EP2165003A1 - Procédé de pvd et dispositif de pvd pour produire des couches fonctionnelles à faible frottement, résistant à l'usure et revêtements ainsi produits - Google Patents

Procédé de pvd et dispositif de pvd pour produire des couches fonctionnelles à faible frottement, résistant à l'usure et revêtements ainsi produits

Info

Publication number
EP2165003A1
EP2165003A1 EP08773386A EP08773386A EP2165003A1 EP 2165003 A1 EP2165003 A1 EP 2165003A1 EP 08773386 A EP08773386 A EP 08773386A EP 08773386 A EP08773386 A EP 08773386A EP 2165003 A1 EP2165003 A1 EP 2165003A1
Authority
EP
European Patent Office
Prior art keywords
magnetron
cathodes
target
cathode
hipims
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08773386A
Other languages
German (de)
English (en)
Inventor
Wolf-Dieter Münz
Stefan Kunkel
Thorsten Zufrass
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Systec System- und Anlagentechnik & Co KG GmbH
Original Assignee
Systec System- und Anlagentechnik & Co KG GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Systec System- und Anlagentechnik & Co KG GmbH filed Critical Systec System- und Anlagentechnik & Co KG GmbH
Publication of EP2165003A1 publication Critical patent/EP2165003A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the 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
    • C23C14/06—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
    • C23C14/0635—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
    • H01J37/3405—Magnetron sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3464—Operating strategies
    • H01J37/3467—Pulsed operation, e.g. HIPIMS

Definitions

  • PVD method and PVD device for producing low-friction, wear-resistant functional layers and coatings produced therewith
  • These layers are characterized by a comparably low coefficient of friction compared to metals and ceramics in the range of 0.1 to 0.2.
  • the two types of coatings differ significantly in their hardness properties and, consequently, also in the wear behavior.
  • Typical hardness values HU plast of W, Nb, or Ti-DLC layers are 15 GPa, while hardness values of 30 to 60 GPa (about 50% of the diamond hardness) are reported for C-DLC layers in the specialist literature.
  • the resistance of C-DLC coatings to abrasive wear is typically lower by a factor of 3 to 4 than that of Me-DLC coatings. This is obviously in the layer structure, as Raman analyzes suggest, but also in the hydrogen content of the two types of layers.
  • Me-DLC layers are usually deposited at a high reactive gas content, for example, an acetylene content of about 50% in proportion to the proportion of the inert gas argon, while in C-DLC layers, the reactive gas content is relatively low in the range of 5 to 20%. For this reason, the hydrogen content of Me-DLC layers is 20 to 25%, while in C-DLC layers a hydrogen content of 10% is observed.
  • Another major difference in the layer properties lies in the inherent compressive stresses of the two types of layers. While compressive stresses in the range of -1 GPa are known for W-DLC layers, those of C-DLC layers can reach values of up to -5 GPa, depending on the layer hardness. This results in considerable problems regarding the adhesive strength of such layers and with increasing layer thickness.
  • the layer thicknesses of C-DLC layers are typically limited to only a few tenths of a micron, and most often only as a "super hard" topcoat of Me-DLC layers in industrial applications.
  • multilayer interlayers have been developed. which contribute to reducing the compressive stress gradient between the substrate and the layer in order to increase the effective layer adhesion (Influence of different interlayers and bias voltage on the properties of aC: H and aC: H: Me coatings prepared by reactive dc magnetron sputtering; , K. Bewilogua, H. Thomsen, R. Wittorf, Surface and Coatings Technology, 201 (2006) 1576-1582), however, this process substantially increases the cost of the manufacturing process of sufficiently thick C-DLC layers.
  • the present invention relates to a particularly economical PVD method and a PVD device for producing particularly adherent, low-friction wear-resistant W-DLC and C-DLC layers with layer hardness HU plast of 40 to 60 GPa, in particular also in C-DLC layers thicknesses made of more than 0.5 microns.
