Plasma thin films

Buddy Ratner s interests include biomaterials, tissue engineering, polymers, biocompatibility, drug delivery, surface analysis, self-assembly, nanobiotechnology, RF-plasma thin film deposition and biomaterials education. He has participated in the launch of six companies based on technologies from his laboratory, and serves as a consultant for numerous other companies. 

Figure C2.13.6. Schematic illustrations of plasma - assisted thin - film deposition.

The aim of breaking up a thin film of liquid into an aerosol by a cross flow of gas has been developed with frits, which are essentially a means of supporting a film of liquid on a porous surface. As the liquid flows onto one surface of the frit (frequently made from glass), argon gas is forced through from the undersurface (Figure 19.16). Where the gas meets the liquid film, the latter is dispersed into an aerosol and is carried as usual toward the plasma flame. There have been several designs of frit nebulizers, but all work in a similar fashion. Mean droplet diameters are approximately 100 nm, and over 90% of the liquid sample can be transported to the flame. 

The requirements of thin-film ferroelectrics are stoichiometry, phase formation, crystallization, and microstmctural development for the various device appHcations. As of this writing multimagnetron sputtering (MMS) (56), multiion beam-reactive sputter (MIBERS) deposition (57), uv-excimer laser ablation (58), and electron cyclotron resonance (ECR) plasma-assisted growth (59) are the latest ferroelectric thin-film growth processes to satisfy the requirements. 

Germanium difluoride can be prepared by reduction (2,4) of GeF by metallic germanium, by reaction (1) of stoichiometric amounts of Ge and HF in a sealed vessel at 225°C, by Ge powder and HgF2 (5), and by GeS and PbF2 (6). Gep2 has been used in plasma chemical vapor deposition of amorphous film (see Plasma TECHNOLOGY Thin films) (7). 

J. Mort and F. Jansen, Plasma Deposited Thin Films, Franklin Book Co., Inc., Elkins Park, Pa., 1986. 

In most cases, CVD reactions are activated thermally, but in some cases, notably in exothermic chemical transport reactions, the substrate temperature is held below that of the feed material to obtain deposition. Other means of activation are available (7), eg, deposition at lower substrate temperatures is obtained by electric-discharge plasma activation. In some cases, unique materials are produced by plasma-assisted CVD (PACVD), such as amorphous siHcon from silane where 10—35 mol % hydrogen remains bonded in the soHd deposit. Except for the problem of large amounts of energy consumption in its formation, this material is of interest for thin-film solar cells. Passivating films of Si02 or Si02 Si N deposited by PACVD are of interest in the semiconductor industry (see Semiconductors). 

Inorganic monomers can be used to plasma-deposit polymer-type films (16). At high plasma energies, the monomers are largely decomposed and can be used to form materials such as amorphous hydrogen-containing siUcon films from SiH for thin-film solar-ceU materials. 

Figure 1.6 Sputtering device for the formation of thin films by the bombardment of a source material by ions extracted from a plasma...

Chain reactions such as those described above, in which atomic species or radicals play a rate-determining part in a series of sequential reactions, are nearly always present in processes for the preparation of thin films by die decomposition of gaseous molecules. This may be achieved by thermal dissociation, by radiation decomposition (photochemical decomposition), or by electron bombardment, either by beams of elecuons or in plasmas. The molecules involved cover a wide range from simple diatomic molecules which dissociate to atoms, to organometallic species with complex dissociation patterns. The... 

The SNMS instrumentation that has been most extensively applied and evaluated has been of the electron-gas type, combining ion bombardment by a separate ion beam and by direct plasma-ion bombardment, coupled with postionization by a low-pressure RF plasma. The direct bombardment electron-gas SNMS (or SNMSd) adds a distinctly different capability to the arsenal of thin-film analytical techniques, providing not only matrbe-independent quantitation, but also the excellent depth resolution available from low-energy sputterii. It is from the application of SNMSd that most of the illustrations below are selected. Little is lost in this restriction, since applications of SNMS using the separate bombardment option have been very limited to date. 

Direct-current sputtering is not generally applicable for the preparation of thin-film solid electrolytes since these compounds are electronic insulators. The target surface would be charged with the same polarity as that of the ions in the plasma, and the sputtering plasma would rapidly break down. 

Very thin films may be also obtained through adsorption of a thin layer from solution [11,71,74] or chemical grafting [98] which is achieved by a polymerization reaction at the surface. A polymer film may also be deposited on the surface by plasma polymerization [99]. It is then, however, usually crosslinked and chemically not well-defined. 

Plasma CVD tends to create undesirable compressive stresses in the deposit particularly at the lower frequencies. This may not be a problem in very thin films used in semiconductor applications, but in thicker films typical of metallurgical applications, the process is conducive to spalling and cracking. 

Using Reaction (4), a thin film of TiN was formed which was then plasma-treated in nitrogen. The coating has low resistivity even after exposure to air after 24 days. This film was successfully applied to sub-half-micron devices. 

The relatively high volatility of Tg[CH = CH2]8 has enabled it to be used as a CVD precursor for the preparation of thin films that can be converted by either argon or nitrogen plasma into amorphous siloxane polymer films having useful dielectric propertiesThe high volatility also allows deposition of Tg[CH = CH2]g onto surfaces for use as an electron resist and the thin solid films formed by evaporation may also be converted into amorphous siloxane dielectric films via plasma treatment. ... 

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. 

Chemical Vapor Deposition and Plasma Deposition/Etching of Thin Films... 

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