WO2012072225A1 - Pièce pourvue d'un revêtement si-dlc et procédé de fabrication de revêtements - Google Patents

Pièce pourvue d'un revêtement si-dlc et procédé de fabrication de revêtements Download PDF

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Publication number
WO2012072225A1
WO2012072225A1 PCT/EP2011/005956 EP2011005956W WO2012072225A1 WO 2012072225 A1 WO2012072225 A1 WO 2012072225A1 EP 2011005956 W EP2011005956 W EP 2011005956W WO 2012072225 A1 WO2012072225 A1 WO 2012072225A1
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Prior art keywords
dlc
sic
mec
layer
sicx
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PCT/EP2011/005956
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German (de)
English (en)
Inventor
Dieter Hofmann
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Amg Coating Technologies Gmbh
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Publication of WO2012072225A1 publication Critical patent/WO2012072225A1/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
    • C23C14/06—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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0084—Producing gradient compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/046—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with at least one amorphous inorganic material layer, e.g. DLC, a-C:H, a-C:Me, the layer being doped or not
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

  • the layer system comprises a cover layer of substantially diamond-like carbon (DLC) having a hardness of at least 15 GPa and an adhesive strength of 3 HF or better.
  • the layer system comprises an adhesion layer and a transition layer, the adhesion layer and possibly the transition layer containing at least one element of the 4th, 5th or 6th subgroup and / or silicon.
  • the cover layer is preferably produced by means of plasma CVD deposition from a carbon-containing gas, such as acetylene, and has a hydrogen content of 5 to 30 atomic%.
  • EP 87 836 discloses a DLC layer system with a 0, l-49, l% share of metallic components, which is deposited, for example by means of sputtering.
  • DE 43 43 354 AI describes a method for producing a multilayer Ti-admih layer system comprising a hard material layer of titanium nitrides titanium carbides and titanium borides and a friction-reducing C-containing surface layer, wherein the Ti and N content is progressively reduced in the direction of the surface.
  • a pulsed plasma jet uses the method described in US 5,078,848 for the preparation of DLC layers. Due to the directed particle radiation from a source with a small outlet cross-section, however, such processes are only conditionally suitable for the uniform coating of larger areas.
  • EP-A-651 069 describes a friction reducing wear protection system of 2-5000 alternating DLC and Si-DLC layers.
  • a process for the deposition of a-DLC layers with an Si intermediate layer and subsequent a-SiC: H transition zone for improving the adhesion is described in EP 600 533.
  • EP 885 983 and EP 856 592 Various methods for producing such layers are described.
  • EP 885 983 for example, the plasma is fed with a DC-heated filament and the substrates are subjected to negative DC voltage or frequencies between 30 and 1000 kHz.
  • US Pat. No. 4,728,529 describes a method for the deposition of DLC using an HF plasma in which the layer formation takes place in a pressure range between 10 ' and 1 mbar from an oxygen-free hydrocarbon plasma, to which noble gas or hydrogen is added as required.
  • DE-C-195 13 614 uses a bipolar substrate voltage having a shorter positive pulse duration in a pressure range between 50-1000 Pa. This layers are deposited in the range of 10 nm to 10 ⁇ layer thickness and a hardness between 15-40 GPa.
  • a CVD method with substrate voltage generated independently of the coating plasma is described in DE-A-198 26 259, whereby preferably bipolar, but also other periodic changed substrate voltages are applied.
  • Some of the tribological Si-DLC coatings known in the prior art have a high hardness of more than 15 GPa and a sliding friction coefficient ⁇ of less than 0.2.
  • the wear resistance and thus the mileage of the components equipped with the known Si-DLC layers such as gears and shafts for drives, engine components from an internal combustion engine, transmission parts from an automotive transmission, connecting rods, gear parts, gears, shafts, bearings, rolling bearings, Ball bearings, needle roller bearings, piston rings, piston pins, cylinder liners, parts of fuel injection device eg for the direct injection of diesel or gasoline for automotive engines, parts of the valve train of a car engine, bucket tappets, drag levers, rocker arms, valve tappets, linear guides, closures for automobile doors, sliding bushes not always meet the high demands of the automotive and aviation industry.
  • a workpiece comprising a base body, optionally one or more intermediate layers and a top layer containing Si-DLC, wherein the cover layer has a hydrogen content of 5 to 20 atomic%.
