Surface-Controlled Chemical Vapor Deposition of Silicon Carbide

Sammanfattning: Polycrystalline cubic silicon carbide, 3C-SiC, has long been investigated in the field of hard coating materials. The typical synthesis method for 3C-SiC coatings is thermal chemical vapor deposition (CVD) using either multicomponent precursors, e.g. methyltrichlorosilane, or a combination of single component precursors, e.g. silane and propane. In this thesis, the fabrication of polycrystalline SiC coatings has been explored from the new aspects on the basis of thermal CVD utilizing silicon tetrachloride (SiCl4) and various hydrocarbons, i.e. toluene (C7H8), methane (CH4) and ethylene (C2H4) as the precursors. The goal of this thesis is to control the surface chemistry in the SiCl4-based SiC CVD and has been accomplished by the following three different approaches: In the first approach to control the surface chemistry of SiC CVD, the difference in the adsorption energy of aromatic and aliphatic hydrocarbons on different SiC crystal planes was utilized. Under identical deposition conditions, a highly <111>-oriented 3C-SiC coating was deposited using C7H8 as the carbon precursor, whereas using CH4 resulted in a randomly oriented 3C-SiC. The results from quantum chemical calculation showed that the active film forming carbon species, i.e. C6H6 in the C7H8 process and CH3 in both C7H8 and CH4 processes, behaved differently when they adsorbed on the 3C-SiC (111) and (110) planes. CH3 is strongly chemisorbed on both planes, while C6H6 is chemisorbed on the (111) plane, but only physiosorbed on the other. The significant difference in the adsorption energy of CH3 and C6H6 on the (111) and (110) planes therefore explains the resulting highly <111>-oriented 3C-SiC from the C7H8 process. Furthermore, the ability to deposit 3C-SiC coatings with alternating highly <111>- and randomly oriented layers by merely switching the carbon precursor between C7H8 and CH4 or C2H4 in a single CVD deposition has further proven that the effect of aromatic hydrocarbons on the preferred growth orientation of 3C-SiC was controlled primarily by the surface chemistry.  The second approach to the surface-controlled SiC CVD was based on the reduction of surface reaction probability (β) for conformal film growth via low-temperature, low-pressure CVD, which was originally proposed by Abelson and Girolami. Their strategies in reducing β, including lowering the temperature and increasing the precursor partial pressure, were successfully adapted to the SiC CVD growth using SiCl4 and C2H4 as the precursors in this thesis, where an elevated temperature and a moderate pressure were used. Moreover, the addition of Cl species as a growth inhibitor to the process further reduced the β, leading to a superconformal SiC growth.  The third approach employed in this thesis for the SiC growth was pulsed CVD. Instead of a continuous and simultaneous SiCl4 and C2H4 flow, the precursors were pulsed alternately into the chamber with each precursor pulse being separated by a H2 purge. In this precursor delivery mode, the gas phase reactions between SiCl4 and C2H4 were avoided and hence the SiC growth was mostly controlled by the surface chemistry. Altering the pulse durations of the precursors led to a variation of growth per cycle (GPC), which was explained by a two-step mechanism. During the SiCl4 pulse, a thin layer of Si is deposited, which is carburized by carbon species produced during the C2H4 pulse. Additionally, the separation of precursor pulses should lead to a large increase in the surface coverage of Cl species, further enhancing the inhibition effect and resulting in a superconformal SiC growth. By using this approach, superconformal SiC coatings were achieved at temperatures where conventional CVD only yielded nonconformal SiC coatings. The observed decline in coating conformality with an elongated purge implied that more surface Cl species were replaced by H during the H2 purge and consequently the inhibition effect was diminished.