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WO2016021671A1 - Film dlc et article revêtu du film dlc - Google Patents

Film dlc et article revêtu du film dlc Download PDF

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Publication number
WO2016021671A1
WO2016021671A1 PCT/JP2015/072299 JP2015072299W WO2016021671A1 WO 2016021671 A1 WO2016021671 A1 WO 2016021671A1 JP 2015072299 W JP2015072299 W JP 2015072299W WO 2016021671 A1 WO2016021671 A1 WO 2016021671A1
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Prior art keywords
evaporation
dlc film
band
main
dlc
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Ceased
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PCT/JP2015/072299
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English (en)
Japanese (ja)
Inventor
滝川　浩史
真 瀧
長谷川　祐史
神谷　雅男
加藤　裕久
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Itoh Optical Industrial Co Ltd
Toyohashi University of Technology NUC
Onward Giken Co Ltd
Original Assignee
Itoh Optical Industrial Co Ltd
Toyohashi University of Technology NUC
Onward Giken Co Ltd
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Application filed by Itoh Optical Industrial Co Ltd, Toyohashi University of Technology NUC, Onward Giken Co Ltd filed Critical Itoh Optical Industrial Co Ltd
Priority to JP2016540727A priority Critical patent/JP6586578B2/ja
Publication of WO2016021671A1 publication Critical patent/WO2016021671A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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

Definitions

  • the present invention relates to a diamond like carbon (hereinafter referred to as "DLC") film and a DLC film coated article, more specifically, a DLC film coated on an article such as a mold, a tool or a sliding member and a film thereof Related items.
  • DLC diamond like carbon
  • the physical properties of DLC also depend on the hydrogen content. Therefore, in general, the properties of DLC include aC (amorphous carbon), ta-C (tetrahedral amorphous carbon), or hydrogen depending on the ratio of sp 2 bond to sp 3 bond and the hydrogen content.
  • -C H (hydrogenated amorphous carbon) or ta-C: H (hydrogenated tetrahedral amorphous carbon).
  • the DLC film is used as a hard protective film such as a mold and a tool. For example, a method of using a hydrocarbon-based gas as a raw material is used for film formation of DLC composed of aC: H.
  • the hydrogen-free contains no hydrogen in the film ta-C or a It has been required to form a DLC film of -C.
  • a film forming method of ta-C or a-C a sputtering method of forming a film using solid graphite as a raw material, a vacuum arc method, etc. are used.
  • a part of the present inventors is disclosed in Japanese Patent Application Publication Nos. 2008-297171 (Patent Document 1), 2008-297477 (Patent Document 2), and 2009-6470 (Patent Document 3).
  • a filtered arc deposition apparatus is used to form a ta-C film.
  • Patent Document 4 discloses mixing of DLC (a-C: H) and Si by mixing Si chloride or Si hydride gas with reactive gas by ECR plasma CVD method.
  • a-DLC-Si film is obtained, and this a-DLC-Si film has a small coefficient of friction.
  • Patent Document 1 describes that the laser PVD method is used together with the ECR plasma CVD method in a method of forming an a-DLC-Si film.
  • JP 2010-5744 A Patent Document 5
  • a tetramethylsilane (TMS, chemical formula: Si (CH 3 ) 4 ) gas is supplied during film formation by the filtered arc deposition method to form Si.
  • TMS tetramethylsilane
  • Si CH 3
  • Patent Document 7 metal is contained in an evaporation source, and a metal-containing DLC is formed using a vacuum arc method or a filtered arc deposition method. It has been described that the membrane.
  • Patent Documents 1 to 3 describe that a ta-C film is formed on a target mold, a tool or a sliding member by a filtered arc deposition method.
  • the ta-C film is hard, has high abrasion resistance, and is chemically stable. However, the heat resistance is insufficient, and there is a problem such as peeling at a high temperature of 700 ° C. or more.
  • the a-DLC-Si film described in Patent Document 4 supplies a gas containing 1% of methane (CH 4 ) and 99% of hydrogen (H 2 ) as a reaction gas into a reaction chamber, and a laser light is a Si target. And evaporated Si is added to the DLC.
  • the DLC film to be formed has a basic structure of aC: H. Therefore, it is clear that the durability is lower than that of hydrogen-free DLC film and ta-C having a high ratio of sp 3 bonds.
  • Patent Documents 6 and 7 disclose that an evaporation source contains an additive metal and a film is formed by vacuum arc. However, in order to obtain sufficient heat resistance, it is necessary to form a DLC film having a sufficiently high ratio of bonds having sp 3 hybrid orbitals (also referred to as sp 3 bonds) (hereinafter, also simply referred to as “sp 3 ratios”). Although the data described in the patent documents do not provide results concerning improvement of the heat resistance of the DLC film. In addition, there is no description on the deposition of the additive metal on the surface of the evaporation source and the discharge failure resulting therefrom, which become a problem when the metal-containing evaporation source is used. In addition, although Patent Document 7 only describes that stable discharge can be achieved with a high density evaporation source, no effective solution has been presented.
  • An object of the present invention is to improve the heat resistance of a DLC film formed on an object, and to provide a hydrogen-free, high hardness DLC film.
  • a first embodiment of the present invention is a DLC film to which other elements other than hydrogen and carbon are added, and the wavelength is set to 500 nm to 600 nm.
  • the G-band derived from the graphite structure, the D-band derived from defects in the graphite structure, and the S-band having a peak with a wavenumber between 1000 and 1200 cm -1 A band is detected in the Raman spectrum, peak intensity and area intensity of the G band are Pg and Ag, peak intensity and area intensity of the D band are Pd and Ad, and peak intensity and area intensity of the characteristic band are When Ps and As, the peak intensity ratio Pd / Pg and the area intensity ratio Ad / Ag are 0.5 or less, and the peak intensity ratio Ps / P It is a DLC film whose d and area intensity ratio As / Ad are 0.01 or more.
  • the G band is a superposition band of the E 2g mode of in-plane vibration and its degenerate mode in graphite, and there is a band in which a peak of a Raman spectrum appears in the vicinity of 1560 cm ⁇ 1 .
  • the D band is a band of superposition of the A 1g mode and its degenerate mode due to asymmetry at the crystal end of graphite, and is a band in which a peak of a Raman spectrum appears around 1360 cm ⁇ 1 .
  • the other element is silicon
  • the content ratio X of silicon to carbon is 0 at. % ⁇ X ⁇ 15 at. % DLC film.
  • a third aspect of the present invention is a DLC film containing the above-mentioned DLC film as the above-mentioned other element and silicon and one or more other element components other than silicon.
  • a fourth aspect of the present invention is a DLC film obtained by adding one or more other element components other than silicon as the other element to the DLC film.
  • the 5th form of the present invention is a DLC film which added boron as said other element to said DLC film.
  • a sixth aspect of the present invention is a DLC film obtained by adding boron and one or more other element components other than boron as the other element to the DLC film.
  • a seventh aspect of the present invention is a DLC film having a refractive index of 2.5 to 3.0 and an extinction coefficient of 0.05 to 0.40 for light of wavelength 550 nm.
  • the ratio sr / t of the occupied area ratio sr of the unevenness due to adhesion and / or detachment of foreign particles on the surface of the DLC film to the film thickness t is 0.01% / nm or less It is a certain DLC film.
  • the ninth form of the present invention is a DLC film coated article having the DLC film coated on the surface of the article.
  • the article is a cutting tool, a cutting tool, a molding tool, a precision mold, a mold for glass press, a press mold for chemically strengthened glass, a molded part, a sliding part, an optical It is a DLC film coated article which is an element, an optical part or a decorative item.
  • a characteristic band abbreviated as S band having a peak between wave numbers of 1000 to 1200 cm -1 is detected.
  • S band a characteristic band abbreviated as S band having a peak between wave numbers of 1000 to 1200 cm -1
  • T band is known to be present on a range of 1000cm -1 ⁇ 1150cm -1.
  • an S band corresponding to the T band appears in a Raman spectrum by visible light with a wavelength of 500 nm to 600 nm.
  • the S band was measured by the Raman spectrum of ta-C to which no other element is added (see Patent Document 1).
  • the fact that the S band is measured in the Raman spectrum of a DLC film to which other elements have been added by incident light having a wavelength of 500 nm to 600 nm has been discovered as a result of intensive studies by the present inventors.
  • the S band is a band derived from the sp 3 bond in ta-C, and indicates that the structure of ta-C is formed to such an extent that the S band is measured even when other elements are added. ing.
  • Conventional DLC films have not been shown to clearly indicate that ta-C is formed when other elements are added.
