WO2007089216A1 - Procédé de dépôt en phase vapeur à plasma et appareil utilisant une commande polarisée bipolaire - Google Patents

Procédé de dépôt en phase vapeur à plasma et appareil utilisant une commande polarisée bipolaire Download PDF

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Publication number
WO2007089216A1
WO2007089216A1 PCT/US2005/031478 US2005031478W WO2007089216A1 WO 2007089216 A1 WO2007089216 A1 WO 2007089216A1 US 2005031478 W US2005031478 W US 2005031478W WO 2007089216 A1 WO2007089216 A1 WO 2007089216A1
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Prior art keywords
plasma
cathode
arc
source
coating
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PCT/US2005/031478
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English (en)
Inventor
Vladimir I. Gorokhovsky
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Gorokhovsky Vladimir I
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Priority to PCT/US2005/031478 priority Critical patent/WO2007089216A1/fr
Publication of WO2007089216A1 publication Critical patent/WO2007089216A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • 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
    • C23C14/0641—Nitrides
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • 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
    • C23C14/48—Ion implantation
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/137—Spraying in vacuum or in an inert atmosphere
    • 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
    • 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
    • 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
    • H01J37/32697—Electrostatic control
    • H01J37/32706—Polarising the substrate

Definitions

  • This invention relates to the application of coatings in a vacuum apparatus.
  • this invention relates to an apparatus which generates a plasma of electrically conducting materials for the application of coatings to surfaces of a substrate by way of condensation of plasma.
  • the apparatus can be used in mechanical engineering, instrument and tool making, in the production of electronic equipment, and in other fields of industry.
  • cathodic arc source in which an electric arc is formed between an anode and a cathode plate in a vacuum chamber.
  • the arc generates a cathode spot on a target surface of the cathode, which evaporates the cathode material into the chamber.
  • the cathodic evaporate disperses as a plasma within the chamber, and upon contact with the exposed surfaces of one or more substrates, coats the substrates with the cathode material, which may be metal, ceramic, etc.
  • An example of such an arc coating apparatus is described in U.S. Pat. No. 3,793,179 issued Feb. 19, 1974 to Sablev, which is incorporated herein by reference.
  • the advanced surface engineering systems combine several plasma sources of different kinds, such as cathodic arc sources, hollow cathode arc sources, magnetrons, electron beam evaporators, thermal resistive evaporators, in a one universal vacuum chamber layout to provide a tool for deposition of multilayer coatings consisting of combinatorial sequence of layers composed of different materials.
  • Such a hybrid vacuum plasma vapor deposition systems can have many electrodes immersed into dense vapor plasma environment and carrying a different potentials relative to neighboring plasma.
  • One of such electrodes is a substrate platform with substrate holders and substrates for coating deposition and vapor plasma treatment.
  • An example of such a vapor plasma deposition apparatus is described in U.S. Pat. Application No. 2004/0168637 published Sep. 2, 2004 to Gorokhovsky, which is incorporated herein by reference.
  • a single current-controlled power source capable of providing a substantially constant direct current can be utilized with various switch configurations to provide current that is delivered through three or more electrodes in a plasma chamber.
  • Multiple power sources are also provided in association with shunt switches for delivering a plurality of sources of direct current in various directions between electrodes in a plasma chamber.
  • the invention overcomes these disadvantages by providing mechanisms for the effective generation of an electron current during the positive portion of the bias voltage pulse period, which is accomplished by connecting the negative pole to an arc cathode capable of emitting a sufficiently intense electron current to prevent the formation of micro-arcs on the substrate surface.
  • current reversing switches are provided to periodically connect substrate to either the negative or the positive pole of the bias power supply.
  • the opposite (positive) pole can be connected either to one or more arc cathodes, or to a separate electrode having a floating potential relative to the plasma, or to other anodes or to the chamber walls.
  • the negative side of the bias power supply has to be connected to a cathodic arc-type electron emitter, which is capable of generating an electron current of substantial magnitude. It can be also connected to the anode, which collects an electron current of substantial magnitude from the cathodic arc source.
  • the fraction of the electron current which can be collected by the substrates is about 0.1% to 10% of the total electron current in a dense low pressure highly ionized plasma, and typically ranges from 10 to 500 amperes.
  • a typical duration of bi-period in this pulsed bias setup ranges from lO ⁇ s to lOO ⁇ s, which corresponds to the frequency range of 10kHz to 100kHz.
  • a typical duty cycle (a ratio of t + /t. between positive and negative portions of the bias voltage during one bi-period) ranges from 20 to 80% depending upon the requirements of different plasma vapor deposition processes.
  • the chamber in the preferred embodiment of the present invention comprises at least one cathodic arc source utilizing either a cold evaporating cathode or a thermoionic cathode or a heated distributed arc cathode, and one or more anodes.
  • cathodic arc source utilizing either a cold evaporating cathode or a thermoionic cathode or a heated distributed arc cathode, and one or more anodes.
  • vapor plasma sources or sputtering sources such as magnetrons, electron beam evaporators and/or thermal evaporators, providing a multiple plasma vapor source hybrid deposition system.
  • the invention provides a coating chamber disposed off of the optical axis of a filtered arc source containing a cathode, wherein an isolated repelling electrode is positioned in the plasma duct, separate from the deflecting electrode, such that the deflecting magnetic field is substantially tangential to a substantial portion of the surface of the repelling electrode.
  • the current applied to the isolated repelling electrode can be varied independently of the current applied to the deflecting electrode, thus allowing the electric field about the repelling electrode to be enhanced and facilitating the function of sustaining the arc in the plasma duct, without altering the deflecting properties of the deflecting electrode.
  • the repelling electrode is disposed within the plasma duct in the path of the plasma stream, the placement and orientation of the repelling electrode thereby creating an electric field which divides the electric current, physically dividing the plasma stream, which merges after passing around the repelling electrode.
  • the invention thus reduces the loss of metal ions at the substrate in a vacuum arc coating apparatus, and improves the quality of the vacuum within the apparatus.
  • the dividing electrode being electrically isolated and independently energized, further serves as an auxiliary anode for sustaining the arc in the plasma duct.
  • This embodiment of the invention is particularly advantageously implemented in a vacuum arc coating apparatus in which two plasma sources disposed on opposite sides of a common plasma duct each generate a plasma stream which combine at the entrance to the plasma duct and flow into the coating chamber.
  • the repelling electrode and/or the deflecting electrode can be maintained at floating potential, or can be connected to the positive poles of separate power sources so that the applied current can be varied independently of one another.
  • the deflecting electrode is surrounded by a baffle for removing macroparticles from the plasma stream, which also serves as a getter pump to remove gaseous contaminants from within the apparatus.
  • a baffle for removing macroparticles from the plasma stream, which also serves as a getter pump to remove gaseous contaminants from within the apparatus.
  • the invention also provides a multiple-cathode apparatus suitable for use in plasma- immersed processes as ion implantation, ion nitriding, ion cleaning and the like.
  • a first filtered arc source containing one or more cathodes generates cathodic evaporate for coating the substrate, while the deflecting and focusing magnetic fields affecting a second filtered arc source are deactivated so that cathodic evaporate does not flow toward the substrates.
  • the second filtered arc source thus functions as a powerful electron emitter for plasma immersed treatment of the substrates.
  • a load lock shutter comprising a metallic grid is disposed between the plasma duct and the coating chamber, to control communication between the plasma source and the coating chamber.
  • the load lock shutter can be closed to contain macroparticles and metal vapor within the cathode chamber(s) and plasma duct, but permit the passage of electrons into the coating chamber to thus increase the ionization level of a gaseous component within the coating chamber.
  • the load lock shutter can be charged with a negative potential, to thus serve as an electron accelerator and ion extractor.
  • load lock shutters may also be provided between the filtered arc source and the plasma duct, and/or between the cathodes and the deflecting electrode within a filtered arc source.
  • the load lock shutters can also be used in conjunction with the deflecting electrode operating as a getter pump, to improve the quality of the vacuum in the chamber.
  • the present invention thus provides an apparatus for the application of coatings in a vacuum, comprising at least one filtered arc source comprising at least one cathode contained within a cathode chamber, at least one anode associated with the cathode for generating an arc discharge, a plasma duct in communication with the cathode chamber and with a coating chamber containing a substrate holder for mounting at least one substrate to be coated, the substrate holder being positioned off of an optical axis of the cathode, at least one deflecting conductor disposed adjacent to the plasma source and the plasma duct, for deflecting a plasma flow from the arc source into the plasma duct, and at least one metal vapor or sputter deposition plasma source disposed in or near a path of the plasma flow, comprising a material to be evaporated.
  • the present invention further provides an apparatus for the application of coatings in a vacuum, comprising at least one filtered arc source comprising at least one cathode contained within a cathode chamber, at least one anode associated with the cathode for generating an arc discharge, a plasma duct in communication with the cathode chamber and with a coating chamber containing a substrate holder for mounting at least one substrate to be coated, the substrate holder being positioned off of an optical axis of the cathode, at least one deflecting conductor disposed adjacent to the plasma source and the plasma duct, for deflecting a plasma flow from the arc source into the plasma duct, at least one metal vapor or sputter deposition plasma source in communication with the plasma duct, the metal vapor or sputter deposition plasma source being positioned off of an optical axis of the cathode, and at least one deflecting conductor disposed adjacent to the metal vapor plasma source and the plasma duct, for deflecting a plasma flow from the
  • the present invention further provides a method of coating an article in a coating apparatus comprising at least one filtered arc source comprising at least one cathode contained within a cathode chamber, at least one anode associated with the cathode for generating an arc discharge, a plasma duct in communication with the cathode chamber and with a coating chamber containing a substrate holder for mounting at least one substrate to be coated, the substrate holder being positioned off of an optical axis of the cathode, at least one deflecting conductor disposed adjacent to the plasma source and the plasma duct, for deflecting a plasma flow from the arc source into the plasma duct, and at least one metal vapor or sputter deposition plasma source in communication with the plasma duct, the method comprising the steps of: a.
  • FIG. 1 is a schematic plan view of a prior art vacuum arc coating apparatus
  • FIG. 2 is a schematic plan view of a single source vacuum arc coating apparatus embodying the invention
  • FIG. 3a is a schematic plan view of a dual-cathode filtered arc source vacuum arc coating apparatus embodying the invention
  • FIG. 3b is a schematic plan view of a double-channel dual-cathode filtered arc source vacuum arc coating apparatus embodying the invention
  • FIG. 4 is a top plan view of a further embodiment of the vacuum arc coating apparatus of FIG. 3 providing a plurality of cathode pairs,
  • FIG. 5a is a side elevation of the arc coating apparatus of FIG. 4,
  • FIG. 5b is a cross-sectional side elevation of a further embodiment of the arc coating apparatus of FIG. 4 having impulse cathodic arc sources,
  • FIG. 5c is a schematic plan view of a dual-cathode filtered arc source vacuum arc coating apparatus of FIG. 4 having impulse laser igniters,
  • FIG. 6 is a front elevation of the dual-cathode filtered arc coating apparatus of FIG. 4,
  • FIG. 7 is a cross-sectional view of a cathode pair in the dual-cathode filtered arc coating apparatus of FIG. 4,
  • FIG. 8a is a schematic plan view of a dual filtered cathodic vacuum arc coating apparatus providing auxiliary anodes within the coating chamber
  • FIG. 8b is a schematic plan view of a dual filtered cathode vacuum arc coating apparatus providing magnetron-arc sources within the coating chamber surrounded by an auxiliary arc anode,
  • FIG. 8c is a schematic plan view of a further embodiment of a dual filtered cathode vacuum arc coating apparatus providing magnetron arc sources within the coating chamber surrounded by an auxiliary arc anode
  • FIG. 8d is a schematic plan view of a dual filtered cathodic vacuum arc apparatus providing a resistive evaporation hot anode (REHA) arc plasma within the coating chamber
  • REHA resistive evaporation hot anode
  • FIG. 8e is a schematic plan view of a dual filtered cathodic vacuum arc apparatus providing a resistive evaporation hot anode (REHA) arc plasma within the plasma duct,
  • REHA resistive evaporation hot anode
  • FIG. 8f is a schematic plan view of a dual filtered cathodic vacuum arc apparatus providing an electron beam evaporation hot anode (EBEHA) arc source within the plasma duct,
  • EBEHA electron beam evaporation hot anode
  • FIG. 8g is a schematic plan view of a dual filtered cathodic vacuum arc apparatus providing an electron beam evaporation hot cathode (EBEHA) arc source within the plasma duct,
  • EBEHA electron beam evaporation hot cathode
  • FIG. 8h is a schematic plan view of a further embodiment of a dual filtered cathodic vacuum arc coating apparatus providing a resistive evaporation hot anode (REHA) arc plasma source within the plasma duct,
  • REHA resistive evaporation hot anode
  • FIG. 8i is a schematic plan view of a further embodiment of a dual filtered cathodic vacuum arc coating apparatus providing a resistive evaporation hot anode (REHA) arc plasma source within the coating chamber,
  • REHA resistive evaporation hot anode
  • FIG. 8k is a schematic plan view of a filtered arc plasma source ion deposition (FAPSID) surface engineering system utilizing different metal vapor deposition sources in filtered arc plasma immersion environment,
  • FAPSID filtered arc plasma source ion deposition
  • FIG. 81 is a schematic side view of the FAPSID surface engineering system of FIG. 8k.
