JP2775263B2 - Member covered with carbon film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Application of the Invention" The present invention has a hydrophilic property and a specific resistance of 5 × 10 ¹³ Ω.
cm or less of carbon or a coating containing carbon as a main component.

According to the present invention, when this is formed on a light-transmitting member such as glass, a silicon nitride film having a light-transmitting property and an adhesive property with the member is formed on this member, and carbon or carbon is mainly formed thereon. The present invention relates to a member having a multilayer structure for forming a coating as a component.

In the present invention, a trivalent or V-valent impurity is added together with hydrogen or fluorine into a protective coating containing carbon or carbon as a main component to control the degree of hydrophilicity, the Vickers hardness, and the electric conductivity. It is something you want to do.

[Prior Art] In general, in a 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. Further, a method of forming a film with a sputtering effect while being a plasma CVD method is also known.
Regarding the coating of a carbon film, which is a typical example, see the patent application “Composite having a carbon film and a method for producing the same” filed by the present inventor (Japanese Patent Application No. 56-146936, September 17, 1981).
Application is known. However, these have a parallel plate type using only a pair of electrodes, two output terminals derived from one high-frequency power supply are connected to each electrode, and a substrate is disposed on one electrode (cathode side), This is a method of forming a carbon film on the upper surface of a flat surface using self-bias generated by itself.

"Conventional problems" In order to use one such high-frequency power source, in a parallel plate type plasma reaction method, a substrate is disposed in close contact with one of the electrodes in parallel and a plasma CVD
Is made.

Therefore, even if mass production is required, the electrode is simply made to have a large area, and the film to be formed is one in which only one film is processed on one electrode surface, and thus the productivity is poor. Further, it is difficult to apply a bias independently to the base or the member, and it is difficult to find a process condition suitable for forming a thin film. Further, with respect to an etching method in which a bias is applied to a base or a member, a large amount cannot be simultaneously processed.

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 present invention has been made for such a purpose.

"Means to Solve the Problems" The present invention relates to such diamond-like carbon (DLC)
And a method of manufacturing the same, in which a pair of electrodes (first and second electrodes) are disposed at one end and the other end of the reaction space so as to be separated from each other for plasma CVD. . Further, 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.

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 a DC or AC bias is provided in this space as needed. A base and a member having a surface to be processed are provided in a space (plasma space) between a pair of electrodes 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 in order 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 phases are approximately 180 ° or approximately 0 ° with respect to the ground, and the phase is adjusted so that alternating voltages having the same phase or the same phase are applied. Adjust and control with the adjuster.

As a result, substantially one high frequency alternating voltage is combined, and a large 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 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 via the independent electromagnetic energy supply means and the matching box, and when approximately 0 °, ie, within 0 ± 30 °, and when approximately 180 °, ie, within 180 ± 30 °. In some cases, the latter, ie, 180 ± 30 ° or less (approximately 1
80 ゜) was excellent. In addition, when the phase degree was within 90 ± 30 °, the plasma was deformed particularly on one electrode side. This is because the phase is made to move ions from one electrode to the other electrode and from the other electrode to one electrode in the reaction space. It is estimated to be.

As the plasma CVD of the present invention, a case of carbon or a DLC (diamond-like carbon film) containing carbon as a main component is shown.

As the formation of this thin film, ethylene (C ₂ H ₄ ), methane (CH ₄ ), acetylene (C ₂ H ₂ ), carbon fluoride (C ₂ F ₆ , C ₃ F ₈ )
Hydrocarbon gas such as or carbon fluoride or CHF ₃ , H ₂ C ₃ F
₆ , H ₃ CF, CH ₂ F _{2 and} other carbon fluoride gases such as carbon fluoride are introduced, and further, a trivalent or V-valent additive, typically diborane (B ₂ H ₆ ) for boron, respectively. , Boron fluoride (BF ₃ )
Further, ammonia (NH ₃ ) and nitrogen fluoride (NF ₃ ) were added.
And the additive of III value or V value in the formed film is
0.1 to 10 atomic%. At this time, hydrogen or fluorine is 5-3
0 atomic% was added. Thus creating a C-C bond similar to diamond having SP ³ orbit, the resistivity (specific ^{resistance) 1 × 10 6 ~5 × 10} 13 Ωcm typically 1 × 10 ⁷ ~5 ×
It has 10 ¹¹ Ωcm and Vickers hardness 700-5000K
g / mm ² , and a film having optical energy bandwidth (referred to as Eg) of 1.0 eV or more, preferably 1.5 to 5.5 eV, having a property similar to that of diamond which is transparent in the visible region.

