两步法制备多孔硅及其表征I:恒电流法(英文)

本工作通过采用电化学极 -化学氧化两步法在 1:1氢氟酸和乙醇溶液中制备出孔径约为 1～ 2 μm ,厚度大经为 6～ 10 μm的多孔硅样品 .首先将 0 .0 3A/cm2 的恒电流施加到p( 10 0 )硅片一段时间 ,然后将该硅片浸到 2 0 %的硝酸溶液中氧化一段时间 .通过此方法获得的多孔硅结构再进一步用扫描电子显微镜和拉曼光谱仪进行表面形貌和光学性质的考察 .所有制备出的多孔硅结构均有光致发光现象 .老化的多孔硅样品 (在干燥器放置一年 )的光致发光谱峰强度明显增强 ,但分别经过苯乙烯和十六碳烯 ( 1)两种有机溶剂处理 1h后的老化多孔硅样品的光致发光强度却没有显著改变 .     

A novel proton-exchange porous silicon membrane production method for μDMFCs

This study introduces a new production method to use as a porous silicon-based proton exchange membrane for μDMFCs. In this respect, EIS, fuel crossover test, and fuel cell performance test at the μDMFC sample cell are performed at room temperature on a porous silicon-based membrane that was produced for passive mode μDMFC as a proton exchange membrane. The reason for performing the fuel crossover test is to ensure the silicon opened pores along the silicon wafer and to examine the fuel permeability of the membrane. The fuel crossover test shows that the fuel cell provides energy for about 60 min with a 50 mL fuel. EIS reveals proton permeability of proton exchange membrane. The calculated value of the conductivity of the membrane is 0.0016 S/cm. OCV of the system is 0.4V, whereas values (with highest power density is 0.1 mW/cm²and with the highest current density is 0.39 mA/cm²) are low. However, porous silicon is not a natural proton conductor. Hence, these values can be increased by different ways such as porous silicon functionalized, or serial connection of fuel cells. On the other hand, the value of OCV is consistent with the previous studies. In sum, this study presents a simple, cost-effective, and short time-consuming method for the production of porous silicon as proton-conducting membrane behavior.     

Wetting properties of flat and porous silicon surfaces coated with a spiropyran

We report the immobilization and characterization of a spiropyran (SP) derivative (1) on smooth Si(100) and porous H-terminated silicon surfaces through a thermal hydrosilylation protocol. Under visible light exposure the SP is in a closed, hydrophobic form, whereas under UV irradiation it converts to a polar, hydrophilic open form named merocyanine (MC). The SP-MC photoinduced isomerization gives a small contact angle (CA) change of 9 degrees for smooth Si(100) samples under sequential irradiation cycles with white and UV light. Irradiation of porous silicon (PS) surfaces, under the same conditions, gave a CA change of 11 degrees. Treatment of PS surfaces, bearing the MC form of chromophore 1, with cobalt(II) ions enhances the wettability switching of the PS surface to a much larger extent, giving rise to a CA variation as high as 32 degrees.     

Porous silicon as functionalized material for immunosensor application

Recently, for sensor application, porous silicon has received a great deal of attention due to the high specific surface area and the easy fabrication using some established processes of the usual silicon technology. We herein, report the development of a novel immunosensors based on porous silicon for antigen detection. The multilayer immunosensor structure was fabricated following the successive steps: APTS self-assembled monolayer (SAM) layer, glutaaldehyde linker, anti-rabbit IgG binding. The insulating properties of the aminopropyl-triethoxysilane (APTS) monolayer were studied with cyclic voltammetry and the molecular structure was characterized with Fourier-transform infrared (FTIR) technique. The binding between antibody and different antigen concentration (rabbit IgG) was monitored by measuring the capacitance-voltage curve of the antibody functionalized EIS structure. A detection limit of 10 ng/ml of antigen can be detected.     

