Vertically oriented Ti-Fe-O nanotube array films: toward a useful material architecture for solar spectrum water photoelectrolysis

In an effort to obtain a material architecture suitable for high-efficiency visible spectrum water photoelectrolysis, herein we report on the fabrication and visible spectrum (380-650 nm) photoelectrochemical properties of self-aligned, vertically oriented Ti-Fe-O nanotube array films. Ti-Fe metal films of variable composition, iron content ranging from 69% to 3.5%, co-sputtered onto FTO-coated glass are anodized in an ethylene glycol + NH4F electrolyte. The resulting amorphous samples are annealed in oxygen at 500 degrees C, resulting in nanotubes composed of a mixed Ti-Fe-O oxide. Some of the iron goes into the titanium lattice substituting titanium ions, and the rest either forms alpha-Fe2O3 crystallites or remains in the amorphous state. Depending upon the Fe content, the band gap of the resulting films ranges from about 380 to 570 nm. The Ti-Fe oxide nanotube array films are utilized in solar spectrum water photoelectrolysis, demonstrating 2 mA/cm2 under AM 1.5 illumination with a sustained, time-energy normalized hydrogen evolution rate by water splitting of 7.1 mL/W.hr in a 1 M KOH solution with a platinum counter electrode under an applied bias of 0.7 V. The surface morphology, structure, elemental analysis, optical, and photoelectrochemical properties of the Ti-Fe oxide nanotube array films are considered.     

Graphene-silicon Schottky diodes

We have fabricated graphene-silicon Schottky diodes by depositing mechanically exfoliated graphene on top of silicon substrates. The resulting current-voltage characteristics exhibit rectifying diode behavior with a barrier energy of 0.41 eV on n-type silicon and 0.45 eV on p-type silicon at the room temperature. The I-V characteristics measured at 100, 300, and 400 K indicate that temperature strongly influences the ideality factor of graphene-silicon Schottky diodes. The ideality factor, however, does not depend strongly on the number of graphene layers. The optical transparency of the thin graphene layer allows the underlying silicon substrate to absorb incident laser light and generate a photocurrent. Spatially resolved photocurrent measurements reveal the importance of inhomogeneity and series resistance in the devices.     

Preparation and photocatalytic activity of N-doped TiO2 nanotube array films

The N-doped TiO₂ nanotube array films were fabricated directly by one-step electrochemical anodic oxidation of Ti foils in an HF electrolyte containing ammonium and nitrate ions. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDX), and ultraviolet–visible (UV–vis) absorption spectroscopy, respectively. The photocatalytic activities were evaluated by the degradation of methyl orange (MO) under visible light irradiation. The results showed that N dopant was successfully introduced into the TiO₂ nanotube array films. The N-doped TiO₂ nanotube array films showed a red shift and an enhancement of the absorption in the visible light region compared to the undoped sample. The photocatalytic activities of the N-doped TiO₂ samples were much higher than those of the undoped sample. A maximum enhancement of photocatalytic activity was achieved for the N-doped TiO₂ sample prepared in 0.07 M HF electrolyte containing 1.0 M NH₄NO₃, and 81% of MO was degraded in 150 min under visible light irradiation.     

S掺杂ZnO薄膜光电特性的研究

采用射频磁控溅射法,在玻璃基片上生长了ZnO:S薄膜。XRD测试表明所制薄膜为六角纤锌矿结构,具有明显的(002)衍射峰。室温下的透射光谱测量结果表明,随着S掺入量的增加,ZnO:S合金薄膜的吸收边向长波长方向移动,但在可见光部分有较高的透过率。在此基础上计算了各样品的禁带宽度,结果表明,在S掺入量小于8%的范围内,随着S掺入量的增加,禁带宽度减小。样品紫外光电导特性明显,在波长365nm、功率4000μW/cm2紫外光源照射下,紫外光与可见光所对应光电流响应之比可达3。     

钴掺杂TiO2纳米管阵列薄膜的制备及其光催化还原性能

用磁控溅射法在ITO玻璃基底上制备Ti-Co合金薄膜,对其阳极氧化处理制备出钴掺杂TiO₂纳米管阵列薄膜,研究了钴掺杂对纳米管阵列薄膜的形貌、结构、吸收光谱以及光催化还原性能的影响。结果表明：钴掺杂TiO₂纳米管阵列薄膜为锐钛矿相,管状阵列的管径均一、排列规整。钴掺杂使薄膜形成(001)择优取向。随着钴掺杂量的提高,薄膜吸收可见光的能力提高。钴含量(原子分数)为0.19%的薄膜光催化性能最优,可见光照150 min后对Cr(VI)的还原率可达98.4%。     

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.     

