EP2279283A1

EP2279283A1 - Method for producing a multicomponent, polymer- and metal-containing layer system, device and coated article

Info

Publication number: EP2279283A1
Application number: EP08716732A
Authority: EP
Inventors: Michael Vergöhl; Thomas Neubert
Original assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Current assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date: 2008-03-27
Filing date: 2008-03-27
Publication date: 2011-02-02
Also published as: WO2009118034A1; US20110111131A1

Abstract

The invention relates to a method for producing layer systems on substrates (22) and to a system for carrying out the method and to an article produced by means of an embodiment of the method. In the method, a first vacuum coating source (32) is irradiated by an irradiating source (11), wherein the first vacuum coating source (32) comprises a first layer material, which is dissolved in a solvent. The second vacuum coating source (43) is applied to the substrate by means of a chemical vapour deposition process. In this way, novel layer systems and mixed layers, in particular mixed layers of polymers and metals or metal oxides, can be applied.

Description

METHOD FOR PRODUCING A MULTICOMPONENT, POLYMER AND METAL-BASED LAYER SYSTEM, DEVICE AND COATED SUBJECT

The invention relates to a method for producing a layer system on a substrate and to a system which is suitable for carrying out the method and to an article produced by means of the method.

The production of layer systems on substrates is of great industrial importance. Layer systems are mostly so-called thin-film systems, which are applied to the substrate by vapor deposition methods. The articles thus produced are used in various fields of technology. As an example sputtered on a substrate metal oxides are called which z. B. in the display, flat glass and automotive industry as well as in precision optics and ophthalmic be applied. On very soft and elastic plastic substrates, during the sputtering process, in particular during magnetron sputtering, process-related technical advantages such as the particularly high hardness and density of the applied layer are reversed: the different coefficients of expansion of the various mechanical and chemical properties of polymers and oxides often lead to poorer performance Layer adhesion and cracking.

In the case of Aufdampfprozessen is trying to compensate for the above defects by applying very loose and relatively soft coatings. However, the quality of the layers thus applied is very poor. Alternatively, attempts are being made to apply pure polymer coatings to plastic substrates, the polymer coatings reacting insensitive to mechanical stresses. However, the polymer coatings often fail to achieve the same desired optical, electrical and mechanical properties as metal or metal oxide films.

In the production of polymer layers, these are often produced from the liquid phase by means of spin coating or dipcoating. An application of the polymer layers in sputtering processes, for example, is usually out of the question, since due to the high particle energies of the ions, the organic bonds are often destroyed. In the prior art, a low energy coating technique called "matrix assisted pulse laser evaporation" for depositing polymers from the gas phase is known to address this problem. This is described, for example, in US Pat. No. 6,025,036. In this case, monomers are in dissolved in a solvent, which is then frozen with liquid nitrogen. A pulsed excimer laser heats the monomer source so generated that solvent and individual monomers pass into the gas phase. From the gas phase, the monomers can then be deposited on the substrate surfaces as a polymer layer.

However, the use of a laser to remove the monomers has some disadvantages. Thus, the generation and control of the laser beam is quite expensive and scaling up to produce large quantities of coated articles is difficult due to the lack of scalability of the laser.

The object of the present invention is to provide a method which does not have the aforementioned problems in the application of different layers to a substrate and allows novel layer systems.

The object is achieved by means of a method according to claim 1. Further embodiments are described in the subordinate claims.

In the method according to the invention, a first vacuum coating source, which consists of at least one first coating material dissolved in a solvent, is positioned. The first coating material bonds better to a substrate than the solvent under a prevailing negative pressure, and the solvent is desorbed from the first vacuum coating source under irradiation by an irradiation source, whereby the first coating material is exposed from an exposed surface of the first vacuum source. coating source is released. Furthermore, a second vacuum coating source, which has at least one second coating material, is positioned. The second coating material is released by a vapor deposition method and the released first and second layer materials are deposited on the substrate in such a way.

The positioning of the first and second vacuum coating sources is such that the released first and second layer materials can deposit from the vacuum coating sources on the substrate. In the prior art, the mastery of these process parameters is well known.

