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.     

First Principle Study on the Rectification of Molecular Junctions Based on the Thiol-ended Oligosilane

The electron transport properties of various molecular junctions based on the thiol-ended oligosilane are investigated through density functional theory combined with non-equilibrium Green's function formalism. Our calculations show that oligosilanes doped by the phenyl and-C10H6 groups demonstrate better rectifying effect and their rectification ratios are up to 15.41 and 65.13 for their molecular junctions. The current-voltage(I-V) curves of all the Au/ modified oligosilane/Au systems in this work are illustrated by frontier molecular orbitals, transmission spectra and density of states under zero bias. And their rectifying behaviors are analyzed through transmission spectra.     

多孔硅的光电化学特性研究

研究了多孔硅的光电化学特性和溶液中的光致电荷转移机一，由Ｐ型单晶硅制备的多孔硅具有Ｐ型半导体的光电性质，且光电流响应高于单晶硅，由于多孔硅表面态能级对光致电荷的陷阱作用，多孔硅呈现了独特的光电流响应和光致电荷转移性质。     

A simple and tailor‐made fabrication of porous silicon carbide from functionalized kraft pulp paper

Porous silicon carbide (SiC) materials were fabricated using the polymer‐derived ceramics method with kraft pulp papers (KPP) and a commercial polycarbosilane, the allylhydridopolycarbosilane (AHPCS), as starting materials. For this, KPP, propargylated KPP, or phosphorylated KPP were used to be impregnated by the AHPCS, with or without Karstedt catalyst. The pyrolysed materials were characterized at different stages, by using thermogravimetric analysis (TGA) coupled with mass spectrometry, X‐ray diffraction (XRD), and scanning electron microscopy (SEM). Depending on the nature of the initial template, various architectured SiC ceramics were successfully obtained with adjustable porosities. The key role of the previous functionalization of the papers was highlighted in terms of interactions at the interface between the polymer and the lignocellulosic handsheets. It led to either replica or sacrificial template methods. Thus, it was possible to tune the open porosity of the porous carbon and β‐SiC materials between 14.8% and 92.9%, with ceramic yields varying from 12% to 71%.     

Novel photoconductive Ag/nanostructure ruthenium oxide/p-type silicon Schottky barrier diode by sol–gel method

A new Schottky photodiode of Ag/RuO₂/p-Si/Al was successfully fabricated using spin-coating technique. The ruthenium oxide (RuO₂) nanoparticles with an average size of 8 nm were synthesized using a sol–gel method. The crystal structure and morphology of the synthesized RuO₂ were analyzed by means of X-ray diffraction, energy dispersive X-ray spectroscopy, transmission electron microscopy and selective area electron diffraction. The rectification ratio of the diode was found to be 112 at ±2 V. The ideality factor and barrier height values of the Ag/RuO₂/p-Si/Al diode were obtained to be 1.47 and 0.55 eV, respectively. The Cheung–Cheung and Norde’s models were used to determine the diode parameters. The photoresponse behavior of the fabricated Ag/RuO₂/p-Si/Al diode was studied under various illumination intensities. The transient photocurrent results indicate that photocurrent under illumination is higher than the dark current and this indicates that the fabricated diode behaves as a photodiode. The capacitance–voltage–frequency measurements indicate that the capacitance of the diode depends on voltage and frequency. The obtained results suggest that the new Ag/RuO₂/p-Si/Al diode can be used an optical switching device for optical sensor applications and are also expected to be generated in the future study.     

DSA-type anode based on conductive porous p-silicon substrate

Porous silicon (PS) thin films have been prepared by electrochemical anodization of p-Si in HF–H₂O–EtOH solution and they have been used as substrate material for the preparation of iridium oxide based electrodes (PS/IrO₂) using the thermal decomposition technique. The morphology and the electrochemical behaviour of the PS/IrO₂ have been studied and the results have been compared with IrO₂ electrodes deposited on a sandblasted p-silicon (p-Si/IrO₂). SEM analyses have revealed that the PS/IrO₂ electrodes are porous, rough and IrO₂ appears to be deposited within some silicon pores, while the p-Si/IrO₂ present a ‘mud-cracked’ surface. Cyclic voltammetries in 1 M HClO₄ have shown that the PS/IrO₂ presents higher surface area than p-Si/IrO₂.     

