US20130327642A1 - Arc evaporation source - Google Patents

Arc evaporation source Download PDF

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Publication number
US20130327642A1
US20130327642A1 US14/001,315 US201214001315A US2013327642A1 US 20130327642 A1 US20130327642 A1 US 20130327642A1 US 201214001315 A US201214001315 A US 201214001315A US 2013327642 A1 US2013327642 A1 US 2013327642A1
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United States
Prior art keywords
target
magnet
ring
rear surface
shaped
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Abandoned
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US14/001,315
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English (en)
Inventor
Shinichi Tanifuji
Kenji Yamamoto
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Kobe Steel Ltd
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Kobe Steel Ltd
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Priority claimed from JP2011118267A external-priority patent/JP5081315B2/ja
Priority claimed from JP2011180544A external-priority patent/JP5081320B2/ja
Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Assigned to KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, LTD.) reassignment KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, LTD.) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TANIFUJI, SHINICHI, YAMAMOTO, KENJI
Publication of US20130327642A1 publication Critical patent/US20130327642A1/en
Abandoned 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • 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
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32055—Arc discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3266—Magnetic control means
    • H01J37/32669—Particular magnets or magnet arrangements for controlling the discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/345—Magnet arrangements in particular for cathodic sputtering apparatus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/345—Magnet arrangements in particular for cathodic sputtering apparatus
    • H01J37/3452—Magnet distribution

Definitions

  • the present invention relates to an arc evaporation source used in a film deposition apparatus that forms a thin film such as a ceramic film composed of a nitride or an oxide or an amorphous carbon film for improving abrasion resistance or the like of mechanical components, etc.
  • a physical vapor deposition of coating the surface of substrates of the parts and the tools with a thin film has been used generally.
  • arc ion plating or sputtering has been known generally.
  • the arc ion plating is a technique of using a cathodic arc evaporation source.
  • a cathode discharge arc evaporation source (hereinafter referred to as an arc evaporation source) generates arc discharge on the surface of a target as a cathode, and instantaneously melts and evaporates the material constituting the target.
  • the material ionized by arc discharge is drawn toward a substrate which is an object to be processed to form a thin film on the surface of the substrate.
  • the arc evaporation source since an evaporation rate of the target is high and an ionization rate of the evaporated material is high, a dense film can be formed by applying a bias to the substrate during film deposition. Therefore, the arc evaporation source has been industrially used for forming an abrasion resistant film on the surface of the cutting tools, etc.
  • Atoms constituting the target which are evaporated by arc discharge are highly dissociated electrolytically or ionized in arc plasmas.
  • transportation of ions from the target to the substrate undergoes the effect of a magnetic field between the target and the substrate, and the trajectory thereof is along lines of magnetic force from the target to the substrate.
  • arc discharge generated between a cathode (target) and an anode when the target is evaporated around electron emission points (arc spots) on the cathode as the center, a molten target before evaporation (macro-particles) are sometimes emitted from the vicinity of the arc spots.
  • a molten target before evaporation are sometimes emitted from the vicinity of the arc spots.
  • Deposition of the macro-particles to the object to be processed causes deterioration of the surface roughness of the thin film.
  • the arc spots move at a high speed, the amount of the macro-particles tends to be suppressed.
  • the moving speed of the arc spots undergoes the effect of a magnetic field applied to the surface of the target.
  • a Patent reference 1 discloses a vacuum arc evaporation source of applying a vertical magnetic field to the surface of the target by providing a ring-shaped magnetic field generating source to the circumference of the target. It is described in the Patent reference 1 that the moving speed of the arc spots is increased and generation of the molten particles can be suppressed by the vacuum arc evaporation source.
  • Patent reference 2 discloses an arc evaporation source in which a magnet is disposed at the back of the cathode.
  • a Patent reference 3 discloses an arc evaporation source comprising an circumferential magnet surrounding the outer circumference of a target and having a direction of magnetization along the direction crossing the surface of the target, and a rear surface magnet having a polarity in the direction identical with that of the circumferential magnet and the direction of magnetization along the direction crossing the surface of the target. It is described in the Patent reference 3 that the straightness of the lines of magnetic force can be improved by the arc evaporation source.
  • a Patent reference 4 discloses an arc evaporation apparatus forming a magnetic field parallel with the surface of a target by a ring-shaped magnet disposed around the target and a solenoid coil at the back thereof. It is described in the Patent reference 4 that induction of arc in accordance with all of tracks from the center to the outer edge of the target is attained according to the arc evaporation apparatus.
  • lines of magnetic force are generated in the direction from the surface of the target to the substrate by two disk-shaped magnets disposed being spaced from each other at the back of the target, the two disk magnets can generate lines of magnetic force at high straightness in a central region.
  • lines of magnetic force emitting from the outer circumference relative to the central region diverge outwardly relative to the axis of the disk magnets. Since this is an inevitable phenomenon as general characteristics of magnets, there is still a room for improvement in inducing the ionized target material efficiently to the substrate.
  • lines of magnetic force at high straightness are generated from the central region of the solenoid coil, but lines of magnetic force emitting from the outer circumference relative to the central region of the solenoid coil diverge outwardly relative to the axis of the solenoid coil.
  • the present invention intends to provide an arc evaporation source capable of controlling lines of magnetic force such that the slope of the lines of magnetic force at the front of the target is vertical, or the slope of the lines of magnetic force at the front of the target is in a direction from the outer circumference to the center (inside) at the front of the cathode.
  • the arc evaporation source according to the present invention includes
  • one of the circumferential magnet and the rear surface magnet is disposed so as to have a polarity where the direction of magnetization is parallel with the front surface of the target, by which the direction of lines of magnetic force passing the evaporation surface of the target becomes substantially vertical to the evaporation surface.
  • the arc evaporation source according to the first invention of the present invention includes
  • the direction of magnetization of the circumferential magnet is along the radial direction
  • the circumferential magnet is disposed surrounding the outer circumference of the target such that the direction of magnetization of the circumferential magnet is along the direction parallel with the front surface of the target, and
  • the magnetic field generating mechanism is disposed ahead of the target such that the axis of the magnetic field generating mechanism is along a direction substantially vertical to the front surface of the target, thereby generating a magnetic field substantially vertical to the front surface of the target.
  • an arc evaporation source according to the first invention of the present invention includes
  • the direction of magnetization of the circumferential magnet is along the radial direction
  • the circumferential magnet is disposed with the front end of the circumferential magnet being situated at the back of the rear surface of the target such that the direction of magnetization of the circumferential magnet is along the direction parallel with the front surface of the target, and
  • the magnetic field generating mechanism is disposed ahead of the target such that the axis of the magnetic field generating mechanism is along the direction substantially vertical to the front surface of the target, thereby generating a magnetic field in a direction substantially vertical to the front surface of the target.
  • an arc evaporation source according to a second invention of the present invention includes
  • the circumferential magnet is disposed surrounding the outer circumference of the target such that the direction of magnetization of the circumferential magnet is along a direction parallel with the front surface of the target,
  • the rear surface magnet is disposed at the back of the target such that the direction of magnetization of the rear surface magnet is along a direction crossing the front surface of the target
  • a magnetic pole in the radial inside of the circumferential magnet and a magnetic pole of the rear surface magnet on the target side have a polarity identical with each other.
  • an arc evaporation source according to the second embodiment of the present invention includes
  • the circumferential magnet is disposed at the back of the rear surface of the target such that the direction of magnetization of the circumferential magnet is along a direction parallel with the front surface of the target,
  • the rear surface magnet is disposed such that the direction of magnetization of the rear surface magnet crosses the front surface of the target,
  • a magnetic pole in the radial inside of the circumferential magnet and a magnetic pole of the rear surface magnet on the target side have a polarity identical with each other and
  • the magnetic field generating mechanism is disposed ahead of the target so as to generate a magnetic field in a direction identical with that of the rear surface magnet and cause the lines of magnetic force that have passed the front surface of the target to pass the radial inside of the magnetic field generating mechanism.
  • an arc evaporation source includes
  • the circumferential magnet is disposed surrounding the outer circumference of the target and has a polarity where the direction of magnetization is along a direction crossing the front surface of the target and directed ahead or behind,
  • the rear surface magnet is disposed at the back of the target, has an inner diameter larger than that of the target, and has a polarity where the direction of magnetization is parallel with the front surface of the target, and
  • the direction of magnetization of the rear surface magnet is directed to the radial inside of the rear surface magnet when the direction of magnetization of the circumferential magnet is directed ahead and
  • the direction of magnetization of the rear surface magnet is directed to a radial outside of the rear surface magnet when the direction of magnetization of the circumferential magnet is directed behind.