  • the top layer has a hydrogen content of 5 to 18 atomic%, preferably 5 to 15 atomic%, and in particular 5 to 10 atomic%;
  • the cover layer has a thickness of 0.4 to 5.0 ⁇ , preferably 0.6 to 3.0 ⁇ , and in particular 0.8 to 2.0 ⁇ ;
  • the top layer has a hardness HU p iast of 15 to 40 GPa, preferably 20 to 40 GPa, and in particular 25 to 40 GPa;
  • the cover layer has a coefficient of friction ⁇ of from 0.05 to 0.20, preferably from 0.05 to 0.15, and in particular from 0.05 to 0.12;
  • the cover layer according to Kalotest with Al 2 0 3 powder in glycerol a coefficient of wear of 0.5 x 10 '15 “ to 3.0 x 10 " 15 m 3 / (Nm), preferably 0.5 x 10 "15 to 2 , 5 x 10 "15 m 3 / (Nm), and in particular 0.5 x 10 " 15 to 1.5 x 10 "15 m 3 / (Nm);
  • the top layer has a measured by Rockwell A test for hard metal bodies or by Rockwell C test for other basic body adhesion HF1 to HF4, preferably HF1 to HF3, and in particular HF1 to HF2; the top layer has an Si content of 5 to 50 atom%, preferably 5 to 30 atom%, and in particular 5 to 25 atom%;
  • the topcoat has a content of from 0.01 to 6.0 atomic% of an additive selected from boron, sulfur and mixtures thereof;
  • the cover layer comprises one or more double layers, alternately layers of Si-DLC and layers of DLC or alternately of layers of Si-DLC and layers
  • Me-DLC with Me-DLC preferably being designed as W-DLC;
  • the cover layer comprises a first layer system with one or more double layers and a second layer system with one or more double layers, wherein the Double layers of the first and second layer systems alternately consist of layers of Si-DLC and layers of DLC, the ratio of the thicknesses of the DLC layers to the Si-DLC layers in the first layer system is greater than or equal to 0.9, preferably greater than 1, 2, and the ratio of the thicknesses of the DLC layers to the Si-DLC layers in the second layer system is less than 0.9, preferably less than 0.8; the alternating layers of Si-DLC and DLC or Me-DLC each have a thickness of 0.1 to 100 nm, preferably 1 to 10 nm, and more preferably 1 to 5 nm; the average silicon content of the cover layer is 5 to 50 atom%, preferably 5 to 30 atom%, and.
  • the workpiece comprises an adhesion layer of Ti, V, Cr, CrN, Zr, Nb, Mo, Hf, Ta, Si or Ni arranged between the cover layer and the base body and adjacent to the base body;
  • the workpiece comprises a first SiCx, MeCx or WCx intermediate layer arranged between the cover layer and the main body or the adhesion layer and adjacent to the main body or to the adhesion layer, and optionally a second DLC mediator layer disposed between the first intermediate layer and the cover layer and adjacent to the first intermediate layer; Si-DLC or Me-DLC, in particular of W-DLC, and in the intermediary layers the following material pairings are present:
  • MeC x Me-DLC where Me-DLC is preferably designed as W-DLC; an arranged between the cover layer and the base body or the adhesive layer and adjacent to the base body or to the adhesion layer first layer system of one or more double layers of silicon carbide (SiC x / WC x), (SiC x / MeC x), (WC x / SiC x) or (MeCx / SiCx) and optionally a second layer system arranged between the cover layer and the first layer system and adjacent to the first layer system, wherein the second layer system comprises a layer or two layers selected from SiC x , (SiC x / DLC), (SiC x / Si-DLC), (SiCx / Me-DLC), in particular (SiC x / W-DLC), or MeCx, (MeC x / DLC), (MeC x / Si-DLC), (MeCx / Me-DLC), in
  • nx (MeC x / SiCx) MeCx Me-DLC where n is an integer greater than or equal to 1 and Me-DLC is preferably carried out as W-DLC and MeCx preferably as WCx; a valve disposed between the cover layer and the base body or the adhesive layer and adjacent to the base body or to the adhesion layer first layer system of one or more bilayers of (SiCx / DLC), (SiC x / Si-DLC), silicon carbide (SiC x / Me-DLC), and in particular (SiC x / W-DLC) or (MeC x / DLC), (MeC x / Si-DLC), (MeCx / Me-DLC), in particular (MeCx / W-DLC) and optionally between the outer layer and the first
  • the second layer system comprises two layers selected from (SiC x / DLC), (SiC x / Si-DLC), (S
  • first layer system second layer system nx SiC x DLC n (SiCx / DLC) SiCx Si-DLC nx (SiCx / DLC) SiCx Me-DLC nx (SiCx / Si-DLC) SiCx DLC nx (SiC x / Si) DLC) SiCx Si-DLC nx (SiC x / Me-DLC) SiCx Si-DLC nx (SiC x / Me-DLC) SiCx DLC nx (SiC x / Si) DLC) SiCx Si-DLC nx (SiC x / Si-DLC) SiCx Me-DLC nx (SiC x / Me-DLC) SiCx DLC nx (SiC x / Me-DLC) SiCx DLC nx (SiC x / Me-DLC) SiCx DLC nx (
