Enhancement of fluorescence of porous silicon upon saturation by liquid crystal

The fluorescence of samples of porous silicon of various morphologies that are filled with a liquid crystal (LC), n-pentyl-n′-cyanobiphenyl (5CB), is studied. The fluorescence spectra of the sample, along with the long-wavelength band of porous silicon with a maximum in the range 627–667 nm, exhibit a short-wavelength band of 5CB with a maximum in the range 385–410 nm. The radiative relaxation times of porous silicon and 5CB lie in the micro- and nanosecond ranges, respectively. It is found that the filling of pores with 5CB enhances the fluorescence of porous silicon by two to three times. This enhancement is caused by non-radiative energy transfer from 5CB to the porous matrix as a result of efficient interactions between LC molecules and pore walls. Using IR spectroscopy, it is shown that the formation of hydrogen bonds between cyano groups of 5CB molecules and silanol groups of pore surface is the predominant type of these interactions. A transfer mechanism is suggested according to which excited associates of 5CB molecules transfer their energy via surface channels to excitons of porous silicon, enhancing its fluorescence.     

A Grand Canonical Monte Carlo Study of Adsorption and Capillary Phenomena in Nanopores of Various Morphologies and Topologies: Testing the BET and BJH Characterization Methods

We report a Grand Canonical Monte Carlo simulation study of Ar adsorption at 77 K in silica nanopores having various morphologies/topologies. Both the morphological and topological disorders are shown to significantly affect the capillary condensation phenomenon. In the case of an ellipsoidal pore, we observe that the filling mechanism is similar to that of a cylindrical pore having the same section area but with a lower condensation pressure. We show that the adsorption/desorption hysteresis loop is asymmetrical for the pore with constrictions while it is symmetrical for the regular cylindrical pore. Moreover, the Ar adsorption isotherm for the constricted pore reproduces the main features of that for the fully disordered Vycor‐like porous matrix. The results for the different pore geometries (having no direct interface with the gas reservoir) indicate that the desorption occurs through cavitation at a pressure driven by the smallest void size. We also consider the validity of the BET and BJH methods for the different porous matrices. Except for the Vycor‐like matrix, the BET surface assessed from Ar adsorption isotherm at 77 K always significantly overestimates the intrinsic surface of the pore (even for a planar surface). The disagreement between the BET surface and the geometrical surface is found to increase as the confinement increases (cylindrical pore) and/or the shape of the pore becomes asymmetrical (ellipsoidal pore). Interestingly, the best agreement between the BET and the geometrical surface is found in the case of the pore with a constriction, i.e. a system that exhibits a surface with both negative and positive curvature regions. This idea is supported by the results for the Vycor‐like matrix, which has a distorted surface (many negative curvature regions combined with positive curvature regions): for this disordered porous matrix, the BET surface is found to underestimate the intrinsic surface. Finally, we show that the pore size determined using the BJH method always underestimates the pore size, in agreement with previous experimental and simulation studies.     

纳米粒子与单晶硅表面碰撞的反弹机理研究

应用分子动力学方法模拟了纳米粒子与单晶硅(001)表面碰撞、反弹飞离的现象，分析了粒子的反弹行为、基体弹性形变和塑性形变的原子构型特征，以及碰撞过程的能量转化.碰撞后单晶硅表面形成半球形的小坑，小坑周围的基体原子呈非晶态.碰撞过程中与颗粒相邻的基体原子立即非晶化，在非晶层外面基体以可恢复的(111)［110］滑移结构存储弹性形变能.在射入过程，基体发生压缩弹性形变；颗粒反弹时基体势能振荡下降,交替形成压缩形变构型和拉伸形变构型.射入过程中存贮的压缩弹性形变能的释放为颗粒提供了反弹、飞离的能量. 关键词： 碰撞 纳米粒子 单晶硅表面 分子动力学模拟     

Self detachment of free-standing porous silicon membranes in moderately doped n-type silicon

