Effect of atomic layer deposition coatings on the surface structure of anodic aluminum oxide membranes

Anodic aluminum oxide (AAO) membranes were characterized by UV Raman and FT-IR spectroscopies before and after coating the entire surface (including the interior pore walls) of the AAO membranes by atomic layer deposition (ALD). UV Raman reveals the presence of aluminum oxalate in bulk AAO, both before and after ALD coating with Al2O3, because of acid anion incorporation during the anodization process used to produce AAO membranes. The aluminum oxalate in AAO exhibits remarkable thermal stability, not totally decomposing in air until exposed to a temperature >900 degrees C. ALD was used to cover the surface of AAO with either Al2O3 or TiO2. Uncoated AAO have FT-IR spectra with two separate types of OH stretches that can be assigned to isolated OH groups and hydrogen-bonded surface OH groups, respectively. In contrast, AAO surfaces coated by ALD with Al2O3 display a single, broad band of hydrogen-bonded OH groups. AAO substrates coated with TiO2 show a more complicated behavior. UV Raman results show that very thin TiO2 coatings (1 nm) are not stable upon annealing to 500 degrees C. In contrast, thicker coatings can totally cover the contaminated alumina surface and are stable at temperatures in excess of 500 degrees C.     

多孔纳米氧化铝薄膜上荧光分子光谱特性研究

通过两步电化学阳极氧化技术制备了孔径为40nm的多孔纳米阳极氧化铝材料(AAO),在AAO薄膜上分别填充了几种有机荧光分子使其形成高度有序的有机-无机复合体发光阵列,测定了此复合体的发射光谱．结果表明,AAO薄膜对有机分子具有较强的结合能力,其结合能力来源于物理和化学的协同作用．在AAO纳米薄膜上的有机荧光分子的最大发射波长均产生了明显的蓝移现象,初步探讨了此现象的机理．有机分子填充进入高度有序的AAO纳米孔阵列之中时,有机分子的聚集形式会发生改变并且也是高度有序的,同时由于极化作用使有机分子沿着纳米孔的轴向具有相对优势的分子取向,使有机分子在AAO纳米薄膜上形成了接近单分子层的高度有序的排列方式,增强了发光效率．     

Field Emission From Ordered Nano-array Structures Based on Porous Aluminum Oxide Templates

This thesis reports my research work of fabricating nanostructures by using nanoporous anodic aluminum oxide (AAO) templates and their field emission properties in the past few years. Some important results obtained are as follows: 1. We first proposed a new concept of fabricating field emitters with ordered nanostructures based on porous aluminum oxide templates such as AAO/Al, metal/AAO, PANI/AAO, CNTs/AAO, Si/AAO and did a lot of research in this field.     

低频交流电沉积金纳米线阵列的AFM研究

迄今,人们已采用许多方法制备纳米材料,如刻蚀技术、化学法和模板法等［1]．其中,引起科学界广泛兴趣的模板法,在合成有序纳米材料上占有极其重要的地位．常用的模板有两种,一种是有序孔洞阳极氧化铝（Anodic Aluminum Oxide,AAO）模板[2],另一种是含有孔洞无序分布的高分子模板．AAO模板具有耐高温,绝缘性好,孔洞分布均匀有序,而且大小可控等特点［3]．可以利用 AAO模板来制备各种纳米纤维和纳米管,如导电聚合物［4]、金属［5]、半导体［6]、碳［7]和其它一些材料．由于纳米材料的应用具有广阔的前景,如光催化、电化学、酶固定等方面,因而不同材料纳米线的制备备受关     

NaGdF4:Eu3+/AAO薄膜的制备与表征

采用水热法在多孔阳极氧化铝(AAO)模板上制备了NaGdF<,4>:Eu<'3+>(摩尔分数5.0%)/AAO薄膜,并研究了制备方法、溶液浓度和退火温度对薄膜样品形貌、结构和发光性质的影响.XRD结果表明,在低于500 ℃退火,得到具有NaGdF<,4>六方相结构的NaGdF<,4>:Eu<'3+>/AAO薄膜;而在5...     