  • the lines of magnetic force can be controlled such that a magnetic force between the target and the substrate is increased and the slope of the lines of magnetic force at the target surface is vertical or in the direction from the outer circumference to the center (inside) of the cathode surface.
  • the lines of magnetic force can be controlled such that slope of the lines of magnetic force at the target surface is vertical or in the direction from the outer circumference to the center (inside) of the cathode surface.
  • the lines of magnetic force of high straightness extending in the direction from the target surface to the substrate can be generated in a wide region at the target surface in the arc evaporation source.
  • FIG. 1( a ) is a side elevational view illustrating a schematic constitution of a film deposition apparatus having an arc evaporation source according to a first embodiment of a first invention of the present invention and ( b ) is a plan view illustrating a schematic constitution of the film deposition apparatus.
  • FIG. 2 is a view illustrating a schematic constitution of an arc evaporation source according to the first embodiment the first invention.
  • FIG. 3 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to an existent example.
  • FIG. 4 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to an exemplary invention of the first invention.
  • FIG. 5 is a view illustrating a schematic constitution of a modified example of an arc evaporation source according to a preferred embodiment of the first invention.
  • FIG. 6( a ) is a side elevational view illustrating a schematic constitution of a film deposition apparatus disposed with an arc evaporation source according to a first embodiment of a second invention of the present invention
  • ( b ) is a plan view illustrating a schematic constitution of the film deposition apparatus.
  • FIG. 7 is a view illustrating a schematic constitution of an arc evaporation source according to the first embodiment of the second invention.
  • FIG. 8 is a view illustrating a schematic constitution of an arc evaporation source according to a second embodiment of the second invention.
  • FIG. 9 is a view illustrating a schematic constitution of an arc evaporation source according to a third embodiment of the second invention.
  • FIG. 10 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to an existent example.
  • FIG. 11 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to a first exemplary invention of a second invention.
  • FIG. 12 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to a second exemplary invention of the second invention.
  • FIG. 13 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to a third exemplary invention of the second invention.
  • FIG. 14 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to a modified example of the second exemplary invention of the second invention.
  • FIG. 15 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to another modified example of the second exemplary invention of the second invention.
  • FIG. 16 are views illustrating a distribution diagram of lines of magnetic force of an arc evaporation source according to a modified example of the third exemplary invention of the second invention.
  • FIG. 17 are views illustrating a distribution of lines of magnetic force of an arc evaporation source according to another modified example of the third exemplary invention of the second invention.
  • FIG. 18( a ) is a side elevational view illustrating a schematic constitution of a film deposition apparatus disposed with an arc evaporation source according to a first embodiment of a third invention of the present invention and ( b ) is a plan view illustrating a schematic constitution of the film deposition apparatus.
  • FIG. 19 is a view illustrating a schematic constitution of an arc evaporation source according to a first embodiment of the third invention.
  • FIG. 20 is a view illustrating a distribution of lines of magnetic force of an arc evaporation source according to the first embodiment of the third invention.
  • FIG. 21 is a view illustrating a distribution of lines of magnetic force in an arc evaporation source according to a comparative example.
  • FIG. 22 is a view illustrating a schematic constitution of the arc evaporation source according to the second embodiment of the third invention.
  • FIG. 23 is a view illustrating a distribution of lines of magnetic force of an arc evaporation source according to the second embodiment of the third invention.
  • FIG. 24 is a view illustrating a schematic constitution of an arc evaporation source according to a third embodiment of the third invention.
  • FIG. 25 is a view illustrating a distribution of lines of magnetic force of an arc evaporation source according to the third embodiment of the third invention.
  • a first invention of the present invention is to be described with reference to FIG. 1 to FIG. 5 .
  • FIG. 1 illustrate a film deposition apparatus 6 provided with an arc evaporation source 1 (hereinafter referred to as a evaporation source 1 ) of the first embodiment according to the first invention.
  • a evaporation source 1 an arc evaporation source 1
  • a film deposition apparatus 6 comprises a chamber 11 , and a rotary table 12 for supporting a substrate 7 as an object to be processed, and an evaporation source 1 which is attached being opposed to the substrate 7 are disposed in the chamber 1 .
  • the chamber 11 has a gas introduction port 13 for introducing a reaction gas into the chamber 11 and a gas exhaust port 14 for exhausting a reaction gas from the inside of the chamber 11 .
  • the film deposition apparatus 6 comprises an arc power source 15 for applying a negative bias to a target 2 of the evaporation source 1 (to be described later), and a bias power source 16 for applying a negative bias to the substrate 7 .
  • Positive electrodes of the arc source 15 and the bias power source 16 are grounded to the ground 18 .
  • the evaporation source 1 comprises a disk-shaped target 2 having a predetermined thickness which is disposed with the evaporation surface being opposed to the substrate 7 and a magnetic field forming unit 8 disposed near the target 2 .
  • the term “disk-shaped” also means a circular cylindrical shape having a predetermined height.
  • the magnetic field forming unit 8 can comprise a circumferential magnet 3 .
  • the chamber 11 acts as an anode. With such a constitution, the evaporation source 1 serves as a cathode discharge arc evaporation source.
  • FIG. 2 is a view illustrating a schematic constitution of the evaporation source 1 according to this embodiment.
  • the evaporation source 1 comprises a disk-shaped target 2 having a predetermined thickness and a magnetic field forming unit 8 disposed near the target 2 .
  • the surface of the target 2 facing the substrate 7 (in the direction to the substrate indicated by a blank arrow) is referred to as “front surface” and the surface facing the opposite side (direction opposite to the substrate) is referred to as “rear surface” (refer to FIG. 1 and FIG. 2 ).
  • the target 2 comprises a material which is selected in accordance with a thin film to be formed on the substrate 7 .
  • the material includes ionizable materials such as metal materials, for example, chromium (Cr), titanium (Ti), and titanium aluminum (TiAl) and carbon (C).
  • the magnetic field forming unit 8 has a solenoid coil 9 as a magnetic field generating mechanism and a ring-shaped (annular or doughnut-shaped) circumferential magnet 3 disposed so as to surround the outer circumference of the target 2 .
  • the circumferential magnet 3 comprises a permanent magnet formed of a neodymium magnet having high coercivity.
  • the solenoid coil 9 is a ring-shaped solenoid that generates a magnetic field in the direction vertical to the front surface (evaporation surface) of the target 2 .
  • the solenoid coil 9 has a number of turns, for example, of about several hundred turns (for example, 410 turns) and is wound around so as to form a coil of a diameter somewhat larger than the diameter of the target 2 .
  • the solenoid coil 9 generates a magnetic field by a current of about 2000 A ⁇ T to 5000 A ⁇ T.
  • the solenoid coil 9 is disposed on the front surface side of the target 2 , and the projection shadow of the solenoid coil 9 as viewed in the radial direction does not overlap the projection shadow of the target 2 .
  • the solenoid coil 9 is disposed so as to be coaxial with the target 2 .
  • a circular target 2 enters substantially coaxially to the inside of a toroidal solenoid coil 9 .
  • the circumferential magnet 3 is a ring body and has a predetermined thickness in the axial direction as described above.
  • the thickness of the circumferential magnet 3 is substantially identical with or somewhat smaller than the thickness of the target 2 .
  • the ring-shaped circumferential magnet 3 comprises, in appearance, two surfaces of toroids (toroidal surfaces) parallel with each other and two circumferential surfaces connecting the two toroidal surfaces in the axial direction.
  • the two circumferential surfaces comprise an inner circumferential surface formed to the inner circumference surface of the toroidal surface and an outer circumferential surface formed to the outer circumference of the toroidal surface.
  • the width for the inner circumferential surface and the outer circumferential surface is a thickness of the circumferential magnet 3 .
  • the circumferential magnet 3 is magnetized such that the inner circumferential surface forms a N-pole and the outer circumferential surface forms a S-pole.
  • the drawing shows a solid arrow from the S-pole to the N-pole, and the direction of the arrow is hereinafter referred to as a direction of magnetization.
  • the circumferential magnet 3 of this embodiment is disposed such that the direction of magnetization is along the direction parallel with the front surface of the target 2 , that is, the direction of magnetization is directed to the target 2 .
  • the circumferential magnet 3 may have a ring-shaped or annular shape integral configuration.
  • the circumferential magnet 3 may also comprise circular cylindrical or cuboidal magnets arranged in a ring-shape or an annular shape so that the direction of magnetization is horizontal to the surface of the target 2 .
