Benefits and limitations of porous substrates as biosensors for protein adsorption

Porous substrates have gained widespread interest for biosensor applications based on molecular recognition. Thus, there is a great demand to systematically investigate the parameters that limit the transport of molecules toward and within the porous matrix as a function of pore geometry. Finite element simulations (FES) and time-resolved optical waveguide spectroscopy (OWS) experiments were used to systematically study the transport of molecules and their binding on the inner surface of a porous material. OWS allowed us to measure the kinetics of protein adsorption within porous anodic aluminum oxide membranes composed of parallel-aligned, cylindrical pores with pore radii of 10-40 nm and pore depths of 0.8-9.6 μm. FES showed that protein adsorption on the inner surface of a porous matrix is almost exclusively governed by the flux into the pores. The pore-interior surface nearly acts as a perfect sink for the macromolecules. Neither diffusion within the pores nor adsorption on the surface are rate limiting steps, except for very low rate constants of adsorption. While adsorption on the pore walls is mainly governed by the stationary flux into the pores, desorption from the inner pore walls involves the rate constants of desorption and adsorption, essentially representing the protein-surface interaction potential. FES captured the essential features of the OWS experiments such as the initial linear slopes of the adsorption kinetics, which are inversely proportional to the pore depth and linearly proportional to protein concentration. We show that protein adsorption kinetics allows for an accurate determination of protein concentration, while desorption kinetics could be used to capture the interaction potential of the macromolecules with the pore walls.     

Cold-wall CVD carbon nanotube synthesis on porous alumina substrates

Carbon nanotubes were synthesized by chemical vapor deposition (CVD) using ethanol vapor as carbon source. Catalysts were Co and Mo metallic particles obtained from the corresponding acetates dissolved in ethanol. Acetate solutions are deposited on porous alumina substrates by dip coating. A dense array of aligned carbon nanotubes perpendicular to the substrate surface grow with 20 min exposure to ethanol vapor flow for substrate temperatures between 650 and 830 °C. Sample analysis is performed with scanning electron microscopy and Raman spectroscopy.     

Humidity sensor structures with thin film porous alumina for on-chip integration

Our aim was to produce a cheap, reliable, low-power and CMOS-MEMS process compatible relative humidity (RH) capacitive sensor that can be incorporated into a state-of-the art wireless sensor network. Porous alumina, produced by electrochemical oxidation of aluminum thin film under anodic bias (AAO, Anodic Aluminum Oxide) was used for the purpose of the sensing layer. We prepared two different capacitive sensor structures on silicon substrate using semiconductor processing steps and anodic oxidation in addition. The first sensor has an ultra-thin, vapor-permeable palladium upper electrode, while in the second case, an electroplated gold-grid is used for the same purpose. The highest achieved average sensitivity is approx. 15 pF/RH%, which is much higher than the values found in product catalogues of discrete, off-the-shelf capacitive humidity sensors (0.2-0.5 pF/RH%).     

Self-referencing substrates for optical interferometric biosensors

Optical interference is a powerful technique for monitoring surface topography or refractive index changes in a thin film layer. Reflectance spectroscopy provides label-free biosensing capability by monitoring small variations in interference signature resulting from optical path length changes from surface-adsorbed biomolecules. Spectral reflectance data can be acquired either by broad wavelength illumination and spectroscopy at a single point, thus necessitating scanning, or by varying the wavelength of illumination and imaging the reflected intensity allowing for acquisition of a spectral image of a large field of view simultaneously. In imaging modalities, intensity fluctuations of the illuminating light source couple into the detected signal, increasing the noise in measured surface profiles. This article introduces a simple technique for eliminating the effects of illumination light power fluctuations by fabricating on-substrate self-reference regions to measure and normalize for the incident intensity, simplifying the overall platform for reflection or transmission-based imaging biosensors. Experimental results demonstrate that the sensitivity performance using self-referencing is equivalent or better than an optimized system with an external reference.     

Dielectric properties of KDP filled porous alumina nanocomposite thin films

A new concept of a composite dielectric thin film fabrication is presented. The fabrication process consists of two stages. The first stage is anodizing a thin aluminum film to produce a porous alumina film that contains an array of nanometer sized parallel pores. The second stage is filling the pores with a saturated KDP (KH2PO4) liquid solution due to capillary forces. After drying KDP nanocrystals are formed inside the pores. This process results in a formation of a composite dielectric thin film composed of the alumina pores walls as one dielectric material and the KDP nanocrystals inside the pores as another dielectric material. The dielectric permittivity of this composite film is higher than that of the porous alumina film at all applied frequencies. The dielectric enhancement is more pronounced at low frequencies due to an interface polarization mechanism. This fabrication process enables controlling the size, composition, and microstructure of the composite dielectric film constituents and thus changing its dielectric properties over a wide range of values.     

