Metal on metal oxide nanowire Co-catalyzed Si photocathode for solar water splitting

We report a systematic study of Si|ZnO and Si|ZnO| metal photocathodes for effective photoelectrochemical cells and hydrogen generation. Both ZnO nanocrystalline thin films and vertical nanowire arrays were studied. Si|ZnO electrodes showed increased cathodic photocurrents due to improved charge separation by the formation of a p/n junction, and Si|ZnO:Al (n(+)-ZnO) and Si|ZnO(N(2)) (thin films prepared in N(2)/Ar gas) lead to a further increase in cathodic photocurrents. Si|ZnONW (nanowire array) photocathodes dramatically increased the photocurrents and thus photoelectrochemical conversion efficiency due to the enhanced light absorption and enlarged surface area. The ZnO film thickness and ZnO nanowire length were important to the enhancements. A thin metal coating on ZnO showed increased photocurrent due to a catalyzed hydrogen evolution reaction and Ni metal showed comparable catalytic activities to those of Pt and Pd. Moreover, photoelectrochemical instability of Si|ZnO electrodes was minimized by metal co-catalysts. Our results indicate that the metal and ZnO on p-type Si serve as co-catalysts for photoelectrochemical water splitting, which can provide a possible low-cost and scalable method to fabricate high efficiency photocathodes for practical applications in clean solar energy harvesting.     

A CdS-modified TiO(2) nanocrystalline photoanode for efficient hydrogen generation by visible light

Cadmium sulfide (CdS) was in situ synthesized onto mesoporous TiO(2) films and used as a sensitizer to fabricate a photoelectrode for hydrogen generation in visible light. The incorporation of CdS extends the optical absorption threshold of a TiO(2) electrode to visible light, enhancing the visible-light-induced photocurrent. A maximum photoconversion efficiency of 3.67% was achieved for this CdS-sensitized TiO(2) electrode under visible light illumination of 100?mW?cm(-2). The hydrogen generation rate obtained at conditions of maximum efficiency is 95.5?μmol?cm(-2)?h(-1). To the best of our knowledge, the hydrogen generation rate is the highest among those reported for a photoelectrochemical cell under the illumination of visible light.     

ZnO films grown on cotton fibers surface at low temperature by a simple two-step process

Zinc oxide (ZnO) films have been synthesized and deposited onto cotton fiber surface using a simple two-step process. At first step, the cotton fiber surface was coated with a conductive layer of zinc-cellulose complex by rinsing the fibers in zinc chloride solution. After that, the growth of ZnO films was carried out in zinc acetate aqueous solution at room temperature, with alkaline aqueous solution drops continuously added under magnetic stirring. The morphology of the as-prepared ZnO-coated cotton fibers was characterized by scanning electron microscopy. Infrared and photoluminescence spectra were used to confirm the existence of ZnO. In addition, the formation mechanism of ZnO-coated cotton fibers is discussed in detail.     

染料敏化太阳能电池的研究进展

光导电极材料在染料敏化太阳能电池(DSSC)中起到关键作用,直接影响到太阳能电池的总效率,所以一直是DSSC研究的热点.介绍了DSSC的基本工作原理,概述了当前DSSC中最流行的TiO<,2>和ZnO两种薄膜光导电极材料的制备方法,并从结构、工艺和转换效率等方面对染料敏化TiO<,2>薄膜太阳能电池和染料敏化ZnO薄膜太阳能电池进行了介绍和讨论;同时简要介绍了目前研究非常热门的叠层染料敏化太阳电池的研究进程,最后展望了染料敏化太阳能电池的未来发展前景.     

Characterizations of spray-deposited lanthanum oxide (La2O3) thin films

A simple and inexpensive spray pyrolysis method was used for the preparation of lanthanum oxide thin films. The films were prepared by spraying 0.1 M lanthanum chloride solution onto the conducting and non conducting glass substrates. The substrate temperature was varied from 523 to 723 K and structural, optical and electrical properties of the films were studied. A photoelectrochemical (PEC) cell was formed using La₂O₃ films as a photoelectrode.     