热塑性聚氨酯基聚合物电解质的制备与表征

采用非溶剂诱导相转化法（NIPS）制备了热塑性聚氨酯/醋酸纤维素（TPU/CA）新型聚合物隔膜。然后,将隔膜浸入液体电解质中得到TPU/CA凝胶聚合物电解质（GPEs）。研究TPU与CA的质量比对GPEs性能的影响。通过X射线衍射（XRD）、扫描电镜（SEM）、热重（TG）、差示扫描量热（DSC）、线性扫描伏安（LSV）、电化学阻抗（EIS）等对TPU/CA膜进行表征。结果表明,在共混隔膜中引入CA可以降低TPU的结晶度,增加隔膜的吸液率。其中,室温下TPU/CA = 7/3基电解质的离子电导率为1.04 mS·cm^-1,电化学窗口为5.1 V(vs. Li/Li⁺)。组装的电池LiFePO₄/TPU/CA/Li在0.5 C循环100次后,仍具有较高的放电比容量和较好的容量保持率,具有良好的循环稳定性。这些结果表明,这种新型的TPU/CA共混GPEs是锂离子电池的理想选择。     

纳米金淀积的多孔硅靶增强样品的激光解吸/电离质谱信号

硅片类型和多孔硅结构的多样性影响了多孔硅表面的激光解吸/离子化质谱(DIOS)(无辅助基质的激光解吸/电离飞行时间质谱(LDI-TOF-MS))数据的重复性和靶的耐储时间。本工作通过在多孔硅的表面淀积金纳米颗粒并将其作为目标靶来增强软物质分子如聚乙二醇和多肽的激光解吸/电离质谱信号。纳米金的淀积钝化了多孔硅表面的Si-H活性基团,增加了靶的耐储时间。用场发射扫描电镜表征了多孔硅淀积金纳米颗粒前后的形貌,用X射线能量色散光谱法分析金的百分含量,结果表明其含量随沉积时间的延长而增加。激光解吸/电离质谱信号的增强可能是由多孔硅及其支持的金纳米颗粒的光学和物理性质引起的,该类型的样品靶在激光解吸/电离飞行时间质谱的应用上结合了多孔硅和金纳米颗粒的双重优势。     

Preparation of hierarchically porous nickel from macroporous silicon

A novel approach for preparing hierarchical porous nickel structures has been developed. It is an aqueous processing of the template, macroporous silicon, which was etched in HF solution to have straight channels. By immersion in a prepared nickel solution, the silicon sidewalls were replaced by nickel deposits to form a total metallic structure. Since silicon framework was gradually consumed during the displacement reactions, the deposited nickel displayed additional feature of being highly porous on the sidewalls. With the initial straight microchannels, the metal structure was hierarchically porous.     

Direct attachment of well-aligned single-walled carbon nanotube architectures to silicon (100) surfaces: a simple approach for device assembly

A new approach for the attachment of vertically-aligned shortened carbon nanotube architectures to a silicon (100) substrate by chemical anchoring directly to the surface has been demonstrated for the first time. The ordered assembly of single-walled carbon nanotubes (SWCNTs) was accomplished by hydroxylating the silicon surface followed by a condensation reaction with carboxylic acid functionalised SWCNTs. This new nanostructure has been characterised by X-ray photoelectron, Raman and Fourier transform infrared (FTIR) spectroscopy as well as scanning electron and atomic force microscopy. The assembly behaviour of SWCNTs onto the silicon surface shows a fast initial step producing isolated functionalised carbon nanotubes or nanotube bundles anchored to the silicon surface followed by a slower step where the adsorbed nanotubes grow into larger aggregates via van der Waals interactions between adsorbed and solvated nanotubes. The electrochemical and optical properties of the SWCNTs directly attached to silicon have also been investigated. These new nanostructures are excellent electrochemical electrodes. They also fluoresce in the wavelength range 650-800 nm. The successful attachment of the SWCNTs directly to silicon provides a simple, new avenue for fabrication and development of silicon-based nanoelectronic, nano-optoelectronic and sensing devices. Compared to existing techniques, this new approach has several advantages including low operating temperature, low cost and the possibility of further modification.     