  • the first embodiment of the present invention is a DLC film containing another element containing ta-C whose S band is measured in a Raman spectrum using a laser beam in the above-mentioned wavelength range. Furthermore, in the first embodiment of the present invention, regarding the G band derived from the graphite structure and the D band derived from the defect of the graphite structure, the peak intensity and area intensity of the G band are Pg and Ag, and the peak intensity of the D band and When the area intensity is Pd and Ad, the peak intensity of the S band called the characteristic band and the area intensity Ps and As have the following relationship.
  • peak intensity ratio Pd / Pg and area intensity ratio Ad / Ag are 0.5 or less
  • peak intensity ratio Ps / Pd and area intensity ratio As / Ad are 0.01 or more. Since the G band is derived from the graphite structure and the D band is derived from the defect of the graphite structure, the peak intensity ratio Pd / Pg is attributed to the ratio of defects of the graphite structure in the DLC film. . Therefore, the fact that the peak intensity ratio Pd / Pg is 0.5 or less indicates that the number of defects in the graphite structure is relatively small.
  • the area intensity ratio Ad / Ag is also 0.5 or less, which indicates that the defects of the graphite structure are relatively small not only in the peak intensity but also in the area intensity. Furthermore, since the peak intensity ratio Ps / Pd and the area intensity ratio As / Ad are 0.01 or more, the S band derived from ta-C is measured with sufficient intensity to the D band derived from the defect of the graphite structure It is understood that the DLC film according to the first embodiment is a DLC film made of ta-C having sp 3 bonds at a predetermined ratio or more.
  • the DLC film of the first embodiment is a DLC film composed of hydrogen-free ta-C having high strength, suitable durability and suitable DLC characteristics, and heat resistance due to the addition of other elements Can be granted.
  • the ratio of sp 3 bond / (sp 2 bond + sp 3 bond) is 0.5 to 0.9
  • the hydrogen content is 0 to 5 at. %
  • the nano-indentation hardness of 40 to 100 GPa, and the density of 2.7 to 3.4 g / cm 3 may be defined as ta-C in some cases (Patent Document 1). What the S band is measured in the Raman spectrum is regarded as ta-C having a high sp 3 ratio.
  • the electrical resistivity is also high, and is about 10 ⁇ 3 ⁇ cm or more.
  • the electrical resistivity is further increased to 10 -2 ⁇ cm or more, and particularly, when the electrical resistivity is 10 ⁇ cm or more, the present invention having a particularly high sp 3 ratio It is a DLC film.
  • the DLC film of the present invention is a film formed without intentionally introducing a gas containing hydrogen into the process chamber, and is a hydrogen-free DLC film substantially free of hydrogen.
  • the hydrogen content It is difficult to completely eliminate it, but the degree is usually 5 at. % Or less. And if it is this grade, mechanical properties such as density and hardness as protective film, heat resistance, abrasion resistance, adhesion resistance, corrosion resistance, light transmittance, electric conductivity, etc., chemical characteristics, electrical
  • the specific hydrogen content is 5 at.%, Because the properties and optical properties are not substantially affected. It means% or less.
  • the other element is silicon
  • the content ratio X of silicon to carbon is 0 at. % ⁇ X ⁇ 15 at. Since it is%, suitable heat resistance can be imparted to the DLC film.
  • the silicon content X is 15 at. If% or less, DLC film appears S band more reliably the Raman spectrum is from being deposited, are formed of the same high hardness DLC structure as ta-C.
  • the content rate X is 15 at. When it becomes larger than%, the S band is not measured in the Raman spectrum, and it is thought that the structure changes. Therefore, the silicon content X is 0 at. % ⁇ X ⁇ 15 at. %, A hydrogen-free DLC film consisting of ta-C is formed, and the addition of Si imparts suitable heat resistance, so that it has good durability as a protective film of an object. .
  • the DLC film may contain silicon and one or more other element components other than silicon as the other elements, and the predetermined characteristic may be further added according to the element component to be added. Can be applied to the DLC film.
  • the fourth aspect of the present invention since one or more other element components other than silicon are added as the other element to the DLC film, it is possible to impart predetermined characteristics according to the added element component. For example, it is possible to improve characteristics other than heat resistance.
  • the fifth aspect of the present invention it is also possible to add boron as the other element to the DLC film, and it is also possible to improve characteristics other than heat resistance such as conductivity.
  • boron and one or more other element components other than boron as the other element it is also possible to add boron and one or more other element components other than boron as the other element to the DLC film, for example, to improve characteristics other than conductivity and heat resistance. It is also possible to add boron and one or more other element components other than boron as the other element to the DLC film, for example, to improve characteristics other than conductivity and heat resistance. It is also possible to add boron and one or more other element components other than boron as the other element to the DLC film, for example, to improve characteristics other than conductivity and heat resistance. It is also possible to add boron and one or more other element components other than boron as the other element to the DLC film, for example, to improve characteristics other than conductivity and heat resistance. It is also possible to add boron and one or more other element components other than boron as the other element to the DLC film, for example, to improve characteristics other than conductivity and heat resistance. It is also possible to add boron and
  • the refractive index is 2.5 to 3.0 and the extinction coefficient is 0.05 to 0.40 for light of wavelength 550 nm, suitable durability is imparted. can do.
  • press molding is repeated and adhesion of the glass material to the molding die surface and the surface of the molded lens are prevented without peeling off the DLC film.
  • the number of times of molding (hereinafter, also simply referred to as "the number of times of molding") is measured without causing a change in shape.
  • the refractive index is in the range of 2.5 to 3.0 and the extinction coefficient is in the range of 0.05 to 0.40, it has been confirmed that the number of times of molding becomes a practically effective value. Therefore, measurement of the refractive index or the extinction coefficient can be used as a method for relatively simply inspecting that a DLC film having suitable durability is obtained.
  • the content of the other element is other than silicon, the refractive index and the extinction coefficient may not necessarily fall within the above range when the content is increased, although the ratio of sp 3 is sufficiently high.
  • the ratio sr / t of the occupied area ratio sr of the unevenness due to adhesion and / or detachment of foreign particles on the surface of the DLC film to the film thickness t is 0.01% / nm Since the DLC film is the following, the surface of the DLC film is smooth and can function as a suitable protective film. That is, the ratio of the occupied area of the unevenness on the DLC film surface to the film thickness due to the attachment or detachment of foreign particles such as droplets is specified to be the limit value of the surface smoothness.
  • vacuum arc plasma constituent particles such as cathode material ions, electrons, cathode material neutral particles (atoms and molecules) are released from the cathode spot, and at the same time, submicron to several hundred microns in size Cathode material particles (droplets) are emitted.
  • the surface roughness is increased mainly by adhesion and detachment of foreign particles such as droplets to the mold on which the DLC film is formed.
  • the droplets by-produced from the graphite cathode material exhibit a graphite structure (sp 2 structure), and there are some in the case of a graphite state or an amorphous state, and many dangling bonds are contained in any state. Because of the relatively high intensity of the D band in the Raman spectrum, the heat resistance is poor, and problems occur in durability at high temperatures. Then, when the droplet starts to graphitize at high temperature, the film around it will be graphitized along with this, and if the graphite component in the DLC film increases, the hardness decreases and it can withstand high temperature It disappears.
  • sp 2 structure graphite structure
  • the film may be deteriorated at high temperature or the glass may be adhered starting from the droplets, or adhesion to the glass lens side or the glass may be adhered to the holes through which the droplets are removed. It will also be.
  • the increase in surface roughness by droplets not only leads to the deterioration of machined surface accuracy and the increase in cutting resistance, but also lowers the film toughness, and the surface becomes rough due to peeling and chipping wear.
  • the holes in which the droplets come off are likely to cause adhesion of the work material and also to cause peeling, and also to increase the coefficient of friction, thereby inducing an increase in cutting temperature and It is desirable that the amount be as small as possible in order to promote cutting failure due to the increase in adhesion of the cutting material and deterioration of the coating.
  • foreign particle mainly refers to a droplet, but it can not be said that dust etc. do not adhere during handling other than this, including these dust particles " It shall be called foreign particle.
  • the DLC coated article is a mold, comprises ta-C, and is provided with the DLC film of the present invention having the above characteristics on a substrate, wherein a glass forming mold, a chemically strengthened glass forming mold, a resin forming Mold, rubber molding die, ceramic molding die, chemical molding die, powder molding die, press die, forging die, casting die, injection molding die, blow molding die, compression molding It can be applied to molds, vacuum forming molds, or extrusion molds, and in particular, glass for molding glass or resin spherical lens or aspheric lens having a diameter of 0.001 mm or more and a thickness of 0.001 mm or more.
