Project description:The role of epitaxial strain and chemical termination in selected interfaces of perovskite oxide heterostructures is under intensive investigation because of emerging novel electronic properties. SrTiO 3 (STO) is one of the most used substrates for these compounds, and along its < 001 > direction allows for two nonpolar chemical terminations: TiO2 and SrO. In this paper, we investigate the surface morphology and crystal structure of SrO epitaxial ultrathin films: from 1 to about 25 layers grown onto TiO 2 -terminated STO substrates. X-ray diffraction and transmission electron microscopy analysis reveal that SrO grows along its [ 111 ] direction with a 4% out-of-plane elongation. This large strain may underlay the mechanism of the formation of self-organized pattern of stripes that we observed in the initial growth. We found that the distance between the TiO 2 plane and the first deposited SrO layer is 0.27 ( 3 ) nm, a value which is about 40% bigger than in the STO bulk. We demonstrate that a single SrO-deposited layer has a different morphology compared to an ideal atomically flat chemical termination.
Project description:A BiVO4 photoanode with exposed (040) facets was prepared to enhance its photoelectrochemical performance. The exposure of the (040) crystal planes of the BiVO4 film was induced by adding NaCl to the precursor solution. The as-prepared BiVO4 photoanode exhibits higher solar-light absorption and charge-separation efficiency compared to those of an anode prepared without adding NaCl. To our knowledge, the photocurrent density (1.26 mA cm-2 at 1.23 V vs. RHE) of as-prepared BiVO4 photoanode is the highest according to the reports for bare BiVO4 films under simulated AM1.5G solar light, and the incident photon-to-current conversion efficiency is above 35% at 400 nm. The photoelectrochemical (PEC) water-splitting performance was also dramatically improved with a hydrogen evolution rate of 9.11 μmol cm-2 h-1, which is five times compared with the BiVO4 photoanode prepared without NaCl (1.82 μmol cm-2 h-1). Intensity-modulated photocurrent spectroscopy and transient photocurrent measurements show a higher charge-carrier-transfer rate for this photoanode. These results demonstrate a promising approach for the development of high-performance BiVO4 photoanodes which can be used for efficient PEC water splitting and degradation of organic pollutants.
Project description:The operation of oxide-based memristive devices relies on the fast accumulation and depletion of oxygen vacancies by an electric field close to the metal-oxide interface. Here, we show that the reversible change of the local concentration of oxygen vacancies at this interface also produces a change in the thermal boundary resistance (TBR), i.e., a thermal resistive switching effect. We used frequency domain thermoreflectance to monitor the interfacial metal-oxide TBR in (Pt,Cr)/SrTiO3 devices, showing a change of ≈20% under usual SET/RESET operation voltages, depending on the structure of the device. Time-dependent thermal relaxation experiments suggest ionic rearrangement along the whole area of the metal/oxide interface, apart from the ionic filament responsible for the electrical conductivity switching. The experiments presented in this work provide valuable knowledge about oxide ion dynamics in redox-based memristive devices.
Project description:Constructing heterojunction is an attractive strategy for promoting photoelectrochemical (PEC) performance in water splitting and organic pollutant degradation. Herein, a novel porous BiVO4/Boron-doped Diamond (BiVO4/BDD) heterojunction photoanode containing masses of ultra-micro electrodes was successfully fabricated with an n-type BiVO4 film coated on a p-type BDD substrate by magnetron sputtering (MS). The surface structures of BiVO4 could be adjusted by changing the duration of deposition (Td). The morphologies, phase structures, electronic structures, and chemical compositions of the photoanodes were systematically characterized and analyzed. The best PEC activity with the highest current density of 1.8 mA/cm2 at 1.23 VRHE was achieved when Td was 30 min, and the sample showed the highest degradation efficiency towards tetracycline hydrochloride degradation (TCH) as well. The enhanced PEC performance was ascribed to the excellent charge transport efficiency as well as a lower carrier recombination rate, which benefited from the formation of BiVO4/BDD ultra-micro p-n heterojunction photoelectrodes and the porous structures of BiVO4. These novel photoanodes were expected to be employed in the practical PEC applications of energy regeneration and environmental management in the future.
Project description:SrTiO3 is of particular interest for numerous applications such as photocatalytic water splitting, as an electrode material for thermoelectrics or as piezoceramics for sensors. Here we report on an advanced CO2 laser vaporization (LAVA) method for the production of faceted, single-phase SrTiO3 nanoparticles with an average particle size of 35 nm. Starting from a coarse SrTiO3 raw powder, spherical SrTiO3 nanoparticles were obtained by a laser-induced gas-phase condensation process. The composition of the nanoparticles corresponds to that of the starting powder, as XRD and FT-IR measurements show. Further hydrothermal treatment at 275 °C for 4 hours leads to the formation of faceted nanocubes with increasing crystallite size, as demonstrated by TEM, HR-TEM and XRD measurements. During a final washing step in 0.1 M HCl, SrCO3 impurities were dissolved and thus single-phase SrTiO3 nanocubes were successfully obtained, as shown by FT-IR, XRD and TEM analyses. The presented process facilitates the production of single-phase, highly crystalline SrTiO3 nanopowders in sufficient quantities for subsequent use in a variety of applications, in particular for hydrogen production by photocatalytic water splitting.