  • nx (MeCx / Me-DLC) MeCx Me-DLC where n is an integer greater than or equal to 1 and Me-DLC is preferably designed as W-DLC and MeCx preferably as WCx; a first layer system consisting of (Si-DLC / SiCx), (Si-DLC / MeCx), preferably (Si-DLC / WC), arranged between the cover layer and the main body or the adhesion layer and adjacent to the main body or to the adhesion layer X ) or (Me-DLC / SiC x ), in particular (W-DLC / SiC x ), (Me-DLC / MeC x ), in particular (W-DLC / WCx) or (DLC / SiC x ), (DLC / MeC x ), preferably (DLC / WCx) and optionally a second layer system arranged between the cover layer and the first layer system and adjacent to the first layer system
  • first layer system second layer system (MeC x / DLC), (MeC x / DLC), (SiC x / Si-DLC), (MeC x / Si-DLC), (SiC x / Me-DLC), in particular (SiC x / W-DLC) or (MeCx / Me-DLC), in particular (MeC x / W-DLC) and in the layer systems the following material pairings are present: first layer system second layer system
  • nx (DLC / MeCx) MeCx Me-DLC where n is an integer greater than or equal to 1 and Me-DLC is preferably designed as W-DLC and MeCx preferably as WCx;
  • the workpiece is a layer system consisting of one or more double layers of (Si-DLC / DLC), (Si-DLC / Me-DLC), which is arranged between the cover layer and the main body or the adhesion layer and adjacent to the main body or to the adhesion layer, in particular (Si-DLC / W-DLC) or (DLC / Si-DLC), (DLC / Me-DLC), in particular (DLC / W-DLC) or (Me-DLC / Si-DLC), in particular (W-DLC / Si-DLC ), (Me-DLC / DLC), in particular (W-DLC / DLC) and optionally an intermediate layer of DLC, Si-DLC or Me-DLC, in particular of
  • nx (Me-DLC / DLC) Me-DLC where n is an integer greater than or equal to 1 and Me-DLC is preferably designed as W-DLC;
  • the workpiece comprises a layer of DLC arranged between the cover layer and the binder body and adjacent to the cover layer;
  • the base body is made of a material selected from steel, steel alloys, titanium, titanium alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, copper, copper alloys, ceramic material, hard metal, tungsten, tungsten alloys, tantalum, tantalum alloys, nickel, nickel alloys, silicon, silicon compounds, bronze, Plastic or a mixture of these materials;
  • the workpiece is an engine part of an internal combustion engine, a transmission part of an automotive transmission, a connecting rod, a gear part, a gear, a shaft, a bearing shell, a rolling bearing, a ball bearing, a needle bearing, a piston ring, a piston pin, a cylinder liner, a part a fuel injection device, for example for the direct injection of diesel or gasoline for automotive engines, a part of the valve train of a car engine, a bucket tappet, a rocker arm, a rocker arm, a valve lifter, a Lmear Inserti, a closing door for automobile doors, a sliding bush or a solar cell.
  • Diamond-like carbon or DLC and methods for depositing coatings from DLC by CVD and / or PVD are well known in the art.
  • the carbon atoms are arranged in a three-dimensional irregular lattice with a large portion of the carbon atoms being sp 3 -hybridized and each covalently bonded to four adjacent carbon atoms.
  • SiCx layer materials which have a metallic or carbidic character and in particular predominantly of silicon or silicon carbide (SiC), of a metal selected from Ti, V, Cr , Zr, Nb, Mo, Hf, Ta, Ni or metal carbide (MeC), or consist of tungsten or tungsten carbide (WC).
  • SiC silicon or silicon carbide
  • MeC metal selected from Ti, V, Cr , Zr, Nb, Mo, Hf, Ta, Ni or metal carbide (MeC)
  • WC tungsten or tungsten carbide
  • the layer materials referred to in the present application as "SiCx", “MeCx” and “WCx” generally have a stoichiometry other than pure SiC, MeC or WC, where X is the Is the ratio of the carbon content relative to the silicon, metal or tungsten content and typically in the range 0.1 ⁇ X ⁇ 2.0, ie each 1 atom% of silicon, metal or tungsten contain the layers 0.1 to 2, 0 atom% carbon.
  • Such layers generally consist of a mixture of several phases, for example of SiC, MeC or WC crystallites, which in a matrix of metallic silicon, metal or tungsten (X ⁇ 1) or a matrix of graphitic, sp -hybridized or possibly diamond-like, sp 3 -hybridized carbon (1 ⁇ X ⁇ 2) are embedded.