When forming a film by the method of the present invention, a reaction between C ₂ F ₆ having a halogen element such as fluorine from an initial state and NH ₃ + H ₂ or C ₂ F ₆
And using the reaction with B ₂ H ₆ + H _2, plasma simultaneously nitrogen (V-valent additives) In addition to the carbide gas during the CVD or by mixing boron (III valent additives), have a hydrophilic surface Alternatively, a multi-layer composite film in which the presence or absence of a carbon-based film having a uniform concentration gradient in the thickness direction or the presence or absence of additives may be controlled.

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

Example 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). Gas system (30)
In the above, hydrogen or argon as a carrier gas is a carbon fluoride gas from (31), and a hydrocarbon gas as a reactive gas such as methane (CH ₄ ) and ethylene (C ₂ H ₄ ) is a gas from (32). Carbon fluoride (C ₂ F ₆ , C ₃ F ₈ ) was converted from (33) to III
The hydrogen or valence gas B ₂ H ₆ or NH ₃ from (34), the disilane (Si ₂ H ₆ ) from (35), and the reaction vessel etching gas nitrogen fluoride or oxygen from (34) 36)
It is introduced into the reaction system (50) via the nozzle (25) through the valve (28) and the flow meter (29).

When hydrogen and dicarbon hexafluoride (C ₂ F ₆ ) are introduced, hydrogen extracts fluorine, and a diamond-like carbon film (also referred to as DLC) having a large number of SP ³ junctions to which fluorine is added by remaining CF bonds. However, in the present invention, including a DLC to which an additive is added, carbon or a coating containing carbon as a main component can be formed.

Also, disilane (Si ₂ H ₆ ) was converted from ammonia (N
By introducing H ₃ ) from (34), a plasma CVD reaction can be caused to form a silicon nitride film.

A first pair of electrodes are formed above and below the reaction vessel (7) to have the same shape, and the first and second electrodes (3-1),
(3-2) is constituted by an 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 the power supply means
Generates a 13.56MHz high frequency voltage and converts its electromagnetic energy to LCR
Matching boxes (16-1) and (16-2) for matching with impedance in the reaction vessel
Having. The matching terminal (4-
1) and (4-2), the respective electrodes (3-1),
Electromagnetic energy is supplied to (3-2). The first and second power supplies (15-1) and (15-2) basically have the same waveform at the same frequency, but may use a fixed-size waveform.

The phase of each power supply is 180 ゜ ± 3 by the phase adjuster (26).
They are controlled within 0 ° of each other.

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) consisting of 10 Hz to 100 KHz. This bias is supplied to the base or the member when the switch (10) is at (11-2).

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 are present in the reaction space (8) at 0.001 to 1.0.
torr For example, 0.05 torr.

In such a space, 0.5-50KW (0.0 per unit area)
05 to 5 W / cm ² ) For example, a first high-frequency voltage of 1 KW (high energy of 0.1 W / cm ² per unit area) is applied. Further, by applying an AC bias by the second alternating voltage, a negative self-bias voltage of -50 to -600 V (for example, the output is 1 KW) is applied on the surface to be formed. A film was formed while the accelerated reactive gas was sputtered on the substrate or the member, and a dense film could be formed.

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 to 4/1, typically 1/1. By changing this ratio, the transmittance and the specific resistance can be controlled. The temperature of the substrate or the 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. 0.1 to 8 μm, for example, 0.5 μm (planar part), and 1 to 3 μm of carbon or a film containing carbon as a main component to which fluorine and hydrogen each having an amorphous structure or a crystal structure that is transparent to visible light are added.
m (projections). The deposition rate was 100-1000 ° / min.

Thus, a film containing carbon as a main component on a glass plate or an organic resin material as a member, and other members, in particular, containing not more than 30 atomic% of hydrogen or fluorine in carbon, and containing boron or fluorine to a concentration of 0.3 to 10 atomic%. A hydrophilic carbon film containing nitrogen was able to be formed.

A first carbon made of only ethylene is provided on the organic material to a thickness of 100 to 2000 mm, and a hydrophilic carbon to which fluorine, nitrogen, and hydrogen are added using C ₂ F ₆ , hydrogen, and ammonia is further provided thereon. It was possible to form a multi-layer coating as a main component.

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) in which an organic resin is provided on an aluminum cylinder is used, and a photoconductor or a protective film is formed thereon.
The C film (45) is formed.

