Monolithically-integrated BiVO4/p+-n GaAs1-xPx tandem photoanodes capable of unassisted solar water splitting

Monolithically-integrated tandem photoanodes were fabricated on substrates consisting of epitaxial n-GaAs_1-xP_x (x ? 0.32) grown on n⁺-GaAs wafers. A p⁺-n junction photovoltaic (PV) cell was first formed by zinc diffusion into the n-GaAs_0.68P_0.32 from a deposited ZnO coating. After diffusion the ZnO serves as a transparent electrical contact to the resulting p⁺-GaAs_0.68P_0.32 surface layer. Transparent, conducting SnO₂:F provides chemical and mechanical protection for the ZnO and the underlying PV cell, and it electrically connects this cell to a top BiVO₄ photocatalyst layer. In some photoanodes, a WO₃ thin film was interposed between the SnO₂:F and BiVO₄. All oxide coatings were produced by ultrasonic spray pyrolysis except WO₃, which was spin coated. Unassisted (unbiased) solar water splitting was achieved, with a solar-to-hydrogen efficiency approaching 2%, without addition of any co-catalyst to the BiVO₄ surface. This work can provide insights to other researchers regarding scalable, low cost approaches for the planar monolithic integration of oxide photoanode materials with PV cells to create new tandem devices.     

用于钙钛矿太阳能电池光阳极的TiO2/ZnTiO3复合物的制备与性能

利用溶胶-凝胶法制备一系列不同Zn/Ti物质的量比的TiO_2/ZnTiO_3复合粉体,并借助XRD分析粉末的晶体结构。将复合粉末制备成膜作为钙钛矿太阳能电池的光阳极,通过SEM表征复合膜的表面形貌,并对所组装电池的性能进行测试。结果显示,Zn/Ti物质的量比对电池的性能有很大影响,当n(Zn)∶n(Ti)=1∶6时,组装的太阳能电池光电转换效率最好。     

染料敏化太阳能电池TiO2光阳极的最新研究进展

纳米TiO_2是目前性能最为优良的染料敏化太阳能电池(DSSC)光阳极材料。结合近年来太阳能电池中TiO_2光阳极的研究进展,简述了TiO_2光阳极的制备方法,详细论述了其结构和材料方面(离子/元素掺杂、复合材料和表面处理)的优化及其敏化,并对其发展及应用前景进行了展望。     

High-efficiency photoelectrochemical water splitting with heterojunction photoanode of In2O3-x nanorods/black Ti–Si–O nanotubes

Constructing heterojunction was an efficient way to promote photoelectrochemical (PEC) water splitting performance of TiO₂-based nano-photoanode. In this work, we demonstrated the feasible preparation of oxygen vacancies-induced In₂O₃ (In₂O_3-x) nanorods/black Si-doped TiO₂ (Ti–Si–O) nanotubes heterojunction photoanode for enhanced PEC water splitting. Black Ti–Si–O nanotubes were fabricated through Zn reduction of the as-annealed Ti–Si–O nanotubes, followed by In₂O_3-x nanorods coupling by a facile electrodepositing and Ar heat treatment. Solar to hydrogen conversion efficiency of the heterojunction photoanode reached as high as 1.96%, which was almost 10 times that of undoped TiO₂. The improved PEC properties were mainly attributed to co-doping effects of Si and Ti³⁺/oxygen vacancy as well as In₂O_3-x decoration, which resulted in enhanced optical absorption and facilitated separation-transport process of photogenerated charge carriers. Charge transfer process in the composite system and hydrogen production mechanism were proposed. This work will facilitate designing TiO₂-based nano-photoanodes for promoting water splitting by integrating with elements doping, oxygen vacancies self-doping and semiconductors coupling.     

Construction of BiVO4 nanosheets@WO3 arrays heterojunction photoanodes by versatile phase transformation strategy

A versatile phase transformation strategy was proposed to synthesize novel BiVO₄ nanosheets (NSs)@WO₃ nanorod (NR) and nanoplate (NP) arrays films. The strategy was carried out by following a three-step hydrothermal process (WO₃→WO₃/Bi₂WO₆→WO₃/BiVO₄). According to the characterization results, plenty of BiVO₄ NSs grew well on the surface of WO₃ NR and NP arrays films, thus forming the WO₃/BiVO₄ heterojunction structure. The prepared WO₃/BiVO₄ heterojunction films were used as the photoanodes for the photoelectrochemical (PEC) water splitting. As indicated by the results, the photoanodes exhibited an excellent PEC activity. The photocurrent densities of the WO₃/BiVO₄ NR and NP photoanodes at 1.23 V (vs RHE) without cocatalyst under visible light illumination reached up to about 1.56 and 1.20 mA/cm^brespectively.     