  • FIG. 8m is a schematic plan view of a dual filtered cathodic vacuum arc coating apparatus providing an off sight electron beam evaporation hot cathode (EBEHC) arc plasma source within the plasma duct,
  • EBEHC off sight electron beam evaporation hot cathode
  • FIG. 8n is a schematic plan view of a dual filtered cathodic vacuum arc apparatus providing an off-sight electron beam evaporation hot anode A) arc plasma source within the plasma duct,
  • FIG. 9 is a schematic plan view of an embodiment of a vacuum arc coating apparatus with a getter pumping system, showing the deflecting electromagnetic fields produced by the deflecting and focusing magnetic coils,
  • FIG. 10 is a graph illustrating the relationship between the repelling electrode voltage and the ion current as a function of the repelling electrode current in the arc coating apparatus of the invention
  • FIG. 11 is a graph illustrating coating thickness distribution as a function of the distance of the substrates from the top in the arc coating apparatus of FIG. 8c,
  • FIG. 12 is a schematic plan view of an embodiment of a vacuum arc coating apparatus utilizing filtered arc sources with an additional filtration stage
  • FIG. 13 is a schematic illustration of a preferred thermal barrier coating architecture
  • FIG. 14 is a graph illustrating operating pressure ranges for various plasma surface engineering processes
  • FIG. 15a is a schematic plan view of an embodiment of a dual filtered arc coating apparatus utilizing a substrate holder connected to one side of a bi-polar DC power supply, while other end is connected to both cathodes of a dual filtered arc source,
  • FIG. 15b is a schematic plan view of an embodiment of a dual filtered arc coating apparatus utilizing a substrate holder connected to one side of a bi-polar DC power supply, while other end is connected to the one cathode of a dual filtered arc source and to the chamber wall (grounded),
  • FIG. 15c is a schematic plan view of an embodiment of a dual filtered arc coating apparatus utilizing a substrate holder connected to one side of a bi-polar DC power supply, while other end is connected to a thermoionic cathode and to the chamber wall (grounded),
  • FIG. 15d is a schematic plan view of an embodiment of a dual filtered arc coating apparatus utilizing a distant auxiliary arc anode and a substrate holder connected to one side of a bi-polar DC power supply, while other end is connected to an auxiliary anode and to the chamber wall (grounded),
  • FIG. 15e is a schematic plan view of an embodiment of FIG. 15a using diodes instead of resistors to close the negative bias current circuit between the arc cathodes and the substrate holder, and
  • FIG. 16 is a graph illustrating a DC pulse bias voltage of the substrate holder generated by embodiments of FIGs. 15 a to e.
  • FIG. 1 illustrates a prior art apparatus for the application of coatings in a vacuum.
  • the apparatus comprises a plasma source comprising cathode 12 disposed in a cathode chamber 14 in communication with a plasma duct 16 in the form of a parallelepiped.
  • Cathode 12 is surrounded by focusing and stabilizing electromagnets 13, and anodes 18 are disposed on planes of the cathode chamber 14 adjacent to the cathode 12 to create an electric arc discharge when current source 19 is activated.
  • a deflecting magnetic system comprises a rectangular coil 20 formed from linear conductors surrounding the plasma duct 16.
  • a focusing coil 21 may also be provided surrounding the plasma duct 16.
  • the plasma duct 16 is in communication with a coating chamber (not shown), in which a substrate holder (not shown) supporting the substrates (not shown) is positioned.
  • the substrate holder is thus located off of the optical axis of the cathode 12, preferably at approximately a right angle, to minimize the flow of neutral particles toward the substrates.
  • deflecting electrode 26 On the walls of plasma duct 16 are mounted plate electrodes 24, 26 provided with diaphragm filters, spaced from the walls of the plasma duct 16 and electrically insulated therefrom, for deflecting the flow of plasma away from the optical axis of the cathode 12 and through the plasma duct 16.
  • deflecting electrode 26 is located on a parallelepiped wall opposite the cathode 12. Deflecting electrode 26 may optionally be located on any wall adjoining the wall on which the cathode 12 is positioned. In these positions, electrode 26 serves both as a baffle which traps macroparticles and as a deflecting element which redirects the plasma stream toward the substrates.
  • Deflecting electrode 26 is shown spaced from the wall of the plasma duct 16, which permits a flow of plasma behind the electrode 26.
  • the deflecting electrode 26 may be at floating potential, or is optionally positively biased by connecting it to the positive pole of an auxiliary current source 26a as shown.
  • Deflecting electrode 24 is shown at a floating potential.
  • a substantial part of the surface of deflecting electrode 26 is disposed outside of the cusp of the magnetic field generated by deflecting coil 20, i.e. in the deflection region of the plasma duct 16, where the tangential component of the magnetic field generated by the deflecting coil 20 is relatively small.
  • the magnetic field does not influence ions directly, a strong tangential magnetic field confines electron clouds which creates an electric field that repels ions.
  • FIG. 2 illustrates a first preferred embodiment of the present invention utilizing a filtered arc source containing a single cathode 12 disposed in a cathode chamber 14 in communication with a plasma duct 16.
  • the cathode chamber 14 is surrounded by focusing and stabilizing electromagnets 13, and anodes 18 are disposed on planes of the cathode chamber 14 adjacent to the cathode 12a and connected to DC power source 19, as in the prior art apparatus.
  • the deflecting magnetic system comprises rectangular coil 20 surrounding the plasma duct 16, and a focusing coil 21 is provided surrounding the plasma duct 16 downstream of the deflecting coil 20.
  • the plasma duct 16 is in communication with a substrate chamber 10 containing the substrate holder 2, positioned off of the optical axis of the cathode 12.
  • the apparatus is provided with at least one deflecting electrode 30 and at least one repelling electrode 32.
  • the deflecting electrode 30 is insulated from the wall of the plasma duct 16 as by insulating spacer 31 and preferably comprises a generally planar conductive plate 30a, optionally with diaphragm filters 30b located on the optically exposed surfaces of the plate 30a and disposed obliquely relative thereto.
  • the deflecting electrode 30 can be considered to consist of either two separate electrode sections 30', 30" which are electrically connected together at the corner of the plasma duct 16, or as a single deflecting electrode 30 with orthogonal sections 30', 30" configured to generally conform to the interior surface of the adjoining walls of the plasma duct 16.
  • the deflecting electrode 30 is preferably spaced from the walls of the plasma duct 16 to minimize obstruction to the flow of plasma through the plasma duct 16, and may be maintained at a floating potential, or optionally positively biased by connection to an auxiliary power source 26b as shown. It is also possible to use the primary current source 19 both to generate an arc current between the cathode 12 and anodes 18 and to bias the deflecting electrode 30. Most of the deflecting electrode 30 is positioned in the deflecting portion of the plasma duct 16, in which the tangential component of the magnetic field generated by the deflecting coil 20 is relatively small. This significantly reduces the effectiveness of the deflecting electrode 30.
  • the deflecting influence of the deflecting electrode 30 can be enhanced by increasing the current applied to the electrode 30, but increasing the current also increases the incidence of arc spot generation and erosion of the cathode 12, which would result in a much higher macroparticle density with little corresponding increase in ion yield at the substrate. Moreover, this commensurately increases the risk of short- circuiting the arc current.
  • a separate repelling electrode 32 electrically isolated from the deflecting electrode 30, is positioned downstream of the deflecting electrode 30 where the transversal component of the magnetic field generated by the deflecting magnetic coil 20 is weakest and the tangential component of the magnetic field is strongest.
  • the repelling electrode 32 is electrically isolated from the deflecting electrode, which facilitates independent control of the bias potential on the repelling electrode 32.
  • repelling electrode 30 is biased through connection to an auxiliary DC current source 26a.
  • the substrates 4 are mounted on the substrate holder 2 in the coating chamber 10.
  • the apparatus is evacuated to the desired pressure using conventional techniques and vacuum pumping apparatus well known to those skilled in the art.
  • the primary current source 19 is activated, creating an arc discharge between the cathode 12 and anodes 18 which begins to evaporate the cathodic material into the cathode chamber 14.
  • the auxiliary current source 26a is energized to bias the repelling electrode 32, creating an electric field of relatively uniform intensity along the wall of the plasma duct 16 opposite the cathode chamber 14.
  • Cathodic evaporate is ejected from cathode 12 in an ionized plasma containing both ionized coating particles and neutral contaminate or macroparticles.
  • the plasma is focused by the magnetic focusing coils 13 and flows past the anodes 18, as is conventional.
  • the plasma stream, with entrained macroparticles vaporized from the evaporation surface of the cathode 12, is thus ejected toward the deflecting electrode 30.
  • the magnetic deflecting coil 20 generates a magnetic field which directs the plasma stream and ions of coating material suspended therein through the plasma duct 16 toward the coating chamber 10, as shown by the arrows in FIG. 2.
  • Neutral macroparticles remain unaffected by the deflecting magnetic field and the electric fields generated around deflecting electrode 30 and repelling electrode 32, and continue in a path generally along the optical axis of the cathode 12, striking the deflecting electrode 30 and either adhering to the electrode 30 or falling to the bottom of the apparatus.
  • the primary cathodic arc source installed in cathode chamber 14 can be similar to the plasma source described in U.S. Pat. No. 3,793,179 issued Feb. 19, 1974 to Sablev, which is incorporated herein by reference.
  • This plasma source utilizes a circular cylinder target.
  • To cover a large area coating zone several cathodic arc sources with cylindrical targets can be installed on the side wall of the cathode chamber 14.
  • the primary cathodic arc source can be of rectangular design, as was described in U.S. Pat. No. 5,380,421 issued Jan. 10, 1995 to V. Gorokhovsky or in International Patent Application No. PCT/CAOO/00380, which are incorporated herein by reference. In this case the cathode target is rectangular covering entire coating zone.
  • the magnetic cusp generated by the deflecting conductor 20a must be oriented toward the coating chamber 42, to guide the plasma stream toward the coating chamber 42.
  • An opposite cusp, which would lead the plasma stream in a direction opposite the coating chamber, is created by the closing conductors 20b of the deflecting coils 20, as shown in FIG. 3b; thus, the closing conductors 20b are maintained remote from the filtered arc source, and the cathodes 12 must be positioned within the cusp of the magnetic field generated by the deflecting conductor 20a of the deflecting coil 20. Any portion of the plasma outside of the cusp of the deflecting magnetic field will be deflected into the back wall (behind the deflecting electrode portion 30') of the cathode chamber 14, and will not reach the substrates 4.
  • linear deflecting and focusing conductors 20a, 21 allow the plasma duct to be of virtually unlimited length.
  • the linear conductors 20a, 21 each generate a cusp of magnetic field lines which curves in two-dimensions, along the direction of plasma flow, but has a height which is limited only by the length of the linear conductors 20a and 21, which allows for the coating of substrates 4 of considerably larger dimensions as described in U.S. Pat. No. 5,435,900 to Gorokhovsky, which is incorporated herein by reference.
  • the deflecting and focusing magnetic fields are thus quasi-two dimensional, in that the cross-section of the cusp (for example as reflected by the plasma flow lines in FIG. 2) is substantially constant in the third dimension.
  • the repelling electrode 32 is preferably biased to a higher positive potential than the deflecting electrode 30.
  • the tangential component of the deflecting magnetic field generated by the deflecting magnetic coil 20 is weak in the deflecting region containing the deflecting electrode 30, this can now be compensated for by increasing the potential applied to, and thus the deflecting effect of, the repelling electrode 32, without risking short circuiting the arc current or misdirecting the plasma flow. This is made possible because the repelling electrode 32 is disposed in a portion of the plasma duct where the tangential magnetic field component is strong.
  • FIG. 3a A further preferred embodiment of the invention having a filtered arc source with two cathodes 12 at one end of a coating chamber 42 is illustrated in FIG. 3a.
  • a vacuum arc coating apparatus 40 provides two plasma sources comprising cathodes 12 disposed within the filtered arc source comprising cathode chambers 44 positioned on opposite sides of the plasma duct 46.