In FIGS. 1 (A) and 1 (B), the plastics (1) is lightweight, and was formed to a thickness of 0.01 to 0.1 [mu] m using ethylene and hydrogen to improve the adhesiveness thereon. Further, a specific resistance is 1 × 10 ^{6 to} 5 × 10 ¹³ Ωcm, preferably 1 × 10 ⁷ to 5 × 10 ^{6 to} 5 × 10 ¹³ Ωcm using a mixed gas of C ₂ F ₆ , NH ₃ and H _2.
A film of 5 × 10 ¹² Ωcm was formed into a carbon film having hydrophilicity to a thickness of 0.2 to 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.

Example 3 This example 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) as a reactive gas, and (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, a silicon nitride film is deposited on these
/ Min.

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

The plasma processing apparatus of FIG. 2 was used in the same manner as in the example.
Then, a plate-shaped substrate holder is disposed in the plasma space (8), and holds the substrate (1) having surfaces to be formed on both surfaces thereof,
This is an example in which a coating is formed in multiple layers, and a glass plate is used as the substrate. This glass sheet is used for cars, motorcycles,
A front window, a side mirror, a side window, a rear window, or a window of a home of an aircraft or a ship, or a window of a home, which is a surface side that is exposed to outside air.

First, the silicon nitride film shown in Example 3 was formed on this substrate. The reaction gas was further removed without exposing the reaction vessel to outside air (especially oxygen). As shown in Example 1, a carbon film to which fluorine was added was formed to a thickness of 0.1 to 5 μm, for example, 0.5 μm. Formed.

In the present invention, in particular, the carbon or trivalent or V
The coating containing carbon as a main component to which fluorine is added in addition to a multivalent additive has a hydrophilic property, and has a specific resistance of 1 × 10 ^{6 to} 5 × 10 ^{6 in} order to prevent adhesion of dust due to generation of static electricity. ¹³ Ωcm
And particularly preferably in the range of 1 × 10 ⁷ to 1 × 10 ¹¹ Ωcm.

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

 FIG. 1 (E) is 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 6 In an example of the present invention, disilane and ethylene were introduced as base materials into a plasma atmosphere, and silicon carbide (Si) was introduced.
xC _1−X 0 <X <1) was formed, and carbon or a film containing carbon as a main component was formed thereon. Then, since the optical energy bandwidth of this 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.

Example 6 This example has the shape 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 shown in FIG. 1, the substrate holder is formed in a plate shape, and the substrates (11) and (11 ') are formed on both surfaces thereof.
As a result, on each of the substrates (11) and (11 '), the silicon nitride films (45-1) and (45-1') are formed only on one surface and carbon or a film containing carbon as a main component (45-1). -2), (45 '
-2) was formed by lamination. As a result, the carbon film (4)
Similarly, a carbon film could be formed on glass or the like in close contact. The productivity was doubled by forming only one surface on which rain was applied. Others are the same as the fourth embodiment.

"Example 6" 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 removal of the coating on the substrate or member or the reaction vessel or holder was performed at a rate of 100 to 300 ° / min. In this embodiment, the material to be etched is carbon or a film containing carbon as a main component (etched with plasma oxygen) and silicon nitride (etched with NF ₃ plasma).

[Effect] By the method of the present invention, it has become possible for the first time to produce a protective film having electric 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 reaction furnace with the base material is a silicon nitride film and carbon or carbon as main components. Coatings, 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 forming these films, 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 the plasma apparatus of the present invention.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C30B 29/04 C30B 29/04 X (72) Inventor Junichi Takeyama 398 Hase, Atsugi-shi, Kanagawa Examiner, Semiconductor Energy Laboratory Co., Ltd. Junko Yoshimizu (56 References JP-A-62-167884 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C23C 16/00-16/56 JICST file (JOIS)

Claims (4)

(57) [Claims] 1. A translucent member having an insulating property, wherein a diamond-like carbon film having a hydrophilic property and a specific resistance of 1 × 10 ^{6 to} 5 × 10 ¹³ Ωcm is provided on the surface of the member. A member covered with a carbon film. 2. A material comprising carbon as a main component on a light-transmitting member or a light-transmitting base material on the member, and an element having a valence of III or V in addition to hydrogen or fluorine as an auxiliary component. A diamond-like carbon film having a specific resistance of 1 × 10 ^{6 to} 5 × 10 ¹³ Ωcm. 3. The method according to claim 2, wherein 0.1 to 10 atomic% of the trivalent or V-valent additive is added, and 5 to 30 atomic% of hydrogen or fluorine is added. A member covered with a carbon film. 4. The light-transmitting member according to claim 1, 2 or 3, wherein the light-transmitting member is a front window, a rear window, a side mirror, a side window of a car, a motorcycle, a bicycle, a ship or an aircraft, or a window of a building. A member covered with a carbon film, comprising: