JP3025743B2 - Hard carbon film forming equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cutting tool such as an electric razor and an apparatus for forming a hard carbon film on the surface of a thin film head semiconductor material. The present invention relates to a device for performing

[0002]

2. Description of the Related Art Conventionally, an apparatus for forming a hard carbon film by a bias plasma CVD method is disclosed in
An apparatus disclosed in JP-A-175620 is known.
This device forms a diamond-like film as a hard carbon film on a substrate by a bias plasma CVD method using an ECR (Electron Cyclotron Resonance) plasma CVD device.

FIG. 12 is a schematic diagram showing an apparatus for forming such a conventional diamond-like coating. Referring to FIG. 12, the microwave generated by microwave supply means 1 is guided to plasma generation chamber 4 through waveguide 2 and microwave introduction window 3. The plasma generation chamber 4 is provided with a discharge gas introduction pipe 5 for introducing a discharge gas such as an argon (Ar) gas. A plasma magnetic field generator 6 is provided around the plasma generation chamber 4.
High frequency magnetic field generated by microwave and plasma magnetic field generator 6
A high-density plasma is formed in the plasma generation chamber 4 by the action of the magnetic field. This plasma is guided to a vacuum chamber 8 in which a substrate 7 is arranged, along a divergent magnetic field generated by a plasma magnetic field generator 6.

A reaction gas introduction pipe 9 for introducing methane (CH ₄ ) gas as a source gas is provided in the vacuum chamber 8. The methane gas introduced into the vacuum chamber 8 by the reaction gas introduction pipe 9 is decomposed by the action of plasma to form a carbon film. Outside the chamber 8, for example, a 13.56 MHz high frequency power source 1
0 is provided, and a predetermined high-frequency voltage (RF voltage) is applied to the substrate holder 11 by the high-frequency power supply 10, thereby generating a negative self-bias on the substrate 7. Since the moving speed of ions in plasma is lower than that of electrons, electrons follow the potential fluctuation during application of the RF voltage, but ions cannot follow. Therefore, when the RF voltage is applied to the substrate 7, many electrons are emitted to the substrate 7, and a negative self-bias is generated in the substrate 7. Therefore, positive ions in the plasma are attracted, and a diamond-like film is formed on the substrate 7.

[0005]

In such a conventional apparatus, a film is formed by mounting a substrate on a substrate holder in a vacuum chamber and then performing vacuum evacuation. Therefore, the number of substrates on which a film can be formed in one process is one,
Or at most two.

Further, in the conventional apparatus, electric discharge occurs near the substrate other than the portion where the film is mounted on the substrate holder.
There is a problem that the temperature of the substrate rises due to this discharge.

An object of the present invention is to provide a hard carbon coating capable of simultaneously processing a plurality of substrates by a single process, preventing an excessive rise in temperature of the substrate, and forming a hard carbon coating on the substrate. An object of the present invention is to provide a forming apparatus.

[0008]

The apparatus for forming a hard carbon film according to the present invention is an apparatus for forming a hard carbon film on a substrate, comprising a vacuum chamber, a substrate holder rotatably provided in the vacuum chamber. A shield cover provided so as to surround the peripheral surface of the substrate holder and having an opening in a part thereof, and plasma generating means for generating plasma in the vacuum chamber and radiating the plasma toward the substrate through the opening. A reactive gas introducing means for supplying a reactive gas containing carbon into the plasma from the plasma generating means, and a high frequency power supply for applying a high frequency voltage to the substrate holder so that the self-bias generated on the substrate becomes negative. .

A hard carbon film forming apparatus according to a first aspect of the present invention is an apparatus for forming an intermediate layer on a substrate and forming a hard carbon film on the intermediate layer, comprising: a vacuum chamber; A substrate holder rotatably provided in the chamber, a shield cover provided so as to surround a peripheral surface of the substrate holder and having first and second openings in a part thereof, and a plasma generated in a vacuum chamber. Generating means for emitting a reaction gas containing carbon into the plasma from the plasma generating means, and a self-bias generated in the substrate being negative. A high-frequency power source for applying a high-frequency voltage to the substrate holder, and an intermediate layer formed in the vacuum chamber to emit material atoms constituting the intermediate layer toward the substrate through the second opening. And a stage.

An apparatus according to a second aspect of the present invention is the apparatus according to the first aspect, wherein the intermediate layer forming means is provided in the vacuum chamber and directs the intermediate layer toward the substrate through the second opening. It is characterized by comprising an evaporation source that emits constituent material atoms, and an ion gun that emits inert gas ions toward the substrate through the second opening simultaneously with the emission of the material atoms from the evaporation source.

