Morphology controlled fabrication and ferroelectric properties of vertically aligned one-dimensional lead titanate nanoarrays

Vertically aligned nanowires and highly uniform nanoporous array thin films of PbTiO(3) are synthesized by varying anodic oxidation conditions of Ti foil followed by hydrothermal reaction in an aqueous Pb(II) acetate trihydrate solution. As-synthesized samples have single crystalline nanowire structure and polycrystalline nanoporous structure, although both are pure PbTiO(3) with a tetragonal phase. The structure of intermediate TiO(2) films obtained from different anodic oxidation conditions determines the structure of the product PbTiO(3). The relationships between these morphological structures and ferroelectric properties are investigated. Piezoresponse force microscopy reveals that both these films show ferroelectricity with clear phase contrast and well-defined hysteresis loops. The saturated longitudinal piezoelectric coefficient field (E(c)) of the nanowire sample is smaller than that of nanoporous thin film. Thus, polarization of nanowire thin film is larger in magnitude and easier to flip than that of nanoporous film.     

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.     

Nitrogen-doped TiO2 nanotube array films with enhanced photocatalytic activity under various light sources

Highly ordered nitrogen-doped titanium dioxide (N-doped TiO(2)) nanotube array films with enhanced photocatalytic activity were fabricated by electrochemical anodization, followed by a wet immersion and annealing post-treatment. The morphology, structure and composition of the N-doped TiO(2) nanotube array films were investigated by FESEM, XPS, UV-vis and XRD. The effect of annealing temperature on the morphology, structures, photoelectrochemical property and photo-absorption of the N-doped TiO(2) nanotube array films was investigated. Liquid chromatography and mass spectrometry were applied to the analysis of the intermediates coming from the photocatalytic degradation of MO. The experimental results showed that there were four primary intermediates existing in the photocatalytic reaction. Compared with the pure TiO(2) nanotube array film, the N-doped TiO(2) nanotubes exhibited higher photocatalytic activity in degradating methyl orange into non-toxic inorganic products under both UV and simulated sunlight irradiation.     

Hydrothermal synthesis of cdS nanoparticle-decorated TiO2 nanobelts for solar cell

We fabricated a solar cell using a hybrid film consisting of CdS nanoparticle-decorated TiO2 nanobelts, which were synthesized via a modified alkaline hydrothermal method. The hybrid film is flexible and contains homogeneous CdS nanoparticle light absorbers. Furthermore, the type II heterostructure of CdS/TiO2 facilitates charge separation in the CdS nanoparticle-decorated TiO2 nanobelts. The solar cell demonstrated a light-electricity power conversion efficiency of 2.52%. Next, we deposited the CdS nanoparticle-decorated TiO2 nanobelts onto a ZnO nanowire array forming an antireflective hybrid structure. The power conversion efficiency of the cell with the hybrid photoanode reached 2.84%.     

Optically transparent carbon nanowire thin film

Thin films of amorphous carbon nanowire (a-CNW) have been fabricated from crossed multi-walled carbon nanotube (MWCNT) thin film. The fabrication was done by means of ion beam irradiation on various substrates. It is found that the a-CNW thin films show electrical conduction behaviour, and electrical conductivity varies after annealing. In addition, the transmission spectra in the visible range reveal that the film has above 90% optical transmission. It can be ascribed to the fact that the decreased crystallinity of MWCNTs by ion beam irradiation has caused the incremental increase of optical transmission. We also report on a method for cutting or destroying a-CNWs using low-energy focused electron beam from a scanning electron microscope.     

Layer-by-layer assembly of TiO2 nanowire/carbon nanotube films and characterization of their photocatalytic activity

We report on the layer-by-layer (LbL) formation of TiO(2)-MWNT-TiO(2) coatings on quartz with either trititanate derived TiO(2) nanowires or Degussa P25 as the photocatalytically active material. The optimized deposition sequence is discussed in detail and the morphology of the prepared coatings is analyzed by SEM and XRD. The heterogeneous photocatalytic performance of the coatings was tested in the methyl orange oxidation reaction. The apparent first order rate constant fell in the 0.01-0.20 h(-1) range over a 2.5 × 2.5 cm(2) film depending on the type and the thickness of the titanate coating. Building a multiwall carbon nanotube layer into the middle of the layer improved the photocatalytic activity for each material for all of the studied thicknesses. P25 based films performed 2-5 times better than TiO(2) nanowire films; however, the pores in the P25 based films were largely blocked because the isotropic P25 nanoparticles form closely packed layers by themselves and even more so with the comparably sized multiwall carbon nanotubes. Therefore, films derived from titanate nanowires appear to be more suitable for use as multifunctional, photocatalytically active filtration media.     

