Controllable fabrication of highly ordered thin AAO template on Si substrate for electrodeposition of nanostructures

In this work, simple fabrication of hexagonally highly ordered porous anodic aluminum oxide (AAO) of Al thin film (1 μm) on Si substrate is described using two-step anodization method for electrochemical synthesis of nanostructures. In this method, the templates were prepared under the controllable conditions of the parameters, which give rise to the possibility of highly ordered nanopore arrays with a well aspect ratio. Pore widening was then fulfilled in 5 wt% phosphoric acid solution at 25 °C. The pore diameter and spacing are proportional to the applied voltage, which is due to the mechanical stress associated with the volume expansion of the aluminum during the anodization according to the mechanical stress model. Pore-widening solution adjusted the pore diameter and thinned the AAO barrier layer at room temperature under the control of etching time. As an application, Cu nanorods arrays embedded in anodic alumina (AAO) template were fabricated by dc electrodeposition. The characterization of the AAO templates and the Cu nanorods produced was made by X-ray diffraction, field emission scanning microscope, energy dispersive X-ray spectroscopy and atomic force microscope (AFM). The images of AFM show that porous AAO template under constant voltage is 40 V which presents the optimum ordering.     

Effect of processing on structural features of anodic aluminum oxides

Morphological features of the anodic aluminum oxide (AAO) templates fabricated by electrochemical oxidation under different processing conditions were investigated. The selection of the polishing parameters does not appear to be critical as long as the aluminum substrate is polished adequately prior to the anodization process. AAO layers with a highly ordered pore distribution are obtained after anodizing in 0.6 M oxalic acid at 20 °C under 40 V for 5 minutes suggesting that the desired pore features are attained once an oxide layer develops on the surface. While the pore features are not affected much, the thickness of the AAO template increases with increasing anodization treatment time. Pore features are better and the AAO growth rate is higher at 20 °C than at 5 °C; higher under 45 V than under 40 V; higher with 0.6 M than with 0.3 M oxalic acid.     

Novel structure formation at the bottom surface of porous anodic alumina fabricated by single step anodization process

A simple approach for the growth of long-range highly ordered nanoporous anodic alumina film in H₂SO₄ electrolyte through a single step anodization without any additional pre-anodizing procedure is reported. Free-standing porous anodic alumina film of 180 μm thickness with through hole morphology was obtained. A simple and single step process was used for the detachment of alumina from aluminum substrate. The effect of anodizing conditions, such as anodizing voltage and time on the pore diameter and pore ordering is discussed. The metal/oxide and oxide/electrolyte interfaces were examined by high resolution scanning transmission electron microscope. The arrangement of pores on metal/oxide interface was well ordered with smaller diameters than that of the oxide/electrolyte interface. The inter-pore distance was larger in metal/oxide interface as compared to the oxide/electrolyte interface. The size of the ordered domain was found to depend strongly upon anodizing voltage and time.     

Synthesis of ordered ZnO nanowire arrays from aqueous solution using AAO template

In this paper we report a simple method that enables the easy fabrication of ordered ZnO nanowire arrays using Anodic Aluminium Oxide (AAO) template. We have used a vacuum injection technique to fill solution into the pores of an AAO template. The AAO template has been fabricated by a two-step anodization process using 0.3 M oxalic acid (H₂C₂O₄) solution under a constant voltage of 40 V. The AAO template formed through this process has been detached from Al substrate via an anodic voltage pulse using perchloric acid (HClO₄) solution (70%). The nanowires of ZnO have been synthesized by injecting the saturated Zn(NO₃)₂ solution into the pores of the detached AAO template using a vacuum pump. The ZnO nanowires synthesized by this technique have been found dense & continuous with uniform diameter throughout the length of the wire. The structural characteristics of AAO template and ZnO nanowires have been studied by Field Emission Scanning Electron Microscope (FESEM), Atomic force microscope (AFM) and Transmission Electron Microscope (TEM).     