  • the circumferential magnet 3 is disposed so as to surround the outer circumference of the target 2 and disposed coaxially with the target 2 .
  • the circumferential magnet 3 is disposed so as not to exceed the range of the thickness of the target 2 .
  • projection shadow of the circumferential magnet 3 overlaps the projection shadow of the target 2 as viewed in the radial direction. That is, the circumferential magnet 3 is disposed such that when the circumferential magnet 3 and the target 2 are projected in the direction parallel with the evaporation surface of the target 2 , respective shadows formed thereby overlap to each other and the shadow of the circumferential magnet 3 is completely contained within the shadow of the target 2 .
  • the circumferential magnet 3 is disposed to the evaporation source 1 such that the front end of the circumferential magnet 3 as the toroidal surface on the front side is situated at the back of (behind) the front surface of the target 2 and the rear end of the circumferential magnet 3 as the toroidal surface on the rear side is situated in front (ahead) of the rear surface of the target 2 .
  • the polarity of the solenoid coil 9 in the constitution described above is such that the N-Pole is on the side of the substrate 7 and the S-pole is on the side of the target 2 .
  • the polarity of the circumferential magnet 3 is such that the N-Pole is on the side of the inner circumferential surface opposing the target 2 and the S-pole is on the side of the outer circumferential surface.
  • identical distribution of lines of magnetic force can be obtained also in the constitution with the polarity opposed to that described above by reversing the direction of the current supplied to the solenoid coil 9 and using a circumferential magnet having the polarity of the inner circumferential surface and the outer circumferential surface being opposite to that of the circumferential magnet 3 .
  • an inert gas such as an argon gas (Ar) is introduced from the gas introduction port 13 and impurities such as oxide on the target 2 and the substrate 7 are removed by gas sputtering. After removing the impurities, inside of the chamber 11 is again evacuated and a reaction gas is introduced from the gas introduction port 13 into the evacuated chamber 11 .
  • Ar argon gas
  • a nitride film, an oxide film, a carbide film, a carbonitride film, an amorphous carbon film, etc. can be formed on the substrate 7 placed on the rotary table 12 .
  • the circumferential magnet 3 is formed of a permanent magnet and has a size of (170 mm outer diameter, 150 mm inner diameter, and 10 mm thickness).
  • lines of magnetic force due to a magnetic field formed by a solenoid coil 9 is introduced from the side of the target 2 under convergence to the inside of the solenoid coil 9 and then directed from the inside of the coil to the surface of the substrate 7 under divergence.
  • the lines of magnetic force passing the front surface (evaporation surface) of the target 2 is inclined in the direction from the outer circumference to the inner circumference of the target 2 , and converge from the rear surface to the front surface of the target 2 .
  • the density of lines of the magnetic force at the front surface (evaporation surface) of the target 2 is increased more compared with the existent example illustrated in FIG. 3( b ).
  • the lines of magnetic force passing the evaporation surface of the target 2 is substantially vertical to the evaporation surface of the target 2 (in other words, substantially parallel with the normal line on the target).
  • the lines of magnetic force passing the evaporation surface of the target 2 are not only substantially vertical to the evaporation surface but are inclined somewhat in the direction from the outer circumference to the inner circumference of the target 2 .
  • the position for disposing the circumferential magnet 3 is not restricted to the position disclosed in the above-mentioned embodiment.
  • the circumferential magnet 3 may also be disposed being displaced toward the rear surface side of the target 2 .
  • the front of the projection shadow as viewed from the radial direction of the circumferential magnet 3 overlaps the back of the projection shadow as viewed from the radial direction of the target 2 . That is, the circumferential magnet 3 is disposed such that projection shadow formed when projecting the circumferential magnet 3 and the target 2 in the direction parallel with the evaporation surface of the target 2 are partially overlapped to each other, and the side of the projection shadow of the circumferential magnet 3 overlaps the back side of the projection shadow of the target 2 .
  • the circumferential magnet 3 can be sometimes disposed such that the circumferential magnet 3 does not surround the outer circumference of the target 2 , that is, the front end of the circumferential magnet 3 is situated at the back of the rear surface of the target 2 as a modified example of the arc evaporation source 1 according to the first embodiment of the first invention.
  • the front of the projection shadow of the circumferential magnet 3 as viewed in the radial direction is situated behind the back of the projection shadow of the target 2 as viewed in the radial direction.
  • the circumferential magnet 3 can be disposed such that the projection shadows formed when projecting the circumferential magnet 3 and the target 2 in the direction parallel with the evaporation surface of the target 2 , do not overlap but the front of the projection shadow of the circumferential magnet 3 is situated at the back of the target 2 .
  • the circumferential magnet 3 may be disposed such that the front end is situated behind the rear surface of the target 2 and the direction of magnetization is along the direction parallel with the front surface of the target 2 at a position where the axis is situated behind the rear surface of the target 2 and the direction of magnetization is along the direction parallel with the front surface of the target 2 at a position where the axis crosses the front surface of the target 2 substantially vertically.
  • the conditions are, for example, such that the intensity of lines of magnetic force at the front surface of the target 2 is about 100 gauss or more, and lines of magnetic force inclined to the central direction of the target is formed at the outer circumference of the target 2 . More preferably, the circumferential magnet 3 is disposed so as to be substantially coaxial with the target 2 (on coaxial axis).
  • a second invention of the present invention is to be described with reference to FIGS. 6 to 17 .
  • FIG. 6 illustrate a film deposition apparatus 106 provided with an arc evaporation source 101 a according to the first embodiment of the second invention (hereinafter referred to as an evaporation source 101 a ).
  • a film deposition apparatus 106 comprises a chamber 111 , and a rotary table 112 for supporting a substrate 107 as an object to be processed and an evaporation source 101 a which is attached being opposed to the substrate 107 are disposed in the chamber 111 .
  • the chamber 111 has a gas introduction port 113 for introducing a reaction gas into the chamber 111 and a gas exhaust port 114 for exhausting a reaction gas from the inside of the chamber 111 .
  • the film deposition apparatus 106 comprises an arc power source 115 for applying a negative bias to a target 102 of the evaporation source 101 (to be described later), and a bias power source 116 for applying a negative bias to the substrate 107 .
  • Positive electrodes of the arc source 115 and the bias power source 116 are grounded to a ground 118 .
  • the evaporation source 101 a comprises a disk-shaped target 102 having a predetermined thickness and disposed with the evaporation surface being opposed to the substrate 107 and a magnetic field forming unit 108 disposed near the target 102 .
  • the term “disk-shaped” also means a circular cylindrical shape having a predetermined height.
  • the magnetic field forming unit 108 comprises a circumferential magnet 103 and a rear surface magnet 104 .
  • the chamber 111 serves as an anode.
  • the evaporation source 101 a serves as a cathode discharge arc evaporation source.
  • FIG. 7 is a view illustrating a schematic constitution of the evaporation source 101 a according to this embodiment.
  • the evaporation source 101 a comprises a disk-shaped target 102 having a predetermined thickness and a magnetic field forming unit 108 disposed near the target 102 .
  • the surface of the target 102 as an evaporation surface, facing the substrate 107 (in the direction to the substrate indicated by a blank arrow) is referred to as “front surface” and the surface thereof facing the opposite side (counter-substrate direction) is referred to as “rear surface” (refer to FIG. 6 and FIG. 7 ).
  • the target 102 comprises a material which is selected in accordance with a thin film to be formed on the substrate 107 .
  • the material includes ionizable materials such as metal materials, for example, chromium (Cr), titanium (Ti), and titanium aluminum (TiAl) and carbon (C).
  • the magnetic field forming unit 108 has a ring-shaped (annular or doughnut-shaped) circumferential magnet 103 disposed so as to surround the outer circumference of the target 102 and a rear surface magnet 104 disposed at the back of the rear surface of the target 102 .
  • the circumferential magnet 103 and the rear surface magnet 104 comprise a permanent magnet formed of a neodymium magnet having high coercivity.
  • the circumferential magnet 103 is a ring body and has a predetermined thickness in the axial direction as described above.
  • the thickness of the circumferential magnet 103 is substantially equal with or somewhat smaller than the thickness of the target 102 .
  • the ring-shaped circumferential magnet 103 comprises, in appearance, two surfaces of toroids parallel with each other (toroidal surfaces) and two circumferential surfaces that connect the two toroidal surfaces in the axial direction.
  • the two circumferential surfaces comprise an inner circumferential surface formed to the inner circumference of the toroidal surface and an outer circumferential surface formed to the outer circumference of the toroidal surface.
