EP2137337A2 - Système stratifié élastique, étanche à la diffusion, électriquement isolant et déposé par plasma - Google Patents

Système stratifié élastique, étanche à la diffusion, électriquement isolant et déposé par plasma

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Publication number
EP2137337A2
EP2137337A2 EP08707792A EP08707792A EP2137337A2 EP 2137337 A2 EP2137337 A2 EP 2137337A2 EP 08707792 A EP08707792 A EP 08707792A EP 08707792 A EP08707792 A EP 08707792A EP 2137337 A2 EP2137337 A2 EP 2137337A2
Authority
EP
European Patent Office
Prior art keywords
layer
layers
diffusion
substrate
multilayer system
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.)
Withdrawn
Application number
EP08707792A
Other languages
German (de)
English (en)
Inventor
Heinz Werner Busch
Udo Heinrich Grabowy
Lisa Kleinen
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.)
Technische Universitat Kaiserslautern
Original Assignee
Technische Universitat Kaiserslautern
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Filing date
Publication date
Application filed by Technische Universitat Kaiserslautern filed Critical Technische Universitat Kaiserslautern
Publication of EP2137337A2 publication Critical patent/EP2137337A2/fr
Withdrawn legal-status Critical Current

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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
    • C23C16/22—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
    • C23C16/26—Deposition of carbon only
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/18—Applying electric currents by contact electrodes
    • A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
    • A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
    • A61N1/372—Arrangements in connection with the implantation of stimulators
    • A61N1/375—Constructional arrangements, e.g. casings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/18—Applying electric currents by contact electrodes
    • A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
    • A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
    • A61N1/372—Arrangements in connection with the implantation of stimulators
    • A61N1/375—Constructional arrangements, e.g. casings
    • A61N1/37512—Pacemakers
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/02—Details
    • A61N1/04—Electrodes
    • A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • Plasmadepon s electrically insulating, diffusion-tight and elastic
  • the invention relates to a multilayer system on a substrate, in particular a multilayer system, the multilayer system is applied to the substrate by means of plasma deposition. Furthermore, the invention relates to the use of such a multilayer system.
  • Diffusion barriers are of great interest for a wide variety of applications. The number of developments and publications in this area is correspondingly high. Most concern the diffusion suppression of oxygen and moisture, e.g. As on PET beverage bottles or organic light-emitting diode systems (OLED). The migration of charge carriers in solid-state layer systems is particularly important in the semiconductor industry and electronics. There, layers are often used as diffusion barriers
  • Silica-based diffusion barriers which have a resistance of> 10 16 ⁇ under dry conditions, are state of the art for reducing the
  • a hydrated layer SiN x O y H z
  • a hydrated layer SiN x O y H z
  • US2006 / 0208634 A1 describes plasma-deposited diffusion barriers based on a gradient layer with organic and inorganic components, the inorganic component consisting essentially of silicon oxynitride (SiO x NyH 2 ) and the organic plasma-polymerized films.
  • the application describes the gradual gradation in the stoichiometries when switching from organic to inorganic component and presents the gradient layer as part of an organic light emitting diode (OLED) for protection against moisture and oxygen.
  • OLED organic light emitting diode
  • US 2007/0020451 A1 describes a barrier layer for protecting organic light-emitting diodes against moisture and oxygen.
  • amorphous carbon layers and layers of "diamond-like glass” (DLG, an amorphous mixture of glass with different proportions of intercalated carbon, hydrogen, silicon, oxygen, fluorine, sulfur, titanium and copper) alternate with one another Polymer layers from. Due to the DLG layers, the layer system has a higher tolerance to strains and, with the same elongation, forms fewer cracks than a sputtered SiO 2 layer.
  • the laminate is intended to protect the hard disk against impact of the write head by moving it into Direction perpendicular to the surface at least twice as high elastic modulus (at least 150 GPa) as parallel to it.
  • US 6891155 shows a dielectric film which maintains its diffusion resistance to ions and moisture even in aqueous solution with an applied electrical potential. It consists of a base layer and a finishing layer, wherein the top layer of different types of layers such. As silicon oxynitrides of various stoichiometric composition, all common dielectrics (nitridic, oxidic, ceramic) and diamond-like carbon can exist. The layer system is to be used in microfluidic systems in so-called "lap-on-a-chip" applications.
