Kinetics of disilane molecule decomposition on the growth surface of silicon in vacuum gas-phase epitaxy reactors

The range of the characteristic decomposition rates of dihydride molecule radicals adsorbed by the silicon surface in the temperature interval 450?C700°C is experimentally found for a number of kinetic models. A relationship between the rate of silicon atom incorporation into a growing crystal and the characteristic rate of disilane molecule pyrolysis on the silicon surface is found. The temperature dependence of the rate of disilane fragment decomposition on the silicon surface is nonmonotonic, and its run depends on temperature conditions. It is shown that the temperature dependence of the molecular decomposition rate on the growth surface is described by a superposition of two activation curves with various activation energies. The activation energies depend on the peculiarity of interaction between the molecular beam and the silicon surface when the filling of surface states with hydrogen is low and high.     

The special features of adsorption and the kinetics of decomposition of monosilane molecules on the epitaxial surface of silicon

Analytic equations relating the rate of the incorporation of silicon atoms into a growing crystal to the characteristic frequency of the pyrolysis of silane molecules on the surface of silicon were obtained over the temperature range corresponding to the epitaxial growth of silicon films. As distinct from the earlier works, it was assumed that adsorbed silicon atoms and monosilane molecules formed double bonds with the surface. The data of technological experiments for the most extensively used pyrolysis models obtained thus far were used to determine the region of the characteristic frequencies of the decomposition of hydride molecule radicals adsorbed on the surface of a silicon plate over the temperature range 450–700°C. The temperature dependence of the frequency of monosilane molecule decomposition was shown to be to a great extent determined by the form of the temperature dependence of the $ \tilde v_{SiH_2 }^0 $ \tilde v_{SiH_2 }^0 preexponential factor. It was also found that the characteristic frequency of the decomposition of silane molecules was sensitive to the stage of pyrolysis at which hydrogen atoms released from silane molecules were captured by the surface. Decomposition occurred at the highest rate if hydrogen molecules were adsorbed at the stage of the adsorption of monosilane. The lowest rate of decomposition was observed if hydrogen molecules were adsorbed at the stage of the decomposition of radicals already captured by the surface. The temperature dependence of the coefficient of adsorption of monosilane molecules was characterized by a negative activation energy of the process for almost all the most important system models over the temperature range of growth. At elevated growth temperatures, the adsorption of monosilane molecules by the surface of silicon proceeded via an intermediate state characterized by the difference of desorption and chemisorption energies on the order of 0.28 eV.     

Hydrogen outgassing mechanism in titanium materials

This paper addresses a hydrogen outgassing mechanism in titanium materials with extremely low outgassing property by investigating the distribution of hydrogen atoms concentration in depth below the surface, and the activation energy for desorption of dissolved hydrogen atoms into the boundary region between the surface oxide layer and the bulk titanium and that of adsorbed hydrogen atoms on the surface. The distribution of hydrogen atoms concentration in depth below the surface was analyzed by a time-of-flight secondary ion mass spectrometry (TOF-SIMS). The activation energy for desorption of dissolved hydrogen atoms was estimated by the thermal desorption spectroscopy (TDS) measurement with various heating rates. The activation energy for desorption of adsorbed hydrogen atoms was estimated by the temperature dependence of the outgassing rate in titanium material. In the titanium material, hydrogen atoms show maximum concentration at the boundary between the surface oxide layer and the bulk titanium. Concentration of hydrogen atoms decreases rapidly at the surface oxide layer, while it decreases slowly in the deep region below the surface layer-bulk boundary by the vacuum evacuation without/with the baking process. The activation energy for desorption of 1.02 eV of dissolved hydrogen atoms into the surface layer-bulk boundary is about three times as large as that of 0.38 eV of the adsorbed hydrogen atoms on the surface. These results suggest that the hydrogen outgassing mechanism in the titanium material is composed the follows processes, i.e. the slow hydrogen atoms diffusion at the surface layer-bulk boundary, quick hydrogen atoms diffusion at the surface oxide layer and rapid desorption of adsorbed hydrogen atoms on the surface. This outgassing mechanism gives very low hydrogen concentration near the surface, which results in the extremely low outgassing rate in titanium materials.     

Specific Features of the Interaction of a Germane Molecule with Germanium Surface in Vacuum in the Presence of Hydrogen Flow

Technical Physics - The temperature dependence of the main kinetic parameters that determine the rate of pyrolysis of adsorbed germane molecules on the surface of the growing germanium layer is...     

