Experimental observation of two‐layer TiO2 nanotube arrays prepared by stepping‐voltage anodization

Two‐layer TiO₂ nanotube arrays were produced by stepping down the anodic voltage during which three nanotube interface structures between the top layer and the second layer were observed by SEM. We detected a polygonal ring structure on the top surface of the second layer and offer direct evidence of the growth of this second tube layer both at the cell boundary and right beneath the bottom of the first tube layer. For these processes, a possible growth mechanism is presented. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Highly defined and ordered top‐openings in TiO2 nanotube arrays

We report a very simple and novel approach to produce anodic TiO₂ nanotube arrays with highly defined and ordered tube openings. It is based on carrying out anodization through a slowly soluble photoresist coating. This eliminates the formation of undesired initiation layers on the tube tops and protects them to a certain extent from etching by the electrolyte.

     

Fabrication and characterization of ZnO-coated TiO2 nanotube arrays

In this study, we prepared highly ordered TiO₂ nanotube arrays on Ti through an anodizing process. Then, utilizing its proven antibacterial properties, we coated our TiO₂ nanotubes (TiO₂-NTs) with ZnO using the sol–gel method. We characterized the morphology, structure, and composition of the ZnO-coated TiO₂ nanotubes (ZnO-TNTs) using field-emission scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy, respectively. We investigated surface topography and roughness of the coatings by atomic force microscopy operated in the tapping mode. Our results revealed impurity-free, anatase-phase TiO₂ nanotubes that are uniformly coated with a ZnO layer. Finally, we tested the antibacterial activity of ZnO-TNTs against Staphylococcus aureus, and found ZnO-TNTs significantly improved the antibacterial properties of Ti implants. We conclude that ZnO-TNTs provide Ti with antibacterial activity, which highlights its potential in orthopedic and dental implants.     

Ru‐doped TiO2 nanotubes: Improved performance in dye‐sensitized solar cells

In the present work we use a series of Ti–Ru alloys, with minor amounts of Ru (0.01, 0.02, 0.05 and 0.2 at%) to grow anodic self‐organized Ru‐doped TiO₂ nanotube layers. When used in dye‐sensitized solar cells (DSSCs), the nanotube layers with an optimum amount of Ru (0.02 at% Ru in the alloy) show a considerable increase in solar cell efficiency (η = 5.2%) under AM1.5 (100 mW/cm²) conditions compared with non‐doped TiO₂ nanotubes (η = 4.3%).

     

Antireflection ln2O3 coatings of self‐organized TiO2 nanotube layers prepared by atomic layer deposition

We report on the uniform anti‐reflection coating of TiO₂ nanotube layers with a secondary material – indium trioxide (In₂O₃) – by atomic layer deposition (ALD). We provide for the first time the detailed evidence of the ALD deposited coating inside nanotubes for three different tube layers with aspect ratio up to ≈80, which is so far the highest aspect ratio reported for ALD‐processed self‐organized anodic TiO₂ nanotubes. We show that uniform In₂O₃coating of the nanotubes strongly influences the overall reflectance of the layers due to intrinsic properties of In₂O₃. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

PbSe/TiO2同轴异质结纳米管的制备及光催化性能

通过溶液法合成了PbSe/TiO2复合纳米管,并对其进行了微观形貌、晶体结构等的表征。结果表明,制得的样品是由PbSe和TiO2两种材料构成的复合材料,致密、均匀的TiO2薄膜包覆在PbSe纳米管表面。以氙灯为模拟光源,通过对甲基橙的降解研究了PbSe/TiO2复合纳米管的光催化性能。结果显示,PbSe与TiO2之间形成的异质结使PbSe/TiO2复合纳米管具有较高的光催化性能,比纯PbSe纳米管的催化降解率提高了约4.5倍。另外,对PbSe/TiO2复合纳米管光催化稳定性也进行了研究。     