The effect of residual stresses in the ZnO buffer layer on the density of a ZnO nanowire array

Density control is a valuable concern in the research of ZnO nanowire arrays. In this study, unannealed and annealed ZnO thin films were used as substrates to fabricate ZnO nanowire arrays. In the unannealed thin film, an inhomogeneous distribution of the nanowire array was found: the density of nanowires decreases with the increase of distance to the edge. In the annealed thin film, the density of nanowire array becomes larger and more homogeneous. Moreover, nanowires are found in high density along microcracks. It is proposed that the residual stresses in the thin film and the density of the nanowire array are in inverse proportion, leading to the results mentioned above. The relationship between residual stresses and the density of nanowires will have potential applications in modifying the density of ZnO nanowire arrays.     

Fabrication of silicon carbide nanowires/carbon nanotubes heterojunction arrays by high-flux Si ion implantation

An array of silicon carbide nanowire (SiCNW)-carbon nanotube (CNT) heterojunctions was fabricated by high-flux Si ion implantation into a multi-walled carbon nanotube (MWCNT) array with a metal vapor vacuum arc (MEVVA) ion source. Under Si irradiation, the top part of a CNT array was gradually transformed into an amorphous nanowire array with increasing Si dose while the bottom part still remained a CNT structure. X-ray photoelectron spectroscopy (XPS) analysis shows that the SiC compound was produced in the nanowire part even at the lower Si dose of 5 × 10(16)?ions?cm(-2), and the SiC amount increased with increasing the Si dose. Therefore, the fabrication of a SiCNW-CNT heterojunction array with the MEVVA technique has been successfully demonstrated. The corresponding formation mechanism of SiCNWs was?proposed.     

Application of TiO2 nanoparticles coated multi-wall carbon nanotube to dye-sensitized solar cells

This study uses the sol-gel method to prepare TiO2 nanoparticle, and further applies TiO2 nanoparticle coating on the surface of the multi-wall carbon nanotube (MWCNT). As a result, TiO2-CNT composite nanoparticles are prepared to serve as photoelectrode material in dye-sensitized solar cell (DSSC). First, after acid treatment of MWCNT is used to remove impurities. Then, the sol-gel method is employed to prepare TiO2-CNT composite nanopowder. X-ray diffraction (XRD) pattern shows that after the TiO2 in TiO2-CNT composite nanopowder has been thermally treated at 450 degrees C, it can be completely changed to anatase phase. Furthermore, as shown from the SEM image, TiO2 has been successfully coated on CNT. The photoelectrode of DSSC is prepared using the electrophoretic deposition method (EPD) to mix the Degassa P25 TiO2 nanoparticles with TiO2-CNT powder for deposition on the indium tin oxide (ITO) conductive glass. After secondary EPD, a thin film of TiO2/CNTs with thickness 17 microm can be acquired. For the prepared TiO2-CNT composite nanoparticles, since MWCNT can increase the short-circuit current density of DSSC, the light-to-electricity conversion efficiency of DSSC can be effectively increased. Experimental results show that the photoelectric conversion efficiency of DSSC using CNT/TiO2 photoelectrode and N719 dye is increased by 41% from the original 3.45% to 4.87%.     

Nanowire array fabricated by Al-Ge phase separation

Phase-separated Al-Ge films, composed of Al nanowire array with diameters ranging from less than 10 to 18 nm embedded in an amorphous Ge matrix, have been prepared by a sputtering method. Similar to lateral phase separation of Al-Si system, sputtered Al and Ge form an Al nanowire array surrounded by a Ge matrix during film growth when the preparation conditions are optimized. Removal of the Al nanowires from the phase-separated Al-Ge films by etching in acid solution provides nanoporous films with a pore density on the order of 10¹⁵ pores/m². Template-assisted growth of Ni nanowires into the nanopores was carried out to increase the potential applications of the phase-separated Al-Ge films.     

ZnO纳米线阵列修饰对材料表面浸润性调控

采用溶胶-凝胶法制备了ZnO薄膜,利用溶剂热沉积法获得大面积均匀ZnO纳米线阵列。通过对水在ZnO材料表面的浸润性研究,发现薄膜材料表面的粗糙度对ZnO膜亲水性有增强作用,而周期性ZnO阵列微结构表面可以实现其疏水性质增强效果。同时从理论上分析了这两种现象的物理机制,讨论了空气填隙对ZnO纳米线阵列表面的浸润性质的敏感性。制备出ZnO纳米线阵列的表观接触角约为103°,具有较强的疏水性质,可为进一步的ZnO光流控研究提供实验基础。     

Solution fabrication and photoelectrical properties of CuInS₂ nanocrystals on TiO₂ nanorod array

