Porous Anodic Aluminum Oxide Template Research Articles

Controlled Synthesis of Germanium Nanowires and Nanotubes with Variable Morphologies and Sizes

We report on the controlled growth of germanium (Ge) nanostructures in the form of both nanowire (NW) and nanotube (NT) with ultrahigh aspect ratios and variable diameters. The nanostructures are grown inside a porous anodic aluminum oxide (AAO) template by low-temperature chemical vapor deposition (CVD) assisted by an electrodeposited metal nanorod catalyst. Depending on the choice of catalytic metals (Au, Ni, Cu, Co) and germane (GeH(4)) concentration during CVD, either Ge NWs or NTs can be synthesized at low growth temperatures (310-370 °C). Furthermore, Ge NWs and NTs with two or more branches can be grown from the same stem while using AAO with branched channels as templates. Transmission electron microscopy studies show that NWs are single crystalline and that branches grow epitaxially from the stem of NWs with a crystalline direction independent of diameter. As-grown NTs are amorphous but can crystallize via postannealing at 400 °C in Ar/H(2) atmosphere, with a wall thickness controllable between 6 and 18 nm in the CVD process. The yield and quality of the NTs are critically dependent on the choice of the catalyst, where Ni appears the best choice for Ge NT growth among Ni, Cu, Co, and Au. The synthesis of structurally uniform and morphologically versatile Ge nanostructures may open up new opportunities for integrated Ge-nanostructure-based nanocircuits, nanodevices, and nanosystems.

Synthesis and photoluminescence properties of ZnO nanowire arrays

AbstractIn this paper we report a chemical method named coordination reaction method to synthesize ZnO nanowire arreys. ZnO nanowires with the diameter about 80nm were successfully fabricated in the channels of the porous anodic alumina (PAA) template by the above coordination reaction method. The microstructures of ZnO/PAA assembly were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The results showed that the ZnO nanowires can be uniformly assembled into the nanochannels of PAA template. The growth mechanism of ZnO nanowires and the conditions of the coordination reaction are discussed. Photoluminescence (PL) measurement shows that the ZnO/PAA assembly system has a blue emission band caused by the various defects of ZnO. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Designing polymeric nanorod arrays for optical waveguide‐based biosensors

AbstractThe optical waveguiding capabilities of polycyanurate thermoset nanorod (PCNs) arrays mounted on planar gold substrates were investigated using optical waveguide spectroscopy (OWS). The nanorods, with diameter of 60 and 150 nm, and length of 650 nm, are formed by thermal polymerization of cyanate ester oligomers within porous anodic aluminium oxide templates. We discuss the waveguiding properties of the PCNs arrays when the nanorod diameter is much smaller (<1/10) than the wavelength of the guided light. We monitored the changes in the waveguiding modes by exchanging the interrod filling environment with water, ethanol, and isopropanol. This study led to a sensing figure of merit as high as 196 reciprocal refractive index units, which is higher than that of other previously studied sensors based on angular modulation. Furthermore, numerical simulations were performed by applying an Effective Medium Theory (EMT) based on the Maxwell‐Garnett approximation for the prediction of the optical properties of anisotropic nanorod arrays. Simulations based on Fresnel equations were used for estimating the optimal fabrication geometry, with varying the nanorod diameter and the interrod distance. Based on these results, we introduce the applicability of the PCNs arrays platform as a concept in optical biosensors and other related applications (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Fabrication and Analysis of Gecko-Inspired Hierarchical Polymer Nanosetae

A gecko's superb ability to adhere to surfaces is widely credited to the large attachment area of the hierarchical and fibrillar structure on its feet. The combination of these two features provides the necessary compliance for the gecko toe-pad to effectively engage a high percentage of the spatulae at each step to any kind of surface topography. With the use of multi-tiered porous anodic alumina template and capillary force assisted nanoimprinting, we have successfully fabricated a gecko-inspired hierarchical topography of branched nanopillars on a stiff polymer. We also demonstrated that the hierarchical topography improved the shear adhesion force over a topography of linear structures by 150%. A systematic analysis to understand the phenomenon was performed. It was determined that the effective stiffness of the hierarchical branched structure was lower than that of the linear structure. The reduction in effective stiffness favored a more efficient bending of the branched topography and a better compliance to a test surface, hence resulting in a higher area of residual deformation. As the area of residual deformation increased, the shear adhesion force emulated. The branched pillar topography also showed a marked increase in hydrophobicity, which is an essential property in the practical applications of these structures for good self-cleaning in dry adhesion conditions.