Photoelectrochemical decomposition of bio-related compounds at a nanoporous semiconductor film photoanode and their photocurrent-photovoltage characteristics

Photoelectrochemical decomposition of bio-related compounds such as amino acids was investigated with a biophotochemical cell comprising a mesoporous TiO₂ thin film photoanode and an O₂-reducing cathode. It was concluded that a kind of Schottky junction formed at the surface of the TiO₂ (called as liquid junction) induced the photodecomposition followed by generation of photocurrent/photovoltage. Complete photodecomposition was investigated by the CO₂ formation yield. The photocurrent-photovoltage (J-V) characteristics of amino acids and other typical bio-related compounds were investigated, and the short circuit photocurrent (J_sc), open circuit photovoltage (V_oc), and Fill factor (ff) were exhibited. Effect of pH on the photodecomposition of phenylalanine and cysteine were studied; for cysteine alkaline conditions gave a high efficiency, which was interpreted by the high electron-donating ability of the dissociated -S⁻ group. The incident light-to-current conversion efficiency (IPCE) of cysteine was 25% at 350 nm. It was for the first time shown that organic acids gave high internal quantum efficiency (η′) over 8 (=800%) in the photodecomposition; for oxalic acid it was 9.3 (=930%) and for butyric acid 8.2. The alternating current impedance spectroscopy of glycine showed that the cell performance is determined by the chemical reactions at TiO₂ or Pt electrodes.     

The preparation of titania nanotubes and its application in flexible dye-sensitized solar cells

Anatase titania nanotube (TNT) is prepared by two-steps hydrothermal growth method. Using the TNTs and titania particles (P25), a highly stable and uniform titania colloid without any sedimentation in 180 days is prepared by hydrothermal treatment. Based on the titania colloid, a flexible dye-sensitized solar cell (DSSC) is fabricated at low temperature. The influence of preparation conditions on the properties of TNTs and titania colloid is discussed by transmitting electron microscopy, scanning electron microscopy, selected area electron diffraction, X-ray diffraction, UV-vis absorption spectra, and Brunauer-Emmet-Teller surface area measurements. Under an optimized condition, a flexible DSSC with light-to-electric energy conversion efficiency of 4.0% is achieved under a simulated solar light irradiation of 100 mW cm⁻² (AM 1.5).     

Activating ZnO nanorod photoanodes in visible light by Cu ion implantation

Utilization of visible light is of crucial importance for exploiting efficient semiconductor catalysts for solar water splitting. In this study, an advanced ion implantation method was utilized to dope Cu ions into ZnO nanorod arrays for photoelectrochemical water splitting in visible light. X-ray diffraction （XRD） and X-ray photo-electron spectroscopy （XPS） results revealed that Cu^＋ together with a small amount of Cu^2＋ were highly dispersed within the ZnO nanorod arrays. The Cu ion doped ZnO nanorod arrays displayed extended optical absorption and enhanced photoelectrochemical performance under visible light illumination （A 〉 420 nm）. A considerable photocurrent density of 18 μA/cm^2 at 0.8 V （vs. a saturated calomel electrode） was achieved, which was about 11 times higher than that of undoped ZnO nanorod arrays. This study proposes that ion implantation could be an effective approach for developing novel visible-light-driven photocatalytic materials for water splitting.     

Progress in light harvesting and charge injection of dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) based on nanocrystalline semiconductors such as TiO₂ are of great interest as an alternative to the conventional solar cells because of their high performance, low-cost production, and environmental advantages. The DSSCs consist of dye molecule coated wide bandgap semiconductor layer, electrolyte, and transparent conducting oxide (TCO) film. When the DSSCs are exposed to solar light, an incident photon creates a bound electron-hole pair in dye sensitizers. Electrons then flow into the oxide nanoparticle anode due to a difference in the energy levels. On the other hand, holes move to the counter electrode through sequential redox reactions in the electrolyte. Therefore, the cell performance is influenced by parameters such as the morphology and optical properties of nanocrystalline oxide films, the electrochemical characteristics of redox electrolytes, and the photochemical properties of molecular sensitizers. In this article, we review the major components of DSSCs such as the oxide semiconductor film, sensitizing dyes, electrolytes, and TCO and discuss their progress to maximize light harvesting and charge injection efficacy. Their electrical, optical, and chemical properties are well correlated to optimize the light harvesting and charge injection of DSSCs. We have also shown recent efforts to improve the energy conversion efficiency, long term stability, sustainability and affordability by modifying or revolutionizing the components of DSSCs. This includes a prospect on the potential commercialization of DSSCs.