  • "graded" SiCx, MeCx or WCx layers are additionally provided, in which X, ie the stoichiometric ratio of carbon to silicon, metal or tungsten, is varied by targeted modification of the deposition parameters in such a way that it steadily increases or decreases.
  • SiCx, MeCx or WCx layers with increasing X or carbon content are primarily provided in order to provide a more or less continuous transition to a subsequently deposited covering layer of Si-DLC or DLC or Me-DLC mediator layers , Such graded SiCx, MeCx, or WCx layers reduce thermal mismatch and improve adhesion.
  • Me-DLC designates diamond-like carbon (DLC) layer materials containing up to 40 atomic%, in particular 5 to 15 atomic%, of a metal selected from Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Ni and W, with tungsten being preferred.
  • a metal selected from Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Ni and W, with tungsten being preferred.
  • the coating is characterized on the inventively coated workpieces by a high temperature resistance.
  • the invention has the further object to provide a method for producing workpieces with a coating system of the type described above.
  • an inert consisting of argon, neon, helium, xenon, krypton or a mixture thereof sputtering gas or a mixture of inert gases and acetylene (C2H2) existing sputtering gas is supplied, wherein the ratio of the gas flows of inert Gas to acetylene is from 95: 5 to 50:50;
  • one or more targets of materials selected from Si, SiC, a mixture of Si and SiC, a mixture of graphite and SiC, a mixture of graphite and Si, a mixture of graphite and Si and SiC, W, WC, Ti, TiC, V, VC, Cr, CrC, Zr, ZrC, Nb, NbC, Mo, Mo 2 C, Hf, HfC, Ta, TaC, Ni or NiC be used x;
  • targets which contain a dopant, such as boron or sulfur;
  • gases containing a dopant such as boron or sulfur are used;
  • - uses unbalanced magnetron cathodes and / or to the workpieces to be coated, a bias potential of up to -300 V, preferably from -50 to -200 V, and in particular from -100 to -200 V is applied;
  • the surface of the workpieces is pretreated by means of ion etching.
  • the deposition of the outer layer and the optional mediator layers takes place in an atmosphere comprising an inert gas consisting of argon, neon, helium, xenon, krypton or a mixture thereof and optionally one or more reactive gases, such as acetylene (C 2 H 2 ). , Methane (CH 4 ), nitrogen (N 2 ), silanes (Si m H n ), in particular monosilane (S1H 4 ), organosilanes, in particular tetramethylsilane (C4H 12 Si) and hexamethyldisiloxane (C 6 H 18 OSi 2 ) and organosilazanes.
  • an inert gas consisting of argon, neon, helium, xenon, krypton or a mixture thereof and optionally one or more reactive gases, such as acetylene (C 2 H 2 ).
  • Methane (CH 4 ) nitrogen
  • silanes Si m H n
  • the atmosphere or the plasma in which the deposition of the top layer of Si-DLC takes place has a hydrogen content of nominally less than 30 atomic%.
  • the nominal content of the hydrogen content refers to completely dissociated gas molecules.
  • the nominal hydrogen content is calculated according to the following equation (I):
  • Equation (I) all gas molecules or atoms are considered to be completely dissociated.
  • MFC Massflow Controllers
  • PLC programmable logic controller
  • the gas flow is usually specified in the unit "standard cubic centimeter per minute" (sccm).
  • the actual stoichiometric composition of the atmosphere or plasma in which the deposition occurs differs due to various effects, such as e.g. the gas species dependent pumping power of turbomolecular pumps, the gas-type dependent conductivities of the vacuum piping and valves between the pump (s) and recipient and the incorporation of the gas atoms in the deposited layer of the calculated according to equation (I) nominal value.
  • the nominal value can be precisely controlled by means of MFC and is therefore used to describe the method according to the invention.
  • FIG. 5 is a secondary ion mass spectrum (SIMS) of a coating
  • FIGS. 6a, 6b devices for PVD coating demonstrate.
  • Figure 1 shows a cross section of a workpiece 10 according to the invention with a base body 1 and a Si-DLC-containing cover layer 6, which has a hydrogen content of 5 to 20 atomic%, preferably 5 to 18 atomic%, in particular 5 to 15 atomic%, and more preferably 5 to 10 atomic%.
  • the cover layer 6 has a silicon content of 5 to 50 atom%, preferably 10 to 30 atom%, and in particular 15 to 25 atom%.
  • the cover layer 6 also contains 0.01 to 6.0 atom% of boron and / or sulfur.
  • the content of hydrogen and silicon is determined by the coating method, in particular the choice of the target material of the magnetron cathodes used.
  • the hydrogen content in the cover layer 6 is in the range of 5 to 6 atomic%.
