TWI460295B - Conductive and protective film and method for producing the same - Google Patents

Description

Conductive protective film and method of producing the same

The present invention relates to a conductive diamond-like carbon (DLC) protective film having high hardness and wear resistance and a method of manufacturing the same.

The conductive protective film is a structure in which the durability of the conductive protective film such as the electrode member is improved by the film having high conductivity and durability, and the conventional diamond-like carbon is based on high hardness and wear resistance. It is used in various materials, but it is not used as a conductive film with high insulation. In recent years, several methods have been developed, but it is difficult to have both electrical conductivity and high hardness and wear resistance. There is no composition used as a conductive protective film.

On the other hand, regarding the manufacture of conductive diamond-like carbon, it is known that a diamond-like carbon (DLC) film structure is controlled by film formation conditions or nitrogen doping, and it is used as a conductive surface-enhancing film layer (Patent Literature) 1), but there is a problem that the hardness is lowered and the conductivity cannot be improved. In addition, as other proposals for the conductive diamond-like carbon film, there is Patent Document 2, but the conductivity and the hardness are inversely proportional. The tendency is to reduce the hardness in order to improve the conductivity, and it is not suitable for the constitution of the protective film. Further, an amorphous carbon film made of a highly toxic diborane or phosphine is proposed, but it is indicated The impedance ratio is as low as 1 × 10 ⁸ Ω ‧ cm, but the impedance ratio is still high (Patent Document 3).

[Patent Document 1] Japanese Patent Publication No. 9-508613

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-217975

[Patent Document 3] Japanese Patent Laid-Open No. 1-245562

The inventors of the present invention have developed a new method for producing a conductive diamond-like carbon protective film that combines high hardness, wear resistance, and electrical conductivity in view of the above-described conventional problems, and has found that the results of repeated research have been found. The present invention has been accomplished in the case of a new conductive diamond-like carbon surface-strengthening coating having high strength.

SUMMARY OF THE INVENTION An object of the present invention is to provide a conductive diamond-like carbon protective film which combines high hardness and wear resistance using a specific film forming method, and a method for producing the same.

In order to solve the above problems, the first aspect of the method for producing a conductive protective film of the present invention relates to a method for producing a conductive protective film for protecting a substrate, which is characterized in that a hydrocarbon-based raw material gas and boron are introduced at a specific ratio. A mixed gas of a doping gas, which is formed on the substrate by a conductive diamond-like carbon film containing a specific amount of boron (B).

A second aspect of the method for producing a conductive protective film of the present invention relates to a method for producing a conductive protective film for protecting a substrate, which comprises a pretreatment process for performing a treatment before ion bombardment on the surface of the substrate. And the surface of the substrate as the pre-treatment described above, which is used as an intermediate layer for electrical resistance contact, and an intermediate layer forming process for film formation, and A mixed gas of a hydrocarbon-based source gas and a boron-doped gas is introduced in a predetermined ratio, and a conductive diamond-like carbon film containing a specific amount of boron is formed on the surface of the intermediate layer to form a diamond-like carbon film, and the combination is performed. In the case of the intermediate layer of the resistance contact and the diamond-like carbon film, the conductivity can be improved.

The foregoing intermediate layer is desirably selected from the group consisting of carbon (C), gold (Au), silver (Ag), indium (In), aluminum (Al), phosphorus (P), titanium (Ti), nickel (Ni), and chromium. (Cr), one or more of ITO (In ₂ O ₃ -SnO ₃ ), ZnO, TiO ₂ and bismuth (si).

The boron (B) doping gas is preferably one or more selected from the group consisting of trimethyl borate (trimethyl borate), trimethyl boron and triethyl boron. .

As the hydrocarbon raw material gas, one or two or more kinds of gas species selected from the group consisting of cyclohexane, benzene, acetylene, methane, butylbenzene, toluene and cyclopentane are used.

The thickness of the above-mentioned diamond-like carbon film is preferably 0.005 to 3 μm, and the thickness of the intermediate layer is preferably 0.005 to 10 μm.

The formation of the intermediate layer may be performed by a plasma CVD method, a sputtering method, an ionization vapor deposition method, a vapor deposition method, a printing method, or electroplating, but is preferably a sputtering method, and is desirably via ionization. The conductive diamond-like carbon film is formed by a vapor deposition method.