  • the DLC coated article is a tool and applied to a cutting tool, it is desirable to have high hardness and adhesion resistance and higher heat resistance in order to maintain high cutting performance, because drill and end mills, It can be used as a cutting tool such as an edge-changing tip for end milling, an edge-changing tip for milling, an edge-changing tip for turning, a metal saw, a cutting tool, a reamer, a tap and the like. Further, it can be used for applications such as a forming punch and a die.
  • a valve operating mechanism such as a camshaft, a valve lifter, an adjusting shim, a piston, a piston ring, a cylinder liner, a connecting rod, a connecting rod, a crankshaft, a bearing, a bearing metal, a chain , Sprockets, chain guides, gears, and other power transmission mechanisms.
  • the article is a cutting tool, a cutting tool, a molding tool, a precision mold, a mold for glass press, a molded part, a sliding part, an optical element, an optical part or a decorative article Therefore, by coating a DLC film containing other elements, it is possible to impart suitable durability.
  • the heat resistance of a cutting tool, a cutting tool, a molding tool, a precision mold, a mold for glass press, and a sliding part is improved, so that it can be used repeatedly under high temperature conditions.
  • FIG. 1 is a schematic configuration view showing an embodiment of a DLC film forming apparatus according to the present invention.
  • FIG. 7 is a schematic perspective view showing the relationship between the main advancing direction and the auxiliary advancing direction of the DLC film forming apparatus shown in FIG. 6; It is the structure schematic which shows the other Example of the DLC film formation apparatus which concerns on this invention. It is the structure schematic which shows the other Example of the DLC film formation apparatus which concerns on this invention. It is the whole flow showing the example of the DLC film formation process concerning the present invention. It is the flow schematic which shows the outline of the evaporation process in step 6 of FIG. It is a flowchart which shows an example of the subroutine performed by step 6 shown in FIG. FIG.
  • FIG. 13 is a flowchart showing a subroutine from point P1 to point Q1 including step 17 of FIG. 12;
  • FIG. 14 is a flow chart showing a subroutine from point P2 to point Q2 including step 18 of FIG. It is a graph which shows the time chart of the main evaporation of the main evaporation material generation part ME corresponding to the evaporation pattern A of FIG. 11, and a sub evaporation material generation part SE, and subevaporation. It is a graph which shows the time chart of the main evaporation of the main evaporation material generation part ME corresponding to the evaporation pattern B of FIG. 11, and a sub evaporation material generation part SE, and subevaporation.
  • silicon is mainly added as another element at the time of film formation of a DLC film, and a method using a vapor deposition source consisting of carbon and a vapor deposition source consisting of silicon, carbon and silicon or silicon carbide or other element substance or There is a method of using a vapor deposition source formed from carbides of other elements, which can be appropriately selected.
  • FIG. 1 is a graph showing changes in Raman spectrum when the DLC film according to the present invention is heat-treated.
  • the Raman spectrum of the DLC film is measured using a laser Raman spectrophotometer (manufacturer: JYOBIN-YVON, model: LABRAM-HR-800) with the laser wavelength of the excitation light source being 515 nm.
  • a DLC film hereinafter, also referred to as a "silicon-containing DLC film” in which silicon is added is formed and prepared on the surface of a base material that has been mirror-polished in advance.
  • a cemented carbide substrate is used as a substrate of this sample.
  • the substrate on which the DLC film is formed is heated to each heat treatment temperature, and the silicon-containing DLC film (silicon content: 3 at.%) Heated to a predetermined heat treatment temperature before the heat treatment
  • the Raman spectrum was measured.
  • the respective heat treatment temperatures are, as shown, 800 ° C., 850 ° C., 900 ° C. and 950 ° C.
  • the ultimate vacuum in the heat treatment apparatus was 3.0 ⁇ 10 ⁇ 2 Pa, and after raising the temperature to each heat treatment temperature for 2 hours, it was held for 1 hour, and then cooled to normal temperature. Before and after the test, argon gas purge was performed.
  • the band H is a hybrid band and is a synthetic band of the G band and the D band. Furthermore, an S band having a peak in the wave number of 1000 to 1200 cm -1 is measured, and the S band will be described later.
  • the H band is measured as a hybrid band. That is, it shows that the structure of the silicon-containing DLC film is substantially maintained even when heat treatment at a high temperature of 800 ° C. to 900 ° C. is performed.
  • spectrum (e) in which the heat treatment temperature is 950 ° C., the G band and the D band are clearly separated, and the hybrid band can not be measured. That is, spectrum (e) indicates that the structure of the silicon-containing DLC film has been changed by the heat treatment, and indicates that the characteristics of the substrate surface as a film have changed.
  • FIG. 2 is a graph showing the change in Raman spectrum when the DLC film of the comparative example is heat-treated, and the DLC film of the comparative example is a DLC film consisting of conventional ta-C to which no silicon is added.
  • a laser beam with a wavelength of 515 nm is used as an excitation light source, and Raman spectrums before heat treatment and at heat treatment temperatures of 800 ° C., 850 ° C., 900 ° C., and 950 ° C. are measured.
  • the spectrum (a) of FIG. 2 the H band which is a hybrid band appears before heat treatment, but in the spectrum (b) of a heat treatment temperature of 800 ° C., the H band which is a hybrid band is already separated.
  • the hybrid band (H band) in the Raman spectrum is not separated even after the heat treatment at a high temperature, as clear measured data showing the improvement of the heat resistance in the DLC film.
  • the present invention and the comparative example are completely distinguished.
  • FIG. 3 is a graph showing the components of each band in the Raman spectrum of the DLC film according to the present invention.
  • the Raman spectrum is measured using a laser Raman spectrophotometer (manufacturer: Japan Spectrometer, model: NRS-1000) with the laser wavelength of the excitation light source being 532 nm.
  • a laser Raman spectrophotometer manufactured by Japan Spectrometer, model: NRS-1000
  • an H band which is a hybrid band and an S band derived from an sp 3 bond in ta-C are measured in a Raman spectrum.
  • the S band is measured also when the wavelength of 515 nm is used as the excitation light source.
  • the H band is a hybrid band consisting of the G band and the D band, and in FIG. 3, the components of the G band and the D band are resolved by fitting. That is, peak intensities Pg, Pd, Ag, and Ad of the G band and the D band can be estimated from the fitting of the H band. Furthermore, since the S band is relatively weak and broad, the peak intensity Ps and the area intensity As are estimated by fitting. It is more preferable to use the least squares method for fitting each band.
  • FIG. 4 is a block diagram showing the configuration of a DLC film forming apparatus according to the present invention.
  • a main evaporation source 2 composed of carbon and a sub-evaporation source 3 composed of another element other than carbon are arranged.
  • the main evaporation source 2 is installed in the main evaporation substance generation unit 8, and the evaporation substance evaporated from the main evaporation source 2 is supplied by the main evaporation substance evaporation means 8a.
  • the secondary evaporation source 3 is installed in the secondary evaporation material generation unit 10, and the secondary evaporation material evaporated from the main evaporation source 3 is supplied by the main evaporation material evaporation means 10a.
  • the main evaporation material generation unit 8 is connected to the processing unit 4 in which the object 6 is disposed through the filter unit 12a, and similarly, the sub evaporation material generation unit 10 is connected to the processing unit 4 through the filter unit 12b. It is done. Therefore, the evaporation substances of the main evaporation source 2 and the sub evaporation source 3 are introduced into the processing unit 4 through the respective filter parts 12a and 12b, and a DLC film to which other elements are added is formed on the surface of the object 6. .
  • the content of the other element to be added can be adjusted by the evaporation amount, the film forming time, and the like.
  • the filter units 12a and 12b have a function of removing impurities generated other than the evaporation substances of the main evaporation source 2 and the sub evaporation source 3.
  • the main evaporation substance evaporation means 8a is a filtered arc evaporation apparatus
  • a droplet consisting of electrically neutral particles and the like is generated from the main evaporation source 2 together with the plasma. Therefore, the filter unit 12a is provided with a filter mechanism that bends or curves the path of plasma advancing from the main evaporation material generation unit 8 to the processing unit 4 by an electromagnetic force, and separates from the droplet.
  • the main evaporation source 2 is an evaporation source of a solid made of carbon, and in the embodiment, a graphite material is used.
  • a vacuum arc method, a laser evaporation method, a pulse laser arc method, a method using vacuum arc and pulse laser arc in combination is used as the main evaporation material evaporation means 8a. Since carbon is evaporated without being introduced, and a high density evaporation source of simple carbon can be used, a high quality DLC film can be formed.
