Thermal stability of HfO2 nanotube arrays

Thermal stability of highly ordered hafnium oxide (HfO₂) nanotube arrays prepared through an electrochemical anodization method in the presence of ammonium fluoride is investigated in a temperature range of room temperature to 900 °C in flowing argon atmosphere. The formation of the HfO₂ nanotube arrays was monitored by current density transient characteristics during anodization of hafnium metal foil. Morphologies of the as-grown and post-annealed HfO₂ nanotube arrays were analyzed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Although monoclinic HfO₂ is thermally stable up to 2000 K in bulk, the morphology of HfO₂ nanotube arrays degraded at 900 °C. A detailed X-ray photoelectron spectroscopy (XPS) study revealed that the thermal treatment significantly impacted the composition and the chemical environment of the core elements (Hf and O), as well as F content coming from the electrolyte. Possible reasons for the degradation of the nanotube at high temperature were discussed based on XPS study and possible future improvements have also been suggested. Moreover, dielectric measurements were carried out on both the as-grown amorphous film and 500 °C post-annealed crystalline film. This study will help us to understand the temperature impact on the morphology of nanotube arrays, which is important to its further applications at elevated temperatures.     

Ni-doped TiO2 nanotube arrays on shape memory alloy

Self-organized Ni-Ti-O nanotube arrays were fabricated through a direct anodization of NiTi shape memory alloy in glycerol-based electrolyte. The growth of Ni-doped TiO₂ nanotube arrays was mainly affected by anodization voltage and temperature. Higher anodization voltage facilitated the growth of uniform nanotube arrays. Large-area open-ended Ni-Ti-O nanotube arrays could form on the surface of the shape memory alloy under a higher anodization temperature. The oxide nanotubes had a gradually changed composition along the growth direction of the nanotube and presented a thermal stability up to 400 °C. The nanotubular oxide demonstrated a much better hydrophilic behavior than that of the traditional oxide layer grown on NiTi substrate through air oxidization. The successful fabrication of Ni-doped TiO₂ nanotube arrays here makes it feasible to further explore excellent physical and chemical as well as biomedical properties of the nanotube-modified surfaces of the NiTi shape memory alloy.     

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     

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.     

Mesoporous nanotube aggregates obtained from hydrothermally treating TiO2 with NaOH

Nanotube aggregates with high porosity were prepared from hydrothermal treatment of TiO₂ particles in NaOH at 130 °C, followed by HCl rinsing to different pH values. Pore structure of the aggregates, which were mainly mesoporous, was characterized by analyzing the N₂ sorption isotherm with different methods including the t-plot and density function theory. The surface area, pore volume and mean pore size of the aggregates increased with the rinsing acidity to reach a maximum (e.g. 400 m²/g in surface area) at pH 1.6 and then decreased with further increase of the acidity. The crystalline phase and composition of the aggregates were, as well, significantly affected by the acidity of the post-treatment rinsing. Large-surface area aggregates were of loosely-attached nanotubes, composed of both anatase TiO₂ and H₂Ti₂O₅·H₂O, obtained under a mildly acidic rinsing condition, while basic or highly acidic conditions resulted in the formation of closely coagulated dense structures consisting of different crystalline phases.     

A study on photo-generated charges property in highly ordered TiO2 nanotube arrays

In this study TiO₂ nanotube arrays were fabricated by potentiostatic anodization of titanium sheet. The X-ray diffraction (XRD) pattern and field emission scanning electron microscopy (FE-SEM) image indicated the TiO₂ nanotube arrays were of pure anatase form and highly ordered. The properties of the photo-generated charges in the nanotube arrays were investigated by transient photovoltage (TPV) technique and surface photovoltage (SPV) technique based on lock-in amplifier with dc bias, in comparison with the commercial powder derived film. The separation processes of the photo-induced charges in the system of TiO₂ nanotubes on Ti have been demonstrated to be correlated with the incident light intensity, surface trapping states, and the interfacial electric field between Ti and TiO₂. The results also show that the highly ordered nanotube film could generate much stronger SPV responses under external electric field than the commercial powder derived film.     