It is preferable that the temperature of the substrate when the conductive diamond-like carbon film is formed is 350 ° C or less, and the thermal deformation of the substrate can be controlled to a minimum by this method, and resistance can be obtained. Wear and A person who is more conductive than a carbon film.

The conductive protective film of the present invention is produced by the method for producing a conductive protective film of the present invention, and has a boron (B) content of 0.01 to 5 atomic % and an indentation hardness of 9000 to 30000 MPa. A specific wear resistance of 1.0×10 ^-19 to 1.0×10 ^-15 m ² /N, and a conductive diamond-like carbon film with an electric resistance of 1.0×10 ^-4 to 1.0×10 ² Ω·cm However, in the present invention, the impedance ratio can be measured by a four-point probe method or a four-point measurement (Van der Pauw) method, and the conductive protective film of the present invention can be obtained for Excellent corrosion resistance in acid ‧ alkali solution or oxidation ‧ ring garden environment

In the present invention, for a diamond-like carbon, a hydrocarbon gas such as trimethyl borate or trimethylboron using a safety gas is doped with boron (0.01 to 5 atomic%), which is produced by a specific film formation method. In the case of conductive diamond-like carbon, a conductive protective film having both high hardness and wear resistance is produced, and an intermediate layer and a diamond-like carbon (DLC) which are subjected to resistance contact (low contact resistance) by combination are used depending on the case. When the film is used, the conductivity is also improved.

According to the present invention, the specific conductive diamond-like carbon (DLC) film formed by the ionization evaporation method is used by using a specific gas species, or by combining the aforementioned diamond-like carbon (DLC) film, and the corresponding When it is necessary to use the intermediate layer of the resistance contact, it can be formed as a conductive surface-enhanced film layer, and has an indentation hardness of 9000 to 30000 MPa, and a specific wear rate of 1.0×10 ^-19 to 1.0×10 ^{-15 .} The abrasion resistance of m ² /N, and the conductive diamond-like carbon (DLC) film having an electric resistance of 1.0 × 10 ^-4 to 1.0 × 10 ² Ω · cm, followed by a conductive protective film as various members And get the composition of the big effect.

[To implement the best form of invention]

In the following, the embodiments of the present invention are described. However, the embodiments are exemplified, and various modifications can be made without departing from the technical spirit of the present invention.

The first embodiment of the method for producing a conductive protective film of the present invention is a method for producing a conductive protective film having a structure in which a conductive protective film 12 is formed on a substrate 10 as shown in FIG. As shown in the prior art, ion bombardment is performed on the substrate 10, and the substrate is plasma-cleaned (step 100 in FIG. 2). The ion bombardment is preferably carried out via a rare gas such as Ar or a rare gas in which H is mixed.

Then, a conductive carbon-based carbon film 12 containing a specific amount of boron is formed on the substrate 10 by introducing a mixed gas of a hydrocarbon-based source gas and a boron-doped gas at a specific ratio (step 102 of FIG. 2). .

As a means for forming the above-described conductive diamond-like carbon film 12, there are known an ionization vapor deposition method, a glow discharge or a plasma CVD method using a high frequency plasma, a photo CVD method by ultraviolet excitation, a microwave CVD method, and a sputtering method. The plating method, the arc discharge method, etc., but the ionization vapor deposition method is the best, and the case where the ionization vapor deposition method is used in the present embodiment is described. In the ionization vapor deposition method, the temperature of the substrate 10 when the film is formed by using the unbalanced plasma is usually 350 ° C or lower, and the thermal deformation of the substrate 10 is used as a minimum.

As an apparatus for carrying out the method for producing a conductive protective film of the present invention, a device having the structure shown in FIG. 5 can be used, and a manufacturing apparatus for a conductive protective film in FIG. 5 and 20 has a vacuum chamber 22, and The upper portion of the vacuum chamber 22 is provided with a substrate holding portion 24 for holding the substrate 10, and the lower portion of the vacuum chamber 22 is provided with an anode 26, a filament 28 and a boron doping gas introduction port 30, and more The hydrocarbon-based material gas introduction port 32 is provided in the side wall 22a of the vacuum chamber 22. However, the hydrocarbon-based material gas introduction port 32 may be provided in the bottom wall 22b or the upper wall 22c of the vacuum chamber 22.

