WO2016017438A1 - カーボン薄膜、それを製造するプラズマ装置および製造方法 - Google Patents

カーボン薄膜、それを製造するプラズマ装置および製造方法 Download PDF

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WO2016017438A1
WO2016017438A1 PCT/JP2015/070413 JP2015070413W WO2016017438A1 WO 2016017438 A1 WO2016017438 A1 WO 2016017438A1 JP 2015070413 W JP2015070413 W JP 2015070413W WO 2016017438 A1 WO2016017438 A1 WO 2016017438A1
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Prior art keywords
carbon
cathode member
discharge
thin film
arc
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PCT/JP2015/070413
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English (en)
French (fr)
Japanese (ja)
Inventor
加藤　健治
高橋　正人
西村　和也
浩 石塚
森口　秀樹
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日本アイ・ティ・エフ株式会社
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Priority to CN201580040273.1A priority Critical patent/CN106661715B/zh
Priority to JP2016538266A priority patent/JP6578489B2/ja
Publication of WO2016017438A1 publication Critical patent/WO2016017438A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material

Definitions

  • the present invention relates to a carbon thin film, a plasma apparatus for manufacturing the carbon thin film, and a manufacturing method.
  • 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.
  • FVA type filtered vacuum arc type
  • 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 soot 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.
  • 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.
  • Patent Document 2 A diamond-like carbon film formed using such a filtered arc evaporation source has been proposed (Patent Document 2).
  • droplets are collected using a duct to suppress the flying of coarse particles.
  • 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.
  • 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.
  • a plasma device capable of suppressing the cracking of the cathode material is provided.
  • a carbon thin film manufactured by suppressing the cracking of the cathode material is provided.
  • 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.
  • 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.
  • ⁇ is the bending strength [MPa]
  • ⁇ is the thermal conductivity [W / mK]
  • ⁇ is the thermal expansion coefficient [/ 10 6 K]
  • E is the Young's modulus [GPa].
  • 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 which is likely to occur when the cathode member is cracked can be further reduced.
  • 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.
  • the cathode member includes a columnar portion having a cross-sectional area larger than 0.785 mm 2 .
  • the thermal shock resistance R represented by the above formula (1) of the cathode member is larger than 7.9.
  • 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.
  • the cathode member has the strength to withstand thermal stress. Therefore, the cathode member can be prevented from cracking.
  • the thermal shock resistance R represented by the above formula (1) of the cathode member is larger than 7.9.
  • a compact film-forming apparatus and its coated article can be provided with a small film thickness of 10 to 20 nm and a high film-forming speed.
  • FIG. 3 is a cross-sectional view of the cathode member taken along line III-III shown in FIG.
  • FIG. 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
  • FIG. 1 is a schematic diagram showing a configuration of a plasma apparatus according to Embodiment 1 of the present invention.
  • 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.
  • 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 eaves holding member 2 is disposed in the vacuum vessel 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 as the cylindrical portion 2A of the holding member 2 rotates.
  • the soot 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.
  • glassy carbon examples include glassy carbon made by Nisshinbo Chemical, or glassy carbon made by Tokai Carbon.
  • glassy carbon, amorphous carbon, amorphous carbon, amorphous carbon, non-graphitized carbon, and vitreous carbon are contained in glassy carbon.
  • 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 source 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 heel holding member 2 holds the substrate 20.
  • 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. 3 is a cross-sectional view of the cathode member 4 taken along the line III-III shown in FIG.
  • the cathode member 4 includes a main body 41 and a protrusion 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.
  • the main-body part 41 and the projection part 42 are produced integrally.
  • the heel body 41 has, for example, a diameter R1 of 64 mm ⁇ and a height H1 of 12 mm.
  • the protrusion 42 has a diameter R2 of 2 mm ⁇ 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.
  • 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.
  • 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 ratio of the cross-sectional area of the protrusion 42 to the cross-sectional area of the main body 41 is about 1/113.
  • the heat transfer component in the projecting portion 42 is reduced, so that it is difficult for heat to escape from the projecting portion 42 and the entire projecting portion 42 is easily soaked, so that thermal distortion is reduced.
  • a sparkless discharge is a discharge in which particles are not generated.
  • a particle means a carbon particle having a size of 5 nm to several ⁇ m.
  • 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).
  • the inside of the vacuum vessel 1 is evacuated through the exhaust port 11, and the pressure in the vacuum vessel 1 is set to 9.9 ⁇ 10 ⁇ 3 Pa.
  • 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).
  • 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.
  • 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).
  • 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.
