ABSTRACT
The chemical and local structures of vanadium oxide (VO x ) thin films prepared by atomic layer deposition (ALD) were investigated by soft X-ray absorption spectroscopy. It is shown that the as-deposited film was a mixture of VO2 and V2O5 in disordered form, while the chemistry changed significantly after heat treatment, subject to the different gas environment. Forming gas (95% N2 + 5% H2) annealing resulted in a VO2 composition, consisting mostly of the VO2 (B) phase with small amount of the VO2 (M) phase, whereas O2 annealing resulted in the V2O5 phase. An X-ray circular magnetic dichroism study further revealed the absence of ferromagnetic ordering, confirming the absence of oxygen vacancies despite the reduction of V ions in VO2 (V4+) with respect to the precursor used in the ALD (V5+). This implies that the prevalence of VO2 in the ALD films cannot be attributed to a simple oxygen-deficiency-related reduction scheme but should be explained by the metastability of the local VO2 structures.
ABSTRACT
Atomic layer deposition was adopted to deposit VOx thin films using vanadyl tri-isopropoxide {VO[O(C3H7)]3, VTIP} and water (H2O) at 135 °C. The self-limiting and purge-time-dependent growth behaviors were studied by ex situ ellipsometry to determine the saturated growth conditions for atomic-layer-deposited VOx. The as-deposited films were found to be amorphous. The structural, chemical, and optical properties of the crystalline thin films with controlled phase formation were investigated after postdeposition annealing at various atmospheres and temperatures. Reducing and oxidizing atmospheres enabled the formation of pure VO2 and V2O5 phases, respectively. The possible band structures of the crystalline VO2 and V2O5 thin films were established. Furthermore, an electrochemical response and a voltage-induced insulator-to-metal transition in the vertical metal-vanadium oxide-metal device structure were observed for V2O5 and VO2 films, respectively.
ABSTRACT
Inverse opal (IO) films of tin dioxide (SnO2) were fabricated on polystyrene (PS) beads (diameter=350 nm (±20 nm) with a spin coating method. To compensate for the large band gap (Eg=3.8 eV), a thin TiO2 shell was deposited on the SnO2-IO films with atomic layer deposition (ALD), which produced shells with thicknesses of 10-40 nm. The morphological changes and crystalline properties of the SnO2 and TiO2-coated SnO2 (herein after referred to as TiO2/SnO2) IO films were investigated with field-emission scanning electron microscopy and X-ray diffraction, respectively. The photoelectrochemical (PEC) behavior of the samples was tested in a 0.1 M KOH solution under 1 sun illumination (100 mW/cm2 with an AM 1.5 filter). The highest PEC performance was obtained with the TiO2(10 nm)/SnO2 IO films, which produced a photocurrent density (Jsc) of 4.67 mA/cm2 at 0.5 V (vs NHE) and was sequentially followed by the TiO2(20 nm)/SnO2-IO, TiO2(30 nm)/SnO2-IO, TiO2 (40 nm)/SnO2-IO and SnO2 IO films. Overall, the thin TiO2 shell covered on the SnO2-IO core enhanced Jsc by 3 orders of magnitude, which in turn the PEC activity. This is mainly ascribed to the extremely low charge-transfer resistance (Rct) in the photoelectrode/electrolyte and at the TiO2/SnO2 interface, as well as the contribution of the photoactive TiO2 layer, which has an Eg of 3.2 eV. Moreover, to improve the electrical conductivity of the core SnO2 IO film, the films were doped with 10 mol % of F. The F- doped films were labeled as the FTO IO film. The Rct of the FTO-IO films decreased because of the improved electronic conductivity, enhancing the PEC performance of the TiO2(10 nm)/FTO-IO films by approximately 20%. The core-shell nanowire mesh nanoarchitecture is therefore suggested to provide an insight for designing the peculiar structure based on the material's properties and the engineering of their band gap energy for highly efficient PEC performance.
