The method of plasma polymerization

 

(57) Abstract:

Usage: when applying polymer coatings to increase the deposition rate of the polymer in the area of the afterglow plasma, for example, in microelectronics for deposition of resistive, passivating dielectric coatings, in other areas of technology. The essence of the invention: at least one of the components polymeropoulos gas is additionally introduced into the area of the glow plasma to activate it. As at least one of the components polymeropoulos gas use unsaturated compounds, including aliphatic, cyclic and aromatic. As a plasma-forming gas use is additionally introduced into the area of the glow plasma component polymeropoulos gas. The temperature of the substrate support equal 20 to +60C. as a plasma-forming gas used argon with a flow rate of 20-200 cm3/min, and the pressure in the reactor support is 0.1 to 1 mm RT.article As a component polymeropoulos gas jet in the area of the glow plasma, use derivatives of benzene, and as a component of the jet in the area of the afterglow plasma methacrylate. The flow of each of the components polymeropoulos gas podderjivayou plasma polymer coatings (thin films) on the surface of the objects for various purposes, made of various materials, and can be used in microelectronics for applying resistin, and passivating dielectric layers, in the medical industry for the application of corrosion protective coatings on surgical instruments and medical equipment, with the same purpose in the production of chemical ware, in the textile industry to impart to the fibers or tissues ready hydrophobic properties by coating on the surface of a thin layer of polymer, and in other areas.

Known method of applying a polymer coating by plasma polymerization, comprising placing the substrate in the reactor, the inlet to the reactor plasma gas, digester gas-discharge plasma (glow or RF discharge), the overlap in the reactor polymeropoulos gas activation molecules polymeropoulos gas under the action of the plasma, the deposition of activated molecules polymeropoulos gas to the substrate with the formation therein of a polymer layer [1]

In this way all the mixture polymerbased gases fed into the region of the glow plasma, and the surface on which precipitates the polymer, is also in the area of the glow plasma (or close to it). This may be the deterioration of the properties of the polymer coating, in particular to reduce the sensitivity of the resist. For example, in the case of plasma-polymerized methyl methacrylate (PMMA), used as electronicist.

Closest to the present invention is a method of coating by plasma deposition from the vapor phase, comprising placing the substrate in the reactor in the zone of the afterglow plasma, the overlap in the reactor plasma gas (or intermediate gas, which itself contains no elements deposited layer), creating in the reactor gas-discharge plasma is low (no higher than 76 mm RT. Art. ) pressure, activation of the plasma gas in the area of the glow plasma, remote from the substrate, to form the set of active particles of this gas, the spatial filtering of this gas with the Department typically unstable particles overlap of the film-forming gas or the carrier gas elements deposited layer, in particular semiconductor) in the area of the afterglow plasma and mixing it with a plasma-forming gas, the activation of a film-forming gas and its interaction with the remaining after spatial filtering of the active particles to the plasma gas, the deposition of active particles of film-forming gas to the substrate St (plasma polymerization), the deposition process is very inefficient, as plasma polymerization in the area of the afterglow, the deposition rate of the polymer is much less than in the case where the substrate directly in the plasma.

When applied polymer films of resists, using plasma, it is desirable along with prevention of significant degradation in plasma molecules polymerbased gas to increase the deposition rate of the polymer in the area of the afterglow, i.e., the efficiency of the coating process.

The aim of the present invention is to increase the deposition rate of the polymer in the area of the afterglow plasma.

The aim is achieved in that in the method of plasma polymerization, comprising placing the substrate in the reactor in the zone of the afterglow plasma, the overlap in the reactor plasma gas, rector of the gas-discharge plasma is low (no higher than 76 mm RT.CT.) pressure, overlap polymeropoulos gas in the zone of the afterglow plasma activation molecules polymeropoulos gas using plasma deposition of activated molecules polymeropoulos gas to the substrate with the formation therein of a polymer layer, according to the invention at least one of the components polymeropoulos gas is additionally introduced into the area of the glow plasma to act is key aliphatic, cyclic and aromatic.

