JPH10203896A - Member having diamond-like carbon thin film formed thereon and its formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a member on which a highly hard diamond-like carbon(DLC) thin film good in adhesivity to a substrate is formed, and to provide a method for forming the same. SOLUTION: An adhered layer 60 comprising a thin layer of a metal selected from a group consisting of Si, W, Ti and Al, a preliminarily treated DLC layer comprising a thin layer of a ceramic selected from a group consisting of SiC, WC, TiC and Al2 O3 and further a thin DLC film 80 are formed on a substrate 3. The formation of the thin DLC film 80 through the adhered layer and the preliminarily treated DLC layer improves the adhesivity of the thin DLC film 80.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a member in which a diamond-like carbon (DLC) thin film is formed on the surface of a substrate and a method for forming the DLC thin film.

[0002]

2. Description of the Related Art Conventionally, molds, tools, sliding members,
A diamond-like carbon (DLC) thin film has been used as a hard coating film for protecting the surface of a recording medium or the like of a magnetic disk device. FIG. 27 is a sectional view showing a member on which a conventional DLC thin film is formed.
FIG. 8 is a cross-sectional view of a conventional DLC thin film forming apparatus using microwave plasma disclosed in JP-A-63-185893. In these figures, reference numeral 1 denotes a vacuum tank for keeping the inside vacuum, 101 a substrate holder for holding the substrate 3 in the vacuum tank 1, 61 a heater provided on the substrate holder 101 to heat the substrate 3, 103 and 104 are reaction gas inlets for introducing a reaction gas into the vacuum chamber 1;
2 is a waveguide for applying a microwave into the vacuum chamber 1,
An electromagnet 105 generates a magnetic field in the vacuum chamber 1.
Reference numeral 91 denotes a member formed by forming the DLC thin film 80 on the base material 3.

Next, the operation will be described. The substrate 3 is held by the substrate holder 101 in the vacuum chamber 1. Next, the base material 3 is heated to 300 to 900 ° C. by the heater 61 and the degree of vacuum in the vacuum chamber 1 is reduced to 10 ⁻³ to 10 ⁻⁵ Torr.
r. Subsequently, the reaction gas inlets 103 and 10
4 supplies a reaction gas such as CH ₄ and C ₂ H ₂ into the vacuum chamber 1, applies a magnetic field to the vacuum chamber 1 by the electromagnet 105, and applies a microwave having an output of 300 to 600 W from the waveguide 102. As a result, microwave plasma is generated in the vacuum chamber 1, and the excited carbon reaches the base material 3.
A DLC thin film is formed on the substrate 3.

[0004]

In the member and the method of forming the above-mentioned conventional diamond-like carbon (DLC) thin film, the adhesion between the DLC thin film and the base material is poor, and such a material is formed on the base material. However, when a DLC thin film is formed, there is a problem that it is peeled off. The present invention has been made in order to solve the above-described problems, and has an object to obtain a member having a DLC thin film having high adhesion to a substrate and a high hardness, and a method for forming the member. .

[0005]

According to a first aspect of the present invention, there is provided a member on which a DLC thin film is formed, wherein a base layer comprises an adhesion layer on a base material and a DLC pretreatment layer on the adhesion layer. Silicon, tungsten, titanium, and a metal thin film selected from the group consisting of aluminum, the DLC pretreatment layer is silicon carbide, tungsten carbide, titanium carbide,
It is made of a ceramic thin film selected from the group consisting of aluminum carbide.

According to a second aspect of the present invention, in the member on which the DLC thin film is formed, the DLC pretreatment layer is made of ceramic having the same metal component as the adhesion layer. DL according to claim 3
In the member on which the C thin film is formed, the DLC pretreatment layer has a carbon component composition that increases from the adhesion layer to the DLC thin film. In the member on which the DLC thin film according to claim 4 is formed, the DLC pretreatment layer includes a plurality of layers containing the same metal component and having different compositions, and a layer having the largest carbon composition is formed on the uppermost layer. Things.

[0007] Claims 5, 6, 7, and 8
In the member having the DLC thin film according to the above, the adhesion layer is made of a metal thin film of silicon, tungsten, titanium, and aluminum, and the DLC pretreatment layer is made of a ceramic containing the same metal component as the adhesion layer.

According to a ninth aspect of the present invention, in the member on which the DLC thin film is formed, the base layer comprises an adhesion layer on the substrate and a DLC pretreatment layer thereon, and the adhesion layer and the DLC pretreatment layer are made of silicon and tungsten, respectively. , Titanium, and aluminum.

According to a tenth aspect of the present invention, there is provided a member on which a DLC thin film is formed, wherein a treatment layer containing a carbon component is formed on a substrate surface. In the member on which the DLC thin film according to claim 11 is formed, the treatment layer is an ion implantation layer of carbon ions. The member on which the DLC thin film according to claim 12 is formed has a distribution in which the amount of carbon in the ion-implanted layer is large near the surface of the base material and decreases as the carbon depth increases. The member on which the DLC thin film according to claim 13 is formed has a treatment layer which is a carbonized layer formed by irradiation and diffusion of carbon ions.

