纳米多孔金薄膜的表面等离子体共振传感特性

对淀积在玻璃衬底上厚度约60 nm的金银合金溅射薄膜进行硝酸腐蚀脱银处理, 得到纳米多孔金薄膜. 利用自建的波长检测型表面等离子体共振(SPR)传感装置研究了腐蚀时间对纳米多孔金薄膜SPR特性的影响, 结果发现纳米多孔金薄膜与水溶液接触后在400-900 nm光谱范围内不具有SPR效应, 而当薄膜置于空气中时会产生明显的传播等离子体共振吸收峰, 其共振波长随腐蚀时间增加逐渐红移. 纳米多孔金薄膜在空气气氛中的SPR效应使其能够用于原位监测气相分子在孔内的吸附, 还可对在液相中吸附的生化分子进行离位测试. 本文对L-谷胱甘肽、L-半胱氨酸、2-氨基乙硫醇三种含巯基的生化小分子在纳米多孔金薄膜内的吸附进行了离位分析, 结果表明与传统的致密金薄膜SPR芯片比较, 纳米多孔金薄膜对这些分子显示出更高的灵敏度和更低的检测下限, 这归功于多孔金的大比表面积使其能够吸附大量的生化小分子. 实验还对乙醇蒸气在纳米多孔金薄膜内的吸附进行了原位监测, 发现吸附平衡所用时间较长, 约为160 min.     

Nanostructured ultra-low-κ porous fluoropolymer composite films via plasma co-polymerization of hydrophobic and hydrophilic monomers and subsequent hydrolysis treatment

A new approach to fabricate porous nanostructured fluoropolymer composite films with a low dielectric constant (κ) was put forward at the first time. Initially, a film (pp-HDFD-PEGMA film) composed of dense, uniform, and well-defined nanospheres was controllably deposited on hydrogen-terminated silicon substrates by simultaneous plasma polymerization and deposition of a fluorine-containing hydrophobic monomer, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decene (HDFD), and a hydrophilic monomer poly(ethylene glycol) methacrylate (PEGMA), using a pulsed plasma polymerization technique. Then, by hydrolysing the plasma co-deposited film in aqueous hydrochloric acid solution to effectively remove the soluble nanospheres or fragments which mainly derived from PEGMA, a nanoporous fluorocarbon film was achieved. Subsequently, a top poly(tetrafluoroethylene) layer was deposited via the magnetron sputtering process to cap and complete an encapsulated structure. The resulting bilayer composite film consisting of a layer of nanostructured fluorocarbon porous film and a layer of encapsulation fluorocarbon polymer has a κ value of 1.8. The morphology investigation of the plasma co-deposited film prior and after acid-treatment by field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) confirmed the form of the nanospheres and nanoporous structure, while the chemical composition and structure analysis by X-ray photoelectron spectroscopy (XPS) revealed that after the acid-treatment, the porous nanostructured film are composed predominantly of mainly fluorocarbon polymer.     

Active sol–gel thin film on nanostructured plasmonic surface

Sol–gel hybrid films based on alkyl bridged polysilsesquioxanes and doped with phenol red molecules, were synthesized for sensing purposes. Doped films changes colour from yellow to orange to red when exposed to hydrochloric acid (HCl) both in solution and gas phases. The synthesis was optimized in order to produce porous films after spin coating. The porosity increases reacting surface area and chemical reactivity of the sensing thin film. Porosity, optical and structural characterizations of these films were investigated by transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FT-IR) and Spectroscopic Ellipsometry (SE). Variation of optical characteristics upon immersion of the film in the solution was characterized by UV–visible (UV–vis) spectroscopy. Moreover the same porous sensitive hybrid film was deposited on gold sinusoidal grating in order to detect variations of the dielectric film optical constant after HCl solution dip. This variation was revealed by monitoring surface plasmon polariton excitations.     