[0011] An apparatus according to a third aspect of the present invention is the apparatus according to the first aspect, wherein the intermediate layer forming means is provided in a vacuum chamber and transfers material atoms constituting the intermediate layer through the second opening. And a target made of the material atoms for sputtering toward a substrate, and an ion gun for emitting inert gas ions toward the target to sputter the target.

In the present invention, the plasma generating means is preferably an electron cyclotron resonance plasma CV.
A D device is used. In the present invention, the shield cover is preferably provided at a distance from the peripheral surface of the substrate holder equal to or less than the mean free path of the gas molecules. More preferably, the shield cover is provided at a distance of 1/10 or less of the mean free path of the gas molecules from the peripheral surface of the substrate holder.

In the present invention, the shield cover is preferably maintained at a predetermined potential, and is more preferably grounded. In the present invention, the material atoms forming the intermediate layer are, for example, Si, Ru, carbon, Ge, or a mixture of these elements and at least one element of carbon, nitrogen, and oxygen. Or Al
A hard carbon coating is formed on a substrate made of a metal or alloy mainly composed of, or stainless steel, via such an intermediate layer.

The concept of hard carbon coating in the present invention includes crystalline diamond and amorphous diamond-like coating.

[0015]

The apparatus of the present invention includes a substrate holder rotatably provided in a vacuum chamber. Therefore, a plurality of substrates can be mounted on the substrate holder, and the number of substrates that can be processed by one evacuation can be increased.

In the present invention, a shield cover is provided so as to surround the peripheral surface of the substrate holder. Plasma is radiated from the plasma generating means through the opening of the shield cover, and a hard carbon coating is formed on the substrate. Is formed. With such a shield cover, it is possible to prevent the occurrence of electric discharge in a portion other than the portion where the film is formed, and it is possible to suppress the temperature rise of the substrate.

According to a first aspect of the present invention, there is provided an intermediate layer forming means for radiating material atoms forming the intermediate layer toward the substrate through the second opening of the shield cover. Therefore, the formation of the intermediate layer and the formation of the hard carbon film can be performed by one evacuation. Further, the formation of the hard carbon coating and the formation of the intermediate layer can be individually controlled. Therefore, after forming a desired intermediate layer on a substrate, a hard carbon coating can be formed.

When forming the intermediate layer, the deposition of the carbon film by the plasma CVD method through the first opening and the deposition of the material atoms constituting the intermediate layer through the second opening are alternately performed. By repeating, the material composition ratio of the intermediate layer can be controlled as desired. Therefore, as the material composition ratio of the intermediate layer approaches the hard carbon coating, a gradient structure that gradually approaches the composition of the hard carbon coating can be obtained. By forming an intermediate layer having such a gradient structure,
It is possible to further improve the adhesion between the substrate and the hard carbon coating.

[0019]

FIG. 1 is a schematic sectional view showing an apparatus for forming a hard carbon film in one embodiment of the present invention. Referring to FIG. 1, a plasma generation chamber 4 is provided in a vacuum chamber 8. One end of the waveguide 2 is attached to the plasma generation chamber 4, and the microwave supply means 1 is provided at the other end of the waveguide 2. Microwave supply means 1
The microwave generated in the above is guided to the plasma generation chamber 4 through the waveguide 2 and the microwave introduction window 3. Argon (Ar) is contained in the plasma generation chamber 4.
A discharge gas introduction pipe 5 for introducing a discharge gas such as a gas is provided. A plasma magnetic field generator 6 is provided around the plasma generation chamber 4. A high-density plasma is formed in the plasma generation chamber 4 by applying a high-frequency magnetic field generated by a microwave and a magnetic field from the plasma magnetic field generator 6.

A cylindrical substrate holder 1 is provided in a vacuum chamber 8.
2 are provided. The cylindrical substrate holder 12 is rotatably provided around an axis (not shown) provided perpendicular to the wall surface of the vacuum chamber 8. A plurality of substrates 13 are mounted at equal intervals on the peripheral surface of the substrate holder 12. In this embodiment, a nickel (Ni) substrate is used as the substrate 13, and 24 pieces are mounted on the peripheral surface of the substrate holder 12. The high frequency power supply 10 is connected to the substrate holder 12.

Around the substrate holder 12, a metal cylindrical shield cover 14 is provided at a predetermined distance. This shield cover 14 is connected to a ground electrode. The shield cover 14 is provided in order to prevent a discharge from being generated between the substrate holder 12 and the vacuum chamber 8 other than where the film is formed due to the RF voltage applied to the substrate holder 12 when the film is formed. Have been.
The gap between the substrate holder 12 and the shield cover 14 is
It is arranged so that the distance is less than the mean free path of the gas molecules. The mean free path of a gas molecule is equal to or less than the average distance that ions and electrons generated for some reason can be accelerated by an electric field and move without collision. Therefore, the substrate holder 12 and the shield cover 14
Is smaller than the mean free path of the gas molecules, thereby reducing the probability that ions and electrons collide with the gas molecules, thereby preventing chain ionization from proceeding.

