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A fast and cost-effective technique is applied for fabricating cobalt and nickel nanopillars on aluminium substrates. By applying an electrochemical process, the aluminium oxide barrier layer is removed from the pore bottom tips of nanoporous anodic alumina templates. So, cobalt and nickel nanopillars are fabricated into these templates by DC electrodeposition. The resulting nanostructure remains on the aluminium substrate. In this way, this method could be used to fabricate a wide range of nanostructures which could be integrated in new nanodevices.
doi:10.1007/s11671-009-9351-5
PMCID: PMC2894324
PMID: 20596338
Nanoporous anodic alumina membranes; Transfer mask; Metallic nanopillars; Electrodeposition
A fast and cost-effective technique is applied for fabricating cobalt and nickel nanopillars on aluminium substrates. By applying an electrochemical process, the aluminium oxide barrier layer is removed from the pore bottom tips of nanoporous anodic alumina templates. So, cobalt and nickel nanopillars are fabricated into these templates by DC electrodeposition. The resulting nanostructure remains on the aluminium substrate. In this way, this method could be used to fabricate a wide range of nanostructures which could be integrated in new nanodevices.
doi:10.1007/s11671-009-9351-5
PMCID: PMC2894324
PMID: 20596338
Nanoporous anodic alumina membranes; Transfer mask; Metallic nanopillars; Electrodeposition
The fabrication of ordered arrays of nanoporous Si nanopillars with and without nanoporous base and ordered arrays of Si nanopillars with nanoporous shells are presented. The fabrication route is using a combination of substrate conformal imprint lithography and metal-assisted chemical etching. The metal-assisted chemical etching is performed in solutions with different [HF]/[H2O2 + HF] ratios. Both pore formation and polishing (marked by the vertical etching of the nanopillars) are observed in highly doped and lightly doped Si during metal-assisted chemical etching. Pore formation is more active in the highly doped Si, while the transition from polishing to pore formation is more obvious in the lightly doped Si. The etching rate is clearly higher in the highly doped Si. Oxidation occurs on the sidewalls of the pillars by etching in solutions with small [HF]/[H2O2 + HF] ratios, leading to thinning, bending, and bonding of pillars.
doi:10.1186/1556-276X-8-42
PMCID: PMC3570473
PMID: 23336430
Nanoporous Si; Pillars; Nanowires; Metal-assisted chemical etching; Nanoimprint lithography
Superhydrophobic nanoporous anodic aluminum oxide (alumina) surfaces were prepared using treatment with vapor-phase hexamethyldisilazane (HMDS). Nanoporous alumina substrates were first made using a two-step anodization process. Subsequently, a repeated modification procedure was employed for efficient incorporation of the terminal methyl groups of HMDS to the alumina surface. Morphology of the surfaces was characterized by scanning electron microscopy, showing hexagonally ordered circular nanopores with approximately 250 nm in diameter and 300 nm of interpore distances. Fourier transform infrared spectroscopy-attenuated total reflectance analysis showed the presence of chemically bound methyl groups on the HMDS-modified nanoporous alumina surfaces. Wetting properties of these surfaces were characterized by measurements of the water contact angle which was found to reach 153.2 ± 2°. The contact angle values on HMDS-modified nanoporous alumina surfaces were found to be significantly larger than the average water contact angle of 82.9 ± 3° on smooth thin film alumina surfaces that underwent the same HMDS modification steps. The difference between the two cases was explained by the Cassie-Baxter theory of rough surface wetting.