The ionization vapor deposition method to which the present invention is applied can decompress the vacuum chamber 22 (for example, vacuum suction to 3 × 10 ^-3 Pa or less), form a film at a low temperature, and excite by electricity. The raw material gas is decomposed to apply a negative voltage to the substrate 10 to deposit a film. Specifically, acetylene (C _{6 )} is introduced into the vacuum chamber 22 of the manufacturing apparatus 20 of the conductive protective film at a specific ratio. H ₆ ) Gas or other hydrocarbon-based source gas and boron-doped gas, using an ion source 29 formed by a hot filament 28 and an anode 26, and generating a hydrocarbon hydrocarbon ion or an excited radical via a DC arc discharge plasma The generated hydrocarbon ions are applied to the substrate 10 biased to a negative voltage of DC, and are solidified by the energy of the bias voltage. As shown in FIG. 1, the conductive species containing a specific amount of boron are used. The carbon film 12 is formed on the substrate 10.

In order to form the conductive diamond-like carbon film 12, one or two selected from the group consisting of cyclohexane, benzene, acetylene, methane, butylbenzene, toluene, and cyclopentane are used as the hydrocarbon-based source gas. The above gas species.

The boron-doped gas is preferably one or more selected from the group consisting of trimethyl borate (trimethyl borate), trimethyl boron and triethyl boron. The mixing ratio of the hydrocarbon-based source gas to the boron-doped gas system is 1 (hydrocarbon-based source gas): 1 (boron-doped gas) to 100:1, and ideally used at 2:1 to 30: The scope of 1 range.

In order to form the conductive diamond-like carbon film 12, it is preferable to use an ionization vapor deposition method because the temperature can be controlled via the filament 28 and the anode 26, and ion bombardment can be controlled via the substrate voltage. It is a case where boron can be activated while maintaining the structure of diamond-like carbon.

In the second embodiment of the method for producing a conductive protective film of the present invention, as shown in FIG. 3, a conductive protective film having a structure in which the intermediate layer 11 is interposed between the substrate 10 and the conductive protective film 12 is formed. As shown in FIG. 4, first, as in the case of the substrate 10, ion bombardment is performed by gas such as Ar, and the substrate is washed (step 100 of FIG. 4).

Next, on the surface of the substrate 10 as the pre-treatment, the intermediate layer 11 for electrical resistance contact is formed (step 101 of FIG. 4), wherein the interlayer 11 is selected from the group consisting of carbon, gold, silver, indium, and aluminum. One or more of a group of phosphorus, titanium, nickel, chromium, ITO (In ₂ O ₃ -SnO ₃ ), ZnO, TiO ₂ and yttrium, and the formation of the intermediate layer 11 is via The plasma CVD method, the sputtering method, the ionization vapor deposition method, the vapor deposition method, the printing method or the plating may be carried out, but the sputtering method is preferred.

Then, in the same manner as in FIG. 2, a conductive gas-like carbon film 12 containing a specific amount of boron is formed by introducing a mixed gas of a hydrocarbon-based source gas and a boron-doped gas at a specific ratio. On the substrate 10 (step 102 of FIG. 4), the conductivity can be improved by the combination of the intermediate layer 11 and the diamond-like carbon film 12 which are electrically contacted in combination, however, the conductive diamond-like carbon film 12 Since the formation is the same as that of FIGS. 1 and 2, detailed description thereof will be omitted.

The gas contained in the intermediate layer 11 is selected from the group consisting of carbon, gold, silver, indium, aluminum, phosphorus, titanium, nickel, chromium, ITO (In ₂ O ₃ -SnO ₃ ), ZnO, TiO ₂ and When the intermediate layer 11 and the diamond-like carbon film 12 which are formed by forming one or two or more kinds of materials formed by the formation of the ruthenium are formed by the electric contact, the electric power loss can be reduced by the contact of the electric group.

According to the method for producing a conductive protective film of the present invention, a boron content of 0.01 to 5 atomic % and an indentation hardness of 9000 to 30000 MPa can be obtained, and the specific wear rate is 1.0 × 10 ^-19 to 1.0 × 10 ^{-15 .} The abrasion resistance of m ² /N, and the conductive diamond-like carbon film having an electric resistance of 1.0×10 ^-4 to 1.0×10 ² Ω·cm, however, the impedance ratio is as follows via a four-point probe method or four It can be measured by the point measurement (Van der Pauw) method.

