JP3438977B2 - Film forming method using plasma CVD device - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to relates to a film forming method using the Help plasma CVD apparatus to form various film, such as a hard carbon film on the substrate.

[0002]

2. Description of the Related Art Conventionally, electric razor blades, semiconductor materials,
In order to improve the characteristics and protect the surface of magnetic heads, piezoelectric materials, or sliding parts of various devices, coatings made of various materials are formed on these surfaces. For example, in the manufacturing process of electric razor blades, ECR
(Electron cyclotron resonance) Plasma CVD (chemical va
A hard carbon film (diamond-like film) is formed on the surface of the Si substrate by using a por deposition apparatus.

FIG. 3 shows the configuration of a conventional ECR plasma CVD apparatus (Japanese Patent Laid-Open No. 3-175620). In the ECR plasma CVD apparatus, a plasma generation chamber (4) and a reaction chamber in which the substrate (11) is to be installed are formed inside the vacuum chamber (10), and the plasma generation chamber (4) includes The microwave generator (1) is connected via the waveguide (2). A microwave introduction window (3) is provided at the connection between the waveguide (2) and the plasma generation chamber (4). A discharge gas introduction pipe (5) for introducing a discharge gas such as argon (Ar) into the plasma generation chamber (4) is connected to the plasma generation chamber (4). Further, a plasma magnetic field generator (6) is provided so as to surround the plasma generation chamber (4). A substrate holder (12) is installed in the reaction chamber in the vacuum chamber (10), and a reaction gas introduction pipe (14) is connected to the substrate holder (12). A high frequency power source (13) is connected to the substrate holder (12).

The microwave from the microwave generator (1) is guided to the plasma generation chamber (4) through the waveguide (2) and the microwave introduction window (3). High-density plasma is formed in the plasma generation chamber (4) by the action of the high frequency magnetic field generated by the microwave and the magnetic field from the plasma magnetic field generator (6). This plasma is guided to the reaction chamber along the divergent magnetic field generated by the plasma magnetic field generator (6).

In the reaction chamber, methane (CH ₄ ) gas as a source gas introduced from the reaction gas introduction pipe (14) is decomposed by the action of plasma, and carbon C is deposited on the substrate (11) on the substrate holder (12). Is deposited on the surface of. Here, a predetermined high-frequency voltage (RF voltage) is applied to the substrate holder (12) by a high-frequency power source (13), and a negative self-bias is generated in the substrate (11), which is a so-called bias plasma CVD method. Is carried out. That is, since the moving speed of ions in plasma is slower than that of electrons, the electrons can follow the potential fluctuation during the application of the RF voltage, but the ions cannot.
Therefore, when an RF voltage is applied to the substrate (11), many electrons are emitted toward the substrate (11), and a negative self-bias is generated in the substrate (11). As a result, positive ions in the plasma are drawn to the substrate (11) side, and as shown in FIG.
A diamond-like coating (15) is formed on (11).

[0006]

However, the conventional EC
In the R plasma CVD apparatus, most of film forming species such as ions and radicals generated by the action of plasma are deposited on the substrate (11) to form a film. Unnecessary film is formed by depositing on the inner wall of the generation chamber (4). Therefore, all of the film-forming species do not contribute to the original film formation, and there is a problem that the film formation rate on the substrate (11) decreases. Further, in a long-time process, the coating film formed on the inner wall of the plasma generating chamber (4) peels off, which adversely affects the coating film on the substrate.

An object of the present invention is to deposit more film forming species than the conventional one among film forming species generated by the action of plasma on a substrate to form a film of good quality at a high film forming rate. film forming method using the plasma CVD equipment which may be to provide.

[0008]

A plasma CVD apparatus used in the present invention is connected to a plasma generating chamber, plasma generating means for generating plasma in the plasma generating chamber, and the plasma generating chamber. The reaction chamber formed by the above, the substrate holder provided in the reaction chamber, and the reaction gas introducing means for introducing the reaction gas into the reaction chamber are provided, and in the plasma generation chamber, the inner peripheral wall of the plasma generation chamber is provided. A cylindrical electrode is installed along the line, and a power source for applying a DC voltage or a high frequency voltage to the cylindrical electrode is connected to the cylindrical electrode.