  • a reciprocating drive device not shown
  • step S6 a carbon thin film (DLC: Diamond Like Carbon) is formed on the substrate 20.
  • step S7 it is determined by the operator of the plasma apparatus 10 whether or not the discharge has stopped. 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.
  • step S7 when it is determined that the discharge has stopped, the shutter 12 is closed (step S8), and then the above-described steps S5 to S8 are repeatedly executed.
  • step S7 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.
  • the carbon thin films manufactured according to the above-described steps S1 to S9 include amorphous carbon thin films, diamond-like carbon thin films, tetrahedral amorphous carbon films, amorphous hard carbon thin films, and hard carbon thin films. .
  • 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.
  • the carbon thin film is formed on the substrate 20 by arc discharge using the cathode member 4 having the protrusion 42 having a diameter of 2 mm ⁇ or more and made of glassy carbon.
  • 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.
  • the axial magnetic field Bz and the 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 Shoe.
  • 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 mm ⁇ is used.
  • FIG. 6 is a diagram showing the protrusion 42 after discharge when glassy carbon (protrusion 42) having a diameter of 5.2 mm ⁇ is used.
  • the vacuum chamber 1 is opened to the atmosphere, and the glassy carbon of the cathode member 4 is confirmed.
  • the diameter of the protrusion 42 is 2 mm ⁇ , 3 mm ⁇ , 5.2 mm ⁇ , 6 mm ⁇ , 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).
  • the arc spot moves in a spiral shape on the surface of the protrusion 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.
  • the amount of heat that generates the thermal stress is a heat transfer component from the arc spot (the same heat amount 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.
  • Table 3 shows the experimental results when the arc current is 80 [A].
  • the arc current is 80 [A]
  • 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
  • the diameter of the protrusion 42 is 3 mm ⁇ , 5.2 mm ⁇ , 6 mm ⁇ , 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.
  • the vacuum chamber 1 is opened to the atmosphere, and the glassy carbon of the cathode member 4 is confirmed.
  • the diameter of the protrusion 42 is 3 mm ⁇ , 5.2 mm ⁇ , 6 mm ⁇ , Spiral discharge traces were confirmed on the side surfaces of the portion 42.
  • the protruding portion 42 When the diameter of the protruding portion 42 is 1 mm ⁇ , 2 mm ⁇ , 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 cross-sectional area of the protrusion 42 of the cathode member 4 should be larger than 0.785 mm 2 .
  • 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 .
  • 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].
  • 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.
  • 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 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.
  • 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).
  • ⁇ is the bending strength [MPa]
  • ⁇ is the thermal conductivity [W / mK]
  • ⁇ is the thermal expansion coefficient [/ 106K]
  • E is the Young's modulus [GPa].
  • the cathode member 4 Since the cathode member 4 has a thermal shock resistance R greater than 7.9, a rapid temperature rise occurs during the 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.
  • Example 1 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 ⁇ , thermal conductivity ⁇ , thermal expansion coefficient ⁇ , Young's modulus E, and thermal shock resistance R of each cathode member.
  • the bending strength ⁇ , thermal conductivity ⁇ , thermal expansion coefficient ⁇ , 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 ⁇ , thermal conductivity ⁇ , thermal expansion coefficient ⁇ , and Young's modulus E.
  • Table 6 shows the results of the vacuum arc discharge test in this example. 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 pulverized 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. .
  • Example 1 For Example 1, Example 2, and Example 3, after confirming that a stable sparkless discharge continued for 40 seconds, forced extinguishing was performed. After forced extinction, the vacuum vessel 1 was opened to the atmosphere and each cathode member was confirmed.
  • Example 1 The cathode members of Example 1, Example 2, and Example 3 all had spiral discharge traces on 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.
  • FIG. 9 is a schematic diagram showing the configuration of the plasma device according to the second embodiment.
  • 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.
  • the vacuum container 1 has a gas supply port 13.
  • the vacuum vessel 110 is made 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 soot 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.
  • the soot power source 105 is connected between the arc evaporation source 103 and the ground node GND.
  • Power supply 106 is connected between vacuum vessel 110 and ground node GND.
  • the trigger electrode 108 is disposed in the vacuum vessel 110 at one end side through the wall 110 ⁇ / b> D of the vacuum vessel 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.
  • the saddle resistor 107 is connected between the trigger electrode 108 and the ground node GND.
  • the soot 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 saddle coil 121 is arranged 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 saddle 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.
  • the coils 120 to 122 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.
  • the plasma apparatus 100 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.
  • carbon thin film 50 includes a substrate 20, intermediate layers 30 and 35, and carbon film 40.