doi:10.1186/1556-276X-6-487
PMCID: PMC3212001
PMID: 21827683
superhydrophobic surfaces; surface modification; hexamethyldisilazane; nanoporous alumina
Stable intrinsic white light–emitting diodes were fabricated from c-axially oriented ZnO nanorods (NRs) grown at 50°C via the chemical bath deposition on top of a multi-layered poly(9,9-dioctylfluorene-co–N-(4-butylpheneylamine)diphenylamine)/poly(9,9dioctyl-fluorene) deposited on PEDOT:PSS on highly flexible plastic substrate. The low growth temperature enables the use of a variety of flexible plastic substrates. The fabricated flexible white light–emitting diode (FWLED) demonstrated good electrical properties and a single broad white emission peak extending from 420 nm and up to 800 nm combining the blue light emission of the polyflourene (PFO) polymer layer with the deep level emission (DLEs) of ZnO NRs. The influence of the temperature variations on the FWLED white emissions characteristics was studied and the devices exhibited high operation stability. Our results are promising for the development of white lighting sources using existing lighting glass bulbs, tubes, and armature technologies.
doi:10.1007/s11671-010-9659-1
PMCID: PMC2920425
PMID: 20730076
Hybrid technology; ZnO nanorods; Polymers; Large area lighting; Flexible low temperature LEDs
Stable intrinsic white light–emitting diodes were fabricated from c-axially oriented ZnO nanorods (NRs) grown at 50°C via the chemical bath deposition on top of a multi-layered poly(9,9-dioctylfluorene-co–N-(4-butylpheneylamine)diphenylamine)/poly(9,9dioctyl-fluorene) deposited on PEDOT:PSS on highly flexible plastic substrate. The low growth temperature enables the use of a variety of flexible plastic substrates. The fabricated flexible white light–emitting diode (FWLED) demonstrated good electrical properties and a single broad white emission peak extending from 420 nm and up to 800 nm combining the blue light emission of the polyflourene (PFO) polymer layer with the deep level emission (DLEs) of ZnO NRs. The influence of the temperature variations on the FWLED white emissions characteristics was studied and the devices exhibited high operation stability. Our results are promising for the development of white lighting sources using existing lighting glass bulbs, tubes, and armature technologies.
doi:10.1007/s11671-010-9659-1
PMCID: PMC2920425
PMID: 20730076
Hybrid technology; ZnO nanorods; Polymers; Large area lighting; Flexible low temperature LEDs
Highly fluorescent nanoparticles of the conjugated polymer poly(9,9-dioctylfluorene) (PFO) with distinct phases were prepared, and their photophysical properties were studied by steady state and time-resolved fluorescence spectroscopy. An aqueous suspension of PFO nanoparticles prepared by a reprecipitation method was observed to exhibit spectroscopic characteristics consistent with the glassy phase of the polymer. We demonstrate that controlled addition of organic solvent leads to partial transformation of the disordered polymer chains into the planarized conformation (β-phase), with the fractions of each component phase dependent on the amount of solvent added. Fluorescence spectroscopy of the PFO nanoparticles containing β-phase indicates efficient energy transfer from the glassy-phase regions of the nanoparticles to the β-phase regions. Salient features of the nanoparticles containing β-phase include narrow, red-shifted fluorescence and increased fluorescence quantum yield as compared to the glassy-phase nanoparticles. Fluorescence lifetime measurements indicate that the increased quantum yield of the β-phase PFO originates from a decrease in the nonradiative decay rate, with little change in the radiative rate. This decrease is likely due to exciton trapping by the β-phase, which leads to a reduction in the energy transfer efficiency to quencher species present within the nanoparticle.
doi:10.1021/la8000762
PMCID: PMC2517098
PMID: 18459748
The template-based methods belong to low-cost and rapid preparation techniques for various nanostructures like nanowires, nanotubes, and nanodots or even quantum dots [QDs]. The nanostructured surfaces with QDs are very promising in the application as a sensor array, also called 'fluorescence array detector.' In particular, this new sensing approach is suitable for the detection of various biomolecules (DNA, proteins) in vitro (in clinical diagnostics) as well as for in vivo imaging.
