EP3423609A1

EP3423609A1 - Hydrogen-free carbon coating having zirconium adhesive layer

Info

Publication number: EP3423609A1
Application number: EP17709580.9A
Authority: EP
Inventors: Joerg Vetter
Original assignee: Oerlikon Surface Solutions AG Pfaeffikon
Current assignee: Oerlikon Surface Solutions AG Pfaeffikon
Priority date: 2016-03-01
Filing date: 2017-02-28
Publication date: 2019-01-09
Also published as: US20190249310A1; JP7106194B2; KR20180123508A; CN108884550A; WO2017148582A1; JP2019512597A; CN108884550B; US10844493B2

Abstract

The invention relates to a coated substrate having a hard material coating, comprising a hard carbon layer of the hydrogen-free amorphous type, wherein the coating comprises a layer between the substrate and the hydrogen-free amorphous carbon layer, consisting of zirconium, and wherein a layer consisting of Zr-C_x can be formed between the zirconium layer and the hydrogen-free amorphous carbon layer, in which a zirconium-monocarbide is formed, and wherein the layer consisting of Zr-C_x and comprising zirconium-monocarbide is applied directly to the zirconium adhesive layer.

Description

Hydrogen-free carbon coating with zirconium adhesive layer

The present invention relates to a hydrogen-free carbon coating, with a zirconium adhesive layer for substrate surfaces, in particular for tool and component surfaces for tribological applications, the carbon coating a hard carbon layer with a hydrogen-free, amorphous carbon structure depending on the CC sp ³ bond content as aC or as ta -C, and may contain other elements, and is associated with the group of DLC layers, and the zirconium adhesive layer is zirconium, with the zirconium adhesive layer applied between the substrate surface and the hard carbon layer, such that atomic bonds are interposed between the substrate Carbon atoms of the carbon layer and zirconium atoms form the zirconium layer.

In the context of the present invention, "zirconium" is to be understood as meaning the chemical element with the element symbol Zr.

Hereinafter, a Zn-x Cx is abbreviated to Zr-Cx for the sake of convenience. X is at% and the following applies: 0 at% <X <50at%, and Zr (at%) + C (at%) = 100 at%, without consideration of impurities. In the case of X = 0 at%, the adhesive layer is a pure zirconium layer. However, the range is preferably 10 at% <X <50at%. For the purposes of the present description, a carbon layer is to be understood as meaning a layer which has an amorphous state carbon matrix detectable by means of volumetric measurement and which can be detected by means of Raman spectroscopy or other suitable measuring methods.

This zirconium layer serves for bonding between the substrate and the hydrogen-free carbon layer. Due to the process, atomic bonds form between the carbon atoms of the hydrogen-free layer and atoms of the zirconium layer. Under certain process conditions, depending on

l

CONFIRMATION COPY Process temperature and the energy of the impinging carbon atoms, it may lead to the formation of a thin Zr-Cx layer between the existing zirconium layer and the hydrogen-free, amorphous carbon layer, Furthermore, it is possible targeted zirconium monocarbide form by the simultaneous deposition of zirconium and carbon, wherein the layer of ZrC optionally, the zirconium monocarbide comprising layer is applied directly to the zirconium existing adhesive layer. In a further embodiment, the transition to the pure carbon layer can also be a multi-layered or graded hydrogen-free aC: Zr layer or ta-C: Zr layer, which is distinguished from the stoichiometric zirconium carbide by a larger atomic proportion of carbon atoms compared to the zirconium atoms.

PRIOR ART Amorphous, carbon-based hard material layers, also called DLC layers, are known from the prior art. However, these types of layers do not always have sufficient adhesion to the substrate, especially if they are hard hydrogen-free layers of the type a-C or ta-C. This is due to the high residual stress state of the layers, which makes it difficult to deposit process-stable adherent layers of this type with excellent functionality.