具有金属薄层的p-Si阴极在碱溶液中的光电化学性能

本文用循环伏安曲线和恒电位极化方法考察了具有金属薄层的p型单晶外延硅(p⁺/p-Si)阴极在碱溶液中的光电化学性能。结果表明,镀有钨-镍合金层的p⁺/p-Si阴极和镀有钯的p⁺/p-Si阴极,使氢析出的光电流明显增加。前者的电位比光电流达到相同值的空白p⁺/p-Si电极向正方移动了0.3V以上,后者移动0.25V。同时对p型外延硅(p⁺/p-Si)阴极比p型单晶硅(p-Si)阴极光响应较大的实验结果作了初步解释。扫描电镜结果显示,钨-镍合金沉积层是由许多不连续的“团块”构成的,而不是连续层。     

高多孔度多孔硅自支撑膜的制备与表征

发光多孔硅由于在光电子学方面的应用前景而引起人们极大的关注[1]．最近多孔硅发光二极管的研究方面取得了重大进展[2]。但是，有关多孔硅的发光机制仍然存在着争论[1，3，4]，利由于消除了单晶硅衬底的影响，对脱离了硅衬底的多孔硅自支撑膜能够进行普通多孔硅所不能进行的一     

Enhancement of the ionic response of field effect transducers using porous silicon

Oxidised porous silicon samples prepared from highly and weakly doped p-type silicon substrates, have been functionalised with calix[4]arene (CA) molecules. They have been used for sodium detection as electrolyte/insulator/silicon (EIS) structures. An over Nernstian behaviour was observed and correlated with physical parameters of porous silicon samples (porosity, resistivity). A generalised Nernstian equation was proposed in order to describe this property. CA functionalised EIS structures based on porous silicon present higher lifetime compared to flat structures.     

Tailored Porous Silicon Microparticles: Fabrication and Properties

The use of mesoporous silicon particles for drug delivery has been widely explored thanks to their biodegradability and biocompatibility. The ability to tailor the physicochemical properties of porous silicon at the micro‐ and nanoscale confers versatility to this material. A method for the fabrication of highly reproducible, monodisperse, mesoporous silicon particles with controlled physical characteristics through electrochemical etching of patterned silicon trenches is presented. The particle size is tailored in the micrometer range and pore size in the nanometer range, the shape from tubular to discoidal to hemispherical, and the porosity from 46 to over 80 %. In addition, the properties of the porous matrix are correlated with the loading of model nanoparticles (quantum dots) and their three‐dimensional arrangement within the matrix is observed by transmission electron microscopy tomography. The methods developed in this study provide effective means to fabricate mesoporous silicon particles according to the principles of rational design for therapeutic vectors and to characterize the distribution of nanoparticles within the porous matrix.     

Electrical-optical properties of nanofiber ZnO film grown by sol gel method and fabrication of ZnO/p-Si heterojunction

Electrical and optical properties of the ZnO film prepared by sol-gel dip coating were investigated and ZnO film was deposited onto p-type silicon to obtain Ag/ZnO/p-Si heterojunction diode. Two dimensional atomic force microscopy images indicate that the ZnO film is formed from the fibers consisted from nanoparticles with grain size of 250-350 nm. The electrical conductivity mechanism of the ZnO film was varied from extrinsic to intrinsic conductivity. The calculated optical band gap of the ZnO film was found to be 3.22 eV. The Ag/ZnO/p-Si diode exhibit a non-linear behavior with ideality factor of n = 4.17 and barrier height of ?_B = 0.79 eV. The electrical properties of the Ag/ZnO/p-Si diode were investigated by current-voltage, capacitance-voltage-frequency and conductance-voltage-frequency measurements.     

Phase assembly-induced transition of three dimensional nanofibril- to sheet-networks in porous cellulose with tunable properties

Ultralight and highly porous cellulose was fabricated via cellulose/sodium hydroxide/urea aqueous solution followed by gelation, coagulation and freeze-drying in the current work. The water content and freeze rate of cellulose coagulated sample are two crucial factors controlling the morphology, density and porosity of porous cellulose, which led to an interesting morphological transition from three dimensional nanofibrillar network to sheet network in porous cellulose. It was proposed that the aggregation and assembly of cellulose-rich phase and crystallization of water-rich phase were closely related to this transition. Based on this concept, a series of cellulose materials with densities varied from 0.129 to 0.330 g cm^?3 and corresponding porosities ranged from 91.4 to 78.0 %, were obtained. The porous celluloses showed a good ductility (strain to fracture is more than 30 %) and high modulus, which also could be tuned by porous morphology. The new understanding on the morphological transition in porous cellulose could be beneficial for the development of “green” porous materials.     