Visible light photoelectrocatalysis with salicylic acid-modified TiO2 nanotube array electrode for p-nitrophenol degradation

This research focused on immersion method synthesis of visible light active salicylic acid (SA)-modified TiO₂ nanotube array electrode and its photoelectrocatalytic (PEC) activity. The SA-modified TiO₂ nanotube array electrode was synthesized by immersing in SA solution with an anodized TiO₂ nanotube array electrode. Scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), UV–vis diffuse reflectance spectrum (DRS), and Surface photovoltage (SPV) were used to characterize this electrode. It was found that SA-modified TiO₂ nanotube array electrode absorbed well into visible region and exhibited enhanced visible light PEC activity on the degradation of p-nitrophenol (PNP). The degradation efficiencies increased from 63 to 100% under UV light, and 79–100% under visible light (λ > 400 nm), compared with TiO₂ nanotube array electrode. The enhanced PEC activity of SA-modified TiO₂ nanotube array electrode was attributed to the amount of surface hydroxyl groups introduced by SA-modification and the extension of absorption wavelength range.     

CdS-sensitized ZnO nanorod arrays coated with TiO2 layer for visible light photoelectrocatalysis

A novel ZnO/CdS/TiO₂ nanorod array composite structure was fabricated by depositing CdS-sensitized layer onto ZnO nanorod arrays via chemical bathing deposition and subsequently coated by TiO₂ protection layer via a vacuum dip-coating process. The films were characterized by x-ray diffraction, field emission scanning electron microscopy, energy dispersive spectrum, and UV–Vis diffuse reflectance spectroscopy. For the films severed as the photoanodes, linear sweep voltammetry and transient photocurrent (i _ph) were investigated in a three-electrode system. The photoelectrocatalytic activity was evaluated by the degradation of methylene blue (MB) under visible light irradiation. The results show that the oriented ZnO nanorods are adhered by relatively uniform CdS-sensitized layer and coated with TiO₂ layer. Both the coated and uncoated CdS-sensitized ZnO nanorod arrays exhibit the visible light response and the photoelectrocatalytic activity on the degradation of MB under visible light irradiation. The ZnO/CdS/TiO₂ nanorod array film possesses stable and superior photoelectrocatalytic performance owing to the TiO₂ thin layer protecting the CdS from photocorrosion.     

Carbon Nanotube Diodes Operating at Frequencies of Over 50 GHz

Radiofrequency (RF) diodes used for fifth and sixth-generation (5G and 6G) mobile and wireless communication networks generally require ultrahigh cut-off frequencies and high integration densities of devices with different functions on a single chip and at low cost. Carbon nanotube diodes are promising devices for radiofrequency applications, but the cut-off frequencies are still far below the theoretical estimates. Here, a carbon nanotube diode that operates in the millimeter-wave frequency bands and is based on solution-processed, high-purity carbon nanotube network films is reported. The carbon nanotube diodes exhibit an intrinsic cut-off frequency over 100 GHz and the as-measured bandwidth can exceed 50 GHz at least. Furthermore, The rectification ratio of the carbon nanotube diode by approximately three times by using yttrium oxide for local p-type doping in the diode channel is improved.     

Physico-chemical, photoelectrochemical and photocatalytic properties of electrodeposited nanocrystalline titanium dioxide thin films

Crystal structure and microstructural properties of titanium dioxide (TiO₂) thin films prepared by cathodic electrodeposition on indium-tin-oxide coated glass substrates from aqueous peroxo-titanium complex solutions have been investigated. The electrodeposited TiO₂ thin film electrode exhibited anodic photocurrent upon visible light irradiation, indicating the typical behavior of n-type semiconductor. The photodecomposition of CH₃CHO by such thin films on exposure to ultraviolet light illumination was also observed.     