  • a disadvantage of the layer system according to US Pat. No. 6,891,155 is the high layer thickness and, at the same time, the low number of layers, which leads to the formation of cracks during loading and stretching. In particular, this system is not suitable for use on flexible substrates.
  • US Pat. No. 5,769,874 describes a diffusion-proof coating which represents a hermetic encapsulation for a medical implant, the encapsulation taking place around a titanium metallic housing.
  • Amorphous carbon films can be deposited by a variety of plasma technology techniques.
  • the deposition method described in WO 03/035928 enables particular deposition conditions and is outstandingly suitable for producing the diffusion-tight core layers and elastic matrix layers based on carbon.
  • the object of the invention is to overcome the disadvantages of the prior art.
  • the object is achieved by a multilayer system on a substrate, wherein the multilayer system is applied to the substrate by means of plasma deposition.
  • the multilayer system is designed such that it has a substantial diffusion tightness with respect to ions, which by the diffusion of the ions in aqueous solution with application of an electric field gradient of more than 10 4 V / m, preferably more than 10 5 V / m, most preferred more than 10 7 V / m generated current I ⁇ on ⁇ 6.5 ⁇ 10 ⁇ 8 A / cm 2 , preferably I ⁇ on ⁇ 6.5x10 '10 A / cm 2 , in particular I ⁇ on ⁇ 1 ⁇ 10 "12 A / cm 2
  • Said field gradient is applied between the non-layered side of the substrate and an electrode positioned 1 mm in front of the surface of the isotonic saline wetted layer system The measurement was carried out with a picoammeter at a wetted area of 10 cm 2 .
  • the multilayer system is characterized in that it is constructed in such a way that it has a substantial diffusion tightness against gases and / or water vapor and / or solvent vapors, wherein the water vapor flow through the layer system ⁇ H2O ⁇ 3.7x10 '8 mbar ⁇ l / (s ⁇ cm 2), preferably ⁇ H 2o ⁇ 3,7x10 "9 mbar ⁇ l / (s ⁇ cm 2), particularly ⁇ H2 o ⁇ 3,7x10" 10 mbar ⁇ l / (s ⁇ cm 2)) and the gas flow ⁇ gas ⁇ 1, 5 ⁇ 10 "7 mbar ⁇ l / (s ⁇ cm 2 ), preferably ⁇ gas ⁇ 1, 5 ⁇ 10 " 9 mbar ⁇ l / (s ⁇ cm 2 ), in particular ⁇ gas ⁇ 1, 5 ⁇ 10 "11 mbar ⁇ l / (s ⁇ cm 2 )
  • a gas- and water vapor-permeable polymer film is coated with the layer system ⁇ H2
  • the Vieifach harshsystem is constructed such that the layer system is largely chemically stable to acids and alkalis in a range of pH between 3 and 10, preferably between 2 and 12, in particular between 0 and 14.
  • the multilayer system is constructed in such a way that an expansion in any direction parallel to the substrate of the multilayer system of less than 4%, in particular less than 10%, very preferably less than 25%, is provided for substantial diffusion tightness.
  • the multilayer system is constructed such that the multilayer system is thermally stable in the range of 0 0 C to 121 0 C, in particular in the range of -10 0 C to 150 0 C and preferably in the range of -50 0 C. to 200 ° C.
  • thermally stable it is understood in the present application that the multilayer system retains its abovementioned properties even during and after heating to the stated temperatures.
  • the multilayer system according to the invention has a substantial degree of diffusion-tightness in aqueous solution or in body fluid.
  • the multilayer system according to the invention which is preferably a biocompatible layer system, can in a single plasma deposition process by intercalating carbon-based and / or carbidic and / or nitridic and / or boridic and / or metal-oxide based electrically insulating, diffusion-tight barrier on different substrates be deposited.
  • the layer system also retains the properties mentioned under thermal, mechanical, chemical and electrical stress.
  • the multilayer system is an effective barrier against the diffusion of gases (such as helium, oxygen, air, water vapor, solvent vapors). It is impermeable to liquids (eg water, solvents, oils) and also serves as a barrier against ions and / or electrons against a potential gradient (eg when an external voltage or opposing electrical boundary and double layers are present).