  • the cathodes 12 each comprise a cathode plate and are respectively surrounded by focusing and stabilizing electromagnets 13, and anodes 18 connected to the positive terminal of DC power supply 19.
  • Plasma duct 46 is in communication with the coating chamber 42, in which a substrate holder 2 supporting substrates 4 is positioned off of the optical axes of both cathode sources 12. In the embodiment shown substrate holder 2 is biased to a negative potential by an independent power supply 26b.
  • a deflecting electrode 50 preferably comprising an electrode plate 50a optionally supporting baffles 50b, is positioned between the plasma sources 12, generally parallel to the direction of plasma flow through the plasma duct 46, and is isolated electrically from the walls of plasma duct 46 by an insulator 51.
  • a conductive shield or shroud 52 may be provided to serve as a baffle for deflecting undesirable macroparticles discharged from cathodes 12 and to insulate the electrode 50 from contaminants.
  • the shroud 52 may be optionally biased to a negative potential, which provides the advantages described below.
  • the magnetic deflecting system comprises coils 20 having deflecting conductors 20a proximate to the corners of the plasma duct 46 adjacent to the cathode chambers 44, and closing conductors 20b (for example as shown in FIG. 7) remote from the plasma duct 46 so as not to influence the direction of plasma flow.
  • the deflecting magnetic fields generated by the conductors 20a direct the plasma stream toward the substrates 4.
  • the cathodes 12 must be positioned within the cusps of the magnetic fields generated by deflecting conductors 20a of the deflecting coils 20.
  • a pair of cathodes 12 disposed in a filtered arc source on opposite sides of the plasma guide 46 at least a portion of the deflecting electrode 50, and the repelling electrode 60, are disposed in alignment with a plane of symmetry between opposite walls of the plasma guide 46.
  • the plane of symmetry extends between the magnetic cusps generated by deflecting conductors 20a, and the repelling electrode 60 is thus positioned between the cusps in a portion of the plasma duct 46 in which the tangential component of the deflecting magnetic fields is strongest.
  • a focusing coil 21 is disposed about the opposite end of the plasma duct 46, for generating focusing magnetic fields within the plasma duct 46.
  • the focusing coil 21 may be a single coil, for example as shown in FIGS. 3a and 3b may comprises focusing conductors 21 a disposed near the end of the plasma duct 46 in communication with the coating chamber 42, the closing conductors 21b therefor being disposed remote from the plasma duct 46 so as not to influence the flow of plasma, as shown in FIG. 7.
  • the focusing coil 21 (or focusing conductor 21a) generates a magnetic focusing field in the same direction as the deflecting magnetic fields generated by the deflecting coils 20, as shown in FIG. 9.
  • the transversal components of the focusing magnetic fields generated by the focusing conductor 21 substantially cancel the deflecting magnetic fields generated by the deflecting coils 20, minimizing the transversal components of these magnetic fields.
  • the tangential components of these magnetic fields overlap and create a substantially uniform magnetic wall which confines the plasma stream away from the walls of the plasma duct 46.
  • a repelling electrode 60 is thus positioned downstream of the deflecting electrode 50 within the plasma duct 46, preferably in the region between deflecting coils 20 and focusing coils 21, where the transversal component of the magnetic fields is weakest and the tangential component of the magnetic fields is strong.
  • Repelling electrode 60 which preferably comprises an electrode plate 60a optionally supporting baffles 60b, is biased positively through a connection with the positive terminal of auxiliary DC power source 26a. It is advantageous to provide the repelling electrode 60 with a separate auxiliary current source 26a, either independent or in addition to another current source (for example 19 as shown in FIG. 3), since the repelling effect of the repelling electrode 60 is directly proportional to its potential.
  • DC source 26a is connected in series with one of the primary power sources 19, through diode 27, so that the repelling electrode 60 always maintains at least the same potential as the anodes 18, and auxiliary power source 26a is used to increase the potential of the repelling electrode 60 beyond the potential of anodes 18.
  • DC sources 19 and 26a may alternatively be electrically independent.
  • An optional focusing electrode 23 may be provided surrounding the repelling electrode 60 near the exit of the plasma duct 46 (along the inner side of the wall of the housing), where the tangential component of the deflecting/focusing magnetic fields is strongest. Applying a positive potential to this focusing electrode, as shown in FIG. 3a, improves the transversal electric field in the same manner as the repelling electrode 60.
  • the substrates 4 to be coated are mounted on the substrate holder 2.
  • the cathode chambers 44 and adjoining plasma duct 46 and coating chamber 42 are sealed and evacuated to the desired pressure using a conventional vacuum pumping apparatus (for example as shown in FIG. 4).
  • the power sources 19, 26a and focusing and deflecting coils 13, 20 are activated and an arc is ignited between each cathode 12 and its surrounding anodes 18.
  • the plasma stream is ejected from cathode 12 and focused within the cathode chamber 44 by focusing electromagnets 13, which also drive the plasma toward the plasma duct 46.
  • Magnetic focusing conductors 20a generate magnetic fields about the corners of the plasma duct 46 at the end adjoining the cathode chamber 44, to deflect the plasma stream through the plasma duct 46 and toward the coating chamber 42.
  • the deflecting magnetic fields generated by the deflecting conductors 20a deflect ionized components of the plasma towards the coating chamber 42, while neutral macroparticles remain unaffected and, entrained in the plasma being deflected out of the cathode chambers 44, strike deflecting electrode 50 and either adhere to it or fall to the bottom of the apparatus 40.
  • the plasma stream is deflected by deflecting coils 20, assisted by deflecting electrode 50, into the plasma duct 46 where it passes repelling electrode 60.
  • the deflecting magnetic fields surrounding the deflecting conductors 20a and focusing coil 21 have a strong tangential component (relative to the plasma stream) inside the plasma duct 46, which acts as a magnetic "wall” to isolate the walls of the plasma duct 46 from the plasma flow.
  • the plasma flows between deflecting coils 20 and focusing coil 21, because the magnetic fields generated by coils 20, 21 traverse the walls of the plasma duct 46 in the same direction, in the region of overlap the transversal components of these deflecting magnetic fields substantially cancel and the tangential components are superposed to create a strong tangential magnetic "wall" which isolates the plasma from the wall of the plasma duct 46.
  • the repelling electrode 60 creates a strong electric field in a direction generally perpendicular to the plasma stream, which repels ions toward the walls of the plasma duct 46.
  • the plasma is thus confined by the electric field generated by the repelling anode 60 and the magnetic fields generated by the deflecting and focusing magnetic coils 20, 21.
  • the primary or "proximal” anodes 18 generate an arc which erodes the cathode 12 and creates a plasma for coating the substrates 4.
  • the deflecting electrode 50 and repelling electrode 60 constitute "intermediate” auxiliary anodes, which deflect and repel the plasma stream within the cathode chamber 44 and plasma duct 46, and in dual-cathode embodiments divide the plasma stream as described above.
  • FIG. 3a also illustrates a "distal" anode 70 disposed within the coating chamber 42, in this embodiment positioned on the side of substrate holder 2 opposite the plasma duct. The distal anode 70 assists in the deflection of the plasma stream in the direction of the substrates 4 before the plasma is pumped out of the apparatus 40.
  • the distal anode 70 is energized by power sources 26b connected between the cathode 12 and the distal anode 70 (and optionally also by a separate power source 26c isolated by diodes 31), so that distal anode 70 always maintains at least the same potential as the repelling electrode 60, and auxiliary power source 26b is used to increase the potential of the distal anode 70 beyond the potential of repelling electrode 60.
  • FIG. 3b thus provides a chain of anodes, proximal anodes 18 local to the cathodes 12; medial anodes such as the repelling electrode 60 and focusing electrode 23, contained within the plasma duct 46, and distal anodes such as the anode 70, which may be disposed anywhere within the coating chamber 42.
  • These anodes combine to create a desired dispersion of electrons and a uniform plasma cloud in the vicinity of the substrates 4.
  • the anodes could be connected to independent power supplies; however, this would result in high power consumption.
  • the chain of anodes can alternatively be connected to the same power supply and rastered.
  • Ionization of the plasma is maximized in the vicinity of an active anode, and rastering through the chain of anodes in this fashion allows for considerable conservation of power while maintaining a high plasma ionization level and mixing the plasma throughout the apparatus to create uniform plasma immersed environment.
  • FIG. 3b illustrates a variation of the embodiment of FIG. 3a, in which a filtered arc source, each containing a pair of cathodes 12, is provided on both sides of the coating chamber 42.
  • This embodiment can be used for plasma immersed treatment of substrates 4, by selectively deactivating the deflecting coil 20 and focusing conductor 21 on one side of the coating chamber 42.
  • plasma streams are generated in both cathode chambers 44.
  • the particulate (metal vapor plasma) component of the plasma stream on the side of the inactive coils 20, 21 remains largely confined within the cathode chambers 44, there being no magnetic driving influence on that side of the coating chamber 42.
  • the cathodes 12 on the side of the inactive coils 20, 21 thus serve as powerful electron emitters, improving ionization of the gaseous component of the plasma flowing past shutter 80a and into the coating chamber 42, and significantly improving the properties of the resulting coating.
  • the filtered arc source on the side of the coating chamber 42 with the deactivated coils 20, 21 is used for emitting electrons to provide a plasma immersed environment for coatings deposited by the other filtered arc source or, as in the embodiment of FIG. 8b, magnetron arc sources, or both.
  • This embodiment of the apparatus can thus be used for any plasma-immersed process, including plasma assisted low pressure chemical vapor deposition (PALPCVD) processes.
  • PLCVD plasma assisted low pressure chemical vapor deposition
  • load lock shutters 80a, 80b may be disposed between each plasma duct 46 and the coating chamber 42.
  • Each load lock shutter 80a, 80b comprises a grid made of stainless steel or another suitable metal having bars preferably between one-half inch and one inch in diameter and one-half inch to one inch openings between the bars, for example as shown in U.S. Pat. No. 5,587,207 issued Dec. 24, 1996 to Gorokhovsky, which is incorporated herein by reference.
  • the load lock shutters 80 may be actuated manually, mechanically, or electrically, and are impervious to the particulate components of the plasma stream (ions and stray macroparticles) but pervious to electrons.
  • the load lock shutters 80a, 80b are selectively independently closed or opened to respectively block or permit a flow of ions and stray macroparticles through to the coating chamber 42
  • the shutter 80a can be opened while shutter 80b remains closed. All plasma sources 12 are active, and thus plasma streams are generated in both cathode chambers 44. However, while the plasma stream generated on the side of the open shutter 80a freely flows into the coating chamber 42, the particulate component of the plasma stream on the side of the closed shutter 80b remains confined within the cathode chamber 44 and plasma duct 46, upstream of the shutter 80b, both by the absence of deflecting and focusing magnetic fields and by the barrier created by the load lock shutter 80b.
  • the load lock shutters 80a, 80b may be maintained at a floating potential, or a strong negative potential may be applied in which case the load lock shutter 80a or 80b will also serve as an ion accelerator, actively forcing positive ions generated by cathodic arc sources inside of plasma guide chamber, into the coating chamber 42 in a manner similar to a Kaufman type ion beam source. Diagnostic ports 84 may optionally be provided to accommodate sensors and/or probes for monitoring the environment within the coating chamber 42.
  • This embodiment of the apparatus can thus be used for any plasma-immersed process, including plasma assisted chemical vapor deposition (CVD) processes.
  • the distal auxiliary anodes 70 surround the rotating substrate holder 2, and thereby help to disperse the plasma uniformly within the coating chamber 42, for example as shown by the plasma flow lines in FIG. 8a, by attracting the ionized gaseous component to all portions of the coating chamber walls.
  • this embodiment is similar to the operation of the embodiment of FIG. 3a, except that in this embodiment the deflecting coils 20 and focusing coil 21 on the side of the closed load lock shutter 80b are deactivated during the plasma immersed process, so that the plasma is not driven through the plasma duct 46 on that side of the apparatus. Even without the load lock shutters 80a, 80b the plasma on the side of the apparatus in which the deflecting coils 20 and focusing coil 21 are deactivated will remain largely confined within the filtered arc source, there being no electromagnetic influence to drive the plasma out of the cathode chamber 44. Electrons will disperse into the plasma duct 46 and coating chamber 42.
  • the closed load lock shutter 80b assists in maintaining the purity of the coating by completely excluding stray ions and macroparticles from entering the coating chamber 42, however the load lock shutters 80a, 80b are not strictly necessary for all plasma immersed applications.
  • FIG. 3a provides proximal anodes 18 for generating an arc discharge at the cathodes 12, whereas in the embodiment of FIG. 8a the positive pole of the power source 19 for the cathode 12 is grounded so that the cathode chamber housing serves as a proximal anode for the cathode 12.