In private cases, the proposed method may differ from the prototype one or more of the following characteristics, namely, that as the plasma gas used is additionally introduced into the area of the glow plasma component polymeropoulos gas; the temperature of the substrate support equal -20 to +60aboutWith that as a plasma-forming gas used argon with a flow rate of 20-200 cm3/min, and the pressure in the reactor support is 0.1-1 mm RT.article as component polymeropoulos gas jet in the area of the glow plasma, use derivatives of benzene, and as a component of the jet in the area of the afterglow plasma, methyl methacrylate; that the flow rate of each component polymeropoulos gas support is 1-10 cm3/min.

In the proposed method, at least one of the components polymeropoulos putting gas in the area of the afterglow plasma, so the structure of this component largely saved and activation of molecules necessary for the implementation of polymerization of this component on the surface of the substrate, is provided by its interaction with the active particle is but in the area of the glow plasma. This is activated in the plasma component is a molecule that is itself capable of polymerization in the plasma, allowing copolymerization of at least two of these components in the area of the afterglow plasma and increases the deposition rate of the polymer in the area of the afterglow compared with cases where only one of these components.

In addition, the proposed method of plasma polymerization by varying the types of components used polymeropoulos gas, their numbers and quantitative composition allows a wide range to modify the structure and properties of deposited polymer coatings and can be used for applying on a substrate a photosensitive resist, when the photosensitive component is filled in the area of the afterglow plasma, where it copolymerization with other activated in the zone of the discharge component.

In Fig. 1 presents a schematic flow tubular reactor for carrying out the method of plasma polymerization.

In Fig. 2 and 3 present respectively the interferogram growth of the polymer film and the graph of its thickness from time to procesoru-similar and the method prototype: section ab in the graphs corresponds to the overlap of only one (the second Fig. 1) monomer methyl methacrylate (MMA) in the area poslesvecheniya plasma, i.e. the method prototype; section cd to overlap only one, but the other (first to Fig. 1) monometr (xylene) in the emitting zone of the plasma, i.e. the method similar; plot bc -- the overlap of both monomers simultaneously in the same reactor, i.e. the proposed method.

In Fig. 4 and 5 presents obtained using a Fourier transform infrared spectrometer firm "Brooker" infrared transmission spectra of the polymer films deposited on silicon substrate 13 where the copolymer toluene and MMA, obtained by the proposed method, 14 plasma-polymerized toluene, 15 polymethylmethacrylate (PMMA), 16 a copolymer of decapetala (DFC) with MMA, obtained by the proposed method, 17 plasma-polymerized DFK, 18 PMMA.

The reactor consists of a quartz tube 1, which is wearing a ring electrodes 2 connected to the HF generator 3 to generate inside the tube of the plasma gas discharge in the stream plasmabased gas, such as argon, through the jet nozzle 4 at the top (for gas) part of the quartz tube 1, and communicating with the last reaction chamber 5 to be pumped using a vacuum pump (not shown). In the lower part of the reaction chamber 5 ralisme, located inside the quartz tube 1, through inlet pipe 9 enter at least one of the components polymeropoulos gas (first pair of monometr) to activate it. Further down the flow of gas in the upper part of the reaction chamber 5, which is a zone 10 of the afterglow plasma, through the inlet pipe 11 is injected at least one other component polymeropoulos gas pairs (second monomer). These two (or more) of the component are mixed in afterglow plasma, and the interaction of the particles is activated the component that has snarled directly to the reaction chamber 5. Activated particles polymeropoulos gas are deposited on a substrate 7 and form it into a polymer layer. To control the deposition process, for example, using a laser interferometer reactor equipped with an optical input 12.

Practical verification of the availability of the invention was performed in the following experiment.