In a concrete configuration, the substrate holder is
A second power supply for applying a high frequency voltage is connected to the substrate holder so that the self-bias generated on the substrate becomes negative.

The plasma generation means is composed of an electron cyclotron resonance plasma source.

Furthermore, the cylindrical electrode is installed at a position surrounding the electron cyclotron resonance point of the electron cyclotron resonance plasma source.

In the method for forming a coating film according to the present invention, in the plasma CVD apparatus of the present invention, a DC voltage or a high frequency voltage is applied to the cylindrical electrode inside the plasma generating chamber while the plasma is being generated inside the plasma generating chamber. It is a thing.

Specifically, the tubular electrode is made of a material containing a material having low adhesion to the coating film to be formed on the substrate, and the DC voltage is applied to the tubular electrode while forming the coating film on the substrate. Alternatively, by applying a high frequency voltage, the coating film attached to the inner surface of the cylindrical electrode is removed by sputtering.

In this case, the film to be formed on the substrate is a hard carbon film, and the material having low adhesion is stainless steel, Fe, Al, Cu, or Ti.

In another specific method, the cylindrical electrode is formed of a material containing a material having high adhesion to the coating film to be formed on the substrate, and while forming the coating film on the substrate,
Alternatively, after forming the coating film, a DC voltage or a high frequency voltage is applied to the tubular electrode to remove the coating film deposited on the inner surface of the tubular electrode by sputtering.

In this case, the film to be formed on the substrate is a hard carbon film, and the material having high adhesion is Si,
C, Ru, or Ge.

In still another specific method, the material of the tubular electrode contains at least one element among the constituent elements of the film to be formed on the substrate, and the tube is formed while forming the film on the substrate. By applying a DC voltage or a high frequency voltage to the cylindrical electrode, the inner surface of the cylindrical electrode is sputtered and the material of the cylindrical electrode is deposited on the substrate.

[0018]

In the plasma CVD apparatus used in the present invention, the plasma generating chamber, the plasma generating means, the reaction chamber, the substrate holder, and the reaction gas introducing means constitute a film forming apparatus similar to the conventional apparatus, and the film forming apparatus is mounted on the substrate holder. A coating can be formed on the substrate. Here, in a state in which a voltage is not applied to the tubular electrode in the plasma generation chamber, the film-forming species that had been deposited on the inner wall of the plasma generation chamber in the conventional apparatus should be deposited on the inner peripheral surface of the tubular electrode in the present invention. become.

However, in the process of forming a film on the substrate,
Alternatively, after the film is formed, by applying a DC voltage or a high frequency voltage to the cylindrical electrode in a state where plasma is generated in the plasma generation chamber, cations in the plasma are sputtered onto the inner peripheral surface of the cylindrical electrode, The coating on the inner peripheral surface of the electrode strip is removed by sputtering. As a result, film formation on the inner peripheral surface of the cylindrical electrode is suppressed as much as possible, and sputtered film forming species are deposited on the substrate surface. Incidentally, when the power of the plasma generating means is relatively low, a coating film having a minute thickness is formed on the inner peripheral surface of the cylindrical electrode, but when the coating film is extremely thin, peeling occurs. There is no fear of. Therefore, even after a long-time process, the problem caused by the peeling of the coating on the inner peripheral surface of the cylindrical electrode does not occur, the number of coating formation species that contributes to the deposition increases, and the deposition rate on the substrate improves. To do.

In a specific configuration, bias plasma CVD is performed by applying a high frequency voltage to the substrate holder so that the self-bias generated in the substrate becomes negative.
The method is carried out, allowing for example the formation of a diamond-like coating.

If an electron cyclotron resonance plasma source is used as the plasma generating means, the plasma density can be further increased and a high quality coating can be formed at a low temperature.

Furthermore, if the cylindrical electrode is installed at a position surrounding the electron cyclotron resonance point of the electron cyclotron resonance plasma source, the film on the inner peripheral surface of the cylindrical electrode can be effectively treated by the high-density plasma. Sputter removal is performed.