  • FIG. 8a provides magnetic deflecting coils 71 surrounding the distal auxiliary anodes 70, which serve to deflect the plasma flow past the substrates 4 within the coating chamber 42.
  • the magnetic fields generated by deflecting coils 71 extend well beyond the electric fields generated by the auxiliary anodes 70, and the plasma flow is dispersed along the magnetic field lines produced by deflecting coils 71.
  • the magnetic fields generated by the deflecting magnetic coils 71 should be oriented in the same direction as the focusing magnetic fields generated by the focusing coils 21.
  • the coils 71 surrounding anodes 70 also allow for the redirection of the plasma flow from one distal anode 70 to another, and the plasma flow can thus be rastered within the coating chamber 42 for a more even coating on the substrates 4.
  • the distal auxiliary anodes 70 can be disposed tangential to the magnetic force lines generated by the deflecting magnetic coils 71, which increases the anode voltage drop and transfers more energy into the plasma; or the distal auxiliary anodes 70 can be disposed transversely to the magnetic force lines generated by the deflecting magnetic coils 71, which to increase the stability of the auxiliary arc discharge and the uniformity of plasma distribution.
  • a plurality of distal auxiliary anodes 70 can be positioned to provide a combination of tangential and transversal anode surfaces, and switching the arc current between these anodes 70 creates a plasma blender, which equalizes the plasma treatment of the substrates 4.
  • a pulsed DC bias power supply 801 having positive and negative poles is connected to the substrate holder 2 via a switching circuit comprising switching elements 501, 502 which utilizing fast switching components, such as solid state elements IGBTs or MOSFETs or vacuum tubes or the like, and two primary power supplies (not shown).
  • the first primary power supply (not shown) has negative 1 " and positive I + poles connected to opposite ends of the switching elements 501, 502.
  • This power supply can be a high voltage low current power supply and is preferably a voltage source supporting a negative bias voltage portion of the pulsed DC bias voltage of the substrate holder 2.
  • the second primary power supply (not shown) has negative 2 " and positive 2 + poles connected to opposite ends of the switching elements 501, 502.
  • This power supply can be a high current low voltage power supply and is preferably a current source supporting a positive bias voltage portion of the pulsed DC bias voltage of the substrate holder 2 and extracts the electron current from the cathodes of the dual filtered arc source.
  • the switching cycle is controlled by a low voltage control device (not shown) which is well known to those skilled in the art.
  • the switching elements 501, 502 thus connect the substrate holder 2 alternately to the positive and negative poles of the pulsed DC bias power supply 801 by periodically applying alternate polarities to the substrate holder output of the pulsed DC bias power supply 801, in the preferred embodiment in periodic intervals, but not necessarily so.
  • the substrate holder 2 can be connected to the negative pole by opening the pair of switches 501a, 502b and closing the pair of switches 501b, 502a.
  • the substrate holder 2 can be connected to the positive pole of power supply by opening the pair of switches 501b, 502a and closing the pair of switches 501a, 502b.
  • the opposite side of the pulsed DC bias power supply is connected to both cathodes of the dual filtered arc source via equalizing inductor 500.
  • the positive voltage is applied to the substrate holder 2 bearing the substrate to be coated by extracting a substantial electron current (typically ranging from 10 to 200 amperes) from the cathodes 12. During this interval the substrates effectively become a distal auxiliary anode relative to the arc cathodes 12.
  • the diodes Dl and D2 close the positive bias current circuit between the arc cathodes 12 and substrate holder 2.
  • the positive (anodic) portion of the pulsed DC bias bi-period is followed by the negative portion when the controlled negative voltage (ranging typically from 50 volts up to 1200 volts) is applied to the substrate holder 2.
  • the resistors Rl and R2 close the negative bias current circuit between the arc cathodes 12 and the substrate holder 2.
  • the magnitude of these resistors Rl, R2 can be chosen to diminish the positive voltage pulse returning to the cathodes 12, which could otherwise eventually extinguish the primary arc discharge.
  • the resistors Rl and R2 can be replaced with diodes D9 and DlO, as illustrated in Figure 15e.
  • the negative bias current circuit closes between the grounded wall of the cathode chamber and the substrate holder 2 via diode D5, which eliminates the need for resistors Rl and R2 around the diodes Dl and D2.
  • the pulse bias power supply can be connected to a distal anode 601 and to the grounded chamber wall, for example via diodes D2 and D5 as illustrated in Figure 15d.
  • the positive voltage is applied to the substrate holder 2 with substrates to be coated by applying a high positive pulse (relative to the plasma potential), and extracting a substantial electron current (typically ranging from 10 to 200 amperes) from the cathodes 12 to the substrate 2 via distal anode 601. During this interval the substrates effectively form a part of the distal auxiliary anode relative to the arc cathodes 12.
  • the diode D2 closes the positive bias current circuit between the arc cathodes 12 and substrate holder 2 via the distal anode 601.
  • the positive (anodic) portion of the pulsed DC bias bi-period is followed by negative portion when a controlled negative voltage (ranging typically from 50 volts up to 1200 volts) is applied to the substrate holder 2.
  • a controlled negative voltage ranging typically from 50 volts up to 1200 volts
  • thermoionic arc hollow cathode 700 with heaters 701 is used to provide a substantial electron current to the substrate holder 2 during the positive portion of the pulsed DC bias bi-period. This is followed by negative bias portion of the pulsed DC bi-period during which the diode D5 closes the negative bias current circuit between the grounded chamber wall and the substrate holder 2.
  • the bias voltage Vbias is negative at the value of -240V during first 6 ⁇ s of the pulse period, when the substrate holder 2 is switched to the negative pole of the bias power supply. At this point the bias current is determined mostly by ions conveyed by the plasma to the substrate surface.
  • the ion current density is given by ii ⁇ c e q e n e (2kT e /mi) 1/2 , where m, is the mass of an ion, T e is the electron temperature, k is the Boltzmann constant, q e is the charge of electron, and c is the constant c ⁇ l.
  • the bias voltage becomes positive as a result of switching the connection of the substrate holder 2 to the positive pole of bias power supply or to a distal anode 601.
  • the bias voltage does not exceed 5 volts, but the bias current, created mostly by electrons conveyed by the plasma to the substrate surface, exceeds 100 amperes with a reversed direction in relation to the ion current.
  • the bias electron current conveyed by the plasma to substrates can be determined as Ib e ⁇ i e A s , where i e is the density of the current of thermalized electrons in plasma, and A s is the substrate area.
  • the velocity of thermalized electrons is given by ⁇ v Te > ⁇ (%kTJ ⁇ m e ) m where me is the mass of an electron.
  • the portion of the electron current which can be collected by the substrates 4 consists of 0.1% to 10% of the total electron current, and typically ranges from 10 to 500 amperes.
  • the ratio i e /i;>10 during the positive part of pulse period with a repetition frequency f>10kHz allows for the substantially complete elimination of the problem of arc breakdown on the substrates, commonly known as "micro-arcing."
  • the maximum frequency of the pulsed DC bias arrangement can be chosen at 100 kHz for practical reasons.
  • the filtered arc source in a filtered arc coating mode will generate metal ions, while in the auxiliary arc discharge mode the filtered arc source will generate electrons to provide plasma immersed environment for ion cleaning (etching), ion nitriding, ion implantation, and plasma assisted low pressure CVD (PALPCVD) processes.
  • etching ion cleaning
  • ion nitriding ion nitriding
  • ion implantation ion assisted low pressure CVD
  • each load lock shutter 80c or 80d being positioned such that when closed it blocks the magnetic cusp generated by the deflecting magnetic system only on one side of the plasma duct 46.
  • Cathodic evaporate from the cathode 12 on that side of the filtered arc source, being trapped within the magnetic cusp, will thus be confined within the filtered arc source by the load lock shutter 80c or 8Od, while cathodic evaporate from the cathode 12 on the other side of the filtered arc source will flow along the (unblocked) magnetic cusp into the plasma duct.
  • the load lock shutters 80c, 80d installed at the exit of a filtered arc source are charged with negative potential, they function as a positive ion beam source (ion extractor), in which case a preferred size of the openings in the load lock shutter is in the range of 100 ⁇ m to 1000 ⁇ m.
  • the load lock shutters 80c, 80d become transparent to the electrons of the auxiliary arc discharge, flowing between the cathode 12 of the filtered arc source and the distal auxiliary anode(s) 70 installed in the coating chamber 42.
  • This positioning of the load lock shutters 80c, 80d between the filtered arc source and the plasma guide 46 can also be implemented in the single-filtered arc plasma source embodiments, for example the embodiment of Figure 8b, either in addition to or instead of the load lock shutters 80a, 80b shown between the plasma duct 46 and the coating chamber 42.
  • a load lock shutter 8Oe can also be positioned between any cathode 12 and its adjacent deflecting electrode 50 in a filtered arc source, to block cathodic evaporate from reaching the deflecting electrode 50 and provide an extremely clean electron flow with virtually no metal vapor dispersion into the plasma duct 46. This can be important in processes such as semiconductor applications, where even a very low metal vapor component can contaminate the substrates 4.
  • Rastering through the chain of proximal-medial-distal anodes in these embodiments allows for the opportunity to sustain the arc between anodes in different stages of the apparatus, which cleans the plasma flow in each stage and draws electrons into the next stage for a maximized plasma immersed environment. It is also possible to provide different metal target in the opposed cathodes 12 of a single filtered arc source, to allow the deposit composite coatings.
  • the evaporation surface of one cathode 12 can be titanium and the evaporation surface of the other cathode 12 can be aluminum, and with the introduction of gaseous nitrogen can produce a composite TiAlN coating.
  • the cathodes 12 of different cathode pairs can be composed of different materials. Accordingly, by selectively deactivating the deflecting coils 20 and focusing coil 21 on one side of the apparatus (and optionally opening and closing the load lock shutters 80a, 80b) it is possible to apply two different types of coatings to the substrates 4, each in a plasma immersed environment.
  • Figures 8b and 8c illustrate a still further variation of this embodiment, in which the distal auxiliary anodes 70 also serve as anodes for magnetron arc plasma sources 90 disposed within the coating chamber 42, optionally surrounded by focusing/steering coils 92.
  • a dense plasma can be generated within the coating chamber 42 by the combination of plasma streams from the cathodes 12 and plasma streams from the magnetrons 90.
  • the magnetrons 90 may be maintained at a high negative potential by grounding the positive pole of the magnetron power source, as illustrated in Figure 8b, or may be provided with a separate power source 94 as illustrated in Figure 8c.
  • the magnetrons 90 may constitute the primary source of cathodic material, and the cathodes 12 can serve as electron emitters, in the manner previously described, by deactivating the deflecting coils 20 and focusing coil 21 and optionally providing load lock shutters (not shown) between the plasma duct 46 and the coating chamber 42.
  • the main disadvantage of magnetron sputtering is a relatively low ionization degree (1 to 3%) and, as a result, a low ion bombardment rate of the substrate 4 to be coated. That leads to poor structure and low adherence of coatings.
  • the productivity of this process is proportional to the concentration of sputtering gas ions (usually Ar + ions), which have a high sputter rate and also cause sputtering of the substrates 4.
  • US Patent 5,160,595 to Hauzer proposes an arc/magnetron coating deposition method in which an edge magnet arrangement is displaceable in the axial direction relative to a preferably fixedly mounted center pole permanent magnet.
  • a cathode sputtering process and/or cathodic arc evaporation process can be achieved depending upon the relative position of the edge magnet arrangement and the center pole magnet.
  • both the low voltage power supply supporting the arc mode and the high voltage power supply supporting the magnetron mode are enabled, to create discharge between negative charged target and positive charged anode.
  • the arc mode is used only for the ion cleaning stage of process.
  • the principal disadvantages of this process is the presence of microparticles of the cathode material in the vapor stream in an arc mode, and a relatively low ionization of sputtered target atoms in the magnetron mode.
  • Figures 8b and 8c overcome these disadvantages by providing a filtered arc plasma immersed magnetron apparatus having a separate cathodes 12 installed in the filtered arc source and magnetron cathodes 90 installed in the coating chamber 42 off of the optical axis of the arc cathodes 12.
  • the distal auxiliary anodes 70 can be installed anywhere in the coating chamber 42, but preferably are disposed in the vicinity of the magnetron sources 90, surrounding the magnetron targets.
  • the distal auxiliary anodes 70 in this configuration thus also serve as arc/magnetron anodes, which are common to both the cathodic arc plasma source 12 (as a distal auxiliary anode 70) and as a magnetron anode for the magnetron source 90 to thereby create both arc-discharge and magnetron-discharge simultaneously.
