Carbon nanotubes growth on silicon nitride substrates

Carbon nanotubes were synthesized on silicon nitride substrates by thermal chemical vapour deposition using an iron precursor catalyst. The nanotubes were characterized by AFM, FESEM, TEM and micro-Raman spectroscopy. The surface topography of the substrate, dense and flat or porous and rough, controlled the catalyst distribution and carbon nanotubes growth. Flat surfaces led to the synthesis of single-walled carbon nanotubes, whereas the porous ones promoted the growth of multi-walled carbon nanotubes of 60 nm diameter. These nanotubes preferentially grew on the porous sites, exhibiting a good substrate-nanotube interface.     

Light-emitting porous silicon

Although porous silicon has been known for more than 35 years, only in 1990 was it recognized that porous silicon shows an increased bandgap and efficient room-temperature photoluminescence in the visible. This paper will give an overview of porous silicon research, with special emphasis on the formation mechanism of microporous silicon in terms of a depletion of holes in the porous region due to quantum confinement and the understanding of the origin of the visible luminescence. The status of research on electroluminescent and other devices based on porous silicon will be discussed, as well as results for other luminescent forms of nanocrystalline silicon.     

Crystallite-size-dependent characteristics of porous silicon

Porous silicon prepared with anodic currents of 5 to 30 mA/cm² are characterized for structural and electronic properties of surface using photoluminescence, grazing angle X-ray diffraction, photoconductivity, thermally stimulated exo electron emission and work function measurements. The observed results indicate that with increasing porosity the crystallite size decreases and the amount of silicon hydride and oxide-type species increases, exhibiting a tendency similar to that of hydrogenated amorphous silicon and hydrogenated microcrystalline silicon. Free-standing powder of porous silicon, characterized by bright photoluminescence at 730 nm, showed crystallites of nanometre dimensions under the transmission electron microscope.     

Some new results in porous silicon

Efforts have been made to see the effect of some standard microelectronic processing steps on porous silicon. Our diffusion experiments for making p-n junctions confirm that this material can withstand high temperatures of the order of 800°C to 1000°C. A new technique for photolithography has been suggested to obtain porous silicon in selected areas. Etch stop method to control the thickness of the porous layer and an organic protective layer for porous silicon have also been suggested. Models proposed by other workers to explain luminescence in porous silicon are not sufficient to explain many experimental observations. A hybrid model is suggested.     

Light emission from porous silicon

Room-temperature visible luminescence observed in porous silicon is one of the most significant discoveries of this decade as it opens up the possibility of silicon-based optoelectronics afresh. The exact mechanism of this different luminescence behaviour of porous silicon, compared to crystalline silicon, is not well established. In this paper results of a combination of infrared absorption, and photoluminescence emission and excitation spectroscopies will be described to show that the nanocrystallite nature of porous silicon and chemical environment at the surface are the important aspects of this novel luminescence behaviour.     

多孔硅的表面吸附性能的研究

通过量子化学的DFT方法,采用模型化学方法和Gaussion 03程序,计算了由不同数目硅原子组成的模型分别吸附某几种氢原子、氧原子、硝酸根的模型和多孔硅表面可能存在的SiHx类物质自由基或分子碎片的红外光谱进行了计算,考察了各模型吸附前后的电荷集居数和红外振动光谱,计算结果表明多孔硅表面吸附氢原子、氧原子以及硝酸根可以削弱相关Si—Si键,导致硅氢氧化合物出现,从而氧化或断裂生成Si—H或Si—O一类分子碎片而引起爆炸。     

Magneto-transport in porous silicon

Magnetoresistance (MR) measurements have been performed in the temperature range 100–300 K on macroporous porous silicon (P.S.) samples. P.S. layers have been prepared by the anodic dissolution of Si in HF acid. The MR has been found to be positive in P.S. for the temperature range 100–300 K and for the entire range of magnetic field (0–5 kG). However the magnitude of the positive MR is found to be much less than expected on the basis of free electron conduction. Also the value of n in the relation Δρ/ρ_o∞Bⁿ for the temperature range 100–300 K is found to be < 2, implying that there is a contribution of some phenomenon other than the free electron conduction to MR. The measured data suggest that it is the contribution of localized state conduction near the Fermi level and in the localized states near the band edges.     

