JP3310647B2 - Member covered with carbon film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to carbon or a coating containing carbon as a main component having a hydrophilic property and a specific resistance of 5 × 10 ¹³ Ωcm or less. The present invention, when forming this on a light-transmitting member such as glass, has a light-transmitting property on this member,
The present invention relates to a member having a multilayer structure in which a silicon nitride film or a silicon carbide film having adhesion to a member is formed, and a carbon or a film containing carbon as a main component is formed thereon. In the present invention, this multilayer film is formed in the same reaction vessel.
According to the present invention, trivalent or pentavalent impurities are added together with hydrogen or fluorine to a protective coating containing carbon or carbon as a main component to control the degree of hydrophilicity, control Vickers hardness, and control electric conductivity. They want control.

[0002]

2. Description of the Related Art In general, in a plasma CVD method, a method of forming a film in a plane on a substrate having a flat surface is considered to be industrially effective. Furthermore, a method of forming a film with a sputtering effect while using a plasma CVD method is also known. A typical example of the coating of a carbon film is described in the patent application “Composite with a carbon coating and a method for producing the same” filed by the present inventor (Japanese Patent Application No. 56-146936, filed Sep. 17, 1981). )It has been known.

[0003]

SUMMARY OF THE INVENTION The present invention relates to carbon or
For a member with a carbon-based film with good adhesion
Is what you do.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method for producing
An undercoat is provided on the undercoat, and carbon or carbon is provided on the undercoat.
It is characterized by a member provided with a film mainly containing silicon.

Further, the present invention has a surface made of an organic resin.
Wherein a base coat is provided on the surface of the member.
And a film containing carbon or carbon as a main component on the undercoat film.
Is provided. Carbon or charcoal of the present invention
Silicon-based coating, DLC (diamond-like carbon
The film) and the undercoat are formed by plasma CVD.

The formation of carbon or a thin film containing carbon as a main component includes ethylene (C ₂ H ₄ ), methane (CH ₄ ), and acetylene.
(C ₂ H ₂ ), hydrocarbon gas such as carbon fluoride (C ₂ F ₆ , C ₃ F ₈ ) or carbon fluoride or CHF ₃ , H ₂ C ₃ F ₆ , H ₃
A carbon fluoride gas such as carbon fluoride such as CF or CH ₂ F ₂ is introduced, and a trivalent or pentavalent additive, typically, diborane (B ₂ H ₆ ) for boron and boron fluoride, respectively. (BF ₃ ) Further, ammonia (NH ₃ ) and nitrogen fluoride (NF ₃ ) were added. The trivalent or pentavalent additive is 0.1% in the formed film.
To 10 at%. At this time, 5 to 30 atomic% of hydrogen or fluorine was added.

[0007] Thus, a CC bond similar to that of diamond having SP ³ orbits is formed, and the specific resistance (specific resistance) is 1 × 10 ⁶
５5 × 10 ¹³ Ωcm, typically 1 × 10 ^{7 to} 5 × 10 ¹¹ Ωcm, Vickers hardness 700 to 5000 Kg / mm ² , optical energy bandwidth (Eg) of 1.0 eV or more, preferably Formed a film having properties similar to those of translucent diamond in the visible region with 1.5-5.5 eV.

In forming a film by the method of the present invention, a reaction between C ₂ F ₆ and NH ₃ + H ₂ or a reaction between C ₂ F ₆ and B ₂ H ₆ + H ₂ having a halogen element such as fluorine from an initial state. In addition to the carbide gas during plasma CVD, nitrogen (pentavalent additive) or boron (trivalent additive) is mixed at the same time to have a hydrophilic surface, and a uniform concentration in the thickness direction. A graded carbon-based coating or a multilayer composite film in which the presence or absence of additives is controlled may be produced.

As the undercoat film of the present invention, a silicon nitride film or
Forms a silicon carbide film. These coatings are non-oxide materials
The adhesion of carbon or carbon-based coatings
Is improved.

[0010] The plasma CVD apparatus used in the present invention includes:
A pair of electrodes (first and second electrodes) are provided at one end and the other end of the reaction space so as to be separated from each other. In addition, it has independent electromagnetic energy supply means and a matching box. And it has a phase adjuster for mutually controlling the phases of the electromagnetic energy supplied to the respective electrodes via the matching box.