  • This "arc enhancement magnetron discharge” which is essentially the magnetron discharge immersed in highly ionized filtered arc plasma environment, provides the best features of both types of discharges: a high rate of ionization through the arc discharge process and high rate of target atomization through the magnetron sputtering process.
  • Figure 8d illustrate a still further variation of the embodiment of Figures 8b and 8c, in which one of the distal auxiliary anodes 70a (the bottom one) also serves as a crucible for evaporation metals 71 having low or moderate melting points, optionally surrounded by focusing/steering coils 92.
  • a dense plasma can be generated within the coating chamber 42 by the combination of plasma streams from the cathodes 12 and plasma stream from the resistive evaporation hot anode-crucible (REHA) arc plasma source 75, heated by the anode arc current and regular resistance heaters 101.
  • the shield 110 may be maintained around the crucible 70a to restrict the anode-evaporating zone.
  • the internal part of the sidewall of the REHA's crucible can be made of insulating ceramic as of alumina or boron nitride (not shown). Concentrating the auxiliary anodic arc plasma on the surface of evaporating metal results in increase of ionization rate of metal vapor plasma, generated by the REHA arc plasma source 70a.
  • the cathodes 12 can serve as electron emitters, in the manner previously described, by deactivating the deflecting coils 20 and focusing coil 21 and optionally providing load lock shutters (not shown) between the plasma duct 46 and the coating chamber 42. Alternatively, the cathodes 12 can supply additional filtered arc plasma stream to merge with metal vapor plasma stream coming from the REHA-crucible 70a.
  • the REHA- metal vapor plasma source 75 is installed inside of the plasma duct 46 of the dual cathode filtered arc source in the area where the deflecting magnetic field is smallest, which is the central area of the deflecting magnetic field cusp.
  • the metal vapor will be partially ionized by interaction with anode arc plasma and propagates toward the substrate to be coated along magnetic field lines of the deflecting magnetic field. Diffusion losses of metal vapor plasma are well suppressed by the convex magnetic field of the deflecting magnetic cusp.
  • an electron beam evaporator is used instead of a resistance heater to evaporate metal from the anode- crucible 70a.
  • the electron beam 125 generated by thermoionic cathode 130 is turned on to 270 degrees by a magnetic field transversal to the plane of Figure 8f. This is important in this embodiment of the invention, to keep the electron beam in the vicinity of the centre of the deflecting magnetic field cusp, where intensity of the deflecting magnetic field is negligible and does not influence the trajectory of electron beam 125.
  • This device optionally provides a compensating magnetic coil 140, surrounding the electron beam evaporator, to correct the trajectory of the electron beam 125 to ensure that it strikes the evaporating metal in the crucible.
  • the crucible in the electron beam evaporator can be maintained at cathode potential while the surrounding shield can serve as a local proximal anode, as is illustrated in Figure 8g.
  • E-Beam Heated Evaporation Cathode E-Beam Heated Evaporation Cathode
  • the ionization rate of metal vapor can reach 90 to 100% by creating a diffused cathodic arc spot in the place where the electron beam impact evaporates metal in the crucible-cathode.
  • the resistive evaporator having a REHA-crucible with evaporating metal, is placed below the centre of the deflecting magnetic cusp on a side of the cusp opposite to the main chamber containing the substrates to be coated.
  • part of the plasma stream generated by cathodes 12 is focused toward the crucible, which allows for an increased ionization rate of metal vapor up to 90%.
  • a resistive evaporator 75 is placed in the centre of a carousel-type substrate holder in the main chamber.
  • the distance between the crucible 70a with evaporating metal 71 and the surrounding substrates to be coated can be minimal, which is especially advantageous for evaporating precision metals (Au, Pt, Pd, etc.).
  • the crucible 70a can be maintained at floating potential or optionally connected to the positive pole of the auxiliary anode power supply (not shown), which makes it a resistive evaporating hot anode (REHA) device.
  • REHA resistive evaporating hot anode
  • Figures 8k and 1 illustrate a still further variation of the embodiments of Figures 8a, 8b, 8c and 8d, in which e-beam evaporators 170a, magnetrons 190 and a resistance evaporator 170b are placed in a substrate chamber 10 for plasma immersion co- deposition of different materials in highly ionized filtered arc plasma environment.
  • e-beam evaporators are installed near a wall of the substrate chamber 10 either opposite or adjacent to the exit opening 14a of the cathode chamber 14 containing the filtered arc source comprising cathodes 12.
  • the focusing and deflecting magnetic fields of the filtered arc source will not affect the position of the electron beam, or consequently the position of the evaporating spot on the surface of the material to be evaporated in the e-beam evaporator crucible 70a.
  • Positioning e-beam evaporators 170a as well as thermal resistance evaporators 75 in front of the auxiliary anode 70 increases the ionization of metal vapor generated by the metal vapor sources.
  • any crucible 170a connected to the positive pole of the arc power supply 19 has to be shielded so that only the evaporated material area is exposed to the arc plasma environment.
  • the magnetrons 190 also can be installed both adjacent to or opposite to the exit flange 14a of the filtered arc source in cathode chamber 14, in the line of sight of the substrates 4. In both cases the filtered arc plasma stream will cross the magnetron targets providing maximum efficiency of ionization and activation of magnetron sputtering flow.
  • the preferable type of magnetron sputtering source used in this embodiment of the invention is an unbalanced magnetron, which can be coupled with the exit focusing coil 21 of the magnetic deflecting system of the filtered arc source.
  • the total gas pressure ranges between 1 and 10 "2 Pa, preferably between 5XlO "1 and 5x10 "2 Pa.
  • the filtered arc source can operate in a co-deposition mode providing a fully ionized metal vapor plasma flow in conjunction with magnetron sputtering deposition.
  • a plasma immersion deposition mode the deflecting magnetic field of the filtered arc source is turned off and an auxiliary arc discharge is established between one or both cathode targets of the primary cathodic arc sources 12 of the filtered arc source and auxiliary anodes 70 disposed in the substrate chamber 10. This allows for increased ionization and activation of both the gaseous and metal atoms components of the magnetron sputtering flow.
  • the total gas pressure ranges between 1 and 10 "4 Pa.
  • the total residual gas pressure can be set at a value below 10 "3 Pa, while in case of reactive evaporation the reactive gas pressure can range between 5x10 " ' and 5x10 "3 Pa.
  • the opposite cathode chamber 14" (shown at the bottom of the figures) can contain the cathode 12 of primary direct cathodic arc source or gaseous plasma source like hollow cathode or thermoionic cathode.
  • the crucible of the metal vapor source 75 can be connected to the positive or negative pole of the arc power supply 19 so that it functions as a distributed arc plasma source in a Filtered E-Beam Heated Evaporated Anode (FEBHEA) mode or Filtered E-Beam Heated Evaporated Cathode (FEBHEC) mode. That provides an ionized anodic arc or cathodic arc metal vapor flow which can be bent or deflected in a curvilinear magnetic field generated about the filtered arc source by deflecting magnetic coils 20, outside the cusp of upstream focusing coils 220b, and subsequently focused by downstream focusing coils 220a toward substrate chamber 10.
  • FEBHEA Filtered E-Beam Heated Evaporated Anode
  • FEBHEC Filtered E-Beam Heated Evaporated Cathode
  • two focusing magnetic coils 21 are disposed on both sides of the bottom primary evaporation source chamber 14 of the filtered arc source.
  • the evaporation material has to be placed in the vicinity of the plane of symmetry between two focusing coils 21. If evaporation source used in this embodiment is electron beam source the electron beam position should be restricted to the area of the magnetic field cusp of the focusing coils 21, where the intensity of the focusing magnetic field is near zero.
  • Two additional side coils 41 can be optionally used for correction the position of the electron beam when deflecting coils of the filtered arc source are activated.
  • a sputter deposition plasma source such as a magnetron can also be installed in a cathode chamber 75 instead of the primary cathodic arc source or metal vapor source with heated evaporated electrode.
  • a sputtering gas such as argon has to be added to gaseous plasma environment for sputtering the magnetron target.
  • the sputtering gas is preferably injected into the chamber in the vicinity of magnetron target.
  • the preferable type of magnetron sputtering source used in this embodiment of the invention is an unbalanced magnetron, which can be coupled with the focusing coils of the primary plasma source of the filtered arc source.
  • the ionized metal vapor stream created by metal vapor source 75 flows along magnetic lines of the focusing magnetic field created by focusing coils 21 toward entrance of the plasma duct 16.
  • the focusing magnetic field created by the coils 21 is overlapped by the deflecting magnetic field of the deflecting coils 20.
  • the metal vapor plasma will be turned along magnetic field lines of the deflecting magnetic coils 20 toward the substrate chamber 10.
  • the electrostatic field created between deflecting electrode 30 and grounded walls of the plasma duct 16 (and further between the repelling electrode 60 and a focusing electrode 23 if provided, not shown in Figures 8m or 8n), will focus the metal ion plasma flow toward substrates 4 to be coated.
  • the optional opposite plasma flow created by the primary plasma source 12 contained in the opposite cathode chamber 14" of the filtered arc source will merge with bottom metal vapor plasma at the exit of the plasma duct 16 in front of the substrate platform 2 in the substrate chamber 10, downstream of the repelling electrode 60.
  • a sputter gas such as argon is injected in the vicinity of magnetron target to a partial pressure typically ranging from 5XlO "4 to 5xlO "3 Torr.
  • the DC or AC voltage is applied to the magnetron target to start sputtering of the target material.
  • the sputter flux will be partially ionized by the magnetron and/or cathodic arc plasma, and trapped by the focusing and deflecting magnetic fields of the plasma duct. Diffusion of ionized metal vapor or sputter metal- gaseous plasma in the direction transversal to the magnetic force lines in a plasma guide is given by
  • D diffusion coefficient of metal vapor or sputter plasma in the absence of a magnetic field
  • n is a parameter ranging from 1 to 2. This equation shows that diffusion flow of metal vapor or sputter plasma in the plasma duct along the magnetic force lines exceeds the diffusion flux in the direction transversal to the magnetic force lines (i.e. toward the walls of the plasma duct) by a factor of B n . This can be used for estimating the effectiveness of transporting of metal vapor or sputter plasma along the curvilinear magnetic field created by the focusing and deflecting magnetic coils 21 of the filtered arc plasma duct.
  • the vacuum pumping system (not shown) is in communication with the interior of the apparatus behind the deflecting electrode 50.
  • a "getter pump” effect is achieved by the constant bombardment of the deflecting electrode 50 with ions such as titanium and zirconium.
  • the deflecting electrode 50 in this embodiment acts as a "vacuum arc plasma trap" which both increases the pumping speed and diverts metal ions from the plasma flow toward the coating chamber 42.
  • This effect can be enhanced by applying a negative or floating potential to a shroud 52 surrounding the deflecting electrode 50, which provides a negative potential in the vicinity of the deflecting electrode that more readily attracts ions and thus increases ion bombardment of the shroud 52, which thus acts as a gettering surface.
  • the shroud 52 is formed from a stainless steel mesh with large openings (e.g. one to three centimeters), and the surface area of the mesh can be maximized (to maximize ion attraction) by providing conductive ribs or plates extending orthogonally relative to the deflecting electrode plate 50a.
  • the deflecting electrode 50 in this embodiment should be regularly removed and cleaned of contaminants and accumulated debris.
  • This embodiment provides the additional advantage of reducing backstreaming of diffusion pump oil vapours, represented by undulating arrows in Figure 9, into the apparatus 40. Oil molecules tend to initially adhere to the deflecting electrode 50 and are quickly trapped by a coating of metal film that forms on the deflecting electrode 50 through ion bombardment.
  • FIGs 4 to 7 illustrate a multiple cathode-pair embodiment of the invention utilizing a conventional vacuum pumping system 8.
  • a plurality of pairs of cathode chambers 44 are disposed in stacked relation on either side of a long vertical plasma duct 46.
  • the stack of cathode chamber pairs on each side of the plasma duct 46 is hinged to the apparatus to allow access to the plasma duct and the coating chamber 42.
  • linear deflecting and focusing conductors 20a, 21 allows the plasma duct to be of virtually unlimited length.
  • a plurality of positively biased repelling electrodes 60 are disposed axially along the plasma duct 46.
  • the apparatus of Figures 4 to 7 operates as described above in relation to the dual cathode embodiment of Figure 3b, driving the plasma flow through a common plasma duct 46 toward a common coating chamber 42.
  • isolating coils 58 are disposed about the interior of the plasma duct 46.
  • isolating coils 58 are isolated from the plasma flow, preferably by a water cooling enclosure and shielded by medial auxiliary anodes 67, and divide the plasma duct into magnetically isolated sections or "cells".