Facile synthesis of porous hollow iron oxide nanoparticles supported on carbon nanotubes

Porous hollow iron oxide nanoparticles (PHNPs) supported on carbon nanotubes (CNTs) were facilely synthesized by etching Fe@Fe_xO_y/CNT with dilute nitric acid aqueous solution at ambient temperature without the assistance of any surfactants and ligands. The mean diameter of hollow iron oxide nanoparticles was about 17 nm, with a wall thickness of about 4 nm. The formation mechanism of PHNPs is discussed based on the characterization results from TEM, XRD and H₂-TPR. The combination of nanoscale Kirkendall effect and selective acid etching is proposed to be responsible for the formation of CNT supported PHNPs, through a transformation from core/void/shell structures to hollow nanoparticles.     

Raman scattering and photoluminescence study of porous silicon formed on n-type silicon

We report Raman scattering and photoluminescence studies on porous silicon film formed on n-type silicon. The Raman spectra over the sample surface exhibit considerable variation whereas the photoluminescence spectra are practically identical. Our results indicate that, well inside the film surface, it consists of spherical nanocrystals of typical diameter ≈ 100Å, while on the edge these nanocrystals are ? 300Å. We further observe that there is no correlation between the photoluminescence peak position and the nanocrystal diameter. This suggests that the origin of the photoluminescence is due to radiative recombination between defect states in the bulk as well as on the surface of the nanocrystal.     

Hydrogen in porous silicon — A review

This review is devoted to summarising the hydrogen-assisted properties and applications of porous silicon (PS). The role of hydrogen as an intermediate product in silicon porosification technology is accentuated. The regularities of hydrogen bonding in PS and its applications for hydrogen storage are listed. The models of hydrogen influence on luminescence and electrical properties of PS are analysed. The corresponding applications of PS for H₂ gas sensors and pH metres are illustrated. Hydrogen-assisted explosion and grafting of PS are discussed. Such a review can be useful for the tailoring of PS properties.     

Determination of Vickers microhardness on porous silicon surfaces

The Vickers microhardness values of two different sets of porous silicon layers were determined at applied load of 98 mN. The sets consisted of Boron-doped substrates anodized at diverse current densities for two different amounts of hydrofluoric acid (HF) in the etching solution. We found that the microhardness of the samples with lower content of HF at the anodization process showed higher values, whereas the Vickers parameter diminishes consistently for higher current densities. A possible explanation of this behavior is proposed.     

Optical sensing of flammable substances using porous silicon microcavities

A porous silicon multilayer, constituted by a Fabry–Pèrot cavity between two distributed Bragg reflectors, is exposed to vapor of several organic species. Different resonant peak shifts in the reflectivity spectra, ascribed to capillary condensation of the vapor in the silicon pores, have been observed. Starting from experimental data, the layer liquid volume fractions condensed in the sensing stack have been numerically estimated. Values ranging between 0.27 (for ethanol) and 0.33 (for iso-propanol) have been found. Time-resolved measurements show that the solvent identification occurs in less then 10 s.     

制备温度对多孔硅光学特性的影响(英文)

本文不同的温度下制备多孔硅.通过荧光光谱、光吸收谱、X射线光电子谱研究了多孔硅的光和结构特性.研究结果表明存在着一个制备临界温度343 K,当制备温度从临界温度之下提高到临界温度之上时,多孔硅的荧光和光吸收从红移转向蓝移,同时硅2p电子结合能也从减小转向增大.     

The potential of porous silicon gas sensors

Recent developments in porous silicon gas sensors have been reviewed. Monitored species detection levels, and the mechanisms of sensing for different sensor designs are also discussed. Porous silicon surface modification methods have been employed for detecting different gas molecules; H₂O, ethanol, methanol, isopropanol, CO_x, NO_x, NH₃, O₂, H₂, HCl, SO₂, H₂S and PH₃.     

Hot-wire chemical vapor deposition of carbon nanotubes

Hot-wire chemical vapor deposition (HWCVD) has been employed for the continuous gas-phase generation of both carbon multi-wall and single-wall nanotube (MWNT and SWNT) materials. Graphitic MWNTs were produced at a very high density at a synthesis temperature of 600 °C. SWNTs were deposited at a much lower density on a glass substrate held at 450 °C. SWNTs are typically observed in large bundles that are stabilized by tube–tube van der Waals’ interactions. However, transmission electron microscopy analyses revealed only the presence of isolated SWNTs in these HWCVD-generated materials.     