Preparation, structure, and optical properties of nanoporous gold thin films

Thin nanoporous gold (np-Au) films, ranging in thickness from approximately 40 to 1600 nm, have been prepared by selective chemical etching of Ag from Ag/Au alloy films supported on planar substrates. A combination of scanning electron microscopy (SEM) imaging, synchrotron grazing incidence small angle X-ray scattering, and N2 adsorption surface area measurements shows the films to exhibit a porous structure with intertwined gold fibrils exhibiting a spectrum of feature sizes and spacings ranging from several to hundreds of nanometers. Spectroscopic ellipsometry measurements (300-800 nm) reveal the onset of surface plasmon types of features with increase of film thicknesses into the approximately 200 nm film thickness range. Raman scattering measurements for films functionalized with a self-assembled monolayer formed from 4-fluorobenzenethiol show significant enhancements which vary sharply with film thickness and etching times. The maximum enhancement factors reach approximately 10(4) for 632.8 nm excitation, peak sharply in the approximately 200 nm thickness range for films prepared at optimum etching times, and show high spot to spot reproducibility with approximately 1 microm laser spot sizes, an indication that these films could be useful as durable, highly reproducible surface-enhanced Raman substrates.     

Photopatterned nanoporosity in polyelectrolyte multilayer films

We report on spatial control of nanoporosity in polyelectrolyte multilayer (PEM) films using photopatterning and its effects on film optical and adsorption properties. Multilayers assembled from poly(acrylic acid-ran-vinylbenzyl acrylate) (PAArVBA), a photo-cross-linking polymer, and poly(allylamine hydrochloric acid) (PAH) were patterned using ultraviolet light followed by immersion in low pH and then neutral pH solutions to induce nanoporosity in unexposed regions. Model charged small molecules rhodamine B, fluorescein, and propidium iodide and the model protein albumin exhibit increased adsorption to nanoporous regions of patterned PEM films as shown by fluorescence microscopy and radiolabeling experiments. Films assembled with alternating stacks of PAH/poly(sodium-4-styrene sulfonate) (SPS), which do not become nanoporous, and stacks of PAH/PAArVBA were patterned to create nanoporous capillary channels. Interdigitated channels demonstrated simultaneous, separate wicking of dimethyl sulfoxide-solvated fluorescein and rhodamine B. In addition, these heterostack structures exhibited patternable Bragg reflectivity of greater than 25% due to refractive index differences between the nanoporous and nonporous stacks. Finally, the PEM assembly process coupled with photo-cross-linking was used to create films with two separate stacked reflective patterns with a doubling in reflectivity where patterns overlapped. The combined adsorptive and reflective properties of these films hold promise for applications in diagnostic arrays and therapeutics delivery.     

Electrochemical synthesis of silver nanoparticles-coated gold nanoporous film electrode and its application to amperometric detection for trace Cr(VI)

A simple and rapid approach for the electrochemical synthesis of Ag nanoparticles-coated gold nanoporous film (AgGNF) on a gold substrate was reported. The solid gold electrode (SGE) was directly anodized under a high potential of 5 V, and then reduced to obtain gold nanoporous film (AuNF) by freshly prepared ascorbic acid. The Ag nanoparticles (AgNPs) were grown on the AuNF electrode by potential-step electrodeposition. The resulting AgGNF composites electrodes were characterized by scanning electron micro...     

Platinum-coated gold nanoporous film surface: electrodeposition and enhanced electrocatalytic activity for methanol oxidation

This report describes the preparation of Pt-nanoparticle-coated gold-nanoporous film (PGNF) on a gold substrate via a simple "green" approach. The gold electrode that has been anodized under a high potential of 5 V is reduced by freshly prepared ascorbic acid (AA) solution to obtain gold nanoporous film electrode. Then the Pt nanoparticle is grown on the electrode by cyclic voltammetry (CV). The resulting PGNF electrode has highly ordered arrangement and large surface area, as verified by scanning electron microscopy (SEM) and CV, suggesting that the nanoporous gold film electrode provides a good matrix for obtaining PGNF with high surface area. Furthermore, the as-prepared PGNF electrode exhibited high electrocatalytic activity toward methanol oxidation in a 0.5 M H 2SO 4 solution containing 1.5 M methanol. The present novel strategy is expected to reduce the cost of the Pt catalyst remarkably.     