In the method of forming a DLC thin film according to a fourteenth aspect, in the step of forming the ion-implanted layer, the surface of the substrate is irradiated with hydrogen ions together with carbon ions.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 FIG. Hereinafter, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of a member on which a diamond-like carbon (DLC) thin film according to a first embodiment of the present invention is formed. In the figure, reference numeral 90 denotes a member used for a mold, a tool, a mechanical part, and the like; A base material 50 such as a cemented carbide is a base layer, and the base layer 50 is composed of the adhesion layer 60 formed on the base material 3 and the DLC pretreatment layer 70 formed thereon. Reference numeral 80 denotes a DLC thin film, and a member 90 is formed by forming the DLC thin film on the base material 3 with the base layer 50 interposed therebetween. In this embodiment, a metal thin film selected from the group consisting of silicon, tungsten, titanium, and aluminum having good adhesion to the base material 3 is used as the adhesion layer 60, and a DLC thin film 80 is used as the DLC pretreatment layer 70. The case where a ceramic thin film selected from the group consisting of silicon carbide, tungsten carbide, titanium carbide, and aluminum carbide having good adhesion is used.

FIG. 2 is a cross-sectional view of a thin film forming apparatus suitable for use in this embodiment. In FIG. 2, reference numeral 1 denotes a vacuum chamber for holding the inside of the vacuum chamber, and 2 denotes an exhaust system for exhausting the vacuum chamber 1. 4, a substrate holder for holding the substrate 3 in the vacuum chamber 1;
5 is a bias means for applying a bias voltage to the base material 3 via the base material holder 4 with respect to an acceleration electrode 15 described later,
Reference numeral 6 denotes a substrate temperature adjusting mechanism provided on the substrate holder 4 for heating and cooling the substrate 3 to adjust the temperature thereof.
An insulating ceramic that electrically insulates the substrate 3 from the substrate holder 4, and 100 is a rotation mechanism that rotates the substrate 3.

Reference numeral 10 denotes a gas ion source provided below the substrate 3 in the vacuum chamber 1 so as to be opposed to the substrate 3. Reference numeral 11 denotes a reaction gas introduction chamber into which a reaction gas is introduced. An orifice (not shown) is provided toward the base material 3 so as to increase the flow path resistance and apply a pressure difference between the flow path resistance and the vacuum chamber 1. Numeral 12 denotes a thermionic emission means provided in the reaction gas introduction chamber 11 and made of, for example, a tungsten wire. Numeral 13 comprises a thin metal wire arranged in parallel, and a thermoelectron extractor provided in the reaction gas introduction chamber 11. An electrode 14 is a reaction gas introduction pipe connected to the reaction gas introduction chamber 11 to introduce a reaction gas into the inside, and an acceleration electrode 15 is provided outside the reaction gas introduction chamber 11 and accelerates ions toward the substrate 3. The reaction gas introduction chamber 11, thermionic emission means 12, thermionic extraction electrode 13, the reaction gas introduction tube 14, and the acceleration electrode 15 constitute the gas ion source 10.

Reference numeral 30 denotes a metal vapor generating source, such as an electron beam evaporation source, an ion plating device, or a metal ion source, provided in the vacuum chamber 1 so as to face the substrate 3 and capable of forming a metal thin film or a ceramic thin film. Here, a metal ion source is used. 31 is a crucible for putting metal raw materials,
32 is a heater for heating the crucible 31, 33 is a thermionic emission means for emitting thermoelectrons, 34 is a thermoelectron extraction means for extracting thermoelectrons from the thermionic emission means 33, 35 is a heat shield for insulating these, and 36 is metal It is an accelerating electrode for extracting ions from the vapor source 30, and the metal vapor source 30
It comprises a crucible 31, a heater 32, a thermoelectron emission means 33, a thermoelectron extraction means 34, a heat shield 35, and an acceleration electrode 36. One end of the bias means 5, the vacuum chamber 1, and the acceleration electrode 15 are grounded.

Next, the operation will be described. First, the substrate 3 is attached to the substrate holder 4, and the vacuum system 1 is
After the inside is evacuated to a degree of vacuum of about 1 × 10 ⁻⁶ Torr, the temperature of the base material 3 is adjusted to about 300 ° C. by the base material temperature adjustment mechanism 6. Then, for cleaning the surface of the base material 3, hydrogen gas is introduced from the reaction gas introduction pipe 14 into the reaction gas introduction chamber 11, and the degree of vacuum in the reaction gas introduction chamber 11 is reduced by one.
X 10 ^-2 to 1 x 10 ^-1 Torr.

Then, the thermoelectron emission means 12 is operated,
A bias voltage of about +50 to 800 V is applied to the thermoelectron extraction electrode 13 to the thermoelectron emission means 12 by a power supply (not shown). In addition, in order to extract ions from the gas ion source 10, a voltage of about +200 to 500 V is applied to the accelerating electrode 15, that is, to the thermionic emission means 12 with respect to the ground potential by a power supply (not shown). The electrons emitted from the thermionic emission means 12 are accelerated toward the thermionic extraction electrode 13 and ionize the hydrogen gas. The substrate 3 is irradiated with the hydrogen ions, and impurities on the surface of the substrate 3 are removed by a reduction reaction. At this time, the bias of the substrate 3 is adjusted to about -200 to -3000 V with respect to the ground potential by the bias means 5 to control the amount and energy of the hydrogen ions to be irradiated on the substrate 3. By setting the energy of the hydrogen ions to 200 to 3000 eV, the reduction reaction of the surface oxide by the hydrogen ions can efficiently proceed, and the cleaning treatment can be performed effectively.