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

A third electrode for applying a DC or AC bias is provided in this space as needed. In a space (plasma space) between a pair of electrodes, a substrate and a member having a surface to be processed are provided using a holder. The reaction space is evacuated and a reactive gas is supplied. Electromagnetic energy of a predetermined electric power and frequency is supplied to each of the pair of electrodes via an electromagnetic energy supply unit and a matching box to convert the reactive gas into plasma. Different high-frequency voltages are applied to the respective electrodes from the respective high-frequency power sources so that the phase is approximately 180 ° or approximately 0 ° with respect to the ground, and the phase is changed so that a symmetrical or in-phase alternating voltage is applied to each electrode. Adjust and control with the adjuster.

As a result, substantially one high frequency alternating voltage is applied, and a high power of KW level is applied to the plasma space to induce high frequency plasma for completely decomposing and ionizing the reactive gas. Further, the other end of each high-frequency power supply is grounded.

In the case of further generation, a DC (self-directed or external DC bias voltage) or an alternating (AC bias voltage) voltage is applied across the base or member. In the case of the self-DC bias method, ions accelerated on one electrode side by the second alternating voltage sputter on the formation surface of the member, and strongly form or etch the formation surface on the member.

When the first alternating voltage is applied to the respective electrodes through the independent electromagnetic energy supply means and the matching box, approximately 0 °, ie, 0 ± 30
In the case of within 180 ° and in the case of approximately 180 ° or 180 ± 30 °, the latter, ie, 180 ±
Excellent within 30 ° (approximately 180 °). Also, 90 ± 30 °
At a phase degree within the range, the plasma was particularly deformed on one electrode side.

[0016] This is a phase in which ions are largely moved from one electrode to the other electrode and from the other electrode to one electrode in both sides of the reaction space, so that the space is made wider and plasma is generated, and the ions are converted into plasma. It is estimated to exercise.

The patent application by the present inventor (Patent Application 56-1)
46930), the plasma CVD apparatus is a parallel plate type using only a pair of electrodes , and two output terminals derived from one high-frequency power source are connected to each electrode, and one electrode (cathode side). A carbon film is formed on the upper surface of the flat surface using a self-bias generated by itself .

In order to use one such high-frequency power source, in a parallel plate type plasma reaction method, a substrate is disposed in parallel and in close contact with one side of an electrode, and a plasma is formed on the upper surface thereof.
CVD is performed. Therefore, even if mass production is not required,
The electrode is simply made to have a large area, and the film to be formed is one in which one layer of the film is processed only on one electrode surface, and the productivity is poor. Further, it is difficult to apply a bias independently to the substrate or the member, and it is difficult to find an optimum process condition for forming a thin film.

[0019] Further, with respect to the etching method in which a bias is applied to a substrate or a member, a large amount of the processing cannot be performed simultaneously. Therefore, a method of forming a film or etching a large number of members at once in a large capacity space has been required. The plasma CVD apparatus used in the present invention can achieve such an object.

[0020]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention will be described below with reference to the drawings.

[0021]

Embodiment 1 FIG. 2 shows an outline of a plasma processing apparatus for performing a method of forming or etching a thin film on a substrate or a member by a plasma reaction method. In the drawing, a reaction vessel (7) of a plasma reactor is separated from the outside by a gate valve (9). In gas system (30), hydrogen or argon as a carrier gas from (31), the hydrocarbon gas is a reactive gas, such as methane (CH _4), ethylene (C ₂ H ₄₎ (32)
More carbon fluoride gas (C ₂ F ₆ , C ₃ F ₈ )
From (33), B ₂ H ₆ or NH ₃ , which is a gas for trivalent or pentavalent, from (34), and disilane (Si ₂ H ₆ ) from (35) is a gas for etching the reaction vessel. Transfer nitrogen fluoride or oxygen from (36) to valve (28) and flow meter (29).
Introduced into (50) via nozzle (25).

When hydrogen and dicarbon hexafluoride (C ₂ F ₆ ) are introduced, hydrogen extracts fluorine, and the diamond-like carbon film having a large number of SP ³ bonds to which fluorine is added by the remaining CF bonds (also known as DLC). However, in the present invention, including a DLC to which an additive is added, carbon or a film containing carbon as a main component can be formed. Disilane (Si ₂ H ₆ ) can be introduced from (35) and ammonia (NH ₃ ) can be introduced from (34) to cause a plasma CVD reaction to form a silicon nitride film.

First and second electrodes (3-1), (3-1), a first pair of electrodes having the same shape are formed above and below the reaction vessel (7).
(3-2) is made of aluminum metal mesh.
Each of these electrodes has first and second electromagnetic energy supply means (15-1) and (15-2). Alternating voltage of 1 to 100 MHz from each power supply means, for example 13.56 MHz
And a matching box (16-1), (16-2) for generating the high frequency voltage of the above and configured to make the electromagnetic energy of the LCR and match the impedance in the reaction vessel.