Characterization of thermal properties of porous silicon film/silicon using photoacoustic technique

We have applied photoacoustic (PA) technique to study the thermal properties of porous silicon (PS) films formed on p-type Si substrates by electrochemical anodic etching. Four PS samples with close thicknesses but greatly different porosities (from 20 to 60%) were examined. From the dependences of the PA signals on the modulation frequency of excitation light measured under a transmission detection configuration (TDC), effective thermal diffusivities for the two-layered PS/Si samples were determined and found to decrease greatly from 0.095 to 0.020 cm² s^-1 as the porosity increased from 20 to 60%. This revised version was published online in August 2006 with corrections to the Cover Date.     

液相渗硅法制备多孔Si/SiC生物形态陶瓷

榉木经高温热解转化为碳模板,通过液相渗硅反应（LSIP）,在1550℃,1.5h渗硅,1700℃排硅制备了保持木材微观结构的多孔Si/SiC陶瓷。利用X-射线衍射分析（XRD）, 扫描电子显微镜（SEM）,压汞技术对样品的物相构成、显微结构和孔径分布进行了分析,利用阿基米德法和三点弯曲法测定了多孔陶瓷的显气孔率、密度和弯曲强度。结果表明,最终产物由主晶相β-SiC和少量的Si组成;控制高温排硅时间可以得到孔隙率为16％~32％的多孔Si/SiC陶瓷,可调控其产物的相组成和力学性能。对LSIP工艺的反应机理进行了探讨。     

An investigation of Zn/ZnO:Al/p-Si/Al heterojunction diode by sol–gel spin coating technique

Present study shows the structural, morphological, optical characterization of sol–gel spin coated ZnO:Al film and investigation of device efficiency of Zn/ZnO:Al/p-Si/Al heterojunction diode structure. X-ray diffraction study indicates that film has hexagonal polycrystalline structure with (002) preferential direction. Atomic force microscope and scanning electron microscope images exhibit that surface of ZnO:Al/p-Si consists of homogenously scattered nanoparticles. The surface roughness of ZnO:Al film is found to be 15.24 nm. The band gap value of ZnO:Al film deposited on glass substrate is calculated to be 3.34 eV. The electrical characterization of Zn/ZnO:Al/p-Si/Al heterojunction structure is made by current–voltage (I–V) and capacitance–voltage (C–V) measurements. From these measurements, the heterojunction structure shows a rectifying behavior under a dark condition. The ideality factor and barrier height of Zn/n-ZnO:Al/p-Si/Al structure are calculated as 3.23 and 0.68 eV. The heterojunction structure have diode characteristic with rectification ratio at 64.4 at +2.0 V in the dark. The results suggest that Zn/ZnO:Al/p-Si/Al heterojunction diode can be successfully used in many optoelectronic applications.     

An experimental and theoretical analysis of molecular separations by diffusion through ultrathin nanoporous membranes

Diffusion based separations are essential for laboratory and clinical dialysis processes. New molecularly thin nanoporous membranes may improve the rate and quality of separations achievable by these processes. In this work we have performed protein and small molecule separations with 15 nm thick porous nanocrystalline silicon (pnc-Si) membranes and compared the results to 1- and 3- dimensional models of diffusion through ultrathin membranes. The models predict the amount of resistance contributed by the membrane by using pore characteristics obtained by direct inspection of pnc-Si membranes in transmission electron micrographs. The theoretical results indicate that molecularly thin membranes are expected to enable higher resolution separations at times before equilibrium compared to thicker membranes with the same pore diameters and porosities. We also explored the impact of experimental parameters such as porosity, pore distribution, diffusion time, and chamber size on the sieving characteristics. Experimental results are found to be in good agreement with the theory, and ultrathin membranes are shown to impart little overall resistance to the diffusion of molecules smaller than the physical pore size cutoff. The largest molecules tested experience more hindrance than expected from simulations indicating that factors not incorporated in the models, such as molecule shape, electrostatic repulsion, and adsorption to pore walls, are likely important.     

Artificial ion channels showing rectified current behavior.