Photoelectrochemical and physical properties of tungsten trioxide films obtained by aerosol pyrolysis

Aerosol pyrolysis (AP) was used for preparing semiconducting films of tungsten trioxide using peroxotungstic acid as a precursor. The films were characterized by SEM, XRD, and by their photoelectrochemical response. Porous, polycrystalline (monoclinic) films of thickness up to 3 μm were prepared. An incident photon to current efficiency (IPCE) of 0.55 at 365 nm was obtained for films of 1 μm thickness on conducting F:SnO₂/glass substrates under depletion conditions, in junctions with aqueous electrolytes. The spectral (photocurrent) response extended into the visible region (up to 470 nm) which is of importance for solar applications like photocatalysis.     

ZnO Coated Anodic 1D TiO2 Nanotube Layers: Efficient Photo‐Electrochemical and Gas Sensing Heterojunction

The authors demonstrate, in this work, a fascinating synergism of a high surface area heterojunction between TiO₂ in the form of ordered 1D anodic nanotube layers of a high aspect ratio and ZnO coatings of different thicknesses, produced by atomic layer deposition. The ZnO coatings effectively passivate the defects within the TiO₂ nanotube walls and significantly improve their charge carrier separation. Upon the ultraviolet and visible light irradiation, with an increase of the ZnO coating thickness from 0.19 to 19 nm and an increase of the external potential from 0.4–2 V, yields up to 8‐fold enhancement of the photocurrent density. This enhancement translates into extremely high incident photon to current conversion efficiency of ≈95%, which is among the highest values reported in the literature for TiO₂ based nanostructures. In addition, the photoactive region is expanded to a broader range close to the visible spectral region, compared to the uncoated nanotube layers. Synergistic effect arising from ZnO coated TiO₂ nanotube layers also yields an improved ethanol sensing response, almost 11‐fold compared to the uncoated nanotube layers. The design of the high‐area 1D heterojunction, presented here, opens pathways for the light‐ and gas‐assisted applications in photocatalysis, water splitting, sensors, and so on.

     

Photoconductivity of Bulk‐Film‐Based Graphene Sheets

Time‐resolved photoconductivity measurements are carried out on graphene films prepared by using soluble graphene oxide. High photocurrent generation efficiency is observed for these graphene‐based films, and the relationships between their photoconductivity and different preparation methods, incident light intensity, external electric field, and photon energies are investigated. Higher photoconductivity is observed with higher photon energy at same incident light intensity. By fitting the experimental data to the Onsager model, the primary quantum yields for charge separation to generate bound electron–hole pairs and the initial ion‐pair thermalization separation distance are calculated.     

通过聚吡咯-聚苯胺共聚物修饰TiO_2纳米管阵列来增强其可见光光催化性能（英文）

纳米管阵列结构的光催化半导体设计一直以来是研究热点,因为纳米管结构有益于对光的吸收和减少载流子的迁移距离。然而,这些材料往往受限于比较差的电荷传输。因此,我们研究了一个易于重复利用的PPy-PANI/TiO2NT光催化剂,其中聚吡咯-聚苯胺共聚物充当光敏剂和电子导体介体。实验所制备的PPy-PANI/TiO2NT复合材料有更高的可见光吸收,更高的电荷分离效率以及在可见光下有156μA的光电流。所有的样品通过XRD,FTIR,SEM,光电流进行表征。通过降解4-NP也证明由聚吡咯-聚苯胺共聚物修饰后的二氧化钛有很好的光催化效果。     

Fabrication and characterization of X-ray array detectors based on polycrystalline PbI2 thick films

Polycrystalline PbI₂ thick films were grown by using close spaced vapor deposition method on glass substrate with a conducting indium–tin-oxide coating. The morphology shows a uniquely oriented film structure with hexagonal platelets accurately being upright on substrate surface. An array detector with 12 pixels was fabricated based on this structure of the thick film. It is shown that the dark current is lower than 3 nA at bias voltage below 500 V, and the dark resistivity is as high as 10¹¹ Ω cm. A mapping of dark current density of the sensitive area of the array detector exhibits a better uniformity in the central area than the fringe area. A quick photocurrent response to X-ray excitation was obtained. The photoresponse rise time about 250 μs was obtained from the detectors and the photocurrent decays in a few seconds. The values of photocurrent are higher about two orders of magnitude than the values of dark current. The distribution of photocurrent is more uniform than that of dark current in the sensitive area of the detector.     