In this article we describe a reliable etching method to fabricate porous silicon free-standing membranes (FSMs) based on a self detachment of the porous layer in moderately doped n-type silicon substrates. We found that stable growth of smooth and straight pores is restricted to a narrow range of etching conditions and, unlike p-type substrates, the lift-off of the membrane is a self-limited process that does not require a large burst of current. The detachment of the porous membrane is independent of the structure of the already porosified layer, meaning that the average pore diameter can be tuned from nano to macro size within the same membrane. We also demonstrate that, despite their limited thickness, FSMs are quite robust and can sustained further processing. Thus, the etching receipt we are proposing here extends the range of sensors and filters that can be fabricated using porous silicon technology.     

Salt crystallization as damage mechanism in porous building materials--a nuclear magnetic resonance study

Salts can damage building materials by chemical reactions or crystallization, which is a serious threat to cultural heritage. In order to develop better conservation techniques, more knowledge of the crystallization processes is needed. In a porous material, the size of a salt crystal is limited by the sizes of the pores. It has been predicted that as a consequence, the solubility of a salt increases with decreasing pore size. This increase seems to be related to an increase of the stress generated by a crystal on the pore wall. It has been suggested that the resulting stress could become high enough to induce failure. We have studied the crystallization of salts in porous materials with well-defined pore sizes. Samples were saturated at 40 degrees C with saturated Na2SO4 and Na2CO3 solutions. Next we have cooled the samples to 0 degrees C and waited for nucleation. After nucleation occurred, the solubility in the porous material was measured with nuclear magnetic resonance (NMR) as a function of the temperature. The measurements on Na2CO3 indeed show an increase in solubility with a decrease in pore size. For Na2SO4, we did not observe a pore size-dependent solubility. However, we have to remark that these results show a metastable crystal phase. The results can be used to calculate the actual pressure exerted by the crystals onto the pore wall.     

Phase transitions of fluids confined in porous silicon: A differential calorimetry investigation

The phase transitions of non-polar organic fluids and of water, confined in the pores of porous silicon samples, were investigated by Differential Scanning Calorimetry (DSC). Two types of PS samples (p^- and p⁺ type) with different pore size and morphology were used (with spherical pores with a radius of about 1.5 nm and cylindrical shape with a radius of about 4 nm respectively). The DSC results clearly show that the smaller the pores are, the larger is the decrease in the transition temperature. Moreover, a larger hysteresis between melting and freezing is observed for p⁺ type than for p^- type samples. A critical review of the thermodynamical properties of small particles and confined fluids is presented and used to interpret and discuss our DSC results. The effects of the chemical dissolution as well as the influence of anodization time are presented, showing that thick p⁺ type porous silicon layers are non-homogeneous. The DSC technique which was used for the first time to investigate fluids confined in porous silicon, enables us to deduce original information, such as the pore size distribution, the decrease in the freezing temperature of confined water, and the thickness of non-freezing liquid layer at the pore wall surface. Received: 11 May 1998 / Revised and Accepted: 29 July 1998     

Ultrasonic waves in porous ceramics with non-spherical holes

Formulae describing the effective elastic moduli of a porous ceramic medium are derived using Eshelby's solution and Maxwell's approximation. The ceramic medium is considered as an infinite matrix, which has uniform elastic properties and encloses non-spherical pores. A numerical evaluation of the velocity of an ultrasonic wave in the ceramic, as function of the porosity and pore shape, is presented. The theoretical results were combined with those obtained experimentally for different firing temperatures of the ceramic.     

