An Investigation into Silane Evolution from Porous Silicon by Temperature Programmed Desorption Method

The gaseous species desorbed from porous silicon (PS) were investigated using the method of temperature programmed desorption (TPD) and fourier transform infrared spectroscopy (FTIR). Silicon wafers (25–50 cm, p^–, FZ) were anodised in 40% HF and HF/C₂H₅OH electrolytes. The PS samples were linearly heated at 1.5 K s^–1 using a custom built heating unit in a oil-free pump backed vacuum chamber at a base pressure of <10^–8 torr. A quadrupole mass spectrometer, which was used as the detector, was fitted in line of sight of the sample at a distance of about 6 mm. It was observed that silane was liberated during the heating of porous silicon samples produced from both electrolytes. The peak temperature at which this occurred was at 570 ± 10 K. This temperature coincides with the temperature of silicon-silicon bond breakage in Si–SiH₃ groups on the pore walls, as shown by the FTIR results. It is proposed that silane formation involves the reaction of the Si-silyl group with moisture: Si–SiH₃ + H₂O Si–OH + SiH₄.     

Diamond Coating of Porous Silicon

Diamond coatings on porous silicon (PS) samples have been obtained by the hot-filament chemical vapor deposition(CVD) technique. We focused our attention on the coating morphology, showing experimentally that high quality diamond coatings may be produced with the PS sample kept at 710°C. The deposited patterns consist of polycrystalline grains with a plane interface with the PS layer.At 790°C, the quality of the coating is improved but the PS layer becomes damaged, and at 650°C the coating consists of diamond-like carbon particles. Besides the temperature, other factors such as the porosity, roughness and chemical activity of the PS layer deserve attention. We observed that one of the limiting factors of the deposition process was the high nucleation time. Two nucleation mechanisms are involved in the growth process. The first nucleation mechanism occurs on the top of the sharp PS features, subsequently to the nucleation a superficial film, and then a second nucleation mechanism occurs over this surface, which allows the growth process to continue. We also observed the presence of ablue-shift in the luminescence spectra following the coating.     

Investigation of Morphology of Porous Silicon Formed on N+ Type Silicon

The properties of porous silicon (PS) are closely connected to its morphology, much investigation has been done in order to correlate the morphological characteristics of PS with the anodisation parameters. In this paper the results of morphological analysis of PS formed on N⁺type substrates of 1 0 0 and 1 1 1 orientation are presented. The dependences of the porosity, thickness of PS, density of pores and of the effective surface on the current density are obtained. Interpretation of these results in terms of diffusion layer and energy levels is given, with special attention given to the low current density case.     

Studies of Deformed Poly(Methyl Methacrylate) Using Positron Annihilation Lifetime Spectroscopy

Abstract

Structural rearrangements in glassy PMMA on polymer plastic deformation and recovery of residual plastic deformation in glassy state were studied by positron annihilation lifetime spectroscopy. Uniaxial compression was shown to be accompanied by a decrease in concentration of free volume microregions in disordered polymer regions, which were characterized by low packing density. Recovery of residual deformation at elevated temperatures but below glass transition point T_g proceeds without any noticeable changes in fractional content of free volume both in disordered and ordered polymer regions. The advantages of positron annihilation lifetime spectroscopy for studying microstructure and structural rearrangements in polymers were discussed.     

Microstructural Analysis of Natural Rubber/Millable Polyurethane Blends Using Positron Annihilation Lifetime Spectroscopy

Positron annihilation lifetime spectroscopy (PALS) was used to investigate the relationship between the free volume properties and miscibility of natural rubber (NR)/millable polyurethane (MPU) blends. The free volume parameters (V_f and I₃) have been found to be increased regularly with an increase in NR concentration in the blend. The morphological analysis of the samples has been performed by scanning electron microscopy. The results obtained from PALS technique have been correlated with the observations from X-ray diffraction analysis and differential scanning calorimetry. Thermogravimetric examination highlighted the enhancement in thermal stability upon blending MPU with NR.     

High-Strength Porous Silicon Carbide Ceramics by an Oxidation-Bonding Technique

Porous silicon carbide (SiC) ceramics were fabricated by an oxidation-bonding process in which the powder compacts are heated in air so that SiC particles are bonded to each other by oxidation-derived SiO₂ glass. Because of the crystallization of amorphous SiO₂ glass into cristobalite during sintering, the fracture strength of oxidation-bonded SiC ceramics can be retained to a relatively high level at elevated temperatures. It has been shown that the mechanical strength is strongly affected by particle size. When 0.6 μm SiC powders were used, a high strength of 185 MPa was achieved at a porosity of ∼31%. Moreover, oxidation-bonded SiC ceramics were observed to exhibit an excellent oxidation resistance.     

