EP4127261A1 - Système de couches barrières et procédé de fabrication d'un système de couches barrières - Google Patents

Système de couches barrières et procédé de fabrication d'un système de couches barrières

Info

Publication number
EP4127261A1
EP4127261A1 EP21715230.5A EP21715230A EP4127261A1 EP 4127261 A1 EP4127261 A1 EP 4127261A1 EP 21715230 A EP21715230 A EP 21715230A EP 4127261 A1 EP4127261 A1 EP 4127261A1
Authority
EP
European Patent Office
Prior art keywords
layer
parylene
layer system
oxide layers
deposited
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21715230.5A
Other languages
German (de)
English (en)
Inventor
Emmy TÖRKER
Franz SELBMANN
Claudia Keibler-Willner
Mario Baum
Maik Wiemer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP4127261A1 publication Critical patent/EP4127261A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/44—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase

Definitions

  • the invention relates to a layer system and a method for producing such a layer system which has barrier properties against oxygen and water vapor.
  • Electronically active materials that are used in a wide variety of electrical assemblies are often highly sensitive to moisture and atmospheric oxygen.
  • a protective layer on the materials to be protected or by housing the assemblies using additional components.
  • solar cells are often protected from moisture and other external influences by means of glass.
  • plastic films are also used for encapsulation. Such plastic films must be coated for an adequate protective effect. For this reason, at least one so-called permeation barrier layer (hereinafter also referred to as a barrier layer) is deposited on them.
  • Barrier layers sometimes offer very different levels of resistance to different permeating substances.
  • the permeation of oxygen (OTR) and water vapor (WVTR) through the substrates provided with the barrier layer under defined conditions is often used to characterize barrier layers (WVTR according to DIN 53122-2-A; OTR according to DIN 53380-3).
  • Coating with a barrier layer reduces the permeation through a coated substrate compared to an uncoated substrate by a factor that can be in the single-digit range or many orders of magnitude.
  • various other target parameters are also often expected from a barrier layer. Examples of this are optical, mechanical and technological-economic requirements.
  • Barrier layers should often be almost completely transparent in the visible spectral range or beyond. If barrier layers are used in layer systems, it is often advantageous if Coating steps for applying individual parts of the layer system can be combined with one another.
  • PECVD processes plasma enhanced chemical vapor deposition
  • barrier layers These can be used when coating a wide variety of substrates for different layer materials. It is known, for example, to deposit Si0 2 and Si 3 N 4 layers with a thickness of 20 to 30 nm on 13 ⁇ m PET substrates [AS da Silva Sobrinho et al., J. Vac. May be. Technol. A 16 (6), Nov / Dec 1998, p. 3190-3198]
  • WVTR 0.3 g / m 2 d
  • OTR 0.5 cm 3 / m 2 d
  • barrier layers by sputtering. Sputtered individual layers often show better barrier properties than PECVD layers.
  • numerous other materials are known which are used, in particular, by reactive sputtering for the production of transparent barrier layers.
  • the layers produced in this way also have insufficient barrier effects.
  • Another disadvantage such layers are due to their low mechanical strength. Damage caused by technologically unavoidable stresses during further processing or use usually leads to a significant deterioration in the barrier effect. This often makes sputtered individual layers unusable for barrier applications.
  • Another disadvantage of sputtered layers is their high costs, which are caused by the low productivity of the sputtering process.
  • barrier layers By means of such PVD processes, different materials can also be deposited directly or reactively on a wide variety of substrates.
  • reactive vapor deposition of PET substrates with Al 2 O 3 is known [Surface and Coatings Technology, Vol.125 (2000), p. 354-360]
  • This barrier effect is also much too weak for materials coated in this way to be able to be used as barrier layers for electrical products. They are often even less mechanically resilient than sputtered individual layers.
  • the cured acrylate film is then coated with an oxidic intermediate layer, to which an acrylate film is in turn applied. This procedure is repeated several times if necessary.
  • the permeation values of a layer stack produced in this way i.e. a combination of individual oxide barrier layers with acrylate layers as intermediate layers, is below the measurement limit of conventional permeation measuring devices. Disadvantages arise here above all in the necessary use of complex system technology.
  • a liquid film initially forms on the substrate, which has to be cured. This leads to increased system contamination, which shortens maintenance cycles.
  • the intermediate layer functioning as a barrier layer is usually produced by means of magnetron sputtering.
  • magnetron sputtering it is disadvantageous that the use of sputtering technology means that a comparatively slow process is used. This results in very high product costs, which result from the low productivity of the technologies used.
  • the invention is therefore based on the technical problem of creating a barrier layer system and a method for producing such a barrier layer system with which the problems from the prior art can be overcome.
  • the barrier layer system should have a high barrier effect against oxygen and water vapor.
  • the barrier layer system is intended to produce a barrier effect both on substrates with flat surfaces, such as for example on plastic films, and on substrates with a profiled surface structure, as is the case with, for example Semiconductor components is given.
  • the barrier layer system should be able to be used as a flexible substrate, have an optical transparency and be biocompatible.
  • a layer system according to the invention with barrier properties against oxygen and water vapor initially comprises an alternating layer system consisting of
  • the alternating layer system of a layer system according to the invention consists of at least two aluminum oxide layers and at least two titanium oxide layers which are deposited alternately on top of one another.