  • the cocoon 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.
  • the heel 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 for producing 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 those shown in FIG. 4.
  • the production of carbon thin film 50 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).
  • a negative voltage is applied to the substrate 20 (step S12).
  • 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
  • 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).
  • step S14 a negative voltage is applied to the arc evaporation source 103 (step S14).
  • step S15 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.
  • step S16 arc discharge occurs, and the intermediate layer 30 having a desired film thickness is formed on the substrate 20 (step S16).
  • 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.
  • 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.
  • 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.
  • 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.
  • the substrate 20 may be subjected to ion bombardment treatment with ions released from the cathode member 104.
  • the method of generating arc discharge from the cathode member 4 is referred to as SLA method
  • the method of generating arc discharge from the cathode member 104 is referred to as FVA method.
  • 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 ⁇ m.
  • the protrusion 42 of the cathode member 4 has a diameter R2 of 3 mm ⁇ 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.
  • 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) Stop the Ar gas, evacuate the inside of the vacuum vessel 1110 to 9.9 ⁇ 10 ⁇ 3 Pa, and then apply a ⁇ 100 V bias voltage 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.
  • 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 ⁇ m 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.
  • 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.
  • the carbon film 40 is formed without forming the intermediate layer 35. It is formed by the FVA method.
  • the film thickness of the intermediate layer 35 is 30 nm, and in Comparative Examples 2 to 5, the total film thickness is 300 nm.
  • 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 mm ⁇ and a thickness of 25 mm.
  • the conventional arc method means arc discharge using the cathode member 1001.
  • Comparative Examples 6 to 8 are obtained by forming the intermediate layer 30 by the conventional arc method and forming the carbon film 40 by the FVA method.
  • the material of the intermediate layer 30 is Cr, W, and Ti, respectively.
  • the film thickness of the intermediate layer 30 is 30 nm, and the total film thickness is 300 nm.
  • Table 10 shows the evaluation of the carbon thin film formed by the SLA method.
  • Example 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.
  • the film thickness of the intermediate layer 35 is 30 nm, and in Examples 2-5, the overall 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.
  • the intermediate layer 30 is formed by the FVA method, and the carbon film 40 is formed by the SLA method.
  • the material of the intermediate layer 30 is Cr, Cr, Cr, CrN, W, and Ti, respectively.
  • the intermediate layer 30 has a film thickness of 30 nm, and the entire film thickness is 300 nm.
  • 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 ⁇ m, and the 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 ⁇ m 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 or 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 size of the substrate is 30 mm in diameter and 5 mm in thickness. 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.
  • 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].
  • the carbon thin films of Comparative Examples 6 to 8 did not peel, but the surface roughness index was 0.0333 to 0.0600 [pieces / mm / nm], and the peel load was 1800 to 2800 [ N].
  • 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 peel load of 3500 to 5000 [N]. large.
  • 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 showing the relationship between the number of irregularities and the size of irregularities.
  • the vertical axis represents the number of irregularities per unit scanning distance and unit film thickness
  • the horizontal axis represents the size of the irregularities of the defect.
  • 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
  • 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.
  • 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.
  • 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].
  • the carbon thin film according to the embodiment of the present invention can greatly reduce the number of defects as compared with the carbon thin film formed by using 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.
  • the number of defects is less than 0.0035 [piece / mm / nm], and unevenness of 10 to less than 20 nm has an adverse effect on the optical lens.
  • the film is suitable for precision mold applications such as molding molds.
  • 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.
  • 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.
  • the number of defects 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.
  • thermal shock resistance R represented by the formula (1) of the cathode member 4 used for forming the carbon film 40 is preferably larger than 7.9, more preferably 12.2 or more.
  • the thermal shock resistance R is greater 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.
  • This invention is applied to a carbon thin film, a plasma apparatus for manufacturing the carbon thin film, and a manufacturing method.

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PCT/JP2015/070413 2014-07-28 2015-07-16 カーボン薄膜、それを製造するプラズマ装置および製造方法 WO2016017438A1 (ja)

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