JPWO2016017438A1 - Carbon thin film, plasma apparatus for manufacturing the same, and manufacturing method - Google Patents

Abstract

Provided is a plasma device capable of suppressing the breakage of a cathode material. The plasma apparatus 10 includes a vacuum vessel 1, an arc evaporation source 3, a cathode member 4, a permanent magnet 5, a power source 7, a trigger electrode 8, and a shutter 12. The arc evaporation source 3 is fixed to the side wall of the vacuum vessel 1 so as to face the substrate 20. The cathode member 4 is made of glassy carbon having protrusions, and is attached to the arc evaporation source 3. The protrusion has a cross-sectional area greater than 0.785 mm2. The permanent magnet 5 applies a magnetic field to the cathode member 4. The power source 7 applies a negative voltage to the arc evaporation source 3. The trigger electrode 8 contacts or separates from the protruding portion of the cathode member 4. A negative voltage is applied to the arc evaporation source 3, the trigger electrode 8 is brought into contact with the protrusion of the cathode member 4 to generate arc discharge, the shutter 12 is opened, and a carbon thin film is formed on the substrate 20.

Description

  The present invention relates to a carbon thin film, a plasma apparatus for manufacturing the carbon thin film, and a manufacturing method.

  2. Description of the Related Art Conventionally, an arc evaporation source used in a thin film forming apparatus for forming a thin film using arc discharge is known as a filtered vacuum arc type (FVA type) arc evaporation source in which coarse particles are prevented from adhering to a substrate. (Patent Document 1).

  This arc evaporation source includes a vacuum vessel, a plasma duct, a porous member, a magnetic coil, and an evaporation source. One end of the plasma duct is attached to the vacuum vessel. The evaporation source is attached to the other end of the plasma duct.

  The magnetic coil is wound around the plasma duct. The magnetic coil guides plasma generated in the vicinity of the evaporation source to the vicinity of the substrate disposed in the vacuum vessel.

  The porous member is attached to the inner wall of the plasma duct and captures coarse particles that have jumped out of the cathode material attached to the evaporation source.

  As described above, the conventional vacuum arc deposition apparatus connects the evaporation source to the vacuum vessel by the plasma duct, captures the coarse particles jumping out from the cathode material by the porous member provided on the inner wall of the plasma duct, and the coarse particles are formed on the substrate. Suppresses flying in.

  A diamond-like carbon film formed using such a filtered arc evaporation source has been proposed (Patent Document 2). In film formation by such a method, droplets are collected using a duct to suppress the flying of coarse particles. However, when the liquid droplet collides with the duct surface, it is scattered as fine particles with a size of 20 nm or less, and the duct itself serves as a guide for the droplet and is transported to the film forming chamber, which is less than 20 nm A large number of particles having a size are formed.

  For this reason, the method of Patent Document 2 discloses a diamond-like carbon film in which the number of irregularities having a height or depth of 20 nm or more is 0.01 or less per unit film thickness. However, the small irregularities were not sufficiently improved.

  Further, the presence of such very small asperities of 10 to 20 nm has not been so much noticed since it has had a large adverse effect due to the asperities of 20 nm or more, but precision molds such as molds for molding optical lenses. In this application, the effect of reducing the number of irregularities of 10 to 20 nm is very large, and a film forming method replacing the FVA method has been demanded.

JP 2002-105628 A JP 2014-062326 A

  In the conventional vacuum arc vapor deposition apparatus, graphite (carbon) is used as a cathode material, and graphite is produced by sintering carbon particles, so there is a grain boundary. As a result, when graphite is used as the cathode material, there is a problem in that the cathode material breaks along the grain boundaries and coarse particles (particles) are generated. Further, a technique has been proposed in which such coarse particles are collected using a plasma duct to suppress the flying of the coarse particles. However, generation of fine particles of 20 nm or less produced by collision of coarse particles with the duct is performed. It was not possible to suppress it sufficiently.

  Therefore, according to the embodiment of the present invention, a plasma apparatus capable of suppressing the breakage of the cathode material is provided.

  In addition, according to the embodiment of the present invention, there is provided a method for producing a carbon thin film capable of producing a carbon thin film while preventing the cathode material from cracking.

  Furthermore, according to the embodiment of the present invention, there is provided a carbon thin film manufactured by suppressing the cathode material from cracking.

  According to the embodiment of the present invention, the carbon thin film includes a carbon film in which the number of irregularities of 20 nm is less than 0.007 [piece / mm / nm] per unit scanning distance and unit film thickness.

  Therefore, unevenness of 10 to 20 nm can be reduced.

Preferably, the carbon film is formed using glassy carbon having a thermal shock resistance R expressed by the following formula (1) larger than 7.9 as a cathode member.
Here, in the formula (1), σ is the bending strength [MPa], λ is the thermal conductivity [W / mK], α is the thermal expansion coefficient [/ 10 ⁶ K], and E is the Young's modulus [GPa]. . When the thermal shock resistance R is larger than 7.9, the thermal shock resistance of the glassy carbon increases with respect to the thermal stress generated on the surface of the cathode member by arc discharge, and the cathode member can be prevented from cracking. Therefore, the unevenness of 10 to 20 nm that is likely to occur when the cathode member is cracked can be further reduced.

According to the embodiment of the present invention, the plasma apparatus includes a vacuum vessel, an arc evaporation source, a cathode member, a holding member, a discharge starting unit, and a power source. The arc evaporation source is fixed to the vacuum vessel. The cathode member is attached to an arc evaporation source. The holding member holds the substrate disposed toward the cathode member. The discharge start means starts discharge. The power source applies a negative voltage to the arc evaporation source. The negative electrode member is made of glassy carbon, has a columnar shape, and includes a columnar portion having a cross-sectional area larger than 0.785 mm ² . Then, the discharge start means starts the discharge so that the plasma is emitted from the columnar portion of the cathode member.

In the plasma device according to the embodiment of the present invention, the cathode member includes a columnar portion having a cross-sectional area larger than 0.785 mm ² . As a result, even if arc discharge is started and the temperature of the cathode member rises rapidly, the cathode member has a strength that can withstand thermal stress. Therefore, the cathode member can be prevented from cracking.

  Preferably, the thermal shock resistance R represented by the above formula (1) of the cathode member is larger than 7.9.

Furthermore, according to the embodiment of the present invention, the method for producing a carbon thin film comprises an arc evaporation source fixed to a vacuum vessel toward a substrate, is made of glassy carbon, has a columnar shape, and A first step of attaching a cathode member including a columnar portion having a cross-sectional area larger than 0.785 mm ^{2, a second} step of applying a negative voltage to the arc evaporation source, and plasma is emitted from the columnar portion of the cathode member And a third step of starting discharge and forming a carbon film on the substrate.