通孔阳极氧化铝膜的制备及其性能的研究

在15% H₂SO₄阳极氧化液中添加硝酸镨制备阳极氧化铝(AAO)膜以提高AAO膜的性能,采用化学腐蚀和微波处理相结合的方法,去除AAO膜的阻挡层,制备通孔的AAO膜。分别研究镨的添加量、氧化电压对AAO膜的厚度和硬度的影响及腐蚀时间、微波处理时间分别对AAO膜的阻挡层的影响,分别用能谱和扫描电镜等对AAO膜进行了表征。在15% H₂SO₄阳极氧化液中添加硝酸镨,制备出的AAO膜具有更大的厚度和硬度,当氧化电压为23 V时,在15% H₂SO₄+0.14 Pr g·L-1混合液中制备的AAO膜的厚度和硬度分别为162 μm和275.1 HV,与在阳极氧化液为15% H₂SO₄溶液中制备的AAO膜的厚度和硬度(150 μm和224.8 HV)相比,分别提高8.0%和22.4%。当氧化电压在19～23 V范围时,AAO膜的厚度随着氧化电压的增大而增加;AAO膜的硬度随着氧化电压的增大而减小。将AAO膜在35 ℃和5% H₃PO₄溶液中腐蚀13 min,再用超声波处理10 min,可得到通孔的AAO膜。腐蚀后AAO膜表面絮状物为Al₂O₃。     

Anodic aluminium oxide: Concurrent SEM and SANS characterisation. Influence of AAO confinement on PEO mean-square displacement

Anodic aluminium oxide (AAO) membranes are macroscopically highly ordered systems made of oriented nano-scale parallel cylindrical channels. The membrane topology is defined by the pore radius, the inter-pores distance and the pore length. We show by a combined SANS and SEM study that the membrane morphology can be tailored by the main anodization parameters: voltage, temperature and anodization duration. We show that the confinement of an hydrophilic polymer (poly(ethylene oxide)) inside the pores is possible. We observe a striking effect of the confinement on the polymer mean-square displacement as measure by high resolution neutron quasi-elastic scattering.     

Study on Fluorescence Characteristic of Quercetin–Nanoporous Anodic Aluminum Oxide Composites

Nanoporous Anodic Aluminum Oxide (AAO), its average diameters of porous were 50 nm, was obtained by two-step electrochemical anodization aluminum process. Highly ordered luminescence arrays formed by filling AAO nanopores with quercetin molecules has been studied by fluorescent spectroscopy in this work. AAO showed stronger adsorption capability of quercetin than Al³⁺-quercetin complex. The mechanism may be physical and chemical adsorption all together. Meanwhile, red shift of the maximum fluorescence peak of quercetin in AAO was observed. The molecular assemblies in the nanopore array are highly ordered and the fluorescence polarization dependence indicates a preferred molecular orientation along the pore axis. This maybe explains the mechanism of molecular luminescence depending on its environment.     

高质量规则多孔氧化铝模板的制备

在合适的条件下利用阳极氧化高纯铝片，可以获得多孔结构的氧化铝，其孔径大小和排列方式都很均匀.由于孔的深度不受限制，因此可以制备出孔深很大的多孔氧化铝.这种多孔结构可以用作制备纳米材料的模板.利用0.3mol/L的草酸溶液在40V的直流电压下，采用二步氧化法获得了高质量的氧化铝多孔模板，其典型孔径值为40—70nm，孔间距约110nm，深度可达毫米量级.分析了溶液温度对结果的影响，比较了单步法和两步法获得的样品的多孔结构，认为低温下的二步氧化法可以获得很好的多孔氧化铝模板. 关键词： 纳米材料 多孔氧化铝 二步氧化法     

Synthesis of highly ordered nanopores on alumina by two-step anodization process

Highly ordered anodic alumina was produced, on RF sputtered aluminium on a conductive glass substrate, by two step anodizing process in 0.4 M sulphuric acid at constant cell potentials of between 5 and 25 V and at a constant current density of 20 mA cm⁻². The temperature was kept constant at 15 °C during both anodization processes. The effects of the anodizing potential, current density, and time on the pore diameters were established. Longer anodization periods result in wider irregular pores with reduced porosity for both constant potential and constant current density anodization processes. The current density increases with increasing constant anodizing potential and generally remains constant with time after a sharp rise. Potential drop during constant current density anodization behaves in a similar manner. We confirm that sulphuric acid has a self-ordering potential of 25 V above which burning occurs.     