多种金属/TiO2核壳纳米棒阵列的通用制备方法

使用了一种具有较大通用性的方法制备了金属/二氧化钛(TiO₂)核壳纳米结构. 采用电沉积方法在多孔氧化铝模板(AAO)孔洞中沉积壁厚均一的TiO₂纳米管,TiO₂纳米管的壁厚可以通过沉积时间来控制,而纳米管的直径和长度则由模板孔洞大小和模板厚度决定. 采用这种方法制备的TiO₂纳米管顶端是开放的,而底端连接在电沉积前溅射在AAO模板背面的金膜上. 这种TiO₂纳米管阵列结构适合进行二次电沉积,以它为模板将Pd、Cu、Fe等金属沉积到纳米管中形成核壳纳米棒结构. 这是一种可以用于制备多种金属/TiO₂核壳纳米结构的通用方法,采用这种方法制备的金属/TiO₂核壳纳米棒结构具有填充率高和取向性好的特点,而且它们的壁厚和长度可以通过分别改变两步电沉积的时间来控制.     

Fabrication of open-ended TiO2 nanotube arrays by anodizing a thermally evaporated Ti/Au bilayer film

Fabrication of TiO₂ nanotube arrays (TNAs) with through-hole morphology is practical significance to enhance the photocatalytic activity of TNAs, as well as expanding their applications. In present work, open-ended TNAs are synthesized on a conductive Au layer by anodizing a thermally evaporated Ti/Au bilayer film. In the anodizing process, the upper Ti layer is transformed into well-aligned TNAs. The barrier layer under the growing TNAs ultimately touches the Au layer and is completely dissolved by the electrochemical etching. In order to avoid the bubble disruption of TNAs caused by the water electrolysis after the Au layer is exposed to the electrolyte, a specific non-aqueous electrolyte is used. The XRD results reveal that the as-formed open-ended TNAs are amorphous and can be transformed into anatase by annealing at 350 °C.     

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%.     

Crystalline orientation preference for TiO2 nanotube arrays with efficient photoelectrochemical properties

Novel TiO₂ nanotube arrays (TiO₂ NTAs) with preferred oriented crystalline structure were firstly achieved by a facile method through anodizing Ti sheets with textured microstructure. Highly oriented crystalline structure of TiO₂ NTAs, with its (004) lattice plane of anatase TiO₂ paralleling to the top surface of TiO₂ NTAs was identified by the results of XRD, which was further confirmed by the regular diffraction spots and lattice fringes with uniform direction in HRTEM images. In comparison with normal randomly oriented TiO₂ NTAs, the quasi-single crystal structure of highly oriented TiO₂ NTAs can suppress the recombination of photogenerated electron–hole pairs and enhance the transfer of photocarriers, as was proved by the photoelectrochemical measurement conducted on both normal TiO₂ and oriented TiO₂ NTAs. The results of this study provide a promising avenue to obtain high photoelectrochemical performance TiO₂ NTAs-based hybrid nanomaterials.     

Optical and electrical characterization of TiO2 nanotube arrays on titanium substrate

Novel oriented aligned TiO₂ nanotube (TN) arrays were fabricated by anodizing titanium foil in 0.5% HF electrolyte solution. It is indicated that the sizes of the TNs greatly depended on the applied voltages to some extent. The electrical properties of the TN arrays were characterized by current-voltage (I-V) measurements. It exhibits a nonlinear, asymmetric I-V characterization, which can be explained that there exists an n-type semiconductor/metal Schottky barrier diode between TN arrays and titanium substrate interface. The absorption edges shift towards shorter wavelengths with the decrease of the anodizing voltages, which is attributed to the quantum size effects. At room temperature, a novel wide PL band consisting of four overlapped peaks was observed in the photoluminescence (PL) measurements of the TN arrays. Such peaks were proposed to be resulted from the direct transition X₁ → X₂/X₁, indirect transition Γ₁ → X₂/X₁, self-trapped excitons and oxygen vacancies, respectively.     

Alumina template-assisted electrodeposition of Bi2Te2.7Se0.3 nanowire arrays

Bi₂Te_2.7Se_0.3 nanowire arrays have been fabricated by electrodeposition into the pores of an anodic aluminum oxide (AAO) template followed by annealing at 300 °C under Ar atmosphere. The as-prepared nanowires were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. The nanowires are uniform single crystalline with diameter of ∼14 nm.     

Synthesis and field emission of diamond-like carbon nanorods on TiO2/Ti nanotube arrays

Highly ordered TiO₂/Ti nanotube arrays were fabricated by anodic oxidation method in 0.5 wt% HF. Using prepared TiO₂/Ti nanotube arrays deposited Ni nanoparticles as substrate, high quality diamond-like carbon nanorods (DLCNRs) were synthesized by a conventional method of chemical vapor deposition at 750 °C in nitrogen atmosphere. DLCNRs were analyzed by filed emission scanning electron microscopy and Raman spectrometer. It is very interesting that DLCNRs possess pagoda shape with the length of 3–10 μm. Raman spectra show two strong peaks about 1332 cm⁻¹ and 1598 cm⁻¹, indicating the formation of diamond-like carbon. The field emission measurements suggest that DLCNRs/TiO₂/Ti has excellent field emission properties, a low turn-on field about 3.0 V/μm, no evident decay at 3.4 mA/cm² in 480 min.     