Microstructure and magnetic properties of electrodeposited Co/Cu multilayer nanowire arrays

Highly uniform Co/Cu multilayer nanowire arrays had been electrodeposited into the nanochannels of porous anodic aluminum oxide template. X-ray diffraction pattern showed that Co and Cu grow in their HCP and FCC structures, respectively. Each nanowire had the same length with 20 μm and the diameter with 50 nm. The thickness of Co was 50 nm and Cu layer was about 5 nm. Magnetic measurements of the nanowire arrays showed that the magnetic coercivity for the applied field parallel to the nanowires is larger than that perpendicular to the anowires. The magnetic coercivity of Co multilayer nanowire arrays is smaller than that of the Co/Cu nanowire arrays and the crystal direction of Co layers were not obviously affected by Cu layer. The Co/Cu nanowire arrays exhibited excellent Giant Magneto Resistive ratio of about 75%.

Enhanced anomalous diffusion of sputtered atoms in nanosized pores

Plasma sputtering deposition of platinum catalysts in porous anodic aluminum oxide (AAO) templates is shown to generate an anomalous superdiffusion concentration profile. The growth of an overlayer between the hexagonal array of pores is shown to enhance the diffusion into the pores, leading to a diffusion coefficient having superlinear time dependence. The Pt clusters in the pores have a mean size of 10 nm and almost concentrate on the inner pore surface, and are present up to a depth of 6 μm.

Laterally organized carbon nanotube arrays based on hot-filament chemical vapor deposition

Lateral porous anodic alumina (PAA) templates were used to organize carbon nanotubes (CNTs) grown by a hot-filament assisted chemical vapor deposition (HFCVD) process. For the CNT growth, we used a modified “home-made” HFCVD system with two independently powered filaments which are fitted respectively on the methane (CH 4) gas line, which serves as a carbon precursor and on the hydrogen (H 2) gas line, which acts as an etching agent for the parasitic amorphous carbon. Various activation powers of the hot filaments were used to directly or indirectly decompose the gas mixtures at relatively low substrate temperatures. A parametric study of the HFCVD process has been carried out for optimizing the confined CNTs growth inside the lateral PAA templates.

The fabrication of nanoporous Pt-based multimetallic alloy nanowires and their improvedelectrochemical durability

A general approach for the fabrication of nanoporous Pt-based multimetallic alloynanowires is reported, which involves electrodeposition of corresponding precursor alloysinto porous anodic alumina templates, followed by a mild dealloying process. Nanoporousternary PtCoNi and PtCoAu as well as quaternary PtRuCoNi nanowires were successfullyfabricated, and their microstructure and composition were examined by transmissionelectron microscopy. Electrochemical tests showed that these porous nanowires exhibithigher electrochemically active surface area and much improved durability compared tocommercially available Pt black, and may find potential applications in electrocatalysis andelectrochemical sensing.

Large-Scale Patterning of Gold Nanopillars in a Porous Anodic Alumina Template by Replicating Gold Structures on a Titanium Barrier

Gold nanopillars are grown in patterns inside a porous anodic alumina template. On selected positions, defined by a gold "seed" pattern, gold is electroplated into the pores, while a barrier layer underneath the porous template blocks the deposition on the rest of the surface. Large-scale arrays of free-standing nanopillar islands are obtained after selective etching of the alumina template.

Synthesis and Characterization of Supported CuInSe2 Nanorod Arrays on Rigid Substrates

Copper indium diselenide nanorod arrays were electrodeposited on tungsten/silicon rigid substrates using porous anodic alumina as growth template. The porous anodic alumina templates were prepared by anodizing aluminum films which were sputtered onto the tungsten/silicon substrates. A selective chemical etching was used to penetrate the barrier layer at the bottom of the alumina channels before electrodeposition, which enables direct electrical and chemical contact with the underside substrate electrode. The as-deposited samples were annealed at 450 °C in vacuum. Scanning electron microscopy revealed that the nanorods were dense and compact with diameter of about 100 nm, length of approximate 1 μm, and the aspect ratio of 10. X-ray diffraction, micro-Raman spectroscopy, and high resolution transmission electron microscopy showed that chalcopyrite polycrystalline structure and high purity CuInSe2 nanorods were obtained. The grain size was large in the rod axial direction. Energy-dispersive X-ray spectroscopy showed the composition was nearly stoichiometric. The energy band gap of this nanorod arrays was analyzed by fundamental absorption spectrum and was evaluated to be 0.96 eV.

Optimization of organized silicon nanowires growth inside porous anodic alumina template using hot wire chemical vapor deposition process

A Hot Wire assisted Chemical Vapor Deposition (HWCVD) process has been developed for producing high-density arrays of parallel, straight and organized silicon nanowires (SiNWs) inside vertical Porous Anodic Alumina (PAA) templates, exploring temperatures ranging from 430 °C to 600 °C, and pressures varying between 2.5 and 7.5 mbar. In order to prevent parasitic amorphous silicon (a-Si) deposit and to promote the crystalline SiNWs growth, we used a tungsten hot wire to partially crack H 2 into atomic hydrogen, which acts like a selective etchant regarding a-Si. Here we describe the optimization route we followed to limit the deposit of a-Si onto the surface of the porous membrane and on the walls of the pores, which led to the possibility to grow SiNWs inside the PAA membranes. Such an approach has high potentialities for device realization, like PIN junctions, FETs or electrodes for Li-ion batteries.

Synthesis and Photoluminescence Enhancement of Silver Nanoparticles Decorated Porous Anodic Alumina

Silver nanoparticles (Ag NPs) were successfully assembled in porous anodic alumina (AAO) templates via a green silver mirror reaction. The Ag NPs/AAO composite templates then were characterized by field emission scanning electron microscopy (FESEM), energy-dispersive X-ray microanalysis (EDX), and X-ray diffraction (XRD). Furthermore, the photoluminescence (PL) properties were also investigated. Compared with the blank AAO, the PL intensity of Ag NPs/AAO templates are enhanced and the maximum enhancement is 2.58 times. Based on the local electric field enhancement effect, the theoretical values were also deduced, which are basically coincident with the experimental.

Sol–gel synthesis of Bi 3.25La 0.75Ti 3O 12 nanotubes

Ferroelectric Bi 3.25La 0.75Ti 3O 12 (BLT) nanotubes were synthesized by sol–gel technique using nanochannel porous anodic aluminum oxide (AAO) templates, and were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). BLT nanotubes with diameter of around 240 nm and the wall thickness of about 25 nm exhibited a single orthorhombic perovskite structure and highly preferential crystal growth along the [1 1 7] orientation, which have smooth wall morphologies and well-defined diameters corresponding to the diameter of the applied template. The formation mechanism of BLT nanotubes was discussed.

Three-dimensional structural engineering of nanoporous alumina by controlled sprinkling of an electrolyte on a porous anodic alumina (PAA) template

The significant effect of anodization current on the morphology of nanopores encourages us to consider a novel method for engineering these nanostructures. In this paper we study a controlled anodization process using controlled electrolyte stirring. This is done using an electrical pump with variable speed for sprinkling an electrolyte on a membrane. The variable voltage applied to the pump can control the temperature gradient and diffusion of the ions which produce the anodization current. Here we show the significant role of pumping and how this effect can be used in the engineering of nanopores as a three-dimensional nanostructure. These experiments are carried out for a variety of anodization voltages and various electrolyte concentrations, and thus we investigate how these parameters in the vicinity of pumping can control the porosity of the template in three dimensions.

Preparation of Mesoporous Silica Fibers in Porous Anodic Aluminum Oxide Template

Mesoporous silica fibers were prepared within porous anodic aluminum oxide membrane (AAO) using a simple Sol-Gel method. The sample was characterized by SEM, XRD, nitrogen adsorption-desorption and TEM. The diameter and the length of the mesoporous silica fibers are depend on the pore diameter and thickness of AAO membrane, respectively. The orientation of the nanochannels in mesoporous silica fibers can be readily controlled by changing the aging environment. For the samples aged with the presence of water, all the nanochannels in the silica fibers are found to be circular around the fibers. However, for the samples aged without water, the nanochan- nels were found to be parallel along the fiber axes.

Preparation and Magnetic Properties of ZnFe2O4Nanotubes

Ordered ZnFe2O4nanotube arrays with the average outer diameter of 100 nm were prepared in porous anodic aluminum oxide template using an improved sol-gel approach. The morphology was studied by transmission electron and field emission scanning electron microscope. X-ray diffraction result shows that the nanotubes were polycrystalline in structure. The magnetic properties of the prepared ZnFe2O4nanotubes were also studied. The results show that the sample shows typical superparamagnetism at room temperature and obvious ferromagnetism below blocking temperature.

Characterization of hotspots in a highly enhancing SERS substrate

Vapor deposition of silver and gold onto a porous anodized aluminum oxide template is shown to produce a SERS substrate with an average surface enhancement factor of 10(7)-10(8). The high level of enhancement is explored using a combination of dark-field Rayleigh scattering and Raman spectroscopy and imaging. The scattering spectrum of the surface indicates a Plasmon resonance at 633 nm and dark-field imaging shows a relatively uniform scattering intensity at this wavelength. These measurements are consistent with the uniform enhanced Raman intensity observed in Raman maps of the substrate. Scanning electron microscopy shows the surface exhibits heterogeneous nanostructures with diameters of approximately 100 nm, the size of the pores in the template. Our measurements indicate that interactions between adjacent structures forming junctions and crevices likely give rise to a high density of hotspots, which provide the extraordinary SERS enhancement. The advantage of substrates prepared in this way is the reproducibly dense distribution of hotspots across the surface, increasing the likelihood that an analyte will experience the largest enhancement.

Template-Assisted Fabrication of Double-Shelled Nanotubes Composed of Inner Shell Pb(Zr0.52Ti0.48)O3and Outer Shell TiO2by Sol-Gel Process with Spin-Coating Technique

ABSTRACTDouble-shelled nanotubes composed of inner shell Pb(Zr0.52Ti0.48)O3(PZT) and outer shell TiO2are successfully fabricated by a spin coating of each sol-gel solution on porous anodic alumina template. Field emission transmission electron microscopy images show that they have a ~ 10 nm wall thickness. The selected area electron diffraction patterns show that they have two mixed crystalline phases of tetragonal PZT and anatase TiO2. The analyses of scanning transmission electron microscopy equipped with energy dispersive X-ray spectroscopy confirm their uniform distribution of each element.

Gradient composition distribution in poly(2,6-dimethylphenylene oxide)/polystyrene blend nanorods

We report formation of nanorods that exhibit a gradient distribution of poly(2,6-dimethylphenylene oxide) and polystyrene (PPO and PS), i.e., the PPO weight fractions in the nanorods increase from top to bottom along the long axis of the nanorods. PPO/PS nanorods with various diameters were prepared by infiltrating porous anodic aluminium oxide (AAO) templates with polymer blend melts. Their morphology was investigated by Fourier transform infrared spectroscopy (FTIR). The gradient distribution of polymer blends in the nanopores is governed by (1) the viscosity difference between the two polymers and (2) the pore diameter. This remains true although PPO/PS blends are compatible in the segmental level. For various diameter nanorods made of PPO/PS blends, the PPO content decreased as the rod diameter became smaller owing to the increased confinement imposed by the nanopores. This leads to a higher rate of capillary rise in smaller nanopores.

Electrochemical glutamate biosensing with nanocube and nanosphere augmented single-walled carbon nanotube networks: a comparative study

We describe two hybrid nanomaterial biosensor platforms, based on networks of single-walled carbon nanotubes (SWCNTs) enhanced with Pd nanocubes and Pt nanospheres and grown in situ from a porous anodic alumina (PAA) template. These nanocube and nanosphere SWCNT networks are converted into glutamate biosensors by immobilizing the enzyme glutamate oxidase (cross-linked with gluteraldehyde) onto the electrode surface. The Pt nanosphere/SWCNT biosensor outperformed the Pd nanocube/SWCNT biosensor and previously reported similar nanomaterial-based biosensors by amperometrically monitoring glutamate concentrations with a wide linear sensing range (50 nM to 1.6 mM) and a small detection limit (4.6 nM, 3σ). These results combined with the biosensor fabrication scheme (in situgrowth of SWCNTs, electrodeposition of metal nanoparticles, and facile enzyme immobilization protocol) create a biosensor that can potentially be scaled for integration into a wide range of applications including the treatment of neurological disorders.