  • the barrier effect of a layer system according to the invention can be further increased if more than two aluminum oxide layers and two titanium oxide layers are deposited alternately on top of one another within the alternating layer system. For economic reasons, it is not expedient to deposit more than six aluminum oxide layers and six titanium oxide layers alternately on top of one another.
  • a layer system according to the invention comprises a first parylene layer which is deposited on a first side of the alternating layer system and has a layer thickness of 0.1 ⁇ m to 50 ⁇ m.
  • the first parylene layer preferably has a layer thickness of 1 ⁇ m to 10 ⁇ m. This layer thickness range fulfills both requirements with regard to good barrier properties of the layer and the economic efficiency of the layer deposition process.
  • an alternating layer system is first formed in which at least two aluminum oxide layers and at least two titanium oxide layers are deposited alternately on top of one another.
  • the aluminum oxide layers and the titanium oxide layers are deposited
  • ALD atomic layer deposition
  • the aluminum oxide layers and titanium oxide layers deposited in the method according to the invention by means of ALD are therefore also jointly referred to below as ALD layers for short.
  • At least one precursor is usually let into a first working chamber, as a result of which functional groups of the precursor react with the surface of a substrate arranged in the working chamber, as a result of which a layer is formed on the surface of the substrate.
  • the deposition of an aluminum oxide layer by means of ALD for a layer system according to the invention is preferably carried out by means of two precursors.
  • a first precursor is first admitted into the first working chamber, from which molecules on the
  • the molecules of the first precursor that do not adhere to the substrate surface or the working chamber walls are removed from the first working chamber by means of a flushing gas.
  • a second precursor is then admitted into the first working chamber, with molecules of the second precursor reacting with the molecules of the first precursor adhering to the surface of the substrate to be coated and consequently forming a layer on the surface of the substrate to be coated.
  • Trimethylaluminum and water are suitable as first and second precursors for the formation of an aluminum oxide layer by means of ALD for a layer system according to the invention.
  • a titanium oxide layer is also formed by means of two precursors in the method according to the invention. Titanium tetrachloride and water, for example, can be used as the first and second precursors.
  • One requirement of a layer system according to the invention is that it has barrier properties with regard to oxygen and water vapor. It is therefore necessary for the individual ALD layers of the alternating layer system of a barrier layer system according to the invention to be deposited as completely closed layers as possible. In the method according to the invention, therefore, both the individual aluminum oxide layers and the individual titanium oxide layers are Alternating layer system deposited with a layer thickness of at least 5 nm each.
  • both the individual aluminum oxide layers and the individual titanium oxide layers of the alternating layer system of a barrier layer system according to the invention are deposited with a layer thickness of 5 nm to 20 nm each.
  • the ALD layers are deposited with a layer thickness of 5 nm to 10 nm.
  • this layer thickness range on the one hand, closed aluminum oxide layers and closed titanium oxide layers with good barrier properties are formed and, on the other hand, from an economic point of view and / or with functional requirements, such as transparency of the layer system with respect to light radiation, it is advantageous if the individual layers of the alternating layer system are not made too thick .
  • an aluminum oxide layer and only then a titanium oxide layer is formed on a substrate.
  • temperatures above room temperature are set within a working chamber selected for the ALD layer deposition process, whereby it is usually more advantageous to support the chemical reactions the higher the temperature is set.
  • How high the temperature in the working chamber is set depends, among other things, on the material of a substrate to be coated and its temperature resistance.
  • temperatures of at least 60 ° C. are set within a first working chamber selected for the ALD processes for depositing the aluminum oxide layers and the titanium oxide layers.
  • How high the temperature in the working chamber is set above 60 ° C depends, among other things, on the material of the substrate to be coated and its temperature sensitivity.
  • the temperature within the first working chamber can be increased to a temperature of at least 60 ° C., for example by means of a radiant heater. Furthermore, it is possible to form a substrate carrier, on which a substrate to be coated with the ALD layers is located, with a heating element, such as a heating plate, for example.
  • the temperature within the first working chamber is set to a temperature in the range from 60.degree. C. to 130.degree.
  • a temperature in the range from 60.degree. C. to 130.degree.
  • both temperature-sensitive substrates such as plastic films, can be coated and, on the other hand, a high deposition rate can be set in this temperature range.
  • the temperature within the first working chamber is set to a temperature in the range from 80.degree. C. to 120.degree. In this temperature range, low-defect aluminum oxide and titanium oxide layers are deposited using ALD at high process speeds.
  • a first parylene layer with a layer thickness of 0.1 ⁇ m to 50 ⁇ m and preferably a layer thickness of 1 ⁇ m to 10 ⁇ m is deposited at least on a first side of the alternating layer system composed of aluminum oxide and titanium oxide layers.
  • a known chemical vapor deposition process is selected as the layer deposition method, which is also referred to as “CVD” for short in relation to the English technical term “Chemical Vapor Deposition” and which is disclosed in US Pat. No. 3,556,881, for example.
  • the CVD deposition process for the parylene layer is preferably carried out at room temperature.