At the bottom the flow of plasma gas portion of the area of illumination of the argon plasma flow tubular reactor (Fig. 1) attempted a pair of the first monomer and the downstream gas in the zone of the afterglow plasma of the pair of the second monomer. As the first monomer used p is DFC), and as the second methyl methacrylate (unsaturated aliphatic compound). Laser interferometer controlled the thickness of the polymer film, asadauskas on the substrate, located perpendicular to the axis of the reactor.

Power is transmitted to the electrodes of the discharge tube was approximately 200 W, the other parameters of the process, in which the copolymerization was carried out, including the reactor pressure P (mm RT.cent.), the temperature of podarkticules t (aboutC) argon flow rate Far(cm3/min), the flow rate of the first monometr Fmon(cm3/min), and consumption of methyl methacrylate Fmma(cm3/min) are shown in table. 1.

The growth rate of the film on the sections ab, bc, cd (Fig. 2 and 3) in the experiment with xylene, and other monomers are presented in table. 2.

Obviously, the growth rate of the film, and hence the efficiency of the deposition process when the copolymerization is much more than the speed of its growth during polymerization of each monomer separately and even greater than the sum of these velocities Vbc> Vab> Vcd, i.e., in this way is a synergistic effect.

In the spectra of copolymers Fig. 4 and 5 contains absorption bands, features, fashion really is a copolymerization process in the area of the afterglow plasma.

The data table. 1 suggests that it is implemented in the described experiment, and possible to achieve the above effect, the ranges of the operating parameters of the process of plasma polymerization (or ranges of values of the quantitative features of the invention) are:

the pressure in the rector of 0.2-0.4 and 0.1-1 mm RT.article.

the temperature of the substrate 0-10 and -20 to +60aboutC;

flow of argon 56-95 and 20-200 cm3/min;

flow components polymeropoulos gas 1-6,6 and 1-10 cm3/min.

1. The METHOD of PLASMA POLYMERIZATION, comprising placing the substrate in the reactor in the zone of the afterglow plasma, the overlap in the reactor plasma gas, digester gas-discharge plasma is low, no higher than 76 Torr, pressure, overlap polymeropoulos gas in the zone of the afterglow plasma activation molecules polymeropoulos gas using plasma deposition of activated molecules polymeropoulos gas to the substrate with the formation therein of a polymer layer, wherein at least one of the components polymeropoulos gas is additionally introduced into the area of the glow plasma to activate it, and as at least one of the components polymeropoulos. the procedure under item 1, characterized in that as the plasma gas used is additionally introduced into the area of the glow plasma component polymeropoulos gas.

3. The method according to p. 1, characterized in that the temperature of the substrate support is equal to 20 + 60oC.

4. The method according to p. 1, characterized in that as a plasma-forming gas used argon with a flow rate of 20 to 200 cm3/min, and the pressure in the reactor support is 0.1 to 1 Torr.

5. The method according to p. 4, characterized in that as component polymeropoulos gas jet in the area of the glow plasma, use derivatives of benzene, and as a component of the jet in the area of the afterglow plasma, methyl methacrylate.

6. The method according to p. 5, characterized in that the flow rate of each component polymeropoulos gas support equal to 1 10 cm3/min.

 

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FIELD: machine engineering, namely strengthening inner surfaces of openings in parts.

SUBSTANCE: method comprises steps of placing cone having apex angle 60 - 70° and made of heat resistant material with low adhesion capability or metal coated with such material in opening along its axis; setting gap between surface of opening and edge of cone base; feeding onto surface of cone jet of particles of coating material and in addition feeding concentric jet of pressurized gas; rotating cone during process of applying coating and moving it together with torch along coated surface. It is possible to rotate part relative to cone; the last is simultaneously rotated in opposite side. In order to clean surface before starting process of coating applying, nozzle of sand blasting or shot blasting apparatus is placed over cone instead of torch. Jet of abrasive powder or shot jet is directed onto surface of cone. Cone is rotated and together with nozzle it is moved along coated surface. Particles of material to be deposited are thrown by means of cone onto walls of opening. Particles with low energy are blown out through gap.

EFFECT: enhanced quality of coating.

3 cl, 1 dwg, 1 ex

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