Structural engineering of nanoporous anodic aluminium oxide by pulse anodization of aluminium

Nanoporous anodic aluminium oxide has traditionally been made in one of two ways: mild anodization or hard anodization. The first method produces self-ordered pore structures, but it is slow and only works for a narrow range of processing conditions; the second method, which is widely used in the aluminium industry, is faster, but it produces films with disordered pore structures. Here we report a novel approach termed "pulse anodization" that combines the advantages of the mild and hard anodization processes. By designing the pulse sequences it is possible to control both the composition and pore structure of the anodic aluminium oxide films while maintaining high throughput. We use pulse anodization to delaminate a single as-prepared anodic film into a stack of well-defined nanoporous alumina membrane sheets, and also to fabricate novel three-dimensional nanostructures.     

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.     

Studies of self-organization processes in nanoporous alumina membranes by small-angle neutron scattering

We performed studies of the self-organization processes in nanoporous alumina membranes at initial and late stages of aluminum anodization by using scanning electron microscopy (SEM) and small-angle neutron scattering (SANS). SEM observations indicated three stages in the self-organization of nanopores in alumina: (1) nucleation of random nanopores with a broad radius distribution, (2) narrowing the radius distribution and (3) slow evolution of the nanoporous structure towards ordering of nanopores into large domains. SANS studies revealed orientational correlation between ordered domains of nanopores, which is characterized by a small misorientation angle. For the samples with high aspect ratios of nanopores, the SANS patterns showed azimuthal smearing, which was attributed to the redistribution of nanopores between the domains during their growth.     

Template-Growth of Highly Ordered Carbon Nanotube Arrays on Silicon

This paper reports on the success in and the key conditions for direct growth of carbon nanotubes of unprecedented uniformity on silicon. The uniformity is ensured through the growth within the highly ordered nanopores of an alumina oxide template, which is in turn formed on silicon through anodization of aluminum of unprecedented thickness evaporated on silicon. The formation of highly ordered nanopore array by anodization of thick aluminum evaporated on a noncompliant substrate such as silicon is made possible through a specially designed process for evaporating thick aluminum of high quality and good adhesion.     

From alumina nanopores to nanotubes: dependence on the geometry of anodization system

The Conventional anodization of commercial aluminum sheets with a phosphoric acid electrolyte was employed for the preparation of alumina nanopore and/or nanotube structures. Modifying the system geometry (the ratio of platinum to aluminum electrode areas) controlled the nature of the anodization process (mild to hard). Nanotube formation was observed after low temperature preferential chemical etching of the defective corners of the hexagonal alumina cells using the same solution from the anodization process. Electrode geometry can be used to combine mild and hard anodization with low temperature etching to tune the alumina morphology from 100% nanopores to 100% nanotubos coverage.     

Study of nanopores ordering in anodic aluminum oxide templates achieved by three step process

Enhancement of naturally-occurred self ordering nanopores in anodic aluminum oxide membrane by performing three-step anodic oxidation process has been reported. Naturally-occurred self ordering of nanopores in anodic aluminum oxide membrane has brought it into the applications of template for fabrication of nanoscale materials. Three-step anodic oxidation method was used to achieve self-ordering of nanopores. Effect of duration of first and second steps on the ordering of nanopores was investigated. The current-time curves recorded during anodization elucidate an almost same behavior for all three steps. Scanning electron micrographs show hexagonally arranged 45 nm pores in a manner which contribute into the formation of highly ordered areas, called domains. Larger ones are clearly observed over the surface, for samples with longer first and second anodization steps.     

多孔阳极氧化铝形成机理的研究综述

铝阳极氧化已经研究了五十多年,涉及铝阳极氧化膜的实验数据十分丰富,然而阳极氧化过程的本质特别是多孔氧化膜的生长机制迄今为止还远未认识清楚。近些年,随着纳米技术的兴起,多孔氧化铝膜作为理想的纳米结构模板材料倍受国内外学者的关注,对多孔氧化铝膜形成机理的研究显得尤为重要。本文对多孔阳极氧化铝的结构、形成机制方面的历史发展和现状进行了综述。指出了大多数学者认同的“酸性场致溶解”理论的缺陷。作者认为铝多孔氧化膜形成机理的研究具有重大的理论意义和实际应用价值,同时也会促进其他多孔阳极氧化物形成机理的认识。     

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.     