Here, a mixed gas of hydrogen gas and an inert gas such as helium, argon, xenon (for example, 50% H ₂ + 50% A) is used as the ion cleaning gas.
The cleaning process may be performed using r). Since the impurity layer on the substrate surface can be ground and removed by sputtering with inert gas ions at the same time as the removal of the oxide on the surface by the reduction reaction with hydrogen ions, the adhesion between the substrate 3 and the underlayer 50 and the DLC thin film 80 can be improved. Can be improved. By the above treatment, impurities such as water, oil and fat components, and surface oxides on the surface of the substrate 3 can be removed,
DLC thin film 8 formed on base material 3 via base layer 50
0 improves the adhesion.

Next, the supply of the ion cleaning gas to the gas ion source 10 is stopped, and the cleaning of the surface of the substrate 3 is terminated.
A voltage of about -0.5 to -3 kV is applied to the substrate 3 with respect to the ground potential, and silicon (Si), tungsten (W), and titanium (Ti) in the crucible 31 are heated by the heater 32.
Alternatively, the metal of aluminum (Al) is heated to generate steam, and thermionic electrons emitted from thermionic electron emitting means 33 are extracted and accelerated by thermionic electron extracting means 34 to generate metal ions. The material 3 is irradiated with Si as an adhesion layer 60 constituting a base layer 50 on the surface thereof,
A metal thin film of W, Ti or Al is formed.

Next, the hydrocarbon-based gas is excited, dissociated and ionized by the gas ion source 10 and the dissociated carbon and carbon ions are irradiated toward the substrate 3 or the hydrocarbon-based gas is evacuated in the vacuum chamber 1. And the metal vapor generation source 30 is operated as described above to form a DLC pretreatment layer 70 on the adhesion layer 60 as SiC, WC, T
A ceramic thin film of iC or Al ₄ C ₃ is formed.

Next, a DLC thin film 80 is formed. First, the temperature of the substrate 3 is adjusted to 100 ° C. to 250 ° C. by the substrate temperature adjusting mechanism 6 for the reason described below. Here is 20
It was brought to 0 ° C. The bias means 5 gives the potential of the substrate 3 to the ground potential as a function V (t) of time t. FIG. 3 shows an example of a bias voltage waveform applied to the base material 3. 3 (a) to 3 (c) show the case where a DC or half-wave rectified or full-wave rectified negative voltage is applied. The voltage value was within several kV, and was -1 kV here. Further, the frequency is set to about several tens Hz to several tens kHz in (b).
0 Hz and 1 kHz. By controlling the voltage value of V (t), the energy given to the ions can be adjusted. Thereby, the adhesion strength and hardness of the thin film can be controlled.

Subsequently, a hydrocarbon-based gas containing carbon (C), which is a material constituting the DLC thin film 80, is introduced from the reaction gas introduction pipe 14 into the reaction gas introduction chamber 11, and the inside of the reaction gas introduction chamber 11 The degree of vacuum is 1 × 10 ^-2 to 1 × 10 ^-1 Torr
To As a reaction gas introduced at this time, for example, a gas such as benzene, toluene, or xylene is used. Then, the thermoelectron emission means 12 is operated, and the thermoelectron emission means 12 is operated.
, A bias voltage of about +50 to 800 V is applied to the thermoelectron extraction electrode 13. A voltage of about +200 to 500 V with respect to the ground potential is applied to the thermoelectron emitting means 12. The electrons emitted from the thermionic electron emitting means 12 are accelerated toward the thermionic extraction electrode 13, and excite, dissociate, and ionize the hydrocarbon-based gas by discharging or irradiating the electrons, thereby dissociating the dissociated carbon and carbon. The ions and the dissociated hydrogen and hydrogen ions are irradiated toward the substrate 3 to form a DLC thin film 80 on the substrate 3. Since the ions are positively charged, the ions are accelerated and extracted from the gas ion source 10 by the acceleration electrode 15 and the energy given to the ions can be adjusted by controlling the negative bias voltage of the substrate 3.

FIG. 4 shows the results of Raman analysis of the DLC thin film when the temperature of the substrate is used as a parameter. When the temperature of the substrate 3 is 250 ° C., a typical spectrum of DLC is shown, whereas when the temperature of the substrate 3 is 300 ° C. or 400 ° C., the spectrum is graphite. For this reason, the temperature of the substrate 3 should be 250 ° C. or lower, but it is not preferable to lower the temperature too much for another reason. That is, if the temperature is lower than 100 ° C.,
The adhesion of the C thin film 80 becomes weak. Therefore, the temperature of the substrate 3 during film formation is controlled from 100 ° C. to 250 ° C. by using the substrate temperature adjusting mechanism 6. By doing so, graphitization of the DLC thin film 80 can be suppressed, and a high-hardness, high-quality DLC thin film 80 can be formed. Note that the temperature range is different from the temperature range of the conventional device shown in FIG. 28 because the type of the device is different.

Further, the rotating mechanism 100 allows the base material 3 to be formed during film formation.
By rotating, the film thickness distribution can be made uniform, and at the same time, it is possible to improve the throwing power to the end of the base material 3, that is, to reduce the film thickness non-uniformity due to the direction and position of the surface. FIG. 5 schematically shows the above process. Further, as shown in FIG. 6, prior to cleaning with hydrogen ions, sputter cleaning with inert gas ions such as argon may be performed. Note that, as described above, the gas ion source 10
Supply gas from the ion cleaning gas to DLC
By switching to a gas for forming a thin film, a single gas ion source 10 performs ion cleaning processing and DLC.
Both thin film formation can be performed, and the apparatus configuration can be simplified and the price can be reduced. Thereby, a mold in which the DLC thin film 80 is formed on the base material 3 via the base layer 50 as shown in FIG.
A member 90 such as a tool or a mechanical part can be formed.