The substrate to which the method of the present invention is applied is not particularly limited, and examples thereof include a glass substrate, a Si substrate, a metal substrate, a ceramic substrate, a plastic substrate, and the like, and various metal plating (for example, gold plating) is applied. Substrate and the like.

Example

The present invention will be more specifically described by the following examples, but these examples are given by way of illustration and not of limitation.

(Example 1)

As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, boron was formed on the quartz glass substrate under the following experimental conditions without performing mold formation. Doping, diamond-like carbon was formed as a film of 1.18 μm.

Implementation conditions

Gas flow rate: raw material gas (benzene): trimethyl borate = 3: 0.5 Sccm

Anode voltage: 45V

Substrate voltage: 2kV

Film formation temperature: 220 ° C

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 14271 MPa, and it is known that the hardness is sufficient, and in addition, the ball-to-disk method is performed. In the friction-wear test of the ball-on-disk tribometer, the friction coefficient was 0.15, and the specific wear was 1.2×10 ^-17 m ² /N. When the impedance ratio was measured by the four-point probe method, the impedance ratio was 4.3. ×10 ⁰ Ω·cm, the boron content was 0.95 atomic%, and the corrosion resistance of the DLC film formed as described above was confirmed to be inferior in performance in an acid ‧ alkali solution or an oxidized ‧ ring environment

However, as the substrate, not only the glass substrate but also the substrate on which the gold substrate is applied to the Si substrate, the metal substrate, the ceramic substrate, the plastic substrate, and the substrate, the same experiment was performed, and it was confirmed that the same result was obtained. It is also possible to apply other electroplated substrates.

The same experiment was carried out as a boron-doped gas using trimethylboron and triethylboron, and it was confirmed that the same result was obtained.

Further, the same experiment was carried out except that the gas conditions of ion bombardment were changed from Ar to Ar mixed H, and it was confirmed that the same result was obtained.

In the case of the hardness test of the film, the micro-Wicker hardness tester or the indentation of the conventional method is used. When the film thickness exceeds a certain critical value, the influence of the substrate is large, and the hardness of the film itself is not known. In order to control the influence, it is generally considered that the depth of the penetration is required to be 10% or less of the film thickness (however, depending on the material of the substrate and the film properties), therefore, the nanoindentation method is developed to become the hardness of the film. measurement, and, in 2002, as ISO14577, made of Drawing nanoindenter, expanding worldwide awareness, and calculating method described in the ISO14577-based indentation hardness _{(indentation hardness) (H iT)} , the contact projection from The surface A _P and the maximum load F are expressed by the following formula (1).

[Number 1]

The friction and wear tester is used for various purposes, and the shape of the folding method or the measuring sub-portion is mostly. The most common method is the friction-wear test by ball-on-disk tribometer. The disk is fixed on a disk-shaped sample having a rigid support, and the ball is pressed by a known precision scale, and the disk is rotated, and the frictional force acting between the ball and the disk is slightly bent in the horizontal direction of the bracket. In addition, the area of the wear scar area at this time was measured, and it was also compared with the abrasion amount.

In the case of the ion bombardment test, the specific wear amount of the sample was measured from the wear scar sectional area by the following formula (2).

[Number 2]

For the formula (2), W is used as the specific wear amount (m ² /N) of the test piece, R is the radius (m) of the folding circle, and S is the sectional area (m ² ) of the folding circle. P is used as the load (N), and L is used as the folding distance (m).

(Example 2)

As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, the intermediate layer was not molded on the quartz glass substrate under the following experimental conditions. Doping, diamond-like carbon was formed as a film of 0.5 μm.

Implementation conditions

Gas flow rate: raw material gas (benzene): trimethyl borate = 2.2: 0.5 Sccm

Anode voltage: 45V

Substrate voltage: 2kV

Film formation temperature: 220 ° C

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 23639 MPa, and it is known that the hardness is sufficient, and in addition, the ball-to-disk method is performed. (Ball-on-disk tribometer) The friction coefficient was 0.14 and the specific wear was 9.2×10 ^-18 m ² /N. When the impedance was measured by the four-point probe method, the impedance ratio was 4.2. ×10 ⁰ Ω·cm, the boron content was 1.3 atomic%, and the corrosion resistance of the DLC film formed as described above was confirmed to be inferior in performance in an acid ‧ alkali solution or an oxidized ‧ ring environment

(Example 3)

As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, the intermediate layer was not molded on the quartz glass substrate under the following experimental conditions. Doping, diamond-like carbon was formed as a film of 0.9 μm.