The matching terminals (4-
Electromagnetic energy is supplied to the electrodes (3-1) and (3-2) via 1) and (4-2). First and second power supplies (15-1),
In (15-2), the same waveform of the same frequency is used in principle, but a fixed-size waveform may be used. The phase of each power supply is a phase adjuster
In (26), they are controlled within 180 ° ± 30 °.

The reactive gas is discharged downward from the nozzle (25). The frequency of the DC power supply (17-2) of the bias voltage and the frequency of the second alternating voltage power supply (17-1) are supplied by bias means (17) having a frequency of 10 Hz to 100 KHz. This bias is supplied to the substrate or member when the switch is on .

Thus, plasma is generated in the reaction space (8). The exhaust system (25) exhausts unnecessary gas through a pressure adjusting valve (21), a turbo molecular pump (22), and a rotary pump (23). These reactive gases have a reaction space (8) of 0.001 to
1.0 torr For example, 0.05 torr.

[0027] In such a space, adding a first high frequency voltage of 0.5 ~50KW (per unit area 0.005 ~5W / cm ²⁾ for example 1 KW (high energy per unit area 0.1W / cm ^2). Further, by applying an AC bias by the second alternating voltage, -50 to -600 V (for example, the output is
A negative self-bias voltage of (KW) was applied, and a reactive gas accelerated by the negative self-bias voltage was sputtered onto a substrate or a member to form a film, and a dense film was obtained. .

The reactive gas was, for example, a mixed gas of ethylene and carbon fluoride. The ratio is C ₂ F ₆ / C ₂ H ₄ = 1/4
44/1, typically 1/1. By changing this ratio, the transmittance and the specific resistance can be controlled. The temperature of the substrate or member (1) is maintained at room temperature to 150 ° C., typically at room temperature without external heating. Thus, the surface to be formed has a specific resistance of 1 × 10 ^{6 to} 5 × 10 ¹³ Ωcm, an optical energy band width of 1.0 to 5.5 eV, and is formed in close contact with an organic resin or other solid inorganic material. May be filmed.

[0029] A carbon or carbon-based coating containing fluorine and hydrogen having an amorphous structure or a crystal structure that is transparent to visible light and containing 0.1 to 8 µm, for example, 0.1 to 8 µm.
5 μm (flat portion) and 1-3 μm (convex portion).
The deposition rate was 100-1000 ° / min.

Thus, on a glass plate, an organic resin material, and other members, a film containing carbon as a main component, in particular, containing not more than 30 atomic% of hydrogen or fluorine in carbon,
It was possible to form a hydrophilic carbon film in which boron or nitrogen was mixed at a concentration of 0.3 to 10 at%.

A first carbon made of only ethylene is provided on the organic material to a thickness of 100 to 2000 mm, and further a C ₂ F ₆
Using hydrogen, hydrogen and ammonia, it was possible to form a multi-layered coating mainly composed of hydrophilic carbon to which fluorine, nitrogen and hydrogen were added.

Example 2 In this example, as shown in FIG. 1 , a film containing carbon as a main component was formed on a main part of an organic material using the apparatus used in Example 1. In FIG. 1 (A), an OPC (organic photosensitive conductor) drum (1) having an organic resin as a base on an aluminum cylinder is used, and a DLC film as a photoconductor or a protective film is formed thereon. (45) is formed.

In FIGS. 1A and 1B , the plastics substrate (1) is lightweight, and has a thickness of 0.01 to 0.1 μm using ethylene and hydrogen to improve the adhesion thereon. Formed. Further, a film having a specific resistance of 1 × 10 ^{6 to} 5 × 10 ¹³ Ωcm, preferably 1 × 10 ^{7 to} 5 × 10 ¹² Ωcm is formed thereon by using a mixed gas of C ₂ F ₆ , NH ₃ and H _2. A carbon film having hydrophilicity was formed to a thickness of about 2 μm. Thus, a coating containing carbon as a main component to which 4.5 atomic% of nitrogen, 10 to 30 atomic% of fluorine and hydrogen were added was produced on the OPC drum by the method of the present invention.