  • the isolating coils 58 can be rastered in sequence in opposite directions (boustrophedonically) to render the plasma stream more uniform as it traverses the plasma duct 46.
  • Figure 12 illustrates coating thickness as a function of distance from the top of the apparatus in an alternating vertical scanning embodiment of the invention.
  • Figures 4 to 7 thus permits a common plasma duct 46 to be of virtually unlimited length, since the isolating coils create separate cells within which the plasma is uniformly distributed, and can be rastered to assist in driving the plasma flow through the elongated plasma duct 46 to the coating chamber 42.
  • the plasma jet is driven through the plasma guide 46 with a helical rotation, the direction of rotation being determined by the direction of the magnetic fields generated by the deflecting coils 20 and focusing coils 21 (and steering and focusing coils of the cathodic arc sources).
  • the helical rotation of the plasma jet causes ions to impact the substrates 4 at an angle, creating an "ion shadow" on the substrates.
  • Periodically changing the direction of all deflecting and focusing magnetic fields in the plasma duct 46 (as well as steering and focusing coils of the cathodic arc sources) similarly changes the direction of helical rotation of the plasma flow, and by allowing ions to bombard the substrates from different angles thus generates a more uniform coating structure, particularly in multi-layer coatings.
  • Figure 5b illustrates a variant of this embodiment in which impulse cathodic arc sources 22 are provided, to allowing for rastering or scanning of the cathodic arc sources 22 in conjunction with the isolating coils 58 during the coating process.
  • impulse cathodic arc sources 22 When the impulse cathodic arc sources 22 are energized, plasma jets are generated in bursts along magnetic field lines created by the deflecting magnetic coils 20 and a rastering system established by scanning the isolating coils 58.
  • These magnetic coils 20, 58 combine to create a magnetic field "wave" which guides the plasma jets toward the coating chamber 42.
  • each impulse By rastering the magnetic fields in conjunction with impulsing of the cathodic arc sources 22, each impulse provides a burst of metal plasma to a different location along the substrates 4.
  • the rastering cycle for the impulse cathodes 22 should be much shorter, for example 10 times shorter, than the scanning cycle for the isolating coils 58.
  • Figure 5c illustrates a still further variation of the embodiment of Figure 5b, in which impulse lasers 360 have been used to ignite impulse vacuum arc discharge on the surface of cathode target 12.
  • the energy accumulated in the capacitors 321 will be released and transformed into kinetic energy of the ablation plasma jet 346 created by interaction of the impulse laser beam 361 with the surface of cathode target 12.
  • the resulting target material plasma stream will be deflected in the curvilinear magnetic field of the filtered arc plasma duct 44, containing the deflecting anode 350 (grounded) with baffles 350a followed by interaction with repelling anode 60 which results in the formation of an ion plasma stream toward substrates 4 to be coated.
  • a non-conductive material like silicon or boron or alumina can be used as a cathode target 12.
  • the power supply 26a can be installed between the repelling anode 60 (positive pole) and ground (negative pole).
  • the filtered arc source can be any kind of plasma source, including hollow cathode plasma sources, and magnetoplasmadynamic accelerators providing a supersonic plasma jet throughout the apparatus.
  • impulse cathodic arc sources, and any other plasma jet sources in order for the plasma jet to retain its integrity the directed kinetic energy of the ion component of the plasma must exceed the chaotic average kinetic energy of the electron component of the plasma (i.e. the electron temperature), which can be described as Ei » K* T e in which E; is the directed kinetic energy of the ion component in electron volts, T e is the chaotic average kinetic energy of the electron component, and K is Bolzmann's constant.
  • the ion component will tend to diffuse into the plasma rather than flow in a directed plasma stream.
  • the chaotic kinetic energy of the electron component is in the order of 1 to 5 electron volts, while the ion component has a much smaller chaotic kinetic energy.
  • the directed kinetic energy of the ion component of the plasma is typically in the order of 20 to 200 electron volts.
  • Another vapor plasma source having an average kinetic energy of emitted atomic particles (evaporating or sputtering atoms/ions) which does not exceed three times the chaotic average kinetic energy of the electron component of the plasma (Ei, a ⁇ 3 ⁇ * T e ) can be installed elsewhere in main chamber 42 or in the plasma duct 46 in a position optically in sight of the substrate holder 2.
  • This source can be a magnetron sputtering plasma source, resistive evaporating plasma source and/or electron beam evaporating plasma source.
  • Figure 12 shows an embodiment of the invention utilizing filtered arc sources with an additional filtration stage.
  • the cathodes 12 are disposed in cathode chambers 44 in communication with filtered plasma ducts 47 which are oriented substantially perpendicular to the optical axes of the cathodes 12, and which in turn are oriented substantially perpendicular to the main plasma duct 46.
  • a repelling electrode 60 is provided in the main plasma duct 46, and deflecting electrodes 50 are positioned along the axis of the plasma duct 46 and at the corners of the filtered plasma ducts 47 opposite the cathodes.
  • Additional medial auxiliary anodes 49 may be provided near the junction of the filtered plasma ducts 47 and the main plasma duct 46, to repel plasma from the apparatus walls.
  • Deflecting conductors 20 are disposed, as in the previous embodiments, so that the magnetic cusps generated thereby follow the plasma path from the cathodes 12 to the substrate holder 2.
  • This embodiment by orienting the main plasma duct 46 off of the axes of the filtered plasma ducts 47, provides the advantage of an additional filtration stage which can be useful in semiconductor and optical applications, where a particularly clean plasma is required.
  • Example 1 Filtered Arc Plasma Immersed Ion Cleaning
  • the arc coating apparatus shown in Figure 3b was used in this process.
  • the apparatus was equipped with two dual-filtered arc sources, having round cathodes 12 measuring 3" in diameter and 2" in height, one filtered arc source having titanium targets and the other having chromium targets.
  • the exit opening of the filtered arc sources was equipped with load lock shutters 80a, 80b, electron-permeable to provide a free passage of electron current from the cathode targets 12 to distal auxiliary anodes 70 to thereby establish an auxiliary arc discharge.
  • Augmented by the auxiliary arc discharge the ionization and activation of the gaseous component of the plasma environment in the coating chamber 42 was significantly increased (up to 30 to 40% in comparison with approximately 1 to 3% gas ionization rate without the auxiliary arc discharge).
  • Both load lock shutters 80a, 80b were locked and cathodic arc sources 12 were activated in at least one filtered arc source, preferably that with the titanium targets.
  • the deflecting magnetic system was not activated.
  • the auxiliary arc discharge was activated between the cathodes 12 of the filtered arc source and the distal auxiliary anodes 70 installed in the coating chamber 42.
  • the total auxiliary discharge current was established at 80 amps.
  • the RF bias power supply was activated and a self-bias potential was established at 600 volts.
  • the ion cleaning stage was performed for 10 minutes.
  • Example 2 Ion Nitriding and Ion Implantation in the Auxiliary Arc Discharge
  • the apparatus and substrate coupons 4 of Example 1 were used in this process.
  • the gas mixture was changed to nitrogen as an ion nitriding gas, injected to create a total pressure ranging from 2 x 10 "4 to 8 x 10 "4 Torr.
  • the substrates 4 were preliminary heated to 300°C to 450 0 C using conventional heaters (not shown) installed in front of the distal auxiliary anodes 70 in the coating chamber 42.
  • a self-bias voltage was established at a range from 100 to 400 volts.
  • the current applied to distal auxiliary anodes 70 was set at 100 amps and the ion nitriding stage was performed for 1 hour.
  • the substrate temperature was set to a lower level, about 150 to 300 0 C, and the bias voltage ranged from 200 to 3000 volts.
  • the ion implantation stage was performed for 1 hour.
  • the ion nitriding and ion implanted layers were characterized by structure, thickness, microhardness depth profile, and surface roughness. It was found that ion nitriding in this process provided a greater roughness of the substrate surface in comparison to ion implantation, while the rate of nitriding was up to one order of magnitude greater than the rate of ion implantation.
  • the rate of ion nitriding for HSS steel had reached up to 1 ⁇ m/hr in comparison with 0.08 to 0.12 ⁇ m/hr for low energy ion implantation with the same 600 volt self-bias on the substrates 4.
  • Example 3 Auxiliary Arc Plasma Immersed Deposition of Chromium Nitride Filtered Arc PVD Coating
  • the apparatus of Figure 3b was equipped with the same cathode targets 12 as in Example 1.
  • the same substrate coupons 4 as in Example 1 were installed on the rotary satellites of substrate holder 2 with single rotation and preheated to 400 0 C by conventional heaters installed in the coating chamber 42.
  • the lock load shutter 80b of the filtered arc source with the chromium cathode targets 12 was opened and the gas was changed to pure nitrogen with total pressure of 2 x 10 ⁇ to 3 x 10 "4 Torr.
  • the deflecting and focusing magnetic coils 13, 20 of the filtered arc source magnetic systems were activated to deflect the chromium plasma stream toward substrates.
  • the total current of the deflecting anode 50 was established at 50 amps, and the total current of the repelling anode was established at 40 amps.
  • the current between chromium cathodes 12 and distal auxiliary anodes 70 was established at 30 amps.
  • the apparatus of Figure 3b was equipped with the same cathode targets 12 as in Example 1.
  • the substrate coupons 4 were made from stainless steel as bars with a 1" width, V2" thickness and 14" length.
  • the substrates 4 were installed on the rotary satellite positions of substrate platform 2, with double rotation.
  • the substrates 4 were preheated to 400 0 C before the deposition stage commenced.
  • a TiN coating was deposited from the filtered arc source having titanium cathode targets 12, while the other filtered arc source with chromium cathode targets 12 was inactive.
  • the current applied to the deflecting anode 50 was established at 60 amps
  • the current applied to the repelling anode 60 was established at 30 amps
  • the current between the titanium cathodes 12 and the distal auxiliary anodes 70 was established at 30 amps to support and auxiliary arc-assisted filtered arc deposition process.
  • the vertical magnetic field created by scanning isolating coils 58 shown in Figures 5 to 7 was directed upward.
  • the vertical magnetic field created by scanning isolating coils 58 was directed downward.
  • the isolating coils 58 were activated in a periodically repeatable pulse mode with the magnetic field vector directed upward for .55 min and, in turn, the magnetic field vector directed downward for .45 min. Scanning the isolating coils 58 in this fashion allowed up to a 90% uniformity of coating thickness over the large area coating zone (14" in this example).
  • the neutral phase atoms, clusters and macroparticles
  • indexable carbide inserts installed on the rotary satellites of the substrate platform 2 with single rotation, were used as substrate coupons 4.
  • the process parameters were established as in Example 2, but in this case the gas mixture was provided as nitrogen + methane + titanium tetrachloride (TiCl 4 ) with total pressure of about 5XlO "4 Torr.
  • TiCl 4 nitrogen + methane + titanium tetrachloride
  • a bi-polar impulse bias voltage with an impulse frequency of 250 kHz and a negative voltage of up to 600 volts was applied to the substrates 4 during this process.
  • the highly activated gaseous plasma environment resulted in a deposition rate for the TiCN coating of up to 3 ⁇ m/hr in this low pressure plasma immersed CVD process.
  • the apparatus of Figure 5b was equipped with impulse cathodic arc sources 12 having cylindrical targets made from pyrolitical graphite.
  • Indexable carbide inserts as substrate coupons 4 were installed on the satellites of substrate platform 2 with single rotation at a rotational speed of 12 r.p.m.
  • the apparatus was evacuated to 5xlO '6 Torr and DC bias voltage from DC bias power supply 29b was set to 1000 volts.
  • the deflecting coils 13 and focusing coils 20 of the filtered arc sources were activated.
  • Deflecting anode 50 was connected to the positive pole of DC power supply 29a while a negative pole was grounded.
  • the repelling anode 60 was connected to another DC power supply 26a in the same manner.
  • the isolating coils 58 were activated to provide vertical scanning with a periodic change in the direction of the vertical magnetic field vector from up to down, with a repetition frequency of 0.5 Hz. All impulse cathodic arc sources 12 were activated with a pulse discharge repetition frequency of 10 Hz.
  • the bias voltage of the substrates 4 was established at to 1000 volts to provide a sublayer between the carbide substrate surface and DLC film, while during deposition the substrate bias was reduced to 100 volts.
  • the rate of deposition of DLC over a 12" high and 20" diameter coating zone reached l ⁇ m/hr.
  • the nanohardness of DLC created in this process reached up to 65Gpa.
  • Example 6 the apparatus of Example 6 was used.
  • the impulse cathodic arc sources 12 were equipped with titanium targets as central electrodes. All other parameters of the process were set up as in Example 6, but the DC bias on the substrates 4 was established at 3000 volts. In this case the duration of the coating process was 2 hours, resulting in titanium implantation of the H13 steel coupons with depth about 1 ⁇ m.