Nanoporous TiO2 and WO3 films by anodization of titanium and tungsten substrates: influence of process variables on morphology and photoelectrochemical response

The photoelectrochemical response of nanoporous films, obtained by anodization of Ti and W substrates in a variety of corrosive media and at preselected voltages in the range from 10 to 60 V, was studied. The as-deposited films were subjected to thermal anneal and characterized by scanning electron microscopy and X-ray diffraction. Along with the anodization media developed by previous authors, the effect of poly(ethylene glycol) (PEG 400) or D-mannitol as a modifier to the NH4F electrolyte and glycerol addition to the oxalic acid electrolyte was studied for TiO2 and WO3, respectively. In general, intermediate anodization voltages and film growth times yielded excellent-quality photoelectrochemical response for both TiO2 and WO3 as assessed by linear-sweep photovoltammetry and photoaction spectra. The photooxidation of water and formate species was used as reaction probes to assess the photoresponse quality of the nanoporous oxide semiconductor films. In the presence of formate as an electron donor, the incident photon to electron conversion efficiency (IPCE) ranged from approximately 130% to approximately 200% for both TiO2 and WO3 depending on the film preparation protocol. The best photoactive films were obtained from poly(ethylene glycol) (PEG 400) containing NH4F for TiO2 and from aqueous NaF for WO3.     

Time‐of‐flight secondary ion mass spectrometry and gas chromatography–mass spectrometry studies of alkanethiol self‐assembled monolayers on nanoporous gold surfaces

The dimerization of alkanethiol mixtures (hexanethiol, octanethiol, and dodecanethiol) to form self‐assembled monolayers (SAMs) from headspace on nanoporous gold surfaces was studied for the first time using gas chromatography (GC/MS) and time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS). The nanoporous gold surfaces were obtained by an acidic etching of a 585‐gold alloy. Field emission scanning electron microscopy (FE‐SEM) was utilized to study the change of the surface geometry and porosity of the gold surfaces before and after etching. Alkanethiols were deposited from the vapor phase above the thiol solutions (headspace) on nanoporous gold plates and nanoporous gold solid‐phase vmicroextraction (SPME) fibers. The nanoporous gold substrates were analyzed by TOF‐SIMS and GC/MS, respectively. The TOF‐SIMS spectra exhibited various gold–sulfur ion clusters and specific peaks related to the adsorption of thiols such as deprotonated monomers, thiolate–Au, dimers (e.g., dialkyl sulfides–Au and dialkyl disulfides–Au). The GC/MS analysis of headspace extractions of alkanethiol mixtures by nanoporous gold SPME fibers showed a high extraction efficiency of alkanethiol, dialkyl sulfide, and dialkyl disulfide when compared with the commercial SPME fibers (DVB‐CAR‐PDMS and CAR‐PDMS). Different GC/MS optimization factors were studied including the extraction time and desorption temperature.     

Nanoporous gold electrode prepared from gold compact disk as the anode for the microbial fuel cell

The electrodes (anode and cathode) have an important role in the efficiency of a microbial fuel cell (MFC), as they can determine the rate of charge transfer in an electrochemical process. In this study, nanoporous gold electrode, prepared from commercially available gold-made compact disk, is utilized as the anode in a two-chamber MFC. The performance of nanoporous gold electrode in the MFC is compared with that of gold film, carbon felt and acid-heat-treated carbon felt electrodes which are usually employed as the anode in the MFCs. Electrochemical surface area of nanoporous gold electrode exhibits a 7.96-fold increase rather than gold film electrode. Scanning electron microscopy analysis also indicates the homogeneous biofilm is formed on the surface of nanoporous gold electrode, while the biofilm formed at the surface of acid-heat-treated carbon felt electrode shows rough structure. Electrochemical studies show although modifications applied on carbon felt electrodes improve its performance, nanoporous gold electrode, due to its structure and better electrochemical properties, acts more efficiently as the MFC’s anode. The maximum power density produced by nanoporous gold anode is 4.71 mW m^?2 at current density of 16.00 mA m^?2, while this value for acid-heat-treated carbon felt anode is 3.551 mW m^?2 at current density of 9.58 mA m^?2.     

Synthesis of nanoporous activated iridium oxide films by anodized aluminum oxide templated atomic layer deposition

Iridium oxide (IrOx) has been widely studied due to its applications in electrochromic devices, pH sensing, and neural stimulation. Previous work has demonstrated that both Ir and IrOx films with porous morphologies prepared by sputtering exhibit significantly enhanced charge storage capacities. However, sputtering provides only limited control over film porosity. In this work, we demonstrate an alternative scheme for synthesizing nanoporous Ir and activated IrOx films (AIROFs). This scheme utilizes atomic layer deposition to deposit a thin conformal Ir film within a nanoporous anodized aluminum oxide template. The Ir film is then activated by potential cycling in 0.1 M H₂SO₄ to form a nanoporous AIROF. The morphologies and electrochemical properties of the films are characterized by scanning electron microscopy and cyclic voltammetry, respectively. The resulting nanoporous AIROFs exhibit a nanoporous morphology and enhanced cathodal charge storage capacities as large as 311 mC/cm².     

