JPS62116767A - Metallic member coated with hard carbon film - Google Patents

Abstract

PURPOSE:To form stable hardened films on various metallic members by providing an intermediate layer consisting of two layers of Cr or Ti and Si or Ge between a hard carbon film and metallic member. CONSTITUTION:The intermediate layer 14 of the lower layer 11 consisting of a Cr or Ti layer and the upper layer 12 consisting of an Si or Ge layer is formed on the various metallic members 10. The hard carbon film 13 is formed via such intermediate layer 14. The above-mentioned lower layer 11 has about >=0.05mum film thickness and adheres well to a metallic substrate 10. The upper layer 12 is about >=0.1mum and improves the adhesiveness between the lower layer 11 and the hard film 13. The intermediate layer 14 is preferably formed by an ion plating method, vapor growth method, etc. The hard carbon film 13 is preferably formed by a plasma polymn. method. The metallic member formed with the hard film having safety and reliability is provided by the above- mentioned method.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a metal member coated with a hard carbon film by plasma polymerization treatment in a gas atmosphere containing hydrocarbons.

[Background of the invention]

BACKGROUND ART Conventionally, a technique for producing a carbon hard film from hydrocarbon gas such as methane under low pressure using a plasma polymerization method has been studied. These membranes are highly crosslinked, are pinhole-free, and are insoluble in common solvents.

It is also called i-carbon or diamond-like carbon because it has extremely high hardness, high electrical resistance, and contains a diamond structure in a part of its structure.

(Literature, I-1, Vora and T, J.

Moravec, J-Appl, Phys., 5
2.6151 (1981), etc.).

The main reason why these carbon hard films are attracting attention is that
In addition to the fact that the film is extremely hard, it also has extremely high thermal conductivity and high chemical corrosion resistance even though it is an insulator.

Therefore, if such hard films could be freely coated on various substances and materials, it would be possible to open up countless applications.

[Conventional technology and problems]

However, carbon hard films formed by plasma polymerization have problems such as peeling depending on the type of underlying substrate, short lifespan, or film formation is impossible. In other words, it is possible to form a hard carbon film on glass, silicone, etc. substrates, but forming it on various metal members such as stainless steel plates, which have a particularly wide range of applications, may cause peeling or powdery particles. Materials that can form a carbon hard film are limited, as the product only accumulates and film formation is not possible.

[Purpose of the invention]

An object of the present invention is to enable coating of various metal members such as stainless steel plates with a carbon hard film, and to provide a metal member on which a stable and reliable hard film is formed.

[Structure of the invention]

The present invention provides a method for forming a carbon hard film formed by plasma polymerization on various metal members such as stainless steel plates with good adhesion (strongly) between the carbon hard film and the metal member. It is possible to coat a hard carbon film by creating a laminated structure with an intermediate layer consisting of two layers that significantly improves the properties.

In the present invention, the thin film layer that can be formed while maintaining strong adhesion of the carbon hard film is formed using various metal thin films, oxide thin films,
As a result of studies on semiconductor thin films, etc., it has been found that it can be formed on thin film layers of silicon (Si) or germanium (Ge), which are group 1 V elements, with extremely good adhesion, stability, and reproducibility. It became clear that the substrate at this time was glass.

However, if we use the knowledge obtained above to form a Si or Ge layer on various metal members such as stainless steel using various thin film formation techniques, and then form a carbon hard film on top of it, the Si The layer or Ge layer has poor adhesion at the interface with various metal members such as stainless steel plates, so peeling often occurs.
Extremely poor stability and reliability. Therefore, it was proposed to further form a contact metal layer made of chromium (Cr) or titanium (Ti) between the Si layer or Ge layer and the metal member. C "Alternatively, the T1 layer greatly contributes to improving the adhesion between various metal members such as stainless steel and the Si or Ge layer, and allows the Si or Ge layer to be firmly formed on the metal member. Therefore, the above By interposing such a two-layer intermediate layer, it has become possible to form carbon hard films on various metal members.

〔Example〕

Embodiments of the present invention will be described below based on the drawings.

FIG. 2 shows an example of a plasma polymerization apparatus for producing a hard carbon film. It is a parallel plate type device in which a high frequency application electrode, that is, a cathode electrode 1 and an anode electrode 2 are arranged in parallel.

A metal member such as a stainless steel plate is used as the cathode electrode 1.
to be installed. Hydrocarbon gas or a mixed gas of hydrocarbon gas and hydrogen or argon is introduced from the gas inlet 6, and the pressure is reduced to 0. Hold it at or below ITorr, 1
High frequency power of 3.56 MHz is applied to generate plasma. At this time, the high frequency power is from several tens of watts to several hundred watts.

The film synthesized by the above method is subjected to X-ray diffraction and It II
According to the analysis results of EED, it has an amorphous structure,
Furthermore, the results of the FT-IrL spectrum indicate that it contains a small amount of hydrogen. In addition, the synthesized film is hard and electrically insulating, and its color is brownish when it is less than 1 micron and black when it is more than 1 micron.

Table 1 shows the film deposition rate and hardness under typical conditions.

Table 1 Figure 1 shows the laminated structure of the metal member of the present invention in which the intermediate layer 14 for forming a carbon hard film formed by the above method on a metal member such as a stainless steel plate has good adhesion. FIG.
A hard carbon layer 13 is formed on the r or T1 layer and the upper layer 12 with a Si or Ge layer interposed therebetween. lower layer 11
adheres strongly to the metal substrate with a film thickness of 0.05 μm or more,
A sufficient effect can be obtained. The Si or Ge layer of the upper layer 12 is interposed to improve the adhesion between the lower layer 11 and the carbon hard film 13, and has a thickness of 0.1 μm.
With the above, sufficient effects can be obtained.

Various thin film forming techniques can be applied to form the lower layer 11 and the upper layer 12. That is, in the present invention, a vacuum evaporation method, an ion blasting method, a sputtering method, or a vapor phase growth method is used as a means for forming the intermediate layer 14. In particular, the intermediate layer formed by the ion blasting method or the vapor phase growth method has excellent step coverage, and can be formed well into grooves and small holes with a width of about several hundred μm and a depth of about several n. Furthermore, the carbon hard film formed by the plasma polymerization method described above can be formed in a very flexible manner, so there is an advantage that the hard film can be coated on metal products having highly uneven surfaces of various shapes.

Note that it is desirable that the formation of the lower layer 11 and the upper layer 12 be performed continuously while maintaining a vacuum state at a substrate temperature of 150° C. or higher.

By the above method, it is possible to form a carbon hard film on various metal members including stainless steel plates.

〔Effect of the invention〕

As is clear from the above description, the present invention not only provides a technology that enables the formation of hard carbon films on various metal members such as stainless steel plates by plasma polymerization, but also provides various machines, Hard film coating for cutting tool parts, general protective film or heat dissipation material for electronic parts,
It can be applied as a decorative item, etc., and can be said to be extremely effective in practical terms.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a carbon hard film coating with a two-layer intermediate layer according to an embodiment of the present invention. FIG. 2 is a side view showing an apparatus for forming a carbon hard film in the present invention. DESCRIPTION OF SYMBOLS 10... Metal member, 11... Lower layer, 12... Upper layer, 13... Carbon hard film, 14... Intermediate layer. Figure 1 Figure 2

Claims (1)

[Claims] In a metal member coated with a hard carbon film by plasma polymerization treatment in a gas atmosphere containing hydrocarbons, an intermediate layer consisting of a lower layer mainly composed of chromium or titanium and an upper layer mainly composed of silicon or germanium is used as the metal member. and the carbon hard film, the metal member being coated with a carbon hard film.