  • argon to acetylene (C 2 H 2 ) in a ratio of 350 sccm to 25 sccm
  • the hydrogen content in the cover layer 6 can be raised to values of up to 20 atom%.
  • one or more magnetron cathodes with targets of silicon (Si), silicon carbide (SiC) and graphite (C) are used. In particular, the following combinations of magnetron cathodes or targets are used:
  • the silicon and hydrogen content of the cover layer 6 are set within the aforementioned limits of 5 to 20 atomic% hydrogen and 5 to 50 atomic% silicon.
  • the Si, SiC and graphite targets contain additives such as boron, aluminum, tungsten, vanadium and / or sulfur, which reduce the coefficient of friction ⁇ of the cover layer 6 and / or increase the electrical conductivity of the Si and SiC targets.
  • the additives contained in the Si, SiC and graphite targets are deposited in the cover layer 6 during sputtering.
  • the cover layer 6 has a content of boron and / or sulfur of 0.01 to 6.0 atom%.
  • the cover layer 6 is 0.4 to 5.0 ⁇ , preferably 0.6 to 3.0 ⁇ , and in particular 0.8 to 2.0 ⁇ thick.
  • the thickness of the cover layer 6 is determined by the product of deposition rate and deposition time or at a variable deposition rate by the time integral of the deposition rate.
  • the deposition rate in turn is a function of several variables, such as number, target size and target material of the magnetron cathodes, sputtering current and the gas mixture used and the geometric arrangement of the parts to be coated and their movement or multiple rotation, etc.
  • zones form in the PVD coating apparatus in front of the respective magnetron cathodes whose content of carbon and silicon atoms differs from one another.
  • a plasma zone is formed, which is essentially free of silicon.
  • a zone in front of a magnetron cathode with SiC target contains both silicon and carbon.
  • the coating zone in front of an Si target then contains both silicon and carbon, so that a Si-DLC layer is deposited on a workpiece 1 located in this coating zone.
  • a volume ratio of argon to acetylene in the sputtering atmosphere of, for example, 350:40 is set by controlling the gas flows introduced via the MFC to 350 sccm of argon and 40 sccm of acetylene.
  • the workpieces to be coated are moved through the coating zones during the coating process by means of a planetary drive within the PVD coating apparatus and preferably by means of a magnetron cathode, which generates a tunnel-like magnetic field and a large-volume plasma in conjunction with electromagnetic field coils Substrate potential caused ion bombardment coated.
  • the workpieces to be coated are mounted on substrate holders.
  • the substrate holders are mounted on a turntable and rotatable about its longitudinal axis.
  • the ratio of the angular velocities C ⁇ S / CO D is a fractionally rational, in particular irrational number, so that the path s (t) is not stationary.
  • each workpiece is once passed through the coating zone in front of each of the magnetron cathodes.
  • a thin layer of Si-DLC or DLC is deposited on the workpiece.
  • the capping layer 6 has a fine structure of alternating layers 6A / 6B / 6A / 6B / ... of Si-DLC and DLC and Me-DLC, respectively, W-DLC ie a fine structure of the form Si-DLC / Me-DLC / Si-DLC / Me-DLC / ...
  • the thickness of the alternating layers 6A and 6B is in the range of 0.1 to 100 nm, preferably 1 to 10 nm, and more preferably 1 to 5 nm.
  • FIG. 2b shows a further embodiment of the invention.
  • a workpiece 11 ' is equipped with a cover layer 6 comprising one or more double layers (6A / 6B) and one or more double layers (6C / 6D).
  • the double layers (6C / 6D) form the upper cover layer and thus the surface of the cover layer 6 or the double layers (6A / 6B) between the double layers (6C / 6D) and the base body 1 are arranged.
  • the double layers (6A / 6B) consist alternately of Si-DLC and DLC and form a layer sequence of the type Si-DLC / DLC / Si-DLC / DLC / ... or DLC / Si-DLC / DLC / Si-DLC /. ..
  • the double layers (6C / 6D) consist alternatively of Si-DLC and DLC and form a layer sequence of the type Si-DLC / DLC / Si-DLC / DLC / ... or DLC / Si-DLC / DLC / Si DLC / ...
  • the double layers (6A 6B) and (6C / 6D) differ from each other by the relative ratio of the thicknesses of the alternating DLC and Si-DLC layers, ie the quotient (layer thickness DLC) / (layer thickness Si-DLC ).
  • the quotient (layer thickness DLC) / (layer thickness Si-DLC) is greater than or equal to 0.9, preferably greater than 1.2.
  • the quotient (layer thickness DLC) / (layer thickness Si-DLC) is smaller than 0.9, preferably smaller than 0.8.