Quantum-dot-sensitized TiO2 inverse opals for photoelectrochemical hydrogen generation

A new nanoarchitecture photoelectrode design comprising CdS quantum-dot-sensitized, optically and electrically active TiO(2) inverse opals is developed for photoelectrochemical water splitting. The photoelectrochemical performance shows high photocurrent density (4.84 mA cm(-2) at 0 V vs. Ag/AgCl) under simulated solar-light illumination.     

Selective atomic layer deposition of metal oxide thin films on patterned self-assembled monolayers formed by microcontact printing

We demonstrate a selective atomic layer deposition of TiO2, ZrO2, and ZnO thin films on patterned alkylsiloxane self-assembled monolayers. Microcontact printing was done to prepare patterned monolayers of the alkylsiloxane on Si substrates. The patterned monolayers define and direct the selective deposition of the metal oxide thin films using atomic layer deposition. The selective atomic layer deposition is based on the fact that the metal oxide thin films are selectively deposited only on the regions exposing the silanol groups of the Si substrates because the regions covered with the alkylsiloxane monolayers do not have any functional group to react with precursors.     

Thin films of TiO2:N for photo-electrochemical applications

Dc-pulsed magnetron sputtering from Ti target in reactive Ar+O2+N2 atmosphere was used to grow stoichiometric TiO2:N and non-stoichiometric TiO2-x:N thin films. X-ray diffraction at glancing incidence, atomic force microscopy AFM, scanning electron microscopy SEM, X-ray photoelectron spectroscopy XPS, and optical spectrophotometry were applied for sample characterization. Measurements of photocurrent versus voltage and wavelength over the ultraviolet uv and visible vis ranges of the light spectrum were performed in order to assess the performance of nitrogen-doped titanium dioxide thin films as photoanodes for hydrogen generation in photoelectrochemical cells, PEC. Undoped TiO2 and TiO2-x films were found to be composed of anatase and rutile mixture with larger anatase crystallites (25-35 nm) while the growth of smaller rutile crystallites (6-10 nm) predominated at higher nitrogen flow rates etaN2 as measured in standard cubic centimeters, sccm. Nitrogen-to-titanium ratio increased from N/Ti = 0.05 at etaN2 = 0.8 sccm for stoichiometric TiO2:N to N/Ti = 0.11 at etaN2 = 0.8 sccm for nonstoichiometric TiO2-x:N thin films. A red-shift in the optical absorbance was observed with an increase in etaN2. Doping with nitrogen improved photoelectrochemical properties over the visible range of the light spectrum in the case of nonstoichiometric samples.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Fast fabrication of long TiO2 nanotube array with high photoelectrochemical property on flexible stainless steel

Oriented highly ordered long TiO2 nanotube array films with nanopore structure and high photoelectrochemical property were fabricated on flexible stainless steel substrate (50 microm) by anodization treatment of titanium thin films in a short time. The samples were characterized by means of field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and photoelectrochemical methods, respectively. The results showed that Ti films deposited at the condition of 0.7 Pa Ar pressure and 96 W sputtering power at room temperature was uniform and dense with good homogeneity and high crystallinity. The voltage and the anodization time both played significant roles in the formation of TiO2 nanopore-nanotube array film. The optimal voltage was 60 V and the anodization time is less than 30 min by anodizing Ti films in ethylene glycerol containing 0.5% (w) NH4F and 3% (w) H2O. The growth rate of TiO2 nanotube array was as high as 340 nm/min. Moreover, the photocurrent-potential curves, photocurrent response curves and electrochemical impedance spectra results indicated that the TiO2 nanotube array film with the nanoporous structure exhibited a better photo-response ability and photoelectrochemical performance than the ordinary TiO2 nanotube array film. The reason is that the nanoporous structure on the surface of the nanotube array can separate the photo electron-hole pairs more efficiently and completely than the tubular structure.     