The gap between the substrate holder 12 and the shield cover 14 is preferably set to a distance of not more than 1/10 of the mean free path of gas molecules. In the present embodiment, the gap between the substrate holder 12 and the shield cover 14 is set to about 5 mm, which is 1/10 or less of the mean free path of gas molecules.

An opening 15 is formed in the shield cover 14.
Has been established. Through this opening 15, plasma is generated
Plasma extracted from chamber 4 is mounted on substrate holder 12
It is radiated to the substrate 13 that has been cut. Vacuum
A reaction gas introduction pipe 16 is provided in the chamber 8.
You. The tip of the reaction gas introduction pipe 16 is located above the opening 15.
Located at FIG. 2 shows the tip of the reaction gas introduction pipe 16.
It is a top view which shows a part vicinity. Referring to FIG.
The gas introduction pipe 16 is provided with CH _Fourgas
Gas introducing section 16a for introducing gas, and the gas introducing section 16a
And a gas discharge portion 16b connected in the vertical direction.
Have been. The gas release unit 16b rotates the substrate holder 12.
It is arranged in a direction perpendicular to the direction A, and
It is provided so as to be located on the upstream side in the upper rotation direction.
You. The gas discharge part 16b has a downward direction of about 45 degrees.
A plurality of holes 21 are formed in the direction. In this embodiment, 8
Individual holes 21 are formed. Is the space between holes 21 central?
Is gradually narrowed toward both sides
I have. By forming the holes 21 at such intervals,
CH introduced from the gas introduction part 16a_FourGas
Are almost uniformly discharged from the holes 21.

An embodiment in which a diamond-like film as a hard carbon film is formed on a nickel substrate using the apparatus shown in FIG. 1 will be described below. First, 24 Ni substrates 13 are mounted on the peripheral surface of the substrate holder 12 at equal intervals.
Next, the inside of the vacuum chamber 8 is evacuated to 10 ^-5 to 10 ^-7 Torr, and the substrate holder 12 is rotated at a speed of about 10 rpm. Next, the discharge gas introduction pipe 5 of the ECR plasma generator is used.
Supply Ar gas at 5.7 × 10 ^-4 Torr and microwave supply means 1 at 2.45 GHz,
A microwave of 0 W is supplied to emit Ar plasma formed in the plasma generation chamber 4 to the surface of the substrate 13. At the same time, the self-bias generated in the substrate 13 becomes −20.
13.56 MHz from the high frequency power supply 10 so that V
Is applied to the substrate holder 12. CH ₄ gas is supplied from the reaction gas introduction pipe 16 at 1.3 × 10 ⁻³ Torr. The CH ₄ gas supplied from the reaction gas introduction pipe 16 is decomposed by the action of the plasma, and the carbon is converted into highly reactive ions or a neutral active state, and is emitted to the surface of the substrate 13.

The above steps are performed for about 15 minutes, and the substrate 1
A diamond-like film having a thickness of 1200 ° was formed on the surface of Sample No. 3. FIG. 10 is a sectional view showing the diamond-like film formed on the substrate in this manner. Referring to FIG. 10, a diamond-like film 21 is formed on substrate 13.

FIG. 3 shows the above embodiment (hereinafter referred to as "Embodiment 1").
FIG. 4 is a diagram showing a relationship between a film formation time and a substrate temperature in the following. Also, in FIG. 3, for comparison, Comparative Example 1 in which a diamond-like coating was formed in the same manner as in Example 1 except that the substrate holder was not rotated, and the apparatus without the shield cover was used without rotating the substrate holder. 9 shows data of Comparative Example 2 in which a diamond-like film was formed.
As shown in FIG. 3, the substrate temperature was about 45 ° C. in Example 1 after 15 minutes of film formation,
The temperature is about 60 ° C. in Comparative Example 1, and about 150 ° C. in Comparative Example 2.
It has become. The reason why the substrate temperature was extremely high in Comparative Example 2 is considered to be that discharge occurred between the substrate holder 12 and the vacuum chamber 8 except for the portion where the film was formed. In Comparative Example 1, the substrate temperature was lower than in Comparative Example 2,
It can be seen that the provision of the shield cover lowers the substrate temperature. Comparing Example 1 with Comparative Example 1, Example 1 has a lower substrate temperature. In the first embodiment, since the substrate holder is rotated, the portion heated by the plasma discharge moves sequentially, and it is considered that the increase in the substrate temperature is suppressed. According to the present invention, an increase in the substrate temperature can be suppressed, so that the type of the substrate can be selected without considering the heat resistance of the substrate.