Magnetic behaviour of a magnetite/silicon nanocomposite

Mesoporous silicon is utilized to infiltrate quite monodisperse iron oxide nanoparticles into the pores. This semiconducting matrix exhibits oriented pores, clearly separated from each other, with an average pore diameter of 55 nm. Iron oxide nanoparticles of 8 nm and 5 nm in size which are coated with a surfactant are prepared by high temperature decomposition in the presence of an organic precursor. The achieved nanocomposite consists of dispersed Fe₃O₄-nanoparticles within the pores and offers magnetic properties which are determined by the morphology of the silicon matrix as well as by the distribution of the particles within the individual pores. Thus, the change of regime between a superparamagnetic and a blocked state of the system can be tuned. Furthermore, magnetic anisotropy between the two magnetization directions, normal and parallel to the sample surface, is observed due to the oriented and separated pores of the template which are quasi-regular arranged. This porous silicon/magnetite composite with its adjustable magnetic properties is also of interest for possible applications in biomedicine due to the low toxicity of both materials.     

Investigation of Porous Silicon Wetting by Raman Scattering

Wetting phenomena in porous silicon layers are experimentally investigated by Raman scattering. The experimental results show a reversible blue-shift of Raman spectra of wetted porous silicon layers with respect to the unperturbed layers. We ascribe the shift to a compressive stress due to the increased lattice mismatch between the porous silicon layer and the bulk silicon substrate in wetting conditions.     

多孔硅光致发光峰半峰全宽的压缩

硅发光对于在单一硅片上实现光电集成是至关重要的.目前已有的使硅产生发光的方法有:掺杂深能级杂质、掺稀土离子、多孔硅、纳米硅以及Si/SiO₂超晶格.声空化所引发的特殊的物理、化学环境为制备光致发光多孔硅薄膜提供了一条重要的途径.实验表明,声化学处理对于改善多孔硅的微结构,提高发光效率和发光稳定性都是一项非常有效的技术.超声波加强阳极电化学腐蚀制备发光多孔硅薄膜,比目前通用的常规方法制备的样品显示出更优良的性质.这种超声波的化学效应源于声空化,即腐蚀液中气泡的形成、生长和急剧崩溃.在多孔硅的腐蚀过程中,由于超声波的作用增加了孔中氢气泡的逸出比率和塌缩,有利于孔沿垂直方向的腐蚀,使多孔硅光致发光峰的半峰全宽压缩到了3.8nm.     

Energy transport in plasma etching of nanoporous dielectric materials

A Monte Carlo routine was developed to simulate the motion and energetics of ions in the pores of a xerogel material under plasma etching conditions. The simulation included the effects of an applied electric field and input conditions for the pore as a function of pressure and applied voltage in the plasma reactor. We were interested in the ion energy in a pore, the ion penetration depth and the effect of ion energy on etching.At low pressures the nanoporous material etches faster than dense silicon dioxide. This is to be expected given the decrease in density and increase in surface area that arises due to the porosity. However, as the pressure is increased, the etch rate decreases dramatically and, eventually, the dense oxide may etch faster than the porous material. CHF₃ was used as the etchant gas and, for this gas, we believe this behavior to be controlled by the ion energy and energy transport in the pores of the xerogel material. As the pressure in the plasma reactor is increased, the incoming ions switch over from etching activation to polymerisation activation. This agrees with the observed crossover in etch rate seen experimentally and with the cessation in etching as pressure is increased. The switch is affected by pore roughness and correlates with the average ion energy in the pore.     

Nanostructuring Si surface and Si/SiO2 interface using porous-alumina-on-Si template technology. Electrical characterization of Si/SiO2 interface