  • the method provides the prerequisite that both types of layers, ie the W-DLC layers widely used in industry and the newer C-DLC layers optionally without target change with sufficient layer thickness with only one intermediate layer, namely tungsten carbide (WC), can be produced in one and the same coating system.
  • WC tungsten carbide
  • PVD processes for the production of microcrystalline or nanocrystalline layers which have a hardness of about 50% of the diamond hardness, ie of about 50 GPa are known (industrial scale manufactured superlattice hard PVD coatings, WD Münz, DB Lewis, PE Hovsepian, C. Schönjahn, A. Ehiasarian, IJ Smith, Surface Engineering, 2001, vol 17 (1), pp. 15-27).
  • Such, also referred to as "super hard” functional layers are deposited on steel, ceramic, carbide or electroplated precoated materials. Due in part to the different coefficients of thermal expansion of the substrate and functional layer, the superhard coatings generally have high internal compressive stresses of sometimes more than -7 GPa.
  • the compressive stress at the substrate / layer transition is reduced by arranging one or more transition layers of different materials with a gradually decreasing or increasing thermal expansion coefficient between the substrate and the superhard functional layer.
  • This "gradation" of the thermal expansion coefficients and the concomitant increase in the adhesive strength succeeds the better, the more transition layers are interposed.
  • one or more additional cathodes is required in each case. Therefore, PVD systems for multi-layer systems are considerably more expensive and more expensive than PVD systems for single layers.
  • the productivity or throughput of PVD systems scales approximately inversely proportionally with the thickness of the overall coating or with the number of layers to be deposited. Accordingly, the achievement of high adhesion by means of multi-layer systems is very costly and limited to specialty products.
  • metal ion pretreatment was developed in conjunction with cathodic arc discharge coating (Handbook of Vacuum Are Science and Technology, by Raymond L. Boxman, Sanders David and Philip J. Martin, (1996), Noyes ISBN 0-8155-1375-5).
  • cathodic arc discharge a plasma with high density of mono- to poly-charged metal ions is formed (IG Brown, F. Feinberg and JE Galvin, J. Appl. Phys. 63 (1988) p 4889).
  • ABS TM EP 0 404 973 A1; Microstructures Of TiN Films Grown By Various Physical Vapor Deposition Techniques, G. Hakansson, L. Hultman, JE Sundgren, JE Greene, WD Münz Surface & Coatings Technology, 1991, Vol.48, No.1, pp.51-67; A New Concept For Physical Vapor Deposition Coating Combining the Method of Arc Evaporation and Unbalanced Magnetron Sputtering WD Münz, F. Hauzer, D. Schulze, B.
  • EP 1 260 603 A2 discloses a PVD process for coating substrates, in which - analogously to the ABS TM process - the substrate is pretreated in the plasma of a high-power pulse magnetron cathode sputtering (HIPIMS).
  • HIPIMS cathode is used, which can be equipped with different metallic targets.
  • Cr or Ti targets are used.
  • Nb or Ta targets are used.
  • Ionized physical vapor deposition (IPVD) is then generated in the HIPIMS plasma: Helmersson, M. Lattemann, J.
  • Bohlmark AP Ehiasarian, JT Gudmundsson, Thin Solid Films , 513 (2006) 1-24) which, after acceleration to about 1200 V, trigger the substrate-cleaning etching process and an adhesion-enhancing ion implantation (AP Ehiasarian, W.-D. Münz, L. Hultman, U. Helmersson, and I. Petrov, Surf Coat, Technol. 267 (2003) 163-164).
  • further coating takes place e.g. by means of UBM cathode sputtering.
  • UBM cathode sputtering For the pretreatment and the coating preferably identical cathodes and identical magnetic field arrangements are used.
  • the object of the present invention is to provide super hard and adherent carbon coatings (eg HU p ⁇ ast to 50 GPa) and a simple and inexpensive method and apparatus for their manufacture.