In a specific coating film forming method, when the tubular electrode is made of a material containing a material having low adhesion to the coating film to be formed on the substrate, the coating film deposited on the inner peripheral surface of the tubular electrode is If the thickness exceeds a certain limit, peeling may occur, but at the same time when the thin film is formed on the substrate, the coating on the inner surface of the cylindrical electrode is removed by sputtering to keep the thickness of the coating below the limit and peeling. It is possible to prevent the occurrence of.

When the tubular electrode is made of a material containing a material having high adhesion to the film to be formed on the substrate,
Since there is no risk of peeling even if the coating becomes relatively thick, it is possible to remove the coating on the inner peripheral surface of the tubular electrode by sputtering after the formation of the coating on the substrate is completed.

In still another specific method, when the cylindrical electrode is formed from a material containing at least one of the constituent elements of the coating film to be formed on the substrate, the power of the plasma generating means is to some extent. By raising
The formation of a coating on the inner peripheral surface of the tubular electrode can be completely prevented, and furthermore, the material for the tubular electrode can be deposited on the substrate by sputtering with the tubular electrode itself as the target. As a result, the constituent elements of the tubular electrode can be included in the coating on the substrate, and the characteristics of the coating can be improved.

[0026]

According to the film forming method using the plasma CVD equipment according to the present invention, among the film forming species generated by the action of the plasma, and the number of film forming species than conventional deposited on the substrate A high quality coating can be formed at a high deposition rate.

[0027]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described in detail below with reference to the drawings. Apparatus Configuration In the plasma CVD apparatus used in the present invention, as shown in FIG. 1, a plasma generating chamber (4) and a reaction chamber in which a substrate (11) is to be installed are formed inside a vacuum chamber (10). The microwave generation device (1) is connected to the plasma generation chamber (4) through the waveguide (2). Waveguide (2)
A microwave introduction window at the connection between the plasma generation chamber and the plasma generation chamber (4)
(3) is provided. A discharge gas introduction pipe (5) for introducing a discharge gas such as argon (Ar) into the plasma generation chamber (4) is connected to the plasma generation chamber (4). Further, a plasma magnetic field generator (6) is provided so as to surround the plasma generation chamber (4).

The above-mentioned configuration is similar to that of the conventional device,
In the present invention, further, inside the plasma generation chamber (4),
A cylindrical electrode (7) is attached through a cylindrical insulator (8), and the cylindrical electrode (7) is attached to the cylindrical electrode (7).
High frequency power supply for applying high frequency voltage of 56MHz
(9) is connected.

Hereinafter, using the above plasma CVD apparatus,
A method of forming a diamond-like coating which is a hard carbon coating on a Si substrate will be specifically described with reference to a plurality of examples.

First Embodiment In this embodiment, the tubular electrode (7) is formed of stainless steel which has low adhesion to the diamond film. In this case, in order to prevent the coating film deposited on the inner peripheral surface of the tubular electrode (7) from peeling off, the tubular electrode is formed at the same time as the film formation on the substrate (11).
(7) The coating on the inner peripheral surface is removed.

First, the substrate (11) is mounted on the substrate holder (12), and the inside of the vacuum chamber (10) is set to 10 ^-5 to 10 ^-7 T.
Exhaust to orr. Next, from the discharge gas introduction pipe (5), Ar
The gas is supplied at 5.7 × 10 ⁻⁴ Torr and the microwave of 2.45 GHz and 300 W is supplied from the microwave generator (1) to generate the Ar plasma formed in the plasma generation chamber (4). It radiates to the surface of the substrate (11). At the same time, an RF voltage is applied from the high frequency power supply (9) to the stainless steel tubular electrode (7) to generate a self-bias of -400V.