Fabrication of Anodic Aluminum Oxide Templates with Small Interpore Distances

The influence of the electropolishing and anodization voltage on surface morphology has been carefully studied for fabrication of ordered anodic aluminum oxide （AAO） templates. In accordance with that in the anodization experiment, the size of small patterns on the foil surface formed from the electropolishing treatment increases with voltage. Using a combined method of small-voltage eleetropolishing and anodization, we have fabricated well ordered templates with much smaller interpore distances compared with that under normal-voltage fabrication conditions. The Ni nanowire arrays with two small diameters are eleetrodeposited through the above templates, exhibiting different magnetic properties. This also helps us to clarify the inner structure of this kind of templates.     

Temperature dependence of a nanoporous Pd film hydrogen sensor based on an AAO template on Si

In this study, hydrogen sensing properties of nanoporous Pd films based on Anodic Aluminium Oxide (AAO) templates grown on a silicon substrate have been investigated at various temperatures (25–100°C) and hydrogen concentrations (100–1000 ppm) to determine the temperature-sensitivity relationship. For this purpose, a hexagonally shaped AAO template of approximately 50 nm in diameter and 700 nm in length with 80 nm interpore distances was fabricated using two-step anodization of an Al film deposited on an n-type (100) oriented oxidized Si substrate. Then, the nanoporous surface of the AAO template was used as a substrate for supporting a nanoporous Pd film of an approximately thickness of 60 nm. The morphologies of the AAO template and Pd film coated on the AAO template were studied mainly by Scanning Electron Microscopy (SEM). Hydrogen sensing properties of the nanoporous Pd film were measured using a resistance transient method. It was found that the sensor response of the nanoporous Pd films on the AAO template was better than the traditional Pd thin film sensors, the sensitivity of the sensor was approximately 1.8% for 1000 ppm H₂, and the detection limit was lower than 100 ppm at room temperature. The highest sensitivity was measured at room temperature.     

Nanoporous alumina membrane prepared by nanoindentation and anodic oxidation

The fabrication of nanopatterned surfaces at large scale attracts the interest of research groups from a wide range of areas as biotechnology, nanoelectronics and nanomagnetism. An extended method to pattern the surface in the nanoscale is the fabrication of ordered arrays of nanoelements based on porous templates as Nanoporous Anodic Aluminium Oxide (NAAO). One of the challenges of the NAAO fabrication, based on self-organized methods, is the control of the symmetry and lattice parameter of the ordered nanoporous films. In this work, we present a combined method based on Atomic Force Microscopy (AFM) nanoimprint and anodic oxidation of Al surface. AFM nanoindentations substitute the first anodization process and even more important, allow us to control the symmetry and the lattice parameter of the ordered arrays. In addition, by using AFM nanoimprint method it is possible to select the region were the ordered alumina grows. We demonstrate that square nanoporous arrays of alumina with lattice parameter of 105 nm can be obtained by this method.     

Influence of defects on the ordering degree of nanopores made from anodic aluminum oxide

Anodic aluminum oxide (AAO) templates with highly ordered nanoporous structure were fabricated by means of the electrochemical anodization under the constant anodic voltage and electrolyte temperature. The dependence of the ordering degree of nanopores on the point defects, dislocation configuration and grain boundary of aluminum is qualitatively analyzed. Experiment results show that the size of the ordered region of nanopores depends strongly on the point defects, dislocation cell configuration.     