  • this object is achieved by using no metallic target for the adhesion-enhancing ion implantation of the substrate surface, but a target which consists of the same material as the intermediate or transition layer between substrate and functional layer.
  • a target which consists of the same material as the intermediate or transition layer between substrate and functional layer.
  • the substrate bias bias
  • Due to the selection of WC as implantation and transition layer material it is advantageous to firmly deposit both the superhard C-DLC and the less hard W-DLC with the unbalanced magnetron on the same layer substructure.
  • the invention accordingly provides a method for depositing low-friction, wear-resistant and adherent, carbon-containing PVD layers on substrates, comprising the steps:
  • Ionized physical vapor deposition IPVD: A review of Helmersson, M. Lattemann, J. Bohlmark, AP Ehiasarian, JT Gudmundsson, Thin Solid Films, 513 (2006) 1-24);
  • MS-WC tungsten carbide
  • highly ionized tungsten carbide sputtering or "IS-WC” encompasses those sputtering or evaporation processes in which a WC target solid state target is converted to a plasma in which more than 10% of the tungsten and carbon atoms, respectively at least single and up to three times positively ionized (eg W 1+ , W 2+ , W 3+ , C 1+ ).
  • Suitable atomization methods include evaporation by means of cathodic arc discharge and high-power impulse sputtering (HIPIMS).
  • step (a) the pretreatment of the substrate surface by high-power pulse magnetron cathode sputtering of tungsten carbide (HIPIMS-WC) is carried out, wherein the electrical pulse power density at the (n) HIPIMS cathode ( n) 1000 to 3000 W em "2 , the pulse duration is 50 to 300 ⁇ s and the pulse interval 0.5 to 500 ms and the substrates a bias voltage of -500 to -1500 V is applied.
  • HIPIMS-WC high-power pulse magnetron cathode sputtering of tungsten carbide
  • Another object of the invention is a PVD device with one or two HIPIMS cathodes with tungsten carbide (WC) target and three or four magnetron cathodes with graphite target (C-target) or tungsten carbide target (WC target ). Further expedient embodiments of the PVD device according to the invention can be found in claims 14 to 19.
  • the invention relates to a layer system in which a substrate with a multilayer, according to claims 1 to 12 by means of highly ionized sputtering of tungsten carbide (IS-WC) and magnetron sputtering of graphite (MS-C) or tungsten carbide (MS-WC) generated Coating, comprising: an implantation layer (61) produced by means of IS-WC;
  • MS magnetron sputtering
  • UBM balanced or unbalanced magnetron
  • the power density of individual pulses is more than 1000 W em "2.
  • the duty factor ie the ratio of pulse duration to In the HIPIMS mode, load factors in the range of less than 0.02 are used in accordance with the invention.
  • the substrates used according to the invention consist of steel, hard metal, ceramic or plastic.
  • the surfaces of the substrates may have a galvanic coating.
  • FIG. 1 is a schematic plan view of a PVD device according to the invention with a HIPIMS and three magnetron cathodes;
  • FIG. 2 is a schematic plan view of a PVD device according to the invention with one HIPIMS and four magnetron cathodes;
  • FIG. 3 shows a schematic plan view of a PVD device according to the invention with two HIPIMS and four magnetron cathodes;
  • FIG. 4 shows a schematic section through a PVD device according to the invention
  • 6a-b show the time profile of the bias voltage of the substrates and the power density of the magnetron cathodes
  • Fig. 1 shows a PVD device 1 according to the invention with a vacuum chamber 2, a HIPIMS cathode 20 and three magnetron cathodes 30, 31, 32.
  • the HIPIMS cathode 20 and each of the magnetron cathodes 30, 31, 32 is provided with a Arrangement of permanent magnets 4 equipped, wherein the magnetic polarity of adjacent cathodes is in each case opposite to each other.
  • the HIPIMS cathode 20 and the magnetron cathodes 30, 31, 32 are equipped with Helmholtz coils 17.
