高度有序多孔阳极氧化铝模板的制备

为了得到纳米孔排列高度有序的多孔阳极氧化铝模板,以0.3 mol·L-1的草酸为电解液研究了模板的制备工艺.采用场发射扫描电子显微镜(FE-SEM)对多孔氧化铝模板的表面形貌进行表征,X射线衍射分析高纯铝及氧化膜的结构.实验结果表明,铝基体不经过高温退火处理,同样能够得到高度有序的氧化铝膜,简化了多孔氧化铝膜的制备工艺.分别讨论了阳极氧化电压和电解液温度对多孔阳极氧化铝膜的形貌及孔径的影响,并对一步法和两步法制得的多孔氧化铝膜进行比较,结果表明,两步阳极氧化法制备的多孔氧化铝模板的有序性优于一步氧化法.XRD分析证实,多孔氧化铝膜由非晶态的Al2O3组成.     

剧烈-温和阳极氧化结合法快速制备有序阳极氧化铝膜的研究

本研究采用剧烈-温和阳极氧化(hard anodization-mild anodization, HA-MA)结合快速制备高度有序多孔阳极氧化铝(porous anodic alumina, PAA)膜的方法, 即先利用HA在铝表面快速形成有序凹坑阵列, 然后再对表面留有有序凹坑的铝基进行温和阳极氧化, 制备出有序PAA膜。研究了剧烈阳极氧化时氧化电压、氧化时间对所制备PAA膜有序度的影响。研究结果表明, HA-MA结合法制备PAA膜的优化HA参数为: 0.3 mol/L硫酸、80 V、10 min。HA-MA结合法所制备PAA膜的有序性和机械稳定性与二步温和阳极氧化法的相近, 但形成有序PAA膜所需的时间为4.5 h, 约为温和阳极氧化法的1/4, 极大地提高了高度有序PAA膜的制备效率。     

用低纯度铝制备AAO模板及其结构研究

在0.3mol/dm3草酸溶液中,通过不同纯度铝的恒电位二次阳极氧化制备了纳米孔氧化铝模板,并用场发射扫描电子显微镜(FE-SEM)和原子力显微镜(AFM)观察模板结构.实验结果表明,一次氧化除膜后低纯度铝基体表面呈现较为规则的六边形结构,这种蜂巢结构有利于二次氧化过程中获得有序度更高的纳米孔模板.低纯度铝制备的模板表面被晶界分隔为微小的区域,只是在较窄区域内才出现六边形规则排列的纳米孔.恒电位40V时所得模板经扩孔处理后,孔径由35nm增大到100nm左右,且孔径大小几乎一致.从纳米孔的有序度来看,由低纯度铝制备模板还需要进一步优化阳极氧化参数.     

Nanoporous anodic alumina obtained without protective oxide layer by hard anodization

In this study, a fast and cost-effective approach is applied for fabricating nanoporous anodic alumina membranes under hard conditions without a protective oxide layer. This structural characteristic is a result of using a two-step anodization strategy under specific hard conditions during the second anodization step (i.e. high stirring rate, low acid electrolyte temperature and concentration). Notice that, after the anodization process, the membrane is detached from the aluminium substrate at the same time that pores are opened. So, after the fabrication process, no additional stages are required for removing both the protective oxide layer and the oxide barrier layer from the top and the bottom of the membrane, respectively. The resulting nanostructures obtained by this approach are defect-free nanoporous anodic alumina membranes with well-defined pores from the top to the bottom. This makes it possible to directly use those membranes in later applications (e.g. templates for replicating nanostructures, filters, optoelectronic devices and so forth) without additional processes and costs.     

One-step anodization fabrication and morphology characterization of porous AAO with ideal nanopore arrays

A fabrication method for one-step anodization of an anodic aluminum oxide (AAO) template with nanopore arrays using pretreated high purity aluminum foil is reported in this article. Morphology of the AAO was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Results showed that porous AAO with ideal nanopore arrays can be fabricated by one-step anodization fabrication technology on high purity aluminum foil which had been anodized at 45?V direct current (DC), in 0°C, 0.5?M H₂C₂O₄ solution for 48 hours. The average pore diameter and the interpore distance were 80?nm and 120?nm, respectively. Nanopores in porous AAO had very narrow size distribution and were arranged into hexagonal array. The formation mechanism of nanopore arrays in porous AAO is discussed. Porous AAO with ideal nanopore arrays provide an ideal template for preparation of many one-dimensional nanomaterials. One-step anodization of AAO is a simpler procedure and more applicable in industrial application than the previous two-step anodization technology.     