Characteristics and self-cleaning effect of the transparent super-hydrophobic film having nanofibers array structures

Transparent super-hydrophobic films were fabricated using the PDMS method and silane process, based on anodization in phosphoric acid. Contact angle tests were performed to determine the contact angle of each film according to the anodizing time. Transmittance tests also were performed to obtain the transparency of each TPT (trimethylolpropane propoxylate triacrylate) replica film according to the anodizing time. The contact angle was determined by studying the drop shape, and the transmittance was measured using a UV-spectrometer. The contact angle increases with increasing anodizing time, because increasing pillar length can trap more air between the TPT replica film and a drop of water. The transmittance falls with increasing anodizing time because the increasing pillar length causes a scattering effect. This study shows that the pillar length and transparency are inversely proportional. The TPT replica film having nanofibers array structures was better than other films in aspect of self-cleaning by doing quantitative experimentation.     

Synthesis and surface characterization of alumina-silica-zirconia nanocomposite ceramic fibres on aluminium at room temperature

Alumina-silica-zirconia nanocomposite (ASZNC) ceramic fibres were synthesized by conventional anodization route. Scanning Electron Microscopy (SEM), Atomic Force microscopy (AFM), X-Ray Diffraction (XRD) and Energy Dispersive X-Ray spectroscopy (EDAX) were used to characterize the morphology and crystalloid structure of ASZNC fibres. Current density (DC) is one of the important parameters to get the alumina-silica-zirconia nanocomposite (ASZNC) ceramic fibres by this route. Annealing of the films exhibited a drastic change in the properties due to improved crystallinity. The root mean square roughness of the sample observed from atomic force microscopic analysis is about 71.5 nm which is comparable to the average grain size of the coatings which is about 72 nm obtained from X-Ray diffraction. The results indicate that, the ASZNC fibres are arranged well in the nanostructure. The thickness of the coating increased with the anodizing time, but the coatings turned rougher and more porous. At the initial stage the growth of ceramic coating increases inwards to the metal substrate and outwards to the coating surface simultaneously. Subsequently, it mainly grows towards the metal substrate and the density of the ceramic coating increases gradually, which results in the decrease of the total thickness as anodizing time increases. This new approach of preparing ASZNC ceramic fibres may be important in applications ranging from gas sensors to various engineering materials.     

Analysis of nanopore arrangement and structural features of anodic alumina layers formed by two-step anodizing in oxalic acid using the dedicated executable software

Anodic porous alumina layers were fabricated by a two-step self-organized anodization in 0.3 M oxalic acid under various anodizing potentials ranging from 30 to 60 V at two different temperatures (10 and 17 ^°C). The effect of anodizing conditions on structural features and pore arrangement of AAO was investigated in detail by using the dedicated executable publication combined with ImageJ software. With increasing anodizing potential, a linear increase of the average pore diameter, interpore distance, wall thickness and barrier layer thickness, as well as a decrease of the pore density, were observed. In addition, the higher pore diameter and porosity values were obtained for samples anodized at the elevated temperature, independently of the anodizing potential. A degree of pore order was investigated on the basis of Delaunay triangulations (defect maps) and calculation of pair distribution or angle distribution functions (PDF or ADF), respectively. All methods confirmed that in order to obtain nanoporous alumina with the best, hexagonal pore arrangement, the potential of 40 V should be applied during anodization. It was confirmed that the dedicated executable publication can be used to a fast and complex analysis of nanopore arrangement and structural features of nanoporous oxide layers.     