  • Example 8 Large Area Plasma Immersed Hybrid Filtered Arc/Magnetron TiCrN/CrN Multi-layer Coatings
  • substrate coupons 4 were l A"x 1 A" indexable carbide (WC-6%Co) inserts, installed on the satellite positions of the substrate platform 2 with double rotation and vertically distributed evenly over a 14" vertical deposition zone.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figure 8c.
  • Two titanium cathode targets 12 were installed on the dual-arc filtered arc source, while both magnetron sources 90 were provided with chromium targets.
  • the substrates 4 were preheated to 400 0 C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and a Ti coating was deposited from the dual arc filtered arc source for a duration of 3 minutes.
  • Pure argon as a plasma-creating gas was injected in the vicinity of the magnetron targets 90 to a total operating pressure 2 x 10 "4 to 4 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the Ti sublayer was held at 600 V, providing extensive ion bombardment of the substrates 4 before the deposition of the main layers.
  • the total current of the auxiliary arc discharge (between the titanium cathodes 12 of the filtered arc source and the distal auxiliary anodes 70 surrounding the magnetron cathodes 90) was set at 100 amps.
  • Example 9 Large Area Filtered Arc Plasma Immersion Ion Vapor Deposition of Corrosion Resistant Platinum Coating for Fuel Cell Plates *
  • the coating chamber 4 layout used for this experiment is shown schematically in Figure 8d.
  • Two titanium cathode targets 12 were installed on the dual-arc filtered arc source, while a crucible 70a in a form of DC heated tungsten foil boat was provided with 150 mg of 99.95% pure platinum.
  • the substrates endplates were preheated to 300 degrees C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and a Ti coating was deposited from the dual arc filtered arc source for a duration of 1 hour.
  • Pure argon as a plasma-creating gas was injected into the main chamber 42 to a total operating pressure of 2 x 10 "4 to 4 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the Ti interlayer was held at -60 V, providing extensive ion bombardment of the substrates before the deposition of the main layers.
  • the total current of the auxiliary arc discharge (between the titanium cathodes 12 of the filtered arc source and the distal auxiliary anode 70) was set at 100 amps.
  • the tungsten boat was heated by DC resistant heating to 1800 degrees C for evaporating platinum.
  • the deflecting magnetic system was deactivated and platinum coating was deposited over an interval of 2 hours.
  • the result was a highly adhesive platinum corrosive resistant coating having 20 nm thickness, providing stable operation of the endplates in a highly corrosive PEMFC environment.
  • the distribution of electrical resistivity over the surface of the endplates was measured by a 4-points probe, showing a uniformity of surface electrical resistance at +/- 5% over the surface of PEMFC endplates. This distribution was not changed after exposing the endplates to a PEMFC water environment over 350 hrs.
  • Example 10 Large Area Filtered Arc Plasma Immersion Ion Vapor Deposition of Corrosion Resistant Platinum Coating having Me/MeN Buffer Multilayer Intermidiate Coating for Fuel Cell Plates
  • substrate proton exchange membrane fuel cell (PEMFC) endplates 6" in diameter were made of aluminum by a stamping process followed by 75 ⁇ m phosphorus nickel electroplating coatings.
  • the plates to be coated were installed on the satellite positions of the substrate platform 2 with double rotation and horizontally distributed evenly over a 14" long deposition zone.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figure 8i.
  • Different pairs of cathode targets 12 were installed on the opposite primary cathodic arc sources of the dual-arc filtered arc source, as is shown in Table 1, while the crucible 70a in a form of DC heated tungsten foil boat was provided with 150 mg of 99.95% pure platinum.
  • the substrate endplates were preheated to 300 degrees C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and a TiN/ZrN superlattice coating was deposited from the dual arc filtered arc source for a duration of 3 hrs to achieve coating thickness of about 3 ⁇ m.
  • Pure nitrogen as a plasma-creating gas was injected into the main chamber 42 to a total operating pressure of 2 x 10 "4 to 4 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the TiN/ZrN interlayer was held at -40 V, providing extensive ion bombardment of the substrates before the deposition of the main layers.
  • the total current of the auxiliary arc discharge between the titanium and zirconium cathodes 12 of the filtered arc source and the distal auxiliary anodes 70 and REHA-crucible 70a was set at 100 amps.
  • Example 11 Large Area Filtered Arc Plasma Immersion Ion Vapor Deposition of Corrosion Resistant Platinum Coating with TiN/ZrN Superlattice Buffer Interlayer for Fuel Cell Plates
  • substrate proton exchange membrane fuel cell (PEMFC) endplates 6" in diameter were made of aluminum by a stamping process followed by 70 ⁇ m phosphorus nickel electroplating coatings.
  • the plates to be coated were installed on the satellite positions of the substrate platform 2 with double rotation and horizontally distributed evenly over a 14" long deposition zone.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figure 8i.
  • One zirconium and one titanium cathode target 12 was installed opposite the primary cathodic arc sources of the dual-arc filtered arc source, while the crucible 70a in a form of DC heated tungsten foil boat was provided with 150 mg of 99.95% pure platinum.
  • the substrate endplates were preheated to 300 degrees C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and a TiN/ZrN superlattice coating was deposited from the dual arc filtered arc source for a duration of 3 hours to achieve a coating thickness of about 3 ⁇ m .
  • Pure nitrogen as a plasma-creating gas was injected into the main chamber 42 to a total operating pressure of 2 x 10 "4 to 4 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the TiN/ZrN interlayer was held at -40 V, providing extensive ion bombardment of the substrates before the deposition of the main layers.
  • the total current of the auxiliary arc discharge between the titanium and zirconium cathodes 12 of the filtered arc source and the distal auxiliary anodes 70 and REHA-crucible 70a was set at 100 amps.
  • Example 12 Large Area Filtered Arc Plasma Immersion Ion Vapor Deposition of Corrosion Resistant Palladium Coating for Fuel Cell Plates
  • substrate PEMFC endplates 6" in diameter made of titanium were installed on the satellite positions of the substrate platform 2 with double rotation and horizontally distributed evenly over a 14" long deposition zone.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figure 8e.
  • Two titanium cathode targets 12 were installed on the dual-arc filtered arc source, while the crucible 70a in a form of an indirect resistance heated alumina crucible was provided with 300 mg of 99.95% pure palladium.
  • the substrate endplates were preheated to 300 degrees C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and a Ti coating was deposited from the dual arc filtered arc source for a duration of 1 hour.
  • Pure argon as a plasma-creating gas was injected in the main chamber 42 to a total operating pressure of 2 x 10 "4 to 4 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the Ti interlayer was held at -40 V, providing extensive ion bombardment of the substrates before the deposition of the main layers.
  • the total current of the auxiliary arc discharge (between the titanium cathodes 12 of the filtered arc source and the distal auxiliary anode 70) was set at 100 amps.
  • the crucible was heated by DC resistant heating to 1600 degrees C for evaporating palladium.
  • the deflecting magnetic system was deactivated and a platinum coating was deposited over an interval of 1 hour.
  • the result was highly adhesive palladium corrosive resistant coating having 60 nm thickness, providing stable operation of the endplates in a highly corrosive proton exchange membrane fuel cell environment.
  • the distribution of electrical resistivity over the surface of the endplates was measured by 4-points probe, showing a uniformity of the surface electrical resistance at +/- 2% over the surface of the PEMFC endplates. This distribution was not changed after exposing the endplates to a PEMFC water environment over 350 hours.
  • Example 13 Large Area Filtered Arc Plasma Immersion Ion Vapor Deposition of Corrosion Resistant Coating for Fasteners
  • the substrates were fasteners such as nuts and washers made of austenitic stainless steel.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figure 8h.
  • the substrates were installed on the satellite positions of the substrate platform 2 with double rotation and horizontally distributed evenly over a 14" long deposition zone.
  • Two molybdenum cathode targets 12 were installed on the dual-arc filtered arc source, while the crucible 70a in a form of a resistance heated graphite crucible was provided with 100 g of 99.9% aluminum.
  • the substrates fasteners were preheated to 300 degrees C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and an Mo interlayer coating was deposited from the dual arc filtered arc source for a duration of 10 minutes.
  • Pure argon as a plasma-creating gas was injected into the main chamber 42 to a total operating pressure of 2 x 10 "4 to 4 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the Mo interlayer was held at -200 V, providing extensive ion bombardment of the substrates before the deposition of the main layer.
  • the total current of the auxiliary arc discharge (between the Mo cathodes 12 of the filtered arc source and the distal auxiliary anode 70) was set at 100 amps.
  • Example 14 Large Area Filtered Arc Plasma Immersion E-Beam Deposition of cubic Boron Nitride coatings.
  • sample substrates were indexable carbide inserts of the same size as in Example 8.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figure 8h.
  • the substrates were installed on the substrate platform 2 and horizontally distributed evenly over a 14" long deposition zone.
  • Two cathode targets 12 made of boron carbide (B 4 C) were installed on the dual-arc filtered arc source, while the crucible of the electron-beam evaporator was provided with 50 g of 99.95% pure compacted boron powder.
  • the substrate inserts were preheated to 300 degrees C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and a boron carbide interlayer coating was deposited from the dual arc filtered arc source for a duration of 20 minutes.
  • Pure argon as a plasma-creating gas was injected into the main chamber 42 to a total operating pressure ranging from 2 x 10 ⁇ to 4 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the boron carbide interlayer was held at -40 V, providing extensive ion bombardment of the substrates before the deposition of the main layer.
  • the total current of the auxiliary arc discharge (between the boron carbide cathodes 12 of the filtered arc source and the distal auxiliary anode 70) was set at 120 amps.
  • the argon was replaced by nitrogen as reactive gas to deposit the following boron carbo-nitride BCN interlayer coating over 20 minutes.
  • the electron-beam gun was activated to start boron evaporation.
  • the boron vapor plasma stream was merged with the boron-carbon filtered arc plasma stream for deposition BCN coating with excess boron concentration over 10 minutes.
  • the deflecting magnetic system of the filtered arc source was deactivated and a boron nitride coating was deposited during an interval of 30 minutes from boron vapor plasma created by the electron beam evaporation of boron in a highly ionized auxiliary arc plasma created between the cathodes of the filtered arc source and distal anode 70.
  • the result was highly adhesive boron nitride coating consisting of more than 80% of a cubic BN phase, as measured by IR absorption spectroscopy.
  • Example 15 Large Area Filtered Arc Plasma Source Ion Deposition of Interfacial Coating for Thermal Barrier Coating System
  • Thermal barrier coatings are currently used to protect engine components from thermal stress.
  • an oxidation-resistant bond coat is often employed.
  • Bond coats are typically in the form of overlay coatings such as MCrAlX (where M is iron, cobalt and/or nickel, and X is yttrium or another rare earth element), or diffusion aluminide coatings.
  • MCrAlX where M is iron, cobalt and/or nickel, and X is yttrium or another rare earth element
  • diffusion aluminide coatings is a notable example of a diffusion aluminide bond coat contains platinum aluminide (Ni(Pt)Al) intermetallic.
  • Contemporary TBCs comprise a complex multi-layer metal-ceramic architecture.
  • the basic architecture of TBC typically consists of a MeCrAlY overlay or aluminide Ni(Pt)Al intermetallic bond coat following by a thick yttria stabilized zirconia (YSZ) base ceramic thermal insulation layer.
  • the temperature on the surface of the TBC can reach up to 1600 0 C, decreasing to the level of 1100-1200 0 C in the bond-coating layer.
  • the critical area which determines the longevity of the TBC and consequently the durability of the blades and vanes, is the boundary between the inte ⁇ netallic bond coating and top thermal insulation ceramic layer.
  • Multi-layer and functionally graded coating architecture is known as an effective way to increase the probability of micro-cracks being arrested in a coating and preventing crack propagation toward the substrate.
  • Multi-layer and nano-structured coatings demonstrate improved crack resistance and allow control of the thermal and intrinsic stresses in coatings.
  • Incorporating a stable oxide interlayer in a bond coating allow further reduction of the inter-diffusion in the bondcoat-to-alumina interface and subsequently reduce the rate of thermally grown oxide scale that causes thermal fatigue of the coated articles.
  • Multi-layer structure of transition bond coating/alumina zone as well as modified ⁇ - alumina scale can reduce the rate of TGO in a high temperature oxidized environment.
  • the modified ⁇ -alumina layer can be encapsulated by 5 to 10 ⁇ m thick YSZ/alumina nano-structured multi-layer coating which can be deposited on top of the alumina scale by filtered arc plasma immersion e- beam evaporation of YSZ.