Electrodeposition of hierarchical ZnO nanorod-nanosheet structures and their applications in dye-sensitized solar cells

We present a two-step electrochemical deposition process to synthesize hierarchical zinc oxide (ZnO) nanorod-nanosheet structures on indium tin oxide (ITO) substrate, which involves electrodeposition of ZnO nanosheet arrays on the conductive glass substrate, followed by electrochemical growth of secondary ZnO nanorods on the backbone of the primary ZnO nanosheets. The formation mechanism of the hierarchical nanostructure is discussed. It is demonstrated that annealing treatment of the primary nanosheets synthesized by the first-step deposition process plays a key role in synthesizing the hierarchical nanostructure. Photovoltaic properties of dye-sensitized solar cells (DSSCs) based on hierarchical ZnO nanostructures are investigated. The hierarchical ZnO nanorod-nanosheet DSSC exhibits improved device performance compared to the DSSC constructed using photoelectrode of bare ZnO nanosheet arrays. The improvement can be attributed to the enhanced dye loading, which is caused by the enlargement of internal surface area within the nanostructure photoelectrode. Furthermore, we perform a parametric study to determine the optimum geometric dimensions of the hierarchical ZnO nanorod-nanosheet photoelectrode through adjusting the preparation conditions of the first- and second-step deposition process. By utilizing a hierarchical nanostructure photoelectrode with film thickness of about 7 μm, the DSSC with an open-circuit voltage of 0.74 V and an overall power conversion efficiency of 3.12% is successfully obtained.     

P-type Cu--Ti--O nanotube arrays and their use in self-biased heterojunction photoelectrochemical diodes for hydrogen generation

Copper and titanium remain relatively plentiful in the earth's crust; hence, their use for large-scale solar energy conversion technologies is of significant interest. We describe fabrication of vertically oriented p-type Cu-Ti-O nanotube array films by anodization of copper rich (60% to 74%) Ti metal films cosputtered onto fluorine doped tin oxide (FTO) coated glass. Cu-Ti-O nanotube array films 1 mum thick exhibit external quantum efficiencies up to 11%, with a spectral photoresponse indicating that the complete visible spectrum, 380 to 885 nm, contributes significantly to the photocurrent generation. Water-splitting photoelectrochemical pn-junction diodes are fabricated using p-type Cu-Ti-O nanotube array films in combination with n-type TiO 2 nanotube array films. With the glass substrates oriented back-to-back, light is incident upon the UV absorbing n-TiO 2 side, with the visible light passing to the p-Cu-Ti-O side. In a manner analogous to photosynthesis, photocatalytic reactions are powered only by the incident light to generate fuel with oxygen evolved from the n-TiO 2 side of the diode and hydrogen from the p-Cu-Ti-O side. To date, we find under global AM 1.5 illumination that such photocorrosion-stable diodes generate a photocurrent of approximately 0.25 mA/cm (2), at a photoconversion efficiency of 0.30%.     

Surface modified TiO2 nanostructure with 3D urchin-like morphology for dye-sensitized solar cell application

Three-dimensional (3D) urchin-like rutile TiO2 powders were synthesized by a mild hydrothermal method without any templates. An individual urchin-like TiO2 powder consists of self-assembled nanorods with a length of about 150 nm and width of about 10 nm. Additionally, the urchin-like TiO2 nanopowders were coated with an ultra-thin ZnO layer in order to modify the surface properties of the nanopowders, and the ZnO layer was confirmed by high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analysis. The ZnO-modified TiO2 was used as a photoelectrode of a dye-sensitized solar cell (DSSC) and the solar cell performances were investigated. In comparison with bare TiO2, ZnO-modified TiO2 improved the photovoltaic performances, i.e., energy conversion efficiency, open circuit voltage, and short circuit current were increased. The higher DSSC performance of ZnO-modified TiO2 was attributed to its higher dye loading and lower charge recombination rate.     