Voltage-dependent artificial ion channels 3 and 4 were synthesized. Two cholic acid derivatives were connected through a m-xylylene dicarbamate unit at 3-hydroxyl groups. Asymmetries were introduced by terminal hydrophilic groups, carboxylic acid and phosphoric acid for 3 and hydroxyl and carboxylic acid for 4. Under basic conditions, these headgroups in 3 and 4 are expected to be dissociate into -1/-2 (pH 8.2) and 0/-1 (pH 7.2), respectively. Single ion channel properties were examined by a planar bilayer lipid membrane method under symmetrical 500 mM KCl at pH 8.2 or 7.2. When 3 and 4 were introduced into the bilayer membrane under application of positive voltage (a positive-shift method), the current values at positive applied voltage were larger than the corresponding ones at the negative applied voltage. The current-voltage plots were fitted by curves through a zero point to show clear rectification properties. The direction of rectification could be controlled by positive- or negative-shift methods. Vectorial alignment of terminal headgroup charges by the voltage-shift incorporation is essential for giving voltage-dependent rectified ion channels.     

Growth of silicon thin film by LPE on porous silicon bilayers

The fabrication of solar cells based on the transfer of a thin silicon film on a foreign substrate is an attractive way to realise cheap and efficient photovoltaic devices. The aim of this work is to realise a thin mono-crystalline silicon film on a double porous silicon layer in order to detach and transfer it on mullite. The first step is the fabrication of a double porous silicon layer by electrochemical anodisation using two different current densities. The low current leads to a low porosity layer and during annealing, the recrystallisation of this layer allows epitaxial growth. The second current leads to a high porosity which permits the transfer on to a low cost substrate. Liquid Phase Epitaxy (LPE) performed with indium (or In+Ga) in the temperature range of 950–1050°C leads to almost homogeneous layers. Growth rate is about 0.35 μm min⁻¹. Crystallinity of the grown epilayer is similar on porous silicon and on single crystal silicon. In this paper, we focus on the realisation of porous silicon sacrificial layer and subsequent LPE growth. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electron transport through rectifying self-assembled monolayer diodes on silicon: Fermi-level pinning at the molecule-metal interface

We report the synthesis and characterization of molecular rectifying diodes on silicon using sequential grafting of self-assembled monolayers of alkyl chains bearing a pi group at their outer end (Si/sigma-pi/metal junctions). We investigate the structure-performance relationships of these molecular devices, and we examine the extent to which the nature of the pi end group (change in the energy position of their molecular orbitals) drives the properties of these molecular diodes. Self-assembled monolayers of alkyl chains (different chain lengths from 6 to 15 methylene groups) functionalized by phenyl, anthracene, pyrene, ethylene dioxythiophene, ethylene dioxyphenyl, thiophene, terthiophene, and quaterthiophene were synthesized and characterized by contact angle measurements, ellipsometry, Fourier transform infrared spectroscopy, and atomic force microscopy. We demonstrate that reasonably well-packed monolayers are obtained in all cases. Their electrical properties were assessed by dc current-voltage characteristics and high-frequency (1-MHz) capacitance measurements. For all of the pi groups investigated here, we observed rectification behavior. These results extend our preliminary work using phenyl and thiophene groups (Lenfant et al., Nano Lett. 2003, 3, 741). The experimental current-voltage curves were analyzed with a simple analytical model, from which we extracted the energy position of the molecular orbital of the pi group in resonance with the Fermi energy of the electrodes. We report experimental studies of the band lineup in these silicon/alkyl pi-conjugated molecule/metal junctions. We conclude that Fermi-level pinning at the pi group/metal interface is mainly responsible for the observed absence of a dependence of the rectification effect on the nature of the pi groups, even though the groups examined were selected to have significant variations in their electronic molecular orbitals.     

超临界二氧化碳中聚(丁二酸-丁二醇/乙二醇)酯(PBES)多孔聚合物的制备与表征

在超临界二氧化碳(scCO2)条件下,制备了可生物降解性的聚(丁二酸-丁二醇/乙二醇)酯(PBES)多孔材料,研究了scCO2的压力、温度对多孔材料的结构形貌和结晶度的影响。 结果表明,材料的孔洞分布、结构形态和结晶度与处理样品的压力、温度关系密切;经过scCO2处理后材料的结晶度有所降低。 孔径均匀分布,为50~200 μm,131 ℃处理样品的孔隙率为55.63%。