As described above, before forming the DLC thin film 80, at least one type of metal thin film selected from the group consisting of titanium, aluminum, silicon, and tungsten is used as the adhesion layer 60 constituting the underlayer 50. To form
Next, as the DLC pretreatment layer 70, SiC, WC, T
By forming at least one type of ceramic thin film selected from the group consisting of iC and Al ₄ C ₃ , the metal thin film as the above-mentioned adhesion layer 60 has a large adhesive force. SiC, Al ₄ C ₃ , Ti
Since the ceramic thin film such as C and WC easily grows and the formation of the ceramic thin film as the DLC pretreatment layer 70 increases the surface hardness, and the DLC thin film 80 easily grows on these ceramic thin films. Base material 3
And the DLC thin film 80 can be improved in adhesion strength,
A member 90 such as a mold, a tool, and a machine part having excellent wear resistance and corrosion resistance can be obtained.

Embodiment 2 This embodiment shows a case where the composition of the carbon component of the ceramic thin film as the DLC pretreatment layer constituting the underlayer gradually changes in the thickness direction. 7 to 10 show members such as molds, tools, and mechanical parts on which the DLC thin film is formed. The DLC thin film 8 in the thickness d direction from the side of the metal thin film of silicon, tungsten, titanium, or aluminum as the adhesion layer 60
The composition of the carbon component in the DLC pretreatment layer 70 gradually increases toward 0, and the carbon composition in the uppermost layer is 90% or more.

Next, the operation will be described. Embodiment 1
In the same manner as in the case of FIG.
After evacuating the inside of the vacuum chamber 1 to a degree of vacuum of about 1 × 10 ⁻⁶ Torr, the temperature of the substrate 3 is reduced to 30 by the substrate temperature adjusting mechanism 6.
Adjust to about 0 ° C. First, by performing a cleaning process on the surface of the substrate 3 in the same manner as in the first embodiment, it is possible to remove impurities such as moisture, oil components, and surface oxides on the surface of the substrate 3. And the underlayer 50 can be improved in adhesion. Next, the gas ion source 1
The supply of the ion cleaning gas to 0 is stopped, and the cleaning process on the surface of the substrate 3 is terminated. Next, the bias means 5 applies -0.5 to
A voltage of about -3 kV is applied, and a heater 32 heats the metal of Si, W, Ti or Al in the crucible 31 to generate steam, and thermionic emission means 33
Thermionic electrons emitted from the
It is pulled out and accelerated to generate metal ions, which are irradiated on the base material 3 and Si, W,
A metal thin film of Ti or Al is formed.

Subsequently, the hydrocarbon-based gas is excited, dissociated, and ionized by the gas ion source 10, and the dissociated carbon and carbon ions are irradiated toward the base material 3.
Alternatively, the inside of the vacuum chamber 1 is made a hydrocarbon gas atmosphere,
By operating the metal vapor generation source 30 as described above, SLC is formed as a DLC pretreatment layer 70 on the above-described metal thin film.
A ceramic thin film of iC, Al ₄ C ₃ , TiC or WC can be formed. Here, in a state where the metal vapor generation source 30 is operated as described above, the hydrocarbon-based gas is excited, dissociated, and ionized by the gas ion source 10, and the dissociated carbon and carbon ions are irradiated. When the ceramic thin film is formed, the amount of the hydrocarbon-based gas to be introduced is gradually increased, while the supply amount of the metal vapor from the metal vapor generation source 30 is gradually decreased. It is possible to form a carbide layer that is gradually increased with respect to the composition of the metal elements Si, W, Ti, and Al.
That is, the carbide layer is made of Si _{2 -X} C _X , W _{2 -X} C _X , Ti _{2 -X}
When represented by C _X or Al _{4 (2-X)} C _3X (0 <x <2), D
DLC with x gradually increasing toward LC thin film 80
A pretreatment layer 70 is obtained. The stress in the film can be controlled by changing the composition, and the stress can be reduced by setting the stress so as to cancel the compressive stress generated by the DLC thin film 80 formed on the underlayer 50. As a result, the adhesion of the DLC thin film 80 can be improved.

Next, as in the case of the first embodiment, the gas ion source 10 is operated to form the DLC thin film 80 on the underlayer 50 on the surface of the substrate 3. Thereby, as a base layer 50 on the surface of the base material 3, a silicon layer is formed from the base material 3 toward the DLC thin film 80, and a carbon layer on which a carbon composition is gradually increased with respect to a composition of a metal element. The formed underlayer 50 is formed, and DLC is formed on the underlayer 50.
A thin film 80 can be formed. The above process is schematically illustrated in FIGS. 5 and 6, but when simultaneously irradiating a metal ion beam and a gas ion beam in the formation of the underlayer shown in the figure, in this embodiment, the ratio between the two with time increases , So that the gas ion beam becomes large.