Effects of additive gases and plasma post-treatment on electrical properties and optical transmittance of ZnO thin films

A zinc oxide (ZnO) thin film as a channel layer in an oxide thin film transistor (TFT) has been characterized by investigating the effects of additive gases (such as hydrogen and oxygen) during growth and plasma treatment (using argon or hydrogen) after growth on its electrical, optical, and structural properties. By decreasing the additive gas ratio of O₂/H₂ or by increasing the treatment time of hydrogen plasma, the electrical resistivities of ZnO films were significantly reduced, and their transmittances and optical bandgap energies were blue-shifted in wavelength. These results were considered to be closely related to the passivation of oxygen vacancies as well as the formation of shallow donors that were induced by the injection of hydrogen in ZnO via gas addition and plasma treatment. In addition, the injection of hydrogen-including additive gas resulted in a decrease in grain size and crystallinity of ZnO films, whereas the plasma treatment hardly affected their crystalline structures.     

Phase-junction Ag/TiO2 nanocomposite as photocathode for H2 generation

Developing anatase/rutile phase-junction in TiO2 to construct Z-scheme system is quite effective to improve its photoelectrochemical activity.In this work,the anatase/rutile phase-junction Ag/TiO2 nanocomposites are developed as photocathodes for hydrogen production.The optimized Ag/TiO2 nanocomposite achieves a high current density of 1.28 mA cm-2,an incident photon-to-current con-version efficiency(IPCE)of 10.8％,an applied bias photon-to-current efficiency(ABPE)of 0.32 at 390 nm and a charge carriers'lifetime up to 2000s.Such enhancement on photoelectrochemical activity can be attributed to:(i)the generated Z-scheme system in the anatase/rutile phase-junction Ag/TiO2 photocath-ode enhances the separation,diffusion and transformation of electron/hole pairs inside the structure,(ii)Ag nanodots modification in the anatase/rutile phases leading to the tuned band gap with enhanced light absorption and(iii)the formed Schottky barrier after Ag nanodots surface modification provides enough electron traps to avoid the recombination of photogenerated electrons and holes.Our results here sug-gest that developing phase-junction nanocomposite as photocathode will provide a new vision for their enhanced photoelectrochemical generation of hydrogen.     

Effects of oxygen content on bioactivity of titanium oxide films fabricated on titanium by electron beam evaporation

The titanium oxide films were fabricated on titanium metal by e-beam deposition technique in various oxygen partial pressures in order to investigate the effects of oxygen content in titanium oxide film on the bioactivity of titanium implant. The nano-sized titanium oxide particles were observed on the surface of specimens. Raman spectra showed that titanium oxide films deposited by e-beam evaporator had oxygen deficient TiO2 structure. The oxygen content in oxide films was calculated from the high resolution XPS spectra of Ti 2p. The densities of HA particles formed on the sample surfaces after immersion test in SBF became higher as the contents of oxygen in titanium oxide films increased. We concluded that the degree of hydroxyl group formation in SBF depended on the stoichiometry of TiO2, which enhanced the bioactivity of titanium.     

PbS量子点/ZnO纳米片复合膜的制备及其光电化学性能

通过两步法合成PbS量子点(QDs)修饰ZnO纳米片复合膜. 首先利用电化学法在掺氟的SnO₂导电玻璃(FTO)上生长ZnO纳米片, 然后在ZnO纳米片上通过逐次化学浴法沉积PbS量子点形成PbS/ZnO复合膜. 利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)详细表征了样品的表面形貌和晶体结构, 并研究了PbS/ZnO复合膜作为量子点敏化太阳能电池光阳极的紫外-可见吸收谱、光电化学性能和表面光电压谱. 对比ZnO纳米片经PbS量子点修饰前后, 发现PbS量子点修饰后光阳极的光吸收和光伏响应均从紫外区拓宽到了可见光区, 同时光电化学性能有了显著提高, 短路电流密度从敏化前的0.1 mA/cm²增加到0.7 mA/cm², 效率由0.04%增加到0.57%. 与单一ZnO纳米片相比, PbS/ZnO复合膜的表面光伏响应强度明显增强, 说明PbS与ZnO之间形成了有利于光生电荷分离的异质结, 从而导致了PbS/ZnO复合膜光电性能的增加.     