Improvement of the durability of porous silicon through functionalisation for biomedical applications

The durability of porous silicon (PS) in solutions was improved by grafting a molecule, 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (TE), with four terminal vinyl groups. With a native PS sample as control, we compared the long-term durability of three modified PS samples: TE-, undec-10-enoic acid (UA)-, and TE/UA(TE first and UA followed)-grafted PS, in a weak organic base of dimethyl sulfoxide, an aqueous mineral solution of CuBr₂, and phosphate buffered saline respectively. Results indicate that TE-grafting is a straightforward and impactful approach to protect PS from oxidation and degradation. Further we used the TE-grafted PS to fabricate a prototype protein microarray by post-grafting UA and subsequently converting UA to nitrilotriacetic acid/Ni²⁺ for binding histidine-tagged proteins.     

Surfactant-associated electrochemical properties of ferrocene adsorbed on a glassy carbon electrode modified with multi-walled carbon nanotubes

The electrochemical properties of ferrocene (Fc) on a glassy carbon (GC) electrode modified by multi-walled carbon nanotubes (MWNTs) in the presence and absence of surfactants have been investigated by progressively voltammetric sweeping. Dihexadecyl phosphate (DHP) and hexadecyl trismethyl ammonium chloride (HTAC) are found to impact the redox reactions of Fc adsorbed on MWNT surfaces. An excess amount of DHP dispatches Fc from MWNTs surfaces, leading to weakly adsorbed configuration of Fc. The formal potential of the adsorbed Fc in the presence of DHP shifts to a lower potential. Cationic surfactant HTAC on MWNT surfaces depresses the redox reactions corresponding to the weakly adsorbed configuration of Fc. It becomes evident that the configuration and hence redox reactions of Fc depend strongly on the presence and concentrations of surfactants on the electrode surfaces and in the buffer solutions.     

Hydrogen isotopic substitution experiments in nanostructured porous silicon

Nanostructured porous silicon is usually prepared by electrochemical anodization of monocrystalline silicon using a fluorine-rich electrolyte. As a result of this process, the silicon atoms conserve their original crystalline location, and many of the dangling bonds appearing on the surface of the nanostructure are saturated by hydrogen coming from the electrolyte. This work presents an IR study of the effects produced by partial substitution of water in the electrolytic solution by deuterium oxide. The isotopic effects on the IR spectra are analyzed for the as-prepared samples and for the samples subjected to partial thermal effusion of hydrogen and deuterium. We demonstrate that, although deuterium is chemically indistinguishable from hydrogen, it presents a singular behaviour when used in porous silicon preparation. We found that deuterium preferentially bonds forming Si-DH groups. A possible explanation of the phenomenon is presented, based on the different diffusivities of hydrogen and deuterium.     

Ellipsometric study of the influence of chemical etching on thin porous silicon structures

The effect of chemical etching on Porous Silicon (PS) samples is studied and quantified by using variable angle spectroscopic ellipsometry (VASE). The main aim of this work is to assess the impact of such etching on the physical properties of electrochemically etched, thin PS antireflection coatings (ARC) for solar cell applications. In this study, detailed models of PS layers etched at constant current densities are created using a graded uniaxial Bruggeman Effective Medium Approximation (BEMA). Changes in porosity, thickness, and optical anisotropy of the PS samples due to chemical etching are determined as a function of etching time after PS formation. Three series of PS films, etched at three different current densities, are investigated. It is shown that significant changes in physical properties occur for chemical etching times longer than ~ 60 s. The anodic etching process for fabricating PS ARC structures can be performed in less than 10 s. Therefore, chemical etching does not lead to significant deviations from the intended PS structure and is not seen as a hindrance to accurate control of processes for fabricating thin PS ARCs.     

Horseradish peroxidase-modified porous silicon for phenol monitoring

In this study, horseradish peroxidase enzyme (HRP) was covalently immobilized on porous silicon (PSi) surface using multistep strategy. First, acid terminations were generated on hydrogenated PSi surface by thermal hydrosilylation of undecylenic acid. Then, the carboxyl-terminated monolayer was transformed to active ester (succinimidyl ester) using N-hydroxysuccinimide (NHS) in the presence of the coupling agent N-ethyl-N′-(3-dimethylaminopropyl) carbodiimide (EDC). Subsequently, the enzyme was anchored on the surface via an amidation reaction. The structure of the PSi layers was observed by scanning electron microscopy (SEM). Infrared spectroscopy (FTIR) and contact angle measurements confirmed the efficiency of the modification at each step of the functionalization. Cyclic voltammetry was recorded using the HRP-modified PSi as working electrode. The results show that the enzymatic activity of the immobilized HRP is preserved and in the presence of hydrogen peroxide, the enzyme oxidizes phenolic molecules which were subsequently reduced at the modified-PSi electrode.