The paper deals with the fabrication of TiO2 planar nanostructures (QDs) by the process of titanium anodic oxidation through an alumina nanoporous template on a silicon substrate. Scanning electron microscopy observation showed that the average diameter of TiO2 QDs is less than 10 nm. Raman spectroscopic characterization of self-organized titania QDs confirmed the presence of an anatase phase after annealing at 400°C in vacuum. Such heat-treated TiO2 QDs revealed a broad emission peak in the visible range (characterized by fluorescence spectroscopy).
doi:10.1186/1556-276X-7-123
PMCID: PMC3305443
PMID: 22333295
quantum dots; biosensing; TiO2; template methods; nanoporous mask
A detailed study of the pore-widening rate of nanoporous anodic alumina layers as a function of the anodization voltage was carried out. The study focuses on samples produced under the same electrolyte and concentration but different anodization voltages within the self-ordering regime. By means of ellipsometry-based optical characterization, it is shown that in the pore-widening process, the porosity increases at a faster rate for lower anodization voltages. This opens the possibility of obtaining three-dimensional nanostructured nanoporous anodic alumina with controlled thickness and refractive index of each layer, and with a refractive index difference of up to 0.24 between layers, for samples produced with oxalic acid electrolytes.
doi:10.1186/1556-276X-7-474
PMCID: PMC3460793
PMID: 22916731
Anodization voltage; Alumina; Nanostructures; Nanoporous anodic alumina; Ellipsometry
Porous anodic alumina (PAA) has been intensively studied in past decade due to its applications for fabricating nanostructured materials. Since PAA’s pore diameter, thickness and shape vary too much, a systematical study on the methods of morphology characterization is meaningful and essential for its proper development and utilization. In this paper, we present detailed AFM, SEM and TEM studies on PAA and its evolvements with abundant microstructures, and discuss the advantages and disadvantages of each method. The sample preparation, testing skills and morphology analysis are discussed, especially on the differentiation during characterizing complex cross-sections and ultrasmall nanopores. The versatility of PAAs is also demonstrated by the diversity of PAAs’ microstructure.
doi:10.1007/s11671-010-9538-9
PMCID: PMC2894103
PMID: 20672104
Microscopy; Nanostructure; Porous; Anodic Alumina; Characterization
Porous anodic alumina (PAA) has been intensively studied in past decade due to its applications for fabricating nanostructured materials. Since PAA’s pore diameter, thickness and shape vary too much, a systematical study on the methods of morphology characterization is meaningful and essential for its proper development and utilization. In this paper, we present detailed AFM, SEM and TEM studies on PAA and its evolvements with abundant microstructures, and discuss the advantages and disadvantages of each method. The sample preparation, testing skills and morphology analysis are discussed, especially on the differentiation during characterizing complex cross-sections and ultrasmall nanopores. The versatility of PAAs is also demonstrated by the diversity of PAAs’ microstructure.
doi:10.1007/s11671-010-9538-9
PMCID: PMC2894103
PMID: 20672104
Microscopy; Nanostructure; Porous; Anodic Alumina; Characterization
We report on an exhaustive and systematic study about the photoluminescent properties of nanoporous anodic alumina membranes fabricated by the one-step anodization process under hard conditions in oxalic and malonic acids. This optical property is analysed as a function of several parameters (i.e. hard anodization voltage, pore diameter, membrane thickness, annealing temperature and acid electrolyte). This analysis makes it possible to tune the photoluminescent behaviour at will simply by modifying the structural characteristics of these membranes. This structural tuning ability is of special interest in such fields as optoelectronics, in which an accurate design of the basic nanostructures (e.g. microcavities, resonators, filters, supports, etc.) yields the control over their optical properties and, thus, upon the performance of the nanodevices derived from them (biosensors, interferometers, selective filters, etc.)
doi:10.1186/1556-276X-7-228
PMCID: PMC3413565
PMID: 22515214
Photoluminescence; Hard anodization; Porous alumina; Pore widening; Heat treatment; Geometric characteristics
Fabrication of metallic nanopillar array structures and their application as electrodes in electrochemical-based biosensors are discussed in this report. Vertically standing nanopillar array structures were fabricated using an electrodeposition technique and their electrochemical characteristics were evaluated. For possible use in biosensing applications, these standing nanopillars should have sufficient mechanical stability to sustain the capillary forces caused by the nanopillar – liquid interactions in aqueous environment and should provide increased signal response in an electrochemical process. Our results showed that the developed nanopillar arrays were mechanically stable in aqueous environments and the nanostructured electrodes exhibited increased electrochemical response compared with flat electrodes.
