Novel Electroless Deposition of Cu<Subscript>3</Subscript>Se<Subscript>2</Subscript> Film on Silicon Substrate by a Simple Galvanic Displacement Process

A novel electroless deposition method for depositing highly uniform adhesive thin films of copper selenide (Cu₃Se₂) on silicon substrates from aqueous solutions is described. The deposition is carried out by two coupled galvanic reactions in a single deposition bath containing copper cations, hydrogen fluoride, and selenous acid: the galvanic deposition of copper on silicon and the subsequent galvanic reaction between the deposited copper with selenous acid in the deposition bath. The powder X-ray diffraction and scanning electron microscopy are used to characterize and examine the deposited films.     

Ion bombardment-induced mechanical stress in plasma-enhanced deposited silicon nitride and silicon oxynitride films

We have studied the influence of different deposition conditions on the mechanical stress of silicon nitride and silicon oxynitride layers formed by plasma-enhanced deposition onto silicon substrates. It appears that the mechanical stress of the as-deposited silicon (oxy)nitride layer is a combined effect of the extent of ion bombardment and the deposition temperature on the hydrogen desorption rate. Deposited films show a tensile stress character when the hydrogen desorption rate is thermally controlled, whereas in the case of an ion-bombardement-controlled hydrogen desorption rate the deposited films have a compressive stress. It is also shown that due to annealing at temperatures above the deposition temperature the films are densified as a result of hydrogen desorption and cross-linking.     

Directed Gas Phase Formation of Silene (H2SiCH2)

The silene molecule (H₂SiCH₂; X¹A₁) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH₄). Exploiting crossed molecular beams experiments augmented by high-level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon-hydrogen bond forming the silylmethyl (CH₂SiH₃; X²A′) complex followed by hydrogen migration to the methylsilyl radical (SiH₂CH₃; X²A′). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H₂SiCH₂; X¹A₁). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon–silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level.     

Detailed Structural Examinations of Covalently Immobilized Gold Nanoparticles onto Hydrogen‐Terminated Silicon Surfaces

The modification of flat semiconductor surfaces with nanoscale materials has been the subject of considerable interest. This paper provides detailed structural examinations of gold nanoparticles covalently immobilized onto hydrogen‐terminated silicon surfaces by a convenient thermal hydrosilylation to form Si? C bonds. Gold nanoparticles stabilized by ω‐alkene‐1‐thiols with different alkyl chain lengths (C₃, C₆, and C₁₁), with average diameters of 2–3 nm and a narrow size distribution were used. The thermal hydrosilylation reactions of these nanoparticles with hydrogen‐terminated Si(111) surfaces were carried out in toluene at various conditions under N₂. The obtained modified surfaces were observed by high‐resolution scanning electron microscopy (HR‐SEM). The obtained images indicate considerable changes in morphology with reaction time, reaction temperature, as well as the length of the stabilizing ω‐alkene‐1‐thiol molecules. These surfaces are stable and can be stored under ambient conditions for several weeks without measurable decomposition. It was also found that the aggregation of immobilized particles on a silicon surface occurred at high temperature (> 100 °C). Precise XPS measurements of modified surfaces were carried out by using a Au–S ligand‐exchange technique. The spectrum clearly showed the existence of Si? C bonds. Cross‐sectional HR‐TEM images also directly indicate that the particles were covalently attached to the silicon surface through Si? C bonds.     

Mathematical simulation of gas-phase deposition of epitaxial silicon films in the Si-C-H and Si-H systems

The effect of experimental conditions on the magnitude and uniformity of the deposition rate of epitaxial silicon obtained by chemical deposition from the gas phase in the SiCl₄-H₂, SiHCl₃-H₂, and SiH₄-H₂ systems (in the temperature ranges from 1300 to 1520 K for the chloride and 1270 to 1370 K for the silane systems) has been examined. Chloride and silane processes are compared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1217–1222, July, 1995.     