Passivation of TiO2 by ultra-thin Al-oxide

The passivation of sol–gel TiO₂ by ultra-thin layers of Al-oxide has been investigated using transient and spectral photovoltage (PV) techniques. The ultra-thin layers of Al-oxide were prepared by the ion-layer gas reaction (ILGAR) technique and modified by thermal treatments in air, vacuum or Ar/H₂S atmosphere. The samples where characterized by elastic recoil detection analysis (ERDA), X-ray photoelectron spectroscopy (XPS), and contact potential difference (CPD) technique. Without an Al-oxide surface layer, electronic states in the forbidden gap of TiO₂ are formed during thermal treatments in vacuum and Ar/H₂S. The trap density is strongly reduced at the TiO₂/Al-oxide interface. The formation of electronic defects is prevented by a closed ultra-thin layer of Al-oxide.     

Effects of impurities containing phosphorus on the surface properties and catalytic activity of TiO2 nanotube arrays

TiO₂ nanotube arrays were prepared by titanium anodic oxidation with either HF or H₃PO₄/NH₄F aqueous electrolyte solutions. The samples were characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscope, photoluminescence spectra (PL) and photocurrent response. Aqueous solutions of methylene blue or Cr(VI) ions were used as the target pollutants to compare catalytic activities of the two nanotube array types. The amorphous impurities containing phosphorus were confirmed by XRD and IR, for the sample synthesized with H₃PO₄/NH₄F electrolytes. They closed a portion of the active sites, acted as recombination centers of photo-generated charges, and were also involved in the negative reactions of competing photo-generated holes or OH radicals. The TiO₂ nanotube arrays formed in the H₃PO₄/NH₄F electrolytes exhibited a stronger fluorescence spectrum, a weaker photocurrent and a lower catalytic activity than the sample fabricated with HF electrolyte without phosphorus impurities.     

Synthesis and bioactivity of highly ordered TiO2 nanotube arrays

The highly ordered TiO₂ nanotube arrays were fabricated by potentiostatic anodization of Ti foils in fluorinated dimethyl sulfoxide (DMSO). TiO₂ nanotube arrays are formed using a 40 V anodization potential for 24 h, with a length of 12 μm, diameter of 170 nm and aspect ration of about 70. The as-prepared nanotubes are amorphous, but can be crystallized as the heat treatment temperature increases. Anatase phase appears at a temperature of about 300 °C, then transforms to rutile phase at about 600 °C. After heat treatment at 500 °C and soaking in SBF for 14d, a thick apatite layer of about 13 μm covers the whole surface of TiO₂ nanotube arrays, indicating their excellent in vitro bioactivity, which is mainly attributed to their high specific surface area and the anatase phase.     

The effect of pre-pattern on the morphology and growth speed of TiO2 nanotube

In this work, we presented a new method which directly acts on the surface of the Ti sheet by mechanical micro-etching using a grating ruling engine. The effect of the pre-pattern on the morphology and growth speed of TiO₂ nanostructure formed on the Ti sheet with the traditional anodization method was investigated. A novel wall structure was observed and the growth speed of TiO₂ nanotube (NT) was greatly affected by the pre-pattern. The wall structure increases the surface-to-volume ratio of the nanotube arrays. The new method provided the possibility of further optimization of fast growth of TiO₂ nanostructure and improving the efficiency of dye-sensitized solar cell (DSSC) and photocatalysis.     

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%.     

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。     

Fabrication, characterization and photoelectrochemical properties of Fe2O3 modified TiO2 nanotube arrays

TiO₂ nanotube (NT) arrays modified by Fe₂O₃ with high sensibility in the visible spectrum were first prepared by annealing anodic titania NTs pre-loaded with Fe(OH)₃ which was uniformly clung to the titania NTs using sequential chemical bath deposition (S-CBD). The photoelectrochemical performances of the as-prepared composite nanotubes were determined by measuring the photo-generated currents and voltages under illumination of UV-vis light. The titania NTs modified by Fe₂O₃ showed higher photopotential and photocurrent values than those of unmodified titania NTs. The enhanced photoelectrochemical behaviors can be attributed to the modified Fe₂O₃ which increases the probability of charge-carrier separation and extends the range of the TiO₂ photoresponse from ultraviolet (UV) to visible region due to the low band gap of 2.2 eV of Fe₂O₃.