Embodiment 3 This embodiment is an example in which silicon nitride is formed as a coating for a base material. In FIG. 2 , disilane (Si ₂ H
₆ ) / NH ₃ was supplied from (35) and ammonia (NH ₃ ) was supplied from (34) to make (Si ₂ H ₆ ) / NH ₃ = 1/3 to 1/10. As in Example 1, high frequency was applied at a pressure of 0.05 torr without external heating. Then, it became possible to form a silicon nitride film on these upper surfaces at a film forming rate of 100 μm / min.

Embodiment 4 This embodiment is shown in FIG. 1 (C). The plasma processing apparatus of FIG. 2 was used in the same manner as in the example. In this example, a plate-shaped substrate holder is disposed in the plasma space (8), and a substrate (1) having surfaces to be formed is held on both sides thereof, and a multilayer coating is formed on the substrate (1). There is a board. This glass sheet is a front window, a side mirror, a side window, a rear window of a car, a motorcycle, an aircraft, or a ship, or a window of a house, and is a surface side of the window which is exposed to the outside air.

First, the silicon nitride film shown in Example 3 was formed on this substrate. The reaction vessel was further excluded without exposing the reaction vessel to outside air (particularly oxygen).
As shown in FIG.
It was formed to a thickness of 5 μm, for example, 0.5 μm.

In the present invention, in particular, the coating mainly composed of carbon or carbon to which fluorine has been added in addition to the trivalent or pentavalent additive has a hydrophilic property and prevents adhesion of dust due to generation of static electricity. To prevent this, the specific resistance is 1 × 10 ⁶ -5 ×
10 ¹³ Ωcm, particularly preferably 1 × 10 ⁷ to 1 × 10 ¹¹ Ω
cm.

In this embodiment, the glass is made of silicon oxide, contains oxygen, and easily reacts with the fluoride gas. Therefore, before forming the DLC, the glass is formed as a light-transmitting and dense buffer layer having oxygen resistance. A silicon nitride film (45-1) having good properties was formed. Then, a carbon film to which fluorine was added or a film (45-2) containing carbon as a main component was laminated on silicon nitride having fluorine resistance than silicon oxide. Longitudinal sectional view of FIG. 1 (C) is not a front window only, side window, mirror - may be a surface.

FIG . 1 (E) shows an example formed on a curved surface. The present invention is excellent because these materials have a strong windbreak in actual use, and are liable to collide with dust of mineral substances, and as a result, devitrification and turbidity are easily generated by abrasion.

Example 5 In an example of the present invention, disilane and ethylene were introduced as base materials into a plasma atmosphere, and silicon carbide (SixC) was introduced.
_1-x 0 <X <1) was formed thereon, and a film composed mainly of carbon or carbon was formed thereon. Then, since the optical energy bandwidth of the silicon carbide was 1.5 to 2.5 eV, a yellow semi-transparent base material could be obtained. It was also very effective in improving the adhesion of the carbon coating.

[0041] "Example 6" This embodiment is in the form of FIG. 1 (D). The apparatus used in Example 1 was a silicon nitride film as a base material, and a hydrophilic carbon film was formed thereon as in Example 4. In the layer of FIG.
The substrate holder is plate-shaped, and each substrate (1
1) and (11 '). As a result, on each of the substrates (11) and (11 ′), the silicon nitride film (4
5-1), (45-1 '), and carbon or carbon-based coatings (45-2), (45'-2) were laminated thereon. As a result, a carbon film could be formed on glass or the like in close contact with the same as the carbon film (4). The productivity was doubled by forming only one surface on which rain was applied. Others are the same as the fourth embodiment.

Example 7 In this example, the apparatus used in Example 1 was used. In FIG. 2 , only oxygen (O ₂ ) or nitrogen fluoride (NF ₃ ) was introduced, and the etching removal of the film on the substrate or the member or the reaction vessel or the holder was performed at a rate of 100 to 300 μm / min. In this embodiment, the material to be etched (etched with a plasma oxygen) coating mainly containing carbon or carbon, a silicon nitride (being etched by the plasma of the NF _3).

[0043]

According to the method of the present invention, an undercoat film is formed.
The carbon or carbon-based coating
A member that can be formed with good adhesion on the member
Can be provided. In addition, undercoating in the same reaction vessel
And to form a film containing carbon or carbon as a main component,
Main component of carbon or carbon without exposing undercoat to outside air
To improve the adhesion.
A member can be provided. Further, according to the present invention,
It has become possible for the first time to produce a protective film having electrical conductivity and a hydrophilic surface. In particular, dust accumulates on a light-transmitting surface such as a window, and when the surface tension is high on a rainy day, even if the user looks through the window from the inside through the window, the outside cannot be seen well due to diffuse reflection of raindrops. In the present invention, a hydrophilic carbon or a film containing carbon as a main component is formed on a translucent substrate or a member by eliminating such a defect.

