DE102004004177B4 - Process for producing thin layers and its use - Google Patents

Abstract

Method for producing diamond-like carbon layers (DLC layers) of thickness d by means of an ion-supported deposition method using the method steps
- Providing a substrate
- Cleaning the substrate by means of a plasma etching process
- Heating the substrate to a process temperature, wherein the process temperature is in the range between 50 ° C and 300 ° C.
- Providing a process atmosphere of a carbon-containing gas mixture of at least one carbon-containing gas and a carrier gas, wherein the base pressure of the process in a range between 1 · 10 ^-4 Pa and 1 · 10 ^-1 Pa, and the working pressure in a range between 1 · 10th ^-2 Pa and 10 Pa
- Depositing a carbon-containing layer of the gas phase on the substrate
Generating an ion current by means of a plasma discharge and applying a negative, pulsed voltage U to the substrate, wherein the voltage in a range from -0.5 kV to -30 kV, the repetition rate of the voltage pulses between 50 Hz and 5000 Hz, the pulse length between 0.5 ...

Description

The The invention relates to a method for producing diamond-like Carbon films (DLC) by means of an ion-based deposition process.

It is well known, a variety of substrate materials with thin films to coat from diamond-like carbon. Diamond-like carbon layers are layers of amorphous, hydrogen-containing carbon (a-C: H), the one big one Hardness and high elasticity, a good corrosion protection, a high chemical resistance, very low coefficient of friction and a smooth surface morphology can have. These properties make the DLC coatings attractive for industrial use Applications such as as low-friction and wear-resistant layers at high mechanical loads. Examples of potential tribological Applications of DLC coatings are the coating of drive components such as gears or shafts and the coating of press and Molds for the forming technique. Their good biocompatibility also allows for a use in the medical field, e.g. as a coating for endoprostheses in the anchoring or joint area and other implants.

Pure DLC layers can today in spite of their fundamentals excellent properties due to their high residual stress, their poor adhesion especially on steel substrates, for example, and their low thermal stability, especially as wear protection only with low, for many Applications are deposited inadequate layer thicknesses or but require elaborately prepared, e.g. with adhesive layers provided, substrates or special dopants. For many Applications therefore only have the option instead of a simple one DLC layer only multilayer coating systems deposit, but on the one hand to a lower hardness and on the other hand leads to a much more complex process.

In the DE 198 26 259 various examples of C-MeC multilayer structures prepared by a plasma CVD method are given. Whereby, for example, the metal (Me) in the metal carbide layer (MeC) may be tungsten, chromium or titanium and the carbon layer consists of amorphous hydrogen-containing carbon (aC: H). However, the need to manufacture the two single-layer systems in separate gas spaces renders this process unsuitable for industrial production.

Also in the EP 0 971 048 For example, a Me-C: H layer and a method for producing such a layer will be described. However, that is in the EP 0 971 048 described method a combination of conventional PVD method, such as DC magnetron sputtering or arc evaporation and plasma-enhanced CVD method by a plasma is ignited by pulsed DC voltage to the substrate.

The US 6,572,935 focuses on the DLC coating of plastics such as PMMA and thus on a coating at low substrate temperatures.

• – Anlegen einer negativ gepulsten Spannung an das Substrat in der Höhe zwischen 100 und 1000 V mit einer Pulsbreite von 20 μs
• – Einbringen des negativ vorgespannten Substrates in ein Plasma, das Ionen mit C und H und B Anteil enthält, wobei die Ionen auf die Oberfläche des Substrates beschleunigt werden und dort eine optisch transparente, kratzfeste, diamantartige Schicht mit 4–8 Prozent Bor bilden.

A method is described for forming an adherent, optically transparent, scratch-resistant, diamond-like coating on a substrate with the steps:

• - Applying a negative pulsed voltage to the substrate in the height between 100 and 1000 V with a pulse width of 20 microseconds
• - Introducing the negatively biased substrate in a plasma containing ions with C and H and B content, wherein the ions are accelerated to the surface of the substrate and form there an optically transparent, scratch-resistant, diamond-like layer with 4-8 percent boron.

The process is carried out at a substrate temperature of 0-200 ° C, at a base pressure of 1.3 · 10 ^-4 Pa and at a working pressure between 0.04 and 0.93 Pa. This process results in DLC layers having a hardness between 27 and 29 GPa with a thickness of 100 to 300 nm at a deposition rate between 0.02 and 0.05 nm / s.

