Reactions of Silicon and Germanium with Halogens, Their Hydrides, and Organic Halogen Derivatives

Gorbunov, A. I.; Belyi, A P; Filippov, G G

doi:10.1070/rc1974v043n04abeh001807

Cited by 26 publications

(4 citation statements)

References 7 publications

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“…The study of the thermodynamics of the Cu-Si system aids in the development of a basic understanding of metalsilicon systems. Some Cu silicides, in particular Cu 3 Si, have shown promise as catalysts, with clear evidence that the oxidation of silicon is catalyzed by Cu 3 Si [3][4][5][6] , and some evidence that Cu 3 Si serves as an effective catalyst in other reactions [7][8][9] . In microelectronics, the use of Cu metallization in VLSI applications depends upon the prevention of the formation of Cu silicides 1,10 .…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic and kinetic study of solid state reactions in the Cu–Si system

Chromik¹,

Neils²,

Cotts³

1999

Journal of Applied Physics

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It has been shown that significant changes in the course of solid state reactions can be realized by decreasing length scale, temperature, or by varying parent microstructures. In the case of the formation of Cu 3 Si by interdiffusion of Cu and Si, previous research has shown that over a large temperature range reaction rates are determined by the rate of grain boundary diffusion of Cu through the growing Cu 3 Si phase. We have examined the effect of replacing crystalline Si with amorphous Si (a-Si) on these solid state reactions, as well as the effect of decreasing the temperatures and length scales of the reactions. Multilayered thin film diffusion couples of Cu and a-Si were prepared by sputter deposition, with most average composite stoichiometries close to that of the equilibrium phase Cu 3 Si. Layer thicknesses of the two materials were changed such that the modulation (sum of the thickness of one layer of Cu and a-Si), λ, varied between 5 and 160 nm. Xray diffraction analysis and transmission electron microscopy analysis were used to identify phases present in as prepared and reacted diffusion couples. Complete reactions to form a single phase or mixtures of the three low temperature equilibrium silicides (Cu 3 Si, Cu 15 Si 4 and Cu 5 Si) were observed. Upon initial heating of samples from room temperature, heat flow signals were observed with differential scanning calorimetry corresponding to the growth of Cu 3 Si. At higher temperatures (> 525 K) and in the presence of excess Cu, the more Cu rich silicides, Cu 15 Si 4 and Cu 5 Si formed. Based on differential scanning calorimetry results for samples with average stoichiometry of the phases Cu 3 Si and Cu 5 Si, enthalpies of formation of these compounds were measured. Considering the reaction of these phases forming from Cu and a-Si, the enthalpies were found to be-13.6±0.3 kJ/mol for Cu 3 Si and-10.5±0.6 kJ/mol for Cu 5 Si. The growth of Cu 3 Si was found to obey a parabolic growth law:

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Section: Introductionmentioning

confidence: 99%

Thermodynamic and kinetic study of solid state reactions in the Cu–Si system

Chromik¹,

Neils²,

Cotts³

1999

Journal of Applied Physics

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“…extremely highly dispersed particles or even twodimensional species such as Cu-Si surface compounds. Similar ideas had already been discussed speculatively a long time ago, 19 and also in a more recent paper. 20 We could explain our results consistently on this basis and by plausible arguments.…”

Section: On the Nature Of The Catalytically Active Speciesmentioning

confidence: 75%

SEM-EDX and SAM-AES Investigations on Rochow Contact Masses

Ehrich

Born

Richter³

et al. 1997

Appl. Organometal. Chem.

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“…Mui 8 proposed that the STC hydrogenation is the RDS because the overall reaction rate is independent of the silicon particle size distribution, as we confirmed in our previous study. 11 Gorbunov et al 17 proposed that, in the reaction of HCl with silicon, the HCl molecules must diffuse to the silicon surface where the chlorine atoms are adsorbed onto the silicon surface to form a layer of chloride silicon. The kinetic order with respect to HCl is close to zero in the case of purified silicon but is 0.5 with technical-grade silicon; in addition, the reaction products, TCS and H 2 , have no effect on the rate, and the order with respect to these products is zero.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

CuCl-Catalyzed Hydrogenation of Silicon Tetrachloride in the Presence of Silicon: Mechanism and Kinetic Modeling

Ding

Wang

Jin

et al. 2014

Ind. Eng. Chem. Res.

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The CuCl-catalyzed hydrogenation of silicon tetrachloride (STC) in the presence of silicon was conducted in a fixed-bed reactor. The solid mass from different reaction stages was collected and characterized using X-ray diffraction (XRD) and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). The characterization results were used to develop a novel reaction mechanism. This mechanism is remarkable in that the Cu−Si surface species acted as both a catalyst and a solid reactant and could be regenerated via Cu diffusion into the bulk silicon phase. Different kinetic models were formulated by employing the Langmuir−Hinshelwood (L−H) and Eley−Rideal (E−R) approaches. Model discrimination was used to select a kinetic model based on the E−R mechanism, in which the surface reaction between the adsorbed STC and gasphase H 2 over the Cu 3 Si active sites was assumed to be the rate-determining step (RDS). The kinetic parameters were estimated using nonlinear regression, and the model predictions were in good agreement with the experimental data.

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Reactions of Silicon and Germanium with Halogens, Their Hydrides, and Organic Halogen Derivatives

Cited by 26 publications

References 7 publications

Thermodynamic and kinetic study of solid state reactions in the Cu–Si system

Thermodynamic and kinetic study of solid state reactions in the Cu–Si system

SEM-EDX and SAM-AES Investigations on Rochow Contact Masses

CuCl-Catalyzed Hydrogenation of Silicon Tetrachloride in the Presence of Silicon: Mechanism and Kinetic Modeling

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