Direct electrochemistry of cytochrome c immobilized on a novel macroporous gold film coated with a self-assembled 11-mercaptoundecanoic acid monolayer

We have successfully constructed a novel gold film with open interconnected macroporous walls of nanoparticles by combining the hydrogen bubble dynamic template synthesis with galvanic replacement reaction. After modified by a self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid (MUA), the three-dimensionally (3D) interconnected macroporous Au film has been used as a biocompatible substrate for the immobilization of cytochrome c. The morphology, structure and electrochemical features of the modified and unmodified macroporous Au films were characterized by field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results reveal that the resultant films had a large electroactive surface area for high protein loading, enhanced electron transfer of cytochrome c, retained electrochemical activity, good stability and repeatability. And the excellent electrochemical behaviors could be attributed to the hierarchical structure of the macroporous Au film constructed by nanoparticles.     

Selective dissolution of the silver component in colloidal Au and Ag multilayers: a facile way to prepare nanoporous gold film materials

Colloidal Au/Ag multilayer films were prepared by alternate assembly of Au nanoparticles with a size of 5 +/- 1.2 nm and Ag nanoparticles with a size of 10 +/- 2.4 nm by using 1,5-pentanedithiol as cross-linker. Nanoporous gold films with a ligament size of 26.7 +/- 4.6 nm were then prepared by selective dissolution of sacrificial templates of silver particles in colloidal Au/Ag multilayers. The complete dissolution of Ag particles in colloidal Au/Ag multilayers in a mixture solution of 3.0 mM HAuCl(4) and 3 M NaCl took place at room temperature without damage of the colloidal Au film. This method to prepare nanoporous gold films was further extended to the preparation of nanoporous gold nanotubes by depositing colloidal Au/Ag film on the inner wall of anodic aluminum oxides (AAO) followed by dissolution of colloidal Ag and removal of AAO templates.     

Electrochemical impedance spectroscopy studies of organic-solvent-induced permeability changes in nanoporous films derived from a cylinder-forming diblock copolymer

In this paper we report electrochemical investigations of the influence of organic solvents dissolved in aqueous solution on the permeability of nanoporous films derived from a cylinder-forming polystyrene-poly(methyl methacrylate) diblock copolymer (CF-PS-b-PMMA). The nanoporous films (ca. 30 nm in pore diameter) were prepared on planar gold electrodes via UV-based degradation of the cylindrical PMMA domains of annealed CF-PS-b-PMMA films (30-45 nm thick). The permeability of the electrode-supported nanoporous films was assessed using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The faradic current of Fe(CN)(6)(3-/4-) decreased upon immersion in aqueous solutions saturated with toluene or methylene chloride (5.8 mM and 0.20 M, respectively). EIS data indicated that the decrease in faradic current mainly reflected an increase in the pore resistance (R(pore)). In contrast, R(pore) did not change in a saturated n-heptane solution, 0.17 M ethanol, or 5.8 mM aqueous solutions of methylene chloride, diethyl ether, methyl ethyl ketone, or ethanol. Atomic force microscopy images of a nanoporous film in aqueous solution with and without 5.8 mM toluene showed a reversible change in the surface morphology, which was consistent with a toluene-induced change in R(pore). The solvent-induced increase in R(pore) was attributed to the swelling of the nanoporous films by the organic solvents, which decreased the effective pore diameter. The reversible permeability changes suggest that the surface of CF-PS-b-PMMA-derived nanoporous films can be functionalized in organic environments without destroying the nanoporous structure. In addition, the solvent-induced swelling may provide a simple means for controlling the permeability of such nanoporous films.     

The Influence of the Electrodeposition Conditions on the Electroanalytical Performance of the Bismuth Film Electrode for Lead Determination

The bismuth film is a great promise as a suitable material to replace the mercury electrodes due to its low toxicity and good cathodic potential range. This work studies the influence of the electrodeposition conditions in the morphology and electroanalytical performance of the bismuth film electrodeposited onto copper electrode. The bismuth films were obtained in nitric or hydrochloric acid solutions with and without the presence of sodium citrate. The films were characterized by field emission scanning electron microscopy (FE‐SEM) and scanning electron microscopy with energy dispersive X‐ray spectrometry (SEM‐EDX). The microscopic analysis of the bismuth film obtained in HCl solution with sodium citrate (BIFE‐Cit) showed more homogeneous structure with higher content of bismuth than the film obtained in HCl only (BiFE‐HCl). The BiFE‐Cit exhibited a better analytical performance for lead with good adherence to the copper substrate.     