纳米多孔阳极氧化铝膜形貌的控制研究

采用38g／L的草酸溶液为电解液,制备了孔洞规则有序,孔径和厚度均一可控的氧化铝模板,并研究了阳极氧化工艺对阳极氧化铝膜形貌的影响。实验结果表明,采用38g／L的草酸溶液作为电解液,经两步法阳极氧化可制得孔径均一,排列规则的多孔阳极氧化铝膜。随着氧化电流密度的升高,氧化膜孔径逐渐增大。电流密度过大,反应放热严重,氧化铝膜孔径均匀性,孔洞形状规则性和有序性都下降。在恒电流密度条件下,氧化膜厚度随着氧化时问的延长呈线性增长,但对氧化铝膜孔径影响较小。     

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。     

Fabrication of free standing anodic titanium oxide membranes with clean surface using recycling process

Large area of self-organized, free standing anodic titanium oxide (ATO) nanotube membranes with clean surfaces were facilely prepared to desired lengths via electrochemical anodization of highly pure Ti sheets in an ethylene glycol electrolyte, with a small amount of NH4F and H2O at 50 V, followed by self-detachment of the ATO membrane from the Ti substrate using recycling processes. In the first anodization step, the nanowire oxide layer existed over the well-arranged ATO nanotube. After sufficiently rinsing with water, the whole ATO layer was removed from the Ti sheet by high pressure N2 gas, and a well-patterned dimple layer with a thickness of about 30 nm existed on the Ti substrate. By using these naturally formed nano-scale pits as templates, in the second and third anodization process, highly ordered, vertically aligned, and free standing ATO membranes with the anodic aluminum oxide (AAO)-like clean surface were obtained. The inter-pore distance and diameter was 154 +/- 2 nm and 91+/- 2 nm, the tube arrays lengths for 25 and 46 hours were 44 and 70 microm, respectively. The present study demonstrates a simple approach to producing high quality, length controllable, large area TiO2 membrane.     

Ultrathin Alumina Membranes for Surface Nanopatterning in Fabricating Quantum‐Sized Nanodots

Using ultrathin alumina membranes (UTAMs) as evaporation or etching masks large‐scale ordered arrays of surface nanostructures can be synthesized on substrates. However, it is a challenge for this technique to synthesize quantum‐sized surface structures. Here an innovative approach to prepare UTAMs with regularly arrayed pores in the quantum size range is reported. This new approach is based on a well‐controlled pore‐opening process and a modulated anodization process. Using UTAMs with quantum‐sized pores for the surface patterning process, ordered arrays of quantum dots are synthesized on silicon substrates. This is the first time in realizing large‐scale regularly arrayed surface structures in the quantum size range using the UTAM technique, which is an important breakthrough in the field of surface nanopatterning.     

Indium oxide nanorods and nanowires on porous anodic alumina

We report indium oxide nanorods and nanowires with controllable microstructure deposited on porous anodic alumina membranes (PAAs). At the beginning of the deposition, indium oxide tends to nucleate on the top of PAAs, not at the bottom of PAAs' nanopores, and grows into nanorods. It is interesting that the indium oxide nanorods on the top of PAA just copy the topography of PAA, and form a new porous layer with the thickness of 40-50 nm. As the deposition goes on, the nanorods cannot maintain the ordered nanopore structure, and evolve into nanowire net. And the nanowires can stand upwards separately, and then fall down as the length goes up, forming an indium oxide entangled nanowires. The structure evolvement is discussed according to the field emission scanning electric microscope images.     

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.     