In this regard, for example, in DE102007010595B4, Kabushiki teaches that when a nitride or carbonitride is used for the interlayer, the adhesion of the amorphous carbon layer (also called DLC, using DLC as the abbreviation of Diamond like Carbon) even at high temperature or can be improved in a high load area. Therefore, Kabushiki proposes adhesion between the substrate and the amorphous carbon (DLC) layer by depositing a multilayered film system between the substrate and the DLC amorphous carbon film. According to the teachings of Kabushiki, this way can the adhesion between substrate and DLC layer can be improved even at high temperature and in a high load area.

The multi-layer coating system according to Kabushiki comprises:

a base layer formed on the substrate comprising a nitride or a carbonitride of an element M _and having a composition of the formula Mi-x- _y CxN _y , wherein x <0.5, y 0.03 and 1-xy are greater than zero, and wherein M is at least one element selected from Groups 4A, 5A, 6A of the Periodic Table, Al and Si, and wherein the element M comprises Ti, Zr, V, Nb, Ta, Cr, Mo, W, Al and Si, and preferably M comprises the elements W, Mo and Ta, and

a gradient layer formed on the base layer containing M, nitrogen and carbon, wherein from the base layer to an amorphous carbon layer on the gradient layer, the contents of the element M and the nitrogen decrease and the carbon content increases, and

a surface layer formed on the gradient layer and comprising an amorphous carbon layer consisting of carbon or consisting of 50 atomic% or more carbon, the remainder consisting of element M, and optionally also

a layer of an element formed between the substrate and the base layer, which element may be selected from among a Group 4A element in the Periodic Table, a Group 5A element, a Group 6A, Al and Si element.

However, the layer structure described above is complex and therefore requires a complicated reactive coating process, which is mostly used in industrial production, e.g. in large-scale production is not desirable because the complexity of the process steps represents a higher risk in terms of a sufficient coating result.

Object of the invention

It is an object of the present invention to provide a

Hard material coating, which comprises a hard hydrogen-free amorphous carbon-based layer, wherein the hard coating a possible simple Layer structure and a very good adhesion to the substrate, even in applications in areas with high loads, has.

It is a further object of the present invention to provide a coating method which enables the production of the coating in a simple manner and with increased process stability.

Solution of the problem according to the present invention

This object is achieved according to the invention by providing a carbon coating as in claim 1.

The carbon coating comprises a hard carbon layer and a zirconium adhesive layer, wherein the carbon layer has a hard, hydrogen-free, amorphous carbon structure and the zirconium adhesive layer is zirconium, and the zirconium adhesive layer is applied between the substrate surface and the hard carbon layer such that process-related atomic bonds between carbon atoms of the hard carbon layer and zirconium atoms of the zirconium adhesive layer, thereby forming a zirconia-carbon Zr-Cx layer having a layer thickness of a few atomic layers or up to several nanometers.

DETAILED DESCRIPTION OF THE PRESENT INVENTION AND ITS PREFERRED EMBODIMENTS Figure 1 a) shows the photograph of a Rockwell C indentation in a carbon coating with chromium adhesive layer.

Figure 1 b) shows the photograph of a Rockwell C impression in a carbon coating according to the present invention.

Figure 2 shows a carbon coating according to the invention with supporting layer.

In a first embodiment of the carbon coating according to the present invention, the Zr-Cx layer is exclusively formed by process-related atomic bonds between carbon atoms of the hard, hydrogen-free, amorphous carbon layer and zirconium atoms of the Zirconium adhesive layer formed such that this Zr-Cx layer has a layer thickness in the atomic region range. The layer thickness of the Zr-Cx layer can be, for example, 2 to 10 atomic layers in this embodiment.

In a further embodiment of the carbon coating according to the present invention, the process conditions are selected such that after deposition of the zirconium adhesive layer, in particular the process temperature and the energy of the carbon atoms impinging on the surface of the zirconium adhesive layer, formation of atomic bonds between carbon atoms of the hard, hydrogen-free , amorphous carbon layer and zirconium atoms promote the zirconium adhesive layer so that in this way the necessary conditions for forming a Zr-Cx layer having a layer thickness of at least 2 atomic layers to about 100 nm are given.

