly grown on Cu substrate using a novel pulse electrodeposition method. Compared with conventional bismuth film grown by direct current electrodeposition, Bi nanoflakes have large number of edge and corner sites. As it has been proven by numerical simulation, sharp edge or corner sites of the nanostructures form strong local electric fields, which boost the catalytic activity for the electrochemical reduction of CO2 in aqueous solution. The Bi nanoflakes showed a high HCOO- faradaic efficiency (FE = 79.5%) at low potential of −0.4 VRHE and achieved a maximum FE close to 100% at −0.6 VRHE, meaning that the shape control of Bi electrocatalyst is indeed an efficient way to reduce the electrical power consumption for HCOO- production. Moreover, Bi nanoflakes were stable during 10 h operation in 0.1 M KHCO3 aqueous solution. The results suggest that tailoring the nanostructure is a key in developing a high performance noble-metal-free electrocatalyst for electrochemical CO2 reduction in aqueous solution.

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 SrTiO

Chemoresistive gas sensors based on two-dimensional (2D) materials including graphene-based materials have attracted significant research interest owing to their potential use in next-generation technologies including the Internet of Things (IoT). The functionalization of 2D materials is considered as a key strategy to achieve superior gas sensing properties such as high selectivity, high sensitivity, and reversible response and recovery, because it can modulate the chemical and electrical properties of 2D materials for more efficient gas sensing. Herein, we present a facile solution process and the room temperature gas sensing properties of chemically fluorinated graphene oxide (CFGO). The CFGO sensors exhibit improved sensitivity, selectivity, and reversibility upon exposure to NH3 with a significantly low theoretical detection limit of ∼6 ppb at room temperature in comparison to NO2 sensing properties. The effect of fluorine doping on the sensing mechanism is examined by first-principles calculations based on density functional theory. The calculations reveal that the fluorine dopant changes the charge distribution on the oxygen containing functional groups in graphene oxide, resulting in the preferred selective adsorption and desorption of NH3 molecules. We believe that the remarkable NH3 sensing properties of CFGO and investigation by first-principles calculations would enlarge the possibility of functionalized 2D materials for practical gas sensing applications such as the IoT.

We synthesized transferrable and transparent anion-engineered molybdenum disulfide thin-film catalysts through a simple thermolysis method by using [(NH4)2MoS4] solution and powder precursors with different sulphur/phosphorus weight ratios. The synthesized sulphur-doped molybdenum phosphide (S:MoP) thin film changed from a two-dimensional van der Waals structure to a three-dimensional hexagonal structure by introduction of phosphorus atoms in the MoS2 thin film. The S:MoP thin film catalyst, which is composed of cheap and earth abundant elements, could provide the lowest onset potential and the highest photocurrent density for planar p-type Si photocathodes. The density functional theory calculations indicate that the surface of S:MoP thin films absorb hydrogen better than that of MoS2 thin films. The structurally engineered thin film catalyst facilitates the easy transfer of photogenerated electrons from the p-Si light absorber to the electrolyte. Anion-engineering of the MoS2 thin film catalyst would be an efficient way to enhance the catalytic activity for photoelectrochemical water splitting.

Bismuth vanadate (BiVO4) has become a hot topic for solar hydrogen generation by water oxidation due to its appropriate band edges, and narrow band gap. However, the actual conversion efficiency achieved with BiVO4-based photoanodes is considerably less than the theoretical values because of drawbacks such as poor electron transportation and slow kinetics of oxygen evolution. In these respects, formation of nanostructured heterojunctions is considered to have a marked effect in terms of improving the photoactivities of BiVO4 photoanodes since it is possible to enhance the charge transfer at the interface and increase light absorption significantly. Herein, we report the synthesis and photoelectrochemical (PEC) properties of various BiVO4-based heterojunction anodes based on stoichiometric BiVO4 by pulsed electrodeposition. We show that WO3 is the optimum bottom layer for a type II band system with BiVO4 among various metal oxides. It is revealed that the photocurrent density of bare WO3 nanorods can be changed drastically by controlling the porosity and aspect ratio and thus BiVO4/WO3 heterojunction anodes show as similar tendency to bare WO3 nanorods. Under the optimum conditions, a BiVO4/WO3 heterojunction anode can lead to a high photocurrent density of 4.55 mA/cm2 and an incident photon to current conversion efficiency of 80% at 1.23 V versus a reversible hydrogen electrode without additional catalyst. Cross-sectional transmission electron microscopy shows that dot-like BiVO4 is well decorated on the entire surface of WO3 nanorods. This systematic study provides a viewpoint on the crucial role of the active area of the bottom layer for high-performance BiVO4-based type II heterojunction photoanodes, and the proposed concept is applicable to various photoelectrode systems.

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.