  By using the method for producing a carbon thin film according to the embodiment of the present invention, even when arc discharge is started and the temperature of the cathode member rises rapidly, the cathode member has the strength to withstand thermal stress. Therefore, the cathode member can be prevented from cracking.

  Preferably, the thermal shock resistance R represented by the above formula (1) of the cathode member is larger than 7.9.

  It is possible to prevent the cathode member from cracking.

  It is possible to provide a compact film forming apparatus and a coated article thereof with a small film thickness of 10 to 20 nm and a large film forming speed.

It is the schematic which shows the structure of the plasma apparatus by Embodiment 1 of this invention. It is a perspective view of the negative electrode member shown in FIG. FIG. 3 is a cross-sectional view of the cathode member taken along line III-III shown in FIG. 2. It is process drawing which shows the manufacturing method of the carbon thin film using the plasma apparatus shown in FIG. It is a figure which shows the projection part after discharge when glassy carbon (projection part) of diameter 2mm (phi) is used. It is a figure which shows the projection part after discharge when glassy carbon (projection part) of diameter 5.2mm (phi) is used. It is a figure which shows the cathode member of the comparative example 1 after a vacuum arc discharge test. It is a figure which shows the cathode member of Example 1 after a vacuum arc discharge test. It is the schematic which shows the structure of the plasma apparatus by Embodiment 2. FIG. It is sectional drawing of the carbon thin film (diamond-like carbon film) manufactured with the plasma apparatus shown in FIG. It is process drawing which shows the manufacturing method of the carbon thin film (diamond-like carbon film) using the plasma apparatus shown in FIG. It is the schematic of the plasma apparatus using the conventional arc method. It is a figure which shows the relationship between the number of uneven | corrugated defects, and the size of an uneven | corrugated defect.

    Embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals and description thereof will not be repeated.

[Embodiment 1]
FIG. 1 is a schematic diagram showing a configuration of a plasma apparatus according to Embodiment 1 of the present invention. Referring to FIG. 1, a plasma apparatus according to Embodiment 1 of the present invention includes a vacuum vessel 1, a holding member 2, an arc evaporation source 3, a cathode member 4, a permanent magnet 5, and power supplies 6 and 7. A trigger electrode 8, a resistor 9, and a shutter 12.

  In the plasma apparatus 10, the x axis, the y axis, and the z axis are defined as shown in FIG.

  The vacuum container 1 has an exhaust port 11 and is evacuated from the exhaust port 11 by an exhaust device (not shown). The vacuum container 1 is connected to the ground node GND.

  The holding member 2 is disposed in the vacuum container 1. The holding member 2 has a cylindrical portion 2A. The cylindrical portion 2A is rotated by a rotating device (not shown) in the yz plane. Then, the substrate 20 can rotate in the yz plane with the rotation of the cylindrical portion 2 </ b> A of the holding member 2.

  The arc evaporation source 3 is fixed to the side wall of the vacuum vessel 1.

  The cathode member 4 is attached to the surface of the arc evaporation source 3 on the substrate 20 side. The cathode member 4 is made of glassy carbon. Glassy carbon is produced by firing and carbonizing a thermosetting resin such as a phenol resin. This glassy carbon is structurally glassy and has no grain boundaries. The cathode member 4 may be made of conductive diamond because there is no grain boundary. Further, the cathode member 4 has a protruding portion protruding toward the substrate 20 side.

  Specific examples of glassy carbon include glassy carbon made by Nisshinbo Chemical, or glassy carbon made by Tokai Carbon. In the embodiment of the present invention, glassy carbon, amorphous carbon, amorphous carbon, amorphous carbon, amorphous carbon, non-graphitized carbon, and vital carbon are included in glassy carbon. And

  The permanent magnet 5 has a ring shape and is disposed in the vicinity of the arc evaporation source 3 outside the vacuum vessel 1. More specifically, the permanent magnet 5 is disposed so that the central axis thereof coincides with the central axis of the arc evaporation source 3. In the permanent magnet 5, the arc evaporation source 3 side is the N pole, and the opposite side of the arc evaporation source 3 is the S pole. Thus, the permanent magnet 5 is disposed on the opposite side of the substrate 20 with respect to the cathode member 4. The permanent magnet 5 applies a magnetic field in the axial direction (the direction from the cathode member 4 toward the substrate 20) to the cathode member 4. The magnetizing direction of the permanent magnet 5 may be an axial direction (a direction from the cathode member 4 toward the substrate 20), and the arc evaporation source 3 side of the permanent magnet 5 may be an S pole.

  Power supply 6 is connected between holding member 2 and ground node GND. The power supply 7 is connected between the arc evaporation source 3 and the ground node GND.

  A part of the trigger electrode 8 is disposed in the vacuum container 1 through the side wall of the vacuum container 1, and the remaining part is disposed outside the vacuum container 1. The trigger electrode 8 is made of, for example, molybdenum (Mo), and is connected to the ground node GND through the resistor 9. The resistor 9 is connected between the trigger electrode 8 and the ground node GND.

  The holding member 2 holds the substrate 20. In this case, the holding member 2 rotates and stops at an arbitrary angle in the yz plane, and holds the substrate 20. The arc evaporation source 3 causes the cathode member 4 to be locally heated by arc discharge between the cathode member 4 and the vacuum vessel 1 to evaporate the cathode material.

  The power source 6 applies a negative voltage to the substrate 20 via the holding member 2. The power source 7 applies a negative voltage to the arc evaporation source 3.

  The trigger electrode 8 contacts or separates from the cathode member 4 by a reciprocating drive device (not shown). The resistor 9 suppresses the arc current from flowing to the trigger electrode 8. The shutter 12 is disposed between the cathode member 4 and the substrate 20 so as to face the cathode member 4.

  The substrate 20 is made of, for example, one of Fe-based metal, Si, tungsten carbide and SiC.

  FIG. 2 is a perspective view of the cathode member 4 shown in FIG. FIG. 3 is a cross-sectional view of the cathode member 4 taken along the line III-III shown in FIG.

  Referring to FIGS. 2 and 3, negative electrode member 4 includes a main body portion 41 and a protrusion portion 42. The main body 41 has a disk shape. The protrusion 42 has a cylindrical shape. The protrusion 42 is arranged on the main body 41 so that the central axis X2 of the protrusion 42 coincides with the central axis X1 of the main body 41. In addition, the main-body part 41 and the projection part 42 are produced integrally.

