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Bismuth vanadate (BiVO4) has emerged as a highly prospective material for photoanodes in photoelectrochemical (PEC) water oxidation. However, current limitations with this material lie in the difficulties in producing stable and continuous BiVO4 layers with efficient carrier transfer kinetics, thereby impeding its widespread application in water splitting processes. This study introduces a new fabrication approach that yields continuous, monoclinic nanostructured BiVO4 films, paving the way for their use as photoanodes in efficient PEC water oxidation for hydrogen production under solar light conditions. The fabrication involves the intercalation of vanadium (V) ions into Bi2O3 films at 450oC. Upon interaction with V ions, the film undergoes a transformation from tetragonal Bi2O3 to monoclinic scheelite BiVO4. This synthesis method enables the fabrication of single monoclinic phase BiVO4 films with thicknesses up to 270 nm. The engineered monoclinic BiVO4 film, devoid of any pinholes that could cause carrier loss, exhibits a robust photocurrent of 1.0 mA/cm2 at 1.23 VRHE in a neutral electrolyte, without requiring additional modifications or doping. Moreover, we demonstrate that the incorporation of a cobalt phosphate (Co-Pi) co-catalyst into the BiVO4 photoanode significantly enhances the lifetime of photogenerated holes by a factor of nine, resulting in a further elevation of the photocurrent to 2.9 mA/cm2. This remarkable PEC enhancement can be attributed to the surface state passivation by the Co-Pi co-catalyst. Our fabrication approach opens up a new facile route for producing large-scale, highly efficient BiVO4 photoanodes for PEC water splitting technology.

The effects of hydrogen incorporation into beta-Ga2O3 thin films have been investigated by chemical, electrical and optical characterization techniques. Hydrogen incorporation was achieved by remote plasma doping without any structural alterations of the film; however, X-ray photoemission reveals major changes in the oxygen chemical environment. Depth-resolved cathodoluminescence (CL) reveals that the near-surface region of the H-doped Ga2O3 film exhibits a distinct red luminescence (RL) band at 1.9 eV. The emergence of the H-related RL band is accompanied by an enhancement in the electrical conductivity of the film by an order of magnitude. Temperature-resolved CL points to the formation of abundant H-related donors with a binding energy of 28 +/- 4 meV. The RL emission is attributed to shallow donor-deep acceptor pair recombination, where the acceptor is a VGa-H complex and the shallow donor is interstitial H. The binding energy of the VGa-H complex, based on our experimental considerations, is consistent with the computational results by Varley et al [J. Phys.: Condens. Matter, 23, 334212, 2011]., Comment: 3 figures

Large reflection losses at interfaces in light emitting semiconductor devices cause a significant reduction in their light emission and energy efficiencies. Metal nanoparticle (NP) surface coatings have been demonstrated to increase the light extraction efficiency from planar high refractive index semiconductor surfaces. This emission enhancement in Au NP-coated ZnO is widely attributed to involvement of a green (~ 2.5 eV) deep level ZnO defect exciting localized surface plasmons in the NPs that non-radiatively decay into hot electrons, which return to ZnO and radiatively recombine. In this work, we achieve a 6 times enhancement of the ultra-violet excitonic emission in ZnO nanorods that are coated with 5 nm Au NPs without the aid of ZnO defects. Cathodoluminescence (CL), photoluminescence (PL) and a novel concurrent CL-PL technique as well as time resolved PL spectroscopy revealed that the increase in UV emission is due to the formation of an additional fast excitonic relaxation pathway that increases the exciton spontaneous emission rate. Concurrent CL-PL measurements ruled out the presence of charge transfer mechanism in the emission enhancement process. While time resolved PL results confirmed the existence of a new excitonic recombination channel that is attributed to exciton relaxation via the plasmon-assisted excitation of rapid non-radiative Au interband transitions. Our results establish that ZnO defect levels ~ 2.5 eV are not required to facilitate Au NP induced enhancement of the ZnO UV emission.