By means of the method according to the invention, it becomes possible to produce layer systems which have properties which are not yet available in the prior art. In particular, monomers and polymers can be deposited on the substrate by means of the first coating material dissolved in a solvent. In this case, the first vacuum coating source is a monomer source which has been frozen, for example by means of liquid nitrogen, and which is heated by the irradiation source. This is done in contrast to the prior art not with an excimer laser, but only with an adjusted irradiation source. The use of an ion beam source as the irradiation source in the method according to the invention has the effect that at low ion energies and high ion currents or high current densities, the first layer material can be dissolved out of the solvent without destroying the first layer material. The second coating material is located on a second vacuum coating source and can thus be deposited on the substrate before, after or simultaneously with the first coating material. In particular, when using a second coating material, which differs greatly in its properties from those of the first coating material, so layer systems are possible whose production was not previously feasible.

The use of an ion beam source contributes in particular to the fact that the method for applying the first coating material can also be realized on a large industrial scale. Until now, this was only possible with great difficulty when using the laser. In this case, the surprising effect of the ion beam source or merely the irradiation by means of direct radiation heating helps to apply the first layer material dissolved in the solvent to the substrate.

In one embodiment of the method according to the invention, the vapor deposition method is a physical vapor deposition method, preferably a magnetron sputtering or reactive magnetron sputtering. Physical vapor deposition processes are already scalable on a large industrial scale. This applies in particular to magnetron sputtering, in which already high reaction rates can be achieved. Also, the thickness of the applied layer is easy to control.

In order to prevent overheating of the first vacuum coating source, the radiation source in the pulsed operation can be used. In this case, high energy inputs occur for a short time, which on the one hand cause removal of the first layer material from the first vacuum coating source, but on the other hand reduce the time-integrated energy input.

Particularly advantageously, the method is used when the substrate has a plastic surface and preferably consists of a plastic. With this method, it is also possible to improve the adhesion of inorganic coatings produced by sputtering or vapor deposition on plastic substrates such as PMMA, PC or PET.

For optimum adhesion of the layers applied to the substrate, it is advantageous if the plastic surface is activated by means of a plasma treatment before the deposition of the first and / or second coating material. This has the advantage that the surface can be better contacted by the first and / or second coating material, which improves the adhesion between the substrate and the first and / or second layer.

In a further embodiment of the method according to the invention, first a layer of the first coating material is deposited on the substrate and then a layer of the second coating material or a mixed layer, ie composite layer, of the first and the second layer material is deposited on the substrate. The first layer of the first coating material forms an adhesive layer between the substrate and the following layers. The term "adhesive layer" is to be understood not only as meaning that the adhesion between the substrate and the first layer is improved, but also the adhesion between the first layer and the second layer is substantially improved. Particularly when using mixed layers, gradient composite layers of different composition can be produced, which can be examined under process parameters in their mechanical properties, such as, for example, bracing, adhesion, hardness and cracking, in various compositions and subsequently produced.

In a further embodiment of the method, the first coating material and the second coating material are simultaneously deposited as a layer on the substrate. As a result, the production of the aforementioned mixed layers is greatly simplified. In this case, the mixed layer designed in this way does not necessarily have to be applied as a first, second or third layer, but can be applied at any desired time.

In a particularly preferred embodiment, the first layer material is a monomer or a polymer. This is particularly advantageous in connection with a plastic substrate or a substrate having a plastic surface, since the first coating material forms the aforementioned adhesive layer in this case. Suitable polymers are, for example, PET, PMMA or PEG.

Furthermore, it is advantageous if the second coating material is a metal, preferably aluminum, silicon, niobium or titanium, or a metal mixture such as In: Sn, or a metal ceramic such as SiO ₂ , Si ₂ N ₄ , Al ₂ O ₃ , NbOx , TiOx, TaOx, In ₂ O ₃ : Sn, MgF ₂ or MgO. By the deposition of metals in pure, alloyed or ceramic form, it is possible to provide the substrates or the substrates having the substrates with a very hard and crack-resistant layer. In this case, the second coating material is preferably applied to a layer of the first coating material consisting of a polymer or monomer or another organic material so as to improve the adhesion between a substrate, particularly preferably a plastic substrate, and the metal layer. In this way, objects can be created which consist of a substrate and have a metal or metal oxide layer which up to now could not be applied to the plastic substrate due to a lack of adhesive strength or could not be applied in the desired quality.