  The main body 41 has, for example, a diameter R1 of 64 mmφ and a height H1 of 12 mm. The protrusion 42 has a diameter R2 of 2 mmφ or more, and a height H2 of several mm or more, for example, 6 mm to 80 mm.

  The cathode member 4 is produced by the following method. A thermosetting resin such as a phenol resin is fired and carbonized to produce cylindrical glassy carbon. Thereafter, the produced glassy carbon may be turned so as to have the protrusions 42 to produce the cathode member 4, or the thermosetting resin may be poured into a mold and molded, and then fired and carbonized. Also good. The method of forming the protrusion 42 is not limited to lathe processing or molding by a mold, and may be etching (including both wet etching and dry etching), and any method capable of forming the protrusion 42. Any method may be used. Moreover, the protrusion part 42 and the main-body part 41 may each be produced separately, the protrusion part 42 is glassy carbon, and the main-body part 41 is made of, for example, sintered graphite or glassy carbon. There may be.

The cross-sectional area of the protrusion 42 in the direction perpendicular to the central axis X2 is π × 3 mm × 3 mm = 28.3 mm ² when the diameter R2 of the protrusion 42 is 6 mmφ, and the main body in the direction perpendicular to the central axis X1 The cross-sectional area of the portion 41 is π × 32 mm × 32 mm = 3215.4 mm ² . As a result, the ratio of the cross-sectional area of the protrusion 42 to the cross-sectional area of the main body 41 is about 1/113.

  As a result, the heat transfer component in the protrusions 42 is reduced, making it difficult for heat to escape from the protrusions 42, and the entire protrusion 42 is easily soaked, so that thermal distortion is reduced.

  Further, since glassy carbon has no grain boundary, atomic carbon is emitted from the cathode member 4 during arc discharge when used as the cathode member 4.

  Therefore, the cathode member 4 can be prevented from cracking.

  As described above, since atomic carbon is released from the cathode member 4, no particles are generated. As a result, when the cathode member 4 is used, a sparkless discharge can be generated. This sparkless discharge is a discharge in which particles are not generated. In this specification, the term “particle” refers to a carbon particle having a size of 5 nm to several μm.

  On the other hand, a sintered body obtained by sintering carbon particles is not suitable as the cathode member 4. The reason is as follows. Since the sintered body of carbon is obtained by pressing and solidifying carbon grains, grain boundaries exist. As a result, when a carbon sintered body is used as the cathode member 4, the cathode member 4 is cracked from the grain boundary during arc discharge, and particles are emitted from the cathode member 4.

  FIG. 4 is a process diagram showing a carbon thin film manufacturing method using the plasma apparatus 10 shown in FIG. Referring to FIG. 4, when the production of the carbon thin film is started, glassy carbon having protrusions 42 is attached to arc evaporation source 3 as cathode member 4 (step S1).

And the inside of the vacuum vessel 1 is exhausted through the exhaust port 11, and the pressure in the vacuum vessel 1 is set to 9.9 * 10 < ^-3 > Pa.

  Then, a negative voltage of −10 V to −300 V is applied to the substrate 20 by the power source 6 (step S2), and a magnetic field is applied to the cathode member 4 by the permanent magnet 5 (step S3). In this case, the magnetic field has a component in the central axis X2 direction of the protrusion 42 of the cathode member 4 and a component in the radial direction of the protrusion 42.

  After step S3, a negative voltage of −15 V to −50 V is applied to the arc evaporation source 3 by the power source 7 (step S4).

  Then, the trigger electrode 8 is brought into contact with the protrusion 42 of the cathode member 4 by a reciprocating drive device (not shown) (step S5), and then the trigger electrode 8 is separated from the cathode member 4. As a result, arc discharge starts and an arc spot appears on the surface of the cathode member 4. This arc spot is a cathode spot in arc discharge and emits light strongly.

  Thereafter, the shutter 12 is opened (step S6). Thus, a carbon thin film (DLC: Diamond Like Carbon) is formed on the substrate 20. Then, it is determined by the operator of the plasma apparatus 10 whether or not the discharge has stopped (step S7). Since the arc spot is intensely emitted, the operator of the plasma apparatus 10 determines that the discharge has not stopped if the arc spot is shining, and that the discharge has stopped if the arc spot does not shine. judge.

  When it is determined in step S7 that the discharge has stopped, the shutter 12 is closed (step S8), and then the above-described steps S5 to S8 are repeatedly executed.

  On the other hand, when it is determined in step S7 that the discharge has not stopped, the shutter 12 is closed when a desired time has elapsed (step S9). This completes the production of the carbon thin film.

  And the carbon thin film manufactured according to the process S1-step S9 mentioned above shall contain an amorphous carbon thin film, a diamond-like carbon thin film, a tetrahedral amorphous carbon film, an amorphous hard carbon thin film, and a hard carbon thin film. .

  In the first embodiment, the power supply 6 may apply a voltage of 0 V to the substrate 20. Further, the carbon thin film may be manufactured with the shutter 12 opened. Furthermore, the magnetic field may not be applied. Therefore, the carbon thin film manufacturing method according to the first embodiment only needs to include at least steps S1, S4, and S5 shown in FIG.

  As described above, the carbon thin film has the protrusions 42 having a diameter of 2 mmφ or more and is formed on the substrate 20 by arc discharge using the cathode member 4 made of glassy carbon.

  As a result, the thermal strain in the protrusion 42 is reduced, and the cathode member 4 (glassy carbon) does not have a grain boundary, so that the cathode member 4 can be prevented from cracking along the grain boundary.

  An experiment in which the diameter (= cross-sectional area) of the protrusion 42 of the cathode member 4 is changed will be described. Table 1 shows the detailed experimental conditions of the experiment using the plasma apparatus 10.

  The axial magnetic field Bz and radial magnetic field Br in Table 1 are values measured at the tip of the protrusion 42 of the cathode member 4 using a 410-SCT type gauss meter manufactured by Lake Shore.

  In the experiment, the discharge state and discharge duration when the heights of the protrusions 42 of the cathode member 4 are all 10 mm and the diameters of the protrusions 42 are changed to 1 mmφ, 2 mmφ, 3 mmφ, 5.2 mmφ, and 6 mmφ. And the discharge trace state was investigated.

  Table 2 shows the experimental results when the arc current is 40 [A].

  FIG. 5 is a diagram showing the protrusion 42 after discharge when glassy carbon (projection 42) having a diameter of 2 mmφ is used. FIG. 6 is a diagram showing the protrusion 42 after discharge when glassy carbon (protrusion 42) having a diameter of 5.2 mmφ is used.