In yet another embodiment of the carbon coating according to the present invention, a process is carried out such that a ZrC layer comprising zirconium monocarbide is formed between the zirconium adhesive layer and the hard, hydrogen-free, amorphous carbon layer. The zirconium monocarbide-containing ZrC layer can be formed by simultaneously depositing zirconium and carbon. The layer thickness of the zirconium monocarbide-containing ZrC layer is, for example, 5 nm to 500 nm in this embodiment.

According to a preferred embodiment of the present invention, the hydrogen-free, amorphous carbon layer is an a-C or ta-C layer.

The hydrogen-free carbon layers, which the person skilled in the art designates as aC layers or ta-C layers, can be produced, for example, by the Are method (unfiltered or filtered) or else by sputtering methods (DC, pulsed DC, RF, HiPIMS), preferably in the case of aC- Layers are deposited.

AC layers are referred to when the relative proportion of the sp ³ - bonding moieties of the CC bonds is equal to or smaller than the proportion of the sp ² - bonding moieties of the CC bonds in the layers. These layers then have hardnesses below 50 GPa. If the proportion of sp ³ bond portions exceeds that of the sp ² bond portions, mention is made of ta-C layers (tetrahedral hydrogen-free amorphous carbon layers) which typically cure above of 50 GPa. It goes without saying that methods known to those skilled in the art for measuring the hardness of thin layers are used.

The zirconium adhesive layer can be deposited, for example, by means of the Are method (unfiltered or filtered) or else by sputtering methods (DC, pulsed DC, RF, HiPIMS).

A peculiarity of ion-cleaning processes based on accelerated metal ions (ie, metal ion-cleaning processes, usually with an applied bias of 500V to 1500V) typically extracted from non-100% ionized metal vapors, in the present case zirconium; is that such process parameters are selectable, so that a thin zirconium layer in the thickness range of a few nm to several 10 nm forms, which forms the zirconium adhesive layer.

With carbon coatings according to the present invention, substrates of, for example, steel, hard metal, aluminum alloys, Cu alloys, ceramics, cermet, or other metallic alloys can be coated. Since the coating temperature for producing the carbon coatings according to the present invention is down to 100 ° C, extremely temperature-sensitive substrates can be coated in terms of substrate materials or other properties.

In particular, for example, cutting tools and forming tools can be coated.

Component components such as valve parts, vane pumps, or automotive parts such as piston pin, piston rings, finger followers, bucket tappets, or household appliances such as cutting blades, scissors, razor blades or medical parts such as implants and surgical instruments, or decorative parts such as watch case can u.a. also be coated with a carbon coating according to the present invention.

As sources of evaporation for the deposition of the zirconium layers, both Are sources with filters and without filters can be used. Likewise, suitable zirconium layers may be sputtered, such as RF, DC; pulsed DC or HiPIMS are deposited. Also, vapor deposition methods such as electron beam evaporation, low-voltage arc evaporation or

Hollow cathode arc evaporation is suitable for depositing the zirconium adhesive layer for the carbon coatings of the present invention. In addition to a-C and ta-C layers, it is also possible to prepare a-C: Me layers or Ta-C: Me layers in a targeted manner. These layers contain at least one metal as a doping element and have compared to the a-C and ta-C layers without doping element changed property profiles, for example, the electrical conductivity is greater. This may thus be advantageous in certain applications. Since the adhesive layer should be made of zirconium according to the present invention, it would be advantageous to use zirconium as the Me method.

The simplest process management results if the zirconium evaporation is carried out simultaneously with the operation of the carbon evaporation by means of Are. Another method is the use of carbon targets in which zirconium has been added.

