JPH02104665A - Carbon film-coated member - Google Patents

Abstract

PURPOSE:To prevent loss of clairvoyance due to dust, water droplets, etc., by forming a hydrophilic light-transmissive film made of carbon or consisting essentially of carbon and having specified resistivity on an insulating light- transmissive member. CONSTITUTION:A hydrophilic light-transmissive film made of carbon or consisting essentially of carbon and having <=5X10<13>OMEGAcm resistivity is formed on the surface of an insulating light transmissive member to be weathered such as the windshield, window of a building, etc. A silicon nitride film is preferably interposed between the film and the member to improve the film adhesion. From 5 to 30atom% of hydrogen or fluorine, 0.1-10% of group III or IV element of the periodic table, etc., can be added as the auxiliary components of the film consisting essentially of carbon. The film can be formed on the member by subjecting a gas contg. hydrocarbons such as C2H4 and desired auxiliary components to a plasma reaction.

Description

Detailed Description of the Invention "Field of Application of the Invention" The present invention has hydrophilicity and has a specific resistance of 5×IQII.
It relates to carbon or a coating mainly composed of carbon having a resistance of ΩC1 or less.

In the present invention, when forming this on a light-transmitting member such as glass, a silicon nitride film having light-transmitting properties and adhesion to the member is formed on the member, and carbon or a carbon-based film is further formed on the silicon nitride film. The present invention relates to a member having a multilayer structure forming a coating as a component.

The present invention adds III-valent or V-valent impurities together with hydrogen or fluorine to carbon or a protective coating mainly composed of carbon, thereby controlling the degree of hydrophilicity, Vickers hardness, and electrical conductivity. This is what I am trying to do.

"Prior Art" Generally, in the plasma CVD method, a method of forming a film in a planar shape on a substrate having a flat surface is considered to be industrially effective. Furthermore, a method is also known in which a film is formed using a plasma CVD method while also producing a sputtering effect. Regarding carbon film coating, which is a typical example,
A patent application filed by the present inventor is known: Composite having a carbon coating and method for producing the same 1 (Japanese Patent Application No. 56-146936, filed on September 17, 1988). However, these have a parallel plate type using only a pair of electrodes, two output ends derived from one high frequency power source are connected to each electrode, and a substrate is arranged on one electrode (cathode side). This method uses self-generated self-bias to form a carbon film on the upper surface of a flat surface.

"Conventional Problems" In order to use such a single high-frequency power source, in the parallel plate type plasma reaction method, a substrate is disposed parallel to and close to the electrode on one side of the electrode, and the plasma CVD is applied to the upper surface of the substrate.
will be done.

Therefore, even if mass production is not required, productivity is poor because the electrodes are simply made to have a large area and a single layer of film is processed only on one electrode surface. Furthermore, it is difficult to independently apply a bias to this substrate or member, making it difficult to find optimal process conditions for thin film formation. Furthermore, with regard to etching methods in which a bias is applied to a substrate or a member, it is not possible to simultaneously process a large amount.

For this reason, there has been a need for a method of forming or etching a film on a large number of members at once in a large capacity space.

The present invention has been made for this purpose.

"Means to Solve the Problem" The present invention is based on diamond-like carbon (DLC).
The present invention provides a member in which a is formed and a method for producing the same, in which a pair of electrodes (first and second electrodes) are arranged at one end and the other end of a reaction space spaced apart from each other for plasma CVD. . Furthermore, each of them has an independent electromagnetic energy supply means and a matching box. It has a phase adjuster that mutually controls the phase of electromagnetic energy supplied to each electrode via a matching box.

Using the electromagnetic energy emitted from each electrode, a large power of KW level is supplied to the reaction space, and the phase of each electrode is controlled to generate a plasma having a synergistic effect in the reaction space.

A third electrode for applying direct current or alternating current bias is provided in this space as necessary. The space between a pair of electrodes (
A substrate and a member having a surface to be processed are placed in a plasma space using a holder. The reaction space is evacuated and a reactive gas is supplied. In order to turn the reactive gas into plasma, electromagnetic energy of a predetermined power and frequency is supplied to each of the pair of electrodes via an electromagnetic energy supply means and a matching box. Different high-frequency voltages are applied to these electrodes from respective high-frequency power sources so that the phases are approximately 180° or approximately 0° with respect to the ground, and the phases are adjusted so that alternating voltages that are symmetrical or in phase with each other are applied. Adjust and control with a regulator.

As a result, substantially one high-frequency alternating voltage is applied, and a large power of KW level is applied to the plasma space to induce high-frequency plasma to completely decompose and ionize the reactive gas. Furthermore, the other end of each high frequency power source is grounded.

