Growth rates, chemical vapor deposition

As anticipated from the foregoing discussion, film growth in chemical vapor deposition can depend strongly on process conditions. The left-hand panel of Fig. 17.3 shows the temperature dependence of the growth rate in an Arrhenius form (i.e., versus 1/TV). At the... 

M. P. Everson, and M. A. Tamor, Investigation of growth rates and morphology for diamond growth by chemical vapor deposition, J. Mater. Res., 7(6) 1438-1444 (1992)... 

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. 

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. 

The preceding treatment is, undoubtedly, an oversimplification. For example, many diatomic molecules dissociate upon adsorption (e.g., H2, SiH, GeH). Each atom from the dissociated molecule then occupies its own distinct surface site and this naturally changes the rate law expression. When these types of details are accounted for, the Langmuir-Hinshelwood mechanism has been very successful at explaining the growth rates of a number of thin-film chemical vapor deposition (CVD) processes. However, more important, our treatment served to illustrate how crystal growth from the vapor phase can be related to macroscopic observables namely, the partial pressures of the reacting species. 

L. Brissoimeau and C. Vafflas, MOCVD Processed Ni Films from Nickelocene. Part I, Growth Rate and Morphology, Chemical Vapor Deposition, Vol.5,1999, pp. 135-142. 

Because of the unique growth mechanism of material formation, the monomer for plasma polymerization (luminous chemical vapor deposition, LCVD) does not require specific chemical structure. The monomer for the free radical chain growth polymerization, e.g., vinyl polymerization, requires an olefinic double bond or a triple bond. For instance, styrene is a monomer but ethylbenzene is not. In LCVD, both styrene and ethylbenzene polymerize, and their deposition rates are by and large the same. Table 7.1 shows the comparison of deposition rate of vinyl compounds and corresponding saturated vinyl compounds. 

Boron-doped diamond (BDD) thin films were synthesized at CSEM (Neuchatel, Switzerland) by the hot filament chemical vapor deposition technique (HF CVD) on p-type, low-resistivity (l-3mQcm), single-crystal, silicon wafers (Siltronix). The temperature of the filament was between 2440 and 2560 °C and that of the substrate was monitored at 830 °C. The reactive gas was a mixture of 1% methane in hydrogen, containing trimethylboron as a boron source (1-3 ppm, with respect to H2). The reaction chamber was supplied with the gas mixture at a flow rate of 51 min giving a growth rate of 0.24 pm h for the diamond layer. The obtained diamond film has a thickness of about 1 pm ( 10%) and a resistivity of 15mQcm ( 30%). This HF CVD process produces columnar, random textured, polycrystalline films [9]. 

Not included in the production figures in Table 5.7-1, is the production of in-situ produced diamond coatings by gas phase pyrolysis (chemical vapor deposition, CVD), which are acquiring increasing industrial importance. The worldwide market for diamond-like- and CBN-coatings (CBN =cubic boron nitride) had a volume in 1993 of 40 million US, with an annual growth rate to 1998 of 30 to 40%. 

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