Hereinafter, an embodiment in which an intermediate layer is formed on a substrate and a diamond-like coating which is a hard carbon coating is formed on the intermediate layer will be described. FIG. 11 is a sectional view of an embodiment in which an intermediate layer is formed on a substrate and a hard carbon film is formed on the intermediate layer. Referring to FIG.
An intermediate layer 22 is formed on the intermediate layer 22.
A hard carbon film 21 is formed thereon.

FIG. 4 is a schematic sectional view showing an apparatus for forming a hard carbon film of an embodiment according to the first and second aspects of the present invention. Referring to FIG. 4, a shield cover 44 is provided around substrate holder 12 provided in vacuum chamber 8. The shield cover 44 has a first opening 45 and a second opening 43. In this embodiment, the first opening 45 and the second opening 43 are formed at substantially opposite positions. The shield cover 44 is connected to a ground electrode. The first opening 45 is formed in the same manner as the opening 15 shown in FIG. 1, and the tip of the reaction gas introduction pipe 16 is located above the first opening 45 similarly to the apparatus shown in FIG. 1. ing.

Below the second opening 43, there is provided an evaporation source 41 for evaporating the material atoms constituting the intermediate layer by an electron beam and radiating it toward the substrate 13. In the vicinity of the evaporation source 41, an ion gun 42 for emitting ions of an inert gas is provided in order to apply energy to material atoms evaporated from the evaporation source 41. In this embodiment, Ar gas is used as the inert gas. In this embodiment, the evaporation source 41 and the ion gun 42
An intermediate layer forming means is configured. Material atoms constituting the intermediate layer are emitted onto the substrate 13 through the second opening 43 by the evaporation source 41 and the ion gun 42.

Other configurations are the same as those of the embodiment shown in FIG. 1, and therefore, the same reference numerals are given and the description is omitted.

An embodiment in which an intermediate layer is formed from a single element as the intermediate layer and a diamond-like coating is formed on the intermediate layer will be described below. First, as in the first embodiment, 24 Ni substrates 13 are mounted on the peripheral surface of the substrate holder 12 at equal intervals. 10 ^-5 to 10 ^-7 in the vacuum chamber 8
After exhausting to Torr, the substrate holder 12 is rotated at a speed of about 10 rpm. Next, an Ar gas is supplied to the ion gun 42 to extract Ar ions, which are emitted to the surface of the substrate 13. At this time, the acceleration voltage of Ar ions is 40
0 eV and the ion current density were set to 0.3 mA / cm ² . Simultaneously with the emission of the Ar ions, the evaporation source 41 is driven to evaporate Ru atoms and emit them to the surface of the substrate 12.
At this time, the evaporation rate of Ru was set to be 420 ° / min in terms of the deposition rate on the substrate 13. The above process is performed for about 5 minutes, and the surface of
An intermediate layer made of u was formed.

Next, from the evaporation source 41 and the ion gun 42,
After stopping the emission of Ru atoms and Ar ions,
4. Ar gas is supplied from discharge gas introduction pipe 5 of the plasma generator.
7 × 10^-FourTorr and microwave
2.45 GHz, 100 W microwave from the feeding means 1
To supply the Ar plasma formed in the plasma generation chamber 4.
The light is emitted to the surface of the substrate 13. At the same time, the substrate 1
3 so that the self-bias generated at 3 becomes -20V.
RF power of 13.56 MHz from the
To the reaction gas inlet tube 16_Fourgas
Is 1.3 × 10 ^-3Supplied in Torr. About the above process
15 minutes, and the film thickness is formed on the intermediate layer formed on the substrate 13.
A 1200 ° diamond-like coating was formed.

As a result of the above two steps, as shown in FIG. 11, an intermediate layer 22 made of Ru is formed on the surface of the substrate 13, and a laminated thin film in which the diamond-like film 21 is formed on the intermediate layer 22 is obtained. Was done. By forming such an intermediate layer 22, the stress in the diamond-like coating 21 can be reduced, and the adhesion between the substrate 13 and the diamond coating 21 can be improved. The presence of the intermediate layer 22 can relieve the thermal stress caused by the difference in the coefficient of thermal expansion between the substrate 13 and the diamond-like coating 21, so that the stress in the diamond-like coating 21 can be reduced. Conceivable.

An embodiment in which a mixed layer of material atoms and carbon is formed as an intermediate layer and a diamond-like coating is formed on the intermediate layer will be described below. In this embodiment, FIG.
A device similar to the device shown in (1) is used.

First, as in the first embodiment, 24 Ni substrates 13 are mounted on the peripheral surface of the substrate holder 12 at equal intervals. 10 ^-5 to 10 ^-7 Torr in the vacuum chamber 8
And the substrate holder 12 is rotated at a speed of about 10 rpm.