In a further embodiment of the method, the first and the second vacuum coating source are spaced apart from one another and are preferably separated from one another by a coating protection. In this way, in particular the more sensitive first layer material can be applied undisturbed by the application method of the second layer material, which increases the yield and thus the layer quality, in particular of the first coating material. For example, a simple shading sheet between the first and the second vacuum coating source can serve as coating protection.

In another embodiment, the uncoated substrate is moved past a movable substrate holder past the first and second vacuum coating sources. In the

Passing by the first and the second vacuum Layering source, the uncoated substrate is coated, wherein the coating may consist of both a plurality of pure layers of either the first or the second layer material or may consist of individual layers of mixed layers, which have both the first and the second layer material.

The abovementioned embodiments of the method according to the invention can be combined with one another within the context of the dependencies of the claims. In particular, a system for coating a substrate with a layer system is suitable for carrying out the method according to the invention, the system comprising a coating chamber, a substrate holder, a first vacuum coating source, preferably of a first coating material dissolved in a solvent, and an irradiation source second vacuum coating source, preferably with a second coating material, and a device for vapor deposition is present, so that the second coating material is deposited on the substrate. The objective aspects of the embodiments of the method according to the invention are in the inventive system for

Implementation of the method applicable and feasible in this. This applies, for example, to the moving substrate holder. Coating chambers are well known in the art and will not be discussed further here.

By means of an embodiment of the method according to the invention, it is possible to produce an article which has a substrate provided with a layer system, wherein the substrate comprises a plastic and the layer system has at least one first and one layer system second layer. The first layer can be formed by a pure polymer layer such as PMMA, PE, PP, PC, PET, PVC, PTFE, a copolymer layer or an organic, non-polymeric layer such. B. from organic color pigments or organic molecules with special groups formed. The second layer may consist of a composite layer of polymer or organic material and metal, such as Si, Al, Ti, Nb, Cu, Cr or C. A composite layer of polymer or organic material and metal ceramics, preferably oxides, but also fluorides and nitrides, such as, for example, SiO 2, Si 3 N 4, Al 2 O 3, NbO x, TiO x, TaO x, In 2 O 3: Sn, MgF 2 or MgO, is advantageous.

Furthermore, the second layer or a further layer arranged on the second layer may also merely be a simple metal or metal-ceramic layer.

In particular, by means of the composite layers, it is possible by means of a layer gradient between the organic material and the metal oxide to produce an adhesion-promoting effect between the substrate and metal or metal-ceramic layers which could not be produced by previous methods. In addition, the elasticity of the usually hard and brittle metal and metal-ceramic layers is increased by the supply of organic layer components and polymers. This results in greater flexibility and stretchability of the layers, less cracking and greater mechanical resistance. With the embodiments of the method, as well as the objects numerous applications can be carried out or produced:

• Preparation of adhesion promoting layers for physical vapor deposition processes

Production of flexible, crack-resistant, optical layer systems on plastic sheets or foils, such as e.g. Antireflection layers, optical filters or contrast-enhancing screens

Plastic films

• Formation of flexible, crack-resistant, optical layer systems as a multilayer stack of high and low refractive index metal oxide-polymer composites

Adherent and flexible scratch-resistant coatings on plastic substrates such as PMMA by means of a physical vapor deposition process

Sub-layers for photocatalytic layers, e.g. anatases TiO2, on plastic substrates like

PMMA by a physical vapor deposition method

• Diffusion barriers for 02 and / or H2O on plastic sheets and foils • Anti-static coatings on plastic sheets and foils

• Electrically conductive oxides on plastic sheets and foils

• Adhesion-resistant deposition of organic layer components with special functional groups for medical technology and chemical analysis.

Moreover, with the method according to the invention, not only is it possible to embed polymers in a coating, but biopolymers can also be incorporated. Thus, completely new properties are realized. These biopolymers can be applied to the layer, for example, as a monomer or else directly as a biopolymer from the source.

Non-limiting examples include: proteins, peptides, polysaccharides (starch, cellulose, glycogen) and polyglucosamine (chitin, chitosan).