New EXAFS Measurements by XEOL and TEY on Porous Silicon

Results of an EXAFS investigation on porous Silicon carried out by X-ray Excited Optical Luminescence (XEOL) and Total Electron Yield (TEY) techniques, at the Si K absorption edge, are reported. For the first time XEOL spectra of porous silicon have been recorded in a wide energy range (1800–2500 eV) and EXAFS signals have been singled out from them. Simultaneous TEY and XEOL measurements yield to different results: in particular TEY-EXAFS is sensitive up to the third coordination shell of Si, while XEOL-EXAFS reveals only the contributions of the first two coordination shells; moreover they show a different dependence on changes of the etching parameters. This evidences the sensitivity of XEOL technique to the local structure of the quantum confined luminescent sites. The dependence of the light emission properties on the main preparation parameters and their influence on the short-range structure of red and yellow porous silicon samples are also investigated.     

Optical Absorption in Porous Silicon

The optical properties of porous silicon (p-Si) are calculated from the electronic band structure obtained by means of an sp₃s^* tight-binding Hamiltonian and a supercell model, in which the pores are columns detched in crystalline silicon (c-Si). The disorder in the pore sizes and the undulation of the silicon wires are considered by the existence of arandom perturbative potential, which produces non-vertical interband transitions, otherwise forbidden. A typical interval around each k-vector (optical window), where non-vertical transitions make an important contribution, depends on the value of the disorder and its order of magnitude is given by l^–1, where l is the localization length. The calculated absorption spectra are compared with experiments, showing good agreement.     

Studies on Gold/Porous Silicon/Crystalline Silicon Junctions

Electrical transport in Gold/porous silicon/crystalline silicon junctions has been studied. The junctions are found to improve when the porous silicon is exposed to a hydrogen plasma before depositing the top metal. The hydrogen passivated junctions exhibited higher current levels and emitted light at lower voltages as compared to the unhydrogenated ones. Internal photoemission measurements were carried out to investigate the gold/porous silicon barrier. The barrier height determined from the Fowler plot is independent of the top material. The temperature dependence of the barrier height is similar to that of the crystalline silicon energy gap.     

Porous Silicon Studied with Time-Resolved Photoluminescence

Porous silicon has been studied with time-resolved photoluminescence, and growth as well as decay curves have been measured at several detection energies, with sample temperatures between 10 and 300 K. In the decay curves, three components are mainly observed, a small one which is very fast, with time scales of the order of nanoseconds or faster, the main component having time scales of the order of milliseconds, and a very small, very slow component, with time scales of the order of seconds. The main components can in most—but not all—cases be fitted well with stretched exponentials containing two fitting parameters. Of these, it comes out that the parameter accounting for disorder or the like depends only little upon detection energy and temperature, whereas the parameter accouting for the development in time decreases substantially for increasing temperature. The results are discussed.     

Pulsed Anodic Anodisation of Porous Silicon Films

Porous Silicon is conventionally made by dc anodisation of silicon. In this paper we have studied the luminescence of porous silicon made by pulsed anodisation as a function of duty cycle and HF concentration. Specifically we show for the first time that the luminescence can be tuned over a wide range in energy.     

Positron annihilation spectroscopic investigation of Al-pillared montmorillonites

We report, for the first time, our result on characterisation of Al-pillared clay using positron annihilation spectroscopy (PAS) along with XRD and BET techniques. Positron life-time spectra for Al-pillared montmorillonite, as received and calcined at different temperature (100–500°C), along with the parent natural clay are measured. The annihilation rate of ortho-positronium (o-Ps) increases monotonically with calcination temperature up to 300°C and falls subsequently. Similar behaviour is seen for the fraction of o-Ps formed. We interpret the initial rise in annihilation rate of o-Ps to be due to the increase in Brønsted acidity with dehydroxylation of pillars. The reduction in annihilation rate on calcination at higher temperatures could be due to loss of acidity and/or due to mesopore formation following delamination of clay structure.     