Fabrication and characterization of all-oxide heterojunction p-CuAlO2 + x/n-Zn1 − xAlxO transparent diode for potential application in “invisible electronics”

Transparent p-n heterojunction diodes have been fabricated by p-type copper aluminum oxide (p-CuAlO_2 + x) and n-type aluminum doped zinc oxide (n-Zn_1 − xAl_xO) thin films on glass substrates. The n-layers are deposited by sol-gel-dip-coating process from zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and aluminum nitrate (Al(NO₃)₃·9H₂O). Al concentration in the nominal solution is taken as 1.62 at %. P-layers are deposited onto the ZnO:Al-coated glass substrates by direct current sputtering process from a prefabricated CuAlO₂ sintered target. The sputtering is performed in oxygen-diluted argon atmosphere with an elevated substrate temperature. Post-deposition oxygen annealing induces excess oxygen within the p-CuAlO_2 + x films, which in turn enhances p-type conductivity of the layers. The device characterization shows rectifying current-voltage characteristics, confirming the proper formation of the p-n junction. The turn-on voltage is obtained around 0.8 V, with a forward-to-reverse current ratio around 30 at ± 4 V. The diode structure has a total thickness of 1.1 μm and the optical transmission spectra of the diode show almost 60% transmittance in the visible region, indicating its potential application in ‘invisible electronics’. Also the cost-effective procedures enable the large-scale production of these transparent diodes for diverse device applications.     

Fabrication of PbS nanoparticle-sensitized TiO₂ nanotube arrays and their photoelectrochemical properties

TiO(2) nanotube arrays (NTAs) are modified with PbS nanoparticles by successive ionic layer adsorption and reaction (SILAR) or electrodeposition, with an aim towards tuning the photoelectrochemical cell to the visible region. The PbS modification of the TiO(2) NTAs results in an increase in the visible light adsorption, however the increase in photocurrent is dependent on the modification method. PbS/TiO(2) NTAs prepared by SILAR and electrodeposition show, respectively, photocurrents of 11.02 and 5.72 mA/cm(2). The increase in photocurrent is attributed to enhanced charge separation efficiency and improved electron transport.     

Sol-gel assisted ZnO nanorod array template to synthesize TiO(2) nanotube arrays

A TiO(2) nanotube array with a large surface area is fabricated on a glass substrate using a ZnO nanorod array and sol-gel process, and the structural characteristics of the TiO(2) nanotube array are investigated. The well-aligned ZnO nanorod array, which is deposited on ZnO seed layer coated glass substrates by the wet-chemical route, is used as a template to synthesize TiO(2)/ZnO composite nanostructures through the sol-gel process. Then, by selectively removing the ZnO template, a TiO(2) nanotube with contours of the ZnO nanorods is fabricated on the ZnO seed layer coated glass. The resultant TiO(2) nanotubes are 1.5?μm long and 100-120?nm in inner diameter, with a wall thickness of ～10?nm. In addition, by adjusting the experimental parameters, such as the dip-coating cycle number or heating rate, porous TiO(2) thick films can also be obtained.     

p型ZnO和ZnO同质p-n结的研究进展

ZnO基注入式发光二极管和激光器件的研究目前仍处于初级阶段．即p型ZnO和ZnOp-n结的制备与特性研究。由于ZnO薄膜中存在较强的自补偿机制，使得很难有效地施行p型元素的掺杂。本文介绍了目前国际上通用的掺杂方法．对不同方法制备的p型ZnO和ZnOp-n结的特点进行了比较分析，并讨论了目前生长高质量的突变型ZnOp-n结所面临的问题。     

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.