Fabrication of novel porous anodic alumina membranes by two-step hard anodization

Porous anodic alumina (PAA) membranes with highly ordered hexagonal cells and a novel pore structure have been fabricated by two-step hard anodization in a H(2)SO(4)-Al(2)(SO(4))(3)-H(2)O system at 40 and 50?V, giving average cell diameters of 77 and 96?nm, respectively. There are several tiny pores embedded in each big shallow pore on the top of the membranes, and there is only one pore in one cell at their bottom. The cells on both sides of the membranes present almost the same periodic arrangement. In order to explore the formation of the novel pore structure, PAA membranes fabricated at different current densities (30-200?mA?cm(-2)) are obtained by maintaining a constant voltage at 40?V. The experimental results show that the interpore distance is not only dependent on the anodization voltage, but is also influenced by the current density, which means that the pore structure of PAA membranes fabricated by hard anodization can be accurately designed and controlled by adjusting the anodization voltage and current density simultaneously.     

Preparation and Analysis of Porous Anodic Alumina Template on Silicon Substrate

Porous anodic alumina (PAA) template is widely used to prepare ordered nanostructure materials. But conventional PAA templates have been restricted for application in micro-electro-mechanical systems (MEMS) technology due to limitations such as shape and brittleness. In this article, a novel process of fabricating alumina porous template based on silicon wafer is described. Porous alumina films were formed by two-step anodization of aluminum layers sputter deposited on silicon wafer. The pore diameters range from 80 to 100 nm. The Pilling–Bedworth ratio of Al/Al₂O₃ was measured and calculated. Thickness of PAA template can be precisely controlled. This research provides an effective tool to nanofabrication in MEMS technology.     

How structure changes in fabrication of large size ordered anodic alumina film?

Large size anodic alumina film has not been used in the industry due to that the fabrication parameters are very difficult to control, but the fabrication of large size anodic alumina is exigent as a template in the fabrication of diverse nano-devices oriented to the industrialization. In this paper, large size (width length = 80 mm × 80 mm) porous ordered anodic alumina film was fabricated by using two-step anodization process as compared to the small size (diameter = 40 mm) anodic alumina film in the structures. Pore size and film thickness of anodic alumina film are strongly related to the size of the anodization film. The large size anodic alumina film has an ideally ordered pattern by applying low voltage. However, with the increase of voltage, the ordered pattern of the PAA films was gradually disrupted, especially in the 70 V due to the local thermal imbalance.     

Conformal anodic oxidation of aluminum thin films

Membrane-based synthesis, also called template synthesis, is a very general approach used to prepare arrays of nanomaterials with monodispersed geometrical features. The most commonly used porous templates are track-etched polycarbonate and porous anodic alumina membranes. Common to all these templates is the fact that the pores are perpendicular to the surface of the membrane. Here, a novel approach is presented, where the pores are synthesized parallel to the surface of the membrane. For the first time, the anodic oxidation of an aluminum thin film is performed laterally, i.e., parallel to the surface of the substrate, instead of perpendicular as usually done. For low anodic oxidation voltages (between 3 and 5 V) we obtain highly regular and ordered pore arrays, at least over a few hundred nanometers length, with a minimum pore size of approximately 3 to 4 nm. With such porous alumina structures, the controlled in-plane organization of arrays of template-grown nanowires and carbon nanotubes for reproducible device fabrication should be much easier.     

Morphological evolution of porous nanostructures grown from a single isolated anodic alumina nanochannel

Porous anodic aluminum oxide (AAO) membranes have been widely used as templates for growing nanomaterials because of their ordered nanochannel arrays with high aspect ratio and uniform pore diameter. However, the intrinsic growth behavior of an individual AAO nanochannel has never been carefully studied for the lack of a means to fabricate a single isolated anodic alumina nanochannel (SIAAN). In this study, we develop a lithographic method for fabricating a SIAAN, which grows into a porous hemispherical structure with its pores exhibiting fascinating morphological evolution during anodization. We also discover that the mechanical stress affects the growth rate and pore morphology of AAO porous structures. This study helps reveal the growth mechanism of arrayed AAO nanochannels grown on a flat aluminum surface and provides insights to help pave the way to altering the geometry of nanochannels on AAO templates for the fabrication of advanced nanocomposite materials.     