Porous Silicon Carrier Matrices in Micro Enzyme Reactors-Influence of Matrix Depth

The influence of the carrier matrix depth was investigated for porous silicon enzyme reactors. For the experiments, <110> oriented silicon, p-type (20–70?Ω?cm), was used. Porous silicon was generated on planar surfaces and on anisotropically pre-etched high aspect-ratio parallel channel reactors. For each type of sample the porous silicon layer was generated for three depths, controlled by the anodisation time, and two current densities, to yield different morphologies. Glucose oxidase (GOx) was immobilised on the porous matrix by standard procedures for immobilisation of enzymes on silica. The enzyme activity of the samples was monitored by a colorimetric assay. The results clearly display the influence of the matrix depth for both the planar and the reactor structures. A 170-fold increase in catalytic turn-over, in comparison to an identical non-porous reference, was recorded for a reactor with an average pore depth of 10?μm. At depths above 10?μm the increase in catalytic efficiency levelled off. For the planar samples the levelling off occurred at an average pore depth of 20?μm.     

预处理对多孔硅形成过程的影响(英文)

本工作初步探讨了开路电位下对硅片进行预处理时多孔硅的形成过程 .电化学极化实验、扫描电镜和拉曼谱学的研究表明 ,预处理可以加速硅 /溶液界面上的化学或电化学反应 ,从而加快多孔硅的生长过程 ,最终导致光致发光的光谱红移 .多孔硅的厚度随预处理时间的增长而减小     

Direct assay of Aplysia tissues and cells with laser desorption/ionization mass spectrometry on porous silicon.

Desorption/ionization on porous silicon (DIOS) is a form of laser desorption mass spectrometry that allows for the direct mass analysis of a variety of analytes without the addition of organic matrix. Protocols are described for the direct analysis of exocrine tissue and single neurons using DIOS-MS. The atrial gland of Aplysia californica was blotted on to porous silicon and analyzed with DIOS-MS in the range m/z 1000-4000. The ability to culture invertebrate neurons directly on porous silicon is also presented. Isolated bag cells regenerated neuronal processes in culture on porous silicon. DIOS-MS allowed the direct detection of the peptides contained in individual cultured neurons indicating that with appropriate protocols, DIOS can be used with biological samples with considerable thickness.     

Enzymatic reaction of the immobilized enzyme on porous silicon studied by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry

Desorption/ionization on silicon mass spectrometry (DIOS-MS) is a matrix-free technique that allows for the direct desorption/ionization of low-molecular-weight compounds with little or no fragmentation of analytes. This technique has a relatively high tolerance for contaminants commonly found in biological samples. DIOS-MS has been applied to determine the activity of immobilized enzymes on the porous silicon surface. Enzyme activities were also monitored with the addition of a competitive inhibitor in the substrate solution. It is demonstrated that this method can be applied to the screening of enzyme inhibitors. Furthermore, a method for peptide mapping analysis by in situ digestion of proteins on the porous silicon surface modified by trypsin, combined with matrix-assisted laser desorption/ionization-time of flight-MS has been developed.     

粉末多孔镍电极电化学阻抗谱及其数学模型

镍电极反应动力学在大多情况下是受固态质子扩散过程控制的，以此为出发点建立了具有明确物理意义的镍电极电阻抗谱（ＥＩＳ）的数学模型，并以该模型为基础，讨论了一些模型参数如双电层电容Ｃｄ１，质子扩散系数Ｄ及活性物质粒子半径ｒ０等改变，电极的不同荷电状态及多孔镍电极中的传质过程对镍电阻阻抗谱的影响，理论模型较好地解释了一些实验结果。     

High surface area nanoporous amorphous silica prepared by dodecanol assisted silica formate sol-gel approach

A simple polycondensation of monocarboxylic acids with silicon alkoxides led to transparent silica gels mainly comprised of silicate species of closed structures. This 'sol-gel formic acid' approach was modified by trapping an organic template (dodecanol) inside the silicate network during the polymerization process. Using this templating approach, porous silica of extremely high surface area, was produced in contrast to non-porous silica obtained by non-templating approach. The S(BET) surface areas of the template assisted samples resulting from the entire pores were found to be up to 725 m(2)/g. The total pore volumes of the samples were in the range of 0.40-0.74 cc/g in which micropore volumes were about 0.15-0.25 cc/g; the porosity depending on the reactants molar ratios of dodecanol, silicon alkoxide and formic acid.     