  • the parylene layer is deposited at temperatures in the range from 20 ° C to 40 ° C. Due to the different temperature requirements when depositing the ALD layers on the one hand and the parylene layer on the other, the parylene layer can preferably be deposited within a second working chamber, which differs from the first working chamber in which the alternating layer system is deposited. Alternatively, however, the alternating layer system and the parylene layer can also be deposited within a working chamber if the working chamber includes, among other things, means with which the different temperature requirements within the working chamber required for the ALD processes and the CVD process can be set.
  • parylene layer poly-para xylylene
  • parylene layer poly-para xylylene
  • parylene C / poly chloro-p-xylylene
  • Parylene F / poly tetrafluoro-p-xylylene
  • Parylene AF4 / poly a, a, a ', a'-tetrafluoro-p-xylylene
  • Parylene D / poly diichloro-p-xylylene or a mixed form of at least two of the parylene embodiments listed above.
  • the precursors for the parylene types mentioned are commercially available.
  • a parylene layer can also consist of parylene types other than those mentioned, i.e. H. Parylene types with other substituents such as bromine, alkyl, acyl, amino or methylamino, aldehyde, cyano and ethynyl groups.
  • a parylene layer made of parylene C is a very economical embodiment.
  • Such a layer causes only low precursor costs, enables a very good process yield, shows a very good barrier effect and has a biocompatibility certified according to ISO 10993. However, the temperature resistance of such a layer is only moderate.
  • parylene F layer material causes higher precursor costs, leads to a lower process yield than parylene C, has a lower barrier effect than parylene C and D, has no certified biocompatibility, but has a better temperature resistance than parylene C.
  • Parylene AF4 also causes higher precursor costs with a lower process yield than Parylene C, shows a lower barrier effect than Parylene C and D, but has better temperature resistance than Parylene F and has a certified biocompatibility.
  • the parylene type Parylene N requires higher precursor costs with a lower process yield compared to Parylene C, has a lower barrier effect than Parylene C, D, F and AF4, has only a lower temperature resistance than Parylene C, but has a certified biocompatibility and is also halogen-free.
  • a parylene layer made of parylene D can usually only be deposited with a low process yield, but has a better temperature resistance than parylene C, causes higher precursor costs and also has no certified biocompatibility.
  • the adhesion of the at least one parylene layer to the previously deposited alternating layer system composed of aluminum oxide and titanium oxide layers can be improved if an adhesion promoter layer is deposited between the alternating layer system and the at least one parylene layer or the alternating layer system has a
  • a silicon-containing layer based on a silane or a silane derivative is preferably deposited as an adhesion promoter layer.
  • 3-Methacryloyloxypropyltrimethoxysilane for example, is suitable as the silane.
  • barrier layer system is deposited on a substrate and, for example, for encapsulating electrical
  • a layer system according to the invention can, however, also itself be used as a flexible substrate which has barrier properties with respect to oxygen and water vapor. For this purpose, however, at least one parylene layer is deposited on both sides of the alternating layer system.
  • Such a layer system according to the invention with barrier properties against oxygen and water vapor can be produced, for example, as follows: At least one first parylene layer is first applied to a substrate by means of CVD, then an alternating layer system of aluminum oxide and titanium oxide layers by means of ALD and then again deposited at least one second parylene layer by means of CVD. Finally, the substrate is removed from the layer stack.
  • a layer system according to the invention is pliable and thus flexible, is characterized by very good barrier properties with respect to oxygen and water vapor and can therefore be used as a flexible substrate with barrier properties.
  • the at least one first parylene layer and / or the at least one second parylene layer with a layer thickness greater than 5 ⁇ m in order to give the layer system the required inherent stability.
  • an elastic mediator layer can be formed between the alternating layer system and the at least one first parylene layer and / or the alternating layer system and the at least one second parylene layer.
  • a silicon-containing layer as described above, can again be used as the elastic mediator layer.
  • the first parylene layer, the second parylene layer and the silicon-containing adhesion promoter layers are preferably deposited in one working chamber and the aluminum oxide and titanium oxide layers are deposited in another working chamber.
  • a release agent is applied to the substrate or a so-called sacrificial layer is deposited on the substrate before the deposition of the first parylene layer, which is destroyed when the substrate is separated from the layer stack will.
  • materials for a release agent or a sacrificial layer for example, surfactants; Polymers (such as photoresists or polyvinyl alcohol) or oxides (such as silicon oxide) are suitable.
  • the layer stack can, for example, be pulled off the substrate mechanically.
  • a glass or a semiconductor wafer, for example, can be used as the substrate.
  • the sacrificial layer used can be removed using a suitable solvent. If, for example, polyvinyl alcohol is used as a release agent or as a sacrificial layer, water, for example, can be used as a solvent.
  • an embodiment of a layer system according to the invention with barrier properties with regard to oxygen and water vapor is an alternating layer system consisting of two to six Aluminum oxide layers and two to six titanium oxide layers, which are arranged alternately and directly one on top of the other (i.e. without further intermediate layers) and comprise at least one parylene layer, the parylene layer either being deposited directly on one side of the alternating layer system or with only one adhesion promoter layer between the parylene layer and the alternating shift system is arranged.
  • FIG. 1 a schematic sectional illustration of a layer system according to the invention deposited on a substrate
  • FIG. 2 shows a schematic sectional illustration of an alternative layer system according to the invention deposited on a substrate
  • 3a, 3b are schematic sectional representations of a further alternative layer system according to the invention.
  • a layer system according to the invention deposited on a substrate 11 is shown schematically in section.
