JPS6047003A - Process and apparatus for plasma polymerization - Google Patents

Abstract

PURPOSE:To make it possible to prepare a variety of composite films which have heretofore been difficult to prepare and to determine exactly the property and structure of a formed film, by separately feeding a plurality of material gases to a plasma space and forming a composite film thereof on a base. CONSTITUTION:A plurality of material gases in the form of monomers at a predetermined ratio fed from material gas inlets 3, 3' to a vacuum tank 1 are converted into plasma by activation by a high-frequency coil 2 and transferred onto a base 4 by an electric field to form a polymer film. According to this process, it is possible to control exactly each of the flow rates of a plurality of materials and to select the composition of a polymer film freely. The composition of a film sensitively reacts with a flow rate of a material gas, so that it is easy to vary the composition of a film composition continuously along the direction of its thickness. Further, when C2H4 gas and TixCly gas, for example, are fed separately, a Ti-containing polyethylene film can be obtained easily, so that it is possible to produce easily a metal atom-bonded film whose metal atom content has heretofore been difficult to control.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thin polymer film using plasma, and particularly to a method for producing a thin polymer film as a composite material using a plurality of materials.

When a helpful monomer gas is electrically turned into plasma, a phenomenon is observed in which a film is formed on the surface of a substrate, container, etc. that is close to the plasma, and this phenomenon is called lasma formation. .

This plasma polymerization can form FPi-containing products from almost any B-containing gas without a catalyst, and the polymerization speed can be easily controlled by controlling the gas pressure, input for plasma generation, etc. However, depending on this method, it is possible to obtain a co-IK aggregate by making a mixture of I and N. 7) It is not possible to precisely control the composition by changing the components in the thickness direction or by stacking polymer film layers alternately.

In addition, there have been attempts to incorporate gold into the polymer film by sputtering during the process of forming the polymer film, but it is impossible to precisely control the amount of metal gold by sputtering. However, the carrier gas pressure required to maintain sputtering is relatively high, which has the problem of damaging the produced film.

This invention aims to make full use of the above-mentioned plasma polymerization, to accurately control the properties and structure of the produced film, and to make it possible to synthesize various composite films that were previously difficult to synthesize. It is something.

The present invention will now be described in detail by way of examples with reference to the drawings.

Figure 1 shows a coupling device for supplying multiple types of materials as gases (1) in a vacuum chamber, and (7) a high-frequency coil 2 for plasma generation outside the vacuum chamber as shown. When wrapping around the glass, the crow part ■ is made of insulating material. 3. 3' is the supply port for raw material waste, and several kinds of raw material gases are supplied to 4 each.
(Even the specified edges are supplied into the vacuum chamber from the respective supply ports 3, 3', etc., as they are. These Lv original #+ gases are of course mixed with inert or active carrier scum and supplied depending on the safety. may be done.

Reference numeral 4 denotes a substrate, and in order to grow a thin film on the other side of the substrate, a negative potential is applied to the supporting table 5 with respect to the frequency wave coil 2 or the raw material gas supply port 3. Reference numeral 6 is an exhaust port υ, through which residual gas is exhausted by a vacuum pump.

In this device, multiple types of L1) IJA material waste supplied into the IT conversion tank 1 of the hanging body at a predetermined ratio from the raw material gas supply port 3.3'N\- are turned into plasma by the high frequency coil 2. is activated, transported onto the substrate by the electric field, and 1! This is the axis that forms the suture membrane. In the plasma, the Kameko υ speed is larger than that of ions, and the preshock of υ spreads outside the plasma region, and this region is a negative position ○ region compared to the plasma center. Become. Therefore, when a substrate is placed in this negative kite cry region, ion groups are transported onto the substrate by a naturally formed electric field even without applying particular LL pressure.

In this plasma and plasma device, the flow rate of each of the raw material gases can be precisely controlled, making it easy to freely select the composition of the polymerized film. Then, the residual gas is immediately exhausted, and the composition of the film responds sharply to the OIL ratio of the raw material gas, and the composition of the film changes continuously in the four directions of the film, or the properties differ in a J-shape. It is also easy to form a film fT.