The UV enhancement of Al-coated ZnO single crystals with a wide range of carrier densities is systematically studied using depth-resolved cathodoluminescence (CL) and photoluminescence (PL) as well as valence band X-ray photoemission spectroscopy (VB-XPS). AN up to 17-fold enhanced PL UV emission for Al-coated ZnO with the highest carrier density (2 x 10^17 cm^-3) was measured, which falls to a 12-fold increase for the lowest carrier density (3 x 10^13 cm^-3). Depth-resolved CL measurements confirm that the enhancement is strongest near the metal coating-ZnO interface consistent with an increased UV emission due to an exciton-localized surface plasmon coupling mechanism. Correlative CL, PL and VB-XPS studies reveal that a number of additional effects to the presence of the Al surface coating also contribute to the UV enhancement factor. These include increased UV enhancement due to the formation of a surface depletion layer induced by the metal surface coating, which also passivates competitive non-radiative surface recombination channels found in uncoated ZnO. Significantly, it was established that the magnitude of the emission enhancement factor can be raised in a controlled way by reducing the thickness of the depletion layer by increasing the carrier density. The contribution of these effects collectively provides an explanation for the large span of enhancement factors reported in the literature., Comment: 22 pages, 10 figures

Metal nanoparticle (NP) surface coatings are known to significantly enhance the ultra-violet luminescence intensity of ZnO. Although there is general agreement that resonantly excited Localized Surface Plasmons (LSPs) in metal NPs can directly couple to excitons in the semiconductor increasing their spontaneous emission rate, the exact mechanisms involved in this phenomenon are currently not fully understood. In this work, LSP-exciton coupling in a ZnO single crystal and ZnO nanorods coated with a 2 nm Al layer has been investigated using correlative photoluminescence and depth-resolved cathodoluminescence and time-resolved photoluminescence spectroscopy. Temperature-resolved cathodoluminescence and photoluminescence measurements from 10 K to 250 K show enhancement factors up to 12 times of the free exciton (FX) emission at 80 K. The FX couple more efficiently to the LSPs in Al compared to the localized donor-bound excitons. Furthermore, a strong polarization dependence of the LSPs with respect to the FX was observed with higher enhanced FX transitions polarized in the same direction as the electric field of the incident excitation. These results indicate that selective enhancement of the ultra-violet excitonic PL in ZnO can be achieved by careful alignment of the crystallographic axes of the ZnO relative to the electric vector of the excitation source., Comment: 20 pages, 9 figures

New insights into controlling nanowire merging phenomena are demonstrated in growth of thin ZnO nanowires using monodispersed Au colloidal nanoparticles as catalyst. Both nanowire diameter and density were found to be strongly dependent on the density of Au nanoparticles. Structural analysis and spectral cathodoluminescence imaging of the c-plane nanowire cross-sections reveal that thin isolated nanowires growing from the Au nanoparticles begin to merge and coalesce with neighbouring nanowires to form larger nanowires when their separation reaches a threshold distance. Green luminescence, which is originated from the remnants of constituent nanowires before merging, is detected at the core of fused nanowires. The distribution of nanowire diameters and green emission were found to be strongly dependent on the density of the Au nanoparticles. The merging phenomenon is attributed to electrostatic interactions between nanowire c-facets during growth and well-described by a cantilever bending model.

Single photon sources are required for a wide range of applications in quantum information science, quantum cryptography and quantum communications. However, so far majority of room temperature emitters are only excited optically, which limits their proper integration into scalable devices. In this work, we overcome this limitation and present room temperature electrically triggered light emission from localized defects in zinc oxide (ZnO) nanoparticles and thin films. The devices emit at the red spectral range and show excellent rectifying behavior. The emission is stable over an extensive period of time, providing an important prerequisite for practical devices. Our results open up possibilities to build new ZnO based quantum integrated devices that incorporate solid-state single photon sources for quantum information technologies.

Room temperature single photon emitters are very important resources for photonics and emerging quantum technologies. In this work we study single photon emission from defect centers in 20 nm zinc oxide (ZnO) nanoparticles. The emitters exhibit bright broadband fluorescence in the red spectral range centered at 640 nm with polarized excitation and emission. The studied emitters showed continuous blinking, however, bleaching can be suppressed using a polymethyl methacrylate (PMMA) coating. Furthermore, hydrogen termination increased the density of single photon emitters. Our results will contribute to the identification of quantum systems in ZnO.