Solution Synthesis of Porous Silicon Particles as an Anode Material for Lithium Ion Batteries

Nanostructured silicon-based materials with porous structures have recently been found to be impressive anode materials with high capacity and cycling performance for lithium-ion batteries. However, the current methods of preparing porous silicon have generally been confronted with the requirement for multiple steps and complex synthesis. In the present study, porous silicon with high surface area was prepared by using a high yielding and simple reaction in which commercial magnesium powder readily reacts with HSiCl₃ with the help of an amine catalyst under mild conditions. The obtained porous silicon was coated with a nitrogen-doped carbon layer and used as the anode for lithium-ion batteries. The porous Si-carbon nanocomposites exhibited excellent cycling performance with a retained discharge capacity of 1300 mA h g⁻¹ after 200 cycles at 1 A g⁻¹ and a discharge capacity of 750 mA h g⁻¹ at a current density of 2 A g⁻¹ after 250 cycles. Remarkably, the Coulombic efficiency was maintained at nearly 100 % throughout the measurements.     

多孔硅的制备与光伏特性研究

采用特制的电解池在不同条件下制备了一系列多孔硅样品。通过测定其ＳＰＳ发现，多孔硅的ＳＰＳ特征带同单晶硅相比有明显蓝移，并且随制备条件不同，蓝移效应也不同。电解质中ＨＦ浓度和电解时间对基ＳＰＳ响应有明显影响，这一现象的出现主要归因于最子线阵的生成。     

Catalytic amplification of the soft lithographic patterning of Si. Nonelectrochemical orthogonal fabrication of photoluminescent porous Si pixel arrays

Photoluminescent, porous silicon pixel arrays were fabricated via a Pt-promoted wet etching of p-type Si(100) using a 1:1:1 EtOH/HF/H2O2 solution. The pixels were fabricated with micrometer-scale design rules on a silicon substrate that had been modified with an octadecyltrichlorosilane (OTS) monolayer patterned using microcontact printing. The printed OTS layer serves as an orthogonal resist template for the deposition of a Pt(0) complex, which preferentially deposits metal species in areas not covered with OTS. The Pt centers generate a localized oxidative dissolution process that pits the Si in the Pt-coated regions, resulting in the formation of a porous silicon microstructure that luminesces around 580 nm upon illumination with a UV source. Scanning electron microscopy and fluorescence microscopy images of the fabricated porous silicon structures showed that features in the size range of approximately 10-150 microm, and possibly smaller, can be generated by this catalytically amplified soft lithographic patterning method. Importantly, the OTS acts as an etch mask, so that, even with significant hole transport, etching is confined to areas coated with the Pt(0) complex.     

发光多孔硅的光谱及电化学研究

单晶硅是E_g为1.1eV的间接带隙半导体材料,在可见光区不发光,不能应用于光电子领域.但是,Canham 1990年首次发现^[1],适当条件下形成的多孔硅在室温下就可发出强度能与Ⅲ-Ⅴ族半导体发光二极管相媲美的可见光。     

Chemical etching of silicon: Smooth, rough, and glowing surfaces

Scanning Force Microscope images of silicon surface morphology are presented for samples exposed to various oxidizing environments followed by oxide removal. These are contrasted with samples exposed to HNO₃/HF solutions. The former samples consistently produced surface roughness on the order of a few nanometers, while the latter solution exhibited surface roughness of several hundred to over a thousand nanometers. This rough surface is photoluminescent and is known as porous silicon. Careful observation of the onset of the reaction (which is proceeded by a concentration dependent induction period) suggests that the reaction mechanism is autocatalytic; some etchant product species catalyzes the further attack of the surface. Surface features of co-existing fluorescing and non-fluorescing regions emphasize the heavy etching present in the porous silicon region. Local control of the porous silicon formation by a photoinduced etching process is reported for the first time suggesting the possibility of a non-resist lithographic procedure.     

多孔硅制备条件对其电致发光特性的影响

应用蒸镀-阳极氧化法制备结构为ITO/PS/p-S i/A l的多孔硅电致发光器件,在7.5V电压下实现了数小时连续电致发光.实验表明,多孔硅电致发光峰位会随着阳极氧化电流密度的增大、腐蚀时间的延长以及HF酸浓度的降低而蓝移.欲制备工作电压较低、发光时间较长、发光效率较高的电致发光样品,则多孔硅制备时的阳极氧化应使用较低电流密度和较短的腐蚀时间.