When the arc current is 40 [A], only when the diameter of the protrusion 42 is 1 mmφ (that is, the cross-sectional area = 0.785 mm ² ), the whole is crushed after the ignition and the discharge is stopped in about 1 sec. . And when the diameter of the projection part 42 is 2 mmφ, 3 mmφ, 5.2 mmφ, 6 mmφ, that is, the cross-sectional area of the projection part 42 is 3.140 mm ² , 7.065 mm ² , 21.226 mm ² , 28.260 mm ² . In some cases, forcible extinguishing was performed after confirming that stable sparkless discharge continued for 40 [sec]. After forcibly extinguishing the arc, the vacuum chamber 1 is opened to the atmosphere, and the glassy carbon of the cathode member 4 is confirmed. As a result, when the diameter of the protrusion 42 is 2 mmφ, 3 mmφ, 5.2 mmφ, 6 mmφ, the cross-sectional area ^{3.140mm 2, 7.065mm 2, 21.226mm 2} , the case is 28.260Mm ^2, the discharge traces of spiral was observed on the side surface of the protrusion 42 of the cathode member 4 (FIG. 5 and 6).

  As described above, when arc discharge is generated using the cathode member 4 provided with the protruding portion 42, the arc spot moves spirally on the surface of the protruding portion 42 by the magnetic field from the permanent magnet 5. As a result, the arc spot does not move to the main body 41. Therefore, the fact that the spiral discharge trace is formed on the protrusion 42 after the discharge is the basis for the movement of the arc spot to the main body 41 does not occur.

  Only when the diameter of the protruding portion 42 is 1 mmφ, the fact that the entire portion was crushed is considered to be because the protruding portion 42 could not withstand thermal stress.

  The amount of heat that generates thermal stress is a heat transfer component from the arc spot (the same amount of heat if the arc current is the same) and a Joule heat generation component when the arc current flows through the protrusion 42. If the arc current is constant, the Joule heat generation component increases as the cross-sectional area of the protrusion 42 decreases. Accordingly, the smaller the cross-sectional area, the greater the amount of heat of the protrusion 42.

As a result, it is considered that only when the cross-sectional area is 0.785 mm ² , the thermal stress due to the amount of heat generated in the protrusion 42 could not be withstood.

  Table 3 shows the experimental results when the arc current is 80 [A].

If the arc current is 80 [A], when the diameter of the protrusion 42 is 1 mm in diameter, is 2 mm, i.e., if the cross-sectional area of the projecting portion 42 is 0.785 mm ^2, a 3.140Mm ^2, after ignition, The whole was crushed and the discharge stopped in about 1 sec. And when the diameter of the protrusion 42 is 3 mmφ, 5.2 mmφ, 6 mmφ, that is, when the cross-sectional area of the protrusion 42 is 7.065 mm ² , 21.226 mm ² , 28.260 mm ² , it is stable. After confirming that the sparkless discharge continued for 40 [sec], the arc was forcibly extinguished. After forcibly extinguishing the arc, the vacuum chamber 1 is opened to the atmosphere, and the glassy carbon of the cathode member 4 is confirmed. As a result, when the diameter of the protrusion 42 is 3 mmφ, 5.2 mmφ, 6 mmφ, Spiral discharge traces were confirmed on the side surfaces of the portion 42.

When the diameter of the protruding portion 42 is 1 mmφ, 2 mmφ, that is, when the sectional area of the protruding portion 42 is 0.785 mm ² or 3.140 mm ² , the protruding portion 42 is subjected to thermal stress when the whole is crushed. This is probably because he could not endure.

  Table 4 shows the experimental results when the arc current is 100 [A].

  The experimental result when the arc current was 100 [A] was the same as the experimental result when the arc current was 80 [A].

From the experimental results described above, when the arc current is 40 [A], when the cross-sectional area of the protrusion 42 of the cathode member 4 is larger than 0.785 mm ² , good discharge can be realized, and the arc current can be realized. When the cross-sectional area of the protrusion 42 of the cathode member 4 is larger than 3.140 mm ² , good discharge can be realized.

Even when the arc current is 40 [A], good discharge can be realized. Thus, it was proved that the cross-sectional area of the protrusion 42 of the cathode member 4 should be larger than 0.785 mm ² .

In addition, the cross-sectional area of the protruding portion 42 of the cathode member 4 is preferably from the viewpoint of realizing good discharge even when the arc current is 40 [A], 80 [A], or 100 [A], 3. Greater than 140 mm ² .

  In the embodiment of the present invention, a discharge having a discharge duration of 40 [sec] is determined as a good discharge. This is because the length of the protrusion 42 is 20 [mm]. This is the time when a part of the protrusion 42 is consumed in the length direction due to discharge. As a result, if the length of the protrusion 42 is longer than 20 [mm], the duration of the discharge becomes longer than 40 [sec], and the time for determining whether or not the discharge is good is 40 It becomes longer than [sec].

  As described above, in the embodiment of the present invention, the cross-sectional area of the protrusion 42 when a part of the protrusion 42 of the cathode member 4 is consumed by discharge over the length direction is determined as a suitable cross-sectional area. .

  Therefore, when the discharge duration is 40 [sec], the significance of the discharge is significantly greater than when the discharge duration is about 1 [sec].

Therefore, the cross-sectional area of the protrusions 42 of 3.140 mm ² or more has a critical significance compared to the cross-sectional area of the protrusions 42 when the discharge duration is about 1 [sec].

  The reason why the cross-sectional area of the protrusion 42 is used as a feature of the protrusion 42 to achieve good discharge is that the cross-sectional shape of the protrusion 42 in the direction perpendicular to the length direction is not limited to a circle but an ellipse. This is because it may be a shape, a polygonal shape with rounded corners (R removal), or a hollow shape such as a pipe.

Further, the thermal shock resistance R of the cathode member 4 is preferably larger than 7.9, more preferably 12.2 or more. The thermal shock resistance R is defined by the following formula (1). In the following formula (1), σ is the bending strength [MPa], λ is the thermal conductivity [W / mK], α is the thermal expansion coefficient [/ 106K], and E is the Young's modulus [GPa].

  Since the cathode member 4 has a thermal shock resistance R larger than 7.9, a rapid temperature rise occurs during vacuum arc discharge, and even when a large thermal stress is generated, it is difficult to pulverize. Therefore, the use of the cathode member 4 can be expected to continue stable sparkless discharge.

  Hereinafter, an experiment in which the thermal shock resistance of the cathode member 4 is changed will be described.