One-dimensional semiconductor architectures are receiving attention in preparing photovoltaic solar cells because of its superior charge transport as well as excellent light-harvesting efficiency. In this study, vertically aligned single-crystalline TiO(2) nanorods array was grown directly on transparent conductive glass (FTO), and then CuInS(2) nanocrystals were deposited on nanorods array by spin coating method to form TiO(2)/CuInS(2) heterostructure films. The resulting nanostructure assembly and composition was confirmed by field-emission scanning electron microscope (FESEM) , transmission electron microscopy (TEM), high-resolution TEM, and X-ray diffraction(XRD). Ultraviolet-visible absorption spectroscopy (UV-vis) data indicates that the absorbance of the nanocomposite film extended into the visible region compared with bare TiO(2) nanorod arrays. The surface photovoltage spectra (SPS) also showed a new and enhanced response region corresponding to the absorption spectrum. These results suggest that the novel CuInS(2) nanocrystals sensitized TiO(2) nanorod array on FTO photoelectrodes has a potential application in photovoltaic devices.     

Growth of spin-capable multi-walled carbon nanotubes and flexible transparent sheet films

Iron-catalyzed spin-capable multi-walled carbon nanotubes (MWCNTs) were grown on a SiO2 wafer by chemical vapor deposition, which was carried out at 780 degrees C using C2H2 and H2 gases. We fabricated a flexible transparent film using the spun MWCNTs. The MWCNT sheets were produced by being continuously pulled out from well-aligned MWCNTs grown on a substrate. The MWCNT sheet films were manufactured by simply carrying out direct coating on a flexible film or glass. The thickness of the sheet film decreased remarkably when alcohol was sprayed on the surface of the sheet. The alcohol spraying increased the transmittance and decreased the electrical resistance of the MWCNT sheet films. The sheets obtained after alcohol spraying had a resistance of -699 omega and a transmittance of 81%-85%. The MWCNT sheet films were heated by applying direct current. The transparent heaters showed a rapid thermal response and uniform distribution of temperature. In addition, we tested the field emission of the sheet films. The sheet films showed a turn-on voltage of -1.45 V/microm during field emission.     

薄膜场发射阴极中纳米线密度的理论优化

现在人们正在研究各种纳米线薄膜 ,因为它们很有可能成为新一代的场发射阴极而被应用于平面显示器等器件中。研究表明 ,除了纳米线的物理特性 ,薄膜的场发射特性也强烈地依赖于纳米线阵列的几何构造。一方面 ,薄膜阴极的纳米线阵列密度要足够大 ,使得大量的场发射源能够产生。另一方面 ,过大的密度带来的屏蔽效应将严重削弱纳米线尖端的局域电场。在本文的参数下 ,利用Ansys软件计算出了纳米线的最佳间距———使得纳米线之间的屏蔽效应可以忽略的最小距离———为纳米线高度的两倍     

聚吡咯／多壁碳纳米管的合成及电化学行为

在含有多壁碳纳米管(MWCNT)的十二烷基苯磺酸钠(SDBS)溶液中电化学氧化吡咯(Py)制得聚吡咯/多壁碳纳米管(PPy/MWCNT)导电复合膜。研究了聚合温度、电流密度、吡咯浓度对PPy/MWC-NT复合膜沉积量的影响,采用交流阻抗谱(EIS)法研究了该导电复合膜的电化学行为,并用扫描电子显微镜对其表面形貌进行了观察。实验结果表明,随着温度的降低、电流密度及吡咯浓度的增大,复合膜沉积量变大。与纯PPy膜相比,PPy/MWCNT复合膜有更好的电子传递行为,而复合膜表面更加粗糙、疏松。     

Characterization of Sol-gel-derived TiO2 and TiO2-SiO2 Films for Biomedical Applications

In order to improve the corrosion resistance and biocompatibility of NiTi surgical alloy, TiO2 and TiO2-SiO2 thin films were prepared by sol-gel method. The surface characteristics of the film, which include surface composition, microstructure and surface morphology, were studied by X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectra (XPS), respectively. A scratching test was used to assess the interface adhesive strength between the film and substrate. The corrosion resistance of NiTi alloy coated with oxide films were studied by anodic polarization curves measurement in biological solution. Additionally, a preliminary study of the in vitro bioactivity of the films was conducted. The results indicated that TiO2 and TiO2-SiO2 (Ti/Si=4:1) films have higher electrochemical corrosion resistance and can be used as protective layers on NiTi alloy. In addition, TiO2-SiO2 composite films have better bioactivity than TiO2 film.     