  • the upper part (6C / 6D), which is in contact with a counter-body, of the Cover layer 6 has a very low coefficient of friction and, after local wear of the upper cover layer of the wear-resistant lower part (6A / 6B) reduces the progression of wear.
  • the silicon content of the cover layer 6 is varied by increasing or decreasing the ratio of the electrical powers and thus the deposition rates of the magnetron cathodes with SiC or Si target relative to the magnetron cathodes with graphite target.
  • the composition of the sputtering gas for example the volume ratio (sccm) of acetylene to argon is varied.
  • the coating process is performed so that the silicon content of the cover layer 6 increases in the direction of a surface normal 16 of the base body 1, ie, with increasing distance from the base body 1.
  • Advantageous developments of the invention are shown in Figures 2a, 2b, 3 and 4. Accordingly, an adhesive layer 2 and / or a first and second mediator layer 3, 4 or a first and second layer system 30, 40 and / or a third mediator layer 5 are arranged between the base body 1 and the cover layer 6.
  • the adhesive layer 2 directly adjoins the base body 1 and optionally the cover layer 6.
  • the first intermediate layer 3 or the first layer system 30 directly adjoins the main body 1 or the adhesive layer 2 and possibly the cover layer 6.
  • the second intermediate layer 4 or the second layer system 40 directly adjoins the main body 1, the adhesion layer 2, the first mediator layer 3 or the first layer system 30 and optionally to the cover layer 6.
  • the third mediator layer 5 directly adjoins the cover layer 6 and the base body 1, the adhesion layer 2, the first mediator layer 3, the first layer system 30, the second mediator layer 4 or the second layer system 40.
  • the respective layers or layer systems in the direction of a surface normal 16 of the base body are identified in ascending order by the reference symbols 2, 3 or 30, 4 or 40, 5 and 6.
  • the embodiments shown in FIGS. 2 a, 2 b, 3 and 4 represent only a subset of the 36 possible combinations of the layers or layer systems 2, 3 or 30, 4 or 40 and 5 between the base body 1 and the cover layer 6.
  • the number 36 of the possible combinations results from the following consideration: Layer or layer system possibilities number
  • the first layer system 30 consists of one or more bilayers n (31, 32), where n is an integer greater than or equal to 1.
  • the second layer system 40 comprises one or two layers 41 or 41, 42.
  • the thickness of the layers 3, 31, 32, 4, 41, 42, 5 is in each case 0.1 to 3.0 ⁇ , preferably 0.1 to 0.8 ⁇ , and in particular 0.1 to 0.6 ⁇ .
  • the adhesive layer 2 improves the adhesive strength of the cover layer 6 and / or reduce the thermal mismatch, i. the difference between the coefficients of thermal expansion of the cover layer 6 and the base body. 1
  • the adhesive layer 2, the intermediary layers or layer systems 3, 30, 4, 40 and or 5 have the additional function of providing a supporting support with increased strength for the cover layer 6.
  • an adhesive layer 2 of Ti, V, Cr, CrN, Zr, Nb, Mo, Hf, Ta, Si or Ni on the base body 1 is provided.
  • a magnetron cathode with a target of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Si or Ni is used.
  • An adhesion layer 2 made of CrN is deposited in a nitrogen-containing gas atmosphere, for example a mixture of argon and nitrogen (N 2 ), ie by means of reactive magnetron sputtering.
  • a first intermediate layer 3 or one or more double layers (31, 32), a second intermediate layer 4, 41 or (41, 42) and / or a third intermediate layer 5 made of SiCx, WCx, Si are expediently used.
  • the thickness of the alternating layers 31 and 32 is in each case 0.1 to 3.0 ⁇ , preferably 0.1 to 1.5 ⁇ and in particular 0.1 to 0.6 ⁇ .
  • the bilayers (31, 32) are sequentially deposited by sputtering alternately with selected magnetron cathodes while the remaining magnetron cathodes are switched off low electrical power below the value required for sputtering deposition.
  • the use of shielding screens is provided, which are moved automatically or by means of electronic control and release or cover the target of the respective magnetron cathode. Such shielding screens commonly used in the art allow the magnetron cathodes to be operated at substantially constant power and to stabilize the sputtering parameters.
  • an Si-DLC layer is first produced by means of one or more magnetron cathodes with an SiC target. Following this, the magnetron cathode with SiC target is switched off or switched off and one or more magnetron cathodes with WC target are switched on in order to deposit a W-DLC layer. If necessary, the above sputtering steps are repeated several times in order to produce a layer system 30 with a plurality of double layers (31, 32).
