Microwave-plasma deposition

The most common frequencies in use for CVD are micro-wave (MW) at 2.45 GHz and, to a lesser degree, radio frequency (RF) at 13. 45 MHz (the use of these frequencies must comply with federal regulations). A microwave-plasma deposition apparatus (for the deposition of polycrystalline diamond) is shown schematically in Fig. 5.18 (see Ch. 7, Sec. 3.4). 

Microwave-Plasma Deposition. The operating microwave frequency is 2.45 GHz. A typical microwave plasma for diamond deposition has an electron density of approximately 10 electrons/m, and sufficient energy to dissociate hydrogen. A microwave-deposition reactor is shown schematically in Fig. 5.18 of Ch. 5.P ]P°]... 

Handbook of Chemical Vapor Deposition 9.3 Glow-Discharge (Microwave) Plasma... 

Figure 5.18. Microwave plasma apparatus for the deposition of diamond.

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). 

Plasma-arc diamond deposition is produced at a higher pressure than in a microwave plasma (0.15 to 1 atm). At such pressure, the average distance traveled by the species between collisions (mean free path) is reduced and, as a result, molecules and ions collide more frequently and heat more readily. 

By increasing the electrical energy in a fixed amount of gas, the temperature is raised and may reach 5000°C or higher.P i Such high temperatures produce an almost complete dissociation of the hydrogen molecules, the CH radicals, and other active carbon species. From this standpoint, arc-plasma deposition has an advantage over microwave-plasma or thermal CVD since these produce much less atomic hydrogen. 

The substrate temperature should be kept between 800 and 1000°C and cooling may be necessary. Gas composition and other deposition parameters are similar to those used in a microwave-plasma system. Deposition rate is low, reported as 0.5 to 1 im/h. 

Inside" processes—such as modified chemical vapor deposition (MCVD) and plasma chemical vapor deposition (PCVD)—deposit doped silica on the interior surface of a fused silica tube. In MCVD, the oxidation of the halide reactants is initiated by a flame that heats the outside of the tube (Figure 4.8). In PCVD, the reaction is initiated by a microwave plasma. More than a hundred different layers with different refractive indexes (a function of glass composition) may be deposited by either process before the tube is collapsed to form a glass rod. 

The U.S. electronics industry appears to be ahead of, or on a par with, Japanese industry in most areas of current techniques for the deposition and processing of thin films—chemical vapor deposition (CVD), MOCVD, and MBE. There are differences in some areas, thongh, that may be cracial to future technologies. For example, the Japanese effort in low-pressure microwave plasma research is impressive and surpasses the U.S. effort in some respects. The Japanese are ahead of their U.S. counterparts in the design and manufacture of deposition equipment as well. 

Figure 5.2. Two of the more common types of low pressure CVD reactor, (a) Hot Filament Reactor - these utilise a continually pumped vacuum chamber, while process gases are metered in at carefully controlled rates (typically a total flow rate of a few hundred cubic centimetres per minute). Throttle valves maintain the pressure in the chamber at typically 20-30 torr, while a heater is used to bring the substrate up to a temperature of 700-900°C. The substrate to be coated - e.g. a piece of silicon or molybdenum - sits on the heater, a few millimetres beneath a tungsten filament, which is electrically heated to temperatures in excess of 2200 °C. (b) Microwave Plasma Reactor - in these systems, microwave power is coupled into the process gases via an antenna pointing into the chamber. The size of the chamber is altered by a sliding barrier to achieve maximum microwave power transfer, which results in a ball of hot, ionised gas (a plasma ball) sitting on top of the heated substrate, onto which the diamond film is deposited.

In addition to microwave plasma, direct current (dc) plasma [19], hot-filament [20], magnetron sputtering [21], and radiofrequency (rf) [22-24] plasmas were utilized for nanocrystalline diamond deposition. Amaratunga et al. [23, 24], using CH4/Ar rf plasma, reported that single-crystal diffraction patterns obtained from nanocrystalline diamond grains all show 111 twinning. 

Whereas a microwave plasma is most commonly used for the PE-CVD of diamond films, an ECR is the only plasma that is used for diamond deposition below 1 Torr [27-29]. Although Bozeman et al. [30] reported diamond deposition at 4 Torr with the use of a planar ICP, there have been a few reports that describe the synthesis of diamond by low-pressure ICP. Okada et al. [31-33] first reported the synthesis of nanocrystalline diamond particles in a low-pressure CH4/CO/H2 ICP, followed by Teii and Yoshida [34], with the same gas-phase chemistry. 

W. Qiu, Y.K. Vohra and S.T. Weir, Role of nitrogen in the homoepitaxial growth on diamond anvils by microwave plasma chemical vapor deposition, J. Mater. Res., 22, 1112-1117 (2007). 

As in earlier reported work (4), the present study has used a large-volume microwave plasma (IMP) facility. The choice is based on the favorable deposition kinetics at microwave frequencies, and on the relative ease of scaling experimental LMP apparatus to industrially useful size. 

The implied capability of these plasma deposits to inhibit corrosion at metal surfaces may be of practical as well as of basic importance. An important consideration in this respect is the rapid rate of deposition for such protective coatings attainable at micro-wave frequencies. Since plasma technology is still in a process of evolution, optimum deposition kinetics cannot yet be stated however, the marked effect of excitation frequency on the deposition of organo-silicones can be documented (10), as in Fig. 3. Here, using terminology and comparative data due to Yasuda et al. (2). it is shown that deposition rates in microwave plasmas exceed those at lower (e.g. radio) frequencies by about an order of magnitude. 

Selective synthesis of acetylene (>90%) from methane was accomplished by microwave plasma reactions.568 Conversion of methane to acetylene by using direct current pulse discharge was performed under conditions of ambient temperature and atmospheric pressure.569 The selectivity of acetylene was >95% at methane conversion levels ranging from 16 to 52%. In this case oxygen was used to effectively remove deposited carbon and stabilize the state of discharge. Similar high... 

Conditions for the deposition of diamond using microwave plasma CVD... 

A large class of coordination compounds, metal chelates, is represented in relation to microwave treatment by a relatively small number of reported data, mainly p-diketonates. Thus, volatile copper) II) acetylacetonate was used for the preparation of copper thin films in Ar — H2 atmosphere at ambient temperature by microwave plasma-enhanced chemical vapor deposition (CVD) [735a]. The formed pure copper films with a resistance of 2 3 pS2 cm were deposited on Si substrates. It is noted that oxygen atoms were never detected in the deposited material since Cu — O intramolecular bonds are totally broken by microwave plasma-assisted decomposition of the copper complex. Another acetylacetonate, Zr(acac)4, was prepared from its hydrate Zr(acac)4 10H2O by microwave dehydration of the latter [726]. It is shown [704] that microwave treatment is an effective dehydration technique for various compounds and materials. Use of microwave irradiation in the synthesis of some transition metal phthalocyanines is reported in Sec. 5.1.1. Their relatives - porphyrins - were also obtained in this way [735b]. 

Organic conductive films, e.g. polyaniline or polythiophene, have an interesting potential application due to their easy processability combined with a low weight. A plasma deposition process is even more interesting from a technical point of view, because it is, as opposed to wet chemistry, much more compatible with production processes in vacuum. The sample used was polymerized by Kruse et al. [454] on a silicon wafer over 20 min in a microwave plasma chamber at 2.45 GHz using 2-iodothiophene (at... 

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