  • the layer system according to the invention initially comprises an alternating layer system consisting of two aluminum oxide layers 12 and two titanium oxide layers 13, which were deposited alternately on top of one another on the substrate 11.
  • the alternating layer system of a barrier layer system according to the invention can comprise up to six aluminum layers 12 and up to six titanium oxide layers 13, which are deposited alternately on top of one another.
  • the individual layers are each 5 nm to 20 nm thick.
  • a plastic film, a glass, a semiconductor wafer or an electrical component such as an integrated circuit, for example, can be used as the substrate 11.
  • the alternating deposition of the aluminum oxide layers 12 and the titanium oxide layers 13 took place in a first working chamber by means of known AFD deposition processes. During the layer deposition, temperatures of more than 60 ° C are reached in the first working chamber set.
  • a parylene layer 14, consisting of the aluminum oxide layers 12 and the titanium oxide layers 13, with a layer thickness of 0.1 ⁇ m to 50 ⁇ m is then deposited in a second working chamber by means of a known CVD deposition process.
  • a layer system according to the invention can alternatively also have a plurality of parylene layers 14 deposited directly on top of one another.
  • Both aluminum oxide and titanium oxide layers deposited by means of ALD and parylene layers deposited by means of CVD are characterized by the fact that they can also be deposited over the entire area on structured surfaces and three-dimensional objects.
  • Another advantage of a layer system according to the invention is that a parylene layer deposited by means of CVD also covers the side edges of the underlying layers and, if necessary, even covers the entire substrate, including its rear side.
  • a layer system according to the invention therefore has very good barrier properties against oxygen and water vapor and is therefore also particularly suitable for encapsulating electrical components which usually have a structured surface.
  • Such an electrical component can comprise, for example, at least one semiconductor component and / or at least one organic component.
  • a layer system according to the invention can be deposited directly on the electrical component.
  • the substrate 11 is then designed as an electrical component.
  • the substrate 11 can also be designed as a plastic film, the plastic film coated with the layer system according to the invention then being used as an encapsulation film for an electrical component.
  • an electrical component can also be produced on a substrate, wherein the substrate is designed as a barrier layer system according to the invention and wherein the substrate with the electrical component located thereon is then encapsulated by means of a further barrier layer system according to the invention.
  • an alternative layer system according to the invention is shown schematically in section, which is deposited on a substrate 21.
  • the substrate 21 is designed as a plastic film consisting of the material polyethylene naphthalate (abbreviation “PEN”).
  • PEN polyethylene naphthalate
  • the alternative layer system according to the invention from FIG. 2 initially comprises an alternating layer system consisting of four aluminum oxide layers 22 and four titanium oxide layers 23, which were deposited alternately on top of one another on the substrate 21 with a layer thickness of 5 nm each.
  • the aluminum oxide and titanium oxide layers were deposited by means of ALD within a first working chamber.
  • An adhesion promoter layer 25 was then produced on the alternating layer system, which ensures better adhesion to a subsequently deposited 2 ⁇ m thick parylene layer 24.
  • the parylene layer 24, consisting of parylene C, is preferably deposited in a second working chamber by means of CVD.
  • a silicon-containing layer in the form of a silane layer was produced as the adhesion promoter layer 25 by admitting a silane as a precursor into the second working chamber before the parylene layer 24 was deposited. In the layer stack described for FIG.
  • a WVTR barrier of ⁇ 6.6 * 10 6 g / (m 2 d) can be determined. In the case of a layer system according to the invention, it was thus possible to demonstrate very good barrier properties.
  • FIGS. 3a and 3b A further alternative layer system according to the invention with barrier properties with respect to oxygen and water vapor is shown schematically as a section in FIGS. 3a and 3b.
  • the layer system according to FIGS. 3a and 3b initially comprises an alternating layer system consisting of three aluminum oxide layers 32 and three titanium oxide layers 33, which are arranged alternately one above the other.
  • a first parylene layer 34a is formed on one side of the alternating layer system and a second parylene layer 34b is formed on the other side of the alternating layer system, a first adhesion promoter layer 35a being deposited between the first parylene layer 34a and the alternating layer system and a second adhesion promoter layer 35b between the second parylene layer 34b and the alternating layer system is.
  • Such a layer system according to the invention can be used as a flexible substrate and at the same time has barrier properties with respect to oxygen and water vapor.
  • the parylene layer 34 a is first deposited on a substrate 31 by means of CVD within a working chamber.
  • the optional adhesion promoter layer 35a can also be deposited in the same working chamber by, for example, admitting a silane into the working chamber.
  • the aluminum oxide layers 32 and the Titanium oxide layers 33 produced alternately by means of ALD.
  • the adhesion promoter layer 35b and the parylene layer 34b are then deposited again in the working chamber suitable for CVD processes.
  • the same method steps are preferably used as for the formation of the adhesion promoter layer 35a.
  • the substrate 31 is separated from the rest of the layer stack in that the layer stack is peeled off from the substrate 31, for example.
  • a semiconductor wafer or a glass for example, can be used as the substrate 31.
  • the separation of the substrate 31 from the rest of the layer stack can be simplified if a release agent is applied to the substrate 31 or a sacrificial layer is deposited on the substrate 31 before the parylene layer 34a is deposited.
  • a surfactant-containing solution for example, can be applied to the substrate 31 as a release agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