In this work, anodic porous alumina thin films with pores in the nanometer range are grown on silicon by electrochemistry and are used as masking material for the nanopatterning of the silicon substrate. The pore diameter and density are controlled by the electrochemical process. Through the pores of the alumina film chemical oxidation of the silicon substrate is performed, leading to the formation of regular arrays of well-separated stoichiometric silicon dioxide nanodots on silicon, with a density following the alumina pores density and a diameter adjustable by adjusting the chemical oxidation time. The alumina film is dissolved chemically after the SiO₂ nanodots growth, revealing the arrays of silicon dioxide dots on silicon. In a next step, the nanodots are also removed, leaving a nanopatterned bare silicon surface with regular arrays of nanopits at the footprint of each nanodot. This silicon surface structuring finds interesting applications in nanoelectronics. One such application is in silicon nanocrystals memories, where the structuring of the oxidized silicon surface leads to the growth of discrete silicon nanocrystals of uniform size. In this work, we examine the electrical quality of the Si/SiO₂ interface of a nanostructured oxidized silicon surface fabricated as above and we find that it is appropriate for electronic applications (an interface trap density below 1–3×10¹⁰ eV⁻¹ cm⁻² is obtained, indicative of the high quality of the thermal silicon oxide).     

The role of surface tension in elastic wave scattering in an inhomogeneous poroelastic medium

It is well known that many porous media such as rocks have heterogeneities at nearly all scales. We applied Biot's poroelastic theory to study the propagation of elastic waves in isotropic porous matrix with spherical inclusions. It is assumed that the heterogeneity dimension exceeds significantly the pore size. Modified boundary conditions on poroelastic interface are used to take into account the surface tension effects. The effective wavenumber is calculated using the Waterman and Truell multiple scattering theory, which relates the effective wave number to the amplitude of the wave field scattered by a single inclusion. The calculations were performed for a medium containing fluid-filled cavities or porous inclusions contrasting in saturating fluid elastic properties. The results obtained show that when we consider elastic wave propagation in poroelastic medium containing soft inclusions, it is necessary to take into account the capillary pressure. The influence of the surface tension depends on the diffraction parameter and it is a maximum in the low frequency range.     

The role of surface tension in elastic wave scattering in an inhomogeneous poroelastic medium

It is well known that many porous media such as rocks have heterogeneities at nearly all scales. We applied Biot's poroelastic theory to study the propagation of elastic waves in isotropic porous matrix with spherical inclusions. It is assumed that the heterogeneity dimension exceeds significantly the pore size. Modified boundary conditions on poroelastic interface are used to take into account the surface tension effects. The effective wavenumber is calculated using the Waterman and Truell multiple scattering theory, which relates the effective wave number to the amplitude of the wave field scattered by a single inclusion. The calculations were performed for a medium containing fluid-filled cavities or porous inclusions contrasting in saturating fluid elastic properties. The results obtained show that when we consider elastic wave propagation in poroelastic medium containing soft inclusions, it is necessary to take into account the capillary pressure. The influence of the surface tension depends on the diffraction parameter and it is a maximum in the low frequency range.     

Unifying the criteria of elastic stability of solids

The elastic stability criterion formulated by Born is based on the convexity requirement of the equilibrium free energy F of a stress-free crystal under small strain fluctuation, that demands the elastic constant tensor C to be positive definite, |C| > 0. For a crystal subject to an external stress, Hill specifies that for the crystal to be stable, the difference between its internal energy change δE and the work done to the system δW must be positive, i.e. δE - δW > 0. Polanyi, Frenkel, and Orowan proposed a different stability criterion based on stress increment for a loaded system, τ(ε + Δε) - τ(ε) > 0 until the limit is reached at dτ/dε = 0. Although known empirically, the formal connection between the different criteria has not been established rigorously. Using finite deformation theory, we show quite simply that the different formulations of the stability criteria originate from the same necessary condition for the convexity of the free energy of the system subject to external loading, f = F - W. However, in practice caution must be taken in implementation of the different criteria; they may lead to quite different results, especially when stability bifurcation occurs.     

A study of porous silicon prepared under different HF concentrations by positron annihilation

Two-dimensional angular correlation of positron-electron annihilation radiation and positron-lifetime experiments have been performed on lightly doped porous silicons prepared under different HF concentrations. Positronium formation in the etched pores and positron trapped in voids are observed in both experiments. A surprising result is found that both positron lifetime and momentum spectra show a reduction in the size of the etched pores with decreasing HF concentration in the etching solution. This trend is different from the intuitive expectation that the pore size increases with increasing porosity. Our result can be explained in terms of the formation mechanism of porous film in lightly doped silicon.     