FeS2/TiO2复合薄膜光电性能

采用溶液浸渍法在ITO导电玻璃表面的多孔TiO2薄膜上沉积了FeS2薄膜.使用Fe2O3粉末保护裸露在外的ITO导电膜在硫气氛中热处理后,制得了FeS2/TiO2复合薄膜.应用B531/H数显测厚指示表、数字式四探针测试仪、XJCM-8太阳电池测试仪等研究了FeS2/TiO2复合薄膜的厚度、ITO导电玻璃的电阻率以及FeS2/TiO2复合薄膜的光电性能.结果表明：此方法制得的FeS2/TiO2复合薄膜具有良好的光电性能;且ITO导电膜的电阻率变化较小.因而适宜制备色素增感太阳能电池（DSSC）.     

Photocatalytic TiO(2) deposition by chemical vapor deposition

Dip-coating, spray-coating or spin-coating methods for crystalline thin film deposition require post-annealing process at high temperature. Since chemical vapor deposition (CVD) process is capable of depositing high-quality thin films without post-annealing process for crystallization, CVD method was employed for the deposition of TiO(2) films on window glass substrates. Post-annealing at high temperature required for other deposition methods causes sodium ion diffusion into TiO(2) film from window glass, resulting in the degradation of photocatalytic efficiency. Anatase-structured TiO(2) thin films were deposited on window glass by CVD, and the photocatalytic dissociation rates of benzene with CVD-grown TiO(2) under UV exposure were characterized. As the TiO(2) film deposition temperature was increased, the (112)-preferred orientations were observed in the film. The (112)-preferred orientation of TiO(2) thin film resulted in a columnar structure with a larger surface area for benzene dissociation. Obviously, benzene dissociation rate was maximum when the degree of the (112) preferential orientation was maximum. It is clear that the thin film TiO(2) should be controlled to exhibit the preferred orientation for the optimum photocatalytic reaction rate. CVD method is an alternative for the deposition of photocatalytic TiO(2).     

Characterization of novel Ag on TiO2 films for surface-enhanced Raman scattering

Novel Ag on TiO2 films are generated by semiconductor photocatalysis and characterized by ultraviolet-visible (UV/Vis) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM), as well as assessed for surface-enhanced Raman scattering (SERS) activity. The nature and thickness of the photodeposited Ag, and thus the degree of SERS activity, is controlled by the time of exposure of the TiO2 film to UV light. All such films exhibit the optical characteristics (lambda(max) congruent with 390 nm) of small (< 20 nm) Ag particles, although this feature becomes less prominent as the film becomes thicker. The films comprise quite large (> 40 nm) Ag islands that grow and merge with increasing levels of Ag photodeposition. Tested with a benzotriazole dye probe, the films are SERS active, exhibiting activity similar to that of 6-nm-thick vapor-deposited films. The Ag/TiO2 films exhibit a lower residual standard deviation (approximately 25%) compared with Ag vapor-deposited films (approximately 45%), which is, however, still unacceptable for quantitative work. The sample-to-sample variance could be reduced significantly (< 7%) by spinning the film during the SERS measurement. The Ag/TiO2 films are mechanically robust and resistant to removal and damage by scratching, unlike the Ag vapor-deposited films. The Ag/TiO2 films also exhibit no obvious loss of SERS activity when stored in the dark under otherwise ambient conditions. The possible extension of this simple, effective method of producing Ag films for SERS, to metals other than Ag and to semiconductors other than TiO2, is briefly discussed.     

医用NiTi合金表面溶胶-凝胶法制备TiO2-SiO2薄膜

采用溶胶－凝胶法在ＮｉＴｉ形状记忆合金表面制备了ＴｉＯ_２－ＳｉＯ_２复合薄膜,在提高医用ＮｉＴｉ合金的抗腐蚀性方面,收到了显著的效果．运用电化学方法对不同组成的ＴｉＯ_２－ＳｉＯ_２薄膜在模拟体液中的腐蚀行为进行了研究,结果表明,随薄膜中 Ｔｉ／Ｓｉ比的增加,ＴｉＯ_２－ＳｉＯ_２薄膜的抗腐蚀性增强．划痕试验表明 ＴｉＯ_２－ＳｉＯ_２（Ｔｉ／Ｓｉ＝４：１）膜与ＮｉＴｉ合金基体具有较高的界面结合强度．用原子力显微镜（ＡＦＭ）对ＴｉＯ_２－ＳｉＯ_２薄膜的表面形貌及表面粗糙度进行观察和分析,解释并讨论了ＴｉＯ_２－ＳｉＯ_２薄膜的配方组成与其抗腐蚀性的关系,ＳｉＯ_２含量较少时,薄膜结构致密,膜层均匀平滑,且膜基结合力好,作为医用ＮｉＴｉ合金的表面保护层,可以使其耐腐蚀性有显著提高．