Système de couches barrières et procédé de fabrication d'un système de couches barrières. L'invention concerne un système de couches offrant des propriétés de barrière vis-à-vis de l'oxygène et de la vapeur d'eau, et un procédé de fabrication d'un système de couches offrant des propriétés de barrière vis-à-vis de l'oxygène et de la vapeur d'eau, comprenant les étapes suivantes : a) formation d'un système de couches alternées, constitué d'au moins deux couches d'oxyde d'aluminium (12; 22; 32) et d'au moins deux couches d'oxyde de titane (13; 23; 33), les couches d'oxyde d'aluminium (12; 22; 32) et les couches d'oxyde de titane (13; 23; 33) étant déposées alternativement par superposition ; b) les couches d'oxyde d'aluminium (12; 22; 32) et les couches d'oxyde de titane (13; 23; 33) étant déposées par dépôt de couche par ALD - atomic layer deposition - d'une épaisseur de couche respective de 5 nm à 20 nm ; c) dépôt par CVD – chemical vapor deposition - d'une première couche de parylène (14; 24; 34a) d'une épaisseur de 0,1 μm à 50 μm sur une première face du système de couches alternées.
EP21715230.5A 2020-03-26 2021-03-25 Système de couches barrières et procédé de fabrication d'un système de couches barrières Pending EP4127261A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020108362.9A DE102020108362A1 (de) 2020-03-26 2020-03-26 Barriereschichtsystem und Verfahren zum Herstellen eines Barriereschichtsystems
PCT/EP2021/057852 WO2021191398A1 (fr) 2020-03-26 2021-03-25 Système de couches barrières et procédé de fabrication d'un système de couches barrières