  • the magnetic fields generated by the Helmholtz coils 17 have a magnetic field strength of 0 to 4 kArn -1 directly in front of the cathode targets.
  • the Helmholtz coils 17 are operated with the same magnetic polarity as the outer segments of the permanent magnets 4
  • the magnetic field lines 18 of the Helmholtz coils 17 encircle the plasma 19 formed by the cathodic gas discharges, and the magnetron cathodes 30, 31, 32 operate in the unbalance mode (UBM) Mode causes a spatial expansion of the plasma zone of the magnetron cathodes 30, 31, 32nd
  • the PVD coating is carried out in a low pressure atmosphere containing at least one of the gases argon, acetylene, methane or nitrogen.
  • a pump station 8 see Fig. 4
  • the pressure in the vacuum chamber 2 is maintained in the range of 0.5 * 10 -3 to 0.1 mbar.
  • a target 21 of the HIPIMS cathode 20 is made of tungsten carbide (WC). It is preferably a tungsten carbide material that is free of binder.
  • WC tungsten carbide
  • the following material combinations are used for the targets 3 of the magnetron cathodes 30, 31, 32:
  • the material sputtered by the cathode targets spreads vapor into the interior of the PVD device 1 and condenses on the surface to be coated substrates 59.
  • the substrates 59 are mounted on supports 6, which allow the substrates 59 on one in front of the cathodes to lead lying circular path.
  • the carriers 6 rotate about their longitudinal axis, as indicated by the annular arrows 71.
  • the PVD device 1 is equipped with a centrically arranged, water-cooled anode 5.
  • the leakage current which flows in conventional PVD devices to the chamber wall 2
  • the leakage current is directed into the central region of the PVD device 1 according to the invention, where it increases the plasma density.
  • the substrates 59 located between the magnetron cathodes 30, 31, 32 and the anode 5 are enveloped on all sides by a virtually homogeneous plasma 19.
  • the positive ions of the process gas generated in the plasma 19 - primarily argon ions - are accelerated upon application of a negative bias voltage to the substrates 59.
  • This process also referred to as ion bombardment, improves the density and homogeneity of the layers condensed from the cathodic sputtering vapor.
  • the PVD device 1 is equipped with one or more independently movable diaphragm devices 80 made of stainless steel.
  • the aperture devices 80 allow one or more of the cathodes 30, 31, 32, 20 to be separately covered and magnetically shielded.
  • FIG. 2 shows a PVD device 1 according to the invention with a HIPIMS cathode 20 and four magnetron cathodes 30, 31, 32, 33.
  • the HIPIMS cathode 20 is arranged between two magnetron cathodes 31, 32.
  • the further reference numerals According to the invention, an opposite cathode pair (eg 31, 33) with graphite targets and the second cathode pair (eg 30, 32) equipped with tungsten carbide targets.
  • a C-DLC or W-DLC functional layer can optionally be deposited in step (d) of the method according to the invention.
  • the Helmholtz coils 17 of the magnetron cathodes 30, 31, 32, 33 are driven so that a closed magnetic field prevails.
  • the Helmholtz coil of the HIPIMS cathode 20 is switched off.
  • the HIPIMS cathode 20 is covered by a movable diaphragm device 81 made of soft magnetic material, so that the field of its permanent magnet 4 is shielded and not affected by the Helmholtz coils 17 of the four magnetron cathodes 30, 31, 32, 33 generated closed magnetic field.
  • arrows 81 ' symbolize the movement of the diaphragm device 81 from its rest position shown in dashed lines into a shielding position in front of the HIPIMS cathode 20.
  • FIG. 3 shows a PVD device 1 according to the invention with two HIPIMS cathodes 20, 40 and four magnetron cathodes 30, 31, 32, 33. In order to keep a clear view of FIG. 3, the diaphragm devices are not shown. The other reference numerals correspond to those of FIG. 1.