As an alternative to the methods proposed so far, it is possible to dispense with the use of a second vacuum deposition source and the associated device for vapor deposition, so that articles with one or more pure polymer layers can also be produced. The advantages of

Ion beam source is then as described above in the greatly improved Aufskalierbarkeit compared to a laser. In addition, the use of the ion beam source can improve the application of the first layer material to a plastic substrate. Possible layer and / or substrate materials can be taken from the previous sections. By means of this method, for example, objects can be produced which have a substrate made of plastic with a pure polymer or copolymer layer applied thereon.

Other aspects of the invention will be discussed in more detail in the embodiments. Show it:

1a, b embodiments of a system according to the invention,

Fig. 2 shows an article according to the invention. In Fig. Ia, a system 1 for performing various embodiments of the method according to the invention is shown. The system 1 has a coating chamber 10 in which an ion beam source 11, a turbo-pump 12 and a rotary motor 13 with an axis of rotation 14 attached thereto are arranged. On the rotation axis 14, a substrate holder 20 for holding substrates 21, 21 'is arranged. The substrate holder 20 is rotated about the rotation axis 14 about the rotation motor 14.

The ion beam source 11 is arranged to irradiate a first vacuum deposition source 31. The irradiation is carried out with low-energy ions with high current densities so as not to destroy the first coating material located in the first vacuum coating source 31.

The first vacuum coating source 31 is made of a deep-frozen first coating material dissolved in a solvent. The first coating material in the present case is a monomer of methyl methacrylate. Upon irradiation of the first vacuum deposition source 31 with the lower energy ions, the solvent becomes the first one

As a result, the first coating material is released from the surface of the first vacuum coating source 31 facing the substrate 21 and deposits on the substrates 21 and 21 'due to the prevailing negative pressure in the coating chamber 10. Upon desorption of the solvent from the first vacuum coating source 31 and the monomers released thereafter, the monomers either combine to form polymers, either on the path between the first vacuum coating source 31 and the substrates 21 and 21 ', respectively the connection to polymers takes place only on the substrate 21 or 21 'itself.

The substrates 21 and 21 'are plastic sheets or films of PMMA. The first

Layer material then forms a polymer layer on the surface of the substrate 21 due to the irradiation, so that a first pure polymer layer is formed on the bare PMMA. However, the method also works when only the uncoated surface of the substrate is made of PMMA.

As already mentioned, there is a negative pressure in the coating chamber 10 which is produced via the turbo-pump 12. The working pressure is in the range between 10 ^"1 to 10 ^{" 7} mbar, wherein preferably a working pressure of 10 ^"2 to 10 ^{" 4} mbar is maintained in the coating chamber.

In addition to the first vacuum coating source 31, there is a second vacuum coating source 41 in the coating chamber 10. The first vacuum coating source 31 and the second vacuum coating source 41 are spatially separated from each other by a coating protector 42, and the meaning of the separation will be described later. The second vacuum coating source 41 comprises a second coating material, which in the present case is titanium. Between the second vacuum coating source

41 and the substrate holder 20, an electric field is applied on the one hand, and below the second vacuum coating source 41 on the other hand there is a magnetron with which a magnetic field can be applied to the second vacuum coating source 41. In the environment between the second vacuum Layering source 41 and the substrate holder 20 is a plasma, as it is known in magnetron sputtering. The coating protection 42 prevents the plasma, and in particular the highly reactive oxygen ions, from extending into the subregion of the coating chamber 10 which lies between the first vacuum coating source 31 and the substrate holder 20. This is to prevent the reactive oxygen ions from being released from the first vacuum coating source 31

Attack monomers by oxidation before they can form a polymer layer on the substrate 21 and 21 '.

The titanium from the second vacuum deposition source 41 is deposited on the substrate 21 'and 21, respectively, by magnetron sputtering. In this case, oxygen is added to the plasma, which is usually formed by argon ions, so that the titanium dissolved out of the second vacuum coating source 41 combines with the oxygen to form a titanium oxide. The titanium oxide is then deposited as a thin layer on the substrate 21 'and 21, respectively.