  • auxiliary evaporation material evaporation means 10a resistance heating evaporation, electron beam evaporation, vacuum arc, filtered arc, laser evaporation, pulsed laser arc, heating cell evaporation, crucible evaporation, nozzle evaporation or organic EL evaporation can be used. . Since the main evaporation material evaporation means 8a does not carry out gas introduction and evaporates the main evaporation material, the evaporation means for evaporating other elements is selected without introducing the gas as well as the secondary evaporation material evaporation means 10a.
  • the degree of vacuum is preferably as low as possible, and a method of improving the degree of vacuum using a more powerful vacuum pump is preferable.
  • a method of promoting degassing in the filter duct by arc discharge before film formation, and a method of advancing the degassing in the furnace by performing an Ar ion etching process before film formation for a long time are also effective. .
  • Table 1 shows the film forming conditions of the DLC films manufactured as the example and the comparative example, and the DLC films are formed on the cemented carbide substrate after the Ar ion etching is performed.
  • the other conditions were the same, and the film was formed with an arc current of 50 A and a degree of vacuum of 5.0 ⁇ 10 ⁇ 3 Pa or less.
  • the DLC films of samples # 01 to 05 are “DLC: Si (1)”, “DLC: Si (2)”, “DLC (1)”, “DLC (2)”, “DLC: It is classified into seven types of Si: H "," DLC: B "and” DLC: Si: B ".
  • the DLC of sample # 01: Si (1) and the DLC of # 02: Si (2) show the film forming conditions of the silicon-containing DLC film according to the present invention as an example.
  • DLC of # 06: B and DLC of # 07: Si: B show the film forming conditions of the DLC film containing other elements as an example.
  • the DLC (1) of sample # 03 and the DLC (2) of # 04 show the film forming conditions of the DLC film to which silicon is not added as a comparative example.
  • DLC: Si: H of sample # 05 TMS vapor is introduced as a raw material of other elements, and a silicon-containing DLC containing hydrogen (described as "DLC: Si: H" in Table 1) is deposited
  • the film forming conditions are shown as another comparative example.
  • the DLC film of each film-forming condition calculates
  • a filtered arc vapor deposition apparatus (referred to as “FAD apparatus”) is used as the main evaporation material evaporation means shown in FIG.
  • a vapor deposition apparatus (referred to as "EB apparatus") is used.
  • a graphite cathode material is used as a main evaporation source of a FAD apparatus, and a silicon material is used as a sub evaporation source. That is, carbon is supplied by the FAD device, and silicon is supplied by the EB device to form a silicon-containing DLC film, as described in “Method for adding other elements” in Table 1.
  • Table 1 describes “DLC: Si (1)” in order to distinguish the other DLC films from the film forming method.
  • the arc current of the main evaporation source is kept constant
  • the acceleration voltage of the EB apparatus is 6 kV
  • the emission current is changed in the range of 80 to 120 mA
  • the evaporation amount of silicon is adjusted. doing.
  • the DLC: Si film of the desired sample # 01 is formed on the substrate.
  • the voltage applied to the film formation substrate is a pulse voltage of about -100V.
  • the heat resistance of DLC: Si (1) of sample # 01 is improved by the addition of silicon, similarly to the result of the Raman spectrum shown in FIG.
  • the sample # 02 in Table 1 has another silicon content of 1 to 10 at.
  • a graphite cathode material to which finely divided silicon carbide is added so as to be% is used as a deposition source of the FAD apparatus, and a DLC: Si film is formed on a substrate.
  • a silicon-containing DLC film formed using a silicon-containing evaporation source is referred to as "DLC: Si (2)". That is, DLC: Si (2) is a silicon-containing DLC film formed by evaporating carbon and silicon from one deposition source (also referred to as "target") by using a silicon-containing deposition source.
  • Sample # 06 is a graphite cathode material similarly doped with finely divided boron carbide
  • sample # 07 is a graphite cathode material doped with finely divided silicon carbide and boron carbide used as a deposition source of the FAD apparatus
  • DLC B film
  • DLC Si: B films formed on the substrate.
  • Table 2 describes the film hardness of the DLC film with respect to the element ratio (at.%) Of silicon contained in the DLC film (referred to as “the Si element ratio in the film” in the table).
  • the Si element ratio in the film depends on the addition amount (at.%) Of silicon added to the target (referred to as “target Si addition amount” in the table), and along with the increase of the target Si addition amount Not only the Si element ratio in the film is increased, but also the film hardness is significantly reduced. This indicates that the sp 3 ratio is low, and although the addition concentration of silicon is within the scope of the present invention, it is not a product of the present invention.
  • Example 1 since the melting point rises from 1,400 ° C. to 2,700 ° C.
  • Example 1 a very high film hardness is obtained, which is suggested to have a high sp 3 ratio, and can be the film of the present invention. Even when other elements other than silicon are added, stable discharge is facilitated by mixing with carbide as a target, and the film of the present invention can be formed.
  • the DLC film according to the present invention has a silicon content of 0 at. % ⁇ X ⁇ 15 at. Although it is characterized in that it is%, the DLC film of the present invention can not be obtained only on the condition of its content.
  • the DLC film according to the present invention is characterized by having an sp 3 ratio such that at least an S band appears in a Raman spectrum.
  • the results in Table 2 indicate that the film quality of the DLC film may also depend on the quality of the target. Therefore, when forming a DLC film with a target to which another element such as metal is added, it is suggested that the DLC film according to the present invention can be formed more reliably by using a suitable target. Furthermore, although the film formation is performed using the FAD apparatus in the present embodiment, the implementation method of the present invention is not limited.
  • the method of using a vacuum arc and a laser arc together is also preferable. This is because it is possible to maintain a stable vacuum arc discharge by causing the laser to evaporate the additive deposited on the surface by the discharge as described above.
  • the laser may be irradiated only at the time of ignition, or may be irradiated constantly during arc discharge, or a method may be used in which the arc discharge is pulsed and the laser is irradiated in synchronization with this.
  • the method of using the above-mentioned filter in combination is more preferable.
  • a DC voltage of about -100 V is applied to the film formation substrate in the FAD apparatus.
  • the spectrum similar to the Raman spectrum shown in FIG. 1 is also measured when DLC: Si (1) of sample # 01 or DLC: Si (2) of sample # 02 is used, and suitable heat resistance is obtained. It has been confirmed to have Sample # 03 in Table 1 is a DLC film to which silicon is not added, and is described as “DLC (1) in the table.
  • DLC (1) uses an evaporation source made of a graphite cathode material by an FAD device. The DLC film formed is shown, and silicon is not added.
  • the pulse voltage to the film formation substrate is about -100 V.
  • the DLC (1) of sample # 03 is DLC: Si (sample # 01). As can be compared with 1), the film is formed under the same film forming conditions as sample # 01 except that the addition of silicon is not performed.
  • the sample # 04 in Table 1 is a DLC film to which no silicon is added, and is deposited using an evaporation source made of a graphite cathode material by the FAD apparatus, and is described as “DLC (2)” in the table.
  • the sample # 04 is a DC voltage of about ⁇ 100 V applied to the film formation substrate, and the film forming conditions other than the evaporation source are the same for comparison with the sample # 02. Under the same film forming conditions as the DLC film for which the Raman spectrum of No.
  • sample # 05 in Table 1 is obtained by introducing TMS vapor using an FAD device, and forming a silicon-containing DLC film containing hydrogen on a cemented carbide substrate. Si: H is called.
  • Table 3 shows the peak position of each band appearing in the Raman spectrum of various DLC films. As shown in FIG. 3, S band, D band and G band appear in the Raman spectrum of the DLC film according to the present invention. Samples # 1 to 11 in Table 3 are DLC films formed on the substrate surface under the film forming conditions shown in Table 1, and the S band, D band, and the S band of the Raman spectrum measured at a laser wavelength of 532 nm as an excitation light source. The peak position of the G band is described in Table 3.
  • the types of DLC films in Table 3 are “DLC: Si (1)”, “DLC: Si (2)”, “DLC (1)”, “DLC (2)” and “DLC: Si” shown in Table 1. : H "five types.
  • samples # 1 to # 4 are "DLC: Si (1)” formed by the FAD apparatus and the EB apparatus, and samples # 5 to # 8 are formed from the silicon-containing evaporation source "DLC: Si (2)
  • Sample # 9 10 is to apply a "DLC (1)” and a DC voltage which is deposited by applying a pulse voltage to the FAD system is deposited "DLC (2)”
  • the sample # 11 is "DLC: Si: H” formed by introducing a TMS gas.