Implementation conditions

Gas flow rate: raw material gas (benzene): trimethyl borate = 1.5: 0.7 sccm

Anode voltage: 45V

Substrate voltage: 2kV

Film formation temperature: 320 ° C

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 17869 MPa, and it is understood that the hardness is sufficient, and in addition, the ball-to-disk method is performed. In the friction-wear test of the ball-on-disk tribometer, the friction coefficient was 0.18, and the specific wear was 1.5×10 ^-17 m ² /N. When the impedance ratio was measured by the four-point probe method, the impedance ratio was 1.8. ×10 ⁰ Ω·cm, the boron content was 2.8 atomic%, and the corrosion resistance of the DLC film formed as described above was confirmed to be inferior in performance in an acid ‧ alkali solution or an oxidized ‧ ring environment

(Example 4)

As a pretreatment, the introduction of Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour. Thereafter, a 0.1 μm Ti intermediate layer was formed on the alumina substrate by sputtering. The film was subjected to B-doped conductive diamond-like carbon under the following experimental conditions, and was formed into a film of 0.8 μm.

Implementation conditions

Gas flow rate: raw material gas (benzene): trimethyl borate = 2.2: 0.5 Sccm

Anode voltage: 45V

Substrate voltage: 2kV

Film formation temperature: 200 ° C

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 21983 MPa, and it is known that the hardness is sufficient, and in addition, the ball-to-disk method is performed. In the friction-wear test of the ball-on-disk tribometer, the friction coefficient was 0.15, and the specific wear was 1.2×10 ^-17 m ² /N. When the impedance ratio was measured by the four-point probe method, the impedance ratio was 5.76. ×10 ^-3 Ω‧cm, the boron content is 1.3 atomic%, and the corrosion resistance of the DLC film formed as described above is confirmed to be inferior in performance in an acid ‧ alkali solution or an oxidized ‧ ring environment .

The same experiment was carried out as a boron-doped gas using trimethylboron and triethylboron, and it was confirmed that the same result was obtained.

Further, as an intermediate layer, carbon, gold, silver, indium, aluminum, phosphorus, titanium, nickel, chromium, ZnO, TiO ₂ and a ruthenium layer each having a thickness of 0.1 μm were formed by a sputtering method, and the same experiment was carried out. Those who get the same result.

Further, the same experiment was carried out except that the gas conditions of ion bombardment were changed from Ar to Ar mixed H, and it was confirmed that the same result was obtained.

(Example 5)

As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, boron was formed on the quartz glass substrate under the following experimental conditions without performing mold formation. Doping, diamond-like carbon was formed as a film of 0.3 μm.

Implementation conditions

Gas flow rate: raw material gas (benzene): trimethyl borate = 1.86: 0.7 sccm

Anode voltage: 70V

Substrate voltage: 4kV

Film formation temperature: 320 ° C

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 11291 MPa, and it is known that the hardness is sufficient, and in addition, the ball-to-disk method is performed. In the friction-wear test of the ball-on-disk tribometer, the friction coefficient was 0.16, and the specific wear was 4.6×10 ^-18 m ² /N. When the impedance ratio was measured by the four-point probe method, the impedance ratio was 4.9. ×10 ^-2 Ω‧cm, the boron content is 2.1 atomic%, and the corrosion resistance of the DLC film formed as described above is confirmed to be inferior in performance in an acid ‧ alkali solution or an oxidized ‧ ring environment .

(Example 6)

As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, 0.1 μm of Ti was deposited on the quartz glass substrate by sputtering under the following experimental conditions. After the film formation was performed on the intermediate layer, B-doped conductive diamond-like carbon was formed as a film of 0.35 μm under the following experimental conditions.