Project description:Addressing the intrinsic charge transport limitation of metal oxides has been of significance for pursuing viable PEC water splitting photoelectrodes. Growing a photoelectrode with conductive nanoobjects embedded in the matrix is promising for enhanced charge transport but remains a challenge technically. We herein show a strategy of embedding laser generated nanocrystals in BiVO4 photoanode matrix, which achieves photocurrent densities of up to 5.15 mA cm-2 at 1.23 VRHE (from original 4.01 mA cm-2) for a single photoanode configuration, and 6.22 mA cm-2 at 1.23 VRHE for a dual configuration. The enhanced performance by such embedding is found universal owing to the typical features of laser synthesis and processing of colloids (LSPC) for producing ligand free nanocrystals in desired solvents. This study provides an alternative to address the slow bulk charge transport that bothers most metal oxides, and thus is significant for boosting their PEC water splitting performance.
Project description:A silver/titanium dioxide nanoplate (Ag/TiO2 NP) photoelectrode was designed and fabricated from vertically aligned TiO2 nanoplates (NP) decorated with silver nanoparticles (NPs) through a simple hydrothermal synthesis and electrodeposition route. The electrodeposition times of Ag NPs on the TiO2 NP were crucial for surface plasmon-driven photoelectrochemical (PEC) water splitting performance. The Ag/TiO2 NP at the optimal deposition time of 5 min with a Ag element content of 0.53 wt% demonstrated a remarkably high photocurrent density of 0.35 mA cm-2 at 1.23 V vs. RHE under AM 1.5G illumination, which was 5 fold higher than that of the pristine TiO2 NP. It was clear that the enhanced light absorption properties and PEC performance for Ag/TiO2 NP could be effectively adjusted by simply controlling the loading amounts of metallic Ag NPs (average size of 10-30 nm) at different electrodeposition times. The superior PEC performance of the Ag/TiO2 NP photoanode was attributed to the synergistic effects of the plasmonic Ag NPs and the TiO2 nanoplate. Interestingly, the plasmonic effect of Ag NPs not only increased the visible-light response (λ max = 570 nm) of TiO2 but also provided hot electrons to promote photocurrent generation and suppress charge recombination. Importantly, this study offers a potentially efficient strategy for the design and fabrication of a new type of TiO2 hybrid nanostructure with a plasmonic enhancement for PEC water splitting.
Project description:Constructing heterojunctions by coupling dissimilar semiconductors is a promising approach to boost charge separation and charge transfer in photoelectrochemical (PEC) water splitting. In this work, we fabricated a highly efficient TiO2/BiVO4 heterojunction photoanode for PEC water oxidation via a simple hydrothermal method. The resulting heterojunction photoanodes show enhanced PEC performance compared to the bare BiVO4 due to the simultaneous improvements in charge separation and charge transfer. Under simulated sunlight illumination (AM 1.5G, 100 mW cm-2), a high photocurrent of 3.3 mA cm-2 was obtained at 1.23 V (vs. the reversible hydrogen electrode (RHE)) in a neutral solution, which exceeds those attained by the previously reported TiO2/BiVO4 heterojunctions. When a molecular Co-cubane catalyst was immobilized onto the electrode, the performance of the TiO2/BiVO4 heterojunction photoanode can be further improved, achieving a higher photocurrent density of 4.6 mA cm-2 at 1.23 V, an almost three-fold enhancement over that of the bare BiVO4. These results engender a promising route to designing an efficient photoelectrode for PEC water splitting.
Project description:Chromium-doped Ga2O3, with intense Cr3+-related red-infrared light emission, is a promising semiconductor material for optical sensors. This work constitutes a comprehensive study of the thermoluminescence properties of Cr-, Mg-codoped β-Ga2O3 single crystals, both prior to and after proton irradiation. The thermoluminescence investigation includes a thorough analysis of measurements with different β- irradiation doses used to populate the trap levels, with preheating steps to disentangle overlapping peaks (TM-TSTOP and initial rise methods) and finally by computationally fitting to a theoretical expression. At least three traps with activation energies of 0.84, 1.0, and 1.1 eV were detected. By comparison with literature reports, they can be assigned to different defect complexes involving oxygen vacancies and/or common contaminants/dopants. Interestingly, the thermoluminescence signal is enhanced by the proton irradiation while the type of traps is maintained. Finally, the pristine glow curve was recovered on the irradiated samples after an annealing step at 923 K for 10 s. These results contribute to a better understanding of the defect levels in Cr-, Mg-codoped β-Ga2O3 and show that electrons released from these traps lead to Cr3+-related light emission that can be exploited in dosimetry applications.
Project description:Well-aligned TiO2 nanotube arrays have become of increasing significance because of their unique highly ordered array structure, high specific surface area, unidirectional charge transfer and transportation features. However, their poor visible light utilization as well as the high recombination rate of photoexcited electron-hole pairs greatly limited their practical applications. Herein, we demonstrate the fabrication of visible-light-responsive heterostructured Cr-doped SrTiO3/TiO2 nanotube arrays by a simple hydrothermal method, which facilitate efficient charge separation and thus improve the photoelectrochemical as well as photocatalytic performances.