• – Reinigen des Substrates mittels Beschuß mit Ionen eines inerten Gases
• – Einlassen eines Precursors der die Elemente C, H, Si und N enthält in die Vakuumkammer
• – Ausbilden eines Plasmas aus dem Precursor und Abscheiden einer Schicht aus den Plasmakomponenten auf dem zwischen 0,2 und 1,2 kV negativ vorgespannten Substrat

WO 00/75394 is directed to an improvement in the layer adhesion of a DLC layer on a substrate and discloses a method for at least partially coating a substrate in a vacuum chamber, comprising the steps of:

• - Cleaning the substrate by bombardment with ions of an inert gas
• - Admitting a precursor containing the elements C, H, Si and N in the vacuum chamber
• - Forming a plasma from the precursor and depositing a layer of the plasma components on the 0.2 to 1.2 kV negatively biased substrate

The frequency of the DC bias voltage can vary between 30 and 1000 Hz. Si-N doped DLC layers with a hardness of 15.8 GPa and multilayer layers with a total thickness of 2.5 μm and a hardness of 21.4 GPa, which also contain DLC layers, are produced by this process. In all its embodiments, WO 00/75394 is based on the adhesion of the DLC layer or the multilayer layers for which the adhesion is better than 22 N by means of a scratch test and which is improved by the Si-N doping of the DLC layer.

The DE 69605280 discloses the deposition of a diamond-like carbon layer on a large scale and at low pressure by means of an "enveloping" plasma ion deposition The plasma is preferably generated by means of an electron source such as a filament or a hollow cathode and a voltage between filament and reactor wall In the direction of the chamber wall, they accelerate and interact with the process gas in the reactor on their way, and the resulting ions are directed to and deposited on the negative (0-3kV) substrate, which is made up of various metals such as M-2 tool steel, 304 stainless steel or AL-390 alloy automotive pistons, however, no relationship between process parameters and layer properties, such as layer hardness, is taught.

The DE 69812092 relates to the field of chemical vapor deposition (CVD) for the production of thin diamond-like carbon layers, especially on pointed or angled surfaces, such as needle points, or razor blade cutting. The invention is explicitly directed to deposition under low energy (100-1000V) ion bombardment to form a dense, thin aC: H layer on a substrate without stem growth.

The DE 19826259 relates to a method of vacuum deposition of a substrate by a plasma CVD method, wherein the voltage applied to the substrate is generated independently of the coating plasma and the substrate voltage is varied during the deposition.

adversely however, in all known methods, the processes are very sensitive to even the smallest changes the boundary conditions react and thus the results, so the Layers, partially different properties, e.g. different Layer thickness, hardness or adhesive strength. The reproducibility of the layer properties is in any case a high challenge. A disadvantage, the PVD method bring along, is in the process occurring occurring, strong directed particle transfer. The material to be deposited leaves the target perpendicular to the target surface. Complex three-dimensional workpieces must therefore in any case be moved through the coating plasma consuming, to be homogeneously coated. This results in a low dynamic coating rate, which is responsible for the economy Process, however, is crucial. In addition, the target positioning, dimensioning and operation also very complicated, for example, a spatially and stoichiometric uniform target removal at To ensure sputtering or arc cathodes. A removal of solids targets also always brings the risk of droplets (solid droplets) with them, which are completely prevented only by elaborate filter techniques can be. Another disadvantage with almost all conventional PVD such as CVD methods are the necessary high process temperatures during deposition wear protection layers, often far beyond 200 ° C lie. This is a coating of temperature-sensitive materials not possible.

task The invention is an economical process for the production of diamond-like carbon layers.

These Task is carried out according to the invention the subject of the independent Claim 1 solved. Advantageous developments emerge from the subclaims.

In the inventive method - claim 1 - to Production of diamond-like carbon layers (DLC layers) Thickness d by means of an ion-based deposition method its process steps provide a substrate. This substrate may e.g. an arbitrarily shaped steel substrate (e.g. Cold work steel 1.2379 (X155CrVMol2-1), stainless steel 1.4305 (X 8 CrNiS 18 9), high-speed steel 1.3343 (S 6-5-2), bearing steel 1.3505 (100Cr6)) such as for components in drive technology or for Forming tools used in plastics or metalworking. It can also be made of another metal alloy on titanium, magnesium, Aluminum or Cobalt base and glass, silicon or ceramic Be material.