Amorphous Silicon: New Insights into an Old Material

Amorphous silicon is synthesized by treating the tetrahalosilanes SiX₄ (X=Cl, F) with molten sodium in high boiling polar and non‐polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine‐containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO?H versus the Me?OH bond either yields H‐ and/or methyl‐substituted methoxy functional silanes. Moreover, compounds, such as Me_nSi(OMe)_4?n (n=0–3) are simply accessible in more than 75 % yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes Me_nSi(OMe)_4?n in excellent (n=0:100 %) to acceptable yields (n=1:51 %; n=2:27 %); the yield of HSi(OMe)₃ is about 85 %. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon‐based products.     

Ag活化的p型硅(111)表面化学镀Ag膜表面形貌研究

A method of electroless silver deposition on silver activated p-type silicon（111） wafer was proposed. The silver seed layer was deposited firstly on the wafer in the solution of 0.005 mol/L AgNO3 ＋0.06 mol/L HE Then the silver film was electrolessly deposited on the seed layer in the electroless bath of AgNO3＋NH3＋acetic acid＋NH2NH2 （pH 10.2）. The morphology of the seed layer and the silver films prepared under the condition of the different bath composition was compared by atomic force microscopy. The reflectance of the silver films with different thickness was characterized by Fourier transform infrared spectrometry. The experimental results indicate that the seed layer possesses excellent catalytic activity toward electroless silver deposition and rotating of the silicon wafer during the electroless silver deposition could lead to formation of the smoother silver film.     

SOME INVESTIGATIONS ON POLY(SULPHUR OXIDE) AND ITS REACTION WITH SILICON TETRACHLORIDE

Abstract

Poly(sulphur oxide) has been prepared by the low temperature thermal decomposition of the lower oxides of sulphur. This yellow, elastic solid resists water hydrolysis. It is unstable at room temperature when stored under vacuum and decomposes slowly to a powdery yellow white cyclic(sulphur oxide) and sulphur dioxide. In the presence of silicon tetrachloride, the thermal decomposition gives rise to an adduct of the lower oxide of sulphur along with the poly(sulphur oxide). The adduct hydrolyses to silica, hydrogen chloride, hydrogen sulphide and hydrogen sulphite. Based on the analysis of the hydrolysed products and the IR data, the adduct is assigned a formula of SiCl₄·2(SO), in which the silicon is hexacoordinated.     

Silicon nitride nanofibers produced by the pyrolysis of SiCl<Subscript>4</Subscript> in H<Subscript>2</Subscript> and N<Subscript>2</Subscript> media

The synthesis of fibrous Si₃N₄ nanostructures by gas-phase chemical deposition during the pyrolysis of silicon tetrachloride in a hydrogen and nitrogen atmosphere was investigated. It was shown that the products contained both amorphous Si₃N₄ nanofibers and their α and β phases both with and without a silicon coating. In addition to the Si₃N₄ nanofibers the products also contained nanoribbons. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 2, pp. 81–84, March–April, 2007.     

Oscillations of open-circuit potential during immersion plating of silicon in CuSO4/HF solutions

The paper analyzes the nature of oscillations of open-circuit potential (OCP) during immersion plating of copper on silicon wafers. The oscillations are observed within well-determined interval of experimental conditions (composition of the electrolyte, doping level of silicon wafers, temperature, viscosity of electrolyte, etc.). Different to other known cases of the electrochemical oscillations, in the present case, there is no external source of the electrical current. We summarize here experimental findings relevant to this phenomenon and analyze possible reasons for the occurrence of the OCP oscillations. The effect is well fit by the general phenomenology of chaos-order transitions in complex chemical systems. We present a model for the oscillatory behavior which involves simultaneous reactions of Cu deposition and oxidation of silicon wafer, generation of local mechanical stress in the system, nonlinear electrochemical etching of silicon, localization of the electric field at the etched surface, etc. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 574–585. The text was submitted by the author in English. Deceased.     