Another embodiment according to the present invention are hydrogen-free, amorphous a-C: X layers or ta-C: X layers.

In addition to metallic elements (commonly referred to as Me) which are added to the layers and thus lead to the a-C: Me layers, it is also possible to add other non-metallic elements (generally designated X) as doping elements for layer optimization, depending on the application. These non-metallic elements may be nitrogen, boron, silicon, fluorine or others. For example, doping with N or Si leads to stress reduction and F leads to a change in the wetting properties (higher wetting angle), as is generally known to the person skilled in the art.

According to a further preferred embodiment of the present invention, the hydrogen-free, amorphous layer is designed as a multilayered layer, wherein the multilayered layer structure comprises alternately arranged individual layers of a type A and a type B, the individual layers of the type A consisting of aC or ta-C and the individual layers of the type B from Me or from aC: Me or ta- C: Me are. In this context, zirconium may be used as Me, for example, such that a multilayer coating of the type aC / Zr or ta-C / Zr or aC / aC: Zr or ta-C / ta-C: Zr and also further combinations such as ta- C / aC: Zr or aC / ta-C: Zr is formed.

With this method, thicker layers can be produced because the total residual stresses in the layers are reduced. For example, the same process is driven as in the embodiment from the phase of deposition of the metallic layer, the layer thickness limited to about 500 nm and then driven the same process many times, for example 6 times, so that in addition to the zirconium adhesive layers further 5 intermediate layers and a Total layer thickness of more than 3 pm arise. This leads to a higher load capacity and wear resistance.

According to a further preferred embodiment of the present invention, the hydrogen-free, amorphous layer is designed as a multilayer layer, wherein the multilayered layer structure comprises alternately arranged individual layers of a type A and a type B, wherein the individual layers of the type A are degraded from aC or ta-C and the individual layers of type B from aC: X or from ta-C: X are. In this context, for example, silicon or nitrogen can be used as X.

Additional arc evaporators may be used to deposit such layers which evaporate the X-element alloyed graphite cathodes, or other suitable PVD methods could be used, e.g. Sputtering method with which the element X is sputtered.

Preferably, the thickness of the single layers of the type A is not more than 2000 nm and not less than 5 nm. Also preferably, the thickness of the single layers of the type B is not more than 2000 nm and not less than 5 nm.

An advantage of this embodiment is also the possibility of a higher layer thickness combined with an optimized stress ratio within the same coating.

According to a further embodiment of the present invention, the Zr layer is applied to the substrate to be coated by means of a metal-ion-cleaning method.

In the case of metal ion bombardment by means of zirconium ions in the unfiltered arc, it may be due to the use of a bias voltage on the substrate, for example from or below - 700 V, at the same time grow a thin zirconium layer. This can then serve as a zirconium adhesive layer according to the invention. In this case, layer thicknesses of 5 to a few 10 nm are desired. According to a further preferred embodiment of the present invention, the hydrogen-free, amorphous layer is a layer of a nanocomposite material which comprises a matrix material and a material embedded in the matrix material, wherein the matrix material is preferably aC or ta-C and the embedded material is metallic carbides with dimensions in the nanometer range, eg with metal-doped amorphous carbon layers, depending on the metal, eg tungsten carbide (WC) or chromium carbides (Cr23C6, Cr3C2) or other carbides of the metallic elements, preferably made of ZrC.

Hard material layers according to the present invention may also include support layers between the substrate and the zirconium adhesive layer on which the hydrogen-free, amorphous carbon layer is deposited, as shown in FIG. Shown is a substrate 205 on which only a support layer 207, then a Zr-Cx layer 209 and then a hydrogen-free amorphous carbon layer is provided. This support layer increases the mechanical strength of the surface. It preferably consists of a material which has a higher toughness than the hydrogen-free, amorphous carbon layers. For example, this support layer may consist of ZrN. Other nitridic (e.g., CrN, AITiN), carbonitridic (e.g., TiCN, ZrNC), or carbidic (e.g., TiC, CrC) or oxynitridic (e.g., CrNO) may serve as a support layer for the a-C or ta-C layer. Preferably, these layers are deposited by means of arcs or sputtering.