  • alternating layers of Si-DLC and DLC or of Si-DLC and Me-DLC, in particular W-DLC with a thickness of 0.1 to 20 nm, are deposited simultaneously in different coating zones in front of the respective magnetron cathodes ,
  • the coating comprises a 1.9 ⁇ thick cover layer 6 of Si-DLC with about 77 atomic% carbon, 15 atomic% silicon and 8 atomic% hydrogen. Between the cover layer 6 and the substrate 1 are successively an adhesive layer 2 of 0.5 ⁇ Cr, a first mediator layer 3 with a thickness of 0.3 ⁇ from WC X and a second mediator layer 4 with 0.3 ⁇ thickness from W-DLC arranged. The transition from the second mediator layer of W-DLC to the Si-DLC capping layer is graded.
  • FIGS. 6a and 6b show schematic plan views of PVD coating devices 100, 100 'for producing the coating systems according to the invention.
  • the PVD Cleaning devices 100, 100 ' comprise a vacuum chamber 110, in which one or more magnetron cathodes (50, 50, 60, 60, 70, 70) are arranged with targets (51, 51, 61, 61, 71, 71).
  • the magnetron cathodes (50, 50, 60, 70, 70) are designed as unbalanced magnetron cathodes which, in conjunction with electromagnetic field coils, generate the tunnel-like magnetic fields on the magnetron cathodes and a far field which encloses a large part of the parts to be coated and before the electrons present the magnetron targets into the coating chamber.
  • the coating devices 100 and 100 differ only in the polarity of the magnetic fields applied to two magnetron cathodes (50, 50).
  • the workpieces 1 to be coated are fastened to substrate holders 90, which are mounted rotatably about their longitudinal axis on a turntable (not shown in FIGS. 6a and 6b). By means of a planetary drive (not shown), the turntable and simultaneously the substrate holder 90 with the workpieces 1 are rotated. The rotation of the turntable and the substrate holder 90 is indicated by circular arrows 91 and 92, respectively.
  • the coating systems according to the invention are deposited in a controlled atmosphere 80 at a pressure of 0.5 ⁇ 10 -3 to 0.05 mbar
  • the PVD coating device 100 is connected to a pump station, in particular to turbomolecular pumps (not shown).
  • Continuously inert gases such as argon, krypton or xenon and possibly reactive gases, such as acetylene (C 2 H 2 ), methane (CH 4), nitrogen (N 2 ) 5 silanes (PV), are continuously introduced into the PVD coating apparatus 100 via one or more feeders 120.
  • the Zu 120 with electrically adjustable valves or mass flow controllers (MFC).
  • Each of the magnetron cathodes (50, 50, 60, 60, 70, 70) is connected to a separately controllable electrical power supply (not shown).
  • the magnetron cathodes are preferably operated with DC voltage or pulsed DC voltage (so-called DC magnetron sputtering).
  • a DC voltage source (not shown) for applying a bias voltage of up to -300 V, preferably -50 to -200 V or an etching voltage of up to -2000 V, preferably -1000 V, to the workpieces 1 to be coated is provided.
  • a pulsed DC voltage source is connected to the substrates.
  • the turntable and the substrate holder 90 are made of an electrically conductive material, such as steel and electrically connected to the DC voltage source for the bias voltage.
  • the bias voltage or the bias potential accelerate ionized gas atoms, for example Ar ions from the plasma 80, to the workpieces to be coated. Due to the ions impinging on the surface of the workpieces, kinetic energy is transferred to the surface atoms (so-called ion bombardment).
  • ion bombardment ion bombardment
  • the layer properties such as hardness, wear resistance and Sc trukt Modell and the proportion of sp 3- bonded carbon optimized.
  • the surface of the workpieces 1 is cleaned prior to deposition of the adhesive layer 2, the mediator layers 3, 4 and optionally 5 or layer systems 30 and 40 or before deposition of the cover layer 6 by means of ion etching, preferably with argon ions.
  • ion etching preferably with argon ions.
  • a voltage of up to - 1000 V is applied to the substrate holder 90 or to the workpieces 1.
  • the properties of the workpieces (10, 11, 11 ', 12, 13) according to the invention and of the cover layers 6 are determined using the following measuring methods: Hardness HUpiast according to ISO EN 14577 with Fischer Scope® H100C from Helmut Fischer GmbH, Sindelfingen (DE) with Vickers diamond point and a test crane from 20 to 50 mN;
  • Elemental composition and hydrogen content by secondary ion mass spectrometry (SEVIS) with cesium ions according to the method of Willich et al. (Willich, M. Wang, K. Wittmack, Quantitative Analysis of WC: H Coatings by EPMA, RBS (ERD) and SIMS, Microchim., Acta 114/115, 525-532 (1994); P. Willich, C.). Steinberg, SIMS depth profile of wear resistant coatings on cutting tools and technical components, Applied Surface Science 179 (2001) 263-268).