阵列碳纳米管的石墨化程度

采用化学气相沉积法制备了阵列碳纳米管薄膜,对阵列碳纳米管的石墨化程度进行了系统研究。利用扫描电子显微镜(SEM)、拉曼光谱(Raman)对样品形貌以及结构进行了表征。探讨了不同实验参数对阵列碳纳米管石墨化程度影响的机理。结果发现,在一定催化剂浓度范围内,催化剂浓度过低时,阵列碳纳米管的石墨化程度较差,而随着催化剂浓度的增加,阵列碳纳米管的石墨化程度逐渐变好;生长石墨化程度较好的阵列碳纳米管需要合适的进液速度,进液速度过低或过高都会使得碳纳米管的石墨化程度变差;此外,生长石墨化程度较好的阵列碳纳米管也需要合适的生长温度,生长温度过低或过高都会使得碳纳米管的石墨化程度变差。     

含水量对TiO2纳米管形貌控制参数的影响

以不同含水量的乙二醇溶液为电解液,采用阳极氧化法制备TiO2纳米管阵列。通过记录反应过程中电导率、粘度及回路电流随时间的变化曲线,研究含水量对电解液粘度、电导率及电流等过程参数的影响,分析了纳米管形貌尺寸与TiO2溶蚀所耗电荷量的关系。粘度初始值和初始电导率均与含水量呈三次关系,相关系数分别为0.992 5和0.977 8。在反应过程中,溶液粘度值有缓慢增加的趋势。由于不同含水量的电解液粘度的不同,H+和OH-数量不同,F-迁移速率不同,电导率-时间曲线及电流-时间曲线具有不同的变化趋势,并对其进行了理论分析。当水体积分数为4%,5%,6%和10%时,纳米管的形貌较为有序并且TiO2纳米管阵列表面的碎片较少,纳米管直径变化范围为50 nm至72 nm,长度变化范围为0.85~1.90 m。F-腐蚀氧化膜时所消耗电量与TiO2氧化膜被腐蚀掉的体积呈一次函数关系,即腐蚀电量越大,腐蚀掉的体积越大,为制备一定形貌尺寸的纳米管提供了一定的控制方法。     

Influence of anodization parameters on the morphology of TiO2 nanotube arrays

TiO₂ nanotube arrays can be fabricated by electrochemical anodization in organic and inorganic electrolytes. Morphology of these nanotube arrays changes when anodization parameters such as applied voltage, type of electrolyte, time and temperature are varied. Nanotube arrays fabricated by anodization of commercial titanium in electrolytes containing NH₄F solution and either sulfuric or phosphoric acid were studied at room temperature; time of anodization was kept constant. Applied voltage, fluoride ion concentration, and acid concentrations were varied and their influences on TiO₂ nanotubes were investigated. The current density of anodizing was recorded by computer controlled digital multimeter. The surface morphology (top-view) of nanotube arrays were observed by SEM. The nanotube arrays in this study have inner diameters in range of 40-80 nm.     

Synthesis of high‐aspect‐ratio,top‐open and ultraflat‐surface TiO2 nanotubes through double‐layered configuration

In this Letter, a novel modified anodization was utilized to synthesize high‐aspect‐ratio, top‐open and ultraflat‐surface TiO₂ nanotubes. The interruption of voltage during anodization leads to the formation of a double‐layered structure. Due to the weak mechanical connection between the upper and the underlying layer, the two parts can be easily detached. Compared with the conventional ultrasonication method to remove the clusters of nanotubes where rough surfaces resulted, this efficient and reliable strategy may facilitate further applications of TiO₂ nanotubes in diverse conditions.