Hard coatings according to the present invention may also be deposited to include one or more further metallic adhesive layers between the substrate and the zirconia adhesive layer. For example, the one further metallic adhesion layer may be a Cr adhesion layer produced by means of metal ion cleaning with Cr ions, onto which the zirconium adhesion layer is then deposited. Hard material layers according to the present invention can also be produced according to the invention with the aid of HiPIMS technology. For example, the hydrogen-free, amorphous layer and / or the support layer and / or the zirconium adhesive layer and / or the one or more intermediate layers can be deposited by means of a HiPIMS method.

According to one embodiment, only the a-C layer is deposited by HiPIMS.

According to another embodiment, both the Zr adhesion layer and the a-C layer are both deposited with HIPIMS.

An advantage of these embodiments is the formation of particularly smooth a-C layers.

Hard material layers according to the present invention can also be produced according to the invention by means of a hybrid technology which combines the HiPIMS and the Are technology.

For example, the hydrogen-free amorphous layer and / or the supporting layer may be deposited by a hybrid Arc / HiPIMS method and the zirconium adhesive layer deposited using a Zr ion metal ion-cleaning process based on the HiPIMS process. Furthermore, a deposition of a thicker Zr adhesive layer can also be carried out directly with the HiPIMS method.

For example, the hydrogen-free, amorphous layer can be deposited by means of a hybrid Are process, the support layer can be deposited by means of a HiPIMS or a hybrid Arc / HiPIMS process and the Zr adhesion layer can be deposited by means of a Zr ion metal ion cleaning process.

These process combinations are to be regarded as examples of inventive methods for producing the hard coatings according to the invention and not as a delimitation of the possible methods for producing the hard coatings according to the invention. Comparison between coatings made according to the invention with a zirconium adhesive layer and prior art coatings with a chromium adhesive layer:

The layer deposits of a-C (hardness of about 40 GPa) and ta-C layers (hardness of about 55 GPa) were realized in a commercial coating plant equipped with arc evaporators.

There were two coating series, each with 6 different processes, for each individual process identical parameter sets were carried out with regard to all process steps. Depending on the coating series, different adhesion layers were deposited on test specimens of steel which had a Rockwell hardness of 60 HRC. In the prior art coating series, the test specimens with chromium adhesive layers were applied by is vaporization prior to deposition of the carbon layers, but in the coating series of the present invention, zirconium adhesive layers were applied by arc evaporation. In the case of the zirconium adhesive layers, deposition was also effected by means of mechanical droplet filtration, either with an attached shield or by means of a shutter arrangement.

The coating steps, as known to those skilled in the art, were initially pumped to high vacuum (0.001 Pa), then a heating step taking into account compliance with a maximum substrate temperature temperature of about 150 ° C. Subsequently, an ion cleaning by means of the AEGD method, then the arc evaporator were ignited with Cr or Zr to deposit the metallic adhesive layer of about 120 +/- 40 nm. For this purpose, appropriate breaks were taken in order not to exceed a maximum temperature of about 150 ° C. In the transition phase for the deposition of the pure carbon layer, the arc evaporators were ignited with suitable graphite cathodes and a voltage of at least 500 V was applied to the substrates, resulting in bombardment with C ions of the metallic intermediate layer. Subsequently, various parameters were set to represent the aC, tA-C layers, so various transitions to the pure coating phase with respect to a bias gradient, ie lowering the applied substrate voltage to lower values, typically below 100V, as well as different pause times to set a maximum Coating temperature and different substrate voltages chosen during the coating. A layer thickness of about 1 pm was deposited on the test specimens. By a suitable combination of applied negative bias and effective coating temperature, whose process fields are known to those skilled in the art (the use of higher bias voltages up to 100V provides the higher hardnesses versus lower biases at the same temperature, and vice versa, higher coating temperatures cause lower hardnesses at constant bias voltage) the different hardnesses were set in the layers. The results of 6 different coating processes with regard to the parameters with the chromium adhesive layers and zirconium adhesive layers were evaluated with regard to the nanohardness as well as the quality of the HRC impression. The hydrogen-free amorphous carbon layers showed the same layer hardness in both Cr-adhesion layers and Zr-adhesion layers.