The problem of adhesion, which is solved in all conventional processes exclusively by the introduction of a bonding agent layer stored between substrate and DLC layer, for example, from Ti, Cr or Si, in the inventive method on technically relevant substrates, such as some steel grades alone by the high particle energy to be solved in the initial phase of the process. This results in implantation of ions and ion mixing of deposited layer and substrate material at the interface, resulting in improved adhesion in many substrates. In addition, the workpiece surface can be prepared chemically or mechanically for the subsequent coating (pretreatment) by a pure implantation step, which can still be preceded in situ by the coating process. On some substrates, both the pretreatment and the ion mixing process can also be done using additional elements besides C and H, such as O, N or Si. Due to the high energy particle bombardment in the pretreatment and ion mixing phase of the process, a graded transition from substrate material to layer material can also be established. Properties such as thermal stability and optical transmission can also be solved by doping with elements such as O or Si. The latter, for example, to values of over 90%.

Before the actual coating process, the surface of the substrate must be cleaned. After the prepurification under atmospheric pressure with, for example, alcoholic (isopropanol), ketonic or aldehydic (acetone) or aqueous solutions (on an alkaline basis), the substrate is introduced into the vacuum chamber, which before further process steps up to a pressure between 1 · 10 ^-4 to 1 · 10 ^-1 Pa is evacuated (base pressure). To generate the noble gas ions, for example Ar ^{(+ n)} (n> = 1), noble gas is introduced into the vacuum chamber and a plasma discharge via a microwave (eg 2.45 GHz) or high / radio frequency (eg 13.56 MHz) ignited. This results in the vacuum chamber, a pressure between 1 × 10 ^-2 to 10 Pa (working pressure at Subtsratreinigungprozess by inert gas ion bombardment) in which the substrate is exposed to a noble gas ion bombardment.

Around in the subsequent coating, the layer adhesion on improve and reduce layer stresses, the substrate can be over a external heating (ia radiant heating) and / or the introduced Plasma power can be brought to temperatures up to 300 ° C. In the particular advantageous embodiment of the process, the temperature remains below 200 ° C to material gentle also to coat temperature-sensitive substrates. These in comparison to conventional PVD or CVD processes low treatment temperatures are due to the high to very high particle energies (1 to 30 keV) of the method in the plasma.

As starting materials (precursor) for the preparation of aC: H layers can be a variety of gaseous or liquid hydrocarbons with or without hydrogen substituents (Si, F, B, N, O, metals), as well as carbonaceous solids (eg graphite), which then Solid source sources such as vacuum evaporator arc or sputtering cathodes are placed in the gas / sublimation phase, can be used. To synthesize the diamond-like carbon layers, a process atmosphere of at least one hydrocarbon-containing gas, such as methane or acetylene or heavy hydrocarbons such as the aromatic benzene (C ₆ H ₆ ), methylbenzene (C ₇ H _B ) or trimethylbenzene (C ₉ H ₁₂ ) and Ar, N, CO, or CO ₂ or mixtures thereof, wherein the base pressure during the deposition process in a range between 1 · 10 ^-4 Pa and 1 · 10 ^-1 Pa, advantageously at 5 · 10 ^-3 Pa and the working pressure in a range between 1 × 10 ^-2 Pa and 10 Pa, advantageously at 1 Pa. The process gas is introduced to the working pressure in the process chamber and at the ignition point (1 · 10 ^-2 Pa - 1 Pa), the plasma source at a power of 200 to 1400 W, advantageously 600 W ignited. The excitation of the gas molecules by the electromagnetic radiation leads to a splitting of the bonds of the process gases, whereby it comes to the generation of a plasma with high proportions of reactive ionized atoms, molecules and / or molecular clusters. The plasma spreads via diffusion in the process chamber. The reactivity of the plasma alone already allows the deposition of a layer on the substrate surrounded on all sides by the plasma.

The Plasma can also influence the energetic states of the plasma surface take the substrates to be coated.

Without However, the application of a high voltage to the substrate is in the Use of hydrocarbons only deposition of soft polymer films possible (Plasma). In the method described here is in a pulsed mode, a negative high voltage in the range of -0.5 to -30 kV the conductive one Workpiece or for insulating substrates, the conductive substrate holder arranged behind it, created. The growing layer on the substrate, shaped arbitrarily can thus be from the positively charged and accelerated to the workpiece Bombarded ions from the plasma. Due to the high electrical voltage, the on the workpieces is applied, the charged particles are always perpendicular to the equipotential surfaces and thus accelerating the workpiece surface. Thus, an attack from all sides is equally guaranteed. The bombardment with the high - energy ions leads to a compression of the deposited material, to a modification of the H content of the Layer as well as a modification of the bonding states in the layer (Hybridizations) and thus to a greater hardness.