     

Integration of individual TiO2 nanotube on the chip: Nanodevice for hydrogen sensing

Titania (TiO₂) exists in several phases possessing different physical properties. In view of this fact, we report on three types of hydrogen sensors based on individual TiO₂ nanotubes (NTs) with three different structures consisting of amorphous, anatase or anatase/rutile mixed phases. Different phases of the NTs were produced by controlling the temperature of post‐anodization thermal treatment. Integration of individual TiO₂ nanotubes on the chip was performed by employing metal deposition function in the focused ion beam (FIB/SEM) instrument. Gas response was studied for devices made from an as‐grown individual nanotube with an amorphous structure, as well as from thermally annealed individual nanotubes exhibiting anatase crystalline phase or anatase/rutile heterogeneous structure. Based on electrical measurements using two Pt complex contacts deposited on a single TiO₂ nanotube, we show that an individual NT with an anatase/rutile crystal structure annealed at 650 °C has a higher gas response to hydrogen at room temperature than samples annealed at 450 °C and as‐grown. The obtained results demonstrate that the structural properties of the TiO₂ NTs make them a viable new gas sensing nanomaterial at room temperature. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

有序TiO2纳米管阵列结构的可控生长及其物相研究

分别在HF水溶液、含NH₄F和H₂O的乙二醇有机溶液中对Ti箔进行阳极氧化,得到TiO₂纳米管阵列结构.该结构高度有序、分布均匀、垂直取向,且通过阳极氧化工艺条件(如阳极氧化电压、电解液的选择与配比以及氧化时间等)可实现对其结构参数(如管径、管壁厚度、管密度、管长等)的有效控制.利用XRD研究了TiO₂纳米管阵列的物相结构.结果表明：退火前的TiO₂纳米管阵列为无定形结构;分别在真空和氧气氛中50 关键词： 2纳米管阵列')" href="#">TiO₂纳米管阵列 阳极氧化 可控生长     

SERS study of Ag nanoparticles electrodeposited on patterned TiO2 nanotube films

In this work, Ag nanoparticles (NPs) were deposited on patterned TiO₂ nanotube films through pulse‐current (PC) electrodeposition, and as a result patterned Ag NPs films were achieved. Scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and X‐ray diffraction (XRD) were used, respectively, to study the morphology, uniformity, and phase structure of the patterned Ag NP films. The size and density of the as‐deposited Ag NPs could be controlled by changing the deposition charge density, and it was found that the patterned Ag NP films produced under a charge density of 2.0 C cm⁻² gave intense UV–vis and Raman peaks. Two‐dimensional surface‐enhanced Raman scattering (SERS) mapping of rhodamine 6G (R6G) on the patterned Ag NP films demonstrated a high‐throughput, localized molecular adsorption and micropatterned SERS effect. Copyright © 2010 John Wiley & Sons, Ltd.     

对碳纳米管阵列的场发射电场增强因子以及最佳阵列密度的研究

研究了外电场、碳纳米管自身线度、尤其管的阵列密度对碳纳米管的场发射性能的影响,从理论上深入探索碳纳米管阵列的电场增强因子并提出改善其场发射电子性能的有效途径.研究结果表明,碳纳米管阵列的电场增强因子的数量级一般为102—103,并对任何长径比的碳纳米管阵列,都对应着一个最佳阵列密度,当碳纳米管阵列密度取此最佳密度值时,其电场增强因子明显提高.这里的理论研究对弄清碳纳米管的场发射机理及实验合成高发射性能的碳纳米管阵列有一定的意义 关键词： 碳纳米管阵列 最佳阵列密度 电场增强因子 长径比     

Applying the statistical experimental method to evaluate the process conditions of TiO2 nanotube arrays by anodization method