The system 1 shown in FIG. 1 a can be operated in several operating modes. In a first operating mode, the substrates 21 and 21 'can first be coated with a polymer layer by means of the ion beam source 11. This is possible because the rotary motor 13 rotates the substrate holder 20 about the axis of rotation 14 and thus all substrates located on the substrate holder can be covered with the polymer layer. After a sufficient thickness of the polymer layer has been produced on the PMMA, the polymer coating process is stopped and the titanium of the second vacuum Layering source 41 is removed from the second vacuum coating source 41 by means of magnetron sputtering. In this way, a second layer is deposited on the first layer of the substrate, which may consist of a titanium oxide, generally of a metal oxide, semi-metal oxide, metal, semi-metal or a metal ceramic. In this way, among other things mechanically flexible high and low refractive optical layers can be deposited. By producing layer stacks, it is thus possible to realize mechanically flexible optical layer systems such as a broadband antireflection layer system or optical filters.

In comparison to previously known substrates made of PMMA, these optical layer systems have good adhesion, since they are not deposited directly on the substrate made of PMMA itself, but rather on a PMMA metal oxide transition layer with stronger toothing and chemical bonding between the polymer and the metal oxide.

Thus, the deposited on the substrate layers have a good quality, in particular, it is prevented that the metal oxide layer is poorly liable or cracks.

As a further mode of operation, first a first layer of a polymer can be deposited on the substrate 21 or 21 'and then, with simultaneous operation of the ion beam source 11 and the magnetron of the second vacuum coating source 41, a mixed layer can be applied during rotation of the substrate holder 20 along the axis of rotation 14, which consists of both a polymer and a metal oxide. In this case, the concentration of the individual components of the mixed layers, ie the weight percentages of the first and the second layer materials, for example via the deposition rates of the first or the second layer material or the rotational speed of the substrate holder 20 can be adjusted. In this way, the layer properties can be changed, which in particular brings new opportunities for hardness, elasticity and the refractive and absorption index and the layer adhesion with it. A further metal or metal oxide layer could also be applied to such a mixed layer by means of magnetron sputtering or another physical vapor deposition process. Other physical deposition methods, such as thermal evaporation, electron beam evaporation or ion beam sputtering, are suitable for applying the second layer material in addition to magnetic sputtering.

FIG. 1b shows a further system I ¹ which is particularly well suited for the production of coated substrates on an industrial scale. The system I ¹ has a coating chamber 10 'into which a substrate holder 20' can be retracted via an entrance lock 15 and driven out via an exit lock 15 '. The guide means of the substrate holder 20 ', which is not shown in the drawing, in the present example, the substrate from right to left. This means in particular that the substrate 22 applied to the substrate holder 20 'is not yet coated on the right-hand input side of the coating chamber 10', but is coated with different layers at the exit from the coating chamber 10 'through the lock 15'. To the right of the lock 15 or to the left of the lock 15 ', ie outside the illustrated coating chamber 10 ', there are adjacent InIine segments for pretreatment and deposition of further layers. Thus, the substrate can be activated in the inline segment to the right of the lock 15 by means of plasma treatment. The coating chamber 10 'is under a

Vacuum, which is comparable to the negative pressure of the system 1 of Fig. Ia, d. H. the negative pressure moves in the same order of magnitude. Again, an ion beam source 11 is shown, which irradiates a first vacuum deposition source 32. The first vacuum coating source 32, like the first vacuum coating source 31 of FIG. 1a, is a first coating material dissolved in a solvent.

The ion beam source 11 extends into the image plane, so that the first vacuum coating source 32 is irradiated with low-energy ions over the entire width of the substrate 22 extending into the image plane, so that a first polymer layer projects over the entire surface projecting into the image plane Width of the substrate 22 may extend. The substrate 22 is a plastic substrate made of PET. The first layer material of the first vacuum deposition source 32 in the present example is polymethyl methacrylate (PMMA), but may also be a polyethylene glycol (PEG). On the substrate 22, therefore, a PMMA layer is first applied. When moving the substrate 22 by means of the movable substrate holder 20 ', the substrate 22 now coated with a first PMMA layer is transported farther to the left beyond a coating protection 44 which separates the coating process of the first layer from the coating process of a second layer. The second coating process takes place by means of a second vacuum Layer Source 43. As shown, the second vacuum deposition source 43 is disposed at a slight angle to the wall of the deposition chamber 10 'such that even some of the second layer material sputtered by magnetron sputtering of the second vacuum deposition source 43 together with some of the first layer material of the first vacuum deposition source 32 may form a mixed layer on the substrate 22.