  • the width for the inner circumferential surface and the outer circumferential surface is a thickness of the circumferential magnet 103 .
  • the circumferential magnet 103 is magnetized such that the inner circumferential surface forms a N-pole and the outer circumferential surface forms a S-pole.
  • the drawing shows a solid (black) arrow from the S-pole to the N-pole and the direction of the arrow is hereinafter referred to as direction of magnetization.
  • the circumferential magnet 103 of this embodiment is disposed such that the direction of magnetization is along the direction parallel with the front surface of the target 102 , that is, such that the direction of magnetization is directed to the target 102 .
  • the circumferential magnet 103 may also has an integrated ring-shaped or annular shaped configuration.
  • the circumferential magnet 103 may also comprise circular cylindrical or cuboidal magnets arranged in a ring-shape or an annular shape so that the direction of magnetization is horizontal to the surface of the target 102 .
  • the circumferential magnet 103 is disposed so as to surround the outer circumference of the target 102 and is disposed coaxially with the target 102 .
  • the circumferential magnet 103 is disposed so as not to exceed the range of the thickness of the target 102 .
  • a projection shadow of the circumferential magnet 103 as viewed in the radial direction overlaps a projection shadow as viewed in the radial direction of the target 102 .
  • the circumferential magnet 103 is disposed such that when the circumferential magnet 103 and the target 102 are projected in the direction parallel with the evaporation surface of the target 102 , respective projection shadows formed by projection overlap to each other and the projection shadow of the circumferential magnet 103 is completely included within the shadow of the target 102 .
  • the circumferential magnet 103 is disposed to the evaporation source 101 a such that the front end of the circumferential magnet 103 which is the toroidal surface on front of the circumferential magnet 103 is situated at the back (behind) of the front surface of the target 102 and the rear end of the circumferential magnet 103 which is the toroidal surface of the front of the circumferential magnet 103 is situated ahead (forward) of the rear surface of the target 102 .
  • circumferential magnet 103 is disposed such that an intermediate position between the front end and the rear end is aligned with an intermediate position between the front surface and the rear surface of the target 102 .
  • the rear surface magnet 104 comprises a non-ring shaped magnetic core 105 and two disk-shaped rear surface magnets 104 A and 104 B sandwiching the magnet core 105 .
  • the disk-shaped rear surface magnets 104 A and 104 B are also non-ring shaped likewise the magnetic core 105 .
  • the term “non-ring shaped” means not an annular shape of a doughnut-like shape in which an aperture is formed in the radial inside but means a solid shape such as a disk-like shape or a circular cylinder shape. That is, “non-ring shape” means such a shape that normal lines directing from the surface to the outward do not intersect each other.
  • the thickness of the magnet at the rear surface side should be increased in order to efficiently extend the lines of magnetic force to the substrate.
  • two magnets that is, disk-shaped rear surface magnets 104 A and 104 B are disposed being spaced apart from each other for increasing the thickness, and the space therebetween is filled with the magnetic core 105 as a magnetic body to prevent lowering of the magnetic force.
  • the disk-shaped rear surface magnets 104 A and 104 B are each magnetized such that one of disk surfaces forms a N-pole and the other of the disk surfaces forms a S-pole.
  • the disk-shaped rear surface magnets 104 A and 104 B sandwich the magnetic core 105 between the surface on the side of the S-pole of the disk-shaped rear surface magnet 104 A and the surface on the side of the N-pole of the disk-shaped rear surface magnet 104 B to direct the magnetization direction to an identical direction.
  • the thus constituted rear surface magnet 104 is disposed to the side of the rear surface of the target 102 such that the direction of magnetization is along the axis of the target 102 , and the direction of magnetization is vertical to the evaporation surface of the target 102 . Further, the rear surface magnet 104 is disposed such that the N-pole side of the disk-shaped rear surface magnet 104 A is directed to the target 102 . The rear surface magnet 104 is disposed such that the axis thereof is substantially aligned with the axis of the target 102 .
  • the evaporation source 101 a is constituted by disposing the circumferential magnet 103 and the rear surface magnet 104 to the target 102 as described above.
  • the direction of magnetization in the circumferential magnet 103 is directed to the direction parallel with the front surface of the target 102 , that is, directed to the target 102 .
  • the magnetic pole on the inner circumference of the circumferential magnet 103 is a N-pole and the magnetic pole of the of the rear surface magnet 104 facing the target 102 is also the N-pole, the magnetic pole in the radial inside of the circumferential magnet 103 and the magnetic pole of the rear surface magnet 104 facing the target 102 have an identical polarity.
  • the magnetic field formed by the circumferential magnet 103 and the magnetic field formed by the rear surface magnet 104 can be combined. This can provide an effect capable of making the direction of the lines of magnetic force that pass the evaporation surface of the target 102 substantially vertical to the evaporation surface, and introducing the lines of magnetic force in the direction of the substrate 107 .
  • the evaporation source 101 a may also be constituted such that the circumferential magnet 103 and the rear surface magnet 104 face the target 102 each at the S-pole.
  • an inert gas such as an argon gas (Ar) is introduced from the gas introduction port 113 and impurities such as oxides on the target 102 and the substrate 107 are removed by gas sputtering.
  • Ar argon gas
  • inside of the chamber 111 is again evacuated and a reaction gas is introduced from the gas introduction port 113 into the evacuated chamber 111 .
  • a nitride film, an oxide film, a carbide film, a carbonitride film, an amorphous carbon film, etc. can be formed over the substrate 107 which is placed on the rotary table 112 .
  • a nitrogen gas (N 2 ) or an oxygen gas (O 2 ), or a hydrocarbon gas such as methane (CH 4 ) may be selected according to the application use and the pressure of the reaction gas in the chamber 111 may be at about 1 to 7 Pa.
  • the target 102 is subjected to discharge by flowing an arc current of 100 to 200 A and applying a negative voltage at 10 to 30 V from the arc power source 115 . Further, a negative voltage of 10 to 200 V may be applied to the substrate 107 by the bias power source 116 .
  • the circumferential magnet 103 and the rear surface magnet 104 are arranged such that the magnetic field on the front surface of the target 102 is 100 gauss or more.
  • the magnetic field on the front surface of the target 102 is more preferably 150 gauss.
  • the distribution state of the lines of magnetic force when film deposition is performed by using the evaporation source 101 a of this embodiment is to be described specifically by the following examples.
  • FIG. 8 is a view illustrating a schematic constitution of an arc evaporation source 101 b used in a film deposition apparatus 106 according to this embodiment.
  • An arc evaporation source 101 b in this embodiment comprises a disk-shaped target 102 having a predetermined thickness and a magnetic field forming unit 108 disposed near the target 102 in the same manner as the arc evaporation source 101 a in the first embodiment of the second invention.
  • the magnetic field forming unit 108 has a ring-shaped (annular) circumferential magnet 103 disposed so as to surround the outer circumference of the target 102 , and a rear surface magnet 104 disposed at the rear surface side of the target 102 .
  • the evaporation source 101 b in this embodiment has the same constitution as that in the arc evaporation source 101 a in the first embodiment of the first invention but it is different only for the arrangement of the circumferential magnet 103 .
  • the circumferential magnet 103 when taking notice on the position of the circumferential magnet 103 relative to the target 102 , it can be seen that the circumferential magnet 103 is disposed to the target 102 being displaced to the side of the rear surface magnet 104 (rear surface side).
  • the front of a projection shadow as viewed in the radial direction of the circumferential magnet 103 overlaps the back of the projection shadow of the target 102 as viewed in the radial direction.
  • the circumferential magnet 103 is disposed such that when the circumferential magnet 103 and the target 102 are projected in the direction parallel with the evaporation surface of the target 102 , respective projection shadows formed by projection partially overlap to each other and such that the front side of the projection shadow of the circumferential magnet 103 overlaps the back of the projection shadow of the target 102 .
  • a central position in the direction of the thickness of the circumferential magnet 103 shown by solid arrows for the circumferential magnet 103 in FIG. 8 that is, an intermediate position between the front end and the rear end of the circumferential magnet 103 is disposed ahead (forward) of the rear surface of the target 102 within a range of the width along the direction of the thickness of the target 102 .
  • the circumferential magnet 103 in this embodiment is disposed to the evaporation source 101 b such that the front end is disposed ahead of the rear surface of the target 102 and the rear end is disposed behind the rear surface of the target 102 .
  • the circumferential magnet 103 in this embodiment is provided to the evaporation source 101 b with the intermediate position between the front end and the rear end being behind (backward) an intermediate position between the front surface and the rear surface of the target 102 .