Reduction of nanoparticle deposition during fabrication of porous anodic alumina

In this paper, we present evidences of nanoparticle deposition on porous anodic alumina (PAA) surface under different anodizing conditions, and discuss the formation mechanism of precipitations. Low-temperature anodization, vigorous stirring and ultrasound-assisted anodization are proposed to reduce the hydrolysis product or hinder its deposition on the surface as well as inside nanopores of PAA. It is discovered that the ultrasound is very efficient to prevent the deposition of Al³⁺ hydrolysis product on PAA. This study is of great value for realizing ordered PAAs with clean surface.     

Voltage-dependent fabrication of nanoporous alumina and the applications to nanocapacitors

We investigated the fabrication of anodized aluminum oxide by anodization processes under DC and AC voltage biases. A two-step anodization process was used to fabricate the anodized aluminum oxide dielectrics in order to regulate the ordered nanopore array at the surface. AC samples showed the distorted nanoporous structure instead of a straight nanopore array in DC samples. As increasing the frequency of AC bias the nanovoid or nanocavity structure was formulated with the increased density of nanovoids. Nanoporous alumina was used for the fabrication of Ni-insulator-Al capacitors. The DC sample shows the tunneling process of an increase in leakage current and breakdown. When a negative voltage is applied to the capacitor device, the small current of 2 nA flows at a voltage of 0 V, indicating the existance of residual leakage current. The AC sample had very low leakage currents of the AAO dielectrics and the AAO hexagonal unit cell formed the nanocapacitor with a capacitance of 1-2 aF.     

阳极氧化法制备有序纳米多孔氧化铝膜的研究

利用电化学阳极氧化的方法,在草酸溶液中,精确控制反应条件,在高纯铝片表面有序生长了纳米多孔氧化铝膜。试验中,分别采用一次阳极氧化和二次阳极氧化方法制备氧化铝膜。利用H3PO4溶液浸泡法对氧化铝膜进行扩孔处理。通过扫描电子显微镜对样品进行表征分析。结果发现,二次阳极氧化制备的氧化铝膜的孔洞分布较一次氧化的更为规则有序,并且孔径大小均匀一致。扫描电镜观察显示,氧化铝膜的扩孔过程可以去掉阻碍层,并调节孔径大小,溶去二次氧化后黏附在氧化层表面的一些杂质,从而使氧化铝模板更为规则有序,孔径均一。这种经过二次阳极氧化和扩孔处理得到多孔阳极氧化铝模板的方法简单,成本较低,可以为后续的纳米材料合成提供高质量的合成模板。     

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.     

Characterization and manipulation of the electroosmotic flow in porous anodic alumina membranes

Porous anodic alumina membranes (PAAMs) have uniform and high-density nanopores, and the dimension and interval of the pores can be easily controlled by varying the anodization conditions. The application of PAAMs could widely impact the cost and efficiency of the liquid-based nanoscale separations. We report here the property of electroosmotic flow in PAAMs, which plays a significant role in the mass transport across these membranes that have charged pore surfaces. By controlling the solution pH and the magnitude and sign of the applied current, the mass transport through these nanoporous membranes can be spatially and temporally manipulated. The effects of electrosurface properties and electrolyte ionic strength on electroosmotic flow were studied. The anion incorporation and adsorption cause the variation of the electrosurface properties of PAAMs, which in turn influence the rate and direction of the mass transport. As compared to the membrane with fixed surface charge, this diversity makes it possible for the PAAMs to be used in various conditions.     

Inside Front Cover: Fabrication of Ideally Ordered Nanoporous Alumina Films and Integrated Alumina Nanotubule Arrays by High‐Field Anodization (Adv. Mater. 17/2005)

A simple, low‐cost approach to fabricating large‐area highly ordered nanoporous alumina films in sulfuric acid solutions through a single‐step high‐field anodization, without the assistance of any additional process, is reported on p. 2115 by Chu and co‐workers. The critical high anodizing potential in the adopted electrolyte system increases with the ageing of solutions after a long period of anodization. Correspondingly, the applicable current density for stable anodization rises significantly, thus leading to high‐speed film growth. Uniform porous anodic alumina films in sulfuric acid solutions under a high electric field of 40–70 V and 1600–2000 A m^–2 are achieved.