PMCID: PMC2426765
PMID: 17722264
nanopillar array structures; nanostructured electrodes; mechanical stability; electrochemical process; biosensors; porous anodic alumina
The use of nanopillar array electrodes (NAEs) for biosensor applications was explored using a combined experimental and simulation approach to characterize the role of reaction kinetics and mass transport in glucose detection with NAEs. Thin gold electrodes with arrays of vertically standing gold nanopillars were fabricated and their amperometric current responses were measured under bare and functionalized conditions. Results show that the sensing performances of both the bare and functionalized NAEs were affected not only by the presence and variation of the nanoscale structures on the electrodes but also by the reaction kinetics and mass transport of the analyte species involved. These results will shed new light for enhancing the performance of nanostructure based biosensors.
doi:10.1186/1754-1611-1-5
PMCID: PMC2241827
PMID: 18271981
Anodization of Al foil under low voltages of 1–10 V was conducted to obtain porous anodic aluminas (PAAs) with ultrasmall nanopores. Regular nanopore arrays with pore diameter 6–10 nm were realized in four different electrolytes under 0–30°C according to the AFM, FESEM, TEM images and current evolution curves. It is found that the pore diameter and interpore distance, as well as the barrier layer thickness, are not sensitive to the applied potentials and electrolytes, which is totally different from the rules of general PAA fabrication. The brand-new formation mechanism has been revealed by the AFM study on the samples anodized for very short durations of 2–60 s. It is discovered for the first time that the regular nanoparticles come into being under 1–10 V at the beginning of the anodization and then serve as a template layer dominating the formation of ultrasmall nanopores. Under higher potentials from 10 to 40 V, the surface nanoparticles will be less and less and nanopores transform into general PAAs.
doi:10.1007/s11671-010-9634-x
PMCID: PMC2897034
PMID: 20676199
Anodic alumina; Nanofabrication; Nanopore; Ultrasmall; Nanoparticle
Anodization of Al foil under low voltages of 1–10 V was conducted to obtain porous anodic aluminas (PAAs) with ultrasmall nanopores. Regular nanopore arrays with pore diameter 6–10 nm were realized in four different electrolytes under 0–30°C according to the AFM, FESEM, TEM images and current evolution curves. It is found that the pore diameter and interpore distance, as well as the barrier layer thickness, are not sensitive to the applied potentials and electrolytes, which is totally different from the rules of general PAA fabrication. The brand-new formation mechanism has been revealed by the AFM study on the samples anodized for very short durations of 2–60 s. It is discovered for the first time that the regular nanoparticles come into being under 1–10 V at the beginning of the anodization and then serve as a template layer dominating the formation of ultrasmall nanopores. Under higher potentials from 10 to 40 V, the surface nanoparticles will be less and less and nanopores transform into general PAAs.
doi:10.1007/s11671-010-9634-x
PMCID: PMC2897034
PMID: 20676199
Anodic alumina; Nanofabrication; Nanopore; Ultrasmall; Nanoparticle
This study investigated the optimization of mesoporous silica thin films by nanotexturing using oxygen plasma versus thermal oxidation. Calcination in oxygen plasma provides superior control over pore formation with regard to the pore surface and higher fidelity to the structure of the polymer template. The resulting porous film offers an ideal substrate for the selective partitioning of peptides from complex mixtures. The improved chemico-physical characteristics of porous thin films (pore size distribution, nanostructure, surface properties and pore connectivity) were systematically characterized with XRD, Ellipsometry, FTIR, TEM and N2 adsorption/desorption. The enrichment of low molecular weight proteins captured from human serum on mesoporous silica thin films fabricated by both methodologies were investigated by comparison of their MALDI-TOF MS profiles. This novel on-chip fractionation technology offers advantages in recovering the low molecular weight peptides from human serum, which has been recognized as an informative resource for early diagnosis of cancer and other diseases.