The second layer material of the second vacuum coating source 43 is silicon, wherein the plasma located between the substrate 22 and the second vacuum coating source 43 is enriched with oxygen to form a reactive plasma, so that the layer deposited on the substrate is a silicon oxide. Of course, a pure metal such as aluminum, chromium or titanium or their ceramic forms could be deposited on the substrate. After a pure

Layer of the second layer material has been deposited on the provided with the first layer and the mixed layer substrate 22, the arranged on the substrate holder 20 'substrate leaves the coating chamber 10' through the lock 15 'for further processing.

As can easily be seen from the example from FIG. 1 b, the method according to the invention and / or its embodiments is simple and scalable for

Deposition of flexible optical layer systems with good layer adhesion and low tendency to crack formation, especially suitable for critical requirements such as outdoor applications or humidity or mechanical stress. Furthermore, layers with improved properties can be produced wherein the improved properties are adjustable, in particular via the mixing between the first and the second layer material in a mixed layer. Furthermore, it is well illustrated in FIG. 1b how the new method or the system for carrying out the method can be integrated into existing processes, wherein the integration is relatively inexpensive and long-term new applications such. B. active components in optoelectronics are possible. This is partly due to the fact that the homogeneous deposition of first and second layers or mixed layers even on large areas such. B. slides or plates is possible. With the systems for carrying out the method and the different embodiments of the method it is possible to realize new and better optical layer systems, such as, for example, As antireflection coatings, filters or selective mirrors, which can be used in the automotive industry, in the field of consumer optics, in ophthalmology, in medical technology, in sensor technology or in display technology.

The in Figs. Ia and Ib shown systems 1 and 1 ', instead of an ion beam source 11 and a radiant heater for irradiating the first

Vacuum coating source 31 and 32, respectively. Even with a metered irradiation of the first vacuum coating source, it is possible to desorb the solvent and to detach the first layer material, so that it can settle in the form of a layer on a substrate.

FIG. 2 is also intended to deal with a coated substrate 23, which by means of various embodiments of the invention

Method can be produced. The coated one Substrate 23 comprises a plastic 230, which represents an uncoated substrate. The plastic 230 itself may be, for example, a PMMA, PC or PET. On this a first layer 231 is applied, which consists of a polymer such as polymethyl methacrylate or polyethylene glycol. On the first layer 231, a mixed layer 232 is applied, which consists of both a first and a second layer material, wherein the first layer material is a polymer and the second layer material is a metal or metal oxide. On the mixed layer 232, a second layer 233 is applied, which consists of the one metal or metal oxide. As alternative materials for substrate and first and second

Layer material is referred to previous sections. The thickness of the various layers can vary between a few nm to a few μm. For optical layer systems, the single-layer thicknesses are in the range between 1 nm and several 100 nm

The coated substrate 23 illustrated herein may then be further processed into articles as previously described or as recited in the claims.

List of reference numbers:

1.1 'system

10,10 'coating chamber 11 ion beam source

12 Turbopurape

13 rotary motor

14 rotation axis 15,15 'locks 20 substrate holder

21, 21 ', 22, 23 substrate

31.32 first vacuum coating source

41.43 second vacuum coating source

42.44 Coating protection 230 Plastic

231,233 shift

232 mixed layer

Claims

claims

1. Method for producing a layer system

(230) on a substrate (21, 21 '; 22; 23) comprising the steps of:

a) positioning a first vacuum deposition source (31; 32) which has at least one first coating material (231) dissolved in a solvent, wherein the first coating material (231) better under vacuum to the substrate (21, 21 ', 22 23) binds as the solvent and the solvent is desorbed from the first vacuum deposition source upon irradiation by an irradiation source (11), whereby the first coating material is released from an irradiation exposed surface of the first vacuum deposition source (31; 32); b) positioning a second vacuum coating source (41; 43) comprising at least one second coating material (233);

c) irradiating the first vacuum coating source (31; 32) by means of an irradiation source (11), wherein the solvent is desorbed by the radiation impinging on the first vacuum coating source (31; 32) and the second coating material (233) is released by a vapor deposition method and the released first and second coating materials (231, 233) are deposited on the substrate (21, 21 ', 22, 23).

2. Method according to claim 1, characterized in that the vapor deposition method is a physical vapor deposition method, preferably magnetron sputtering or reactive magnetron sputtering, and / or the irradiation source is a heating beam or an ion source or an electron beam source.