  • FIG. 4 shows a cross section of a PVD device according to the invention.
  • the HIPIMS cathode 20 is connected to a high power electrical pulse generator 10.
  • the high-power pulse generator 10 is designed to generate on the target of the HIPIMS cathode 20 electrical power densities of 1000 to 3000 W em "2 with a pulse duration of 50 to 300 ⁇ s and a pulse interval of 0.5 to 500 ms.
  • the magnetron cathode 30 is connected to a DC power supply 11, which generates, based on the target electric power densities of 5 to 20W em "2 at a discharge voltage of -300 to -800 V at ground potential.
  • DC power supply and pulse current power supply means an electrical current or voltage source a pulse current power supply 12 is provided, which can be switched by means of a switch 13.
  • the other magnetron cathodes 31, 32, not shown in FIG. 4, are each driven in the same way as the magnetron cathode 30 with their own DC and pulse current power supply units which are identical to 11 or 12, respectively.
  • the magnetron cathodes 30, 31, 32 are connected in parallel to a common DC power supply 11 and a common pulse current power supply 12.
  • the substrate carriers 6 are mounted on a turntable 7. Both the turntable 7 and the substrate carrier 6 are made of electrically conductive material.
  • the turntable 7 is connected to a common-mode power supply 14, which allows the substrates 59 to apply a negative bias voltage of up to -1500 V with respect to ground potential.
  • the inventive method comprises three or four consecutive steps (a), (b) and (d) or (a), (b), (c) and (d).
  • the third step (c) is optional and is not carried out according to the invention if the functional layer deposited in step (d) is thinner than 0.5 ⁇ m.
  • step (a) of the method the surface of the substrates 59 is first pretreated by means of HIPIMS.
  • the HIPIMS cathode 20 is operated with an electric power density of 1000 to 3000 W em "2, a pulse duration of 50 to 300 microseconds and a pulse interval of 0.5 to 500 ms.
  • Is applied to the substrates 59 a negative bias voltage of -500 to -1500 V.
  • the high-power pulses generate discharges at the HIPIMS cathode, whereby their target is atomized and the tungsten atoms are multiply ionized in the HIPIMS plasma.
  • tungsten ions with up to three times positive charge (W 3+ ) as well as single positive carbon ions (C 1+ ) are generated (see Fig. 7a).
  • W 3+ positive charge
  • C 1+ single positive carbon ions
  • the HIPIMS discharge takes place virtually over the whole area (or in the area of the conventional racetrack).
  • the one to multiply positively charged tungsten and carbon ions are greatly accelerated in the field of negative substrate potential and fall with high kinetic energy on the substrate surface, which they erode partially (ion etching) and partly penetrate (ion implantation), with an implantation layer 61 is formed, such as it is shown in Figures 5a to 5f.
  • step (b) the operating parameters of the HIPIMS cathode 20 of step (a) are maintained and the negative bias voltage of the substrates 59 is reduced to -30 to -250 V such that the kinetic energy of the tungsten ions is less than that required for ion etching and implantation Value falls and the tungsten ions or atoms condense on the substrate surface.
  • a first transition layer 62 is deposited.
  • step (a) up to three times positively charged tungsten ions (W 3+ ) as well as single positive carbon ions (C 1+ ) are also produced in step (b) in the HIPIMS plasma (see Fig. 7a-b).
  • an optional second transition layer 63 is deposited by means of magnetron sputtering or with simultaneous use of magnetron sputtering and HIPIMS.
  • the magnetron cathodes 30, 32 are each operated with electrical power densities of 5 to 20 W em "2 and discharge voltages of -300 to -600 V.
  • a functional layer 64 is deposited by means of magnetron sputtering, wherein the magnetron cathodes 30, 31, 32, 33 (see FIG. Fig. 2) with electrical power densities of 5 to 20 W em '2 and discharge voltages of -300 to -800 V are operated.
