Plasma-deposited polymer films

It is clear that a very important measurement both from a technological and mechanistic point of view is the rate at which a surface is etched or the rate at which a polymer film is deposited in a plasma. Essentially all studies of etching or polymerizing plasmas include etching or polymerization rate measurements. Many of these measurements have required that the substrate be removed from the plasma system Often the substrates are carefully weighed before and after exposure to the plasma and often a profilometer is used to measure the step height... 

By the process described above, a plasma film could be obtained that had high enough electrical conductivity to allow direct electrodeposition of copper. The bulk resistivity of film measured by a four-point probe was 2.6 x 10 " ohm-cm for the copper-containing polymer film when deposition was stopped after 18 min at HOW. This value is critical if a uniform electrolytic deposit is to be obtained. For safety, deposition was carried out until a total film thickness of 150nm was obtained, giving a nearly pure metallic layer thick enough to allow subsequent electroplating. 

Polymer ashing is another process related method. This process is fairly complex and involves patterning of a polymer layer during the release. First, structures are partially released by a timed etch. Next, a polymer film is deposited onto the partially released structures. This film is patterned into support posts that hold the structure in position as the remainder of the sacrificial layer is etched away. Because the polymer support structures hold the devices in place, there is no concern for special drying techniques. Finally, the polymer supports are burned away, typically by ashing in an oxygen plasma.This leaves behind fully released and free-standing microstructures. 

Plasma polymerizations were carried out in an apparatus described previously [4]. This apparatus incorporates a vacuum bell jar containing two parallel circular electrodes spaced 3 cm apart, each having a surface area of 40 cm. Polymer films were deposited in a 20 kHz glow discharge on 0.1 mm thick stainless steel tape placed on the lower electrode. Polymer depositions were performed under the following constant conditions current density, j = 1 mA/cm monomer vapour pressure, p = 0.3 Torr and discharge duration, t = 20 s. ... 

Likewise, bond energies for the sum of the Is-electrons of the elements 0, C and N in the deposited plasma polymers are measured and summarized in TABLE 4. It should be noted that the polymer films were deposited with 15 seem Ar as carrier gas. 

Plasma-based CVD may also be used to deposit polymer films (plasma polymerization). In this case the precursor vapor is a monomer that becomes crosslinked in the plasma and on the surface to form an organic or inorganic polymer film. These films have very low porosity and excellent surface coverage. When plasma depositing films from organo-silane precursors, oxygen can be added to the plasma to oxidize some of the silicon in the film. 

Plasma-deposited siUcon nitride contains large amounts of hydrogen, typically in the range of 20—25 atomic % H, and has polymer-like properties. The electrical resistivity of the film depends on the deposition temperature, the film stoichiometry, and the amounts of hydrogen and oxygen in the film. 

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. 

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. 

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. ... 

As stated, the capability of plasma deposits to reduce the access of water to corrosion-sensitive surfaces may be an important motivation for their application in corrosion protection. In order to study this property, Kapton polyimide film was selected as the substrate because of its high inherent permeability to water and its ability to resist elevated temperatures. The response of Kapton film overcoated by PPHMDSO to the permeation of water vapor is shown in Fig. 1. Clearly, the presence of the organo-silicone plasma film greatly reduces water permeation. The magnitude of the effect is much enhanced when plasma polymers are produced at high T and p. 

Plasma surface treatment of many polymers, including fabrics, plastics, and composites, often occurs. The production of ultra-thin films via plasma deposition is important in microelectronics, biomaterials, corrosion protection, permeation control, and for adhesion control. Plasma coatings are often on the order of 1 100 nm thick. 

Characterization of this tumbler reactor was carried out via the deposition rate measurement of a plasma polymer film on silicon wafers under different conditions. In the longitudinal direction, the deposition rate decreases significantly when the plasma moves from the central plasma zone to the remote zone. With appropriate shielding, the decay in deposition rate in the longitudinal direction can be effectively reduced. By means of the stirring, a uniform distribution of the plasma deposition is achieved within the chamber. 

Quantitative characterization of plasma-polymer films, especially of ultrathin fluorinated carbon plasma polymer films, has been performed by ToF-SIMS to study changes in the surface composition and molecular distribution. CFX films on silicon and polyethylene terephthalate (PET) substrates were exposed to a pulsed Ar/CHF3 plasma by varying the deposition time from 10-90 s.111-113 The results show differences in film growth and CFX cross linking for the silicon and PET substrates.111... 

X-ray photoelectron spectroscopy (XPS) was used for elemental analysis of plasma-deposited polymer films. The photoelectron spectrometer (Physical Electronics, Model 548) was used with an X-ray source of Mg Ka (1253.6 eV). Fourier transform infrared (FTIR) spectra of plasma polymers deposited on the steel substrate were recorded on a Perkin-Elmer Model 1750 spectrophotometer using the attenuated total reflection (ATR) technique. The silane plasma-deposited steel sample was cut to match precisely the surface of the reflection element, which was a high refractive index KRS-5 crystal. 

Cold-rolled steel panels were purchased from Advanced Coating Technologies, Inc. (Hillsdale, Michigan). Silane chemicals (methylsilane, trimethylsilane, and tetramethylsilane) were purchased from Petrarch Systems, Inc. The silane plasma-deposited steel was then dip-coated with a polymer film 10-25 pim thick. The polymer coating resins used were silane-modified polymers with functionalities such as hydroxyl, acrylate, or amine. 

For the cyclic corrosion test, a layer of acrylosilane polymer coating (10-25 fim thick) was dip-coated onto the plasma-deposited substrates. The coated samples were then subjected to 25 scab cycles. The test results are plotted in Fig. 7. Corrosion performance (as described by the length of scribe creep) was correlated to the wattage used for plasma film deposition. As discussed in the previous section, the chemical structure and properties correlated with the deposition conditions, especially the power level applied. Therefore, atomic compositions for plasma polymers deposited at different power levels were also plotted in Fig. 7.A... 

Analysis of Plasma Deposited Flurocarbon Coatings on Polymer Films and Wool Fibers... 

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