Active oxidation: Silicon etching and oxide decomposition basic mechanisms using density functional theory

The etching of silicon atom from the Si(1 0 0)-p(2 × 2) surface, i.e. the desorption of SiO molecules from this surface, either clean or pre-oxidized, is investigated at the density functional theory level. The reaction paths for desorption are given as a function of the initial oxidation state of the extracted silicon atom. The associated activation energies and the atomic configurations are discussed. Particularly, it is shown that desorption of SiO molecules takes place during conventional thermal oxide growth (∼2 eV activation) via non-oxidized silicon atoms. Further SiO extraction mechanisms of higher silicon oxidation states required higher temperatures. In particular, doubly oxidized silicon atoms (Si²⁺) are able to decompose with an activation of ∼4 eV which corresponds to the actual temperature where decomposition of oxides is observed. This confirms the statement that decomposition of oxide layer nucleates at the interface with silicon where Si²⁺ has been detected thanks to XPS experiment.     

Effect of diluent gas on silicon film deposition from a free jet of monosilane-diluent mixture activated by electron-beam plasma

Thin silicon films were synthesized by the gas-jet electron beam plasma chemical vapor deposition method from monosilane-argon, monosilane-argon-helium, and monosilane-argon-hydrogen mixtures. Addition of argon to the argon-silane mixture increased the deposition rate of silicon films, whereas addition of helium and hydrogen to the same mixture decreased the growth rate. It is shown that the process of silicon film deposition by this method from argon-monosilane mixture is primarily governed by fast secondary electrons, and argon dilution of mixture leads to increasing concentration of fast secondary electrons and increasing deposition rate of silicon films. Dilution of the initial mixture with helium or hydrogen causes a decrease in the deposition rate either due to gas-dynamic behavior of the supersonic jet of the mixture of light and heavy gases, or due to the etching effect of metastable helium atoms or hydrogen atoms on the surface of the growing silicon film.     

Silicon etching in Cl2 environment

The ion-beam-assisted etching of silicon in Cl₂ environment is considered. The theoretically calculated dependences of silicon etching rate on the flux of Cl₂ molecules at different ion current densities are compared with experimentally measured. The composition of the adsorbed layer is determined. It is found that SiCl₂ molecules prevail in the adsorbed layer. The reciprocal of relative concentration of SiCl₂ molecules in the adsorbed layer linearly depends on the ion-to-neutral flux ratio.     

Density and thermodynamics of hydrogen adsorbed on the surface of single-walled carbon nanotubes

A method is proposed for calculating the adsorption of hydrogen in single-walled carbon nanotubes. This method involves solving the Schrödinger equation for a particle (hydrogen molecule) moving in a potential generated by the surrounding hydrogen molecules and atoms forming the wall of the carbon nanotube. The interaction potential for hydrogen molecules is taken in the form of the Silvera-Goldman empirical potential, which adequately describes the experimental data on the interaction between H₂ molecules (including the van der Waals interaction). The interaction of hydrogen molecules with carbon atoms is included in the calculation through the Lennard-Jones potential. The free energy at a nonzero temperature is calculated with allowance made for the phonon contribution, which, in turn, makes it possible to take into account the correlations in the mutual arrangement of the neighboring molecules. The dependences of the total energy, the free energy, and the Gibbs thermodynamic potential on the applied pressure P and temperature T are calculated for adsorbed hydrogen molecules. These dependences are obtained for the first time with due regard for the quantum effects. The pressure and temperature dependences of the hydrogen density m(P, T) are also constructed for the first time.     

The effect of adsorbed atomic hydrogen on the growth of ultrathin silicon films on Ge(100) studied by positron-annihilation-induced Auger electron spectroscopy (PAES)

The effects of adsorbed atomic hydrogen on the stability of silicon films grown on a Ge(100) substrate were studied by using positron-annihilation-induced Auger electron spectroscopy (PAES) and electron-induced Auger electron spectroscopy (EAES). PAES is almost exclusively sensitive to the topmost atomic layer due to the trapping of positrons in an image potential well just outside the surface before annihilation. This surface specificity was exploited in the study of film stability and interfacial mixing during the growth of silicon on Ge(100). The PAES results show that the prior adsorption of hydrogen prevented the segregation of germanium on top of the deposited silicon, and that the hydrogen adsorption was useful in growing a thermally stable structure.     