  • the composite coating reduces heat transfer to the substrate, thereby reducing deformation-related cracking of the coating. It also minimizes grain growth during high-temperature deposition and exposure.
  • the anticipated coating architecture is shown in Figure 13. It consists of multi-layer MeCrAlY/alumina bondcoat-to- ⁇ -alumina interface, optionally doped with platinum (5- lO ⁇ m), modified fine grain ⁇ -alumina interlayer 0.5-1.5 ⁇ m thick optionally doped with yttria, zirconia or chromia followed by alumina-to-topcoat interface (5-10 ⁇ m) having nano-structured multi-layer alumiria/zirconia, or alumina/YSZ architecture.
  • the operating pressure range for different plasma processing technologies is represented in Figure 14.
  • filtered vacuum arc plasma can operate over a wide pressure range, from about 5 mTorr to about 10 ⁇ 6 Torr, overlapping most vacuum PVD processes.
  • This system is equipped with two large area dual filtered arc sources, two unbalanced magnetrons (25 kW ea.), two e-beam evaporators (6 kW ea.) and DC thermal resistance evaporation source. It has a rotatable substrate holder assembly 2 connected to a DC pulse bias power supply.
  • the substrate chamber 10 is also equipped with optical emission plasma diagnostic equipment, which allows the operator to monitor in situ the intensity of optical emission radiation of atomic particles during the coating deposition process.
  • a spectral-optical thickness monitor enables in situ measurement of EB-PVD dielectric coating thickness.
  • This system is also equipped with electrostatic Langmuer probes and ion collector probes to measure distribution of plasma ion current density in the highly ionized filtered arc immersion plasma environment. Position of electron beams of E- beam evaporators is monitored by miniature video cameras.
  • a foil or thin sheet metal specimen made of NiCrAlY alloy was used to characterize deposition rate and coating thickness uniformity.
  • Substrate temperature during deposition of an ⁇ -alumina interlayer ranged from 900 0 C to 1200 0 C.
  • the built-in substrate heater is employed incorporated into the rotating substrate holder platform 2 and connected to the heater power supply by powerful sliding contacts having protect shields against short circuits in the metal vapor plasma environment ( Figures 8k and 81).
  • the substrate foil strip specimen 4, or coupon was installed on the rotating substrate holder 2, which was connected to both the bias power supply and to the DC current power supply for direct current resistance heating of the foil.
  • the powerful high current feeds through the graphite/copper-based sliding electrical contacts.
  • the arc enhanced unbalanced magnetron sputtering of NiCrAlY in co-deposition mode with aluminum filtered arc plasma deposition was used.
  • the argon operating pressure during magnetron deposition was set at 1 mTorr.
  • a filtered arc source was used to generate the flow of 100% ionized aluminum plasma coinciding with magnetron sputtering.
  • a small dope of silica was provided by an Al/6%Si target of the filtered arc source.
  • the cycle of depositing the NiCrAlY sub-layer was followed by depositing an ultra-thin alumina layer by the filtered arc source with aluminum targets operating in oxygen-reactive gaseous plasma environment with operating oxygen pressure 0.2-0.4mTorr.
  • the magnetron source was turned off during deposition of the alumina interlayers.
  • the time of deposition of the NiCrAlY sub-layers was 10' while for the alumina interlayers it was 2'.
  • the thermal resistance evaporation of platinum as a dope to alumina was used continuously in conjunction with a magnetron/filtered arc coating deposition process.
  • Deposition of about 5 ⁇ m thick multi-layer NiCrAlY/alumina segment layer was followed by deposition of 1.5 ⁇ m ⁇ -alumina diffusion barrier interlayer coating.
  • Co- deposition of ⁇ -alumina by evaporation of carborundum by E-beam evaporator was used as a seed (template) dope to enhance formation of the ⁇ phase in polycrystalline alumina layer.
  • the ⁇ -alumina interlayer was encapsulated by alumina/zirconia multi-layer top coating segment by using co-deposition of alternative layers of alumina and zirconia by E-beam evaporators with alumina and zirconia evaporation material in conjunction with filtered arc deposition of alumina in an oxygen-reactive atmosphere.
  • Oxygen pressure during filtered arc immersion E-beam evaporation of oxide coatings was set at 0.1-0.2 mTorr.
  • the structure and morphology of the interfacial coating were examined by SEM as well as metallurgical micro-cross-sectional analysis.
  • the resulting interfacial multi-layer coating appeared to be uniform, pin-hole free and stable in an oxidizing atmosphere up to 1200degC.
  • Example 15 Deposition of DLC coating by FEBHEA.
  • the apparatus of Figure 8n was used for deposition carbon DLC coatings by Filtered E-Beam Heated Evaporated Anode (FEBHEA).
  • Pyrolitical graphite as an evaporating material (HEA target) was placed in a crucible of the FEBHEA plasma source 75.
  • Indexable carbide inserts as substrate coupons 4 were installed on the platform 2 with single rotation at a rotational speed of 12 r.p.m.
  • the apparatus was evacuated to 5xlO '6 Torr.
  • the deflecting coils 20 and focusing coils 21 of the filtered arc sources were activated.
  • Deflecting anode 50 was connected to the positive pole of a DC power supply while a negative pole was connected to the thermoionic cathode 12.
  • the repelling anode 60 was connected to another DC power supply in the same manner.
  • the focusing coils 21 were activated to establish a magnetic cusp surrounding the E-Beam evaporator 75, such that the electron beam from the electron beam evaporator was positioned in the area where the magnitude of the focusing magnetic field approached 0.
  • the anodic arc current between the thermoionic cathode 12 and HEA crucible 75 was set at 240 amperes.
  • a 13.56 MHz/5kW RF generator with matching network was used as a bias power supply (not shown in the Figure 8n) for a DLC coating deposition process.
  • the autopolarization bias voltage of the substrates 4 was established at 1000 volts to provide a sublayer between the carbide substrate surface and the DLC film, while during deposition the substrate bias was reduced to 100 volts.
  • the residual gas pressure during DLC deposition was held at 0.01 mTorr.
  • the rate of deposition of DLC over a 6" high and 20" diameter coating zone reached 0.5 ⁇ m/hr.
  • the micro-hardness of DLC created in this process reached up to 35Gpa.
  • EXAMPLE 16 High Temperature Conductive CrNZCrAl(Si)N Nano-structured Multilayer Coating with Lanthanum Chromate Top Layer for Solid Oxide Fuel Cell (SOFO Interconnect Plates.
  • the substrate simulating the SOFC interconnect plates was a thin sheet strip specimen 4cm x Ism x 0.025cm in size made of 304 Stainless Steel having surface roughness R a ⁇ 20 nm.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figures 8k and 1.
  • the substrate thin sheet strip specimen, or coupon was installed on the rotating substrate holder by single rotation fixture, to which was connected the bias power supply (as shown in Figures 8k and 1).
  • the substrate was heated by conventional radiation heaters installed in the coating chamber 4.
  • One chromium target and one aluminum/6%Si cathode target 12 were installed opposite to each other in the primary cathodic arc sources of the dual-arc filtered arc source, while the resistance evaporation metal vapor source in a form of DC heated tungsten foil boat (having alumina coating to reduce chemical interaction with evaporating material)) was provided with 100 mg of 99.95% pure lanthanum.
  • the substrate was preheated to 400 degrees C before the deposition stage commenced.
  • the deflecting magnetic system 13 of the filtered arc source was activated and a CrN/Al(Si)N nano-structured multilayer coating was deposited from the dual arc filtered arc source for a duration of 3 hours to achieve a coating thickness of about 2um .
  • Pure nitrogen as a plasma-creating gas was injected into the main chamber 42 to a total operating pressure of 4 x 10 "4 to 6 x 10 "4 Torr.
  • the substrate bias voltage during deposition of the CrN/ Al(Si)N coating was held at -60 V, providing extensive ion bombardment of the substrates before the deposition of the main layers.
  • the total current of the auxiliary arc discharge between the chromium and aluminum cathodes of the filtered arc source and the distal auxiliary anode was set at 100 amps.
  • the rotation speed of the substrate platform was set at 10 rpm.
  • the nano-structured CrN/CrAl(Si)N multi-layer coating consists of CrN interlayers alternating with superlattice CrAl(Si)N layers. Each of the CrN interlayers was deposited by evaporating chromium cathode target for 20 seconds while the aluminum target was switched off. Each of the CrAl(Si)N superlattice interlayers was deposited by co-evaporating Cr and Al/6%Si targets for 10 sec.
  • the 360 segments of nano-structured multilayer CrN/CrAl(Si)N cermet coating consisting of CrN interlayers having thickness of about 3 nm followed by CrAl(Si)N interlayers having a thickness of about 2 nm, were deposited to total thickness of about 1.8 ⁇ m.
  • the resistance heating evaporator was activated to evaporate the lanthanum.
  • the primary cathodic arc source with aluminum target was switched off and nitrogen was changed on oxygen as reactive gas creating a conditions for coinciding deposition of lanthanum chromate upper layer.
  • the substrate simulating the SOFC interconnect plates was a thin sheet strip specimen 4cm x Ism x 0.025cm in size made of 430 Stainless Steel having a surface roughness R a ⁇ 20 nm.
  • the coating chamber 4 layout used for this experiment is shown schematically in Figures 8k and 1.
  • the substrate thin sheet strip specimen, or coupon was installed on the rotating substrate holder by single rotation fixture, to which was connected the bias power supply (as shown in Figures 8k and 1).
  • the substrate was heated by conventional radiation heaters installed in the coating chamber 4.
  • Co (99.95% purity) targets were installed in the primary cathodic arc sources of the dual-arc filtered arc source No.2, while the resistance evaporation metal vapor source in the form of a DC heated tungsten foil boat (having alumina coating to reduce chemical interaction with evaporating material) was provided with 100 mg of 99.95% pure MnO 2 .
  • the substrate was preheated to 400° C before the deposition stage commenced.
  • the bi-polar pulsed DC bias power supply was utilized in this deposition process.
  • the switching arrangement is shown in Figure 15b.
  • the primary voltage source used in this setup had an adjustable voltage ranging from 50 to 1200 volts.
  • the current source used in this setup had a maximum current up to 340 amperes.
  • the repetition frequency was 50 kHz with a 20% duty cycle (20 ⁇ s duration of bi-period with 4 ⁇ s positive high current bias followed by 16 ⁇ s of the negative bias voltage portion of bi-polar DC pulse bi- period).
  • the deflecting magnetic system 13 of the filtered arc source No.l was activated and a CoCrAlYO/AlO bottom nano-structured bond layer coating was deposited from the dual arc filtered arc source No.l for a duration of 1.5 hours to achieve a coating thickness of about 1 ⁇ m .
  • Pure oxygen as a plasma-creating gas was injected into the main chamber 42 to a total operating pressure of 4 x 10 "4 to 6 x 10 "4 Torr.
  • the negative portion of the bi-polar pulsed DC bias voltage during deposition of the CoCrAlYO/AlO coating was held at -60 V.
  • the total current of the auxiliary arc discharge between the CoCrAlY and aluminum cathodes of the filtered arc source No.l and the distal auxiliary anode was set at 150 amps.
  • the rotation speed of the substrate platform was set at 6 rpm.
  • a nano-structured CoCrAlYO/ AlO bond coating consisting of CoCrAlYO interlayers alternating with AlO layers was deposited consisting of 500 bi-layers having thickness of about 2 nm each, to a total thickness of the bottom bond coating segment of about 1 ⁇ m.
  • the resistance heating evaporator was activated to evaporate the MnO 2 .
  • filtered arc source No.l was turned off and filtered arc source No.2 with Co cathodic targets was turned on.
  • the highly adhesive (Mn,Co)3O4 spinel top segment coating with thickness approximately 2.5 ⁇ m was deposited on a top of the CoCrAlYO/AlO bottom bond coating segment.

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Abstract

L'appareil selon l'invention pour l'application de revêtement dans le vide comprenant une conduite de plasma entourée d'un système de déflexion magnétique communicant avec une première source de plasma et une chambre de revêtement dans laquelle un support de substrat est disposé hors de l'axe optique de la source de plasma, comporte au moins une électrode de déflexion montée sur une paroi ou plus de la conduite de plasma. Dans certains modes de réalisation, une alimentation en énergie à impulsions bipolaires en courant continu comportant des bornes d'entrée et de sortie et un circuit de commutation commute alternativement une direction du courant appliquée au support de substrat, pour empêcher la formation de micro-arcs sur la surface du substrat.
PCT/US2005/031478 2005-09-01 2005-09-01 Procédé de dépôt en phase vapeur à plasma et appareil utilisant une commande polarisée bipolaire WO2007089216A1 (fr)

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