JP2616797B2 - Method of forming plasma polymerized film - Google Patents

Description

The present invention relates to a method for forming a plasma polymerized film in which an amorphous carbon film containing hydrogen or fluorine is coated on a substrate by using plasma.

2. Description of the Related Art When a hydrophobic film is deposited on a substrate having a hydrophilic surface, the adhesive force between the substrate and the film is not always sufficient.

In such a case, a hydrophilic surface is hydrophobized by applying a surfactant such as hexamethyldisilazane on a substrate in order to enhance adhesion, and then a hydrophobic film is deposited. A method is used.

However, the use of surfactants such as hexamethyldisilazane shows excellent adhesion to substrates with substituted hydrogens such as OH, NH3, and COOH groups, but such functional groups Substrates, metal substrates, ceramic substrates,
It is not very effective for glass substrates and the like.

On the other hand, in the method of coating a hydrocarbon, fluorocarbon or fluorohydrocarbon, or an amorphous carbon film containing hydrogen or fluorine obtained by plasma polymerization of a mixture thereof onto a substrate, which for this carbon film is considerably hydrophobic Even when such a substrate is used, the adhesive force between the substrate and the film is very weak.

In this case, even if a surfactant such as hexamethyldisilazane is used to enhance the adhesive force, it does not work effectively for the reasons described above.

Problems to be Solved The present invention relates to a method for forming an amorphous carbon film containing hydrogen or fluorine obtained by plasma-polymerizing hydrocarbon, fluorocarbon or fluorohydrocarbon, or a mixture thereof on a substrate. It is an object of the present invention to provide a method for forming a plasma polymerized film having a strong adhesive force.

(Means for Solving the Problems) The present invention provides a method for forming an amorphous carbon film on a substrate, the method comprising the steps of: forming an organic compound containing a carboxyl group or an organic compound containing an amino group or an imino group on the substrate in advance; A film is formed by plasma-polymerizing a compound (hereinafter, referred to as a lower film), and then an amorphous carbon film (hereinafter, referred to as an upper film) is formed.

By using the lower layer film as a medium between the substrate and the upper layer film, the adhesive strength can be remarkably increased.

The kind of the organic compound containing a carboxyl group and the organic compound containing an amino group or an imino group are not particularly limited, but a compound having an unsaturated bond in a molecule is preferable.

Raw materials for the upper layer film include hydrocarbons such as methane, ethane, propane, ethylene, butylene, propylene, acetylene, butadiene, isoprene, benzene, toluene and xylene, or carbon tetrafluoride, carbon difluoride or octafluorocarbon Fluorinated carbon such as fluorinated tetracarbon, or monofluorinated hydrocarbon (FH3C), difluorinated hydrocarbon (F2
H2C) or a fluorinated hydrocarbon such as trifluorinated hydrocarbon (F3HC) can be used.

Alternatively, a mixture of these hydrocarbons, fluorocarbons, fluorinated hydrocarbons and the like may be used.

Preferably, a raw material having an unsaturated bond in the molecule is suitable for the polymerization reaction.

For the substrate, metal, ceramics, glass, resin, or the like can be used.

 Hereinafter, embodiments of the present invention will be described in detail.

Example 1 An aluminum substrate was placed in an airtight container, and surface treatment was performed with plasma at a high frequency of 200 KHz and power of 100 W for 30 seconds while flowing hydrogen at a flow rate of 10 cc / min.

Thereafter, methacrylic acid vapor was introduced into the closed container, and plasma treatment of methacrylic acid was performed at a high frequency of 200 KHz and power of 100 W for 10 seconds to form a lower layer film on the substrate.

Further, while flowing a mixed gas of butadiene at a flow rate of 10 cc / min and hydrogen at a flow rate of 5 cc / min, a butadiene plasma treatment was performed at a high frequency of 200 KHz and power of 100 W for 5 minutes to form a hydrophobic upper layer film on the substrate. .

Example 2 A chromium substrate was placed in an airtight container, and surface treatment was performed with plasma at a high frequency of 200 kHz and a power of 100 W for 30 seconds while flowing hydrogen at a flow rate of 10 cc / min.

After that, vinylamine vapor was introduced into the closed container, and vinylamine plasma treatment was performed at a high frequency of 200 KHz and power of 100 W for 10 seconds to form a lower layer film on the substrate.

Further, while flowing a mixed gas of butadiene at a flow rate of 10 cc / min and hydrogen at a flow rate of 5 cc / min, a butadiene plasma treatment was performed at a high frequency of 200 KHz and a power of 100 W for 5 minutes to form a hydrophobic upper layer film on the substrate. .

The hydrophobic upper film formed by the method of the above two embodiments has a remarkable adhesive strength with the substrate as compared with a polymerized film formed by plasma treatment of butadiene directly formed on an aluminum substrate or a chromium substrate. It was found to increase.

(Effects of the Invention) According to the present invention, when an amorphous carbon film is formed by plasma-polymerizing hydrocarbon, fluorocarbon, fluorocarbon or a mixture thereof on a substrate, an intermediate layer is formed to form an amorphous carbon film. There is a feature that a film having extremely strong adhesive strength can be formed.

Although the present invention can be effectively used as a passivation film for ICs, it can also be used as a rust-stopping metal hydrophobic treatment and variously changing the film thickness so that it can be used as a decorative color film for metal. There is.

Claims (1)

(57) [Claims] When a film formed by plasma polymerization of hydrocarbon, fluorocarbon, fluorocarbon, or a mixture thereof is formed on a substrate, an organic compound containing a carboxyl group as an intermediate layer between the substrate and the film; Alternatively, a method for forming a plasma-polymerized film, comprising forming a film obtained by plasma-polymerizing an organic compound containing an amino group or an imino group.