Peculiarities of the growth kinetics of silicon-germanium alloy layers from silane and germane with an additional heated element in the vacuum chamber

To study the disintegration of the molecules of hydrides at the surface of the growing layer and their influence on the rate of the epitaxial process a model of the growth kinetics of Si_1?x Ge_x alloy layers from silane and germane by the molecular beam epitaxy method with SiH₄ and GeH₄ gas sources is considered. Through comparison of numerical simulation data and experimental relationships, the steady-state growth kinetics has been studied and a comparative analysis carried out of the efficiency of entry of Ge(Si) atoms into the growing layer both in the presence of Si and Ge atomic flows in the reactor (the so-called hot-wire method) and in their absence. The growth rates obtained with this method of epitaxial growth and with one of its modifications where the use is made of a sublimating silicon bar as an additional heated element have been compared. Peculiarities in the behavior of the dependence of the layer growth rate on its composition have been revealed and explained.     

碱金属修饰的多孔石墨烯的储氢性能

基于第一性原理深入研究了碱金属原子(Li,Na,K)修饰的多孔石墨烯(PG)体系的储氢性能,并且通过从头算分子动力学模拟了温度对Li-PG吸附的H2分子稳定性的影响.研究结果表明,PG结构的碳环中心是碱金属原子最稳定的吸附位置,PG单胞最多可以吸附4个碱金属原子,Li原子被束缚最强,金属原子间无团聚的倾向;H2分子通过极化机制吸附在碱金属修饰的PG结构上,每个金属原子周围最多可以稳定地吸附3个H2分子;Li-PG对H2分子的吸附最强(平均吸附能为-0.246 eV/H2),Na-PG对H2分子的吸附较弱(平均吸附能为-0.129 eV/H2),K-PG对H2分子的吸附最弱(平均吸附能为-0.056 eV/H2),不适合用做储氢材料;在不考虑外界压强且温度为300 K的情况下,Li-PG结构可稳定地吸附9个H2分子,储氢量为9.25 wt.%;在400 K时,有7个吸附H2分子脱离Li-PG的束缚,在600-700 K的范围内,吸附H2分子全部脱离了Li-PG体系的束缚.     

Dynamics of water molecules adsorbed by silica and resin SGK-7

This paper has presented neutron spectroscopy data on the dynamics of light water molecules adsorbed in the cation exchanger (ion-exchange resin) SGK-7 and on the surface of aerosils (highly dispersed pyrogenic silica) with different levels of hydration. The measurements have been performed on a DIN-2PI spectrometer (Frank Laboratory of Neutron Physics of the Joint Institute for Nuclear Research, Dubna, Russia). The characteristics of the diffusive and vibrational motions of adsorbed water molecules have been determined from the experimental neutron scattering spectra. The data obtained in the quasi-elastic neutron scattering region have been analyzed using a model accounting for the effects of restricted translational and rotational diffusion. The results have demonstrated a significant decrease in the diffusion mobility of adsorbed water molecules as compared to conventional (bulk) water. In particular, the self-diffusion coefficient decreases several times, and the diffusion rate is the lower, the smaller is the thickness of the hydration layer. The dependences of the intensity and half-width of the quasi-elastic scattering peak on the magnitude of the neutron momentum transfer q in the scattering process exhibit a nonmonotonic character. This indicates manifestation of the effects of restricted translational diffusion, rotational diffusion, and jump diffusion. The partial distributions of vibrational frequencies of hydrogen atoms of water molecules adsorbed by the cation exchanger and aerosils have been obtained from the inelastic neutron scattering data.     

IR spectroscopic study of surface properties of amorphous water ice

The state of the surface of amorphous ice with a specific surface area of about 160 m²/g obtained by the condensation of water vapor at 77 K is studied by IR spectroscopy. As the temperature increases to 130–160 K, absorption bands of surface hydroxyl groups vanish, whereas changes in bands characteristic of hydroxyl groups in the bulk of ice are indicative of a phase transition of ice from amorphous to the polycrystalline structure. The surface sites of amorphous ice are characterized with low-temperature adsorption of carbon monoxide. It is shown that there are two types of CO adsorption sites, free hydroxyl groups and oxygen atoms of surface coordinately unsaturated water molecules. Upon adsorption of nitrogen, methane, and carbon monoxide, in addition to the perturbation of surface OH groups, reversible changes in the spectrum are observed in the region of vibrations of bulk hydroxyls, which indicate that the strength of hydrogen bonds between water molecules in the surface layer of icy particles increases approaching the strength of these bonds in the crystal and that the ice surface becomes less amorphous. These results indicate that the properties of the ice surface layer substantially depend on the presence of adsorbed molecules.     