Nanoporous oxide formation by anodic oxidation of Nb in sulphate–fluoride electrolytes

The influence of hydrofluoric acid (HF) concentration and applied potential on the processes of anodic oxidation of Nb in sulphuric acid solution was studied by chronoamperometry, electrochemical impedance spectroscopy and scanning electron microscopy. During the first stage of the process, a compact barrier film is formed. On top of this film, a porous overlayer starts to form, then the nanopores grow into an ordered nanostructure. Subsequently, secondary 3D flower-shaped structures begin to form. These structures gradually spread all over the surface as an irregular multilayer film. The rates of the process of porous overlayer formation and subsequent growth of nanopore arrays increase with applied potential as well as with the HF concentration. The films have been characterised ex situ by electrochemical impedance spectroscopy at open circuit potential and capacitance vs. potential measurements to follow the different stages of nanoporous film formation with electrochemical methods. The impedance spectra and capacitance vs. potential curves have been interpreted using previously proposed models for the amorphous semiconductor/electrolyte interface. An attempt to rationalise the mechanism of nanoporous layer growth is presented by using the conceptual views of the mixed-conduction model and recent ideas for porous film formation on valve metals.     

PdAu合金泡沫膜的制备及其对乙醇的电催化活性（英文）

采用氢气泡动态模板电沉积法制备了三维多孔Au掺杂的Pd合金泡沫膜。采用场发射扫描电子显微镜(SEM)、能量分散X射线光谱仪(EDX)、X射线衍射(XRD)和X射线光电子能谱(XPS)对三维多孔PdAu合金泡沫膜的形貌和结构特征进行了表征。由于特殊的多孔结构和电子效应,Au掺杂的PdAu合金泡沫膜与单种多孔Pd膜相比,在碱性介质中对乙醇的电氧化具有高电催化活性。     

耐蚀Zn-Al合金材料的组合材料芯片方法优选

应用组合材料芯片方法, 通过离子束溅射法制备了全组分范围的Zn-Al薄膜样品阵列. 沉积得到的多层薄膜经370 ℃扩散处理2 h形成合金薄膜. 通过扫描俄歇能谱仪(AES)、X射线衍射仪(XRD)及扫描电子显微镜(SEM)对样品的成分、结构和形貌进行表征. 结果显示, 在低温退火后, 合金薄膜成分均匀, 结晶良好, 表面致密. 材料芯片上的样品在0.1 mol·L-1氯化钠溶液中的极化电阻测试结果表明, 对于全组分的Zn-Al合金薄膜, Al摩尔分数在87%附近的成分具有最高的极化电阻值.进一步的实验发现, 在83%-86%这一较宽的摩尔分数区间内, 极化电阻值均保持在105 Ω·cm-2以上, 比传统热镀锌镀层的极化电阻高1个数量级.     

SnO2 thin films prepared by dip-coating from microwave synthesized colloidal suspensions

Tin(IV) oxide thin films have been prepared by dip-coating. The suspensions used for these depositions have been synthesized by microwave-induced thermohydrolysis of tin tetrachloride aqueous solutions in the presence of hydrochloric acid. Single or multiple depositions were tested, on glass substrates as well as on pure SiO2. The obtained thin films were characterized by optical microscopy, interferometric roughness measurements (Micromap), scanning electron microscopy, secondary ion mass spectroscopy, and scanning tunneling microscopy.     

Buildup of gold nanoparticle multilayer thin films based on the covalent-bonding interaction between boronic acids and polyols

A novel method for the fabrication of gold nanoparticle multilayer films based on the covalent-bonding interaction between boronic acid and polyols, poly(vinyl alcohol) (PVA), was developed. The multilayer buildup was monitored by UV-vis absorbance spectroscopy, which showed a linear increase of the film absorbance with the number of adsorbed Au layers and indicated the stepwise and uniform assembling process. The atomic force microscopy (AFM) image showed that a compact gold multilayer thin film was successfully assembled. The residual boronic acid group on the surface of thin film could incorporate glycosylated-protein horseradish peroxidase (HRP), and good catalytic activity for H2O2 could be observed.