Publications (1)

Publication Number Publication Date
EP4127261A1 true EP4127261A1 (fr) 2023-02-08

Family

ID=75278037

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21715230.5A Pending EP4127261A1 (fr) 2020-03-26 2021-03-25 Système de couches barrières et procédé de fabrication d'un système de couches barrières

Country Status (5)

Country Link
US (1) US20230077923A1 (fr)
EP (1) EP4127261A1 (fr)
KR (1) KR20220158784A (fr)
DE (1) DE102020108362A1 (fr)
WO (1) WO2021191398A1 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3556881A (en) 1962-03-01 1971-01-19 Union Carbide Corp Encapsulated chemical product
US4383003A (en) * 1980-09-22 1983-05-10 General Electric Company Transfer lamination of copper thin sheets and films, method and product
DE59609370D1 (de) 1995-03-14 2002-07-25 Empa Abscheiden von diffusionssperrschichten in einer niederdruckplasmakammer
DE19548160C1 (de) 1995-12-22 1997-05-07 Fraunhofer Ges Forschung Verfahren zur Herstellung organisch modifizierter Oxid-, Oxinitrid- oder Nitridschichten durch Vakuumbeschichtung und danach beschichtetes Substrat
US20170130061A1 (en) * 2015-11-09 2017-05-11 Hzo, Inc. Hybrid parylene-metal oxide interstacked coatings
DK3567619T3 (da) * 2018-05-08 2021-01-04 Abiomed Europe Gmbh Korrosionsresistent permanent magnet og intravaskulær blodpumpe omfattende magneten