Implementation conditions

Gas flow rate: raw material gas (benzene): trimethyl borate = 1.5: 0.7 Sccm

Anode voltage: 45V

Substrate voltage: 3kV

Film formation temperature: 200 ° C

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 9530 MPa, and it is known that the hardness is sufficient, and in addition, the ball-to-disk method is performed. The friction coefficient of the ball-on-disk tribometer was 0.15, and the specific wear was 3.7×10 ^-18 m ² /N. When the impedance was measured by the four-point probe method, the impedance ratio was 2.0. ×10 ^-4 Ω‧cm, the boron content is 2.8 atomic%, and the corrosion resistance of the DLC film formed as described above is confirmed to be inferior in performance in an acid ‧ alkali solution or an oxidized ‧ ring environment .

(Example 7)

As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, the IT0 of 0.1 μm was sputtered on the quartz glass substrate under the following experimental conditions by sputtering. After the film formation was performed on the intermediate layer, B-doped conductive diamond-like carbon was formed as a film of 0.3 μm under the following experimental conditions.

Implementation conditions

Gas flow rate: raw material gas (benzene): trimethyl borate = 1.5: 0.7 Sccm

Anode voltage: 45V

Substrate voltage: 3kV

Film formation temperature: 200 ° C

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 9867 MPa, and it is known that the hardness is sufficient, and in addition, the ball-to-disk method is performed. In the friction-wear test of the ball-on-disk tribometer, the friction coefficient was 0.16, and the specific wear was 3.6 × 10 ^-18 m ² /N. When the impedance ratio was measured by the four-point probe method, the impedance ratio was 2.4. ×10 ^-4 Ω‧cm, the boron content is 2.8 atomic%, and the corrosion resistance of the DLC film formed as described above is confirmed to be inferior in performance in an acid ‧ alkali solution or an oxidized ‧ ring environment .

(Comparative Example 1)

As a pretreatment, after introducing Ar into 14 sccm, a substrate voltage of 2 kV, and an anode current of 0.8 A for 1 hour of ion bombardment, a carbon-coated carbon film of undoped boron was formed on the alumina substrate as a film of 1.1 μm. .

Implementation conditions

Gas flow rate: raw material gas (benzene) 3sccm

Anode voltage: 45V

Substrate voltage: 2kV

When the hardness of the conductive diamond-like carbon (DLC) film formed as described above is measured, the indentation hardness of the nanoindentation method is 23,211 MPa, and it is known that the hardness is sufficient, and in addition, the ball-to-disk method is performed. In the friction-wear test of the ball-on-disk tribometer, the friction coefficient was 0.11, and the specific wear was 5.0×10 ^-18 m ² /N. When the impedance ratio was measured by the four-point probe method, the impedance ratio was 2.7. ×10 ³ Ω‧cm.

10‧‧‧Substrate

11‧‧‧Intermediate

12‧‧‧ Conductive DLC film

20‧‧‧ Conductive protective film manufacturing device

22‧‧‧vacuum chamber

22a‧‧‧ Sidewall

22b‧‧‧ bottom wall

22c‧‧‧Upper wall

24‧‧‧Substrate support

26‧‧‧Anode

28‧‧‧filament

29‧‧‧Ion source

30‧‧‧Boron doping gas inlet

32‧‧‧Carbide-based raw material gas inlet

Fig. 1 is an enlarged cross-sectional explanatory view showing a first embodiment of the conductive protective film of the present invention.

FIG. 2 is a flow chart showing an example of a procedure of a case where the surface of the substrate is covered by the first embodiment of the conductive protective film of the present invention.

Fig. 3 is an enlarged cross-sectional explanatory view showing a second embodiment of the conductive protective film of the present invention.

FIG. 4 is a flow chart showing an example of a procedure of a case where the surface of the substrate is covered by the second embodiment of the conductive protective film of the present invention.

FIG. 5 is a schematic explanatory view showing an example of a manufacturing apparatus for forming a conductive protective film of the conductive protective film of the present invention.