  • the multilayer system is composed of components other than the layers or layer systems presented in the above-cited references.
  • the multilayer system by the novel arrangement of the individual components in the layer system on a more extensive functionality than all systems described.
  • the multilayer system on a substrate at least one core layer (D), preferably comprises at least two matrix layers (E), at least one adhesion promoter layer to the substrate (GSB) and a final layer of the multilayer system on the side facing away from the substrate (GBO), wherein between the different layers Transition gradient layers (GED, GDE) are provided, wherein the core layers (D) of amorphous carbon layers, aC: H and / or ta-C: H and / or ta-C and / or DLCH and / or AIO x and / or SiO x and / or ZrO x and / or TaO x and / or TiO x and the elastic matrix layers (E) consist of aC: H and / or PLCH and / or HC polymers and / or plasma-polymerized layers.
  • GED Transition gradient layers
  • the multilayer system further comprises, in addition to these layers, an insulating layer A consisting of aC: H and / or PLCH and / or aC: H (soft) and / or aC: HN and / or PLCHN and / or plasma polymerized layers between the substrate and the first Substrate near elastic matrix layer.
  • an insulating layer A consisting of aC: H and / or PLCH and / or aC: H (soft) and / or aC: HN and / or PLCHN and / or plasma polymerized layers between the substrate and the first Substrate near elastic matrix layer.
  • a bonding agent layer (GSA) between substrate and layer A is applied and a bonding agent layer (GSA) between substrate and layer A is applied and a
  • GAB Gradient transition layer
  • the multilayer system comprises a number n of the diffusion-tight core layers (D), which lies between 1 and 200, in particular between 3 and 9.
  • D diffusion-tight core layers
  • the number of elastic matrix layers E in such a layer system preferably assumes a value which is increased by one over the number of core layers, i. the number of elastic matrix layers is n + 1 when n is the number of core layers.
  • the thickness of the diffusion-tight core layers (D) is preferably between 3 and 150 nm, preferably between 3 and 75 nm and in particular between 3 and 30 nm.
  • the thickness of the elastic matrix layers (E) is preferably between 10 and 300 nm, preferably between 10 and 200 nm and in particular between 10 and 100 nm.
  • the diffusion-tight core layers are distributed equidistantly or randomly or else with increasing density towards the middle of the layer system B in the elastic matrix layers. In the latter case, the thickness of the elastic matrix layers E in the middle of the multilayer system is thinner than at the edge.
  • the thickness of the matrix layer (E) is 2 to 100 times, preferably 3 to 70 times, the thickness of the core layers.
  • the thickness of the matrix layer is approximately (Y 0 / YE) 0 ' 5 times the thickness of the core layer.
  • YD is the elastic modulus of the diffusion-proof core layer
  • Y E is the elastic modulus of the diffusion-proof core layer
  • the layer system further comprises a first transition gradient layer (GED) between elasticity layers (E) and core layers (D) and a second transition gradient layer (GDE) between core layer (D) and elasticity layer (E).
  • GED first transition gradient layer
  • GDE second transition gradient layer
  • the thickness of the two transition-gradient layer is between 0.5 and 30 nm, preferably between 0.5 and 20 nm and in particular between 0.5 and 10 nm.
  • the transition gradient layers GSA and GSB in the multilayer system have a coefficient of thermal expansion between 10 and 150 ppm / K, preferably between 15 and 100 ppm / K, in particular between 15 and 70 ppm / K.
  • the size ppm / K refers to an expansion in three dimensions.
  • the elasticity layers (E) particularly preferably have a modulus of elasticity between 1 and 70 GPa, preferably between 3 and 50 GPa and in particular between 3 and 20 GPa.
  • the multilayer system as the substrate connecting layer, which is in contact with the substrate, an insulating layer A, which consists of a-C: H and / or DLCH and / or PLCH and / or HC polymers and / or a plasma-polymerized layer.
  • the system can have a substrate-comprising outer layer (GBO, K, V), wherein the substrate-distant final layer comprises a-C: H and / or DLCH and / or ta-C: H and / or ta-C and / or PLCH.
  • a substrate-comprising outer layer GEO, K, V
  • the substrate-distant final layer comprises a-C: H and / or DLCH and / or ta-C: H and / or ta-C and / or PLCH.