As described above, the gas ion source 10
And a metal vapor generation source 30 capable of forming a metal thin film or a ceramic thin film. After forming the base layer 50 on the surface of the base material 3, the DLC can be continuously performed without opening to the atmosphere.
A thin film 80 can be formed. In the example shown in FIG. 7, before the DLC thin film 80 is formed, a silicon layer having high adhesion is formed, and then silicon carbide Si _(2-X) C _{X in which the} carbon composition is gradually increased with respect to the silicon composition. The layer contains a silicon carbide SiC component having high hardness, and a carbon component in which the DLC thin film 80 easily grows in a portion near the DLC thin film 80 is increased in the film, so that the adhesion strength between the base material 3 and the DLC thin film 80 is improved. Thus, a member 90 such as a mold, a tool, and a mechanical part having excellent wear resistance and corrosion resistance can be obtained. Also, as shown in FIGS. 8, 9 and 10, W, Ti, A
The same effect is obtained when 1 is used.

Embodiment 3 Although similar to the second embodiment, in this embodiment, the DLC pretreatment layer includes a plurality of layers having different compositions. That is, the difference is that the composition changes stepwise. The description of the same parts as in the second embodiment is omitted. FIG. 11 is a cross-sectional view showing a member according to the present embodiment, in which a DLC pretreatment layer composed of a plurality of ceramic layers having a different composition of Si carbide is formed on a substrate 3 on which an adhesion layer 60 made of Si is formed. 70 is formed.
Of the plurality of ceramic layers having different compositions, the layer having the largest carbon composition (90% or more carbon composition) is formed on the uppermost layer, that is, on the DLC thin film 80 side. This facilitates the growth during the formation of the DLC thin film 80 and improves the adhesion between the DLC thin film 80 and the DLC pretreatment layer 70. The combination of the layers having different compositions is set so as to cancel the compressive stress generated when the DLC thin film 80 is formed on the substrate 3 via the underlayer 50.

Similar effects are obtained when W, Ti, or Al is used as shown in FIGS. Further, as shown in FIG.
The same effect can be obtained by forming a layer having a SiC and carbon composition of 90% or more as the LC pretreatment layer 70. The same effect is obtained even in the case where W shown in FIG. 16 is used.

The above process is the same as that shown in FIGS. 5 and 6, but when simultaneously irradiating a metal ion beam and a gas ion beam in the formation of the underlayer shown in FIG. It changes step by step. As described above, the adhesion strength of the DLC thin film 80 can be increased, and a member 90 having excellent wear resistance and corrosion resistance can be obtained.

Embodiment 4 FIG. In this embodiment, a metal selected from the group consisting of Si, W, Ti, and Al having good adhesion to the base material 3 or the DLC thin film 80 is used as an adhesion layer and a DLC pretreatment layer that constitute a base layer. The case where a thin film is used will be described. FIG. 17 is a cross-sectional view showing a DLC thin film forming apparatus suitable for use in this embodiment.
a and 30b. The description of the same parts as in the first embodiment is omitted.

Next, the operation will be described. In the same manner as in the first embodiment, in FIG. 17, after the inside of the vacuum chamber 1 is evacuated to a degree of vacuum of about 1 × 10 ⁻⁶ Torr by the exhaust system 2,
The temperature of the substrate 3 is adjusted to about 300 ° C. by the substrate temperature adjusting mechanism 6. First, by performing the same cleaning treatment on the surface of the substrate 3 as in the first embodiment, it is possible to remove impurities such as moisture, oils and fats, and surface oxides on the surface of the substrate 3. And the underlayer 50 can be improved in adhesion.

Next, the supply of the ion cleaning gas to the gas ion source 10 is stopped, and the cleaning process of the surface of the substrate 3 is completed. Next, a voltage of about -0.5 to -3 kV is applied to the base material 3 with respect to the ground potential by the bias means 5, and the Si in the crucible 31 is heated by the heater 32 of the first metal vapor generation source 30a. Al, Ti or W
Is heated to generate steam, and thermionic electrons emitted from thermionic emission means 33 are extracted by thermionic extraction means 3.
By 4, withdraw, accelerate, generate metal ions,
This is irradiated onto the base material 3 to form a metal thin film of Si, Al, Ti or W as an adhesion layer constituting a base layer on the surface thereof. Subsequently, the DLC pretreatment layer 7 is formed on the adhesion layer 60 by the second metal vapor generation source 30b in the same manner as described above.
A metal thin film of Si, Al, Ti or W as 0 is formed. Next, as in the case of the first embodiment, the gas ion source 10 is operated to form the DLC thin film 80 on the underlayer 50 on the surface of the substrate 3. Thus, a member 90 such as a mold, a tool, and a mechanical part having the DLC thin film 80 formed on the base material 3 via the base layer 50 as shown in FIG. 1 can be formed. FIG. 18 schematically shows an example of the above process. In FIG. 18, prior to cleaning with hydrogen ions, sputter cleaning with inert gas ions may be performed.

As described above, before the formation of the DLC thin film 80, the base layer 50 composed of the adhesion layer 60 and the DLC pre-treatment layer 70 is formed from the substrate 3 toward the DLC thin film 80. , Si, W, Ti, and Al, at least one metal selected from the group consisting of Si, W, Ti, and Al
By using at least one kind of metal selected from the group consisting of, the base layer 50 has good adhesion between the adhesion layer 60 made of a metal having good adhesion to the base material 3 and the DLC thin film 80, and DLC The base material 3 and the DLC thin film 80 are composed of the DLC pretreatment layer 70 made of a metal which is easy to grow.
The adhesion strength of the base layer 5 can be improved.
Since 0 is composed of two kinds of metal thin films, the range in which the stress in the film can be controlled is expanded, and the stress is set so as to cancel the compressive stress generated by the DLC thin film 80 formed on the underlayer 50. Thereby, the stress can be relaxed, and the adhesion of the DLC thin film 80 can be improved,
A member 90 such as a mold, a tool, and a machine part having excellent wear resistance and corrosion resistance can be obtained.