The fabrication of ordered nanoporous metal films based on high field anodic alumina and their selected transmission enhancement

A two-step high field anodization and a controllable barrier layer removing process have been used for the fabrication of porous anodic alumina (PAA) with different morphologies. Based on the PAAs, porous noble metal films with widely tunable pore size and inter-pore distance have been realized by a simple sputtering method. Their morphology and optical properties were studied with a field-emission scanning electron microscope, and ultraviolet and ultraviolet-visible spectrophotometers. An enhanced light transmission of the nanoporous metal films was detected. The transmissivity of a normal incidence light can be enhanced over ten times within a certain selected wavelength range. The intensity and position of the transmission peak depend on the morphology and porosity of the metal films.     

Vertically Oriented Titania Nanotubes Prepared by Anodic Oxidation on Si Substrates

Vertically oriented titania nanotube arrays were fabricated by anodization of titanium film deposited on silicon substrates under different processing conditions. The anodic formation of nanoporous titania on silicon substrate was investigated in aqueous solutions mixed with highly corrosive Na₂SO₄/NaF/citric acid. In the result of the anodization of titanium film deposited at room temperature, a very thin layer of ~70 nm having a worm-like structure was grown on the top of the porous layer. But, in the case of titanium film deposited at 500deg, vertically oriented TiO₂ nanotube arrays were formed. The average tube outer diameter of the nanotube was 74 nm to 100 nm. The longest nanotube of 681 mum was obtained at 15 V and 30 min. The current density transient curve recorded during anodization under a constant voltage showed a typical behavior for self-organized pore formation.     

Template-based fabrication of nanowire-nanotube hybrid arrays

The fabrication and structure characterization of ordered nanowire-nanotube hybrid arrays embedded in porous anodic aluminum oxide (AAO) membranes are reported. Arrays of TiO(2) nanotubes were first deposited into the pores of AAO membranes by a sol-gel technique. Co?nanowires were then electrochemically deposited into the TiO(2) nanotubes to form the nanowire-nanotube hybrid arrays. Scanning electron microscopy and transmission electron microscopy measurements showed a high nanowire filling factor and a clean interface between the Co nanowire and the TiO(2) nanotube. Application of these hybrids to the fabrication of ordered nanowire arrays with highly controllable geometric parameters is discussed.     

Lithography-free in situ Pd contacts to templated single-walled carbon nanotubes

We report a metalization technique for electrically addressing templated vertical single-walled carbon nanotubes (SWNTs) using in situ palladium (Pd) nanowires. SWNTs are synthesized from an embedded catalyst in a modified porous anodic alumina (PAA) template. Pd is electrodeposited into the template to form nanowires that grow from an underlying conductive layer beneath the PAA and extend to the initiation sites of the SWNTs within each pore. In this way, individual vertical channels of SWNTs are created, each with a vertical Pd nanowire back contact. Further Pd deposition results in annular Pd nanoclusters that form on portions of SWNTs extending onto the PAA surface. Two-terminal electrical characteristics produce linear I-V relationships, indicating ohmic contact in the devices.     

End-closed NiCoFe-B nanotube arrays by electroless method

A novel approach is obtained during the fabrication of NiCoFe-B nanotube arrays via electroless method. Porous anodic aluminum oxide (AAO) templates fabricated by anodization of aluminum foil were sensitized using PdCl₂ solution and immersed into electroless plating baths at room temperature to produce nanotube arrays. Compositional and morphological properties of the nanotube arrays are characterized. Results indicates the formation of end-closed nanotubes with the dimension of 100-130 nm in outside diameter, which is determined by the pore size of the AAO template, and about 15 nm in thickness of tube walls. The possible formation mechanism of end-closed metallic nanotube arrays is discussed.     