Surprisingly, defying identical process flows in all of the numerous retest attempts with each chrome arc evaporator and zirconium arc evaporator showed that the bond strength of carbon coatings comprising a zirconium adhesive layer according to the present invention was much higher compared to the carbon coatings containing a chromium adhesive layer included in the prior art. The adhesion class according to the Rockwell C method (HRC method) of both coatings was measured and is shown by way of example in FIG. 1. FIG. 1 a) shows the photograph of a Rockwell C impression in a carbon coating with chromium adhesive layer and FIG. 1 b) the photo of a Rockwell C impression in a carbon coating on a steel component hardness about 60 HRC, with zirconium adhesive layer according to the present invention deposited under identical process conditions. The Zr adhesive layer provided an excellent adhesion class HF1 to HF2, regardless of the process control and location in the coating chamber, while the adhesion classes HF2 to HF4 were found for Cr adhesive layers. A possible explanation of the better adhesion safety in the inventive coatings with zirconium adhesive layers, determined by means of the HRC method, could be that the deposition of the carbon layers on the chromium adhesive layers can result in the formation of several carbides and thus brittle Cr-C phases can be formed. On the contrary, the use of zirconium adhesive layers according to the present invention will not form a more brittle phase but rather a more "ductile" phase, which under some circumstances may comprise zirconium monocarbide (ZrC) of one or more inert process gases (eg, helium, neon, or argon) and / or metals and acceleration of these onto the substrate surface may produce a sputtering or implantation effect on the surface, when these ion cleaning processes are primarily intended for impurities such as native Oxides or even organic impurities, it is often sufficient to work only with inert gas ions.These processes, as well as the said arc enhanced glow discharge (AEGD) process are known to those skilled in the art is the ion cleaning with sufficiently high intensity (adjustable bs pw. above the level of bias voltage) and / or duration, sufficient atoms are knocked out of the substrate surface to provide good film adhesion in the post-ion cleaning process metal ion cleaning process or coating.

Analogous to the ion cleaning method of this application in which in addition to the process gas, or even exclusively, metal ions are used, is understood as a metal ion cleaning method (or called metal ion etching) another etching method. In the metal ion cleaning process, one or more metal sources of, for example, chromium or zirconium are operated, which have the effect of accelerating ionized metals onto the substrate surface. Primarily dependent on the magnitude of the applied bias voltage and the amount of current applied to the metal source, the energy and amount of vaporized (eg in Arc processes) or sputtered (eg sputtering or HIPIMS processes) material can be adjusted specifically. Thus, it is possible for a person skilled in the art, in addition to a cleaning of the substrate surface by means of the abovementioned metal ions, to achieve a net application by means of metal ion bombardment on the substrate. With a constant evaporation amount, it is primarily the height of the applied bias voltage that determines whether there is a material application of the metals used on the substrate. Will higher bias voltages used (from about 700 V) takes place in addition to the cleaning of the substrate surface even the implantation of the metal ions used in the substrate surface, which can be done some 10 nm deep. Depending on the material, however, a net order of a few 10 nm may occur for the same process parameters. Those skilled in the art, these methods are well known, which is why the embodiments mentioned in this application should not be construed as limiting the invention.