  • the substrate-comprising sealing layer has bonding centers coordinated with a connection system on the surface remote from the substrate.
  • the binding centers comprise functional groups, in particular nitrogen-containing and / or oxygen-containing functional groups.
  • the functional groups may include amino groups -NH 2 , carboxyl groups -COOH, hydroxy groups -OH and / or impurities, and generally anchor points for forming carbonyl and / or ester and / or ether bonds.
  • the substrate is a polymer-like substrate and includes parylenes.
  • the attachment system comprises a polymer-like material, in particular parylenes.
  • the multilayer system can be designed as a UV filter and the transmission of electromagnetic radiation having wavelengths between 200 and 400 nm can be less than 20%, preferably less than 10% and in particular less than 5%, the filter effect being independent of the substrate.
  • the multilayer systems according to the invention are characterized by a high body compatibility.
  • human epithelial, endothelial, as well as blood cells and keratinocytes show no defense reactions to the layer system.
  • the multilayer system according to the invention shows the properties mentioned in different environments, such. In vacuum, in air and in other gases, in solutions (aqueous and other solvent based) and especially in the biological environment, in plant and animal systems, and more particularly in the human body, both in extracellular space, in organs, tissues and tissues in physiological fluids (such as blood or lymph) but also in engineered tissues, cell cultures, and fluids that simulate physiological fluids.
  • the invention further relates to a plurality of devices which are provided with a multilayer system according to the invention.
  • the encapsulations of the devices include the multilayer systems.
  • Examples are electrically active medical implants, in particular implants for functional electrostimulation (FES), implants with electrode systems for detecting bioelectric potential differences, for recording neuronal innervation patterns, implants for electrical stimulation of nerve fibers, neuroprostheses, pacemakers, implants for dynamic myoplasty, implants for diaphragmatic or phrenic nerve stimulation with an encapsulation.
  • FES functional electrostimulation
  • Electromechanical implants in particular artificial hearts, VAD (ventricular-assisted devices) systems, total artificial heart systems with an encapsulation,
  • Solvents gasolines, corrosive liquids, hygroscopic solids and powders, fuel storage containers, in particular gasoline, hydrocarbons, hydrogen and highly volatile explosive mixtures, gaskets and covers, fabrics and clothing.
  • the invention also encompasses the use of the multilayer system according to the invention in all the aforementioned devices.
  • FIG. 1 Arrangement of the diffusion-tight core layers (D) and the elastic
  • the sequence E / GED / D / GDE / E is repeated n times in layer system (B).
  • the layer system B is bonded either to the transitional layer GSB to the substrate or to the transition layer GAB to a layer A previously deposited in the same process on the substrate.
  • a further elastic matrix layer E or an additional body-compatible terminating layer K in the case where E does not have sufficient body compatibility
  • an additional protective layer V or a transitional layer GBO which provides a permanent bond another layer (or a layer system or an adhesive or a solid) guaranteed, z.
  • binding sites matched to the attachment system eg, functional groups and /
  • FIG. 2 Layer system B (from FIG. 1) deposited on substrate S (left side) or on a layer A previously deposited on substrate S in the same process.
  • the circles each show the section (detail view of layer system B) shown in FIG.
  • FIG. 3a-c Schematic representation of the diffusion-tight multilayer system. Black thin lines represent the diffusion-tight
  • Figure 3b Layer system B as a diffusion barrier in the loaded state. In the case of mechanical and / or temperature-induced (expansion) expansion of the layer system, the diffusion-tight core layers D remain intact. The stress is absorbed by the elastic matrix layers.
  • Figure 3c Even under extreme loads, the diffusion tightness of
  • Layer system B obtained. Possible microcracks in occasional diffusion-tight core layers are compensated by the large number of remaining intact layers. Damage directly superimposed layers D will be statistically distributed over the entire loaded length of the layer. The path of the species to be kept (gas, liquids, ions) through the layer system is considerably extended in this case; The diffusion-tightness can be maintained over a correspondingly long period of time and the functionality of the coated component can be ensured over this period.
  • FIG. 4 Tuning of the layer thicknesses of the elastic matrix layers E for maximum protection of the diffusion-tight core layers D.
  • the latter are in the interior of the layer system B with higher density (smaller distance) in the Embedded matrix layers.