If further generation is desired, a direct current (self- or externally applied direct current bias voltage) or alternating current (alternating current bias voltage) voltage is applied across the substrate or member. In the case of the self-direct current bias method, ions accelerated on one electrode side by the second alternating voltage sputter on the formation surface of the member, strongly forming a film or etching on the formation surface.

When the first alternating voltage is applied to each electrode through independent electromagnetic energy supply means and matching boxes, and when it is within approximately 0°, that is, 0 ± 30°, and when it is within approximately 180°, that is, 180 ± 30°. In this case, the latter, i.e. 180 ± 30
within 180° (approximately 180°), and 90±3
When the phase angle was within 0°, the plasma was particularly biased toward one electrode.

This is done by creating a phase that causes ions to move greatly from one electrode to the other electrode and from the other electrode to the other electrode in the reaction space, making the space wider, turning it into plasma, and causing the ions to move. It is estimated to be.

As the plasma CVD of the present invention, the case of carbon or a film mainly composed of carbon, that is, DLC (diamond-like carbon B) will be shown.

To form this thin film, ethylene (CJa), methane (
CH4), acetylene (CJzL carbon fluoride (CzF
Hydrocarbon gases or fluorocarbons or C) IF, such as CJI.

A carbon fluoride gas such as HlCsFi, HsCF, C1bh, etc. is introduced, and a III- or V-valent additive is added, typically diborane (Bz) for boron, respectively.
ui).

Boron fluoride (BFff), ammonia (NH, ), and nitrogen fluoride (NF3) were added. The amount of the III-valent or V-valent additive in the formed film was 0.1 to 10 atomic %.

At this time, 5 to 30 atomic percent of hydrogen or fluorine was added. In this way, a C-C bond similar to that of diamond with SP3 orbital is created, and the resistivity (specific resistance) is 1×lOh.
~5×1OI3ΩC – typically 1×1O? ~5×10
with a Vickers hardness of 700 to 5
000Kg/am", optical energy band width CEg) is 1.OeV or more, preferably 1.5 to 5.5e
A film having characteristics similar to those of diamond, which is transparent in the visible region and has V, was formed.

When forming a film using the method of the present invention, plasma C
In addition to carbide gas, nitrogen (7-valent additive) or boron (■-valent additive) was mixed into VD to create a hydrophilic surface and to create a uniform concentration gradient in the thickness direction. A film containing carbon as a main component or a multilayer composite film in which the presence or absence of additives is controlled may be produced.

The manufacturing method of the present invention will be described below according to the drawings.

"Example 1" FIG. 2 shows an outline of a plasma processing apparatus for carrying out a method of forming or etching a thin film on a substrate or member by a plasma reaction method.

In the drawing, a reaction vessel (7) of the plasma reactor is separated from the outside by a gate valve (9). Gas system (30)
, the carrier gas hydrogen or argon (
From 31), reactive gases such as hydrocarbon gases, such as methane (CH4) and ethylene (czna), and from (32), fluorocarbon gases such as fluorocarbons (CzFb, C3F@).
From (33), BtH, which is a gas with valence or V
b or NH, from (34), disilane (Si, H,
) from (35), nitrogen fluoride or oxygen, which is an etching gas for the reaction vessel, from (36), a valve (28),
A nozzle (25) passes through the flow meter (29) into the reaction system (50).
).

When hydrogen and dicarbon hexafluoride (CzFb) are introduced, the hydrogen pulls out the fluorine, resulting in a diamond-like carbon film (
(Although also referred to as DLC, the present invention refers to carbon or a film containing carbon as a main component, including DLC to which additives are added).

In addition, disilane (SiJi) was introduced from (35) and ammonia (NI+3) was introduced from (34), and plasma CVD
A reaction can be caused to form a silicon nitride film.

A first pair of electrodes having the same shape are provided above and below this reaction container (7) to form first and second electrodes (3-1).

(3-2) is made of aluminum metal mesh.

Each of the electrodes has first and second electromagnetic energy supply means (15-1) and (15-2). An alternating voltage of 1 to 100 MIIz, for example, a high frequency voltage of 13.56 MH2, is emitted from the supply means which is each power source,
Matching boxes (16-1) and (16-2) are provided to match the electromagnetic energy to the impedance inside the reaction vessel, which is composed of LCR. The terminals introduced from this matching box (4-1), (4-2
), electromagnetic energy is supplied to each electrode (3-1) and (3-2). The first and second power supplies (1
5-1) and (1 and 5-2) are basically the same waveform with the same frequency, but a constant multiplication waveform may also be used.

The phase of each power supply is set to 180 by the phase adjuster (26).
They are controlled to within "±30" of each other.

The reactive gas is emitted downward from the nozzle (25).