Tensile strain engineering of Si thin films using porous Si substrates

Highly tensile strained (up to 2.2%) thin monocrystalline silicon (mc-Si) films were fabricated by a simple and low-cost method based on the in-plane expansion of meso-porous silicon (PS) substrates upon low temperature oxidation. To control the film thickness below 100 nm, an original “two wafer” technique was employed during the porosification process. This method enables the fabrication of a 60 nm thick mc-Si films on 250 μm thick meso-porous silicon substrates over areas as large as 2 in. with a surface roughness and cleanliness comparable to that of standard Si wafers. Crack-free 60 nm thick Si films can be strained up to 1.2% by controlled low temperature oxidation of the PS substrate. Structural and strain analysis of the PS/mc-Si structures performed by transmission electron microscopy and micro-Raman scattering spectroscopy are reported.     

Large-scale, reliable and robust SERS-active nanowire substrates prepared using porous alumina templates

nanowire arrays for surface-enhanced Raman scattering applications. These nanowire films were synthesized via electrodeposition using porous alumina templates of varying order, thickness and pore diameters. Mechanical polishing has been shown to be a very effective method to prepare nanowire arrays with monodisperse length over comprehensively large dimensions. On the other hand, a convenient synthesis route has been suggested that allows the formation of nanoparticle rrays using very thin and/or large area porous alumina films. It is reckoned that even films with the smallest obtainable pore sizes can be utilized to prepare large area, fine nanoparticle arrays. Such arrays may also find use in other areas, such as solar cells and electrochemistry. Preliminary Raman experiments indicated that the nanowire/nanoparticle arrays are indeed surface-enhanced Raman scattering-active. Finally, the potentials offered by the reported processing methods for fabricating substrates with predictable and high Raman amplifications are discussed.     

Microstructural analysis of WO3 thin films on alumina substrates

WO₃ thin films have been deposited by thermal evaporation on an alumina oxide single crystal and annealed either in oxygen or in air. The morphology and the crystallographical structure for the as-deposited and the annealed films have been investigated by reflection high energy electron diffraction, atomic force microscopy and transmission electron microscopy. During annealing the WO₃ thin films recrystallise and undergo important morphological and structural changes: the annealed films exhibit large grains which have the monoclinic structure in epitaxial orientations. These grains are made of twinned microdomains, which are elongated in the [100] direction resulting of a preferential growth along the direction that corresponds to the smallest lattice parameter of WO₃.     

Optical properties of porous anodic aluminum oxide thin films on quartz substrates

Porous anodic aluminum oxide (AAO) thin films on quartz substrates were fabricated via evaporation of a 100-nm thick Al, followed by anodization with different durations and pore widening and Al removal by chemical etching. The transmittance and reflectance of AAO films on quartz substrates were measured by optical spectrophotometry. The microstructure and morphology were examined by scanning electron microscopy. The pore diameter of AAO films after pore widening and Al removal is 60 ± 4 nm and the interpore distance is 88 ± 5 nm. It is found that the reflectance decreases and the transmittance increases with the increase of the anodization time and pore widening. Compared to a bare substrate, the transmittance of AAO films after pore widening and Al removal is about 3.0% higher, while the reflectance is about 3.0% lower over a wide wavelength range. Additionally, after pore widening and Al removal, when AAO films are prepared on both sides of the quartz substrate, the highest transmittance is about 99.0% in the wavelength range 570-680 nm. The optical constants and thickness of AAO films after pore widening and Al removal were retrieved from normal incidence transmittance data. Results show that the refractive index is lower than 1.25 in the visible optical region and that the porosity is about 0.70.     

Fabrication and characterization of vertically aligned carbon nanotubes on silicon substrates using porous alumina nanotemplates

An ethylene-air laminar diffusion flame successfully provided silicon substrates of anodic aluminum oxide (AAO) template with vertically oriented well-aligned carbon nanotubes. Field emission scanning electron microscopy (SEM) showed that open-tipped carbon nanotubes consisting of tube elements with the same length and diameter uniformly coated the template. High-resolution transmission electron microscopy (TEM) analyses revealed these nanotubes to be multiwalled carbon nanotubes, some well graphitized. It was found that cobalt catalyst particles, but not the porous aluminum templates, helped the growth of carbon nanotubes through graphitization and bonding of carbon nanotubes to the silicon substrates.     

Rationally designed porous silicon as platform for optical biosensors

Optical porous silicon multilayer structures are able to work as sensitive chemical sensors or biosensors based in their optical response. An algorithm to simulate the optical response of these multilayers was developed, considering the optical properties of the individual layers. The algorithm allows designing and customizing the porous silicon structures according to a given application. The results obtained by the simulation were experimentally verified; for this purpose different photonic structures were prepared, such as Bragg reflectors and microcavities. Some of these structures have been derivatized by the introduction of aminosilane groups on the porous silicon surface. The algorithm also permits to simulate the effects produced by a non uniform derivatization of the multilayer.     