In addition, it has been found that the raw 1#1 gas can be used not only as a monomer-free gas but also as a non-compound gas.
From 3.3' to 4, a Tl-containing polyenalene film can be grown into H&.

In this way, a heavy film in which sieve molecules and gold llI41Attons θ are bonded has a large electrical constant and a small resistivity at υ. Although ilj is expected to be useful as an r material, conventionally it has been difficult to control the free eL of the surprise atom val=8M.

Gold tt'-4 originals-1- or nothing mixed in with the 1 power.
Instead of the liquid Q as described in 11/llυ above, the liquid Q can be supplied to the reaction zone by evaporating it in a vacuum.

The polymerization apparatus shown in FIG. 2VC is connected to the raw material gas supply port 3' line evaporation phase 7 to the vacuum chamber 1. A heating filament 8 is disposed in the IC in the evaporation tank 7, and the molten compound heated and evaporated here is supplied in gaseous form into the vacuum tank 1 from the supply port 3'. Scraps, ) IH wrinkles can be controlled by a squeezer or shank 9.

By separately providing evaporation@7 in this way, the evaporation right 7
In addition to lowering the internal pressure to facilitate evaporation and ease the placement of the heating filament, the seven strands introduced into the vacuum chamber 1 come into contact with the heating filament 8 and decompose.
It is possible to prevent unexpected V components from being mixed into the polymer film.

As shown in Fig. 3, the heating filament 8 for vaporization is placed directly in the vacuum chamber l, and this combining device has the advantage that the structure of the raw material supply device into the plasma is inside the bacteria. There is.

Such a device produces ethylene, monomer gas,
Using butadiene, methyl meccrylate, etc., A, N,,,02, etc. are used as a base gas, and metal grains such as AA, In, Sn, etc. are mixed in by resistance heating to form a composite film with low specific resistance. I was able to do 1@ easily. An example of this is shown in the table below. When glass glass is used as a substrate for these finite films, it is possible to improve the adhesion to the glass by mixing silicone into the glass.

In addition, in each of the above coupling devices, the coil is placed outside the empty tank for applying the high-frequency TI4 field, but of course it may be placed inside the vacuum tank, or a capacitor-type applying device f: May be used. Furthermore, excitation by light can also be used to generate plasma. In this case, since light of a specific wavelength is absorbed depending on the type of monomer, only a specific monomer can be excited.

As mentioned above, this method involves supplying the monomers, monomers, hemisomers, compounds, etc. that form the composite film individually into the glass tube, transporting them onto the substrate, and polymerizing them. Therefore, it is possible to freely control the components of the plasma collection film, and it is also possible to obtain a targeted film with a layered composition, and it is also possible to polymerize a removal film with low resistivity, which is similar to that of Kim Gonghyun. Plasma submergence method won't let you down! I [we had a nice nature meeting @1
This has the effect of easily changing the texture of F.

[Brief explanation of drawings]

Figures 1, 2, and 3 respectively show the village of Togane Equipment, which was used to carry out the plasma therapy of this V-emission ψ. 1: Vacuum chamber 2: High wave coil 3: @ supply port 4:
Substrate 6: Exhaust port 7 Two steamers 8: Heating filament
9: Shafta

Claims (1)

[Claims] 1) In a plasma polymerization method in which a flooded monomer gas is turned into plasma and a polymer film is formed on a substrate, several kinds of material gases are individually supplied to a plasma space, and a polymer film is formed on a substrate. 2) Vacuum reactor, a supply port for introducing molten monomer gas into the container, an exhaust port for discharging the molten monomer gas, and a top Holding tank medium O
A plasma characterized by comprising a plasma device for applying a high-frequency electric field to convert gas into plasma, and a plurality of supply devices each having a gradient for separately supplying a raw material gas of compound ridges to the plasma space. Polymerization equipment, 3) The above-mentioned complex supply equipment is configured to supply monomer gas exclusively and to an evaporation tank installed in the tank. plasma polymerization equipment