纳米孔阵列阳极氧化铝膜的制备和表征

本文通过在0℃、0.5mol·L^-1的草酸溶液中阳极氧化高纯铝片的方法制得了阳极氧化铝(AAO)膜，并用扫描电子显微镜(SEM)和原子力显微镜(AFM)对AAO膜的形貌和结构进行了表征。结果表明，阻挡层AAO膜中大小一致的膜胞在铝/氧化铝界面上排成六方形阵列;有孔层AAO膜中含有高度有序的纳米孔阵列和膜胞阵列，并且孔的直径和膜胞的尺寸都具有较窄的分布。另外，考察了阳极氧化电压对膜胞尺寸、孔径大小、孔密度和膜胞密度的影响，表明在一定的电压范围内，膜胞和孔径都随电压的升高而增大，而孔密度和膜胞密度却随电压的升高而减小。     

用AFM研究阳极氧化铝的不稳定生长

用原子力显微镜(AFM)研究了多孔阳极氧化铝(AAO)模板的不稳定生长. 结果表明:AAO模板的不稳定生长导致了纳米孔道结构有序度的降低.在H₃PO₄溶液中生长的AAO模板孔道结构稳定性较差;而在H₂C₂O₄溶液中生长的AAO模板稳定性依赖于氧化电压和电流密度,在低电压和电流密度下稳定性较好,高电压和电流密度下稳定性较差. 充分利用这种不稳定生长特性,通过控制AAO模板的阳极氧化条件,可得到具有分枝孔道结构的特殊模板,这为利用模板法制备各种Y形或T形纳米线、管提供了新的发展空间.     

Anodic alumina membranes with defined pore diameters and thicknesses obtained by adjusting the anodizing duration and pore opening/widening time

The through-hole porous anodic aluminum oxide (AAO) membranes were fabricated by a simple two-step anodization of aluminum in 0.3?M oxalic acid, 0.3?M sulfuric acid, and 2?wt.% phosphoric acid solutions under different operating conditions followed by the removal of the remaining Al substrate and the pore opening/widening process. The effect of duration of the second anodizing step on the thickness of the porous oxide layer and the influence of other anodizing conditions such as applied voltage, type of electrolyte, and purity of the substrate on the rate of porous oxide growth were discussed in detail. The pore opening procedure for all synthesized membranes was optimized, and the influence of the duration of chemical etching on structural features of AAO membranes, especially pore diameter, was studied. The rate of pore widening was established for AAO membranes formed in various anodizing electrolytes and for different temperatures of 5?wt.% H₃PO₄ used for alumina dissolution.     

模板法制备枝状Pt纳米线

一维纳米材料的制备是近年来纳米材料的研究热点. 利用具有纳米尺度的孔洞阵列模板沉积各种材料构筑纳米线的方法具有制备简便和成本较低等优点[1,2]. 常用的模板有多孔阳极氧化铝(AAO)、多孔硅和聚合物等, 其中AAO模板具有耐高温, 绝缘性好, 孔洞分布均匀, 孔径、孔深大小可控等特点, 是模板法研究的热点. 通过模板法电化学沉积制备各种金属纳米线已有很多报道[3～8], 本研究小组也曾报道了模板法电化学沉积Au等纳米线的制备及性质[9～12], 但用该方法制备的金属纳米线都为单一的线状结构. 组成当代大规模集成电路的基本器件一般具有3个或3个以上的电极. 单一的线状结构纳米线, 不能满足纳米电子学对纳米材料和纳米器件性能研究的需要. 在纳米器件的特性研究和探索中, 枝状或Y形纳米结的制备有重要的意义, 它是纳米器件从理论到实用化的必备条件. Sui等[13]用模板法成功制备了枝状碳纳米管, 但用AAO模板制备枝状金属纳米线的研究至今还未见报道. 本文通过控制铝片的阳极氧化条件, 先制备出具有分枝状孔洞结构的AAO模板, 再用电化学法沉积金属Pt, 实现了枝状Pt纳米线的可控生长. 这对其它金属枝状纳米线的制备以及进一步掺杂、构筑纳米原型器件等具有显著的实用价值.     