  When the plasma apparatus 100 is used and the arc current is 80 [A] under the test conditions shown in Table 1, four types of cathode members (Comparative Example 1, Example 1, Example 2) are tested under the test conditions shown in Table 5. And Example 3) A vacuum arc discharge test was conducted for each. The cathode members of Comparative Example 1, Example 1, Example 2, and Example 3 are made of glassy carbon and have a columnar shape with substantially the same dimensions. Each cathode member of Example 1, Example 2, and Example 3 corresponds to the protrusion 42 of the cathode member 4 in the first embodiment.

  Table 5 shows the bending strength σ, thermal conductivity λ, thermal expansion coefficient α, Young's modulus E, and thermal shock resistance R of each cathode member. The bending strength σ, thermal conductivity λ, thermal expansion coefficient α, and Young's modulus E of each cathode member shown in Table 5 are values at about 20 to 30 ° C. Each thermal shock resistance R shown in Table 5 is calculated by the above formula (1) using the values of bending strength σ, thermal conductivity λ, thermal expansion coefficient α, and Young's modulus E.

  The results of the vacuum arc discharge test in this example are shown in Table 6. When the vacuum arc discharge test was performed three times for each of the cathode members of Comparative Example 1, Example 1, Example 2, and Example 3, the same result was obtained for all three times.

  The cathode member of Comparative Example 1 was crushed instantaneously after the discharge was ignited, and the discharge was stopped. The cathode member of Comparative Example 1 after the vacuum arc discharge test is shown in FIG. The cathode member of Comparative Example 1 had a thermal shock resistance R as low as 7.9 and could not withstand a rapid temperature rise when the discharge was ignited. .

  On the other hand, in the cathode members of Examples 1, 1 and 3 having a thermal shock resistance R greater than 7.9, stable sparkless discharge occurred. Therefore, it can be seen that when the thermal shock resistance R of the cathode member is larger than 7.9, the sparkless discharge continues stably.

  About Example 1, Example 2, and Example 3, after confirming that the stable sparkless discharge continued over 40 seconds, it forcibly extinguished. After forced extinction, the vacuum vessel 1 was opened to the atmosphere and each cathode member was confirmed.

  As for the cathode member of Example 1, Example 2, and Example 3, the spiral-shaped discharge trace remained in all the side surfaces. From this point, it can be seen that the arc spot moved spirally on the side surfaces of the cathode members of Example 1, Example 2, and Example 3 during the vacuum arc discharge. That is, it can be evaluated that the cathode members of Example 1, Example 2, and Example 3 suppress the movement of the arc spot to a part other than the cathode member. FIG. 8 is a photograph of the cathode member of Example 1 after the vacuum arc discharge test.

[Embodiment 2]
FIG. 9 is a schematic diagram showing the configuration of the plasma device according to the second embodiment. Referring to FIG. 9, plasma apparatus 100 according to the second embodiment is similar to plasma apparatus 10 shown in FIG. 1, except that arc evaporation source 103, power supplies 105 and 106, resistor 107, trigger electrode 108, and vacuum vessel. 110 and coils 120 to 122 are added, and the rest is the same as the plasma apparatus 10.

  In the plasma apparatus 100, the vacuum container 1 has a gas supply port 13.

  The vacuum vessel 110 is formed of a cylindrical member that is curved in an arc shape. The vacuum vessel 110 has an opening 110A and walls 110B, 110C, and 100D. The vacuum container 110 is fixed to the side wall of the vacuum container 1 so that one end on the opening 110 </ b> A side penetrates the side wall of the vacuum container 1. As a result, the internal space of the vacuum vessel 110 communicates with the internal space of the vacuum vessel 1.

  The arc evaporation source 103 is fixed to the wall 110 </ b> D of the vacuum vessel 110. The arc evaporation source 103 is connected to the negative electrode of the power source 105.

  The cathode member 104 is fixed to the surface of the arc evaporation source 103 on the substrate 20 side. The negative electrode member 104 has a disk shape and is made of at least one element selected from the periodic table 4A, 5A, and 6A group elements, B, and Si, and any of these nitrides.

  Power source 105 is connected between arc evaporation source 103 and ground node GND. Power supply 106 is connected between vacuum vessel 110 and ground node GND.

  One end of the trigger electrode 108 is disposed in the vacuum container 110 via the wall 110 </ b> D of the vacuum container 110 and faces the cathode member 104. The other end of the trigger electrode 108 is connected to the resistor 107. The trigger electrode 108 is made of Mo, for example.

  Resistor 107 is connected between trigger electrode 108 and ground node GND.

  The coil 120 is disposed around the vacuum vessel 110 in the vicinity of the cathode member 104. The both ends of the coil 120 are connected to a power source (not shown). The coil 120 is provided for extracting plasma.

  The coil 121 is disposed around the vacuum vessel 110 at a substantially central portion between the opening 110A of the vacuum vessel 110 and the wall 110D. The both ends of the coil 121 are connected to a power source (not shown). The coil 121 is provided to bend the plasma along the arc shape of the vacuum vessel 110.

  The coil 122 is disposed around the vacuum container 110 in the vicinity of the opening 110 </ b> A of the vacuum container 110. The both ends of the coil 122 are connected to a power source (not shown). The coil 122 is provided for converging the plasma.

  When a current flows through the coils 120 to 122 by a power source (not shown), the coils 120 to 122 generate a magnetic field inside the vacuum vessel 110. This magnetic field bends ions that have jumped out of the protrusion 1042 of the cathode member 104 into an arc shape along the vacuum container 110, and causes the ions to reach the substrate 20. The particles and neutral particles that have jumped out of the cathode member 104 collide with the walls 110 </ b> B and 110 </ b> C of the vacuum vessel 110 and do not reach the substrate 20.

  Therefore, if the plasma apparatus 100 is used, a carbon thin film having very few particles, that is, a very small surface roughness can be produced.

  Moreover, if the plasma apparatus 100 is used, a high-quality carbon thin film with few impurities can be manufactured.

  FIG. 10 is a cross-sectional view of a carbon thin film (diamond-like carbon film) manufactured by the plasma apparatus 100 shown in FIG. Referring to FIG. 10, carbon thin film 50 includes a substrate 20, intermediate layers 30 and 35, and carbon film 40.

  The intermediate layer 30 is formed on one main surface of the substrate 20. The intermediate layer 30 is composed of at least one element selected from the periodic table 4A, 5A, and 6A group elements, B, and Si, and nitrides thereof. As the 4A, 5A, and 6A group elements, Cr, Ti, and W are particularly preferable, and nitrides such as CrN and TiN can also be used.

  The intermediate layer 35 is made of diamond-like carbon and is formed in contact with the intermediate layer 30.

  The carbon film 40 is formed in contact with the intermediate layer 35.

  FIG. 11 is a process diagram showing a method of manufacturing a carbon thin film (diamond-like carbon film) using the plasma apparatus 100 shown in FIG.