  • the S band having a peak between wave numbers of 1000 and 1200 cm -1 is a band derived from sp 3 bond in ta-C, and the S band is measured in the Raman spectrum measurement of samples # 1 to # 3. It is done. Therefore, the silicon-containing DLC films of samples # 1 to # 3 have the same strength as the ta-C film, and further, they are provided with suitable heat resistance by the addition of silicon.
  • DLC Si (2) of sample # 5-8 shown in Table 3, silicon (Si) content of a DLC film is 0.8 at. % To 12.8 at. %, And the S band is measured in Raman spectroscopy. The silicon content is approximately 15 at. Up to about%, an S band appears in each Raman spectrum, indicating that a silicon-containing DLC film having a hydrogen-free ta-C type structure is formed.
  • Si H of sample # 11 contains silicon by the introduction of TMS gas and further contains hydrogen, and the peak of the S band is not observed.
  • Table 4 shows the ratio of peak intensities (Pg, Pd, Ps) of G band, D band and S band in Raman spectrum of samples # 1 to # 11.
  • Table 5 shows area intensity (Ag, Each ratio of Ad, As) is shown.
  • the peak intensity ratio Pd / Pg is attributed to the ratio of the defect of the graphite structure in the DLC film. It is Peak intensity ratio Pd / Pg indicates that preferably 0.5 or less, defects of the graphite structure is relatively small, a silicon-containing DLC film having a suitable strength is formed.
  • the area strength ratio Ad / Ag is also preferably 0.5 or less, which indicates that a suitable silicon-containing DLC film is formed.
  • the peak intensity ratio Ps / Pd and the area intensity ratio As / Ad be 0.01 or more. That is, the S-band derived from ta-C is measured with sufficient strength to the D-band derived from defects in the graphite structure, and the silicon-containing DLC film is a ta-C film having sp 3 bonds at a predetermined ratio or more. The fact indicates that a high quality DLC film is formed. Similarly, it is preferable that the peak intensity ratio Ps / Pg and the area intensity ratio As / Ag have higher values.
  • Table 6 describes the refractive index and the extinction coefficient as optical measurement values for the DLC films of samples # 1 to 11, and further, a glass lens is formed using a glass lens molding die on which each DLC film is formed. The number of times that can be molded is measured.
  • the refractive index and extinction coefficient of each DLC film are calculated by optical simulation from the reflectance characteristics of the DLC film measured in the wavelength range of 380 nm to 780 nm using a spectral reflectance meter. doing.
  • the refractive index and extinction coefficient shown in Table 5 are values for light of 550 nm.
  • the DLC film whose spectral reflectance was measured is formed on a cemented carbide substrate which is a mold for molding a glass lens, and DLC: Si (1), DLC: Si (2), DLC (1) ), DLC (2), and DLC: Si: H film formation conditions.
  • a glass preform material glass transition point 608 ° C., softening point 713 ° C.
  • the glass lens is molded in a nitrogen atmosphere at a molding temperature of 683 ° C. and a press load of 400 kgf. ing.
  • the number of times that molding can be performed hereinafter simply referred to as “the number of times of molding can be repeated without causing the adhesion of the glass material to the molding die surface or the change of the surface shape of the molded lens Also referred to as
  • the number of molding times is larger.
  • samples # 1 to # 3 and samples # 5 to # 8 which are silicon-containing DLC films whose S bands were measured in the Raman optical spectrum
  • the number of molding times is 500 or more. That is, it can be seen that it has excellent heat resistance and maintains excellent durability against repeated loads.
  • sample # 4 the S band is not measured, and the number of moldings is less than 500 times as compared with samples # 1 to # 3 and samples # 5 to # 8.
  • samples # 9 and # 10 in which silicon is not added the number of times of molding is less than 500, and the extinction coefficient is relatively small, less than 0.05.
  • Sample # 11 is a silicon-containing DLC film containing hydrogen is formed count has a smallest value by comparing the smallest is 50, refractive index between the sample # 1-10. Therefore, as an evaluation method of a silicon-containing DLC film, using the number of refractive index and extinction coefficient, the refractive index of the wavelength of 550nm to light 2.5-3.0 and the extinction coefficient is 0.05 to 0.40 It can be seen that a suitable silicon-containing DLC film of molding durability can be obtained.
  • FIG. 5 is a schematic view of a DLC film forming apparatus schematically showing the main evaporation source 2, the main traveling direction 7, the sub evaporation source 3 and the sub traveling direction 9 according to the present invention.
  • FIG. 4 shows an example of a DLC film forming apparatus as a block diagram, in Figure 5, the main evaporation source 2 and the main traveling direction 7 and the sub evaporation source 3 for the relationship of the sub-moving direction 9 will be described.
  • the schematic diagram shown in (5A) based on coating surface central area 6a of the object 6, linearly from the main evaporation source 2 and the auxiliary evaporation source 3, each of the evaporation material is the main traveling direction 7 sub traveling direction 9
  • the other element-containing DLC film is formed on the surface of the target 6.
  • the other-elements-containing DLC film can be suitably formed on the surface of the object 6.
  • Carbon is supplied from the main evaporation source 2 as the main evaporation material, and other elements other than carbon and hydrogen are supplied from the secondary evaporation source 3 as the secondary evaporation material to form a DLC film containing other elements.
  • the main evaporation material evaporated from the main evaporation source 2 is bent once, reaches the coated surface central region 6a of the object 6 along the main traveling direction 7, and
  • the auxiliary evaporation material evaporated from the evaporation source 3 is bent once and reaches the coated surface central area 6 a along the auxiliary traveling direction 9.
  • the traveling direction of the evaporation material by the electromagnetic force to separate impurities such as droplets.
  • the angle ⁇ between the main advancing direction 7 and the sub advancing direction 9 is 180 ° or less, the other element-containing DLC film can be suitably formed on the surface of the object 6.
  • the main evaporation material is made to travel in a curved shape by electromagnetic force from the main evaporation source 2 and separated from the droplets contained in the main evaporation material. Finally, the coated surface central area 6 a is reached along the main traveling direction of the object 6. Further, in (5C), the secondary evaporation material from the secondary evaporation source 3 goes straight in the same manner as (5A) and reaches the coated surface central region 6a along the secondary traveling direction 9. Similarly, if the angle ⁇ between the main advancing direction 7 and the sub advancing direction 9 is 180 ° or less, the other element-containing DLC film can be suitably formed on the surface of the object 6.
  • FIG. 6 is a schematic view showing an embodiment of a DLC film forming apparatus 1 according to the present invention.
  • the DLC film forming apparatus 1 shown in FIG. 6 is a T-shaped filtered arc vapor deposition apparatus, and includes a main evaporation material generating unit 8, a filter unit 12, and a processing unit 4.
  • the main evaporation material generating unit 8 includes a main evaporation source 2 provided with a shield 30, a power supply 22 for applying a voltage to the main evaporation source 2, an anode 28 connected to the power supply 22, and a current limiting resistor.
  • a trigger electrode 26 connected to the power supply 22 via 24 and an arc stabilization coil 32 for stabilizing the generated arc are provided.
  • a vacuum arc is generated on the surface of the main evaporation source 2 by the trigger electrode 26 to generate a plasma of the main evaporation material.
  • the plasma is induced to the filter unit 12 by the plasma extraction coil 34, and the main evaporation material including the droplets travels along the mixing path 48.
  • the plasma advancing in the mixing advancing path 48 is guided to the main advancing path 18 at the bending portion 46 by the plasma bending coil 36, and the droplet advances in the droplet advancing direction 40 and is collected by the droplet collecting portion 42 .
  • the plasma from which the droplets are separated is guided to the main traveling path 18 by the plasma guide coil 38 and introduced into the processing unit 4.
  • the object 6 is installed on the mounting base 44.
  • An electron beam vapor deposition apparatus 17 (EB apparatus) is disposed in the sub-evaporation material generation unit 10, and the sub-evaporation source 3 made of another element is irradiated with an electron beam from the electron beam irradiation unit 17a.
  • the coevaporation material rises along the side travel path 20 and reaches the coated surface 6 b. Therefore, the DLC film is formed on the coated surface 6b by the main evaporation material traveling through the main traveling path 18, and at the same time, the sub-evaporation material supplied via the sub traveling path 20 is added.