Kinetic analysis of photoelectrochemical hydrogen evolution over p-type silicon in acidic aqueous solutions of electrolytes

The kinetics of photoelectrochemical hydrogen evolution at p-Si single crystals in acidic aqueous solutions of electrolytes under pulse photoexcitation was studied. Despite a low stability of the silicon surface under the experimental conditions, a distinct interrelation between the characteristic time of interfacial charge transfer and stationary current was found. The determination of the characteristic transfer time does not need the detailed elaboration of generation-recombination processes in the semiconductor. The steady-state current density was shown to be determined both for the dark current and photocurrent by the surface charge density. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1724–1728, October, 2000.     

The Effect of Surface Terminations on the Initial Stages of TiO2 Deposition on Functionalized Silicon

As atomic layer deposition (ALD) emerges as a method to fabricate architectures with atomic precision, emphasis is placed on understanding surface reactions and nucleation mechanisms. ALD of titanium dioxide with TiCl₄ and water has been used to investigate deposition processes in general, but the effect of surface termination on the initial TiO₂ nucleation lacks needed mechanistic insights. This work examines the adsorption of TiCl₄ on Cl−, H−, and HO− terminated Si(100) and Si(111) surfaces to elucidate the general role of different surface structures and defect types in manipulating surface reactivity of growth and non-growth substrates. The surface sites and their role in the initial stages of deposition are examined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Density functional theory (DFT) computations of the local functionalized silicon surfaces suggest oxygen-containing defects are primary drivers of selectivity loss on these surfaces.     

钴析氧催化剂原位制备及其结合半导体硅的光解水制氢性能

将发展成熟的硅光伏电池与析氧催化剂(OEC)结合,在近中性环境下光解水制备了氢气。采用原位制备方法,在硅光伏材料上电沉积钴形成无定形Co-OEC膜,有效促进光生电荷分离,实现了利用AM1.5组合滤波片模拟太阳光照射下水分解制氢气。 结果表明,在K₂B₄O₇缓冲溶液(pH=9.2)中,0 V(vs NHE)电压下沉积400 s形成的无定形Co-OEC具有良好的催化析氧效果,在无外加电压且模拟太阳光照射下,析氧电流密度可达1.7×10^-2 A/cm²,产氧速率为1.28 mol/(h·m²),且具有良好的稳定性。     

Hydrogen Evolution Efficiency at Illuminated Silicon

The change of kinetic characteristics of photoelectrochemical hydrogen evolution at p-type silicon in acid aqueous electrolyte solutions under prolonged continuous illumination is studied. It is shown that, during the transfer of full charge Q _t < 150 C/cm² through the silicon/electrolyte interface, the interrelation between the reciprocal time of the charge transfer into electrolyte and the steady-state current remains linear. In this case, a Tafel-like relation links the interfacial charge to the steady-state electrode current. Passing current through the electrode even further results, at Q _t > 350 C/cm², in breaking-down the direct relation between the current and the charge transfer time, despite the electrode's retaining high photosensitivity. The effect is probably caused by significant energy and structure distortions in the surface layer of silicon.     

Analysis of silicon carbonitride films by laser mass spectrometry

The possibilities of laser mass spectrometry in determining the main composition of silicon carbonitride films (SiC _x N _y ) deposited on a substrate made of germanium and gallium arsenide are considered. The conditions of laser sampling were selected and the instrument was adjusted to identify the major components of films synthesized by the plasma deposition. The instrument was calibrated by neat silicon compounds to obtain quantitative data on the concentrations of carbon, nitrogen, oxygen, and silicon. A calibration method was proposed, and the concentration of hydrogen in the layers of silicon carbonitride was estimated.     