  • a third embodiment of the second invention is to be described referring to FIG. 9 .
  • FIG. 9 is a view illustrating a schematic constitution of an arc evaporation source 101 c used in a film deposition apparatus 106 according to this embodiment.
  • the arc evaporation source 101 c in this embodiment is different from the arc evaporation source 101 a in the first embodiment of the second invention in that it has a solenoid coil 109 as a magnetic field generating mechanism.
  • a disk-shaped target 102 having a predetermined thickness a disk-shaped target 102 having a predetermined thickness
  • a ring-shaped circumferential magnet 103 disposed so as to surround the outer circumference of the target 102 a rear surface magnet 104 disposed at the back of the target 102 , etc. are substantially identical with those in the first embodiment.
  • the solenoid coil 109 is a ring-shaped solenoid that generates a magnetic field in the direction identical with that of the rear surface magnet 104 .
  • the solenoid coil 109 has a number of turns, for example, about several hundreds of turns (for example, 410 turns) and is wound around so as to form a coil of a diameter somewhat larger than the diameter of the target 102 .
  • the solenoid coil 109 generates a magnetic field by a current of about 2000 A ⁇ T to 5000 A ⁇ T.
  • the solenoid coil 109 is disposed in front of the target 102 and a projection shadow of the solenoid coil 109 as viewed in the radial direction does not overlap the projection shadow of the target 102 .
  • the solenoid coil 109 is disposed so as to be coaxial with the target 102 .
  • a current is supplied to the thus disposed solenoid coil 109 to generate a magnetic field inside the solenoid coil 109 that flows from the target 102 to the substrate 107 .
  • lines of magnetic force passing the front surface of the target 102 can pass the solenoid coil 109 .
  • the solenoid coil 109 When the solenoid coil 109 is disposed as described above, an effect capable of suppressing divergence of lines of magnetic force that have passed the evaporation surface of the target 102 thereby maintaining a high density of lines of magnetic force as far as the surface of the substrate 107 can also be obtained in addition to the effect of the first embodiment. Further, when the solenoid coil 109 is disposed between the target 102 and the substrate 107 , an effect capable of improving the ion transporting efficiency from the target 102 to the substrate 107 can also be expected.
  • the arc evaporation sources 101 a to 101 c of the first embodiment to the third embodiment of the second invention are different respectively for the arrangement of the circumferential magnet 103 , presence or absence of the solenoid coil 109 , etc., distributions of generated lines of magnetic force are also different respectively.
  • the distribution diagrams of lines of magnetic force illustrated in FIG. 10( a ), FIG. 11( a ), FIG. 12( a ), and FIG. 13( a ) illustrate distributions of lines of magnetic force from the rear surface magnet 104 to the surface of the substrate 107 .
  • the right end illustrates a position for the surface of the substrate 107 .
  • the distribution diagrams of the lines of magnetic force illustrated in FIGS. 10( b ), FIG. 11( b ), FIG. 12( b ), and FIG. 13( b ) are enlarged views at the circumference of the target 102 in FIG. 10( a ) to FIG. 13( a ), respectively.
  • the size of the target 102 is (100 mm diameter ⁇ 16 mm thickness).
  • the size for each of the disk-shaped rear surface magnets 104 A and 104 B is (100 mm diameter ⁇ 4 mm thickness).
  • the size of the magnetic core 105 is (100 mm diameter ⁇ 30 mm thickness).
  • the size of the circumferential magnet 103 is (150 mm inner diameter, 170 mm outer diameter, and 10 mm thickness).
  • the intensity of the magnetic field at the surface of the target 102 is 150 gauss or more.
  • FIGS. 10( a ) and 10 ( b ) a distribution diagram of lines of magnetic force is to be described at first for an existent example, that is, in a case of using only the rear surface magnetic 104 .
  • lines of magnetic force emitting from the rear surface magnet 104 are directed to the surface of the substrate 107 under divergence while being inclined to the outer circumferential direction of the rear surface magnet 104 .
  • lines of magnetic force passing the evaporation surface of the target 102 diverge from the rear surface to the front surface of the target 102 while being inclined in the outer circumferential direction of the target 102 .
  • lines of magnetic force emitting from the rear surface magnetic 104 are suppressed from diverging at a position for the circumferential magnet 103 and the density of the lines of magnetic force passing the target 102 is higher than that of the existent example particularly near the center of the target 102 .
  • the lines of magnetic force passing the evaporation surface of the target 102 are substantially vertical to the evaporation surface of the target 102 (that is, substantially parallel with the normal line on the target).
  • lines of magnetic force emitting from the rear surface magnet 104 are suppressed from diverging at a position for a circumferential magnet 103 and the density of lines of magnetic force passing a target 102 is higher than that of the existent example particularly near the center of the target 102 .
  • the lines of magnetic force passing the evaporation surface of the target 102 are substantially vertical to the evaporation surface of the target 102 (that is, substantially parallel with the normal line on the target). Further, when the exemplary invention is compared with the existent example, from the center to the rear surface side in the direction of the thickness of the target 102 , it can be seen that the lines of magnetic force at the outer circumference of the exemplary invention are more parallel relative to the normal line on the target. Accordingly, it can be said that the density of the lines of the magnetic force in the target 102 is more uniform than that of the existent example.
  • FIGS. 14( a ) and 14 ( b ) illustrate a distribution of lines of magnetic force in an modified example to the exemplary invention.
  • the arc evaporation source illustrated in FIGS. 14( a ) and 14 ( b ) has a target 102 , a circumferential magnet 103 , and a rear surface magnet 104 in the same manner as in the arc evaporation source 101 b in FIGS. 12( a ) and 12 ( b ) according to the second embodiment of the second invention.
  • the circumferential magnet 103 is disposed behind the rear surface of the target 102 different from the arc evaporation source 101 b in FIGS. 12( a ) and 12 ( b ).
  • the front end of the circumferential magnet 103 is situated behind the rear surface of the target 102 by about 5 mm to 10 mm.
  • FIGS. 15( a ) and 15 ( b ) illustrate a distribution of lines of magnetic force in another modified example to the exemplary invention.
  • the arc evaporation source illustrated in FIGS. 15( a ) and 15 ( b ) has a target 102 , and an circumferential magnet 103 in the same manner as the arc evaporation source 101 b in FIGS. 12( a ) and 12 ( b ) according to the second embodiment of the second invention.
  • a solenoid coil 110 which is a ring-shaped solenoid having the same constitution as that of the solenoid coil 109 is used instead of the surface magnet 104 comprising the permanent magnet.
  • the position of the circumferential magnet 103 to the target 102 in the arc evaporation source of FIGS. 15( a ) and 15 ( b ) is substantially identical with the position for the circumferential magnet 103 of the arc evaporation source 101 b in FIGS. 12( a ) and 12 ( b ).
  • the solenoid coil 110 is disposed substantially coaxially with the target 102 at a position substantially identical with that of the rear surface magnet 104 in FIGS. 12( a ) and 12 ( b ).
  • the solenoid coil 110 has about 100 mm inner diameter, 200 mm outer diameter, and about 50 mm thickness.
  • the solenoid coil 110 is disposed behind the target 102 by about 64 mm.
  • the magnetic force of the solenoid coil 110 is adjusted such that the magnetic flux density at the front surface of the target 102 is substantially identical with the case of using the rear surface magnet 104 .
  • lines of magnetic force emitting from the rear surface magnet 104 is restricted from diverging at a position of the circumferential magnet 103 , and the density of the lines of magnetic force passing the target 102 is higher than that of the existent example particularly near the center of the target 102 .
  • Lines of magnetic force that have passed the evaporation surface of the target 102 and are being diverged are suppressed from diverging at the position of the solenoid coil 109 and again become substantially parallel with the normal line on the target.
  • lines of magnetic force passing the evaporation surface of the target 102 are substantially vertical to the evaporation surface of the target 102 , or inclined centrally to the target 102 .
  • the lines of magnetic force in the third exemplary invention become most parallel to the normal line on the target in the direction of the thickness of the target 102 from the center to the rear surface, compared with the existent example and the first and second exemplary inventions.
  • FIGS. 16( a ) and 16 ( b ) illustrate a distribution of lines of magnetic force in a modified example of the exemplary invention.
  • the arc evaporation source illustrated in FIGS. 16( a ) and 16 ( b ) has a target 102 , a circumferential magnet 103 , a rear surface magnet 104 , and a solenoid coil 109 in the same manner as the arc evaporation source 101 c of FIGS. 13( a ) and 13 ( b ) according to the third embodiment of the second invention.