  • the DLC film forming apparatus 1 shown in FIG. 6 is the film forming method of the sample # 11 shown in Table 1, and realizes the same film forming conditions as “DLC: Si (1)” shown in Tables 1 to 5. Specifically, “DLC: Si (1)” is deposited using the apparatus shown in FIG.
  • FIG. 7 is a schematic perspective view showing the relationship between the main advancing direction and the auxiliary advancing direction of the DLC film forming apparatus shown in FIG.
  • the same reference numerals are given to the members described in FIG. 6, and the detailed description will be omitted.
  • FIG. 7 shows a part of the DLC film forming apparatus of FIG. 6, and clearly shows the relationship between the main traveling path 18 and the sub traveling path 20.
  • the main traveling direction 7 of the main evaporation material is horizontal, but as shown in FIG. 7, in the sub traveling direction 9, the sub evaporation material rises from the lower traveling path inlet 20a below to the upper traveling path outlet 20b It is arranged to do.
  • the main evaporation material travels horizontally from the main travel path outlet 18a to the object, and the sub evaporation material travels vertically from the sub travel path outlet 20b to the object.
  • the auxiliary evaporation material generation means is a laser evaporation device, laser light is made incident from the laser incident window 4a provided in the processing unit 4 and the laser light is emitted to the auxiliary evaporation source provided below the entrance 20a of the auxiliary traveling path. To evaporate the co-evaporated substance.
  • FIG. 8 is a schematic view showing another embodiment of the DLC film forming apparatus 1 according to the present invention.
  • the auxiliary traveling path 62 is connected to the processing unit 4 adjacent to the main traveling path 18.
  • the auxiliary evaporation material generation unit 61 has a structure similar to that of the main evaporation material generation unit 8 although the description of the power supply etc. is omitted, and is constituted by an FAD device that generates plasma from the auxiliary evaporation source 3 by vacuum arc. ing.
  • the sub-evaporation material generation unit 61 is provided with a sub-evaporation source 3 and an arc stabilization coil 69, and generates plasma in the same manner as the main evaporation material generation unit 8. Furthermore, a bending portion 64 is provided, and plasma is induced in the secondary traveling direction 9 by the plasma bending coil 68.
  • the droplets are collected by the droplet collision wall 66 because they are not affected by the magnetic field of the plasma bending coil 68. Further, by providing a rib or the like on the droplet collision wall, the droplet can be collected more reliably.
  • FIG. 9 is a schematic view showing another embodiment of the DLC film forming apparatus 1 according to the present invention.
  • the auxiliary traveling path 72 is connected to the filter unit 12, and although not shown, a plasma bending coil is provided for the auxiliary traveling path 72. That is, each plasma is bent at the bending portion 46, the sub advancing direction 9 and the main advancing direction 7 overlap, and the sub evaporation material and the main evaporation material travel in the common traveling direction 80.
  • a sub evaporated substance generator 71 in FIG. 9 sub traveling path 72 and has FAD devices consist primarily traveling passage 18, the main evaporator material mainly traveling passage 18 as a common progressive method 80.
  • FIG. 10 is an overall flow diagram showing an example of the other element containing DLC film forming step according to the present invention.
  • N means "No” and Y means "Yes”.
  • step 2 it is determined whether or not the main evaporation material generation unit ME is in the activated state, and when it is possible to supply the main evaporation material from the main evaporation material generation unit ME to the processing unit PU, it becomes Y, and the process proceeds to step 3. If the main evaporation material generation part ME is not in the activated state, it becomes N, and is in the standby state until the main evaporation material generation part ME is activated. Similarly, in step 3, it is determined whether the sub-evaporation material generation unit SE is in the activated state, and when the sub-evaporation material generation unit SE is in the state where the main evaporation material can be supplied to the processing unit PU, Y is obtained.
  • step 5 the main evaporation time Tm of the main evaporation material generation part ME and the sub evaporation time Ts of the sub evaporation material generation part SE simultaneously advance, and the process proceeds to step S6 via the point P.
  • step 6 several evaporation patterns are executed according to the settings, the evaporation in step 6 is finished, and the process proceeds to step 7 via point Q.
  • step 7 when it repeats evaporation, it becomes Y, returns to step S6 via point P, and repeats evaporation. If the evaporation is not repeated in step 7, the result is N, and the control flow of the DLC film deposition apparatus ends (END).
  • FIG. 11 is a schematic flow diagram showing an evaporation process in step 6 of FIG.
  • the main evaporation material and / or the auxiliary evaporation material are supplied from the main evaporation material generation part ME and the auxiliary evaporation material generation part SE, but as shown in FIG. 11, the cases of evaporation patterns A to K are considered.
  • the main evaporation in the main evaporation material generation part ME and the side evaporation in the side evaporation material generation part SE simultaneously start, the main evaporation ends first, and the side evaporation ends later.
  • the main evaporation in the main evaporation material generation part ME and the co-evaporation in the co-evaporation material generation part SE start simultaneously, the sub-evaporation ends first, and the main evaporation ends later.
  • the main evaporation in the main evaporation material generation part ME starts first, and the secondary evaporation in the sub evaporation material generation part SE starts later.
  • the main evaporation in the main evaporation material generation part ME and the sub-evaporation in the sub evaporation material generation part SE end simultaneously, and in the evaporation pattern E, the main evaporation in the main evaporation material generation part ME ends first, The co-evaporation in the evaporation material generation part SE ends later.
  • the sub-evaporation in the sub-evaporation material generation part SE ends first, and the main evaporation in the main-evaporation material generation part ME ends later.
  • the sub-evaporation in the sub-evaporation material generation part SE starts first, and the main evaporation in the main-evaporation material generation part ME starts later.
  • the main evaporation in the main evaporation material generation part ME and the sub-evaporation in the sub evaporation material generation part SE end simultaneously, and in the evaporation pattern H, the main evaporation in the main evaporation material generation part ME It ends first, and the side evaporation in the side evaporation material generation part SE ends later.
  • the sub-evaporation in the sub-evaporation material generation part SE ends first, and the main evaporation in the main-evaporation material generation part ME ends later.
  • the evaporation patterns J and K shown in FIG. 11 are for performing only main evaporation in the main evaporation material generation part ME and for performing sub-evaporation only in the sub evaporation material generation part SE. That is, the deposition source which is disposed and a case made of a carbon material containing other elements, when forming a primary evaporation material alone or a layer comprising a sub evaporated substance only, evaporation patterns J, K are used. Therefore, the control of the film formation is the same as in the conventional film formation process, and the evaporation material is supplied only from the main evaporation material generation part ME or the sub evaporation material generation part SE.
  • FIG. 12 is a flow chart showing an example of a subroutine executed in step 6 shown in FIG.
  • evaporation patterns A to K as shown in FIG. 11 are selected, but an example of a subroutine shown in FIG. 12 shows a film forming process when evaporation patterns J and K are not included.
  • the evaporation patterns J and K are steps for forming a film using only the main evaporation material generation part ME or the secondary evaporation material generation part SE, it is sufficient to prepare a subroutine for controlling one evaporation source. The steps of performing the evaporation patterns J and K are not shown.
  • step 12 it is determined whether or not the main evaporation time Tm has reached the main evaporation start time Tms, and in the case of Y, the process proceeds to step 13. If the step 12 is N, the process returns to the step 12 and waits until the main evaporation time Tm becomes the main evaporation start time Tms. In step 13, main evaporation of the main evaporation material generation part ME and side evaporation of the sub evaporation material generation part SE are simultaneously started, and the process proceeds to step 14. In addition, since step 13 is simultaneous start, it may be determined in step 12 whether or not the secondary evaporation time Ts has reached the secondary evaporation start time Tss.
  • step 15 If the step 15 is N, the evaporation is continued until the main evaporation time Tm becomes the main evaporation end time Tme since the process returns to the step 15.
  • Step 16 the main evaporation of the main evaporation material generation part ME and the sub-evaporation of the sub evaporation material generation part SE end at the same time, and the process proceeds to Step 7 of FIG. Similarly, since step 16 is simultaneous termination, it may be determined in step 15 whether or not the secondary evaporation time Ts has reached the secondary evaporation end time Tse.
  • step 17 of FIG. 12 the main evaporation of the main evaporation material generation part ME and the side evaporation of the sub evaporation material generation part SE are started with a time difference, and the process proceeds to step 14. Further, in step 18 of FIG. 12, the main evaporation of the main evaporation material generation part ME and the sub-evaporation of the sub evaporation material generation part SE end with a time difference, and the process proceeds to step 7 of FIG.