In particular, when the light-transmitting substrate is a glass member such as silicon oxide, the film that can be formed only by replacing the reactive gas in the same reactor is a silicon nitride film and carbon or carbon. Coatings as components, both of which are non-oxide materials. Further, it is effective to use a silicon nitride film, which is a fluorine gas resistant film, as a base material because the substrate is not damaged by fluorine. At the time of film formation, the film formation temperature was formed at room temperature to 150 ° C., which was almost the same temperature, and the productivity was improved.

[Brief description of the drawings]

FIG. 1 shows an example in which a film is formed on a substrate or a member of the present invention, and an essential part thereof.

FIG. 2 shows an outline of a plasma apparatus of the present invention.

[Explanation of symbols]

 1 Substrate 45 DLC

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Junichi Takeyama 398 Hase, Atsugi-shi, Kanagawa Prefecture Examiner, Semiconductor Energy Laboratory Co., Ltd. Naoyuki Miyazawa (56) References JP-A-63-145776 (JP, A) JP-A Sho JP-A-58-185418 (JP, A) JP-A-62-133068 (JP, A) JP-A-63-153275 (JP, A) JP-A-58-1226972 (JP, A) A) JP-A-62-270774 (JP, A) JP-A-62-157602 (JP, A) JP-A-63-217303 (JP, A) JP-A-62-174379 (JP, A) (58) Survey Field (Int. Cl. ⁷ , DB name) C23C 16/27 B32B 9/00

Claims (14)

(57) [Claims] An undercoat is provided on a surface of a member in a reaction vessel, and a carbon or carbon-based film is formed on the undercoat in the reaction vessel without exposing the inside of the reaction vessel to outside air. provided, a film mainly containing carbon or carbon covered with film mainly containing carbon or carbon, wherein the this <br/> showing a hydrophilic member. 2. The member according to claim 1 , wherein the member is made of glass, and is covered with carbon or a film containing carbon as a main component. 3. A member having a surface made of an organic resin, wherein a base coat is provided on a surface of said member in a reaction vessel, and said base coat is provided in said reaction vessel without exposing said inside of said reaction vessel to outside air. A film containing carbon or carbon as a main component is provided on the coating, and the film containing carbon or carbon as a main component is mainly made of carbon or carbon characterized by exhibiting hydrophilicity.
A member covered with a film as a component. 4. The method according to claim 3, wherein said organic resin is used.
The member having the surface is an OPC drum provided with an organic resin.
Characterized by being carbon or carbon as a main component
A member covered with a membrane . 5. The method according to claim 1, wherein
The specific resistance of the carbon or the film containing carbon as a main component is 5 × 1
Carbon or carbon characterized by being not more than 0 ¹³ Ωcm
A member covered with a film mainly composed of 6. The method according to claim 1, wherein
Vickers hardness of the film containing carbon or carbon as a main component
Is in the range of 700 to 5000 kg / mm ^2.
Part covered with carbon or a film containing carbon as the main component
Wood . 7. The method according to claim 1, wherein
The energy bang of the carbon or the film containing carbon as a main component
Characterized in that the gate width is in the range of 1.0 to 5.5 eV.
Member covered with carbon or a film containing carbon as a main component . 8. The method according to claim 1, wherein
The carbon or the film containing carbon as a main component contains nitrogen.
Covered with a film mainly containing carbon or carbon and wherein
Components . 9. The method according to claim 8, wherein the nitrogen is 0.1 to 0.1.
Charcoal characterized by being contained at a concentration of 10 atomic%
A member covered with a film containing silicon or carbon as a main component . 10. A any one of claims 1 to 9, a film mainly containing carbon or carbon primary carbon or carbon, characterized in that a diamond-like carbon film
A member covered with a film as a component. 11. The any one of claims 1 to 9, a film mainly containing carbon or carbon characterized in that it is a diamond-like carbon film of amorphous structure
A member covered with carbon or a film containing carbon as a main component . 12. The any one of claims 1 to 11, wherein the base coating is a silicon nitride film
A member covered with carbon or a film containing carbon as a main component . 13. The any one of claims 1 to 11, wherein the base coating is silicon carbide film
A member covered with carbon or a film containing carbon as a main component . 14. The any one of claims 1 to 11, wherein the base coating is carbon, which is a film made of a material represented by _{Si x C (1-x)} (0 <X <1) Or charcoal
A member covered with a film mainly composed of silicon .