Diamond CVD

The low-pressure vapor-phase process is based on chemical vapor deposition (CVD) and the material is often referred to as Vapor-phase diamond, diamond coating, or CVD diamond . CVD diamond will be used in this book. 

Diamond coatings are also produced by physical vapor deposition (PVD). Such coatings however are a mixture of sp (graphite) and sp (dianrand) bonds and are considered a different material usually referred to as diamond-like carbon (DLC). They are reviewed in Ch. 14. 

CVD-diamond coatings are polycrystsdiine, as opposed to natural and high-pressure synthetic diamond which are normally single crystals. This polycrystalline characteristic has important bearing on the general properties of the coatings as shown in Sec. 4.0. 

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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. 

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. 

A large number of CVD diamond deposition technologies have emerged these can be broadly classified as thermal methods (e.g., hot filament methods) and plasma methods (direct current, radio frequency, and microwave) [79]. Film deposition rates range from less than 0.1 pm-h to 1 mm-h depending upon the method used. The following are essential features of all methods. 

Fig. 7. Bachmann diagram for CVD diamond film growth (adapted from [80].)...

These compounds generally decompose into two stable primary species the methyl radical (CH3) and acetylene (C2H2).P 1 The methyl radical is considered the dominant compound in generating the growth of CVD diamond.P2][23] Direct deposition from acetylene, although difficult experimentally, has been accomplished, with a marked increase in the crystallinity of the diamond deposit.P" ... 

Most CVD-diamond processes require a plasma (see Ch. 5. Sec. 9). Two types of plasma are currently used for the deposition of diamond microwave plasma (non-isothermal) and arc plasma (isothermal). 

Some actual and potential applications of CVD diamond are summarized in Table... 

DLC has properties similar to CVD diamond and it is easier to process without the high-temperature substrate requirements and with little restriction on size. However, it has several disadvantages low deposition rate, high internal stress, and availability only in thin coatings. A number of important applications have been developed with a promising future. 

The structure of a-C H DLC consists of an essentially amorphous network with isolated clusters dominated by the sp configuration (graphite) with some sp (diamond). Hydrogen is believed to play an essential role in determining the bonding configuration by helping to form the sp bond, probably in a manner similar to the formation of CVD diamond. 

The properties of DLC are summarized and compared with those of CVD diamond in Table 7.5.[44]-[47]... 

DLC coatings are already in production in several areas (optical and IR windows) and appear particularly well-suited for abrasion and wear applications due to their high hardness and low coefficient of friction. They have an extremely smooth surface and can be deposited with little restriction of geometry and size (as opposed to CVD diamond). These are important advantages and DLC coatings will compete actively with existing hard coatings, such as titanium carbide, titanium nitride, and other thin film... 

Norton CVD Diamond, Technical Bulletin from Norton Co., Northboro, MA (1992)... 

Like synthetic diamond, C-BN is normally obtained by high-pressure processing. Efforts to synthesize it by CVD at low pressure are promising. It is deposited in an electron-cyclotron-resonance (ECR) plasma from a mixture of BF3 and either ammonia or nitrogen at 675°C on an experimental basis.F l Like CVD diamond, it is also deposited by the hot-filament method using diborane and ammonia diluted with hydrogen at 800°C.P 1... 

With such properties, it could be the ideal material for many semiconductor applications, such as high-power and high-frequency transistors and cold cathodes, or in the harsh environment found in internal-combustion and jet engines. With the advent of CVD diamond, it is now possible to take advantage of these properties. 

Diamond, however, is not the universal semiconductor panacea it is an indirect bandgap semiconductor and does not lase. In addition, present semiconductor materials, such as silicon and gallium arsenide, are solidly entrenched with a well-established technology, and competing with them will not be an easy task. CVD diamond will also compete with silicon carbide, which has also an excellent potential as a high-performance semiconductor material and is considerably easier and cheaper to produce. 

Heat sinks, in the form of thin slices prepared from single-crystal natural diamond, are already used commercially but are limited in size to approximately 3x3x1 mm. These single-crystal diamonds are gradually being replaced by CVD diamond, which is now available in shapes up to 15 cm in diameter. P6]-[28] gQg - gf cVD diamond may remain a... 

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