  • the thickness of the elastic matrix layers increases toward the outside (to the substrate side and to the surface side).
  • FIG. 5 Ternary representation of amorphous carbon layers, arranged according to the bonding conditions and the hydrogen content in the layer according to John Robertson, Diamond-like amorphous carbon, Mat Sei Eng R 37 (2002) 129.
  • FIG. 6 Increasing the diffusion-tightness of a 130 ⁇ m thick polyethylene (PE) film through a 30 nm thick amorphous carbon layer (diffusion-tight core layer D1 (type 1)).
  • PE polyethylene
  • D1 diffusion-tight core layer
  • FIG. 1 shows the basic structure of the layer system.
  • the layer system consists of thin, diffusion-tight layers, so-called
  • D in FIG. 1 which in thicker elastic less dense layers so-called "elastic
  • Transitions between the layers are seamless.
  • transitional layers which are also referred to as “gradient layers" in FIG. 1 with GED or
  • GDE change the layer properties, such as
  • the system shown in FIG. 1 has the following layer sequence:
  • FIG. 2 shows the application of the multilayer system to a substrate.
  • the entire layer system is plasma deposited and is either directly on a substrate, which is designated in Fig. 2 with S or on a previously in the same Process deposited on the substrate layer, which is designated in Fig. 2 with A applied.
  • Multi-layer system can be applied to different substrates, such as polymers, metals, ceramics, oxides or nitrides.
  • substrates such as polymers, metals, ceramics, oxides or nitrides.
  • various coatings on the abovementioned materials eg other layers applied in PVD, CVD and plasma technological processes (eg metallic, carbidic, oxidic, nitridic and ceramic layers), different lacquers (eg polyurethane PU ) and polymer coatings (such as parylene) and plasma deposited polymer layers.
  • Embodiment 1 constructed from rf-plasma-deposited aqueous amorphous carbon layers of different composition and layer properties:
  • Embodiment 1 ensures the diffusion-tightness described here on the substrates parylene, polyethylene (PE), polyurethane (PU) and polypropylene (PP).
  • the gradient transition layers GED and GDE form the transition between the aC: H layers of different stoichiometry and have layer thicknesses of about 7 nm. Are not listed in the table.
  • the embodiment 1 described here applied to a 130 micron thick PE film reduces the diffusion of helium through the film of 4.5x10 "3 mbar I / (s cm 2) at a flow rate of 1 x10 '9 mbar I / (s cm 2 ) at a helium overpressure of 400 mbar
  • the layer system without substrate described in Example 1 has a breakdown voltage of 260 V.
  • the layer system described in Example 1 reduces the ion flux in iostonic saline to currents below 1pA / cm 2 at temperatures between 0 and 70 0 C.
  • Embodiment 2 constructed from rf-plasma-deposited aqueous amorphous carbon layers of different composition and layer properties and plasma-polymerized layers
  • Embodiment 2 ensures the diffusion-tightness described here on the substrates parylene, polyethylene (PE), polyurethane (PU) and polypropylene (PP).
  • the gradient transition layers GED and GDE form the transition between the aC: H layers of different stoichiometry and have layer thicknesses of about 7 nm. Are not listed in the table.
  • Embodiment 2 described here applied to a 130 micron thick PE film for example, reduces the diffusion of helium through the film of 4.5x10 "3 mbar I / (s cm 2) at a flow rate of 1 x10" 9 mbar I / (s cm 2 ) at a helium overpressure of 400 mbar.
  • the layer system described in Embodiment 2 without substrate has a breakdown voltage of 350 V.
  • the layer system described in Embodiment 2 reduces the ion flux in iostonischer saline to currents below 1 pA / cm 2 at temperatures between 0 and 70 0 C.
  • Suitable deposition conditions at the beginning of the process ensure a permanent connection of the layer system to the substrate (substrate).
  • the transition layer designated GSA or GSB in FIG. 2 is applied (GSA: gradient transition layer) between substrate and layer system A 1 GSB: gradient transition layer between substrate and layer system B).
  • the permanent connection of the layer system to the substrate is ensured in two ways, depending on the type of substrate used.
  • a partial mixing of the two materials is achieved by introducing layer atoms and / or layer molecules under the surface of the substrate.