  The process diagram shown in FIG. 11 is obtained by adding steps S11 to S16 to the process diagram shown in FIG. 4, and the other processes are the same as the process diagram shown in FIG.

  Referring to FIG. 11, when the production of carbon thin film 50 is started, it consists of at least one element selected from periodic table 4A, 5A, 6A group element, B, Si, and any of these nitrides. The metal cathode member 104 is attached to the arc evaporation source 103 (step S11).

  Then, a negative voltage is applied to the substrate 20 (step S12). Thereafter, a magnetic field for extracting plasma is applied by the coil 120, a magnetic field for converging the plasma is applied by the coil 122, and only ions (Cr ions, etc.) emitted from the cathode member 14 are vacuumed in an arc shape. A magnetic field for bending along the container 110 is applied by the coil 121 (step S13).

  Then, a negative voltage is applied to the arc evaporation source 103 (step S14). Subsequently, the trigger electrode 108 is brought into contact with the cathode member 104 (step S15), and then the trigger electrode 108 is pulled away from the cathode member 104.

  Thereby, arc discharge occurs and the intermediate layer 30 having a desired film thickness is formed on the substrate 20 (step S16).

  Thereafter, the substrate 20 is rotated 180 degrees and held, and the above-described steps S1 to S9 are sequentially performed to form the intermediate layer 35 made of diamond-like carbon on the intermediate layer 30, and then the carbon film 40 is formed on the intermediate layer. 35 is formed. As a result, a series of operations is completed.

  11 includes the steps S1 to S9 described in the first embodiment. Therefore, if the carbon thin film is manufactured according to the process diagram shown in FIG. 11, the cathode member 4 is formed as in the first embodiment. The carbon thin film can be produced by preventing sparks and performing stable sparkless discharge.

  In the manufacture of the carbon thin film 50, the intermediate layer 30 may be formed on the substrate 20 by a sputtering method instead of the steps S11 to S16 shown in FIG. That is, the intermediate layer 30 allows ions (Cr ions or the like) emitted from the cathode member 104 to enter the vacuum vessel 110 formed of a cylindrical member curved in an arc shape disposed between the cathode member 104 and the substrate 20. It may be formed by a sputtering method in which ions (Cr ions or the like) emitted from the cathode member 104 reach the substrate 20 by bending in a circular arc along the vacuum vessel 110.

  Furthermore, the surface shape of the intermediate layer formed by the sputtering method is smooth compared to the arc method. Therefore, ions emitted from the cathode member 104 are linearly distributed from the cathode member 104 to the substrate 20 without using the arcuate cylindrical member disposed between the cathode member 104 and the substrate 20 by sputtering. The intermediate layer 30 may be formed by reaching the substrate 20.

  Further, the substrate 20 may be subjected to ion bombardment treatment with ions emitted from the cathode member 104 before step S11.

(Example)
Hereinafter, examples in the second embodiment will be described.

  In the embodiment, a method of generating arc discharge from the cathode member 4 is referred to as an SLA method, and a method of generating arc discharge from the cathode member 104 is referred to as an FVA method.

  In the embodiment, the substrate 20 is ion bombarded by using the FVA method, and then the intermediate layer 30 is deposited on the substrate 20 by using the FVA method, and the intermediate layer 35 having a thickness of 30 nm is formed by using the SLA method. A carbon film (diamond-like carbon) 40 was formed on the intermediate layer 35 by using the SLA method to form the carbon thin film 50. The film thickness of the carbon film (diamond-like carbon) 40 is 0.24 μm.

  In the embodiment, the protruding portion 42 of the cathode member 4 has a diameter R2 of 3 mmφ and a height H2 of 70 mm.

A specific method for manufacturing the carbon thin film 50 is as follows.
1) The substrate 20 is mounted on the holding member 2.
2) The inside of the vacuum vessel 1 110 is evacuated to 9.9 × 10 ⁻³ Pa by a rotary pump, a turbo molecular pump and a cold trap not shown.
3) Ar gas is allowed to flow from the gas supply port 13 into the vacuum vessel 1 and 110, and the pressure inside the vacuum vessel 1 and 110 is adjusted to 0.5 Pa by a pressure adjustment valve (not shown).
4) The holding member 2 is rotated, and a bias voltage of −800 V is applied to the substrate 20 by the power source 6.
5) A 40 A direct current is passed through each of the coils 120-122.
6) A voltage of +15 V is applied to the vacuum vessel 110 by the power source 106.
7) An arc current of 70 A is supplied from the power source 105, the discharge is ignited to the cathode member 104 by the trigger electrode 108, and ion bombarding of the substrate 20 is performed for 90 seconds by the FVA method.
8) The Ar gas is stopped, the inside of the vacuum vessel 1 110 is evacuated to 9.9 × 10 ⁻³ Pa, and a bias voltage of −100 V is applied to the substrate 20 by the power source 6.
9) A 40 A direct current is passed through each of the coils 120-122.
10) The holding member 2 is rotated, and a voltage of +15 V is applied to the vacuum vessel 110 by the power source 106.
11) An arc current of 70 A is passed by the power source 105, the discharge is ignited to the cathode member 104 by the trigger electrode 108, and an intermediate layer is formed for 12 minutes by the FVA method. In this case, the film thickness of the intermediate layer is 30 nm.
12) Stop the flow of current through the coils 120 to 122, and stop the power source 105.
13) Stop the power supply 106.
14) The cathode material 4 is ignited by the trigger electrode 8 and a 0.27 μm carbon film (diamond-like carbon) is formed by the SLA method in the order of film formation conditions I and II shown in Table 7.

  Table 8 shows the evaluation of the carbon thin film formed by the conventional FVA method.

  In Table 8, Comparative Examples 2 to 4 are obtained by forming the intermediate layer 35 and the carbon film 40 made of diamond-like carbon by the FVA method. In Comparative Example 5, the carbon film 40 is formed without forming the intermediate layer 35. It is formed by the FVA method. In Comparative Examples 2 to 4, the film thickness of the intermediate layer 35 is 30 nm, and in Comparative Examples 2 to 5, the entire film thickness is 300 nm.

  Table 9 shows the evaluation of the carbon thin film in which the intermediate layer 30 is formed by the conventional arc method and the carbon film 40 is formed by the FVA method. FIG. 12 is a schematic view of a plasma apparatus using a conventional arc method. The plasma apparatus 1000 shown in FIG. 12 is the same as the plasma apparatus 100 except that the cathode member 4 of the plasma apparatus 100 shown in FIG. The cathode member 1001 is made of Cr having a diameter of 64 mmφ and a thickness of 25 mm. In the embodiment of the present invention, the conventional arc method means arc discharge using the cathode member 1001.