WSx and MoSx nanodots are synthesized from (NH4)2WS4 and (NH4)2MoS4 precursors using a solvothermal method, and applied to organic photovoltaic cells (OPVs) and organic light emitting diodes (OLEDs) as hole injection layers (HILs). The optical band gaps of WSx and MoSx nanodots are 3.55 and 3.1 eV, respectively, and these nanodots show their strongest photoluminescence (PL) emission at 438 and 436 nm. The work functions of the nanodots increased from 4.3–4.4 to 5.0–5.1 eV following ultraviolet/ozone (UVO) treatment. By sandwiching thin layers of UVO-treated WSx and MoSx as HILs, the power conversion efficiency of OPVs dramatically increases from 1.51% to 3.0% and 2.95%, comparable to that of poly(3,4 ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) based devices (3.23%). This increased OPV efficiency is believed to come from the increased work function, large band gap, and PL properties of nanodots. The UVO-MoSx based OLED shows a higher maximum luminance efficiency (14.7 cd A−1) compared to PEDOT:PSS based devices (13.1 cd A−1). In addition, this study confirms that the stabilities of the OPV and OLEDs in air can be prolonged by using UVO-treated WSx or MoSx nanodots as HILs. These results demonstrate the great potential of synthesized WSx or MoSx nanodots for use as HILs in optoelectronic devices.

The characteristic differences between MoS2 and WS2 nanosheets and nanodots are investigated. The nanosheets were formed by liquid-phase sonication, while the nanodots were formed by breaking the nanosheets through heating the solvent ethylene glycol. The nanosheets and nanodots were approximately 0.7–2 nm thick, with slight deviation. Most of the nanosheets were longer than 100 nm, and most of the nanodots were shorter than 5 nm. As the bulk materials were transformed into nanosheets and/or nanodots, the absorption peaks and Raman peaks shifted to shorter wavelengths. Photoluminescence peaks were observed at 500 and 445 nm in the MoS2 and WS2 samples smaller than 100 nm. In the X-ray diffraction spectra, only the (002) peak was present in the nanosheets, while no peak was detected for the nanodots due to their small size. No detectable differences between the nanosheets and nanodots were observed in the transmission electron micrographs, synchrotron radiation photoemission spectra, or work function measu...

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 MoS

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.

A novel synthesis method to prepare Si3N4 nanowires from amorphous silicon nitride (a-Si3N4) powder synthesized by a low-temperature vapor-phase reaction method was investigated. Highly crystalline α-Si3N4 nanowires were synthesized by heat treatment of the a-Si3N4 powder under ammonia atmosphere. The surface of the nanowires was smooth and clean without any attached particles. The thickness of the nanowires was in the range of ∼200–300 nm with lengths of tens of micrometers. The nucleation of nanowires from the reaction between SiO and N2 occurs on the surface of the a-Si3N4 powder, which is covered by a thin layer of SiO2, and the nanowires grow from the rearrangement of Si and N atoms of the a-Si3N4 powder. The reduction of SiO2 to SiO by ammonia was promoted in the presence of a Ni catalyst; therefore, the growth was observed at a lower temperature when Ni was added to the a-Si3N4 powder than in the presence of added Fe. The growth of α-Si3N4 nanowires occurs along the [100, 101] direction and follows the vapor–solid–solid mechanism.

We demonstrate that wafer-scale, transferable, and transparent thin-film catalysts based on MoS2, which consists of cheap and earth abundant elements, can provide a low onset potential of 1 mA cm−2 at 0.17 V versus a reversible hydrogen electrode and the high photocurrent density of 24.6 mA cm−2 at 0 V for a p-type Si photocathode. c-Domains with vertically stacked (100) planes in the transferable 2H-MoS2 thin films, which are grown via a thermolysis method, act as active sites for the hydrogen evolution reaction, and photogenerated electrons are efficiently transported through the n-MoS2/p-Si heterojunction.

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 ef...

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 (BiVO

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.

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. Electronic supplementary material The online version of this article (doi:10.1186/s11671-016-1437-2) contains supplementary material, which is available to authorized users.

The band edge positions of semiconductors determine functionality in solar water splitting. In article number https://doi.org/10.1002/advs.201800727, Ki Tae Nam, Ho Won Jang, and co‐workers demonstrate cascade photoanodes with ligand engineered manganese oxide co‐catalyst nanoparticles to achieve enhanced photoelectrochemical performance. The proposed concept has considerable potential to explore a new efficient solar water splitting system.

J–V curves for four different ZnO electrodes with different dye and solution combination in 2 h sensitizing time. Figure S2. (a) J–V curves of DSSCs fabricated with nanostructured ZnO photoanodes as a function of dye adsorption time at 50 °C (all films were deposited under 300 mTorr and the thicknesses of all films were fixed to be 6.7 μm) and (b) as function of sample aging after fabrication. Table S1. Device parameters of dye-sensitized ZnO nanostructured photoanodes under simulated AM 1.5 G light illumination (a) as a function of dye adsorption time at 50 °C (the thicknesses of the films were fixed to be 6.7 μm) and (b) as function of sample aging after fabrication. Table S2. Dye loading of DSSCs fabricated with nanostructured ZnO photoanodes deposited under different ambient oxygen pressures. The thickness of the photoanodes was fixed to be 10 μm. Table S3. Statistical analysis of device parameters for five different DSSCs fabricated with nanostructured ZnO photoanodes deposited by PLD using the optimized condition. Figure S3. J–V curves of five different DSSCs fabricated with nanostructured ZnO photoanodes deposited by PLD using the optimized condition. Figure S4. The incident photon-to-current conversion efficiency (IPCE) spectrum of a DSSC with a nanostructured ZnO photoanode deposited under 300 mTorr by PLD. Figure S5. J–V curves of 300 mTorr 5-μm ZnO photoanodes deposited by PLD using PLD coupled with Pt/ITO/PEN flexible substrate. (DOCX 226 kb)

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.