Adhesion studies of latex film surfaces on the meso- and nanoscale

In this paper the effects of surface roughness and annealing temperature (T) of latex coating films on adhesion are discussed for the different stages of the film formation process. The surface free energy of latex films was assessed in terms of practical work of adhesion (W) (or adherence) using a custom-built adhesion-testing device (ATD), atomic force microscopy (AFM), and contact angle measurements. For preannealed latex films surface roughness averages (R_a) were determined from AFM height images and were related to the values of W obtained from ATD measurements at room temperature. The results obtained using these tests exhibiting surface behavior on different length scales indicate a dependence of the measured adhesion on surface roughness and temperature, as well as on the length scale of the measurements.First preannealed samples were studied, which were obtained by heat treatment above the respective glass transition temperatures (T_g). Increasing the temperature of preannealing resulted in a decrease of the adherence observed in ATD experiments at room temperature. However, on the nanoscale, using AFM, no significant variation of the adherence was observed. This observation can be explained by roughness arguments. Preannealing decreases roughness which results in lower adherence values measured by ATD while for essentially single asperity AFM experiments roughness has an insignificant effect. Specimens were also annealed over a constant period of time (90 min) at different temperatures. At the end of the heat treatment, adhesion was measured at the treatment temperature by ATD. The amplified effect of temperature observed in this case on adherence is attributed to the combination of roughness decrease and increasing test temperature. In a third set of experiments completely annealed samples were studied by ATD as well as by AFM as a function of temperature. With increasing T values ATD showed a decrease in adherence, which is attributed to a decreasing surface free energy of the annealed films at elevated T values. AFM, on the other hand, showed an opposite trend which is assigned to increasing penetration of the tip into the tip/wetting polymer samples versus increasing temperature. Finally, annealing isotherms as a function of time were investigated by ATD in situ at different temperatures. This last set of experiments allowed us to optimize annealing time and temperature to achieve complete curing.     

Effect of fabrication parameters on morphological and optical properties of highly doped p-porous silicon

Porous silicon (PS) layers were fabricated by anodization of low resistive (highly doped) p-type silicon in HF/ethanol solution, by varying current density, etching time and HF concentration. Atomic force microscopy (AFM) and field emission scanning electron microscope (FESEM) analyses were used to investigate the physical properties and reflection spectrum was used to investigate the optical behavior of PS layers in different fabrication conditions. Vertically aligned mesoporous morphology is observed in fabricated films and with HF concentration higher than 20%. The dependence of porosity, layer thickness and rms roughness of the PS layer on current density, etching time and composition of electrolyte is also observed in obtained results. Correlation between reflectivity and fabrication parameters was also explored. Thermal oxidation was performed on some mesoporous layers that resulted in changes of surface roughness, mean height and reflectivity of the layers.     

Two-step sputtered ZnO piezoelectric films for film bulk acoustic resonators

This study investigates high-performance ZnO piezoelectric films used for thin film bulk acoustic resonators (TFBAR). The ZnO piezoelectric film was deposited on a Pt/Ti electrode using an RF magnetron sputter by a two-step method at room temperature. The Pt/Ti electrode was deposited by a DC sputtering system, on which, ZnO piezoelectric films were deposited in one step and in two steps to minimize roughness in the first step and produce the preferred orientation in the second. Both field-emission scanning electron microscopy (FESEM) and atom force microscopy (AFM) revealed that ZnO piezoelectric film deposited by two-step sputtering exhibited favorable characteristics, such as a rigidly precise surface structure with surface roughness of 7.37 nm, even better than in one-step sputtering. Examining the ZnO thin film by X-ray diffraction (XRD) showed a much higher c-axis-preferring orientation than in one-step sputtering. The reflection coefficient of the resonator device was measured using an HP8720 network analyzer. The frequency response of the FBAR device exhibited a return loss of -25 dB at a resonant frequency of 2212 MHz with a high coupling coefficient of 6.7%. PACS 68.55.Jk; 43.35.Ns; 81.15.-z     

不同分枝结构多孔氧化铝膜的制备和光学特性

在阳极氧化铝的制备过程中,采用二次氧化方法,通过降低二次氧化过程中的电压,使之变为初始电压的1n,得到了具有n个分枝结构的纳米孔径的氧化铝膜.利用岛津UV3101分光光度计测试了样品的透射光谱与偏振光谱.结果表明,在可见和近红外波段,线型孔径结构的多孔铝膜比Y型和枝状结构的多孔铝膜具有更好的透射性能,在偏振性能方面也有优势,更适合作含金属微偏振器件的膜板材料.