  In Table 9, in Comparative Examples 6 to 8, the intermediate layer 30 is formed by the conventional arc method, and the carbon film 40 is formed by the FVA method. And in the comparative examples 6-8, the material of the intermediate | middle layer 30 is Cr, W, and Ti, respectively. Moreover, in Comparative Examples 6-8, the film thickness of the intermediate | middle layer 30 is 30 nm, and the whole film thickness is 300 nm.

  Table 10 shows the evaluation of the carbon thin film formed by the SLA method.

  In Table 10, in Examples 2 to 4, the intermediate layer 35 and the carbon film 40 made of diamond-like carbon were formed by the SLA method, and in Example 5, the carbon film 40 was formed without forming the intermediate layer 35. It is formed by the SLA method. In Examples 2-5, the film thickness of the intermediate layer 35 is 30 nm, and in Examples 2-5, the total film thickness is 300 nm.

  Table 11 shows the evaluation of the carbon thin film in which the intermediate layer 30 is formed by the FVA method and the carbon film 40 is formed by the SLA method.

  In Table 11, in Examples 6 to 11, the intermediate layer 30 is formed by the FVA method, and the carbon film 40 is formed by the SLA method. In Examples 6 to 11, the material of the intermediate layer 30 is Cr, Cr, Cr, CrN, W, and Ti, respectively. Moreover, in Examples 6-11, the film thickness of the intermediate | middle layer 30 is 30 nm, and the whole film thickness is 300 nm.

  In Tables 8 to 11, the surface roughness index is the number of irregularities of 10 to 20 nm measured using a stylus type surface shape measuring instrument having a stylus tip radius of 1.25 μm as a unit scanning distance [mm] and The unit thickness is divided by [nm]. The surface profile measuring instrument is a model Dektak 150 from Veeco. The scanning distance was 5 mm, the operation time was 30 seconds, and the load was 1.5 mgf. The reason for selecting a stylus having a stylus tip radius of 1.25 μm is that the number of irregularities depends on the tip radius of the stylus.

  The adhesion index 1 was evaluated by applying a 150 kgf load (C scale) with a Rockwell hardness tester and observing the carbon film around the indentation with a CCD microscope at a magnification of 300 times. is there. The test machine was model ARK-600 manufactured by Akashi.

  Adhesion index 2 uses a ball-on-disk type friction and wear tester, inclines the load up to 5000 N in engine oil at 10 N / sec, and determines the point of sharp change in the friction coefficient as the peel load. It is carried out, and the presence / absence of peeling of the substrate disk and the peeling load (N) are obtained. The material of the ball is SUJ2, the size is 3/8 inch in diameter, 3 balls per test are fixed on a circle of 18 mm in diameter, and a predetermined test load is applied. , And rotated at a constant rotation speed of 30 rpm. The test was terminated when the test load reached 5000 N at the maximum. The apparatus is model EFM-III-EN manufactured by ORIENTEC. As the type of engine oil, Idemitsu Zepro Tooling SN / GF5 (5W-30) was filled in a test container, and balls and a disk substrate were immersed therein.

  The substrate has a diameter of 30 mmφ and a thickness of 5 mm. Further, the substrate material was a carburized material of SCM415, and the film formation surface was mirror-polished so that the surface roughness Ra was less than 10 nm and the maximum surface roughness Rmax was less than 100 nm.

  As shown in Table 8, the carbon thin films of Comparative Examples 2 to 5 have a small surface roughness index of 0.0073 to 0.0267 [pieces / mm / nm], but are peeled off, and the peeling load is 900 to 1200 [ N].

  As shown in Table 9, the carbon thin films of Comparative Examples 6 to 8 do not peel, but the surface roughness index is 0.0333 to 0.0600 [pieces / mm / nm], and the peel load is 1800 to 2800 [ N].

  The carbon thin films of Examples 2 to 5 shown in Table 10 peel off, but the surface roughness index is as small as 0.0005 to 0.0013 [pieces / mm / nm], and the peeling load is 1600 to 2800 [N]. is there.

  The carbon thin films of Examples 6 to 11 shown in Table 11 have a small surface roughness index of 0.0017 to 0.0067 [pieces / mm / nm], do not peel, and have a peeling load of 3500 to 5000 [N]. large.

  Therefore, by forming the intermediate layer 30 by the FVA method and the carbon film 40 by the SLA method, a carbon thin film having a small surface roughness index and a large peeling load can be formed without peeling.

  FIG. 13 is a diagram illustrating the relationship between the number of uneven defects and the size of the uneven defects. In FIG. 13, the vertical axis represents the number of irregularities per unit scanning distance and unit film thickness, and the horizontal axis represents the size of the irregularities of the defect.

  In FIG. 13, the black bar graph shows the relationship between the number of concave and convex defects and the size of the concave and convex defects in the carbon thin film formed using the FVA method, and the white bar graph shows the carbon according to the embodiment of the present invention. The relationship between the number of uneven defects in a thin film and the size of the uneven defects is shown.

  Referring to FIG. 13, the carbon thin film according to the embodiment of the present invention has 1.2 defects / mm / nm with irregularities of 10 nm or more and less than 20 nm, and defects with irregularities of 20 nm or more and less than 30 nm. , Having a defect with an unevenness of 30 nm or more and less than 40 nm, 0.4 [piece / mm / nm], and having an unevenness of 40 nm or more and less than 50 nm.

  On the other hand, the carbon thin film formed using the FVA method has 10.8 [pieces / mm / nm] of defects with unevenness of 10 nm or more and less than 20 nm, and 5.8 [ Pieces / mm / nm], and defects having irregularities of 30 nm or more and less than 40 nm are 3.0 [pieces / mm / nm] and defects having irregularities of 40 nm or more and less than 50 nm are 2.4 [pieces / mm / nm]. nm].

  Therefore, the carbon thin film according to the embodiment of the present invention can greatly reduce the number of defects compared to the carbon thin film formed by using the FVA method.

  In this embodiment, instead of forming the intermediate layer 30 by the FVA method, the intermediate layer 30 may be formed by the sputtering method. In this case as well, the number of defects on the surface of the carbon film (diamond-like carbon) can be greatly reduced.

  Further, the ion bombardment process by the FVA method may not be performed.

  A carbon thin film 50 in which a metal intermediate layer having an overall film thickness of about 30 nm is formed on the substrate surface using the FVA method on the substrate surface, and then a carbon film having a film thickness of about 300 nm is formed by the SLA method. The number of defects (surface roughness index) on the surface of the carbon film (= diamond-like carbon) was 0.0067 [piece / mm / nm] or less as shown in Table 9. Therefore, the number of defects (surface roughness index) is preferably less than 0.0070 [pieces / mm / nm], more preferably less than 0.0035 [pieces / mm / nm], and particularly preferably. Is less than 0.0015 [pieces / mm / nm].