F:

Fluenz

U:

Spannung

d:

Schichtdicke ist,

konstant gehalten wird.The high energy of the ions can be compared to conventional deposition methods such as the sputtering or vacuum arc coating method or the CVD method, the deposition rate can be increased and still the necessary high hardness can be achieved, the process temperature, as mentioned, less than or equal to 200 ° C. The decisive factor is that the particle energy offered for more deposited layer volumes is increased, ie (FU / d), where

F:

fluence

U:

tension

d:

Layer thickness is,

is kept constant.

This can by the appropriate litigation in the case described here Procedure done.

The highest deposition rates with simultaneously high hardness could be achieved by ignition of an Ar plasma with the addition of methylbenzene. The use of other gas species such as CH ₄ or N ₂ or even a gas mixture with Ar or CO _{2 also} led to diamond-like carbon layers but with lower growth rate or lower hardness.

The significantly lower deposition rate when using light hydrocarbons such as methane or acetylene as a carbon source is due to the less favorable C: H ratio or the higher proportion of free H radicals when using these precursors. In this case, both less C is released for deposition and at the same time more reactive H ⁺ ions, so that there is a higher etch rate. In sum, this results in a low deposition rate of max. 1 μm / h.

conventional Plasma CVD methods can for procedural reasons offer only small particle energies from the plasma. When used of heavy hydrocarbons as precursors is therefore only one Deposition of soft polymer films possible because the decisive Parameter of particle energy is clearly too low and therefore only little energy during the deposit can be deposited in the layer, but for the necessary Modification of the bonding conditions, Breaking chains and rings as well as hybridization is needed. High rate deposition of hard a-C: H layers from this type of precursor is therefore not possible with conventional plasma CVD methods.

The Frequency of the high voltage pulses may be as described herein Method can be set between 50 Hz and 5000 Hz, advantageously 2000 Hz are used, the rising edge of the pulses advantageously 130 ns long and the duration of the pulses is about 0.5-50 μs, advantageously 1 μs.

The ion bombardment can be expressed by an ion fluence F in the unit [particle / cm ² ]. Typical deposition rates for DLC layers in this process are between 0.5 μm / h and 5 μm / h. The advantage of this method is above all in the high-rate deposition, ie greater than 2 μm / h.

Surprisingly, it was possible to establish a relationship between the particle energy E _in offered per deposited layer volume, which is composed of the fluence F of the ions, the applied pulse voltage U and the layer thickness d: e in = F · U / d results and the layer hardness are found. The layer hardness was determined dynamically with the help of a nanoindenter based on the principle of Oliver and Pharr with a Berkovich diamond tip. This now allows the reproducible production of diamond-like carbon layers with a hardness in an interval of 1 to 30 GPa. Depending on the application of such carbon layers, different hardnesses are necessary since other properties such as abrasion resistance, etc. are also associated with the hardness. It is therefore indispensable for the economical production of diamond-like carbon layers to be able to adapt the method for producing such layers quickly and reliably to the respective requirement and thus also to realize deposition of hard layers with high rates at moderate coating temperatures.

In an advantageous method - claim 2 - is the Substrate prior to deposition of the carbonaceous layer with pretreated with an ion implantation step (pretreatment). This additional Process step increased et al the adhesion of the layer to the substrate.

In Another advantageous method - claim 3 - is with providing a process atmosphere of a carbonaceous Gas mixture of at least one carbon-containing gas and a carrier gas about that also provided a doping gas. This is especially true Applications in the field of semiconductor electronics have the advantage that the buyer the layers produced by this method a starting material with a homogeneous basic funding for his further own processes receives. For mechanical or optical applications, for example in the field of automotive engineering or the optics, can over the Dopings for These applications require properties such as coefficient of friction or transparency be adjusted in accordance with the application.

In a further advantageous process - claim 4 - the carbonaceous gas is carbon (C), methane (CH ₄ ), acetylene (C ₂ H ₂ ), an aromatic such as benzene (C ₆ H ₆ ), methylbenzene (C ₇ H ₈ ) or trimethylbenzene (C ₉ H ₁₂ ), or another heavy CH compound. All these substances are industrially easy to produce and are suitable - in addition to their egg property as a carbon dispenser - therefore especially for an economical coating process.