Analysis of light elements in superposed layers by Monte Carlo simulation of EELS spectra

A Monte Carlo code, previously set up to simulate electron energy loss spectra of carbon films on silicon at 100 kV, has been extended to the analysis, at 300 kV, of a Si/SiO₂/Si structure; the final goal is the determination of the oxygen concentration in SiO_x precipitates embedded in a Si matrix. The upgrading of the programme has required the introduction of relativistic kinematics and relativistic corrections to elastic and inelastic cross sections.The Si/SiO₂/Si samples have been prepared by CVD deposition of a 16 nm thick silicon film onto a silicon wafer covered with a 11 nm thick thermal oxide. The thickness of both films has been checked by transmission electron microscopy on cross sections. The EELS experiments have been performed on planar sections, in regions of different thickness; the EELS spectra have been acquired with a parallel 666 Gatan spectrometer, fitted to a Philips CM 30 TEM/STEM, operating at 300 kV. The stoichiometry of the SiO_x can be obtained by the ratioing of the areas under the OK and SiK edges, taking advantage of the possibility given by the Monte Carlo simulation to separate the background electrons from the one suffering the characteristic energy loss. The agreement between experiments and calculations in the case examined is satisfactory, so that the application of this procedure to SiO_x precipitates is promising.     

The Detection and Reactivity of Silanols and Silanes Using Hyperpolarized 29Si Nuclear Magnetic Resonance

Silanols and silanes are key precursors and intermediates for the synthesis of silicon‐based materials. While their characterization and quantification by ²⁹Si NMR spectroscopy has received significant attention, it is a technique that is limited by the low natural abundance of ²⁹Si and its low sensitivity. Here, we describe a method using p‐H₂ to hyperpolarize ²⁹Si. The observed signal enhancements, approaching 3000‐fold at 11.7 T, would take many days of measurement for comparable results under Boltzmann conditions. The resulting signals were exploited to monitor the rapid reaction of tris(tert‐butoxy)silanol with triflic anhydride in a T₁‐corrected process that allows for rapid quantification. These results demonstrate a novel route to quantify dynamic processes and intermediates in the synthesis of silicon materials.     

Surface characterization of the SiOx films prepared by a remote atmospheric pressure plasma jet

The deposition rate and surface properties of SiO_x films were prepared and investigated using remote atmospheric pressure plasma (APP) jet. The APP, generated with low frequency power at 16 kHz, was fed with tetraethoxysilane (TEOS)/air gas mixture. After deposition, the SiO_x films were analyzed for chemical characteristics, elemental composition, surface morphology, and hardness. It was found that the deposition substrate temperature is the key factor to affect the deposition rate of remote APP chemical vapor deposition process. Fourier transform infrared (FTIR) spectra indicated that APP deposited SiO_x films are an inorganic feature. XPS examination revealed that the SiO_x films contained approximately 30% silicon, 58% oxygen and 12% carbon. Atomic forced microscopy (AFM) analysis results indicated a smooth surface of SiO_x films in deposition under higher substrate temperature. Also, pencil hardness tests indicated that the hardness of APP deposited SiO_x films was greatly improved with increasing substrate temperatures. Copyright © 2008 John Wiley & Sons, Ltd.     

Si/C phases from the IR laser-induced decomposition of divinylsilane

Transversely excited atmospheric (TEA) CO₂ laser-induced decomposition of divinylsilane in the gas phase yields unsaturated C₂–C₄ hydrocarbons, benzene and vinylsilane, and it represents a convenient process for chemical vapour deposition of thin solid films composed of silicon carbide and polycarbosilane. © 1998 John Wiley & Sons, Ltd.     

Effect of oxidative treatment on the electrochemical properties of aligned multi-walled carbon nanotubes

Vertically aligned multi-walled carbon nanotubes (MWNTs) were grown on the surface of electroconductive silicon substrate by catalytic chemical vapor deposition (CCVD) of a mixture of toluene and ferrocene vapors at 800°С. The anisotropic structure of the array that is due to the mutual orientation of MWNTs makes such materials attractive for use as supercapacitor electrodes. The effect of iron nanoparticles encapsulated in MWNTs as a result of synthesis on the electrochemical capacity of the sample in a 1 М H₂SO₄ solution was studied. Iron was removed during the thermal treatment of the MWNT array in a 20% H₂SO₄ solution under the normal or hydrothermal conditions. The contribution of redox processes involving iron was shown to be comparable to the contribution of the double-layer capacity of MWNTs. The hydrothermal treatment allows easy separation of the array from the silicon substrate without any loss of electric coupling of MWNTs.