离心成型结合模板法制备孔径均匀的多孔氧化铝陶瓷

将等直径的发泡聚苯乙烯(EPS)小球排列成有序的模板,通过在模板内离心成型制备孔径均匀的多孔氧化铝陶瓷.研究了多孔陶瓷孔结构的调整方法,分析了离心参数对孔壁生坯密度的影响,借助了TG-DTG曲线确定了焙烧工艺,用扫描电镜表征了最终产物的显微结构.结果表明,多孔陶瓷的孔结构可以通过改变小球的直径和所承受的附加载荷来调整.当氧化铝浆料的固相含量超过50%(体积分数),离心成型的物质分离现象被抑制,孔壁具有较高的生坯密度63.4%和烧结密度98.8%,当烧结产物的孔隙率从75.6%增加到83.2%,压缩强度由3.2MPa降到1.78MPa.     

多孔氧化铝陶瓷的凝胶注模成型

选用石墨粉作为造孔剂,加入已分散良好的氧化铝浆料中,球磨均匀后注模成型。成型后的坯体在1520℃保温烧结2h,获得了分布均匀,孔径为15－30μm的多孔氧化铝陶瓷。     

多孔氧化铝蓝色发光的光谱分析

采用电化学方法在硫酸和草酸溶液中制备了具有纳米结构的多孔氧化铝。在紫外光激发下，草酸中得到的多孔氧化铝可发射出明亮的蓝光，而硫酸中制得的样品几乎不发光。通过紫外可见吸收光谱、激发光谱、傅里叶变换红外光谱及X射线光电子能谱等分析，这种发光被归结于样品中缺陷的存在，而不同的电解液对缺陷的形成有很大影响。     

The dielectric properties of alumina substrates for microelectronic packaging

The dielectric characterization of alumina substrate materials used in high-performance microelectronic packaging is described. These materials included both pure and impure polycrystalline substrates and, as a reference standard, pure and chromium-doped single crystals of alumina. For each material the permittivity () and dielectric loss () has been measured over a frequency range of 0.5 kHz to 10 MHz, at room temperature, and correlated with the structure and composition as determined by supplementary techniques. At room temperature the pure substrates show the frequency independence of both and , characteristic of pure single-crystal material. The permittivity (= 10.1) agrees closely with the average of the anisotropic values for the single crystal but the dielectric loss is an order of magnitude higher than in the single crystal, giving tan 1.5 × 10^–3. The impure substrates compared with the pure, show a small increase in and a marked, frequency-dependent increase in dielectric loss. Measurements have also been made in both the high- and low-temperature ranges (i.e. 20 to 600 ° C and 77 to 293 K, respectively) in order to establish the variation of permittivity with temperature and frequency. At temperatures below 200 °C the temperature coefficient of permittivity, [( –1)( + 2)]^–1 (/T) _p is about 9 × 10^–6 K^–1 for the pure materials but this increases rapidly with impurity addition.     

氧化铝多孔支撑体的研究

用挤出成型的方法制备高性能陶瓷膜用Ａｌ２Ｏ３〉９９％支撑体，制备中受初闰度、烧成温度、粘结等因素的影响，因此可以调节一个或几个因素来控制支撑体的性能。用硬脂酸铝为造孔剂，调节支撑体的孔径和气孔率时发现造孔剂质量分数〈５％和〉５％在坯体中的分布不同，成孔的作用也不一样，造孔剂用量〈５％时，对成孔作用不大，〉５％时成孔明显，但造孔剂的添加量不宜超过１５％。     

Constrained densification in boehmite–alumina mixtures for the fabrication of porous alumina ceramics

It is demonstrated that inherent constrained densification characteristics of the bimodal size distributed powders can be utilized to fabricate porous alpha alumina. Seeded boehmite was mixed with coarse alpha alumina particles to produce various compositions of bimodal mixtures. The densification behaviour of the mixtures was correlated with shrinkage and microstructural evolution. The mixtures sintered at 1200 °C contained more than 30% porosity and the mechanical strength of the mixtures was increased by 2–4 fold relative to the coarse particles alone with similar porosity (<5 MPa). © 1998 Chapman & Hall     

Controllable fabrication of porous alumina templates for nanostructures synthesis

Porous alumina templates (AAO) has attracted significant interest due to the fact that they are readily fabricated through a simple procedure and are extremely popular templates in nanoscience studies. In this paper, the effects of different pore-widening treatments on the pore quality of the AAO templates were investigated. Results show that, through a highly controllable chemical pore-widening process at low temperature, different pore dimensions and diameters of the AAO templates can be easily achieved in a nanometer-scale way without changing the interpore distance. Combining with anodization voltage control, AAO templates with desired size distribution can be obtained, which will be extremely useful in template technology and masks for lithographic application. Also, silver nanorods/wires of different dimensions have been fabricated from above AAO templates after pore diameter adjustments. Such nanostructure materials hold high potential for electronics, optics, mechanics and sensing technology.