In a further advantageous method - claim 5 and 6 - is as a carrier gas, a noble gas such as argon (Ar), or a gas such as nitrogen (N ₂ ), oxygen (O ₂ ), carbon monoxide (CO) or carbon dioxide (CO ₂ ) and as doping silane, silazane or siloxane, in particular SiH ₄ , HMDS, HMDSO and derivatives, or fluorine precursors such as hexafluorobenzene, fluorobenzene, tetrafluoroethylene, hexafluoroethane, and other fluorohydrocarbons, or organometallic precursors or a combination of these carrier and / or doping gases used , The advantage of using gaseous or liquid precursors is that the necessary doping elements are therefore available homogeneously in the gas space and do not flow from the source in a highly directional manner, as in the case of solid sources.

In a further advantageous method - claim 7 - is the carbonaceous gas mixture over Electromagnetic alternating fields ionized. This procedure has the advantage that the energy to be introduced for ionization is very easy to adapt to the respective gas species.

In a further advantageous method - claim 8 - is the carbon-containing gas mixture additionally via a vacuum arc discharge or transferred a Ionenabtrag in the plasma state. This method is suitable especially when using carbon solids, such as. Graphite, then over Vacuum evaporator arc or sputtering cathodes in the gas / sublimation phase is brought. In this way, additional carbon can be made available for example, to further increase the C: H ratio. Even if here from an additional Procedural step, the exclusive use of Carbon solids to provide the carbonaceous process atmosphere not be excluded.

In further advantageous methods, the substrate - claim 9 - of steel, magnesium, a titanium or aluminum alloy, a cobalt or cobalt-chromium alloy, silicon, glass or ceramic. To increase, for example, the service life of forming or cutting tools, bearing components such as balls or housings, or of drive components such as shafts and gears, usually made of steels such as 100Cr6 / 52100, X155CrVMol2-1 / D2, X8CrNiS189 / 303 or 42CrMoS4 It is advantageous to provide the steel products with low friction and hard wear protection layers such as DLC coatings. But also for optical components such as lenses, lenses and windows for optical systems, or for large-scale applications such as window glass, etc., a wear-resistant and chemically inert surface, as they form DLC layers, required by many industries. An increase in long-term stability is becoming increasingly important, especially in medicine in the field of human implants due to the ever-increasing life expectancy of the population. It is therefore particularly advantageous with the inventive method also typically used for implants materials, such as titanium alloys (eg TiAl ₆ V ₄ , TiAl ₆ Nb ₇ , TiNi), CoCr alloys, medical steels (eg 316L) or ceramic workpieces (eg Al ₂ O ₃ ) to coat - claim 12 -.

In Another advantageous method - claim 10 - is the Process temperature kept below 200 ° C. Especially with substrates that already have a certain pretreatment obtained, such as hardened steels, may be too high a substrate temperature in coating basic properties of the substrate, such as. the hardness, ductility or breaking strength by phase transformations and / or microstructural transformations disadvantageous change. Below 200 ° C the risk of such processes is very low, leaving the original ones Properties of the substrate are retained as core properties but the surface properties adapted to the respective application requirements and thus sustainable can be improved.

In further advantageous method - claim 11 - applies the ion current at each point of the substrate almost perpendicular to the substrate surface on. Due to the high electrical voltage of -0.5 kV to -30 kV, the on the workpieces is applied, the positively charged particles are always perpendicular to the equipotential surfaces and thus accelerating the workpiece surface. Thus, a uniform shelling guaranteed from all sides. Especially when coating complex three-dimensional objects, such as. Forming tools, gears, Waves or hip implants, is a uniform surface coating without the workpiece to have to move and the high deposition rate particularly economical.