  • the negative bias voltage on the substrate is reduced continuously or stepwise from a value between -1500 and -500 V to a value between -250 and -30 V.
  • the magnetron cathodes are pulsed at a frequency of 50 to 250 kHz in step (d).
  • the electric power density of the magnetron cathodes 31, 32 is increased continuously or stepwise in step (c).
  • the functional layers are deposited in step (d) in a gas mixture of argon and acetylene at a pressure of 10 -3 to 0.1 mbar.
  • the proportion of acetylene is 5 to 20%, based on the proportion of the inert gas argon (ie 5 to 20 parts by volume of acetylene per 100 parts by volume of argon).
  • the magnetron cathodes 31 and 33 equipped with C targets as shown in FIG. 2 are used.
  • the magnetron cathodes 30 and 32 equipped with WC targets according to FIG. 2 are used.
  • the proportion of acetylene is up to 50%, based on the argon content (ie, up to 50 parts by volume of acetylene per 100 parts by volume of argon).
  • FIG. 5a schematically shows a cross section through the surface of a substrate 59 provided with a coating 60 according to the invention.
  • the Coating 60 comprises the implantation layer 61 produced in step (a), the first transition layer 62 deposited in step (b) and the functional layer 64 generated according to step (d).
  • HIPIMS or magnetron sputtering (MS) and the material of Cathode targets - tungsten carbide (WC) or graphite (C) are the layers 61, 62 and 64 shown in Fig. 5a labeled with HIPIMS-WC and MS-WC.
  • FIG. 5 b shows a further substrate 59 coated according to the invention with an implantation layer 61 and a first transitional layer 62 produced by HIPIMS-WC, as well as a functional layer 64 which has been deposited by means of MS-C.
  • Figures 5c and 5d correspond to Figures 5a and 5b, but differ from the latter by the second transition layer 63 added by means of MS-WC.
  • Figures 5e and 5f illustrate two further advantageous embodiments of the coating according to the invention, in which the second transition layer 63 is produced by means of simultaneous HIPIMS and MS deposition.
  • FIG. 6 a schematically illustrates the time profile of the negative bias voltage at the substrate 59 and the electrical power density at the magnetron cathodes in the method according to the invention.
  • the implantation layer 61 is generated at high negative bias voltage by means of HIPIMS-WC.
  • the first transition layer 62 is deposited at a reduced negative bias voltage by means of HIPIMS-WC, while for HIPIMS-WC the operating parameters from step (a) are maintained.
  • the second transition layer 63 is created by means of simultaneous HIPIMS-WC and MS-WC. The operating parameters for HIPIMS-WC from step (a) are retained.
  • the functional layer 64 is deposited by means of MS-C alone.
  • step (d) the magnetron cathodes are operated with WC targets (MS-WC) instead of C targets (MS-C).
  • Fig. 6b shows the time course of the negative bias voltage to the substrate 59 and the electric power density at the magnetron cathodes, with respect to Fig. 6a in step (c) changed course of the electric power density of the magnetron cathodes, which is increased continuously or stepwise and does not have a constant value from the beginning.
  • MS-C is replaced by MS-WC.
  • the inventive method is performed so that the first and second transition layer 62 and 63 each have a thickness of 0.1 to 0.5 microns.
  • the functional layer 64 preferably has a diamond-like atomic structure (DLC or diamond-like carbon) and has a thickness of 0.5 to 5.0 ⁇ m.
  • DLC diamond-like carbon
  • the carbon atoms are covalently bonded in tetrahedral formation with each other, but deviating from diamond, there is no crystalline long-range order.
  • the plastic hardness HU plast (diamond probe with 200 ⁇ m radius) measured according to DIN EN ISO 14577 of the coating 60 according to the invention is greater than 40 GPa, preferably greater than 50 GPa, and particularly preferably up to 60 GPa.
  • the adhesive strength was determined by means of a scratch test in accordance with DIN EN 1071-3.