  • the circumferential magnet 103 is disposed behind the rear surface of the target 102 different from the arc evaporation source 101 c of FIGS. 13( a ) and 13 ( b ).
  • the front end of the circumferential magnet 103 is situated behind the rear surface of the target 102 by about 5 mm to 10 mm.
  • an allowable range in accordance with the size of each of the constituent members and the density of the generated lines of magnetic force is present for the distance between the front end of the circumferential magnet 103 and the rear surface of the target 102 in order to form a magnetic field substantially equivalent with that of the distribution diagram of lines of magnetic force in FIGS. 13( a ) and 13 ( b ).
  • the allowable range is about twice the thickness of the target 102 .
  • FIGS. 17( a ) and 17 ( b ) illustrate a distribution of lines of magnetic force in another modified example of the exemplary invention.
  • the arc evaporation source illustrated in FIGS. 17( a ) and 17 ( b ) has a target 102 , a circumferential magnet 103 , and a solenoid coil 109 in the same manner as the arc evaporation source 101 c in FIGS. 13( a ) and 13 ( b ) according to the third embodiment of the second invention.
  • a solenoid coil 110 is used instead of the rear surface magnet 102 comprising the permanent magnet.
  • the position of the circumferential magnet 103 to the target 102 is substantially equal with the position in the arc evaporation source 101 c in FIGS. 13( a ) and 13 ( b ).
  • the solenoid coil 110 has the substantially identical constitution with that of the solenoid coil 110 in FIGS. 15( a ) and 15 ( b ) and is disposed substantially coaxially with the target 102 at a position substantially identical with that of the rear surface magnet 104 in FIGS. 13( a ) and 13 ( b ).
  • the solenoid coil 110 is disposed behind the target 102 by about 64 mm.
  • a third invention of the present invention is to be described with reference to FIGS. 18 to 25 .
  • FIG. 18 illustrate a film deposition apparatus 206 provided with an arc evaporation source 201 a according to the first embodiment of the third invention (hereinafter referred to as an evaporation source 201 a ).
  • a film deposition apparatus 206 comprises a chamber 211 , and a rotary table 212 for supporting a substrate 207 as an object to be processed, and an evaporation source 201 a which is attached being opposed to the substrate 207 are disposed in the chamber 201 .
  • the chamber 211 has a gas introduction port 213 for introducing a reaction gas into the chamber 211 and a gas exhaust port 214 for exhausting a reaction gas from the inside of the chamber 211 .
  • the film deposition apparatus 206 comprises an arc power source 215 for applying a negative bias to a target 202 of the evaporation source 201 a (to be described later), and a bias power source 216 for applying a negative bias to the substrate 207 .
  • Positive electrodes of the arc source 215 and the bias power source 216 are grounded to a ground 218 .
  • the evaporation source 201 a comprises a disk-shaped target 202 having a predetermined thickness which is disposed with the evaporation surface being faced to the substrate 207 and a magnetic field forming unit 208 a disposed near the target 202 .
  • the term “disk-shaped” also means a circular cylindrical shape of a predetermined height.
  • the magnetic field forming unit 208 a comprises a circumferential magnet 203 and a rear surface magnet 204 a .
  • the chamber 211 acts as an anode.
  • the evaporation source 201 a serves as a cathode discharge arc evaporation source.
  • FIG. 19 is a view illustrating a schematic constitution of the evaporation source 201 a according to this embodiment.
  • the evaporation source 201 a comprises the disk-shaped target 202 having a predetermined thickness and the magnetic field forming unit 208 a disposed near the target 202 .
  • the surface of the target 202 facing the substrate 207 (in the direction to the substrate indicated by a blank arrow) is referred to as “front surface (target front surface)” and the surface facing the opposite side is referred to as “rear surface” (target rear surface) (refer to FIG. 18 and FIG. 19 ).
  • the target 202 comprises a material which is selected in accordance with a thin film to be formed on the substrate 207 .
  • the material includes ionizable materials such as metal materials, for example, chromium (Cr), titanium (Ti), and titanium aluminum (TiAl), and carbon (C).
  • the magnetic field forming unit 208 a has a ring-shaped (annular or doughnut-shaped) circumferential magnet 203 disposed so as to surround the outer circumference of the target 202 and a ring-shaped (annular or doughnut-shaped) rear surface magnet 204 a disposed coaxially with the circumferential magnet 203 on the side of the rear surface of the target 202 .
  • the circumferential magnet 203 and the rear surface magnet 204 a each comprise a permanent magnet formed of a neodymium magnet having high coercivity.
  • the evaporation source 201 a is constituted by arranging the target 202 , the circumferential magnet 203 , and a rear surface magnet 204 a by substantially aligning the axes thereof to each other.
  • the circumferential magnet 203 is a ring body as described above and has an inner diameter which is somewhat larger (by about 1 to 2 times) than the diameter of the target 202 , and has a predetermined thickness along the axial direction.
  • the thickness of the circumferential magnet 203 is substantially equal with or somewhat smaller than the thickness along the axial direction of the target 202 .
  • the ring-shaped circumferential magnet 203 comprises, in appearance, two surfaces of toroids (toroidal surfaces) parallel with each other and two circumferential surfaces connecting the two toroidal surfaces in the axial direction.
  • the two circumferential surfaces comprise an inner circumferential surface formed to the inner circumference of the toroidal surface and an outer circumferential surface formed to the outer circumference of the toroidal surface.
  • the width for the inner circumferential surface and the outer circumferential surface is a thickness of the circumferential magnet 203 (thickness in the axial direction).
  • the shape of the inner circumferential surface of the circumferential magnet 203 is formed such that when the circumferential magnet 203 and the target 202 are projected along the direction crossing the front surface of the target 202 , the shape of the projection shadow of the inner circumferential surface of the circumferential magnet 203 and the shape of the projection shadow of the target 202 are similar to each other.
  • the circumferential magnet 203 has a N-pole at the front toroidal surface (front end surface) facing the substrate 207 and a S-pole at the rear toroidal surface (rear end face) facing the opposite side.
  • the drawing shows arrows directing from the rear toroidal surface (S-pole) to the front toroidal surface (N-pole) of the circumferential magnet 203 and the direction of the arrow is hereinafter referred to as the direction of magnetization.
  • the circumferential magnet 203 of this embodiment is disposed such that the direction of magnetization is along the direction crossing the front surface of the target 202 and is directed forward.
  • the circumferential magnet 203 preferably has an integrated ring-like or annular shape.
  • the circumferential magnet 203 may also comprise a plurality of circular cylindrical or cuboidal magnets arranged in a ring-like or annular shape such that the direction of magnetization is along the direction crossing the front surface of the target 202 and is directed forward.
  • the circumferential magnet 203 is disposed coaxially with the target 202 so as to surround the outer circumference of the target 202 .
  • the front toroidal surface of the circumferential magnet 203 is on a plane identical with the front surface of the target 202 and they are flush with each other, or is disposed ahead of the front surface of the target 202 .
  • the target 202 is disposed such that the front surface thereof does not exceed the range of the thickness of the circumferential magnet 203 . Accordingly, in this embodiment, they are arranged such that a projection shadow of the circumferential magnet 203 as viewed in the radial direction overlaps a projection shadow of the target 202 as viewed in the radial direction. That is, the circumferential magnet 203 is disposed such that the projection shadows, which are formed when the circumferential magnet 203 and the target 202 are projected in a direction parallel with the front surface (evaporation surface) of the target 202 , overlap to each other and the projection shadow of the circumferential magnet 203 is completely included in the projection shadow of the target 202 .
  • the circumferential magnet 3 is disposed to the evaporation source 201 a such that the front end face is on a plane identical with the front surface of the target 202 or situated ahead of the front surface of the target 202 .
  • the rear surface magnet 204 a is a ring body having a diameter substantially identical with that of the circumferential magnet 203 and has an inner diameter and an outer diameter substantially equal with those of the circumferential magnet 203 . Accordingly, the rear surface magnet 204 a has an inner diameter somewhat larger than the diameter of the target 202 (about 1 to 2 times) and a predetermined thickness along the axial direction. The thickness of the circumferential magnet 203 is somewhat larger than the thickness of the target 202 and about twice the thickness of the circumferential magnet 203 .
  • the ring-shaped rear surface magnet 204 a also comprises, in appearance, two toroidal surfaces (front end face and rear end face) parallel with each other and two circumferential surface connecting the two toroidal surfaces in the axial direction (inner circumferential surface and outer circumferential surface) in the same manner as the circumferential magnet 203 .