Next, while supplying Ar gas at 5.7 × 10 ^-4 Torr from the discharge gas introducing pipe 5 of the ECR plasma generator, the microwave supply means 1 supplies 2.45 GHz.
A microwave of z, 100 W is supplied to radiate the Ar plasma formed in the plasma generation chamber 4 to the surface of the substrate 13. At the same time, the high frequency power supply 10 supplies 13.5 V so that the self-bias generated in the substrate 13 becomes -20V.
An RF voltage of 6 MHz is applied to the substrate holder 12 and CH ₄ gas is supplied from the reaction gas introduction pipe 16. C at this time
As shown in FIG. 5, the supply amount of the H ₄ gas is gradually increased with the passage of time, and is set to 100 sccm, that is, 1.3 × 10 ⁻³ Torr after 5 minutes.

At the same time as the film forming process by the ECR plasma generator, the ion gun 42
While emitting r ions, the evaporation source 41 emits Ru atoms. At this time, the acceleration voltage of Ar ions is set to 400
eV and ion current density are set to 0.3 mA / cm ² . Further, as shown in FIG.
The film forming speed is gradually reduced from 420 ° / min. As the time elapses, and is set to 0 ° / min. After 5 minutes. When the evaporation rate of Ru reaches 0 ° / min, that is, after 5 minutes, Ar from the ion gun 42
Stop emitting ions.

As described above, the formation of the carbon film by the plasma CVD method in the first opening 45 and the formation of the second opening 43
Is performed at the same time, an intermediate layer in which Ru and C are mixed is formed as an intermediate layer. In this embodiment, by performing the above steps for about 5 minutes, the substrate 13
A mixed layer of Ru and C having a total film thickness of 200 ° was formed on the surface of. As shown in FIGS. 5 and 6, over time, R
The amount of deposited u is reduced and the amount of carbon film formed is increased. Therefore, the intermediate layer has a gradient structure in which the Ru content gradually decreases and the C content gradually increases as the distance from the surface of the substrate 13 increases.

Next, on the intermediate layer thus formed,
A diamond-like coating was formed. The supply partial pressure of the CH ₄ gas supplied from the reaction gas introduction pipe 16 is set to 1.3 × 10 ⁻³ To.
rr is kept constant, and the film formation processing by the ECR plasma generator in the above process is continuously performed. This step is performed for about 15 minutes, and a film thickness of 1200
Was formed.

As a result, a laminated film was formed on the substrate in which an intermediate layer of Ru and C having a graded structure and a diamond-like film were laminated. With the intermediate layer having such a tilted structure, the adhesion between the substrate and the diamond-like coating can be enhanced as compared with the intermediate layer of the single element.

Hereinafter, an evaluation test of the adhesion of the diamond-like film formed by using the apparatus of the above embodiment was performed. As a sample, a sample in which a diamond-like film was directly formed on a Ni substrate (Example 1), a sample in which an intermediate layer made of Ru was formed on a Ni substrate, and a diamond-like film was formed on this intermediate layer (Example 1) 2) Ru on Ni substrate
A sample in which an intermediate layer composed of a mixed layer of C and C was formed, and a diamond-like coating was formed on the intermediate layer (Example 3),
A sample (Example 4) was used in which an Si evaporation source was used as an evaporation source, an intermediate layer made of Si was formed on a Ni substrate, and a diamond-like coating was formed on the intermediate layer. The adhesion was evaluated using a constant load (load = 1) using a Vickers indenter.
kg). 50 samples
The number was evaluated by counting the number of detached diamond-like films on the Ni substrate. Table 1 shows the results.

[0042]

[Table 1]

As is clear from Table 1, Examples 2, 3 and 4 in which the intermediate layer was provided were Examples 1 to 3 in which the intermediate layer was not provided.
The number of occurrences of peeling is smaller than that. Therefore, it is understood that the adhesion of the diamond-like coating is improved by providing the intermediate layer. In particular, as is apparent from Example 3, it can be seen that the adhesion of the diamond-like coating is dramatically improved by forming the intermediate layer having the inclined structure composed of Ru and C.

As is clear from the comparison between Example 2 and Example 4, it is understood that Ru is superior to Si as a material atom constituting the intermediate layer with respect to the Ni substrate.

FIG. 7 is a schematic sectional view showing an apparatus for forming a hard carbon film of an embodiment according to the first and third aspects of the present invention. Referring to FIG. 7, a shield cover 44 is provided around substrate holder 12 provided in vacuum chamber 8. The shield cover 44 has a first opening 45 and a second opening 43. In this embodiment, the first opening 45 and the second opening 43 are formed at substantially opposite positions. The shield cover 44 is connected to a ground electrode. The first opening 45 is formed in the same manner as the opening 15 shown in FIG. 1, and the tip of the reaction gas introduction pipe 16 is located above the first opening 45 similarly to the apparatus shown in FIG. 1. ing.