Microstructure and mechanical characteristics of nanodiamond-SiC compacts

Superhard nanodiamond-SiC ceramics are prepared by infiltrating liquid Si into porous nanodiamond compacts under pressure. Synthesized samples are 2.2 mm thick and 3–4 mm in diameter. The effect of particle size of dynamically synthesized nanodiamond powders on silicon infiltration and SiC phase formation is studied. It is established that silicon does not penetrate into the pores of nanodiamond powders if the original particle size is smaller than 0.5–1.0 μm. The critical pore size for infiltration is 100–200 nm. A study of the microstructure of the samples showed the presence of the nanometer-and submicron-scale SiC phase. The ultrasound velocities are measured in the prepared compacts, and the elastic moduli are calculated. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 4, 2004, pp. 734–736. Original Russian Text Copyright ? 2004 by Ekimov, Gromnitskaya, Mazalov, Pal’, Pichugin, Gierlotka, Palosz, Kozubowski.     

多孔硅材料光学Anderson局域的研究

本文基于Anderson局域效应和有限时域差分(FDTD)计算方法,对具有一定无序性的多孔硅材料内光的横向局域进行了理论分析,考察了不同无序度、孔洞排列的不同方式对硅材料光学性质的影响。计算结果表明,多孔硅内光的行为和多孔硅的结构参数有很大关系。当结构参数合适时,光束可以呈现比较明显的横向局域效果。适当改变材料中孔道的排列方式,可以有效的调节光在材料中的传播方式与局域效果。设计了具有"边墙"效果的孔洞排列方式,不仅能够固定光斑的位置,而且还可实现光束的局域增强效果。     

New method for growing silicon carbide on silicon by solid-phase epitaxy: Model and experiment

A new method of solid-state epitaxy of silicon carbide (SiC) on silicon (Si) is proposed theoretically and realized experimentally. Films of various polytypes of SiC on Si(111) grow through a chemical reaction (at T = 1100–1400°C) between single-crystal silicon and gaseous carbon oxide CO (at p = 10–300 Pa). Some silicon atoms transform into gaseous silicon oxide SiO and escape from the system, which brings about the formation of vacancies and pores in the silicon near the interface between the silicon and the silicon carbide. These pores provide significant relaxation of the elastic stresses caused by the lattice misfit between Si and SiC. X-ray diffraction, electron diffraction, and electron microscopy studies and luminescence analysis showed that the silicon carbide layers are epitaxial, homogeneous over the thickness, and can contain various polytypes and a mixture of them, depending on the growth conditions. The typical pore size is 1 to 5 μm at film thicknesses of ～20 to 100 nm. Thermodynamic nucleation theory is generalized to the case where a chemical reaction occurs. Kinetic and thermodynamic theories of this growth mechanism are constructed, and the time dependences of the number of new-phase nuclei, the concentrations of chemical components, and the film thickness are calculated. A model is proposed for relaxation of elastic stresses in a film favored by vacancies and pores in the substrate.     

Surface characterization of porous silicon after pore opening processes inducing chemical modifications

In this paper, we present a study on the porous silicon surface with the aim of filling porous silicon layers with organics. We discuss on two processes used to remove the outer parasitic layer created during the porous silicon formation. We demonstrate that these etching processes influences the surface properties, in particular wetting ability. By XPS and infrared absorption spectroscopy studies, we show that a SF₆ plasma treatment does not modify irreversibly the chemistry of porous silicon surface, nor the surface morphology. We also point out that NaOH etching does bring significant morphological modifications and influences the hydrophilicity of the porous silicon surface. This last treatment increases the polar groups (SiO) concentration on the pore surface and therefore allows a better filling of a porous silicon layer with organics, like dibromo-EDOT which can be thermally converted into PEDOT.