Embodiment 5 In this embodiment, a case is described in which an ion-implanted layer is formed by implanting carbon ions into a substrate as a treatment layer containing carbon formed on the surface of the substrate. FIG. 19 shows a member according to this embodiment, and 51 is a treatment layer. FIG. 20 is a sectional view of a DLC thin film forming apparatus suitable for use in this embodiment. Next, the operation will be described. In the same manner as in the first embodiment, in FIG. 20, after evacuating the vacuum chamber 1 to a degree of vacuum of about 1 × 10 ⁻⁶ Torr by the exhaust system 2, Adjust the temperature of Step 3 to about 300 ° C.

Next, before forming the DLC thin film, ion implantation with carbon ions is performed. First, a hydrocarbon-based gas containing a carbon element such as benzene, toluene, or xylene is introduced into the reaction gas introduction chamber 11 through the reaction gas introduction pipe 14,
The degree of vacuum in the reaction gas introduction chamber 11 is 1 × 10 ⁻² to 1 × 10 ⁻¹
Torr. Then, the thermoelectron emission unit 12 is operated, and a bias voltage of about 50 to 800 V is applied to the thermoelectron extraction electrode 13 to the thermoelectron emission unit 12 by a power supply (not shown). Further, in order to extract ions from the gas ion source 10, a voltage of about +200 to 500 V is applied to the accelerating electrode 15, that is, to the thermionic emission means 12 with respect to the ground potential from a power supply (not shown). Electrons emitted from the thermionic electron emitting means 12 are used as thermionic extraction electrodes 1
It accelerates toward 3, and excites, dissociates, and ionizes a hydrocarbon-based gas containing a carbon element. The substrate is irradiated with the ionized carbon ions. At this time, the substrate 3 is moved in the negative direction with respect to the ground potential by the bias means 5.
By applying a bias of about 10 to -30 kV, ion implantation is performed, and an ion implantation layer as the processing layer 51 is formed. Subsequent to this processing, a DLC thin film 80 as described in the first embodiment is formed.

FIG. 21 schematically shows the above process.
Further, as shown in FIG. 22, hydrogen ion cleaning is performed prior to ion implantation, so that the adhesion between the substrate 3 and the DLC thin film 80 can be further improved. FIG.
Prior to the hydrogen ion cleaning in the above, sputter cleaning using inert gas ions may be performed.
By forming the ion-implanted layer with the energy of carbon ions at 10 to 30 keV before forming the DLC thin film 80 in this manner, a region in which the base material and the carbon atoms are mixed is formed. The adhesion of the DLC thin film can be improved, and a member 90 such as a mold, a tool, and a machine part having excellent wear resistance and corrosion resistance can be obtained.

FIG. 23 shows the relationship between the ion implantation energy and the distribution of the implantation amount in the depth direction. The distribution of the implantation amount in the implantation depth direction depends on the implantation energy. With the depth as the peak point, it gradually decreases to both sides. As the implantation energy increases, the peak point moves to a deeper implantation depth. Therefore, for example, the ion implantation energy is shown in FIG.
In other words, by giving a distribution as shown in FIG. 4, that is, performing low-energy implantation for a long time and high-energy implantation for a short time, as shown in FIG. The closer to the surface, the higher the density, and the distribution can be such that the carbon injection amount is maximum near the surface of the substrate 3. Thus, the DLC thin film 80
In the process of ion implantation before formation, by giving carbon ions an energy distribution, the distribution of carbon atoms in the depth direction from the surface of the substrate 3 of the implanted layer can be controlled, and the substrate 3 and the DLC thin film can be controlled. The member 90 such as a mold, a tool, and a machine part having excellent abrasion resistance and corrosion resistance can be obtained.

Also, in the process of ion implantation into the base material 3, by using hydrogen ions together with carbon ions, hydrogen ions selectively etch the graphite component of the implanted layer. Thus, the adhesion strength between the base material 3 and the DLC thin film 80 can be improved, and a member 90 such as a mold, a tool, and a machine part having excellent wear resistance and corrosion resistance can be obtained.