Anodic alumina membranes with defined pore diameters and thicknesses obtained by adjusting the anodizing duration and pore opening/widening time

The through-hole porous anodic aluminum oxide (AAO) membranes were fabricated by a simple two-step anodization of aluminum in 0.3 M oxalic acid, 0.3 M sulfuric acid, and 2 wt.% phosphoric acid solutions under different operating conditions followed by the removal of the remaining Al substrate and the pore opening/widening process. The effect of duration of the second anodizing step on the thickness of the porous oxide layer and the influence of other anodizing conditions such as applied voltage, type of electrolyte, and purity of the substrate on the rate of porous oxide growth were discussed in detail. The pore opening procedure for all synthesized membranes was optimized, and the influence of the duration of chemical etching on structural features of AAO membranes, especially pore diameter, was studied. The rate of pore widening was established for AAO membranes formed in various anodizing electrolytes and for different temperatures of 5 wt.% H₃PO₄ used for alumina dissolution.

     

一种新的WO3纳米管的制备方法

一维纳米材料因可用来构造高性能纳米器件的结构单元而成为纳米材料研究的热点．目前的研究重点集中在材料的制备和结构性能表征方面,已发展了多种制备方法,主要有模板法、V-L-S法、L-L-S法和V-S法等,其中阳极氧化铝(AAO)模板法是制备一维材料的好方法．AAO模板的制备工艺已相当成熟,     

Fabrication of three dimensional interconnected porous carbons from branched anodic aluminum oxide template

In this communication, the morphology of double branched anodic aluminum oxide (AAO) templates from linear down or step down function of anodizing voltage is discussed. The interconnected AAO film is obtained when the thin pore wall at the final branched channels is dissolved by chemical etching. The three-dimensional interconnected porous carbons are fabricated by carbonization of polyimide film which is negative replicated from the layered interconnected AAO template.     

模板法制备高度有序的聚苯胺纳米纤维阵列

近年来,利用化学或物理方法制备多种材料的纳米有序阵列复合结构已成为学术界的研究热点．用具有纳米孔洞的模板(多孔阳极氧化铝、多孔硅以及聚碳酸脂膜)制备的金属、半导体、碳纳米管等材料的纳米有序阵列复合结构已在润滑、微电极、单电子器件、传感器、垂直磁记录、场致电     

氧化铝模板上定向纳米碳管的快速生长及超声切短

在阳极氧化铝（AAO）模板上电沉积催化剂,快速生长了定向纳米碳管,纳米碳管以顶部生长模式生长.采用了超声的方法来切短露头于AAO模板的纳米碳管,增加纳米碳管膜的定向性.结果显示随着超声时间的增加,纳米碳管的定向性增加.位于纳米碳管膜顶部的催化剂在碳管切短的同时被去除,得到了顶部开口的纳米碳管.解释了纳米碳管被超声切短的机理.     

Anodic films containing zirconia nanoparticles for corrosion protection of AA1050 aluminum alloy

In this paper, production of anodic aluminum oxide (AAO) is based on a parameter-optimized literature scheme. Highly ordered tubular structures are achieved as a starting point for subsequent modification steps. These steps include sealing of AAO pores. Sealing is here attempted via the spontaneous adsorption of ZrO₂ nanoparticles on preformed AAO. Nanoparticles are synthetized by several different methods, in particular, the innovative water-free microwave-assisted synthesis. These novel water-free nanoparticles are, here for the first time, used for AAO sealing and corrosion protection. Increase in corrosion resistance is tested by electrochemical methods.     