Boron doping of silicon by excimer laser irradiation in a reactive atmosphere

UV excimer lasers have been used to dope semiconductors by a one-step process in which the laser serves both to melt a controlled thickness of a sample placed in dopant ambient and to photodissociate the dopant molecules themselves. Here we report the boron doping of silicon by means of an ArF (193 nm) excimer laser. Dopant atoms are obtained by photolysis of BCl₃ or pyrolysis of BF₃ molecules. The doping is performed both in gas ambient and using only an adsorbed layer. We have investigated the dependence of doping parameters such as laser pulse repetition and gas pressure on the subsequent boron impurity profiles and the dopant incorporation rate. These results indicate that the laser doping process is dopant-flux limited for BF₃ and externally rate limited for BCl₃.     

锂原子修饰B6团簇的储氢性能研究

利用密度泛函理论研究B₆和Li_mB₆ (m= 1–2)团簇的结构及其储氢性能. 结果表明, 氢分子在B₆团簇的三种可能结构中均发生解离吸附, Li原子在B₆团簇表面不发生团聚,每一个Li原子均吸附几个氢分子. 其中以两个Li原子修饰笼形B₆团簇吸附完整氢分子数最多,储氢质量分数为20.38%, 氢分子的平均吸附能为1.683 kcal/mol,表明了它在常温常压条件下作为储氢材料的可行性. 关键词： mB₆ (m=1-2)团簇')" href="#">Li_mB₆ (m=1-2)团簇 密度泛函理论(DFT) 吸附能 储氢性能     

Polarized luminescence of erythrosine molecules adsorbed on a semiconductor-dielectric structure

The dependences of the degree of polarization of fluorescence of erythrosine molecules adsorbed on Ge-GeO₂ structures on the thickness of the oxide layer, the surface charge, and the concentration of erythrosine are studied. The values of reorientation barriers and times of vibrational relaxation of adsorbed molecules are found. The effect of the surface charge, the thickness of the oxide layer, and the concentration of water molecules on the rotational-vibrational relaxation of adsorbed erythrosine molecules is revealed.     

Features and mechanisms of growth of cubic silicon carbide films on silicon

The mechanisms and specific features of the growth of silicon carbide layers through vacuum chemical epitaxy in the range of growth temperatures from 1000 to 700°C have been considered. The structure of the heterojunction formed has been studied using the results of the performed investigations of photoluminescence spectra in the near-infrared wavelength range and the data obtained from the mass spectrometric analysis. It has been found that, in the silicon layer adjacent to the 3C-SiC/Si heterojunction, the concentration of point defects significantly increases and the dislocation structure is not pronounced. According to the morphological examinations of the surface of the growing film, by analogy with the theory of thermal oxidation of silicon, the theory of carbidization of surface silicon layers has been constructed. A distinctive feature of the model under consideration is the inclusion of the counter diffusion fluxes of silicon atoms from the substrate to the surface of the structure. The growth rate of films and the activation energy of diffusion processes have been estimated. The performed experiments in combination with the developed growth model have explained the aggregates of voids observed in practice under the silicon carbide layer formed in the silicon matrix and the possibility of forming a developed surface morphology (the island growth of films) even under conditions using only one flow of hydrocarbons in the reactor.     

Structural studies of thin silicon layers repeatedly implanted by carbon ions

The composition and structure of homogeneous SiC_1.4 and SiC_0.12 layers produced by multiple implantation of 40-, 20-, 10-, 5-, and 3-keV carbon ions into silicon were studied by electron microscopy, x-ray diffraction, Auger spectroscopy, and IR spectroscopy. The temperature dependences of the IR transmittance peak parameters obtained in the range 200–1400°C indicate that the increase in the number of carbon atoms that are bound to silicon atoms and are involved in absorption is caused by the formation and breaking of hexagonal, near-tetrahedral, and multiple Si-C bonds and by the decomposition of optically active strong carbon clusters. The high crystallization temperature of SiC (1200°C) in the SiC_1.4 layer is explained by the presence of stable multiple Si-C bonds and strong carbon clusters. Strong carbon clusters are shown to exist in the implanted SiC_0.12 layer, and their decomposition is found to affect the formation of tetrahedral bonds in the temperature range 1200–1400°C.