Embodiment 6 FIG. In this embodiment, FIG.
9 shows a case where a carbonized layer is formed by carbon ions as the treatment layer 51 shown in FIG. Next, the operation will be described. In the same manner as in the first embodiment, after evacuating the vacuum chamber 1 to a degree of vacuum of about 1 × 10 ⁻⁶ Torr by the exhaust system 2 in FIG. Is adjusted to about 300 ° C. Next, carbonization by carbon ions is performed before forming the DLC thin film. First, a hydrocarbon-based gas containing a carbon element such as benzene, toluene, or xylene is introduced into the reaction gas introduction chamber 11 through the reaction gas introduction pipe 14, and the degree of vacuum of the reaction gas introduction chamber 11 is reduced to 1 degree.
× 10 ^-2 to 1 × 10 ^-1 Torr. Then, the thermoelectron emitting means 12 is operated, and the thermoelectron emitting means 12 is connected to the thermoelectron extracting electrode 13 by a power source (not shown).
A bias voltage of about 00V is applied. In addition, in order to extract ions from the gas ion source 10, a voltage of about +200 to 500 V is applied to the accelerating electrode 15, that is, to the thermionic emission means 12 with respect to the ground potential by a power supply (not shown). The electrons emitted from the thermionic emission means 12 are accelerated toward the thermionic extraction electrode 13 to excite, dissociate, and ionize a hydrocarbon-based gas containing a carbon element. The substrate is irradiated with the ionized carbon ions. At this time, the biasing means 5 biases the substrate 3 in the negative direction with respect to the ground potential by about −50 to −1000 V, and irradiates the surface of the substrate 3 with an ion current of about 100 to 2000 mA. Diffusion of carbon to the surface is performed, and a carbonized layer is formed by carbon ions. Subsequent to this processing, the DLC thin film 8 as described in the first embodiment is used.
0 is formed.

FIG. 26 schematically shows the above process.
Prior to carbonization, cleaning with hydrogen ions may be performed on the surface of the base material 3. As described above, DLC
Before the thin film 80 is formed, the surface of the substrate 3 is irradiated with carbon ions irradiated from the gas ion source 10 at an acceleration energy of about 50 eV to about 1000 eV and a current of about 100 to about 2,000 mA to perform carbonization. Since a carbonized layer is formed on the surface of the base material 3 and the hardness of the surface of the base material 3 is increased, the presence of a carbon component in the surface layer of the base material 3 facilitates the growth of the DLC thin film 80. And the DLC thin film 80 can be improved in adhesion strength, and a member 90 such as a mold, a tool, and a mechanical part having excellent wear resistance and corrosion resistance can be obtained.

[0044]

As described above, according to the first aspect of the present invention, an adhesion layer made of a metal thin film selected from the group consisting of silicon, tungsten, titanium, and aluminum, silicon carbide, tungsten carbide, titanium carbide, Since a diamond-like carbon (DLC) thin film is formed on the substrate through a DLC pretreatment layer made of a ceramic thin film selected from the group consisting of aluminum carbide,
The adhesiveness of the thin film is good, the surface hardness is high due to the ceramic thin film, and the DLC thin film is easy to grow at the time of formation. Therefore, a member excellent in abrasion resistance and corrosion resistance can be obtained.

According to the second aspect of the present invention, since the DLC pretreatment layer is made of a ceramic having the same metal component as the adhesion layer, a DLC thin film having better adhesion can be obtained, and the same effect as above can be obtained. . According to the invention of claim 3, D
In the LC pretreatment layer, the carbon composition increases from the adhesion layer toward the DLC thin film. According to the invention of claim 4, the DLC pretreatment layer is composed of a plurality of layers having different compositions. Is formed on the uppermost layer, so that the stress of the DLC thin film can be reduced,
A DLC thin film which is easy to grow and has good adhesion is obtained, and the same effect is obtained.

According to the fifth, sixth, seventh and eighth aspects of the present invention, the adhesion layer is made of silicon, tungsten, titanium and aluminum, and the DLC pretreatment layer is made of ceramic having the same metal component as the adhesion layer. A DLC thin film having good adhesion can be obtained, and the same effect can be obtained. According to the ninth aspect of the present invention, since the adhesion layer and the DLC pretreatment layer are each made of a metal thin film selected from the group consisting of silicon, tungsten, titanium, and aluminum, a DLC thin film having good adhesion can be obtained. It works.

According to the tenth aspect of the present invention, the treatment layer containing a carbon component is formed on the surface of the base material. According to the eleventh aspect of the invention, the treatment layer is an ion-implanted layer of carbon ions. According to the invention of Item 12, the distribution of the amount of carbon in the ion-implanted layer is made large near the surface of the base material, so that a DLC thin film having good adhesion can be obtained, and the same effect can be obtained.

According to the thirteenth aspect of the present invention, since the treatment layer is a carbonized layer, the surface hardness is increased, and a DLC thin film which is easy to grow and has good adhesion is obtained, and the same effect is obtained.

According to the fourteenth aspect, since hydrogen ions are irradiated together with carbon ions when forming the ion-implanted layer, the graphite formed on the base material is selectively etched to obtain a DLC thin film having good adhesion. And have the same effect.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a member on which a DLC thin film is formed according to Embodiment 1 of the present invention.

FIG. 2 is a sectional view showing a DLC thin film forming apparatus according to Embodiment 1 of the present invention.

FIG. 3 is a waveform diagram of a voltage applied by a bias unit in the first embodiment of the present invention.

FIG. 4 is a Raman spectrum diagram showing the film forming temperature dependence of a thin film according to the first embodiment of the present invention.

FIG. 5 is an explanatory diagram illustrating a thin film forming process according to the first embodiment of the present invention.

FIG. 6 is an explanatory diagram showing a thin film forming process according to the first embodiment of the present invention.

FIG. 7 is a cross-sectional view showing a member on which a DLC thin film is formed according to Embodiment 2 of the present invention.

FIG. 8 is a sectional view showing a member on which a DLC thin film is formed according to a second embodiment of the present invention.

FIG. 9 is a cross-sectional view showing a member on which a DLC thin film is formed according to Embodiment 2 of the present invention.

FIG. 10 is a cross-sectional view showing a member on which a DLC thin film is formed according to Embodiment 2 of the present invention.

