Fabrication of titanium oxide nanotube arrays by anodic oxidation

The formation of titanium oxide nanotube arrays on titanium substrates was investigated in HF electrolytes. Under optimized electrolyte and oxidation conditions, well-ordered nanotubes of titania were fabricated. Topologies of the anodized titanium change remarkably along with the changing of applied voltages, electrolyte concentration and oxidation time. Electrochemical determination and scanning electron microscope indicate the nanotubes are formed due to the competition of titania formation and dissolution under the assistance of electric field. A possible growth mechanism has also been presented.     

Self-cleaning characteristics on a thin-film surface with nanotube arrays of anodic titanium oxide

Self-cleaning of a surface of nanotube arrays of anodic titanium oxide (ATO) is demonstrated. The ATO was prepared in fluoride ion containing sulfate electrolytes with a structure of 0.4 μm length, 100 nm pores diameter, 120 nm interpore distance, 25 nm pore wall thickness, a 8×10⁹ pores cm⁻² pore density, and 68.2% porosity. Prepared as thin films either directly from a Ti foil or on a glass substrate, these arrays have the property that water drops spread quickly over the surface of the films without irradiation. In contrast, a flat anatase TiO₂ film requires irradiation with UV light for several minutes before the contact angle decreases to zero. The observed self-cleaning behavior of the ATO thin films is due to the capillary effect of the nanochannel structure and the superhydrophilic property of the anatase TiO₂ surface inside the tube.     

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.     

微流控技术制备ZnO纳米线阵列及其气敏特性

利用微流控技术在微通道中制备了Zn O纳米线阵列,通过X射线衍射和扫描电子显微镜分别对纳米线的物相和表面形貌进行了表征.结果发现,合成的Zn O纳米线具有良好的c轴择优取向性和结晶度.同时,对Zn O纳米线阵列在丙酮、甲醇和乙醇气体中的气敏特性进行了研究,测试结果表明:在最佳工作温度(475?C)下,纳米线阵列对200 ppm(1 ppm=10-6)丙酮气体的最大灵敏度可达8.26,响应恢复时间分别为9和5 s;通过与传统水热法制备的Zn O纳米线的气敏性能相比较发现,基于微流控技术制备的纳米线阵列具有更高的灵敏度和更快的响应恢复速度.最后,从材料表面氧气分子得失电子的角度对Zn O纳米线气敏机理进行了讨论.     

The sensitivity and dynamic response of field ionization gas sensor based on ZnO nanorods

Field ionization gas sensors based on ZnO nanorods (50–300 nm in diameter, and 3–8 μm in length) with and without a buffer layer were fabricated, and the influence of the orientation of nano-ZnO on the ionization response of devices was discussed, including the sensitivity and dynamic response of the ZnO nanorods with preferential orientation. The results indicated that ZnO nanorods as sensor anode could dramatically decrease the breakdown voltage. The XRD and SEM images illustrated that nano-ZnO with a ZnO buffer layer displayed high c-axis orientation, which helps to significantly reduce the breakdown voltage. Device A based on ZnO nanorods with a ZnO buffer layer could distinguish toluene and acetone. The dynamic responses of device A to the NO _x compounds presented the sensitivity of 0.045 ± 0.007 ppm/pA and the response speed within 17–40 s, and indicated a linear relationship between NO _x concentration and current response at low NO _x concentrations. In addition, the dynamic responses to benzene, isopropyl alcohol, ethanol, and methanol reveals that the device has higher sensitivity to gas with larger static polarizability and lower ionization energy.     

Synthesis and gas sensing characteristic based on metal oxide modification multi wall carbon nanotube composites

A new type of gas sensing material based on metal oxide modification multi wall carbon nanotube (MO/MWCNT) composites is presented since the interface between the composites enhance the carrier density so as to improve the gas sensitivity. Three kinds of MO/MWCNT composite materials, such as ZnO/MWCNT, SnO₂/MWCNT and TiO₂/MWCNT, have been acquired in situ growth using catalytic pyrolysis method. The MO nano particles have decorated on side of MWCNTs, whereas the introduction of SnO₂ nano particles makes part of MWCNT showing two-dimensional form of carbon nano-wall structure. Among four kinds of cathode of ZnO/MWCNTs, SnO₂/MWCNTs, TiO₂/MWCNTs and pure MWCNT composite film, TiO₂/MWCNTs composite has the lowest threshold electric field required to draw current of 12 μA has been found to be ∼1.2 V/μm, and also TiO₂/MWCNTs composite has the highest sensitivity of 16% to ethanol. The TiO₂/MWCNTs composite is superior to the others both in vacuum electron transportation and gas sensitivity.     

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)     

Negative index photonic crystal lenses based on carbon nanotube arrays

We report a novel utilization of periodic arrays of carbon nanotubes in the realization of diffractive photonic crystal lenses. Carbon nanotube arrays with nanoscale dimensions (lattice constant 400 nm and tube radius 50 nm) displayed a negative refractive index in the optical regime where the wavelength is of the order of array spacing. A detailed computational analysis of band gaps and optical transmission through the nanotubes based planar, convex and concave shaped lenses was performed. Due to the negative-index these lenses behaved in an opposite fashion compared to their conventional counter parts. A plano-concave lens was established and numerically tested, displaying ultra-small focal length of 1.5 μm (～2.3 λ) and a near diffraction-limited spot size of 400 nm (～0.61 λ).     

