CVD techniques

Many materials have been deposited by PECVD. Typically, the use of a plasma allows equivalent-quaUty films to be deposited at temperatures several hundred degrees centigrade lower than those needed for thermal CVD techniques. Often, the plasma-enhanced techniques give amorphous films and films containing incompletely decomposed precursor species such as amorphous siUcon (i -Si H) and amorphous boron (i -B H). 

Figure 15 shows the variation of diamond deposition rates by various activated CVD techniques as well as the HP—HT technique (165). It can be seen that the highest growth rate of activated CVD diamond synthesis is stiU an order of magnitude lower than the HP—HT technique. However, CVD has the potential to become an alternative for diamond growth ia view of the significantly lower cost of activated CVD equipmeat and lower miming and maintenance costs. 

Fig. 15. Variation of diamond deposition rates by various activated CVD techniques as well as the HP—HT technique (165).

The activated CVD diamond techniques can be mote attractive in cases where the huge capital investment (several hundred million dollars) requited for the HP—HT technology is not available or where the high level of technical knowledge requited for HP—HT synthesis is not available. In addition, most wear-resistant apphcations requite diamond coatings only of the order of a few micrometers thick. Such coatings can be deposited ditecdy on the finished product without the need for further finishing if CVD techniques are employed. 

Scientists from Politecnico di Milano and Ineos Vinyls UK developed a tubular fixed-bed reactor comprising a metallic monolith [30]. The walls were coated with catalytically active material and the monolith pieces were loaded lengthwise. Corning, the world leader in ceramic structured supports, developed metallic supports with straight channels, zig-zag channels, and wall-flow channels. They were produced by extrusion of metal powders, for example, copper, fin, zinc, aluminum, iron, silver, nickel, and mixtures and alloys [31]. An alternative method is extrusion of softened bulk metal feed, for example, aluminum, copper, and their alloys. The metal surface can be covered with carbon, carbides, and alumina, using a CVD technique [32]. For metal monoliths, it is to be expected that the main resistance lies at the interface between reactor wall and monolith. Corning... 

The expanding thermal plasma chemical vapor deposition (ETP CVD) technique has been developed in the group of Schram [20, 556] and has been used for the... 

The deposition of a wide range of materials using beams of elemental sources in high-vacuum apparatus (10-4—10-8 torr), essentially by physical methods, is known as molecular beam epitaxy (MBE)8 12 and atomic layer epitaxy (ALE). These methods will be mentioned where there is an overlap with CVD techniques, but will not be fully reviewed. (They are mentioned also in Chapter 9.15). 

Table 2 Main classes of conventional precursors used in CVD techniques.

Initially, the main disadvantage of using single-source precursors was their lack of volatility. However, the advent of ultralow-pressure and vacuum CVD techniques, along with the use of alternative delivery methods which do not rely primarily on precursor volatility, means that many compounds that are essentially nonvolatile can now be considered as potential CVD precursors. A major problem that remains, however, is that of stoichiometry control a molecular precursor containing two (or more) elements in a specific ratio, as desired within the thin film to be grown, will not necessarily deposit those elements in the same proportions. 

These compounds were studied as potential single-source precursors. However, although they gave clean deposition routes to powders of II VI materials, their nonvolatility means that thin-film growth by conventional CVD techniques was hampered, although it could be improved using new delivery techniques. 

Meng G, Song H, Xia C, Liu X, and Peng D. Novel CVD techniques for micro- and IT-SOFC fabrication. Fuel Cells 2004 4 48-55. 

Deposition of a metal film on the backside by evaporation or CVD techniques and subsequent annealing. 

The chemical vapour deposition (CVD) technique can be regarded as an extension of the sublimation method used for the preparation of single crystals discussed before, but adapted to thin him growth implying deposihon on substrates. A schematic diagram of a horizontal hot-wall CVD apparatus is shown in Fig. 3.15. 

Ellison, A., Silicon Carbide Growth by High Temperature CVD Techniques, Ph.D. thesis, Linkoping University, 1999. 

A carbon-deposited film was prepared from the alumina film with 30-nm channels by the CVD technique using propylene. Fluorination was carried out by direct reaction of the film with dry fluorine gas (purity 99.7%). The film was placed in a nickel reactor and was allowed to react with 0.1 MPa of fluorine gas for 5 days at a predetennined temperature in the range of 50 to 200°C. Then the fluorinated carbon nanotubes were separated by dissolving the alumina film with HF. A schematic drawing of the fluorination process is given in Fig. 10.1.15. 

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