Below the second opening 43, a target 46 made of material atoms constituting the intermediate layer is provided. In the vicinity of the target 46, ions of an inert gas are sputtered on the target 4 to sputter the target 46.
6 is provided with an ion gun 47 for emitting radiation. In this embodiment, Ar gas is used as the inert gas. In the present embodiment, the target 46 and the ion gun 47 constitute an intermediate layer forming unit. In this embodiment, a thin film head 48 is mounted on the substrate holder 12 as a substrate. The target 46 and the ion gun 47 emit the material atoms constituting the intermediate layer onto the thin film head 48 through the second opening 43.

The ions from the ion gun 47 irradiate not only the target 46 but also the thin film head 48.

The other structure is the same as that of the embodiment shown in FIG. 1, and therefore, the same reference numerals are given and the description is omitted.

An embodiment in which an intermediate layer is formed from a single element as the intermediate layer and a diamond-like coating is formed on the intermediate layer will be described below. First, 24 thin film heads 48 are provided on the peripheral surface of the substrate holder 12 in the same manner as in the first embodiment.
Are installed at equal intervals. 10 ^-5 to 10 in the vacuum chamber 8
^-7 Torr and evacuate the substrate holder 12 to about 10 rpm.
Rotate at speed. Next, Ar gas is supplied to the ion gun 47 to take out Ar ions and emit them to the surface of the target 46 made of Si. At this time, the acceleration voltage of Ar ions was 900 eV, and the ion current density was 0.3
mA / cm ² was set. Perform the above steps for about 2 minutes,
On the surface of the thin film head 48, an intermediate layer made of Si having a thickness of 60 ° was formed.

Next, after the emission of Ar ions from the ion gun 47 is stopped, Ar gas is supplied at 5.7 × 10 ^-4 Torr from the discharge gas introduction pipe 5 of the ECR plasma generator, and microwave supply means is provided. 1 to 2.45GH
A microwave of z, 100 W is supplied to radiate the Ar plasma formed in the plasma generation chamber 4 to the surface of the thin film head 48. At the same time, the high frequency power supply 10 is set so that the self-bias generated in the thin film head 48 becomes -20V.
13.56 MHz RF voltage is applied to the substrate holder 12, and CH ₄ gas is supplied from the reaction gas introduction pipe 16 to 1.3 × 1.
Supply at 0 ^-3 Torr. The above process is performed for about 2.5 minutes, and a film thickness of 20 is formed on the intermediate layer formed on the thin film head 48.
A diamond-like coating of 0 ° was formed.

As a result of the above two steps, the thin film head 48
An intermediate layer made of Si was formed on the surface of the substrate, and a laminated thin film having a diamond-like film formed on the intermediate layer was obtained. By forming such an intermediate layer, the stress in the diamond-like coating can be reduced, and the adhesion between the substrate and the diamond coating can be improved. Due to the presence of the intermediate layer,
It is considered that the thermal stress generated due to the difference in the coefficient of thermal expansion between the substrate and the diamond-like coating can be reduced, so that the stress in the diamond-like coating can be reduced. In forming the intermediate layer, not only the target but also the thin film head are irradiated with Ar ions, so that an intermediate layer having higher adhesion is formed.

An embodiment in which a mixed layer of material atoms and carbon is formed as an intermediate layer and a diamond-like coating is formed on the intermediate layer will be described below. In this embodiment, FIG.
A device similar to the device shown in (1) is used.

First, 24 thin film heads 48 are mounted on the peripheral surface of the substrate holder 12 at equal intervals. Vacuum chamber 8
The inside is evacuated to 10 ^-5 to 10 ^-7 Torr, and the substrate holder 1 is evacuated.
2 is rotated at a speed of about 10 rpm.

Next, Ar gas is supplied at 5.7 × 10 ^-4 Torr from the discharge gas inlet pipe 5 of the ECR plasma generator, and 2.45 GH is supplied from the microwave supply means 1.
A microwave of z, 100 W is supplied to radiate the Ar plasma formed in the plasma generation chamber 4 to the surface of the thin film head 48. At the same time, the high frequency power supply 10 is set so that the self-bias generated in the thin film head 48 becomes -20V.
13.56 MHz RF voltage is applied to the substrate holder 12, and CH ₄ gas is supplied from the reaction gas introduction pipe 16.
At this time, the supply amount of CH ₄ gas was changed as shown in FIG.
Gradually increase with time, 100s after 3 minutes
ccm, that is, 1.3 × 10 ⁻³ Torr.

At the same time as the film formation processing by the ECR plasma generator, the ion gun 47
Emits Ar ions. At this time, the acceleration voltage of the Ar ions was 900 eV, and the ion current density was 0.3 mA / c.
It is set to m ^2. Further, as shown in FIG. 9, the ion current density is gradually decreased with time,
Set to be mA / cm ² .