  • the critical load L C2 of the coating 60 according to the invention is greater than 40 N, preferably greater than 50 N, and particularly preferably greater than 60 N.
  • FIG. 7a shows a comparison of the optical emission spectra of the HIPIMS and MS plasmas of a device according to the invention in the wavelength range of 200 to 250 nm.
  • the radiation emitted by the HIPIMS or MS plasma at a distance of 5 cm parallel to the target surface of the HIPIMS The cathode 20 and the magnetron cathode 30, respectively, were recorded by means of an integrating CCD-equipped optical spectrometer.
  • the HIPIMS cathode was designed with an electrical power density of 2000 W em "2 , a pulse duration of 100 ⁇ s and a pulse interval of 500 ms.
  • the power density at the magnetron cathode was 50 W em "2 a mixture of argon and acetylene in the ratio of 4 was used as process gas.:. 6 * used 10 3 mbar at a pressure of 4.4
  • the intensity of the MS Plasma is multiplied by 10.
  • the emission of the HIPIMS plasma is considerably more intense than that of the MS plasma, which is particularly evident at higher energies or at small wavelengths of 200 to 225 nm. plasma to a considerable extent by singly or doubly positively charged tungsten ions (W 1+, 2+ W). in addition to W and W 1+ 2+ also occur spectral lines of three positive charges Wolframions (W 3 +). the latter is a testament for the high energy density of HIPIMS plasma.
  • Fig. 7b shows the optical emission spectra of the HIPIMS and MS plasma in the wavelength range of 425 to 450 nm.
  • the operating parameters are consistent with those of Fig. 7a.
  • the intensity of the MS plasma was multiplied by 3 for better illustration.
  • emission lines of simply positively charged carbon ions (C 1+ ) and of argon atoms (Ar) are present, which are missing in the spectrum of the MS plasma.
  • FIG. 8 shows the plastic hardness HU plast of a coating 60 produced according to the invention as a function of the proportion of acetylene in a process gas composed of acetylene and argon.
  • a C-DLC functional layer 64 was deposited by means of magnetron sputtering of graphite (MS-C) on a simple transition layer 62 produced by means of high-power pulse magnetron cathode sputtering of tungsten carbide (HIPIMS-WC).
  • the magnetron cathode were operated with a power density of 6 W em "2.
  • the supplied argon flow was 400 seem (standard cubic centimeters per minute). Surprisingly, it was at a acetylene flow of about 30 seem, that is, only 7% of acetylene moiety, Achieved a maximum value of hardness of nearly 50 GPa.

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Abstract

L'invention concerne un procédé de PVD (dépôt en physique en phase vapeur) et un dispositif de PVD pour générer des couches de DLC (analogue au diamant) présentant une adhérence supérieure et des substrats revêtus selon le procédé de PVD. Les substrats à revêtir sont prétraités par pulvérisation magnétron pulsée haute puissance (HIPIMS) de carbure de wolfram (WC) et sont dotés d'une couche de transition de WC. Ensuite, une couche de C-DLC ou W-DLC est produite par pulvérisation cathodique magnétron (MS).
EP08773386A 2007-06-20 2008-06-11 Procédé de pvd et dispositif de pvd pour produire des couches fonctionnelles à faible frottement, résistant à l'usure et revêtements ainsi produits Withdrawn EP2165003A1 (fr)

Applications Claiming Priority (3)

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DE102007028813 2007-06-20
DE102007058356A DE102007058356A1 (de) 2007-06-20 2007-12-03 PVD-Verfahren und PVD-Vorrichtung zur Erzeugung von reibungsarmen, verschleißbeständigen Funktionsschichten und damit hergestellte Beschichtungen
PCT/EP2008/004657 WO2008155051A1 (fr) 2007-06-20 2008-06-11 Procédé de pvd et dispositif de pvd pour produire des couches fonctionnelles à faible frottement, résistant à l'usure et revêtements ainsi produits

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