  • the steps from step 11 to step 13 shown in FIG. 12 correspond to the simultaneous start of main evaporation and secondary evaporation of the initial steaming patterns A to C in FIG. 11, and the steps to step 14 to 16 in FIG. 11 corresponds to simultaneous completion of main evaporation and co-evaporation of the initial steaming patterns A, D, and G in 11;
  • FIG. 13 is a flow chart showing a subroutine from point P1 to point Q1 including step 17 of FIG.
  • step 21 it is determined whether or not the main evaporation of the main evaporation material generation part ME starts first, and in the case of Y, the process proceeds to step 22.
  • step 22 it is determined whether the main evaporation time Tm is the main evaporation start time Tms, and in the case of Y, the process proceeds to step 23, and in step 23, main evaporation of the main evaporation material generation unit ME starts and the process proceeds to step 24.
  • step 22 In the case where the main evaporation time Tm is N at which the main evaporation time Tm is not the main evaporation start time Tms in step 22, the process returns to the step 22 and is repeated until the main evaporation start time Tms is reached, so that the process is on standby.
  • step 24 it is determined whether the secondary evaporation time Ts is the secondary evaporation start time Tss, and in the case of Y, the process proceeds to step 25.
  • step 25 secondary evaporation is started in the secondary evaporation material generation part SE, Proceed to step 14 of 12.
  • step S22 if the sub-evaporation time Ts is not N at the sub-evaporation start time Tss, the process returns to step S22, and is repeated until the sub-evaporation start time Tss is reached. If it is determined in step 21 that the main evaporation of the main evaporation substance generation unit ME does not start first, the process proceeds to step 26 where N is obtained. In step 26, it is determined whether the sub-evaporation time Ts is the sub-evaporation start time Tss, and if Y, the process proceeds to step 27. In step 27, the sub-evaporation material generation unit SE starts the sub-evaporation and the process proceeds to step.
  • step 26 If the sub-evaporation time Ts is not N at the sub-evaporation start time Tss at step 26, the process returns to the step 26 and is repeated until it reaches the sub-evaporation start time Tss, so that the process waits.
  • step 28 it is determined whether the main evaporation time Tm is the main evaporation start time Tms, and in the case of Y, the process proceeds to step 29.
  • step 29 the main evaporation of the main evaporation material generation part ME starts, and FIG. Go to step 14 of.
  • the process returns to the step 28 and is repeated until the main evaporation start time Tms is reached, so the process is on standby.
  • the flow in steps 22 to 25 in FIG. 12 corresponds to the case where the main evaporation in evaporation patterns D to F starts first, and the flow in steps 26 to 29 in FIG. 12 starts from the secondary evaporation in evaporation patterns G to I. It corresponds to the case of starting.
  • FIG. 14 is a flow chart showing a subroutine from point P2 to point Q2 including step 18 of FIG.
  • step 31 it is determined whether or not the main evaporation of the main evaporation material generation part ME ends open first, and in the case of Y, the process proceeds to step 32.
  • step 32 it is determined whether the main evaporation time Tm is the main evaporation end time Tme, and in the case of Y, the process proceeds to step 33, and in step 33, the main evaporation of the main evaporation material generation unit ME ends and the process proceeds to step.
  • step 34 it is determined whether the sub-evaporation time Ts is the sub-evaporation end time Tse, and in the case of Y, the process proceeds to step 35.
  • step 35 the sub-evaporation is completed in the sub-evaporation material generating part SE Proceed to step 7 of FIG. 10 connected via point Q.
  • step 34 If it is determined in step 34 that the auxiliary evaporation time Ts is not N at the auxiliary evaporation end time Tse, the process returns to step 34 and is repeated until the auxiliary evaporation end time Tse is reached, so the auxiliary evaporation continues. If it is determined in step 31 that the main evaporation of the main evaporation substance generation unit ME does not end first, the process proceeds to step 36 where N is obtained. In step 36, it is determined whether the sub-evaporation time Ts is the sub-evaporation end time Tse, and in the case of Y, the process proceeds to step 37.
  • step 36 if the sub-evaporation time Ts is not N for the sub-evaporation end time Tse, the process returns to step 36 and is repeated until the sub-evaporation start time Tse is reached. It is determined whether the evaporation time Tm is the main evaporation end time Tme, and in the case of Y, the process proceeds to step 39, and the main evaporation of the main evaporation material generation part ME is completed in step 39, and connection is made via point Q2 and point Q in FIG. Proceed to step 7 of FIG.
  • step 38 if the main evaporation time Tm is not N for the main evaporation end time Tme, the process returns to step 38 and is repeated until the main evaporation end time Tms is reached, so the main evaporation continues.
  • the flow of steps 32 to 35 in FIG. 14 corresponds to the case where the main evaporation in evaporation patterns B, E and H shown in FIG. 11 ends first, and the flow of steps 36 to 39 in FIG. This corresponds to the case where the sub-evaporation in the illustrated evaporation patterns C, F and I ends first.
  • FIG. 15 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern A of FIG.
  • the main evaporator and the secondary evaporation running evaporated and main evaporator signal substance generator ME S (ME) and signal S sub evaporated substance generator SE (SE) is a positive value Become.
  • the main evaporation start time Tms of (15A) and the subevaporation start time Tss of (15B) are simultaneous, and the main evaporation and the coevaporation start simultaneously.
  • the main evaporation end time Tme of (15A) and the subevaporation end time Tse of (15B) are also simultaneous, and the main evaporation and the coevaporation are simultaneously ended.
  • FIG. 16 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern B of FIG. Similarly, in the evaporation pattern B, the main evaporation start time Tms of (16A) and the subevaporation start time Tss of (16B) are simultaneously, and the main evaporation and the coevaporation start simultaneously.
  • the signal S (ME) becomes 0 at the main evaporation end time Tme of (16A) first, and then the secondary of (16B)
  • the signal S (SE) becomes 0 at the evaporation end time Tse.
  • FIG. 17 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern C of FIG. Similarly, in the evaporation pattern C, the main evaporation start time Tms of (17A) and the subevaporation start time Tss of (17B) are simultaneously, and the main evaporation and the coevaporation start simultaneously.
  • the signal S (SE) becomes 0 at the secondary evaporation end time Tse of (17B) first, and then the main of (17A)
  • the signal S (ME) becomes 0 at the evaporation end time Tme.
  • FIG. 18 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern D of FIG.
  • the signal S (ME) since the main evaporation starts first and the secondary evaporation starts later, the signal S (ME) becomes a positive value at the main evaporation start time Tms of (18A) first, and then (18B)
  • the signal S (SE) has a positive value at the secondary evaporation start time Tss.
  • the main evaporation end time Tme of (18A) and the subevaporation end time Tse of (18B) are simultaneously, and the main evaporation and the subevaporation are simultaneously ended, and the signal S (ME) and the signal S (SE) Is 0 at the same time.
  • FIG. 19 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern E of FIG.
  • the signal S (ME) since the main evaporation starts first and the secondary evaporation starts later, the signal S (ME) becomes a positive value at the main evaporation start time Tms of (19A) first, and then (19B)
  • the signal S (SE) has a positive value at the secondary evaporation start time Tss.
  • the signal S (ME) becomes 0 at the main evaporation end time Tme of (19A) first, and then (19B)
  • the signal S (SE) becomes 0 at the sub-evaporation end time Tse of
  • FIG. 20 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern F of FIG.
  • the signal S (ME) since the main evaporation starts first and the secondary evaporation starts later, the signal S (ME) becomes a positive value at the main evaporation start time Tms of (20A) first, and then (20B)
  • the signal S (SE) has a positive value at the secondary evaporation start time Tss.
  • the signal S (SE) becomes 0 at the secondary evaporation end time Tse of (20 B) first, and then the main (20 A) The signal S (ME) becomes 0 at the evaporation end time Tme.
  • FIG. 21 is a graph showing the main evaporation and auxiliary evaporation time charts of the main evaporation material generating portion ME and the auxiliary evaporation material generating portion SE corresponding to the evaporation pattern G of FIG.
  • the signal S (SE) becomes a positive value at the secondary evaporation start time Tss of (21 B), and then (21 A)
  • the signal S (ME) has a positive value at the main evaporation start time Tms.
  • the main evaporation end time Tme of (21A) and the subevaporation end time Tse of (21B) are simultaneously, and the main evaporation and the subevaporation are simultaneously ended, and the signal S (ME) and the signal S (SE) Is 0 at the same time.
  • FIG. 22 is a graph showing the main evaporation and auxiliary evaporation time charts of the main evaporation material generating portion ME and the auxiliary evaporation material generating portion SE corresponding to the evaporation pattern H of FIG.