Also Published As

Publication number Publication date
DE102020108362A1 (de) 2021-09-30
WO2021191398A1 (fr) 2021-09-30
KR20220158784A (ko) 2022-12-01
US20230077923A1 (en) 2023-03-16

Similar Documents

Publication Publication Date Title
EP1711643B1 (fr) Procede de production d'un systeme de couche barriere ultra
DE102014105939B4 (de) Verfahren zur Herstellung einer Entspiegelungsschicht auf einer Silikonoberfläche und optisches Element
EP1727925A1 (fr) Procede et dispositif pour former de fines couches de nitrure de silicium sur des surfaces supports
DE3833501A1 (de) Verfahren und einrichtung zum anbringen vielschichtiger optischer interferenzschichten auf substraten mit komplexer oberflaechenform
DE2751221A1 (de) Verfahren zur aufbringung eines reflexionsvermindernden belages auf unterlagen aus organischem material
WO2009127373A1 (fr) Système de couches barrières transparent
DE102011017403A1 (de) Verfahren zum Abscheiden eines transparenten Barriereschichtsystems
DE10223359B4 (de) Mikromechanisches Bauteil und Verfahren zur Herstellung einer Anti-Haftschicht auf einem mikromechanischen Bauteil
EP2288646B1 (fr) Procédé de dépôt d'un revêtement protecteur augmentant la résistance mécanique sur un substrat de matière plastique
EP1778890B1 (fr) Procede de fabrication d'un reacteur pour la decomposition de gaz
WO2009118034A1 (fr) Procédé pour produire un système de couches multicomposant contenant des polymères et des métaux, dispositif et objet revêtu
EP2699705B1 (fr) Procédé de dépôt d'un système de revêtement de barrière transparente
EP4127261A1 (fr) Système de couches barrières et procédé de fabrication d'un système de couches barrières
EP2468915B1 (fr) Procédé de séparation de couches diélectriques sous vide et utilisation du procédé
DE102008028540A1 (de) Verfahren zum Abscheiden einer Gradientenschicht auf einem Kunststoffsubstrat sowie Kunststoffsubstrat mit einer Gradientenschicht
EP3133184B1 (fr) Procede de formation d'une couche a haute transmission lumineuse et/ou a faible reflexion lumineuse
EP1294959B1 (fr) Procede pour produire un ensemble multicouche multifonctionnel sur un substrat en matiere plastique transparent, et ensemble multicouche multifonctionnel produit selon ce procede
DE10201492B4 (de) Optisches Schichtsystem
DE102016100914B4 (de) Verfahren zur Herstellung einer porösen Brechzahlgradientenschicht
DE2737792C3 (de) Verfahren zur Verbesserung der Haftung von Poly-p-xylylenen auf Substraten durch Aufbringen einer Organosilanschicht
DE102006043943A1 (de) Verfahren zum Aufbringen von Schichten auf Substraten mit gekrümmten Oberflächen
DE102016100907B4 (de) Verfahren zur Herstellung eines reflexionsmindernden Schichtsystems
DE102016118440A1 (de) Aktivierte 3-D-Nanooberfläche, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102019135574A1 (de) Verfahren zum Herstellen einer heterogen strukturierten Beschichtung eines optoelektronischen Bauelements, sowie ein optoelektronisches Bauelement mit einer solchen Beschichtung
EP2558609B1 (fr) Procédé pour revêtir un substrat à l'intérieur d'une chambre à vide au moyen d'un dépôt chimique en phase vapeur assisté par plasma

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220928

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)