Phospholipids as an alternative to direct covalent coupling: surface functionalization of nanoporous alumina for protein recognition and purification

Anodic aluminum oxide (AAO) substrates with aligned, cylindrical, non-intersecting pores with diameters of 75 nm and depths of 3.5 or 10 μm were functionalized with lipid monolayers harboring different receptor lipids. AAO was first functionalized with dodecyl-trichlorosilane, followed by fusion of small unilamellar vesicles (SUVs) forming a lipid monolayer. The SUVs' lipid composition was transferred onto the AAO surface, allowing us to control the surface receptor density. Owing to the optical transparency of the AAO, the overall vesicle spreading process and subsequent protein binding to the receptor-doped lipid monolayers could be investigated in situ by optical waveguide spectroscopy (OWS). SUV spreading occurred at the pore-rim interface, followed by lateral diffusion of lipids within the pore-interior surface until homogeneous coverage was achieved with a lipid monolayer. The functionality of the system was demonstrated through streptavidin binding onto a biotin-DOPE containing POPC membrane, showing maximum protein coverage at 10 mol% of biotin-DOPE. The system enabled us to monitor in real-time the selective extraction of two histidine-tagged proteins, PIGEA14 (14 kDa) and ezrin (70 kDa), directly from cell lysate solutions using a DOGS-NTA(Ni)/DOPC (1:9) membrane. The purification process including protein binding and elution was monitored by OWS and confirmed by SDS-PAGE.     

Porous alumina membranes with branched nanopores as templates for fabrication of Y-shaped nanowire arrays

Porous anodic alumina membranes with Y-branched and double-branched nanopores were fabricated by the stepwise reduction of anodizing potential during the second step of anodization carried out in 0.3 M oxalic acid. The process of nanoporous layer formation and influence of anodizing parameters on structural features of as-obtained anodic aluminum oxide (AAO) membranes were discussed in detail. The pore rearrangement process occurring after the potential decrease was investigated on the basis of the current density vs. time curves, and results were correlated with the field-emission scanning electron microscope images of the pore bottoms taken after different anodizing durations. It was found that the reorganization of nanopores begins after 600 and 500 s from the time of the potential reduction to 42 and 30 V and the process seems to be completed after about 900 and 800 s, respectively. The through-hole AAO membranes were used as templates for the fabrication of gold and polystyrene nanowires via electrochemical deposition and simple immersing in the polymer solution, respectively. The arrays of hierarchically branched nanowires were synthesized, and the dimensions of nanowires were consistent with the shape and structure of used AAO templates.

     

用模板法制备TiO2纳米线阵列膜及光催化性能的研究

用溶胶-凝胶技术在多孔阳极氧化铝模板的有序微孔内制备了高度取向的TiO2纳米线阵列膜光催化剂.用XRD,AFM和SEM等手段对样品进行了表征.结果表明,TiO2纳米线阵列膜晶型为锐钛矿,从AFM图像中可以看出TiO2纳米线线径分布均匀一致,取向性极好,直径与AAO模板的孔径大小一致.以其对吖啶橙的降解效果作为评价光催化活性的标准,与相同条件下制备的TiO2/玻璃膜相比,TiO2纳米线阵列膜具有很好的催化活性.     

Synthesis of Various Metal/TiO2 Core/shell Nanorod Arrays

We present a general approach to fabricate metal/TiO₂ core/shell nanorod structures by two-step electrodeposition. Firstly, TiO₂ nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of thenanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO₂ nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.     

多孔氧化铝模板催化制备定向碳纳米管阵列

Well-aligned open-ended multi-walled carbon nanotube (MWCNT) arrays were prepared via chemical vapor deposition (CVD) method in porous anodic aluminum oxide (AAO) templates without depositing any transition metals as catalyst. Effects of the CVD temperature and heat treatment were studied in detail.Well-aligned open-ended MWCNT arrays were obtained at the CVD temperature above 600 ℃; when CVD temperature is reduced to around 550 ℃, CNTs, CNFs and other structures existed at the same time; no CNTs or carbon nanofibres (CNFs) could be found as the CVD temperature is below 500 ℃, and only amorphous carbon in the porous AAO template was found. Experimental results showed that the AAO template is catalytic during the CVD process, and it has the following two effects: to catalyze thermal decomposition of acetylene and to catalyze conversion of carbon decomposed from acetylene into CNTs or CNFs. Heat treatment could improve the graphitization degree, but it might also introduce new defects.