10‧‧‧Substrate

12‧‧‧ Conductive DLC film

Claims (16)

A method for producing a conductive protective film, and a method for producing a conductive protective film for protecting a substrate, comprising: a pretreatment process for performing pre-treatment by ion bombardment on the surface of the substrate, and using a hydrocarbon-based material gas and The gas flow rate of the boron-doped gas is a mixed gas introduced in the range of 2:1 to 30:1 by the hydrocarbon-based raw material gas, and the boron content is 0.01 to 5 atomic% using a DC power source. And the indentation hardness is 9000~30000MPa hardness, the wear resistance is 1.0×10 ^-19 ~1.0×10 ^-15 m ² /N, and the impedance is 1.0×10 ^-4 ~1.0×10 ² Ω. . A conductive carbon-coated carbon film of cm is formed on the substrate of the pretreatment. A method for producing a conductive protective film, a method for producing a conductive protective film for protecting a substrate, comprising: a pretreatment process for performing pre-treatment by ion bombardment on a surface of the substrate, and a surface of the substrate before the pretreatment Forming an intermediate layer forming the intermediate layer of the resistive contact, and forming a gas flow rate using the hydrocarbon-based raw material gas and the boron-doped gas, and the hydrocarbon-based raw material gas: the boron-doped gas is 2:1 to 30 The mixed gas introduced in the range of 1:1, using a DC power supply, has a boron content of 0.01 to 5 atomic%, and an indentation hardness of 9000 to 30000 MPa, and a specific friction consumption of 1.0 × 10 ^-19 to 1.0 × 10 ^-15 m. ² / N resistance to wear, and the impedance is 1.0 × 10 ^-4 ~ 1.0 × 10 ² Ω. A conductive carbon-coated carbon film of cm is formed on the substrate of the pretreatment. The method for producing a conductive protective film according to claim 2, wherein the intermediate layer is selected from the group consisting of carbon, gold, silver, indium, aluminum, phosphorus, titanium, nickel, chromium, and ITO (In ₂ O ₃ - One or more of SnO ₃ ), ZnO, TiO ₂ and strontium are formed. The method for producing a conductive protective film according to the second aspect of the invention, wherein the intermediate layer is formed by a plasma CVD method, a sputtering method, an ionization vapor deposition method, an evaporation method, a printing method, or a plating method. Conductor. The method for producing a conductive protective film according to the second aspect of the invention, wherein the intermediate layer has a thickness of 0.005 to 10 μm. The method for producing a conductive protective film according to the first aspect of the invention, wherein the boron-doped gas is one or two selected from the group consisting of trimethyl borate, trimethylboron and triethylboron. More than one. The method for producing a conductive protective film according to the second aspect of the invention, wherein the boron-doped gas is one or two selected from the group consisting of trimethyl borate, trimethylboron and triethylboron. More than one. The method for producing a conductive protective film according to the first aspect of the invention, wherein the hydrocarbon-based raw material gas is selected from the group consisting of cyclohexane, benzene, acetylene, methane, butylbenzene, toluene and cyclopentane. One or more of the group of gases. The method for producing a conductive protective film according to the second aspect of the invention, wherein the hydrocarbon-based raw material gas is selected from the group consisting of cyclohexane. One or more kinds of gas species of benzene, acetylene, methane, butylbenzene, toluene and cyclopentane. The method for producing a conductive protective film according to the first aspect of the invention, wherein the conductive diamond-like carbon film is formed by an ionization vapor deposition method. The method for producing a conductive protective film according to the second aspect of the invention, wherein the conductive diamond-like carbon film is formed by an ionization vapor deposition method. The method for producing a conductive protective film according to the first aspect of the invention, wherein the thickness of the diamond-like carbon film is 0.005 to 3 μm. The method for producing a conductive protective film according to the second aspect of the invention, wherein the thickness of the diamond-like carbon film is 0.005 to 3 μm. The method for producing a conductive protective film according to the first aspect of the invention, wherein the temperature of the substrate when the diamond-like carbon film is formed is 350 ° C or lower. The method for producing a conductive protective film according to the second aspect of the invention, wherein the temperature of the substrate when the diamond-like carbon film is formed is 350 ° C or lower. A conductive protective film which is a conductive protective film formed on a substrate by a method for producing a conductive protective film according to any one of claims 1 to 15, which is characterized in that the boron content is 0.01 ~5 atomic%, and the indentation hardness is 9000~30000MPa hardness, the specific wear rate is 1.0×10 ^-19 ~1.0×10 ^-15 m ² /N, and the resistivity is 1.0×10 ^-4 ~ 1.0×10 ² Ω. A conductive carbon-like carbon film made of cm.