Reaction Kinetics in CVD

The study of reaction kinetics in flow reactors to derive microkinetic expressions also rehes on an adequate description of the flow field and well-defined inlet and boundary conditions. The stagnation flow on a catalytic plate represents such a simple flow system, in which the catalytic surface is zero dimensional and the species and temperature profiles of the estabhshed boundary layer depend only on the distance from the catalytic plate. This configuration consequently allows the application of simple measurement and modehng approaches (Sidwell et al., 2002 Wamatz et al., 1994a). SFRs are also of significant technical importance because they have extensively been used for CVD to produce homogeneous deposits. In this deposition technique, the disk is often additionally forced to spin to achieve a thick and uniform deposition across the substrate (Houtman et al., 1986a Oh et al., 1991). 

In the case of control by surface reaction kinetics, the rate is dependent on the amount of reactant gases available. As an example, one can visualize a CVD system where the temperature and the pressure are low. This means that the reaction occurs slowly because of the low temperature and there is a surplus of reactants at the surface since, because of the low pressure, the boundary layer is thin, the diffusion coefficients are large, and the reactants reach the deposition surface with ease as shown in Fig. 2.8a. 

Figure 2.8. Rate-limiting steps in a CVD reaction (a) surface reaction kinetics control, (b) diffusion control.

Chemical vapor deposition processes are complex. Chemical thermodynamics, mass transfer, reaction kinetics and crystal growth all play important roles. Equilibrium thermodynamic analysis is the first step in understanding any CVD process. Thermodynamic calculations are useful in predicting limiting deposition rates and condensed phases in the systems which can deposit under the limiting equilibrium state. These calculations are made for CVD of titanium - - and tantalum diborides, but in dynamic CVD systems equilibrium is rarely achieved and kinetic factors often govern the deposition rate behavior. 

Mass transfer and chemical kinetic factors in CVD include the flow of initial substances and gaseous products through the system, the transport of reactants from the gas phase to the substrate surface, the transport of the gaseous products from the substrate surface to the bulk gas, as well as the reactions taking place at the substrate surface . ... 

Chemical vapor deposition (CVD) of carbon from propane is the main reaction in the fabrication of the C/C composites [1,2] and the C-SiC functionally graded material [3,4,5]. The carbon deposition rate from propane is high compared with those from other aliphatic hydrocarbons [4]. Propane is rapidly decomposed in the gas phase and various hydrocarbons are formed independently of the film growth in the CVD reactor. The propane concentration distribution is determined by the gas-phase kinetics. The gas-phase reaction model, in addition to the film growth reaction model, is required for the numerical simulation of the CVD reactor for designing and controlling purposes. Therefore, a compact gas-phase reaction model is preferred. The authors proposed the procedure to reduce an elementary reaction model consisting of hundreds of reactions to a compact model objectively [6]. In this study, the procedure is applied to propane pyrolysis for carbon CVD and a compact gas-phase reaction model is built by the proposed procedure and the kinetic parameters are determined from the experimental results. 

A review article on the CVD processes used to form SiC and Si3N4 by one of the pioneers in this area, Erich Fitzer [Fitzer, E., and D. Hegen, Chemical vapor deposition of silicon carbide and silicon nitride—Chemistry s contribution to modem silicon ceramics, Angew. Chem. Int. Ed. Engl, 18, 295 (1979)], describes the reaction kinetics of the gas-phase formation of these two technical ceramics in various reactor arrangements (hot wall, cold... 

In general, carbides, nitrides, and borides are manufactured in the vapor phase in order to form high-purity powders. This procedure is fundamentally different than a strict CVD process, since in powder synthesis reactors, deposition on seed particles may be desirable, but deposition on the reactor walls represents a loss of product material. As we will see, in CVD, heterogeneous deposition on a surface will be sought. Aside from this issue of deposition, many of the thermodynamic and kinetic considerations regarding gas phase reactions are similar. 

In the traditional surface science approach the surface chemistry and physics are examined in a UHV chamber at reactant pressures (and sometimes surface temperatures) that are normally far from the actual conditions of the process being investigated (catalysis, CVD, etching, etc.). This so-called pressure gap has been the subject of much discussion and debate for surface science studies of heterogeneous catalysis, and most of the critical issues are also relevant to the study of microelectronic systems. By going to lower pressures and temperatures, it is sometimes possible to isolate reaction intermediates and perform a stepwise study of a surface chemical mechanism. Reaction kinetics (particularly unimolecular kinetics) measured at low pressures often extrapolate very well to real-world conditions. 

Kinetic studies of EVD [121] indicate that the electrolyte layer growth is parabolic with time, as shown in Fig. 49, and the diffusion of both electrons and holes is the limiting step of such electrochemical reactions [122], The CVD-EVD technique produces fine-grained films of electrolyte with 40 — 50 pm thickness. 

This review of CVD principles, reactions, and applications begins with an introduction to the fundamental processes involved in CVD processing. These include thermodynamics, kinetics, and transport issues. Then the discussion briefly touches on the desirable qualities of the deposit that is formed. Next the chemistry and precursors are introduced, to familiarize the reader with common reactions that are widely used, followed by a brief discussion of nonconventinal or enhanced CVD technologies. Finally, the CVD of several technologically significant materials is reviewed to illustrate the direction of current work in the field. 

As in other physiochemical processes, CVD can be best understood by examining the reaction/deposition in a fundamental manner. Thermodynamics, kinetics, and heat,... 

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