3. The method according to any one of claims 1 or 2, characterized in that the irradiation source (11) is pulsed or operated in radio frequency.

4. The method according to any one of the preceding claims, characterized in that the substrate (21, 21 '; 22; 23) has a plastic surface

(231) and preferably consists of a plastic.

5. The method according to claim 4, characterized in that the plastic surface (231) before the deposition of the first and / or second layer material (231, 233) is activated by plasma treatment.

6. The method according to any one of the preceding claims, characterized in that first a layer of the first layer material (231) on the substrate (21, 21 '; 22; 23) is deposited and then a layer of the second layer material (231) or a mixed layer

(232) is deposited from the first and the second layer material on the substrate.

7. The method according to any one of the preceding claims, characterized in that the first layer material (231) and the second layer material (233) are deposited simultaneously as a layer on the substrate (21, 21 '; 22; 23).

8. The method according to any one of the preceding claims, characterized in that the first layer material (231) is a monomer or a polymer, preferably an organic monomer or

Polymer, is.

9. The method according to claim 8, characterized in that the polymer is a PE (polyethylene), PP (polypropylene), PVC (polyvinyl chloride), PS (polystyrene), PTFE (polytetrafluoroethylene), PMMA

(Polymethyl methacrylate), PA (polyamide), polyester, PC (polycarbonate) or PET (polyethylene terephthalate), PEG (polyethylene glycol) or polyacrylic acid.

10. The method according to claim 8, characterized in that the polymer is a biopolymer, preferably a protein such as enzymes, hair, silk, DNA, RNA, or a carbohydrate such as cellulose, wood, paper, starch, chitin, or a polyhydroxyalkanoate ,

11. The method according to any one of the preceding claims, characterized in that the second layer material (233) is a metal, preferably Si, Al, Nb, Ta, Bi, Zn, Sn, Mg, Hf, Zr, Ag, Wf or Ti, a Metal mixture, preferably In: Sn or ZnO: Al, or a ceramic, preferably SiO 2, Si 3 N 4, A 12 O 3, NbO x, TiO x, TaO x, In 2 O 3: Sn, MgF 2 or MgO (all oxides from above, nitrides from above and mixtures thereof), and preferably deposited in ceramic form on the substrate.

12. The method as claimed in one of the preceding claims, characterized in that the first and the second target (31, 41, 32, 43) are spaced apart from one another and are preferably separated from one another by a coating protection (42, 44).

13. The method according to any one of the preceding claims, characterized in that the substrate (21, 21 ', 22, 23) on a movable substrate holder (20; 20') on the first and second vacuum coating source (31, 41; 32, 43) is preceded.

14. System (1; 1 ') for coating a substrate with a layer system, the system comprising a coating chamber (10; 10'), a substrate holder (20; 20 '), a first vacuum deposition source (31; a first layer material (231) dissolved in a solvent and an irradiation source, characterized in that a second vacuum coating source (32, 43) with a second layer material (233) is present and a device for vapor deposition is present, so that the second layer material (233 ) is deposited on the substrate (21, 21 '; 22; 23).

15. An article (200) having a substrate (23) provided with a layer system, wherein the substrate is a plastic and the layer system (233) at least a first and a second layer and the first layer contains polymers and the second layer comprises a metal or metal oxide.

16. An article according to claim 15, characterized in that the layer system has an anti-reflection layer, scratch-resistant layer, barrier layer against oxygen and / or water vapor or a transparent conductive layer.

17. Use of an article according to claims 15 or 16 as a cluster cover in the automobile,

Display with antireflective coating, plastic disc with coating according to claim 14; Plastic disc in the automobile, audio video area: CD, DVD, Blue-ray disc with a scratch-resistant coating.

18. A method for producing a layer system on a substrate, comprising the following steps:

a) positioning a first vacuum deposition source, which consists of at least one dissolved in a cryogenic solvent first layer material, the first layer material under negative pressure better binds to the substrate than the solvent and the solvent under irradiation by an ion source from the first vacuum coating source is desorbed, whereby the first layer material is released from an exposed surface of the first vacuum coating source; b) irradiation of the first vacuum coating source by means of an ion source, wherein the light sources applied to the first vacuum coating source the ions are desorbed from the first vacuum coating source and the released first layer material is deposited on the substrate.