FIG. 11 is a sectional view showing a member on which a DLC thin film is formed according to a third embodiment of the present invention.

FIG. 12 is a cross-sectional view showing a member on which a DLC thin film is formed according to Embodiment 3 of the present invention.

FIG. 13 is a sectional view showing a member on which a DLC thin film is formed according to Embodiment 3 of the present invention.

FIG. 14 is a cross-sectional view showing a member on which a DLC thin film is formed according to Embodiment 3 of the present invention.

FIG. 15 is a sectional view showing a member on which a DLC thin film is formed according to Embodiment 3 of the present invention.

FIG. 16 is a sectional view showing a member on which a DLC thin film is formed according to Embodiment 3 of the present invention.

FIG. 17 is a sectional view showing a DLC thin film forming apparatus according to a fourth embodiment of the present invention.

FIG. 18 is an explanatory diagram showing a thin film forming process according to Embodiment 4 of the present invention.

FIG. 19 is a sectional view showing a member on which a DLC thin film is formed according to a fifth embodiment of the present invention.

FIG. 20 is an explanatory diagram showing a DLC thin film forming apparatus according to Embodiment 5 of the present invention.

FIG. 21 is an explanatory diagram showing a thin film forming process according to a fifth embodiment of the present invention.

FIG. 22 is an explanatory diagram showing a thin film forming process according to a fifth embodiment of the present invention.

FIG. 23 is a diagram showing the relationship between the ion implantation energy and the distribution of the implantation dose in the depth direction.

FIG. 24 is a diagram showing a distribution of ion implantation energy with respect to time according to the fifth embodiment of the present invention.

FIG. 25 is a diagram showing a distribution of carbon atoms in a depth direction of a base material according to Embodiment 5 of the present invention.

FIG. 26 is an explanatory diagram illustrating a thin film forming process according to a sixth embodiment of the present invention.

FIG. 27 is a sectional view showing a member on which a conventional DLC thin film is formed.

FIG. 28 is a sectional view showing a conventional DLC thin film forming apparatus.

[Explanation of symbols]

3 base material, 50 underlayer, 51 treatment layer, 60 adhesion layer, 70 DLC pretreatment layer, 80 DLC thin film, 90
Element.

Claims (14)

[Claims] In a member in which a diamond-like carbon thin film is formed on a base material via a base layer, the base layer is composed of an adhesion layer formed on the base material and a DLC layer formed on the adhesion layer. The adhesion layer is made of a metal thin film selected from the group consisting of silicon, tungsten, titanium, and aluminum, and the DLC pretreatment layer is made of a group consisting of silicon carbide, tungsten carbide, titanium carbide, and aluminum carbide. A member having a diamond-like carbon thin film formed thereon, comprising a ceramic thin film selected from the group consisting of: 2. The member having a diamond-like carbon thin film according to claim 1, wherein the DLC pretreatment layer is made of ceramic containing the same metal component as the adhesion layer. 3. The DLC pretreatment layer is characterized in that the carbon component composition is larger than the metal component composition from the adhesion layer toward the diamond-like carbon thin film.
A member on which the diamond-like carbon thin film according to claim 2 is formed. 4. The DLC pre-treatment layer comprises a plurality of ceramic layers containing the same metal component and having different compositions.
3. A layer having the largest carbon composition among the plurality of ceramic layers is formed as an uppermost layer.
A member on which the diamond-like carbon thin film according to the above is formed. 5. The member according to claim 2, wherein the DLC pretreatment layer is made of a ceramic containing silicon. 6. The member having a diamond-like carbon thin film formed thereon according to claim 2, wherein the DLC pretreatment layer is made of a ceramic containing tungsten. 7. The DLC pre-treatment layer is made of a ceramic containing titanium.
A member having the diamond-like carbon thin film according to any one of the above. 8. The member having a diamond-like carbon thin film formed thereon according to claim 2, wherein the DLC pretreatment layer is made of a ceramic containing aluminum. 9. In a member in which a diamond-like carbon thin film is formed on a base material via a base layer, the base layer is formed of an adhesion layer formed on the base material and a DLC layer formed on the adhesion layer. A member having a diamond-like carbon thin film formed thereon, wherein the adhesion layer and the DLC pretreatment layer are each formed of a metal thin film selected from the group consisting of silicon, tungsten, titanium, and aluminum. 10. A member in which a diamond-like carbon thin film is formed on a substrate, wherein a treatment layer containing a carbon component is formed on the surface of the substrate. . 11. The treatment layer is an ion-implanted layer formed by implanting carbon ions.
A member on which the diamond-like carbon thin film according to the above is formed. 12. The diamond-like carbon thin film according to claim 11, wherein the amount of carbon in the ion-implanted layer is large in the vicinity of the surface of the base material, and has a distribution decreasing as the depth increases. Components. 13. The member having a diamond-like carbon thin film according to claim 10, wherein the treatment layer is a carbonized layer formed by irradiation and diffusion of carbon ions. 14. A first step of forming an ion-implanted layer by implanting carbon ions into the surface of a substrate by irradiating carbon ions, and irradiating dissociated carbon and carbon ions and dissociated hydrogen and hydrogen ions. In the method for forming a diamond-like carbon thin film having a second step of forming a diamond-like carbon thin film on the ion-implanted layer, the method further comprises irradiating the substrate surface with hydrogen ions together with carbon ions in the second step. A method for forming a diamond-like carbon thin film.