Enhancement of crystallinity and optical properties of bilayer TiO2/ZnO thin films prepared by atomic layer deposition

Bilayer and multilayer thin films are becoming increasingly important in the development of faster, smaller and more efficient electronic and optoelectronic devices. One of the motivations of applying bilayer or multilayer structures is to modify the optical properties of materials. Atomic layer deposition (ALD) is a variant of Chemical Vapour Deposition that can produce uniform and conformal thin films with well controlled nanostructures. In this study, we have demonstrated new findings of the use of ALD fabricated bilayer TiO2/ZnO thin films with enhanced crystallinity and optical properties. TiO2 films have been deposited at 300 degrees C for 1000 (51 nm in thickness) or 3000 (161 nm in thickness) deposition cycles onto glass and Si substrates. ZnO films are subsequently deposited on the TiO2 layers at 280 degrees C for 500 deposition cycles (55 nm). The crystallinity and optical properties of the TiO2/ZnO thin films have been analysed by X-ray diffraction, photoluminescence, UV-Vis spectroscopy, Atomic Force Microscopy and Scanning Electron Microscopy. XRD diffraction pattern confirmed the presence of ZnO with wutrtize crystal structure and TiO2 with anatase structure. It shows that the crystallinity of the TiO2 films has been improved with the deposition of ZnO. The intensity of UV luminescence has increased by almost 30% for TiO2/ZnO bilayer as compared to the single layer TiO2. The possible mechanism for the enhancement of the optical properties of bilayer TiO2/ZnO thin films will be discussed.     

ZnO调制改性染料敏化太阳能电池TiO2光阳极研究

采用丝网印刷的方式制备了染料敏化太阳能电池的TiO2薄膜光阳极、TiO2-ZnO复合薄膜光阳极以及TiO2/ZnO双层薄膜光阳极,研究了ZnO对TiO2薄膜光阳极的调制改性作用。研究结果表明分别以醋酸锌和ZnO直接掺杂制备的TiO2-ZnO复合薄膜光阳极同未掺杂的TiO2薄膜光阳极相比,以醋酸锌为原料制备的复合薄膜光阳极使电池转换效率提高了1倍,而由于微米量级的ZnO的粒径大,用其作原料制得的复合薄膜光阳极反而使电池的转换效率有所降低。以醋酸锌为原料制备的TiO2/ZnO双层薄膜光阳极同TiO2薄膜光阳极相比,电池转换效率提高了13倍,通过性能优化后电池的转换效率达到4.7%。     

Surfactant-mediated growth of nanostructured zinc oxide thin films via electrodeposition and their photoelectrochemical performance

Zinc oxide (ZnO) thin films were electrodeposited from an aqueous zinc acetate solution onto fluorine-doped thin oxide (FTO) coated conducting glass substrates. The effect of organic surfactants like polyvinyl pyrrolidone (PVP), sodium dodecyl sulfate (SDS), polyethylene glycol (PEG), ethylene glycol (EG) and polyvinyl alcohol (PVA) on their structural, morphological, optical and photoelectrochemical properties was studied. The x-ray diffraction patterns revealed the formation of phase-pure ZnO thin films. The films deposited using organic surfactants exhibit different surface morphologies. It was observed that the organic surfactants play important roles in modifying the surface morphology and size of the crystallites. A compact granular morphology was observed for the ZnO samples grown without organic surfactants. The films exhibit nanoparticles of size 100-150?nm for PVP, EG and PVA mediated growth. The vertically aligned thin and compact hexagonal crystallites stem from the SDS, whereas microporous corrugated morphology is observed for PEG-mediated growth. All the samples exhibit room temperature photoluminescence (PL). Oxygen vacancies contribute to the active luminescent centers for the emission of green light in ZnO thin films. PL gets quenched for the SDS surfactant. All the samples were post-treated with ethanol to remove stray surfactant molecules. FTIR study was used to confirm the removal of adsorbed surfactant molecules from the samples. Moreover the samples are photoelectrochemically (PEC) active and exhibit the highest photocurrent of 231?μA, a photovoltage of 492?mV and 0.42 fill factor for the ZnO:SDS films.