As described above, the formation of the carbon film in the first opening 45 by the plasma CVD method and the formation of the second opening 43
Is performed simultaneously, thereby forming an intermediate layer in which Si and C are mixed as an intermediate layer. In this embodiment, by performing the above steps for about 3 minutes, the total thickness of Si and C
Was formed. As shown in FIGS. 8 and 9, the amount of Si is reduced and the amount of carbon film formed is increased with time. Therefore, in this intermediate layer, the thin film head 4
8, the Si content gradually decreases as the distance from the surface increases,
It has a gradient structure in which the content of C gradually increases.

Next, on the intermediate layer thus formed,
A diamond-like coating was formed. The supply partial pressure of the CH ₄ gas supplied from the reaction gas introduction pipe 16 is set to 1.3 × 10 ⁻³ To.
rr is kept constant, and the film formation processing by the ECR plasma generator in the above process is continuously performed. This process is performed for about 2.5 minutes, and a film thickness of 2 is formed on the intermediate layer of the thin film head 48.
A diamond-like coating of 00 ° was formed.

As a result, a laminated film was formed on the substrate by laminating an intermediate layer made of Si and C having a graded structure and a diamond-like film. With the intermediate layer having such a tilted structure, the adhesion between the substrate and the diamond-like coating can be enhanced as compared with the intermediate layer of the single element.

In the above embodiment, an ECR plasma generator has been described as an example of the plasma generating means. However, the present invention is not limited to this. For example, other plasmas such as a high-frequency plasma CVD apparatus and a DC plasma CVD apparatus may be used. A CVD device can be used.

[0060]

According to the apparatus of the present invention, a cylindrical substrate holder is provided in a vacuum chamber, and a large number of substrates can be mounted on the substrate holder. Therefore, the number of substrates that can be processed by one evacuation can be increased.

Further, since the shield cover is provided around the substrate holder, it is possible to prevent discharge from occurring in the vicinity of the substrate other than where the film is formed. Therefore, it is possible to form a film while maintaining the substrate at a low temperature, and it is not necessary to consider the heat resistance of the substrate.

In the apparatus according to the first aspect of the present invention, an intermediate layer forming means is further provided. Therefore, the intermediate layer can be formed on the substrate in one evacuation step.

Further, the thin film forming step by the plasma generating means and the thin film forming step by the intermediate layer forming means are alternately performed,
By changing the conditions for forming each thin film, the material composition ratio of the intermediate layer can be changed. Therefore, an intermediate layer having an inclined structure can be formed as the intermediate layer, and the adhesion between the substrate and the hard carbon coating can be further improved.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an apparatus for forming a hard carbon film according to an embodiment of the present invention.

FIG. 2 is a plan view showing the vicinity of a tip portion of a reaction gas introduction pipe in the embodiment shown in FIG.

FIG. 3 is a diagram showing a relationship between a film forming time and a substrate temperature in an example according to the present invention.

FIG. 4 is a schematic cross-sectional view showing an apparatus for forming a hard carbon film according to a second embodiment of the present invention.

FIG. 5 is a graph showing the relationship between the film formation time and C when forming an intermediate layer having an inclined structure using the apparatus of the embodiment according to the second aspect of the present invention.
Diagram showing the relationship between the H ₄ flow rate.

FIG. 6 is a diagram showing a relationship between a film forming time and an evaporation rate when an intermediate layer having an inclined structure is formed using the apparatus according to the second embodiment of the present invention.

FIG. 7 is a schematic cross-sectional view showing an apparatus for forming a hard carbon film of an example according to a third aspect of the present invention.

FIG. 8 is a graph showing the relationship between the film formation time and C when forming an intermediate layer having an inclined structure using the apparatus of the embodiment according to the third aspect of the present invention.
Diagram showing the relationship between the H ₄ flow rate.

FIG. 9 is a diagram showing a relationship between a film formation time and an ion current density when an intermediate layer having an inclined structure is formed using the apparatus according to the embodiment according to the third aspect of the present invention.

FIG. 10 is a sectional view of an embodiment in which a diamond-like coating is formed directly on a substrate.

FIG. 11 is a sectional view of an embodiment in which an intermediate layer is formed on a substrate and a diamond-like film is formed thereon.