At the same time, an RF voltage of 13.56 MHz is applied to the substrate holder (12) from the high frequency power source (13) so that the self-bias generated on the substrate (11) becomes -50V. From the reaction gas introduction pipe (14), CH ₄ gas was added to 1.3 ×
Supplied at 10 ^-3 Torr. The CH ₄ gas supplied from the reaction gas introduction pipe (14) is decomposed by the action of plasma, and the carbon generated by this is turned into a highly reactive ion or a neutral active state, and the carbon of the substrate (11) is discharged. Emitted to the surface.

The above steps were carried out for about 3 minutes to form a diamond-like coating (15) having a film thickness of 2600 angstroms on the surface of the substrate (11).

On the other hand, as a comparative example, RF is applied to the cylindrical electrode (7).
A diamond-like coating was formed on the surface of the substrate (11) under the same conditions as in Example 1 except that no voltage was applied. Then, according to the first example and the comparative example, the thickness of the diamond-like coating formed on each substrate and the thickness of the coating formed on the inner peripheral surface of the tubular electrode were measured.

As a result, as shown in Table 1 below, when the film thickness of the coating film formed on the inner peripheral surface of the cylindrical electrode of Comparative Example was 1,
The film thickness of the coating film formed on the inner peripheral surface of the cylindrical electrode of the first embodiment was 0.65.

[0036]

[Table 1]

As is clear from this result, according to the first embodiment, the coating film on the inner peripheral surface of the electrode can be made thinner by about 35% than the conventional one. It is considered that this is because the coating film on the inner peripheral surface of the electrode was sputtered by the self-bias voltage generated by the RF voltage applied to the electrode. Therefore, the first
According to the embodiment, the process can be performed for a long time until the thickness of the coating film on the inner peripheral surface of the electrode reaches its limit, and thus the thickness of the coating film on the substrate can be increased.

Further, Table 2 below compares the film thicknesses of the diamond-like coatings formed on the substrate in the above-mentioned first embodiment and comparative example.

[0039]

[Table 2]

As is clear from this result, according to the first embodiment, a diamond-like coating thicker than the conventional one can be obtained. It is considered that this is because the film forming species was radiated to the substrate surface by sputtering the film on the inner peripheral surface of the electrode and contributed to the film formation.

Second Embodiment In this embodiment, the cylindrical electrode (7) is formed by using Si, which has a high adhesiveness with the diamond film. In this case, since there is no fear that the coating film deposited on the inner peripheral surface of the tubular electrode (7) will be peeled off, the coating film on the inner peripheral surface of the electrode is removed after the film formation on the substrate (11) is completed.

First, the Si substrate (11) is placed on the substrate holder (12).
And attach the inside of the vacuum chamber (10) to 10 ^-5 to 10
-Exhaust to ⁷ Torr. Next, while supplying Ar gas at 5.7 × 10 ⁻⁴ Torr from the discharge gas introducing pipe (5),
2.45GHz, 300W from microwave generator (1)
To supply Ar plasma generated in the plasma generation chamber (4) to the substrate (11) surface.

At the same time, an RF voltage of 13.56 MHz is applied to the substrate holder (12) from the high frequency power source (13) so that the self-bias generated on the substrate (11) becomes -50V. From the reaction gas introduction pipe (14), CH ₄ gas was added to 1.3 ×
Supplied at 10 ^-3 Torr. The CH ₄ gas supplied from the reaction gas introduction pipe (14) is decomposed by the action of plasma, and the carbon generated by this is turned into a highly reactive ion or a neutral active state, and the carbon of the substrate (11) is discharged. Emitted to the surface.

The above steps were carried out for about 3 minutes to form a diamond-like coating (15) having a film thickness of 2400 angstroms on the surface of the substrate (11).

After that, Ar gas was supplied from the discharge gas introducing pipe (5) at 5.7 × 10 ⁻⁴ Torr, and microwave of 2.45 GHz and 300 W was supplied from the microwave generator (1), At the same time that Ar plasma is generated in the plasma generation chamber (4), an RF voltage is applied to the cylindrical electrode (7) from a high frequency power source (9) to generate a self-bias of -400V. Perform the above steps for about 30 minutes,
The coating film attached to the inner peripheral surface of the cylindrical electrode (7) is removed by sputtering.