doi:10.1007/s11426-010-4121-x
PMCID: PMC3004293
PMID: 21179395
Mesoporous silica thin film; Oxygen plasma; Low molecular weight proteome
We report on the fabrication and morphology/structural characterization of a porous anodic alumina (PAA)/PtSi nano-template for use as matrix in template-assisted Si nanowire growth on a Si substrate. The PtSi layer was formed by electroless deposition from an aqueous solution containing the metal salt and HF, while the PAA membrane by anodizing an Al film deposited on the PtSi layer. The morphology and structure of the PtSi layer and of the alumina membrane on top were studied by Scanning and High Resolution Transmission Electron Microscopies (SEM, HRTEM). Cross sectional HRTEM images combined with electron diffraction (ED) were used to characterize the different interfaces between Si, PtSi and porous anodic alumina.
doi:10.1186/1556-276X-6-414
PMCID: PMC3211510
PMID: 21711948
Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.
doi:10.1186/1556-276X-7-342
PMCID: PMC3443033
PMID: 22731888
carbon nanotubes; nanohybrids; palladium nanoparticles; titanium oxide; 81.07.-b; 81.15.Gh; 81.07.De
Here we present an optofluidic surface enhanced Raman spectroscopy (SERS) device for on-chip detection of vasopressin using an aptamer based binding assay. To create the SERS-active substrate, densely packed, 200 nm diameter, metal nanotube arrays were fabricated using an anodized alumina nanoporous membrane as a template for shadow evaporation. We explore the use of both single layer Au structures and multilayer Au/Ag/Au structures and also demonstrate a facile technique for integrating the membranes with all polydimethylsiloxane (PDMS) microfluidic devices. Using the integrated device, we demonstrate a linear response in the main detection peak intensity to solution phase concentration and a limit of detection on the order of 5.2 μU/mL. This low limit of detection is obtained with device containing the multilayer SERS substrate which we show exhibits a stronger Raman enhancement while maintaining biocompatibility and ease or surface reactivity with the capture probe.
doi:10.1016/j.bios.2009.09.040
PMCID: PMC2818342
PMID: 19857952
SERS-active substrate; Nanotube array; Optofluidic device; Aptamer; Vasopressin
We study the effects of patterned surface chemistry on the microscale and nanoscale morphology of solution-processed donor/acceptor polymer-blend films. Focusing on combinations of interest in polymer solar cells, we demonstrate that patterned surface chemistry can be used to tailor the film morphology of blends of semiconducting polymers such as poly-[2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene] (MDMO-PPV), poly-3-hexylthiophene (P3HT), poly[(9,9-dioctylflorenyl-2,7-diyl)-co-benzothiadiazole)] (F8BT), and poly(9,9-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylendiamine) (PFB) with the fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). We present a method for generating patterned, fullerene-terminated monolayers on gold surfaces, and use microcontact printing and Dip-Pen Nanolithography (DPN) to pattern alkanethiols with both micro- and nanoscale features. After patterning with fullerenes and other functional groups, we backfill the rest of the surface with a variety of thiols to prepare substrates with periodic variations in surface chemistry. Spin coating polymer:PCBM films onto these substrates, followed by thermal annealing under nitrogen, leads to the formation of structured polymer films. We characterize these films with Atomic Force Microscopy (AFM), Raman spectroscopy, and fluorescence microscopy. The surface patterns are effective in guiding phase separation in all of the polymer:PCBM systems investigated, and lead to a rich variety of film morphologies that are inaccessible with unpatterned substrates. We demonstrate our ability to guide pattern formation in films thick enough of be of interest for actual device applications (up to 200 nm in thickness) using feature sizes as small as 100 nm. Finally, we show that the surface chemistry can lead to variations in film morphology on length scales significantly smaller than those used in generating the original surface patterns. The variety of behaviors observed and the wide range of control over polymer morphology achieved at a variety of different length scales have important implications for the development of bulk heterojunction solar cells.