One embodiment a series of measurements to the surprising found connection of layer hardness and A will be in the following closer to the drawing illustrated. It shows

1 Development of the layer hardness as a function of the particle energy introduced per volume.

In 1 is the dependence of Schichthär te as a function of the particle energy introduced per volume. The dashed line is only for better clarity. F is the ion fluence determined by Rutherford Backscattering Spectroscopy (RBS), U is the pulse voltage and d is the total layer thickness. It can be seen that with higher per volume of introduced particle energy, the layer hardness increases until it finally reaches a maximum. If the particle energy introduced per volume is further increased, the hardness of the layer decreases again. Corresponding determinations of the hydrogen content of the measured layers show that in the range 1 of the 1 Thus, before the maximum hardness, an increase in the particle energy introduced per volume leads to a decrease in the hydrogen content and formation of new CC bonds. These bonds are both sp ² and sp ³ bonds. The latter lead to an increase in the layer hardness. In the area 2 of the 1 , ie after the maximum hardness, the increase in the particle energy introduced per volume leads to a destruction of the sp ³ bonds, which then converted into sp ² bonds again lead to a reduction in hardness.

In order to obtain the maximum achievable for a given working gas composition (hydrocarbons and other carrier gases) hardness with increasing deposition rate, simultaneously with the deposition rate increase and the deposited energy per layer volume must be increased, which is equivalent to the constant hold of the E _in parameter.

1

Area increasing hardness

2

Area decreasing hardness

Claims (12)

Method for producing diamond-like carbon layers (DLC layers) of thickness d by means of an ion-supported deposition method with the method steps - Providing a substrate - Cleaning the substrate by means of a plasma etching process - Heating the substrate to a process temperature, wherein the process temperature in the range between 50 ° C and 300 ° C - providing a process atmosphere of a carbon-containing gas mixture of at least one carbon-containing gas and a carrier gas, wherein the base pressure of the process in a range between 1 · 10 ^-4 Pa and 1 · 10 ^-1 Pa, and the working pressure in a range between 1 x 10 ^-2 Pa and 10 Pa; depositing a carbonaceous layer from the gaseous phase on the substrate; generating an ionic current by means of a plasma discharge and applying a negative, pulsed voltage U to the substrate, the voltage being in a range of -0 , 5 kV to -30 kV, ie e repetition rate of the voltage pulses between 50 Hz and 5000 Hz, the pulse length between 0.5 .mu.s and 50 .mu.s and the ion current to an ion fluence F on the substrate characterized in that the hardness H of the diamond-like carbon layer in a range of 1 GPa to 30 GPa is set via the parameter E _in = F · U / d formed from the process parameters F, U, d at a deposition rate of the layer between 0.5 μm / h and 5 μm / h. Method according to claim 1, characterized that the substrate before deposition of the carbonaceous layer is pretreated with an ion implantation step. Method according to claim 1 or 2, characterized that with the provision of a process atmosphere of a carbonaceous Gas mixture of at least one carbon-containing gas and a carrier gas also at least one doping gas is provided. Process according to one of claims 1 to 3, characterized in that as the carbonaceous gas carbon (C), methane (CH ₄ ), acetylene (C ₂ H ₂ ), an aromatic such as benzene (C ₆ H ₆ ), methylbenzene (C ₇ H ₈ ) or trimethylbenzene (C ₉ H ₁₂ ) or another heavy CH compound is used. A method according to claim 3, characterized in that the doping gas is a silane, silazane or siloxane, in particular SiH ₄ , HMDS, HMDSO and derivatives, fluorine precursors such as hexafluorobenzene, fluorobenzene, tetrafluoroethylene, hexafluoroethane, and other fluorohydrocarbons, organometallic precursors or a combination thereof or carrier and these doping gases is used. Method according to one of claims 1 to 5, characterized in that a noble gas such as argon (Ar), or nitrogen (N ₂ ), oxygen (O ₂ ), carbon monoxide (CO) or carbon dioxide (CO ₂ ) is used as the carrier gas. Method according to one of Claims 1 to 6, characterized that the carbon-containing gas mixture ionizes via alternating electromagnetic fields becomes. Method according to one of claims 1 to 7, characterized that the carbon-containing gas mixture additionally via a vacuum arc discharge or an ion removal is transferred to the plasma state. Method according to one of claims 1 to 8, characterized that as a substrate steel, magnesium, a titanium or aluminum alloy, a Cobalt or cobalt-chromium alloy, silicon, glass or ceramic is used. Method according to one of claims 1 to 9, characterized that the process temperature is kept below 200 ° C. Method according to one of claims 1 to 10, characterized that the ionic current at each point of the substrate is almost vertical on the substrate surface is accelerated. Use of a method according to one of claims 1 to 11 for coating a component of the automotive or mechanical engineering, the Drive, bearing or engine technology, a tool for forming, Machining or other material processing, a component the pharmaceutical or chemical industry, a medical Implant or an optical component.