Laser Induced Degradation of Photoluminescence Intensity of Porous Silicon

The evolution, under vacuum, of the photoluminescence (PL) intensity of porous silicon (PS) has been studied as function of anodisation conditions, laser line and post-anodisation treatments. It was shown that the degradation of the PL intensity depends on the internal structure of PS. In particular, the degradation is important for PS layers formed essentially by crystallites having small size or where amorphous phase exists. The experimental results have been interpreted using a theoretical model, which takes into account the variation with time of the local concentration of the luminescent centers.     

Electrochemical Aspects of Porous Silicon Formation

The electrochemistry of porous silicon formation has been investigated by different electrochemical as well as surface analytical methods. The kinetics of pore nucleation was observed as small steps in fast current and potential pulse transients. Oxidic intermediates were identified by ex-situ XPS. Cyclic voltammetry in solutions of different HF concentration was correlated with the etching rate of silicon dioxide. On the basis of these experimental data, an electrochemical model for the porous silicon formation is presented.     

AC Conductivity of Porous Silicon from Monte Carlo Simulations

The AC conductivity of a percolation model with local energetical disorder for porous Silicon in three dimensions, (), is studied by Monte Carlo simulations. The model includes both diffusion and recombination processes and () is obtained by a Fourier transform of the mean-square displacement of the carriers, where hopping diffusion of a single type of carrier (either an electron or an exciton) and two types of carriers (an electron and a hole) are considered. It is found that at low temperatures, the behavior of () depends sensitively on the type of carrier considered.     

快中子辐照直拉硅中的空位型缺陷

利用正电子湮没谱(PAS)及Fourier变换红外吸收光谱(FTIR)技术研究了快中子辐照直拉硅(CZSi)中辐照缺陷.研究发现,经快中子辐照后的硅中会有大量的单空位型缺陷VO及多空位型缺陷V2和V2O;经200～450℃热处理后,FTIR光谱中出现的720和919.6 cm-1红外吸收峰为单空位型缺陷,其正电子寿命与VO的寿命接近,约为290 ps;经450～600℃热处理后,随单空位型缺陷VO消失,V4型缺陷浓度迅速增加,600℃热处理后其浓度达到最大(相对浓度约为70％).     

Conduction and Luminescent Properties of Wet Porous Silicon

Carrier transport and photoluminescence-quenching mechanisms in reverse-biased p-type porous silicon in contact with an aqueous electrolyte are investigated. Concerning transport mechanisms investigation, experiments are based on the study of the photo-induced current as a function of the porous layer thickness. The liquid-impregnated porous silicon skeleton is found under equipotential conditions. Transport of electrons (supplied by the substrate) in porous silicon is shown to be dominated by a diffusion process. Photoluminescence-quenching is investigated by using a reverse-biased p-type porous silicon illuminated at 365 and 809 nm simultaneoulsy. The first illumination generate photoluminescence and the second supplies carriers in the substrate. A progressive photoluminescence-quenching has been observed, under a constant applied voltage, by increasing progressively the electron concentration in the porous layer. This original experiment allows to reject the hypothesis of an electric-field-induced separation of carriers as the photoluminescence-quenching mechanism in wet porous silicon, while it strongly supports the mechanism based on Auger recombination.     

Electrical Control of the Reflectance of Porous Silicon Layers

In this paper we demonstrate the filling of porous silicon (PS) layers with liquid crystals (LC's) in order to control the reflectance electrically. The preparation of PS and the choice of the right group of LC's will be presented. Especially an oxidation of PS is necessary so that the methods and parameters of oxidation will also be discussed. As a first result the increasing and decreasing of the thickness oscillations in the reflectance as a function of the applied voltage can be observed.     

Raman Scattering from Metal-Deposited Porous Silicon

Raman scattering from porous silicon layer into which silver is immersion-plated was studied. Ag-deposited samples show extra Raman bands. Heat treatment of the Ag-deposited samples results in a great decrease in such Raman bands. Also dipping in hydrofluoric acid solution causes a spectral change. Some comments on the assignment of the Raman peaks of the Ag-deposited porous silicon are given, and the structure of porous silicon on which metal is immersion-plated is discussed.     

Contactless Characterization of Porous Silicon Structures by Four-Wave Mixing and Microwave Techniques

We apply optical contactless techniques, namely the four-wave-mixing and microwave harmonics generation for the characterization of nanocrystalline free-standing films and platelets of microcrystalline porous silicon. We observe (i) full carrier localization and significant lifetime shortening in free-standing films, which is thought to be a manifestation of their low-dimensional confinement, (ii) increased carrier lifetime in microcrystalline porous silicon, presumably originating from passivated surface states at the surface of pores.