The frequency of the bias voltage DC power supply (17-2) and the second alternating voltage power supply (17-1) is set to 1OH2 to 100KH2.
The biasing means (17) consists of: This bias is then supplied to the substrate or member when the switch (10) is in (11-2).

Plasma is thus generated in the reaction space (8).

The exhaust system (25) includes a pressure adjustment valve (21), a turbo molecular pump (22), and a rotary pump (23).
Unnecessary gas is exhausted through the process.

These reactive gases are present in the reaction space (8) at a concentration of 0.001 to
It was set to 1.0 torr, for example, 0.05 torr.

In this space, a first high frequency voltage of 0.5 to 50 KW (O, OQ 5 to 5 W/cm" per unit area), for example, IKW (0.IW/cmtO high energy per unit area) is applied. Furthermore, a second alternating voltage is applied. By applying an AC bias voltage, -50 to -600V is applied to the surface to be formed.
A negative self-bias voltage (for example, the output is IKW) is applied, and a reactive gas accelerated by this negative self-bias voltage is sputtered onto a substrate or member to form a film, and a dense film is formed. We were able to.

The reactive gas was, for example, a mixed gas of ethylene and carbon fluoride. The ratio is CzF6/CJi = 1/4~4/
1, typically 1/1. By varying this ratio, transmittance and specific resistance can be controlled. The temperature of the substrate or member (1) is room temperature to 150°C1
Typically, it is maintained at room temperature without external heating.

Thus, the resistivity on the surface to be formed is 1 x 106 to 5 x 10'3.
Ωcm, 1.0 to 5.5 in the optical energy band
eV, and can be formed into a film in close contact with organic resins or other solid inorganic materials. A film containing carbon or carbon as a main component to which fluorine and hydrogen are added and has an amorphous or crystalline structure that is transparent to visible light.
It was made to have a thickness of 8 μm, for example, 0.5 μm (flat portion) and 1 to 3 μm (convex portion). The deposition rate was 100-1000 people/min.

In this way, coatings containing carbon as a main component on glass plates, organic resins, and other members, particularly those containing hydrogen or fluorine in carbon at 30 atomic % or less, and containing 0.3 to 1
A hydrophilic carbon film containing boron or nitrogen at a concentration of 0 atomic % could be formed.

A first carbon made of only ethylene is provided on an organic material to a thickness of 100 to 2000 people, and the main component is hydrophilic carbon to which fluorine, nitrogen, and hydrogen are added using C2F4, hydrogen, and ammonia. It was possible to form a multilayer coating.

"Example 2" This example is an example in which a film containing carbon as a main component was formed on the main part of an organic material using the apparatus used in Example 1, as shown in FIG.

In Fig. 1 (A), an OPC (optical photoconductor) drum (1) in which an organic resin is provided on an aluminum part is used, and D is used as a photoconductor or a protective film on the drum.
An LC film (45) is formed thereon.

In Figures 1 (A) and (B), this plastic (1) is lightweight, and in order to improve its adhesion to the plastic, ethylene and hydrogen are used to make it 0.01 to 0.1 μm thick. was formed. Furthermore, by using a mixed gas of CzF6, NH3, and H2, the specific resistance is 1×10h~5×10”Ω.
cI11 preferably I XIO' ~ 5 XIO"Ωc
A hydrophilic carbon film was formed to a thickness of 0.2 to 2 μm. In this way, a film containing carbon as a main component to which 4.5 at. % of nitrogen and 10 to 30 at. % of fluorine and hydrogen were added could be produced on the OPC drum by the method of the present invention.

“Example 3J This example is an example in which silicon nitride is formed as a coating for the base material.

Disilane (SfJ6)/NH in Figure 2 as a reactive gas.
3 from (35), ammonia (N) lx) from (34)
Supply from (SizH5)/NHs = 1/3 to 1
/10. High frequency waves were applied at a pressure of 0.05 torr, the same as in Example 1, without external heating.

This made it possible to form a silicon nitride film on these upper surfaces at a deposition rate of 100 people and 7 minutes.

"Example 4" This embodiment is shown in FIG. 1(C).

The plasma processing apparatus shown in FIG. 2 was used in the same manner as in the example. This is an example in which a plate-shaped substrate holder is placed in a plasma space (8), holds a substrate (1) having a surface to be formed on both sides, and a multilayer coating is formed thereon, and this substrate is made of glass. There is a board. These glass plates are the front windows, side mirrors, side windows, and rear windows of automobiles, motorcycles, airplanes, and ships, or windows of homes, and are troublesome to expose to the outside air.

First, the silicon nitride film shown in Example 3 was formed on this substrate. Reactive gases were further removed from the reaction vessel without exposing it to outside air (particularly oxygen), and a fluorine-doped carbon film of 0.1 to 5 μm, for example 0.5 μm, was applied thereon as shown in Example 1. formed to a thickness.