  • the width of the inner circumferential surface and that of the outer circumferential surface is a thickness of the circumferential magnet 203 along the axial direction.
  • the rear surface magnet 204 a is formed such that the inner circumferential surface forms a N-pole and the outer circumferential surface forms a S-pole.
  • the drawing shows solid arrows indicating the direction of magnetization from the outer circumferential surface (S-pole) to the inner circumferential surface (N-pole) of the rear surface magnet 204 a .
  • the rear surface magnet 204 a of this embodiment is disposed such that the direction of magnetization is parallel with the front surface of the target 202 and is directed to the radial inside.
  • the front end surface of the circumferential magnet 203 and the inner circumferential surface of the rear surface magnet 204 a have an identical polarity and, in this state, the respective directions of magnetization are vertical to each other.
  • the magnetic field formed by the circumferential magnet 203 and the magnetic field formed by the rear surface magnet 204 a can be combined.
  • the direction of lines of the magnetic force passing the evaporation surface of the target 202 can be made substantially vertical to the evaporation surface.
  • this also provides an effect capable of generating lines of magnetic force of high straightness that extend from the surface of the target 202 to the substrate 207 in a wide region on the surface of the target 202 .
  • the front end face of the circumferential magnet 203 and the inner circumferential surface of the rear surface magnet 204 a may suffice that the magnetization direction of the circumferential magnet 203 and the magnetization of the rear surface magnet 204 a are in the directions vertical to each other. Accordingly, the polarity of the circumferential magnet 203 and the polarity of the rear surface magnet 204 a may be reversed to those of the configuration described above shown in FIG. 2 , in which the direction of magnetization of the circumferential magnet 203 and the direction of magnetization of the rear surface electrode 204 a may be reversed respectively.
  • an inert gas such as an argon gas (Ar) is introduced from the gas introduction port 213 and impurities such as oxides on the target 202 and the substrate 207 are removed by gas sputtering.
  • Ar argon gas
  • inside of the chamber 211 is again evacuated and a reaction gas is introduced from the gas introduction port 213 into the evacuated chamber 211 .
  • a nitride film, an oxide film, a carbide film, a carbonitride film, an amorphous carbon film, etc. can be formed on the substrate 207 placed on the rotary table 212 .
  • a nitrogen gas (N 2 ) or an oxygen gas (O 2 ), or a hydrocarbon gas such as methane (CH 4 ) may be selected according to the application use and the pressure of the reaction gas in the chamber 211 may be at about 1 to 10 Pa.
  • the target 202 is subjected to discharge by flowing an arc current of 100 to 200 A and applying a negative voltage of 10 to 30 V from the arc power source 215 . Further, a negative voltage of 10 to 200 V may be applied to the substrate 207 by the bias power source 216 .
  • the circumferential magnet 203 and the rear surface magnet 204 such that the magnetic field on the front surface of the target 202 is 100 gauss or more.
  • the magnetic field on the front surface of the target 202 is more preferably 150 gauss.
  • a distribution diagram of lines of magnetic force illustrated in FIG. 20 shows a distribution of lines of magnetic force from the back of the rear surface magnet 204 a to the surface of the substrate 207 .
  • the right end shows a position for the surface of the substrate 207 .
  • the size of the target 202 is (100 mm diameter ⁇ 16 mm thickness).
  • the size of the circumferential magnet 203 is (150 mm inner diameter, 170 mm outer diameter, and 10 mm thickness), and the distance from the surface of the target 202 to the circumferential magnet 203 is 5 mm.
  • the size of the rear surface magnet 204 a is (150 mm inner diameter, 170 mm outer diameter, and 20 mm thickness), and the distance from the surface of the target 202 to the rear surface magnet 204 a is 40 mm.
  • the intensity of the magnetic field at the surface of the target 202 is 150 gauss or more.
  • lines of magnetic force emitting radially inside from the rear surface magnet 204 a extend substantially vertical to the target 202 while changing the progressing direction so as to be along the axial direction of the rear surface magnet 204 a .
  • Such lines of magnetic force are combined with the lines of magnetic force emitting from the circumferential magnet 203 and pass the evaporation surface of the target 202 .
  • lines of magnetic force of high straightness that extend in the direction to the substrate are generated in a wide region at the evaporation surface of the target 202 .
  • a great amount of vertical lines of magnetic force (vertical components) are generated in the wide region at the evaporation surface of the target 202 .
  • Electron emission points (arc spots) on the cathode side generated in the film deposition apparatus 206 tend to be trapped to a place where the components of the magnetic force substantially parallel with the evaporation surface of the target 202 are present, that is, to a place where the components of lines of magnetic force vertical to the evaporation surface of the target 202 are not present. That is, the first exemplary invention can avoid a disadvantage that the arc spots moving at a high speed on the evaporation surface of the target 202 move to the outside of the evaporation surface of the target 202 beyond the outer circumference of the target 202 . Thus, the arc spots can be retained on the evaporation surface of the target 202 .
  • FIG. 21 illustrates a distribution of lines of magnetic force generated in the evaporation source according to this comparative example.
  • the evaporation source according to the comparative example comprises a target and an circumferential magnet identical with those of the evaporation source 201 a according to the first embodiment, and also has a rear surface electromagnet 220 comprising a solenoid coil instead of the rear surface magnet 204 a of the evaporation source 201 a .
  • the evaporation source according to this comparative example has a constitution similar with that of the arc evaporation device disclosed in the cited Patent reference 4.
  • the distribution diagram of lines of magnetic force shown in FIG. 21 shows a distribution of lines of magnetic force from the back of the rear surface electromagnet 220 to the surface of the substrate.
  • the right end shows a position for the surface of the substrate.
  • the size of the target is (100 mm diameter ⁇ 16 mm thickness).
  • the size of the circumferential magnet is (150 mm inner diameter, 170 mm outer diameter, and 10 mm thickness), and the distance from the surface of the target 202 to the circumferential magnet 203 is 5 mm.
  • the size of the rear surface electromagnet 20 is (50 mm inner diameter, 100 mm outer diameter, and 25 mm thickness) and the distance from the surface of the target 202 to the rear surface electromagnet 20 is 45 mm.
  • the magnetic field intensity at the surface of the target 202 is 150 gauss or more.
  • lines of magnetic force emitting from the outer circumference relative to the central region within the diameter of the solenoid coil diverge outwardly relative to the axis of the solenoid coil just after leaving the solenoid coil.
  • the diverged lines of magnetic force further diverge in the target and are directed sideway of the target without reaching the front surface of the target.
  • a distribution of lines of magnetic force corresponding to the portion of circles P illustrated in FIG. 20 for explaining the first exemplary invention is not present to the outer circumference of the target in this comparative example. That is, it can be said that retainment of the arc spots on the evaporation surface of the target is difficult in this comparative example.
  • a second embodiment of the third invention is to be described with reference to FIG. 22 and FIG. 23 .
  • FIG. 22 is a view illustrating a schematic constitution of an arc evaporation source 201 b according to a second embodiment of the third invention (hereinafter referred to as an evaporation source 201 b ).
  • a film deposition apparatus 206 according to this embodiment has an evaporation source 201 b to be described later instead of the evaporation source 201 a according to the first embodiment of the second invention.
  • constitutions other than the evaporation source 201 b are identical with those described in the first embodiment of the third invention, and identical constituent elements carry same reference numerals, for which descriptions are to be omitted.
  • the evaporation source 201 b in this embodiment comprises a disk-shaped target 202 having a predetermined thickness and a magnetic field forming unit 208 b disposed near the target 202 in the same manner as the evaporation source 201 a in the first embodiment of the third invention.
  • the magnetic field forming unit 208 b has a circumferential magnet 203 and a rear surface magnet 204 a alike the first embodiment and, further, has a rear surface magnet 204 a and has a rear surface magnet 204 b (second rear surface magnet) having the same constitution as that of the rear surface magnet 204 a , which is a ring body having a diameter substantially identical with that of the circumferential magnet 203 .
  • the ring-shaped rear surface magnet 204 b is disposed at the back of the rear surface magnet 204 a and coaxially with the rear surface magnet 204 a and the circumferential magnet 203 .
  • the direction of magnetization of the rear surface magnet 204 b is parallel and identical with the direction of the magnetization of the rear surface magnet 204 a .
  • the rear surface magnet 204 a and the rear surface magnet 204 b are adjacent to each other, the distance between them is not always arbitrary. It is preferred that the rear surface magnet 204 a and the rear surface magnet 204 b are disposed being close to each other so that repulsion exerts between the rear surface magnet 204 a and the rear surface magnet 204 b to each other.