In the context of this invention, hydrogen-free amorphous carbon layers are understood as meaning all carbon layers whose hydrogen content is <5 at.%, Preferably <2 at.%, Whereby any impurities are not taken into consideration. However, suitable characterization methods, such as elastic recoil detection analysis (ERDA), rutherford backscattering (RBS) or secondary ion mass spectroscopy (SIMS) for determining the chemical composition of the layers according to the invention are known to the person skilled in the art.

Claims

claims

A carbon coating on a substrate surface, wherein the coating comprises a hard carbon layer and a zirconium adhesive layer, and wherein the carbon layer has a hard, hydrogen-free, amorphous carbon structure and the zirconium adhesive layer is zirconium and the zirconium adhesive layer is between the substrate surface and the hard carbon layer and between the zirconium adhesive layer and the hard carbon layer is formed a Zr-Cx layer comprising atomic bonds between carbons of the hard carbon layer and zirconium atoms of the zirconium adhesive layer and has a layer thickness of 2 atomic layers to 500 nm.

2. Layer system according to claim 1, characterized in that between the substrate and the zirconium adhesive layer, a support layer is deposited.

3. Layer system according to claim 2, characterized in that the support layer of nitrides and / or carbides and / or oxides is composed of at least one element of the group comprises by the third, fourth, fifth or sixth group of the Periodic Table and AI, Si, B. and the group of lanthanides is formed.

4. Carbon coating according to one of the preceding claims, characterized in that the layer thickness of the Zr-Cx layer is 2 atomic layers to 30 nm.

5. Carbon coating according to one of the preceding claims, characterized in that the Zr-Cx layer contains zirconium monocarbide and has a layer thickness of 5 nm to 500 nm. Carbon coating according to one of the preceding claims, characterized in that the hydrogen-free, amorphous carbon layer comprises an aC or ta-C layer or consists of an aC and / or ta-C layer.

Carbon coating according to one of the preceding claims 1 to 5, characterized in that the hydrogen-free, amorphous carbon layer comprises an aC: Me or ta-C: Me layer and / or consists of an aC: Me or ta-C: Me layer, wherein Me a metallic element or a combination of metallic elements.

Carbon coating according to one of the preceding claims 1 to 5, characterized in that the hydrogen-free, amorphous carbon layer comprises an aC: X or ta-C: X layer and / or consists of an aC: X or ta-C: X layer, wherein X is a non-metallic element or a combination of metallic elements.

Carbon coating according to one of the preceding claims 1 to 5, characterized in that the hydrogen-free, amorphous carbon layer is designed as a multilayer layer, wherein the multilayered layer structure comprises alternately deposited individual layers of a type A and a type B, and the individual layers of the type A aC or ta-C layers are.

A carbon coating according to claim 9, characterized in that the individual layers of the type B a-C: Me or ta-C: Me or metallic layers consisting of Me are.

A carbon coating according to claim 9, characterized in that the individual layers of the type B a-C: X or ta-C: X are layers.

Carbon coating according to one of the preceding claims 1 to 5, characterized in that the hydrogen-free, amorphous Carbon layer is designed as a multilayer layer, wherein the multilayered layer structure comprises alternately deposited single layers of a type A and a type B, and the individual layers of the type A aC: Me or ta-C: Me or aC: X or ta-C: X layers and the individual layers of type B are metallic layers consisting of Me.

Method for depositing a carbon coating according to one of the preceding claims, characterized in that the hydrogen-free, amorphous carbon layer is deposited by means of an arc vaporization and / or filtered arc evaporation and / or a sputtering process, in particular a HiPIMS process.

Method for depositing a carbon coating according to one of the preceding claims 1 to 12, characterized in that the zirconium adhesive layer is deposited by means of an ion cleaning method with Zr ions or by means of a filtered arc evaporation and / or a sputtering and / or a HiPIMS method becomes.

Method for depositing a carbon coating according to claim 5, characterized in that the zirconium monocarbide in the Zr-C layer is formed by simultaneous deposition of zirconium and carbon on the zirconium adhesive layer.