doi:10.1021/ja804088j
PMCID: PMC2702008
PMID: 18983150
A new solid-state, Al2O3 nanopore sensor with enhanced surface properties for the real-time detection and analysis of individual DNA molecules is reported. Nanopore formation using electron beam based decomposition transformed the local nanostructure and morphology of the pore from an amorphous, stoichiometric structure (O to Al ratio of 1.5) to a hetero-phase crystalline network, deficient in O (O to Al ratio of ~0.6). Direct metallization of the pore region was observed during irradiation, thereby permitting the potential fabrication of nano-scale metallic contacts in the pore region with potential application to nanopore-based DNA sequencing. Dose dependent phase transformations to purely γ and/or α-phase nanocrystallites were also observed during pore formation allowing for surface charge engineering at the nanopore/fluid interface. DNA transport studies revealed an order of magnitude reduction in translocation velocities relative to alternate solid-state architectures, accredited to high surface charge density and the nucleation of charged nanocrystalline domains. The unique surface properties of Al2O3 nanopore sensors makes them ideal for the detection and analysis of ssDNA, dsDNA, RNA secondary structures and small proteins. These nano-scale sensors may also serve as a useful tool in studying the mechanisms driving biological processes including DNA-protein interactions and enzyme activity at the single molecule level.
doi:10.1002/adfm.200902128
PMCID: PMC3546516
PMID: 23335871
We investigated the effect of nanoscale topography on neurite development in pheochromocytoma (PC12 cells) by culturing the cells on substrates having nanoscale pillars and pores with sizes comparable with filipodia. We found that cells on nanopillars and nanopores developed fewer and shorter neurites than cells on smooth substrates, and that cells on nanopores developed more and longer neurites than cells on nanopillars. These results suggest that PC12 cells were spatially aware of the difference in the nanoscale structures of the underlying substrates and responded differently in their neurite extension. This finding points to the possibility of using nanoscale topographic features to control neurite development in neurons.
PMCID: PMC2673821
PMID: 17722518
nanopillars; nanopores; substrates; neurite extension; PC12 cells
One-dimensional cobalt nanostructures with large aspect ratio up to 450 have been prepared via a template-free hydrazine reduction route under external magnetic field assistance. The morphology and properties of cobalt nanostructures were characterized by scanning electron microscopy, X-ray diffractometer, and vibrating sample magnetometer. The roles of the reaction conditions such as temperature, concentration, and pH value on morphology and magnetic properties of fabricated Co nanostructures were investigated. This work presents a simple, low-cost, environment-friendly, and large-scale production approach to fabricate one-dimensional magnetic Co materials. The resulting materials may have potential applications in nanodevice, catalytic agent, and magnetic recording.
doi:10.1007/s11671-010-9807-7
PMCID: PMC3212205
Cobalt nanowires; Magnetic field assistance; Hydration hydrazine reduction
Self-aligned nanoporous TiO2templates synthesized via dc current electrochemical anodization have been carefully analyzed. The influence of environmental temperature during the anodization, ranging from 2 °C to ambient, on the structure and morphology of the nanoporous oxide formation has been investigated, as well as that of the HF electrolyte chemical composition, its concentration and their mixtures with other acids employed for the anodization. Arrays of self-assembled titania nanopores with inner pores diameter ranging between 50 and 100 nm, wall thickness around 20–60 nm and 300 nm in length, are grown in amorphous phase, vertical to the Ti substrate, parallel aligned to each other and uniformly disordering distributed over all the sample surface. Additional remarks about the photoluminiscence properties of the titania nanoporous templates and the magnetic behavior of the Ni filled nanoporous semiconductor Ti oxide template are also included.
doi:10.1007/s11671-007-9073-5
PMCID: PMC3246376
Titanium oxides; Nanoporous materials; Electrochemical anodization