  • a distribution diagram of lines of magnetic force illustrated in FIG. 23 shows a distribution of lines of magnetic force from the back of the rear surface magnet 204 b to the surface of the substrate 207 .
  • the right end indicates a position for the surface of the substrate 207 .
  • the size of a target 202 is (100 mm diameter ⁇ 16 mm thickness).
  • the size of a circumferential magnet 203 is (150 mm inner diameter, 170 mm outer diameter, and 10 mm thickness), and the distance from the surface of the target 202 to the circumferential magnet 203 is 5 mm.
  • the size of the rear surface magnet 204 a is (150 mm inner diameter, 170 mm outer diameter, and 20 mm thickness) and the distance from the surface of the target 202 to the rear surface magnet 204 a is 60 mm.
  • the size of the rear surface magnet 204 b is (150 mm inner diameter, 170 mm outer diameter, and 20 mm thickness) and the distance from the surface of the target 202 to the rear surface magnet 204 b is 90 mm.
  • the distance between the rear surface magnet 204 a and the rear surface magnet 204 b is 10 mm.
  • the magnetic field intensity at the surface of the target 202 is 150 gauss or more.
  • a great amount of lines of magnetic force of high straightness emit from the rear surface magnet 204 a and the rear surface magnet 204 b in a radially inward direction.
  • Lines of magnetic force extend substantially vertically to the target 202 while changing the progressing direction so as to be along the axial direction of the rear surface magnet 204 a and the rear surface magnet 204 b .
  • the lines of magnetic force are combined with the lines of magnetic force emitting from the circumferential magnet 203 and pass the evaporation surface of the target 202 .
  • Lines of magnetic force at high straightness are generated from the evaporation surface of the target 202 to the direction of the substrate in a wide region at the evaporation surface of the target 202 .
  • a great amount of lines of magnetic force (vertical components) are generated in the wide region at the evaporation surface of the target 202 .
  • regions where the components of lines of magnetic force vertical to the evaporation surface are not substantially present are formed to the outer circumference of the target 202 alike the regions indicated by the circles P in FIG. 20 for the first exemplary invention. Accordingly, also in this exemplary invention, the disadvantage that arc spots move to the outside of the evaporation surface of the target 202 beyond the outer circumference of the target 202 can be avoided and the arc spots can be retained on the evaporation surface of the target 202 .
  • FIG. 24 is a view illustrating a schematic constitution of an arc evaporation source 201 c according to the third embodiment of the third invention (hereinafter referred to as an evaporation source 201 c ).
  • film deposition apparatus 206 according to this embodiment is provided with the evaporation source 201 c to be described later instead of the evaporation source 201 b according to the second embodiment of the third invention.
  • other constitutions than the evaporation source 201 c are identical with those described for the second embodiment of the third invention, and identical constituent elements carry same reference numerals, for which descriptions are to be omitted.
  • the evaporation source 201 c in this embodiment comprises a disk-shaped target 202 having a predetermined thickness and a magnetic field forming unit 208 c disposed near the target 202 in the same manner as the evaporation source 201 b in the second embodiment of the third invention.
  • the magnetic field forming unit 208 c has a circumferential magnet 203 , a rear surface magnet 204 a , and a rear surface magnet 204 b in the same manner as the second embodiment of the third invention and, further, comprises a single magnetic body 209 in the radial inside of the rear surface magnet 204 a and the rear surface magnet 204 b.
  • the magnetic body 209 is a non-ring shaped magnetic core which constitutes a core for the rear surface magnet 204 a and the rear surface magnet 204 b .
  • the magnetic body 209 is disposed so as to penetrate the rear surface magnet 204 a and the rear surface magnet 204 b , and has a disk-shape or circular columnar shape having a diameter identical with the inner diameter of the rear surface magnet 204 a and the rear surface magnet 204 b .
  • the “non-ring shaped” means not an annular shape in which an aperture is formed in the radial inside like a doughnut but means a solid configuration such as a disk shape or a circular cylindrical shape.
  • the rear surface magnet 204 a and the rear surface magnet 204 b are disposed so as to surround the outer circumference of one magnetic body 209 in close contact therewith.
  • the front end face of the rear surface magnet 204 a is substantially flush with the front end face of the magnetic body 209
  • the rear end face of the reference magnet 204 b is substantially flush with the rear end face of the magnetic body 209 .
  • the target 202 , the circumferential magnet 203 , the rear surface magnet 204 a , a rear surface magnet 204 b , and the magnetic body 209 are disposed coaxially such that their axes are aligned with each other.
  • the inner circumferential surfaces of the rear surface magnet 204 a and the rear surface magnet 204 b are in close contact with the lateral surface of the magnetic body 209 .
  • lines of magnetic force emitting from the end faces of the rear magnet 204 a and the rear magnet 204 b can be induced linearly through the magnetic body 209 in the axial direction of the rear surface magnet 204 a and the rear surface magnet 204 b.
  • FIG. 25 a distribution of lines of magnetic force generated in the evaporation source 201 c according to a third embodiment of the third invention is to be described.
  • the distribution diagram of lines of magnetic force illustrated in FIG. 25 shows a distribution of lines of magnetic force from the back of the rear surface magnet 204 b to the front surface of the substrate 207 .
  • the right end indicates a position for the surface of the substrate 207 .
  • the size of the target 202 is (100 mm diameter ⁇ 16 mm thickness).
  • the size of the circumferential magnet 203 is (150 mm inner diameter, 170 mm outer diameter, and 10 mm thickness) and the distance of the circumferential magnet 203 from the surface of the target 202 is 5 mm.
  • the size of the rear surface magnet 204 a is (150 mm inner diameter, 170 mm outer diameter, and 20 mm thickness) and the distance from the surface of the target 2 to the rear surface magnet 204 a is 60 mm.
  • the size of the rear surface magnet 204 b is (150 mm inner diameter, 170 mm outer diameter, and 20 mm thickness), and the distance from the surface of the target 202 to the rear surface magnet 204 b is 90 mm.
  • the distance between the rear surface magnet 204 a and the rear surface magnet 204 b is 10 mm.
  • the size of the magnetic body 209 is (150 mm diameter ⁇ 50 mm height).
  • the magnetic field intensity at the surface of the target 202 is 150 gauss or more.
  • the lines of magnetic force extend substantially vertically to the target 202 while changing the progressing direction so as to be along the axial direction near the axis of the magnetic body 209 .
  • the lines of magnetic force are combined with the lines of magnetic force emitting from the circumferential magnet 203 and pass the evaporation surface of the target 202 . Lines of magnetic force of higher straightness than those in the second exemplary invention shown in FIG.
  • FIG. 23 for the second exemplary invention and FIG. 25 for this exemplary invention are compared.
  • the range and the configuration of the distribution for the lines of magnetic force are substantially identical between FIG. 23 and FIG. 25 .
  • the lines of magnetic force illustrated in FIG. 25 are concentrated so as to converge further to the vicinity of the axes of the magnetic body 209 and the target 202 than the lines of magnetic force illustrated in FIG. 23 . Accordingly, the straightness and the density of the entire lines of magnetic force are increased more in FIG. 25 than those in FIG. 23 .
  • regions in which the components of lines of magnetic force vertical to the evaporation surface are not substantially present are formed to the outer circumference of the target 202 in the same manner as in FIG. 23 for the second exemplary invention described above. Accordingly, also in this exemplary invention, the disadvantage that arc spots move to the outside of the evaporation surface of the target 202 beyond the outer circumference of the target 202 can be avoided and the arc spots can be retained on the evaporation surface of the target 202 .
  • the target 202 is not restricted to the disk-shaped shape but may also be a polygonal, for example, tetragonal shape.
  • the circumferential magnet 203 and the rear surface magnets 204 a and 204 b are not restricted to the toroidal shape but may also be an annular polygonal, for example, tetragonal shape.
  • the present invention is applicable to an arc evaporation source for a film deposition apparatus that forms thin films.

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  • Physics & Mathematics (AREA)
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JP2011-118267 2011-05-26
JP2011118267A JP5081315B2 (ja) 2011-02-23 2011-05-26 アーク式蒸発源
JP2011180544A JP5081320B2 (ja) 2011-02-23 2011-08-22 アーク式蒸発源
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CN111032907A (zh) * 2017-08-21 2020-04-17 堺显示器制品株式会社 蒸镀装置、蒸镀方法以及有机el显示装置的制造方法

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EP2679702A4 (en) 2016-03-02
US20180371605A1 (en) 2018-12-27

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