Vertically oriented TiO₂ nanotube arrays were successfully produced by the anodization technique in NH₄F/H₃PO₄ electrolyte. The structure and morphology were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). It is found that TiO₂ nanotube arrays annealed at 500 °C containing 100% anatase phase and entirely converted into rutile at 800 °C. The response surface methodology (RSM) and Box-Behnken design were applied to find the optimal factor conditions in production of TiO₂ nanotube arrays. Based on the results in preliminary experiments, we selected anodization time, anodization voltage and NH₄F concentration as the key factors to investigate their effects on responses. The regression models were built by fitting the experimental results with a second-order polynomial. By using the regression models, the optimal factor conditions were obtained as follows: anodization time of 300 min; anodization voltage of 15.39 V; NH₄F concentration of 0.50 M. Corresponding to the optimal factor conditions, the predicted average length and diameter of nanotube array were 1429 nm and 33 nm, respectively. Confirmation experiments using the optimized conditions were performed: TiO₂ nanotube arrays were obtained with an average tube length of 1420 nm and average tube diameter of 36 nm. The experimental results are in good agreement with the predicted results.     

Photoelectrochemical property and photocatalytic activity of N-doped TiO2 nanotube arrays

N-doped TiO₂ nanotube arrays (NTN) were prepared by anodization and dip-calcination method. Hydrazine hydrate was used as nitrogen source. The surface morphology of samples was characterized by SEM. It showed that the mean size of inner diameter was 65 nm and wall thickness was 15 nm for NTN. The ordered TiO₂ nanotube arrays on Ti substrate can sustain the impact of doping process and post-heat treatment. The atomic ratio of N/Ti was 8/25, which was calculated by EDX. Photoelectrochemical property of NTN was examined by anodic photocurrent response. Results indicated the photocurrent of NTN was nearly twice as that of non-doped TiO₂ nanotube arrays (TN). Photocatalytic activity of NTN was investigated by degrading dye X-3B under visible light. As a result, 99% of X-3B was decomposed by NTN in 105 min, while that of TN was 59%.     

基于一维TiO_2纳米管阵列薄膜的β伏特效应研究

介绍了一种采用宽禁带半导体二氧化钛纳米管阵列薄膜材料制备β伏特效应同位素电池的方法.通过对金属钛片的电化学阳极氧化制备了垂直定向、有序排列的二氧化钛纳米管阵列薄膜,研究了退火条件对二氧化钛纳米管阵列薄膜半导体光电性能的影响.通过与镍-63辐射源的集成封装,形成三明治结构镍-63/二氧化钛纳米管阵列薄膜/钛片的β伏特同位素电池.实验结果表明,基于氩气氛围下450?C退火的黑色二氧化钛纳米管阵列薄膜具有高的氧空位缺陷浓度和宽的可见-紫外吸收光谱.在使用β辐射总能量为10 m Ci的镍-63辐射源时,同位素电池的开路电压为1.02 V,短路电流75.52 n A,最大有效转换效率为22.48%.     

Auto‐barrier‐thinning effect under rapid anodization of nanoporous alumina membrane

We have developed a rapid non‐steady anodization technique that leads to an in‐situ auto‐thinning of the barrier layer due to a space charge limited condition that modifies the local fields at the interfaces of the Al‐Al₂O₃‐electrolyte ternary system. Unlike steady‐state growth, in this non‐steady case an unequal movement of the boundaries of barrier takes place which etches the electrolyte‐oxide interface more than the oxide grows at the oxide‐metal interface, leading to a thinner barrier layer and favouring its complete removal via wet‐etching process. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Direct‐current nanogenerator based on ZnO nanotube arrays

Due to the special structure of a nanotube (NT), the different potential from piezoelectricity can be naturally divided by the hollow of the tube when the NT is bent or deformed. Furthermore, both the bent/deformed inner and outer wall can form a steady voltage/current, which might enhance the output voltage/current. We demonstrate a direct‐current nanogenerator (NG) based on zinc oxide (ZnO) NT arrays driven by an ultrasonic wave. The average output voltage is ca. 0.10 mV and the current density is ca. 0.069 μA/mm². Our study shows that the maximum power output of the ZnO NT array NG is 0.112 nW and the power density is 1.4 nW/cm². The success of energy harvesting from ZnO NTs reveals the potential of using nanogenerators for tubular piezoelectric materials. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)