Self-organized regular arrays of anodic TiO2 nanotubes

The formation of self-organized regular arrays of oxide nanotubes lies in a delicate balance between the oxide growth rate and the oxide etching rate and a lattice mismatch between the grown metal oxide and the underlying valve metal. The requisites for their fabrication are the electropolishing and a two-step anodization. The most uniform and self-organized regular arrays of anodic TiO2 nanotubes among those known so far are reported as another example of valve metal oxide nanotube arrays since regular arrays of anodic aluminum oxide nanochannels were produced. Our findings can be generalized to fabricate self-organized regular arrays of other valve metal oxides.     

Controlled Assembly of Highly Raman‐Enhancing Silver Nanocap Arrays Templated by Porous Anodic Alumina Membranes

A convenient nanoscale technique is reported for the fabrication of highly ordered hemispherical silver nanocap arrays templated by porous anodic alumina (PAA) membranes as robust and cost‐efficient surface‐enhanced Raman scattering (SERS) substrates. This geometry produces a high Raman signal due to its periodic hexagonal arrangements and control of the gap between the nanostructures in the sub‐10‐nm regime. The surface structure can be tuned further to optimize the enhancement factor according to optional PAA fabrication and silver deposition parameters. Finite‐difference time‐domain calculations indicate that the structure may possess excellent SERS characteristics due to the high density and abundance of hot spots.     

Micropatterned arrays of porous silicon: toward sensory biointerfaces

We describe the fabrication of arrays of porous silicon spots by means of photolithography where a positive photoresist serves as a mask during the anodization process. In particular, photoluminescent arrays and porous silicon spots suitable for further chemical modification and the attachment of human cells were created. The produced arrays of porous silicon were chemically modified by means of a thermal hydrosilylation reaction that facilitated immobilization of the fluorescent dye lissamine, and alternatively, the cell adhesion peptide arginine-glycine-aspartic acid-serine. The latter modification enabled the selective attachment of human lens epithelial cells on the peptide functionalized regions of the patterns. This type of surface patterning, using etched porous silicon arrays functionalized with biological recognition elements, presents a new format of interfacing porous silicon with mammalian cells. Porous silicon arrays with photoluminescent properties produced by this patterning strategy also have potential applications as platforms for in situ monitoring of cell behavior.     

Mechanical constraint and release generates long, ordered horizontal pores in anodic alumina templates

We describe the formation of long, highly ordered arrays of planar oriented anodic aluminum oxide (AAO) pores during plane parallel anodization of thin aluminum 'finger' microstructures fabricated on thermally oxidized silicon substrates and capped with a silicon oxide layer. The pore morphology was found to be strongly influenced by mechanical constraint imposed by the oxide layers surrounding the Al fingers. Tractions induced by the SiO(2) substrate and capping layer led to frustrated volume expansion and restricted oxide flow along the interface, with extrusion of oxide into the primary pore volume, leading to the formation of dendritic pore structures and meandering pore growth. However, partial relief of the constraint by a delaminating interfacial fracture, with its tip closely following the anodization front, led to pore growth that was highly ordered with regular, hexagonally packed arrays of straight horizontal pores up to 3 μm long. Detailed characterization of both straight and dendritic planar pores over a range of formation conditions using advanced microscopy techniques is reported, including volume reconstruction, enabling high quality 3D visualization of pore formation.     

退火对有序孔洞氧化铝膜荧光性能的影响

用阳极氧化法在草酸溶液或硫酸溶液中制备了有序阵列孔洞的氧化铝膜．研究了在不同温度下、不同气氛中退火对多孔氧化铝膜荧光性能的影响．结果表明,随着退火温度的升高,发光带的强度也随之增强;与此同时,发光带的峰位出现蓝移．当退火温度Ｔ_ａ＝５００℃时,在草酸中制备的氧化铝膜的发光强度最强;而在硫酸中制备的膜,其发光最强的退火温度为４００℃．当 Ｔ≤４００℃时,氧化铝膜的发光强度基本上与退火气氛无关;当 Ｔ_ａ＝５００℃时,在草酸中制备的膜在空气中退火后的发光强度高于在真空中退火后的发光强度．在草酸中制备的氧化铝膜的发光带明显比在硫酸中制备的膜强得多．电子自旋共振的实验结果表明,蓝光发光带来自多孔氧化铝膜中的Ｆ^＋心．我们还对多孔氧化铝膜发光特性的机制进行探讨．