Oxygen Vacancies In Grain Boundaries Research Articles

Controllable Distribution of Oxygen Vacancies in Grain Boundaries of p‐Si/TiO2 Heterojunction Photocathodes for Solar Water Splitting

AbstractSilicon is a promising photocathode material in photoelectrochemical water splitting for hydrogen production, but it is primarily limited by photocorrosion in aqueous electrolytes. As an extensively used protective material, crystalline TiO2 could protect Si photoelectrode against corrosion. However, a large number of grain boundaries (GBs) in polycrystalline TiO2 would induce excessive recombination centers, impeding the carrier transport. This paper describes the introduction of oxygen vacancies (Ovac) with controllable spatial distribution for GBs to promote carrier transport. Two kinds of Ovac distribution, Ovac along GBs and Ovac inside grains, are compared, where the latter one is demonstrated to facilitate carrier transport owing to the formation of tunneling paths across GBs. Consequently, a simple p‐Si/TiO2/Pt heterojunction photocathode with controllable Ovac distribution in TiO2 shows a +400 mV onset potential shift and yields an applied bias photon‐to‐current efficiency of 5.9 %, which is the best efficiency reported among silicon photocathodes except for silicon homojunction.

Controllable Distribution of Oxygen Vacancies in Grain Boundaries of p-Si/TiO2 Heterojunction Photocathodes for Solar Water Splitting.

Silicon is a promising photocathode material in photoelectrochemical water splitting for hydrogen production, but it is primarily limited by photocorrosion in aqueous electrolytes. As an extensively used protective material, crystalline TiO2 could protect Si photoelectrode against corrosion. However, a large number of grain boundaries (GBs) in polycrystalline TiO2 would induce excessive recombination centers, impeding the carrier transport. This paper describes the introduction of oxygen vacancies (Ovac ) with controllable spatial distribution for GBs to promote carrier transport. Two kinds of Ovac distribution, Ovac along GBs and Ovac inside grains, are compared, where the latter one is demonstrated to facilitate carrier transport owing to the formation of tunneling paths across GBs. Consequently, a simple p-Si/TiO2 /Pt heterojunction photocathode with controllable Ovac distribution in TiO2 shows a +400 mV onset potential shift and yields an applied bias photon-to-current efficiency of 5.9 %, which is the best efficiency reported among silicon photocathodes except for silicon homojunction.

Band engineering via grain boundary defect states for large scale tuning of photoconductivity in Bi1−xCaxFe1−yTiyO3−δ

Spark plasma sintered Bi1−xCaxFe1−yTiyO3−δ (BCFTO) (x = y = 0.05 and 0.1) nanoparticle ceramics are studied for photoconductivity properties. As-prepared (AP) BCFTO hosts a large concentration of grain boundary (GB) oxygen vacancies (OV), whereas air annealed (AA) BCFTO have significantly suppressed GB OV. X-ray absorption near edge spectroscopy study confirms that Fe and Ti remain in 3+ and 4+ oxidation states, respectively. Thus, lattice OV created when only Ca2+ is substituted in BiFeO3 are charge compensated in Ca and Ti codoped BiFeO3. This ascertains that BCFTO is devoid of lattice OV. Photoconductivity studies show four orders of more photocurrent arising from GB OV contributions in BCFTO-AP compared to that in BCFTO-AA samples. A large increase in the activation energy for the AA samples (0.4 eV to 1.6 eV) compared to that for the AP samples (0.06 eV to 0.5 eV) is obtained from ln ω vs 1/T Arrhenius plots. This further substantiates the suppression of GB OV resulting in poor photoconductivity. Diffuse band edges observed in Kubelka-Munk plots of BCFTO-AP samples are a consequence of OV defect states occupying the bulk bandgap. In the absence of OV defect states, band edge becomes sharper. Density functional theory (DFT) calculations further support the experimental observations. DFT study shows that the presence of Ca and Ti does not enhance the photocurrent as these codopants do not produce mid-bandgap states. The mid-bandgap defect states are attributed only to the unsaturated bonds and OV at the GB in BCFTO. These studies manifest a critical role of OV residing at the GB in tuning the photoconductivity and, hence, the photoresponse of BCFTO.

Reactive Element Effects in High-Temperature Alloys Disentangled

Reactive elements—REs—are decisive for the longevity of high-temperature alloys. This work joins several previous efforts to disentangle various RE effects in order to explain apparently contradicting experimental observations in alumina forming alloys. At 800–1000 °C, “messy” aluminum oxy-hydroxy-hydride transients initially formed due to oxidation by H2O which in turn undergo secondary oxidation by O2. The formation of the transient oxide becomes supported by dispersed RE oxide particles acting as water equivalents. At higher temperatures, electron conductivity in impurity states owing to oxygen vacancies in grain boundaries (GBs) becomes increasingly relevant. These channels are subsequently closed by REs pinning the said vacancies. The universality of the emerging understanding is supported by a comparative first-principles study by means of density functional theory addressing RE(III): Sc2O3, Y2O3, and La2O3, and RE(IV): TiO2, ZrO2, and HfO2, that upon reaction with water, co-decorate a generic GB model by hydroxide and RE ions. At 100% RE coverage, the GB model becomes relevant at both temperature regimes. Based on reaction enthalpy ΔHr considerations, “messy” aluminum oxy-hydroxy-hydride transients are accessed in both classes. Larger variations in ΔHr are found for RE(III)-decorated alumina GBs as compared to RE(IV). For RE(III), correlation with GB width is found, increasing with increased ionic radius. Similarly, upon varying RE(IV), minor changes in stability correlate with minor structural variations. GB decorations by Ce(III) and Ce(IV) further consolidate the emerging understanding. The findings are used to discuss experimental observations that include impact of co-doping by RE(III) and RE(IV).

Resistance switching in polycrystalline BiFeO3 thin films

We report resistance switching effects in polycrystalline pure BiFeO3 films prepared by a sol-gel method. By current-voltage and conductive atomic force microscope (c-AFM) measurements, resistance switching effects are observed in BiFeO3 films annealed at and above 650 °C. A fresh sample can be transformed into a low-resistive state by applying a high positive voltage without forming process and then be switched to a high-resistive state by applying a negative voltage. Both c-AFM and retention results suggest that the redistribution of oxygen vacancies in grain boundaries could play a key role on the resistance switching in the polycrystalline pure BiFeO3 films.