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.     

Characterization of lipid bilayer formation in aligned nanoporous aluminum oxide nanotube arrays

Aligning lipid bilayers in nanoporous anodized aluminum oxide (AAO) is a new method to help study membrane proteins by electron paramagnetic resonance (EPR) and solid-state nuclear magnetic resonance (NMR) spectroscopic methods. The ability to maintain hydration, sample stability, and compartmentalization over long periods of time, and to easily change solvent composition are major advantages of this new method. To date, 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) has been the only phospholipid used for membrane protein studies with AAO substrates. The different properties of lipids with varying chain lengths require modified sample preparation procedures to achieve well formed bilayers within the lining of the AAO substrates. For the first time, the current study presents a simple methodology to incorporate large quantities of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC), DMPC, and 1,2-dipalmitoyl-3-sn-phosphatidylcholine (DPPC) phospholipids inside AAO substrate nanopores of varying sizes. (2)H and (31)P solid-state NMR were used to confirm the alignment of each lipid and compare the efficiency of alignment. This study is the first step in standardizing the use of AAO substrates as a tool in NMR and EPR and will be useful for future structural studies of membrane proteins. Additionally, the solid-state NMR data suggest possible applications of nanoporous aluminum oxide in future vesicle fusion studies.     

基于收缩高密度碳纳米管阵列的柔性固态超级电容器

柔性超级电容器因其加工方式灵活,具有高的能量密度和可剪裁可弯曲的特性,近年来受到广泛的关注.碳纳米管阵列凭借其自身良好的电化学性能、高效的电荷转移率和良好的循环寿命被视为理想的能量储存材料.然而原始碳纳米管阵列密度较小,且因管间较弱的相互作用力使得其在加工和转移过程中容易倒塌散落,从而限制了碳纳米管阵列直接用于组装柔性电子器件.本文应用无水乙醇对阵列进行收缩处理,在保持阵列高度取向优势的前提下大大增加了阵列的密度和机械强度,同时使用生物相容性好的聚乙烯醇(PVA)导电凝胶包埋碳纳米管阵列来制备柔性固态超级电容器件.PVA包埋的阵列复合体在折叠、弯曲过程中既能保持良好的机械稳定性和柔性,又能保持碳纳米管的高度取向性.使用原位电氧化对碳纳米管阵列外壁进行简单的电化学修饰,可以进一步提高该复合器件的性能.该方法为未来研发可穿戴电子器件以及可植入医学器件提供了新思路.     

Fabrication and optical properties of platinum nanowire arrays on anodic aluminium oxide templates

Arrays of Pt nanowires, fabricated by electrodepositing Pt metal into nanoporous anodic aluminium oxide (AAO) templates, exhibit a preferable optical absorption band in the ultraviolet-visible (UV-VIS) spectra and present a blueshift as the wire aspect ratio increases or its radius decreases. This type of optical property of Pt nanowire/porous alumina composites has been theoretically explored using Maxwell－Garnett (MG) effective medium theory. The MG theory, however, is only applicable to nanowires with an infinitesimally small radius relative to the wavelength of an incident light. The nanowire radius is controlled by the pore radius of the host alumina, which depends on anodizing conditions such as the selected electrolyte, anodizing time, temperature and voltage. The nanowire aspect ratios depend on the amount of Pt deposited into the nanopores of AAO films. The optical absorption properties of the arrays of Pt nanowires with diameters of 24, 55 and 90 nm have been investigated by the UV-VIS spectra, which show that the extinction maximum (λ_max) shifts to shorter wavelength side as the wire aspect ratio increases or its radius decreases. The results are qualitatively consistent with those calculated based on the MG theory.     

Fabrication of thin-film transistor based on self-assembled single-walled carbon nanotube network

Thin-film transistor based on controllable electrostatic self-assembled monolayer single-wall carbon nanotubes (SWNTs) network has been fabricated by varying the density of nanotubes on the silicon substrate. The densities of SWNTs network have been investigated as a function of concentration and assembly time. It has been observed that the density of SWNTs network increases from 0.6 µm⁻² to 2.1 µm⁻², as the average on-state current (I_on) increases from 0.5 mA to 1.47 mA. The device has a current on/off ratio (I_on/I_off) of 1.3×10⁴ when I_on reaches to 1.34 mA.     