In the present invention, particularly this carbon or III-valent or V
The film whose main component is carbon to which fluorine has been added in addition to fluorine additives has hydrophilic properties and prevents the adhesion of dust due to the generation of static electricity, so its specific resistance is 1X10' to 5X10''
ΩCl11 range, particularly preferably lXlO7 to lXl
The range was 0"Ωcam.

In this example, the glass is made of silicon oxide, contains oxygen, and easily reacts with fluoride gas, so it is used as a buffer layer with oxygen resistance before forming DLC, which is transparent and has good density. A silicon nitride film (45-1) was formed. Then, a fluorine-doped carbon film or a carbon-based film (
45-2) were laminated.

The vertical cross-sectional view of FIG. 1(C) may be of not only the front window but also the side window or mirror surface.

FIG. 1(E) shows the structure formed on a curved surface.

The present invention is excellent because these materials are subject to strong wind blowing in actual use, and mineral dust is likely to collide with them, resulting in devitrification and turbidity due to abrasion.

[Example 6J In an example of the present invention, disilane and ethylene were introduced into the plasma atmosphere as base materials, and silicon carbide (Si
xCl-x O<X<l), and carbon or a film containing carbon as a main component was formed thereon. Then, the optical energy band width of this silicon carbide is 1.5 to 2.5 eV.
Therefore, it was possible to create a yellow semi-transparent base material. Furthermore, it was extremely effective in improving the adhesion of the carbon film.

"Example 6" This example has the shape shown in FIG. 1(D). Example 1 was used as the device, and a silicon nitride film was formed as the base material in the same manner as in Example 4, and a hydrophilic carbon film was formed thereon. In the layer shown in FIG. 1, the substrate holder is formed into a plate shape, and the respective substrates (11), [11'], and (11') are disposed on both sides of the board holder. As a result, each substrate (11), (1
Silicon nitride film (45-1) on only one side on 1 (11°)
.

(45-1°) and carbon or carbon-based coatings (45-2) and (45'-2) were laminated thereon. As a result, like the carbon film (4), a carbon film could be formed in close contact with glass or the like. By forming it only on one surface that is exposed to rain, we were able to double productivity. The rest is the same as in Example 4.

"Example 6" This example used the apparatus used in Example 1.

In Figure 2, oxygen (02) or nitrogen fluoride (NF,
), and the coating on the substrate, member, reaction vessel, or holder could be etched and removed at a rate of 100 to 300 people/min. In this embodiment, the etched materials are carbon or carbon-based coatings (etched with plasma oxygen), silicon nitride (etched with NFi plasma).

"Effects" The method of the present invention makes it possible for the first time to produce a protective film that has electrical conductivity and a hydrophilic surface. Especially when dust accumulates on translucent surfaces such as windows, and on rainy days, when there is surface tension, even if you try to look outside through the window from inside, you will not be able to see the outside clearly because of the diffused reflection of raindrops. The present invention eliminates these drawbacks and forms a hydrophilic carbon or carbon-based coating on a transparent substrate or member. In particular, when the transparent substrate is a glass material such as silicon oxide, the film that can be formed by simply replacing the reactive gas in the same reactor as the base material is a silicon nitride film and carbon or carbon as the main components. coatings, both of which are non-oxide materials. Furthermore, it is effective to use a silicon nitride film, which is a fluorine gas-resistant film, as the base material because the substrate is not damaged by fluorine. When forming these films, the film formation temperature was approximately the same, from room temperature to 150°C, and productivity could be improved.

[Brief explanation of the drawing]

FIG. 1 shows an example in which a coating is formed on a substrate or member of the present invention and its essential parts. FIG. 2 shows an outline of the plasma apparatus of the present invention.

Claims (1)

[Scope of Claims] 1. A translucent member having insulating properties, the translucent carbon or carbon having hydrophilicity on the surface of the member and having a specific resistance of 5×10^1^3 Ωcm or less. A member covered with a carbon film, characterized in that it is provided with a film mainly composed of. 2. Carbon is the main component on the translucent member or the translucent base material on the member, and an element of valence III or V in the periodic table of elements is added as a subcomponent in addition to hydrogen or fluorine. A member covered with a carbon film characterized by: 3. In claim 1, the carbon is characterized in that 0.1 to 10 atomic % of the III-valent or V-valent additive is added, and 5 to 30 atomic % of hydrogen or fluorine is added. A member covered with a membrane. 4. In claim 1, the translucent member is attached to a car, motorcycle, bicycle, etc. on the side that can be exposed to wind and rain.
front window, rear window of a ship or aircraft,
A member covered with a carbon film characterized by consisting of a side mirror, a side window, or a window of a building.