  In Table 11, in Examples 7 to 10, the number of defects (surface roughness index) is less than 0.0035 [pieces / mm / nm], and unevenness of less than 10 to 20 nm adversely affects the optical lens. The film is suitable for precision mold applications such as molding molds.

  Furthermore, the film formed by the manufacturing method has a metal intermediate layer 30 laid at the interface between the base material and the carbon film, so there is no peeling due to the Rockwell hardness test, and high surface pressure sliding. The peeling load resistance in the test is also a film that cleared 5000 [N], and the film is also excellent in adhesion and wear resistance.

  As shown in Table 10, when the intermediate layer 35 made of diamond-like carbon and the carbon film 40 are formed only by the SLA method without forming the intermediate layer 30 by the FVA method, there is a decrease in adhesion. The number of defects (surface roughness index) is 0.0013 [piece / mm / nm] or less, and can be a film suitable for precision mold applications.

  On the other hand, in the comparative examples (conventional examples) shown in Tables 8 and 9, the number of defects (surface roughness index) is larger than 0.0067 [piece / mm / nm], and even in terms of surface roughness, precision molds are used. The film was not suitable for use, and peeled off in the Rockwell hardness test. The peeling load resistance in the high surface pressure sliding test was low, and the film was weak in terms of adhesion.

  The thermal shock resistance R represented by the formula (1) of the cathode member 4 used for forming the carbon film 40 is preferably greater than 7.9, more preferably 12.2 or more.

  When the thermal shock resistance R is larger than 7.9, the thermal shock resistance of the glassy carbon increases with respect to the thermal stress generated on the surface of the cathode member by arc discharge, and the cathode member 4 can be prevented from cracking. Therefore, it is possible to form the carbon film 40 in which the number of irregularities of 10 to 20 nm that are likely to occur when the cathode member 4 is cracked is further reduced.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description of the embodiments but by the scope of claims for patent, and is intended to include meanings equivalent to the scope of claims for patent and all modifications within the scope.

  The present invention is applied to a carbon thin film, a plasma apparatus for manufacturing the carbon thin film, and a manufacturing method.

  1,110 vacuum vessel, 2 holding member, 3,103 arc evaporation source, 4,104,1001 cathode member, 5 permanent magnet, 6,7,107 power supply, 8,108 trigger electrode, 9,109 resistance, 10, 100, 1000 Plasma device, 11 Exhaust port, 12 Shutter, 20 Substrate, 30, 35 Intermediate layer, 40 Carbon film, 41 Main body part, 42 Protrusion part, 50 Carbon thin film, 120 Coil

Claims (12)

  The number of irregularities of 10 to 20 nm measured by a stylus type surface shape measuring instrument having a stylus tip radius of 1.25 μm is less than 0.007 [piece / mm / nm] per unit scanning distance and unit film thickness. Carbon thin film with a certain carbon film.   2. The carbon thin film according to claim 1, wherein the number of irregularities of 10 to 20 nm is less than 0.0035 [piece / mm / nm] per unit scanning distance and unit film thickness. 3. The carbon according to claim 1, wherein the carbon film is formed using glassy carbon having a thermal shock resistance R expressed by the following formula (1) greater than 7.9 as a cathode member. Thin film.
Here, in the formula (1), σ is the bending strength [MPa], λ is the thermal conductivity [W / mK], α is the thermal expansion coefficient [/ 10 ⁶ K], and E is the Young's modulus [GPa]. . A metal layer formed on the substrate in contact with the carbon film;
4. The carbon thin film according to claim 1, wherein the metal layer is made of at least one element selected from the periodic table 4A, 5A, and 6A group elements, B, and Si, and nitrides thereof. . A vacuum vessel;
An arc evaporation source fixed to the vacuum vessel;
A cathode member attached to the arc evaporation source;
A holding member for holding a substrate disposed toward the cathode member;
A discharge starting means for starting discharge;
A power source for applying a negative voltage to the arc evaporation source,
The cathode member is made of glassy carbon, has a columnar shape, and includes a columnar portion having a cross-sectional area larger than 0.785 mm ² ,
The discharge start means is a plasma device that starts discharge so that plasma is emitted from the columnar portion of the cathode member. The plasma apparatus according to claim 5, wherein the cathode member has a thermal shock resistance R expressed by the following formula (1) greater than 7.9.
Here, in the formula (1), σ is the bending strength [MPa], λ is the thermal conductivity [W / mK], α is the thermal expansion coefficient [/ 106K], and E is the Young's modulus [GPa].   The plasma apparatus according to claim 5 or 6, wherein a shape of a discharge mark formed on an outer peripheral surface of the columnar portion of the cathode member is a spiral shape after the discharge. First, a cathode member made of glassy carbon, having a columnar shape, and including a columnar portion having a cross-sectional area larger than 0.785 mm ² is attached to an arc evaporation source fixed to a vacuum vessel toward the substrate. 1 process,
A second step of applying a negative voltage to the arc evaporation source;
And a third step of starting discharge so that plasma is emitted from the columnar portion of the cathode member and forming a carbon film on the substrate. The method for producing a carbon thin film according to claim 8, wherein the cathode member has a thermal shock resistance R represented by the following formula (1) greater than 7.9.
Here, in the formula (1), σ is the bending strength [MPa], λ is the thermal conductivity [W / mK], α is the thermal expansion coefficient [/ 106K], and E is the Young's modulus [GPa]. A fourth step of forming an intermediate layer made of at least one element selected from periodic group 4A, 5A, 6A group element, B, Si and any of these nitrides between the carbon film and the substrate; In addition,
In the carbon film, the number of irregularities of 10 to 20 nm measured by a stylus type surface shape measuring instrument having a stylus tip radius of 1.25 μm is 0.007 [piece / mm per unit scanning distance and unit film thickness. / Nm] is a manufacturing method of the carbon thin film of Claim 8 or Claim 9.   The intermediate layer contains ions released from the metal cathode member into the vacuum container made of a cylindrical member curved in an arc shape disposed between the metal cathode member and the substrate. The method for producing a carbon thin film according to claim 10, wherein the carbon thin film is formed by an arc discharge method or a sputtering method in which the ions are bent in a circular arc shape along the line and reach the substrate.   The said intermediate | middle layer is a manufacturing method of the carbon thin film of Claim 10 formed by sputtering method using a metal cathode member.