  • the signal S (SE) becomes a positive value at the secondary evaporation start time Tss of (22B), and then (22A)
  • the signal S (ME) has a positive value at the main evaporation start time Tms.
  • the signal S (ME) becomes 0 at the main evaporation end time Tme of (22A) first, and then (22B)
  • the signal S (SE) becomes 0 at the sub-evaporation end time Tse of
  • FIG. 23 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern I of FIG.
  • the signal S (SE) becomes a positive value at the secondary evaporation start time Tss of (23B) first, and then ( The signal S (ME) has a positive value at the main evaporation start time Tms of 23A).
  • the signal S (SE) becomes 0 at the secondary evaporation end time Tse of (23B) first, and then (23A) The signal S (ME) becomes 0 at the main evaporation end time Tme of.
  • FIG. 24 is a graph showing a time chart of main evaporation and sub-evaporation of the main evaporation material generation part ME and the sub evaporation material generation part SE corresponding to the evaporation pattern J of FIG.
  • the signal S (ME) has a positive value at the main evaporation start time Tms of (24A), and the signal S (ME) becomes at the main evaporation end time Tme. It is 0.
  • the signal S (SE) remains zero.
  • the film is formed of the main evaporation material and the auxiliary evaporation material, so that the main evaporation material consisting of carbon is the secondary evaporation material of another element Can be added. It is possible to select from various evaporation patterns according to the composition of the evaporation source, the material and use of the substrate surface, or when another film is coated on the surface of the DLC film.
  • FIG. 25 is a surface observation image obtained by observing the DLC film surface according to the present invention by an electron microscope.
  • (25A) is a surface observation image of sample number # 7
  • (25B) is a sample number # 12.
  • the condition of surface irregularities can be evaluated relatively easily as follows. First, using an electron microscope, a DLC film formed on a mirror-polished cemented carbide substrate or a silicon wafer is observed at an acceleration voltage of 5 kV and a magnification of about 500 times. Since the droplets are observed as white dots, unevenness of the entire surface is calculated by calculating the area ratio of the white light spots using commercially available software (for example, Mitani Shoji Co., Ltd. WinROOF). The occupied area of can be calculated.
  • Table 7 shows the ratio sr / t of the occupied area ratio sr of the unevenness due to adhesion and / or detachment of foreign particles on the surface of the DLC film to the film thickness t, and the unevenness of the DLC film surface to which other elements are added is It was 0.01% / nm or less.
  • the sample number # 12 formed into a film for comparison is a sample using normal vacuum arc vapor deposition (without a filter). Even in the case of using vacuum arc deposition, when the number of foreign particles including droplets is large, the number of times of molding is small, and in the same sample, sr / t was 0.01% / nm or more.
  • the ratio Np / t to the film thickness t (mm) of the number Np (pieces / mm 2 ) of convex portions having a diameter of 0.1 ⁇ m or more among the irregularities on the surface of the DLC film to which other elements except # 12 are added is 1 .5 x 10 8 (pieces / mm 3 ) or less.
  • the ratio Nh / t of the number Nh of recesses having a diameter of 0.1 ⁇ m or more (number / piece / mm 2 ) to the film thickness t (mm) among the irregularities of the DLC film surface to which other elements except # 12 are added is 1. It was less than 0 ⁇ 10 8 (pieces / mm 3 ).
  • the peak intensity and the area intensity of the G band are Pg and Ag
  • the peak intensity and the area intensity of the D band are Pd
  • the peak intensity and the area intensity of the S band which is called the characteristic band
  • Ps, As peak intensity ratio Pd / Pg and area intensity ratio Ad / Ag are 0.5 or less
  • peak intensity ratio Ps / Pd and area intensity ratio As / Ad are 0.01 or more.
  • the peak intensity ratio Pd / Pg is attributed to the ratio of defects of the graphite structure in the DLC film. . Therefore, the fact that the peak intensity ratio Pd / Pg is 0.5 or less indicates that the number of defects in the graphite structure is relatively small. Similarly, the area intensity ratio Ad / Ag is also 0.5 or less, which indicates that the defects of the graphite structure are relatively small not only in the peak intensity but also in the area intensity.
  • the DLC film according to the first embodiment is a DLC film made of ta-C having sp 3 bonds at a predetermined ratio or more. According to the DLC film of the first embodiment, it is a DLC film composed of hydrogen-free ta-C having high strength, suitable durability and suitable DLC characteristics, and heat resistance due to the addition of other elements Can be granted.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention vise à améliorer la résistance thermique d'un film de carbone de type diamant (DLC) formé sur un objet cible et à fournir un film de DLC exempt d'hydrogène présentant une dureté élevée. La présente invention concerne un film de DLC ayant un élément autre que l'hydrogène ou le carbone ajouté à celui-ci et, lorsque le spectre Raman est mesuré à l'aide d'une lumière laser d'une longueur d'onde de 500 à 600 nm, une bande G dérivée d'une structure de graphite, une bande D dérivée d'un défaut de structure de graphite, et une bande caractéristique abrégée par bande S et ayant un pic de longueur d'onde compris entre 1 000 et 1 200 cm-1 sont détectées. Lorsque l'intensité du pic et l'intensité de l'aire de la bande G sont Pg et Ag, l'intensité du pic et l'intensité de l'aire de la bande D sont Pd et Ad, et l'intensité du pic et l'intensité de l'aire de la bande caractéristiques sont Ps et As, le rapport d'intensité des pics Pd/Pg et le rapport d'intensité des aires Ad/Ag ne sont pas supérieurs à 0,5 et le rapport d'intensité des pics Ps/Pd et le rapport d'intensité des aires As/Ad sont d'au moins 0,01.
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JP2020050912A (ja) * 2018-09-27 2020-04-02 日産自動車株式会社 摺動部材及び該摺動部材を用いた摺動装置
WO2020149318A1 (fr) * 2019-01-18 2020-07-23 日東電工株式会社 Corps stratifié
WO2020209133A1 (fr) * 2019-04-10 2020-10-15 株式会社リケン Élément coulissant et segment de piston
JP2020200803A (ja) * 2019-06-12 2020-12-17 Ｔｐｒ株式会社 ピストンリング
KR20210066060A (ko) * 2019-11-27 2021-06-07 한국재료연구원 적외선 광학렌즈 보호용 ta-C 보호막 및 이의 코팅방법
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JP7021402B1 (ja) * 2021-09-30 2022-02-16 Ｔｐｒ株式会社 摺動部材
WO2022209023A1 (fr) 2021-03-30 2022-10-06 株式会社リケン Segment de piston et son procédé de fabrication
US11821524B2 (en) 2019-12-17 2023-11-21 Kabushiki Kaisha Riken Combination of cylinder and piston ring
KR20250025236A (ko) * 2023-08-14 2025-02-21 경북대학교 산학협력단 하이포이드 기어 제조방법

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JP2020003022A (ja) * 2018-06-29 2020-01-09 Ｔｐｒ株式会社 ピストンリング
JP2020050912A (ja) * 2018-09-27 2020-04-02 日産自動車株式会社 摺動部材及び該摺動部材を用いた摺動装置
JP7230399B2 (ja) 2018-09-27 2023-03-01 日産自動車株式会社 摺動部材及び該摺動部材を用いた摺動装置
WO2020149318A1 (fr) * 2019-01-18 2020-07-23 日東電工株式会社 Corps stratifié
WO2020209133A1 (fr) * 2019-04-10 2020-10-15 株式会社リケン Élément coulissant et segment de piston
JP2020200803A (ja) * 2019-06-12 2020-12-17 Ｔｐｒ株式会社 ピストンリング
KR20210066060A (ko) * 2019-11-27 2021-06-07 한국재료연구원 적외선 광학렌즈 보호용 ta-C 보호막 및 이의 코팅방법
KR102284890B1 (ko) * 2019-11-27 2021-08-04 한국재료연구원 적외선 광학렌즈 보호용 ta-C 보호막 및 이의 코팅방법
US11821524B2 (en) 2019-12-17 2023-11-21 Kabushiki Kaisha Riken Combination of cylinder and piston ring
US11746903B2 (en) 2021-03-30 2023-09-05 Kabushiki Kaisha Riken Piston ring and method for manufacturing same
WO2022209023A1 (fr) 2021-03-30 2022-10-06 株式会社リケン Segment de piston et son procédé de fabrication
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KR20230052960A (ko) * 2021-09-30 2023-04-20 티피알 가부시키가이샤 슬라이딩 부재
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US11867294B2 (en) 2021-09-30 2024-01-09 Tpr Co., Ltd. Sliding member
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