Then, the thickness of the diamond-like coating formed on the substrate according to the second embodiment and the thickness of the coating formed on the inner peripheral surface of the tubular electrode were measured and compared with the above comparative example.

As a result, as shown in Table 3 below, when the film thickness of the coating film formed on the inner peripheral surface of the cylindrical electrode of Comparative Example was 1,
The film thickness of the coating film formed on the inner peripheral surface of the cylindrical electrode of the second embodiment was 0.81.

[0048]

[Table 3]

As is clear from this result, according to the second embodiment, the film adhered to the inner peripheral surface of the electrode can be effectively removed by sputtering. If the above process is further continued, it is possible to completely remove the coating film attached to the inner peripheral surface of the electrode.

Third Embodiment In this embodiment, the composition of the coating film formed on the Si substrate is controlled by using the above plasma CVD apparatus.
The apparatus configuration of this embodiment is the same as that of the second embodiment, and the film forming process is the same as that of the first embodiment, but the microwave power generated by the microwave generator (1) is 0. ~
The composition of the diamond-like coating (15) obtained on the substrate (11) under different microwave power is investigated by varying in the range of 800W.

First, the Si substrate (11) is placed on the substrate holder (12).
And attach the inside of the vacuum chamber (10) to 10 ^-5 to 10
-Exhaust to ⁷ Torr. Next, while supplying Ar gas at 5.7 × 10 ⁻⁴ Torr from the discharge gas introducing pipe (5),
The microwave of 2.45 GHz is supplied from the microwave generator (1) to generate Ar formed in the plasma generation chamber (4).
The plasma is radiated on the surface of the substrate (11). At the same time, S
RF from the high frequency power supply (9) to the cylindrical electrode (7) made of i
A voltage is applied to generate a self-bias of -500V.

At the same time, an RF voltage of 13.56 MHz is applied to the substrate holder (12) from the high frequency power source (13) so that the self-bias generated on the substrate (11) becomes -50V. From the reaction gas introduction pipe (14), CH ₄ gas was added to 1.3 ×
Supplied at 10 ^-3 Torr. The CH ₄ gas supplied from the reaction gas introduction pipe (14) is decomposed by the action of plasma, and the carbon generated by this is turned into a highly reactive ion or a neutral active state, and the carbon of the substrate (11) is discharged. Emitted to the surface.

As a result, a diamond-like coating (15) is formed on the surface of the substrate (11).

FIG. 2 shows the composition ratio of Si and C of the diamond-like coating film obtained in the third embodiment described above in relation to the microwave power. As shown in the figure, when the microwave power is 300 W or less, Si is not contained in the film.
Is included, and the amount of Si increases with the increase in microwave power.

This means that when the microwave power is 300 W or less, the coating film is deposited on the inner peripheral surface of the cylindrical electrode (7) at a low film forming rate, and the inner peripheral surface of the electrode is not sputtered, but the microwave power is increased. When the power exceeds 300 W, the amount of ions sputtered on the cylindrical electrode increases, so that the coating film on the inner peripheral surface of the electrode is completely removed by sputtering. Further, when the microwave power increases and the amount of ions increases, the Si electrode This is because the inner peripheral surface of No. 1 starts to be sputtered and the sputtered atoms mix into the coating film on the substrate.

Therefore, according to the third embodiment, by controlling the microwave power, it is possible to remove the coating adhered to the inner peripheral surface of the cylindrical electrode and control the composition of the coating formed on the substrate. is there.

The above description of the embodiments is for explaining the present invention, and should not be construed as limiting the invention described in the claims or limiting the scope. Further, the configuration of each part of the present invention is not limited to the above embodiment, but various modifications can be made within the technical scope described in the claims. For example, the cylindrical electrode (7) is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape, or a plurality of flat plate electrodes arranged in a circle to form a substantially cylindrical electrode. Needless to say, the same effect can be obtained. It is also possible to adopt a configuration in which a DC voltage is applied to the cylindrical electrode (7) to remove the coating film on the inner peripheral surface of the cylindrical electrode (7) by sputtering.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration of a plasma CVD apparatus used in the present invention.