单根Sb掺杂ZnO微米线非平衡电桥式气敏传感器的制作与性能

通过使用化学气相沉积法,成功制备出超长、大尺寸的Sb掺杂ZnO微米线.基于非平衡电桥原理,利用单根Sb掺杂ZnO微米线作为非平衡电桥的一个桥臂,制作出了可以在室温环境下工作的气敏传感器原型器件.结果表明:室温下测得该传感器对20,50,100和200 ppm(1 ppm=10^-6)不同浓度的丙酮及乙醇气体的响应-恢复曲线均呈现为矩形形状,在空气及被测气体中均有稳定的电流值,并随着探测气体浓度的增大,器件的响应值也在逐渐增加.此外,还发现器件对丙酮气体具有更好的选择性,当丙酮气体浓度为200 ppm时,该传感器的响应时间为0.2 s,恢复时间为0.3 s,响应度高达243%.通过与普通电导式气敏传感器对比发现,采用这种非平衡电桥结构传感器可以明显地提高响应度,使响应和恢复时间更快.此外,还研究了器件的气体探测机理.     

Plasmonic sensor with variable claddings based on metallic slit arrays

We propose a plasmonic sensor with variable refractive index(RI), which exhibits high sensitivity and extraordinary optical transmission(EOT). Its variable RI is attributed to its dielectric layers and metallic slit arrays.According to simulation results, the third resonant wavelength has a wavelength sensitivity of 800 nm/RIU and an ultra-high transmittance of 0.8 by adjusting the RIs of the upper and lower dielectrics, incident light angle,and structural geometric parameters. With its unique features, the proposed structure holds considerable potential for extensive application to metal–dielectric grating sensors operating at visible and near-infrared frequencies.     

基于PET基片的柔性石墨烯应变计加工方法

针对PET塑料耐温性能较差,与标准微纳加工工艺不兼容等问题,开发了面向PET塑料基底材料的光刻、镀膜等微纳加工工艺。通过CVD生长、转移等方式将单层石墨烯薄膜附着于0.5 mm厚PET基底,并采用微纳加工的方式制备了柔性石墨烯压阻应变计。工艺结果表明,本研究所提出的加工方法适用于以PET塑料作为衬底材料的柔性微纳器件的制作。通过对PET塑料衬底施加应变并测量石墨烯的电阻变化率,可计算出石墨烯的压阻应变系数约为1.3。     

基于有限元软件分析碳纳米管的最佳阵列密度

利用有限元软件ANSYS,对碳纳米管的最佳阵列密度进行了分析。针对碳纳米管阵列静电场分布的特点,建立了碳纳米管的模型,确定了模型的边界条件。为了便于对计算结果进行对照,在分析时采用的参数是:阵列周期T=2000nm,单根碳纳米管长度L=1μm,顶端半径r=2nm。通过计算得到了单根碳纳米管的场增强因子为321。在长度L和顶端半径r不变的情况下,使用了参数化设计语言,计算了在不同周期(200～4000μm)下碳纳米管场增强因子随周期变化的情况,进一步利用Fowler Nordheim函数得到最佳阵列周期(1600μm)。结果证明,利用有限元软件,其分析过程不仅正确性,而且实用,并且为此类问题的解决提供了一个通用的方法。     

Nanocrystalline cerium oxide coated fiber optic gas sensor

A clad-modified fiber optic sensor with nanocrystalline CeO₂ is proposed for gas detection. As-prepared and annealed CeO₂ (500 °C) samples have been used as gas sensing media. The spectral characteristics of the fiber optic gas sensor are studied for various concentrations of ammonia, ethanol and methanol gases (0–500 ppm). The sensor exhibits linear variation in the spectral peak intensity with the gas concentration. The characteristics of the sensor are also studied for gas selectivity. The time response characteristics of the sensor are reported.     

大电流密度碳纳米管场致发射阴极阵列的研制

 设计了一种由TiN，Al，Fe和牺牲层构成的堆栈式催化剂层结构，采用微波等离子体化学气相沉积法实现碳纳米管阵列高速笔直生长。SEM和TEM结果表明，生长出来的碳纳米管为典型的多壁碳纳米管，长度和直径均匀，排列整齐并垂直于基底，生长速率大于5 μm/min，晶格缺陷少。场致发射测试结果表明：碳纳米管的发射阵列具有良好的电流发射稳定性，最大电流密度大于6 A/cm2。紫外光电子能谱法（UPS）测试出碳纳米管的功函数为4.59 eV，则相应的场致发射陈列的场增强因子大于1 400。     

基于银纳米线电极-rGO敏感材料的柔性NO2气体传感器

使用银纳米线作为材料制备柔性叉指电极,用还原氧化石墨烯(reduced graphene oxide, rGO)作为气体敏感材料制备出柔性气体传感器,并研究其对二氧化氮气体的响应特性以及柔韧性能.实验结果表明,制备的以银纳米线作为电极的r GO气体传感器可以实现室温下对浓度为5-50 ppm (1 ppm=10^–6)的NO2气体的检测,对50 ppm的NO2的响应能够达到1.19,传感器的重复性较好,恢复率能够保持在76%以上,传感器的灵敏度是0.00281 ppm^-1,对浓度为5 ppm的NO2气体的响应时间是990 s,恢复时间是1566 s.此外,传感器在0°-45°的弯曲角度下仍表现出优异的电学特性与气体传感性能,所制备的器件具有相对稳定的导电性和较好的弯曲耐受性.