  • the mass spectrometer of the SIMS instrument was calibrated using the results of Elastic Recoil Detection (ERD) from three comparative samples.
  • a total of ten workpieces were coated by the process according to the invention with a top layer of Si-DLC having a hydrogen content of less than 20 atomic%.
  • the substrate used was 6 mm thick 100Cr6 steel plates measuring 40 mm x 60 mm. The plates were cleaned in alkaline media with ultrasound, rinsed in water and dried spot-free with hot air and vacuum application. Subsequently, the plates were mounted on a substrate holder which was mounted on a turntable in the vacuum chamber of a PVD coating system. The vacuum chamber was closed and pre-evacuated by means of backing pumps (gate valves and subsequently roots pumps).
  • a high vacuum pressure of less than lxl0 was "5 mbar produced which were temporarily pre-heated with a radiant heater to improve degassing of the parts.
  • the mixture was then introduced via a mass flow controller argon until a total pressure of 5xl0" by means of turbo-molecular pumps 3 mbar was reached. All plates were first etched for 30 minutes with argon ions at a -600 V etch voltage applied to the substrates to remove any contaminants present from the surface. Subsequently, by means of DC magnetron sputtering in the same argon atmosphere successively (i) an approximately 0.5 ⁇ thick adhesive layer of Cr, and (ii) a first mediator layer of SiC applied.
  • Acetylene was subsequently introduced by means of a Massflow controller, whereby for the production of (iii) a second intermediate layer SiCx (with X> 1) with continuously increased carbon content in the layer, the acetylene flow was increased in the range of 0 to 80 sccm, whereby in the last part of the acetylene ramp Deposition of Si-DLC with increasing carbon content was present.
  • the first and second intermediate layer each have a layer thickness of about 0.2 ⁇ m.
  • Si-DLC cover layers were deposited on the samples with variable ratio of silicon to carbon and different layer structure. The thickness of the Si-DLC cover layers produced is in the range of 1 to 2 ⁇ m.
  • a magnetron cathode with SiC target and optionally one or two magnetron cathodes with graphite target was used.
  • the layer deposition took place in a mixture of argon and acetylene, wherein the supplied argon flow was set constant to 300 sccm and the acetylene flow to values between 15 and 120 sccm.
  • the parts were set for 15 Cooled in the vacuum chamber for minutes and then the chamber was flooded with air to atmospheric pressure and the parts were removed from the chamber.

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Abstract

Pièce (13) qui comporte un corps de base (1), éventuellement une couche d'adhérence (2) et / ou plusieurs couches intermédiaires (3, 4, 30, 40, 5) et une couche de recouvrement (6) contenant Si-DLC et ayant une teneur en hydrogène de 5 à 20 en pourcentage atomique. Un procédé permettant d'appliquer sur des pièces un revêtement par dépôt physique en phase vapeur comporte une ou plusieurs étapes S1 à SN (N = 1, 2, 3), une couche de recouvrement contenant Si-DLC étant déposée à l'étape SN au moyen d'une ou de plusieurs cathodes de magnétron à cible contenant du silicium et éventuellement d'une ou de plusieurs cathodes de magnétron à cible graphite dans une atmosphère présentant une teneur nominale en hydrogène inférieure à 30 en pourcentage atomique.
PCT/EP2011/005956 2010-11-30 2011-11-28 Pièce pourvue d'un revêtement si-dlc et procédé de fabrication de revêtements WO2012072225A1 (fr)

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WO2013156107A1 (fr) * 2012-04-20 2013-10-24 Amg Coating Technologies Gmbh Revêtement contenant si-dlc, dlc et me-dlc et procédé de fabrication de revêtements
CN107614944A (zh) * 2015-07-31 2018-01-19 日本活塞环株式会社 活塞环及其制造方法
CN111041482A (zh) * 2019-12-25 2020-04-21 苏州涂冠镀膜科技有限公司 一种用于半导体封装模具内腔的复合涂层及其制备方法

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Publication number Priority date Publication date Assignee Title
WO2013156107A1 (fr) * 2012-04-20 2013-10-24 Amg Coating Technologies Gmbh Revêtement contenant si-dlc, dlc et me-dlc et procédé de fabrication de revêtements
CN107614944A (zh) * 2015-07-31 2018-01-19 日本活塞环株式会社 活塞环及其制造方法
CN107614944B (zh) * 2015-07-31 2019-07-23 日本活塞环株式会社 活塞环及其制造方法
CN111041482A (zh) * 2019-12-25 2020-04-21 苏州涂冠镀膜科技有限公司 一种用于半导体封装模具内腔的复合涂层及其制备方法

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