FIG. 12 is a schematic sectional view showing a conventional hard carbon film forming apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Microwave supply means 2 ... Waveguide 3 ... Microwave introduction window 4 ... Plasma generation chamber 5 ... Discharge gas introduction pipe 6 ... Magnetic field generation means 8 ... Vacuum chamber 10 ... High frequency power supply 12 ... Substrate holder 13 ... Substrate 14 ... Shield cover 15 ... Opening 16 ... Reaction gas introduction pipe 41 ... Evaporation source 42 ... Ion gun 43 ... Second opening 44 ... Shield cover 45 ... First opening 46 ... Target 47 ... Ion gun

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiichi Kiyama 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (56) References JP-A-3-177576 (JP, A) JP-A-5-140730 (JP, A) JP-A-4-346653 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 16/00-16/54

Claims (11)

(57) [Claims] 1. An apparatus for forming a hard carbon film on a substrate, comprising: a vacuum chamber; a substrate holder rotatably provided in the vacuum chamber; and a device surrounding a peripheral surface of the substrate holder. is, have a opening in a part thereof, further a sea <br/> Rudokaba held at a predetermined potential, the plasma is generated within the vacuum chamber, the plasma in the substrate through the opening Plasma generating means for radiating toward the substrate, a reactive gas introducing means for supplying a reactive gas containing carbon into the plasma from the plasma generating means, and a high frequency voltage applied to the substrate so that a self-bias generated in the substrate becomes negative. A high-frequency power supply to be applied to the holder; 2. An apparatus for forming a hard carbon film on a substrate, comprising: a vacuum chamber; a substrate holder rotatably provided in the vacuum chamber; and a device surrounding a peripheral surface of the substrate holder. is, have a opening in a part thereof, further a shield cover is grounded, the plasma is generated within the vacuum chamber, plasma generating means for radiating toward the substrate to the plasma through the opening A reaction gas introduction unit that supplies a reaction gas containing carbon in plasma from the plasma generation unit; and a high-frequency power supply that applies a high-frequency voltage to the substrate holder so that a self-bias generated in the substrate becomes negative. A hard carbon film forming apparatus comprising: 3. An apparatus for forming an intermediate layer on a substrate and forming a hard carbon coating on the intermediate layer, comprising: a vacuum chamber; and a substrate holder rotatably provided in the vacuum chamber. , provided so as to surround the periphery of the substrate holder, a part of the have a first and a second opening, further maintained at a predetermined potential
A shield cover that is, the plasma is generated within the vacuum chamber, and a plasma generating means for radiating toward the substrate to the plasma through the first opening, the carbon in the plasma from the plasma generation means A reactive gas introducing means for supplying a reactive gas containing: a high-frequency power supply for applying a high-frequency voltage to the substrate holder such that a self-bias generated in the substrate is negative; An intermediate layer forming means for radiating material atoms constituting the intermediate layer toward the substrate via the opening; and a hard carbon film forming apparatus. 4. An apparatus for forming an intermediate layer on a substrate and forming a hard carbon coating on the intermediate layer, comprising: a vacuum chamber; and a substrate holder rotatably provided in the vacuum chamber. , provided so as to surround the periphery of the substrate holder, the first, and have a second opening in a part thereof, and <br/> shield cover being further grounded, the plasma in the vacuum chamber A plasma generating means for generating and radiating the plasma toward the substrate through the first opening; a reactive gas introducing means for supplying a reactive gas containing carbon into the plasma from the plasma generating means; A high-frequency power supply for applying a high-frequency voltage to the substrate holder so that a self-bias generated in the substrate becomes negative; and an intermediate layer provided in the vacuum chamber and facing the substrate through the second opening. An intermediate layer forming means for radiating material atoms constituting: a hard carbon film forming apparatus. 5. An evaporation source provided in the vacuum chamber, wherein the evaporation source emits material atoms constituting the intermediate layer toward the substrate through the second opening, and The hard carbon film formation according to claim 3 , further comprising: an ion gun configured to emit ions of an inert gas toward the substrate through the second opening at the same time as the emission of material atoms from the source. apparatus. 6. The intermediate layer forming means is provided in the vacuum chamber and is configured to sputter material atoms forming the intermediate layer toward the substrate through the second opening. 5. The hard carbon film forming apparatus according to claim 3 , further comprising: a target comprising: and an ion gun configured to emit ions of an inert gas toward the target in order to sputter the target. 6. Wherein said plasma generating means, the hard carbon film forming apparatus according to any one of claims 1 to 6, which is an electron cyclotron resonance plasma CVD device. Wherein said shield cover, the hard carbon film forming apparatus according to any one of the mean free path or less of the distance separating claim are provided 1-7 of gas molecules from the peripheral surface of the substrate holder. Wherein said shield cover, hard carbon film according to any one of the mean free Claim 1/10 is provided spaced below the distance of travel 1-7 of gas molecules from the peripheral surface of the substrate holder Forming equipment. 10. A material atom constituting the intermediate layer is S
The hard carbon film forming apparatus according to any one of claims 3 to 9, wherein the hard carbon film forming apparatus is i, Ru, carbon, Ge, or a mixture of these elements and at least one element of carbon, nitrogen, and oxygen. 11. The hard carbon film forming apparatus according to claim 1, wherein said substrate is a substrate made of a metal or alloy containing Ni or Al as a main component, or stainless steel.