FIG. 2 is a graph showing the relationship between the composition of a film formed on a substrate and microwave power.

FIG. 3 is a diagram showing a configuration of a conventional plasma CVD apparatus.

FIG. 4 is a cross-sectional view showing a state where a diamond-like coating is formed on a substrate.

[Explanation of symbols]

(1) Microwave generator (2) Waveguide (3) Microwave introduction window (4) Plasma generation chamber (5) Discharge gas introduction pipe (6) Plasma magnetic field generator (7) Cylindrical electrode (8) Insulator (10) Vacuum chamber (11) Substrate (12) Board holder

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Seiichi Kiyama 2-5-5 Keihan Hon-dori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. (56) Reference JP-A-4-291713 (JP, A) Special Features Kaihei 5-335279 (JP, A) JP-A-6-252054 (JP, A) JP-A-4-329679 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C23C 16 / 00-16/56 C30B 29/04 H01L 21/205 H01L 21/31 H05H 1/46

Claims (5)

(57) [Claims] 1. A substrate is coated on a substrate using a plasma CVD apparatus.
A method for forming a film, wherein a plasma CVD apparatus
Plasma is generated in the plasma generation chamber and the plasma generation chamber.
Connect to the plasma generating means and plasma generating chamber
Formed in the reaction chamber and the substrate heater provided in the reaction chamber.
And the reaction gas for introducing the reaction gas into the reaction chamber.
In addition to being equipped with a means for introducing a plasma,
A substantially cylindrical electrode is installed along the inner wall of the plasma generation chamber
And the tubular electrode has the coating film to be formed on the substrate.
It is made of materials including materials with low adhesion to
While plasma is generated in the plasma generation chamber,
By applying DC voltage or high frequency voltage to the electrode
The coating on the inner surface of the tubular electrode.
Using a plasma CVD apparatus characterized by removing
Film forming method. 2. The hard carbon coating is to be formed on the substrate.
The material having low adhesion is stainless steel, F
The alloy according to claim 1, which is e, Al, Cu, or Ti.
A film forming method using a plasma CVD apparatus. 3. A substrate is coated on the substrate by using a plasma CVD apparatus.
A method for forming a film, wherein a plasma CVD apparatus
Plasma is generated in the plasma generation chamber and the plasma generation chamber.
Connect to the plasma generating means and plasma generating chamber
Formed in the reaction chamber and the substrate heater provided in the reaction chamber.
And the reaction gas for introducing the reaction gas into the reaction chamber.
In addition to being equipped with a means for introducing a plasma,
A substantially cylindrical electrode is installed along the inner wall of the plasma generation chamber
And the tubular electrode has the coating film to be formed on the substrate.
It is made of materials including materials with high adhesion and
While plasma is generated in the plasma generation chamber,
By applying DC voltage or high frequency voltage to the electrode
The coating on the inner surface of the tubular electrode.
Using a plasma CVD apparatus characterized by removing
Film forming method. 4. A hard carbon coating is to be formed on the substrate.
The material having high adhesion is Si, C, Ru,
Alternatively, the plasma CVD apparatus according to claim 3, which is Ge.
A method for forming a film using. 5. A substrate is coated on the substrate using a plasma CVD apparatus.
A method for forming a film, wherein a plasma CVD apparatus
And the plasma generating chamber, of generating a plasma in a plasma generation chamber
Connect to the plasma generating means and plasma generating chamber
Formed in the reaction chamber and the substrate heater provided in the reaction chamber.
And the reaction gas for introducing the reaction gas into the reaction chamber.
In addition to being equipped with a means for introducing a plasma,
A substantially cylindrical electrode is installed along the inner wall of the plasma generation chamber
And the material of the tubular electrode is to be formed on the substrate.
Contain at least one of the constituent elements of the coating
The DC voltage is applied to the cylindrical electrode while forming the coating on the substrate.
Or by applying a high frequency voltage,
The surface is sputtered and the material for the cylindrical electrode is deposited on the substrate.
Film formation using a plasma CVD apparatus characterized by
Method.