  • the deposition conditions are selected so that ions of average energy (eg between 20 and 200 eV, in particular between 40 and 100 eV and in particular between 50 and 75 eV) penetrate into uppermost layers of the substrate.
  • the multifunctional multilayer system then grows out of this composite transition layer.
  • the breakage of saturated bonds existing on the substrate surface provides free bonds to the surface of the substrate to which molecules and / or ions of the growing layer material can covalently bond.
  • Reactive plasmas such as oxygen plasmas, carbon dioxide plasmas
  • / or ion bombardment eg with noble gas ions, eg argon
  • nitrogen plasma and / or mixtures of reactive plasmas e.g. Oxygen and / or carbon dioxide
  • noble gas plasmas eg helium, argon
  • the layer system is provided on the substrate distant side with a so-called finishing layer.
  • Four solutions for the final layer tailored to the respective use of the layer are presented. These final layers are designated in FIG. 1 by E, K, V or GBO.
  • the finishing layer is either the elastic matrix layer E already used in the layer system B or an additionally applied body-compatible layer K (in the case where a layer system B is chosen in which E has insufficient body compatibility).
  • Solution 3 is an additional applied before mechanical wear or chemical attack Protective protective layer V.
  • the fourth solution is the GBO transitional layer, which guarantees a permanent bond between another layer (or a layer system or an adhesive or a solid), eg.
  • Binding functionalities such as functional groups such as amino groups -NH 2 , and other nitrogen-containing and / or oxygen-containing functional groups such as carboxyl groups -COOH, hydroxy groups -OH). and / or foreign atoms (eg silver) as well as generally anchor points for the formation of carbonyl and / or ester and / or ether bonds.
  • Diffusion-tightness is understood as meaning the complete suppression or extreme delay of the particle transport by the layer system. Cause of such a particle transport are usually concentration gradient.
  • the layer system contains diffusion-tight "core layers" of sufficient density, which prevents penetration of the constituents mentioned by high crosslinking.
  • Metallized plastics have been used with great success in food packaging since the 1970s.
  • Aluminum layers can be inexpensively manufactured in high speed metallizers. With layer thicknesses of 20 nm, the diffusion of 12 ⁇ m thick PET films can be improved by a factor of 100.
  • Transparent diffusion barrier layers use silicon oxide, some silicon nitride or combinations of both. Even with these materials, a reduction of gas permeability by at least a factor of four, but usually achieved by more than an order of magnitude.
  • the layer system is either constructed entirely of chemically inert compounds or provided with at least one chemically inert final layer on the side facing away from the substrate.
  • the layer system is designed such that a partial swelling of the layer side facing away from the substrate does not impair the diffusion-tightness of the overall system.
  • the deformation energy dissipation mechanism described here there are also limits to the deformation energy dissipation mechanism described here. If the strain is too strong, the energy is also deposited in the diffusion-tight core layers D and microcracks can form which influence the diffusion-tightness. To increase the tolerance of the entire layer system with respect to deformations, a plurality of diffusion-tight core layers D are therefore arranged in alternation with the elastic matrix layers E. With strong stretching of the Layer system, the forming microcracks are statistically distributed over the entire layer surface. Through the layer system diffusing particles (molecules, atoms, ions) must make their way along the diffusion-tight core layers D until they reach a crack. In this way, the path of the particles to be held by the layer system is considerably extended and maintain the diffusion-tightness of the layer system over a correspondingly long period.
  • diffusing particles molecules, atoms, ions
  • the number n of sequences of diffusion-tight core layers / elastic matrix layers including the transition layers GDE and GED listed in FIG. 1 is matched to the respective application.
  • the elastic matrix layers are provided with variable layers which are matched to the respective layer system (including the substrate and any subsequent layers).
  • FIG. 4 shows the layer sequence substrate side / GSA or
  • the diffusion-tight core layers are arranged in the middle of the layer system with higher density.
  • load eg deformation by bending
  • the outer layer areas are exposed to stronger deformations.
  • neutral plane in the layer system, which under load of the
  • the z. B. Under mechanical stress fall z. B. bending by movements of the substrate, for. B. in that the underlying substrate is a movable component, for. B. in that the substrate is a movable, oscillatory membrane, z. B. in that the substrate is a movable film, the z. B. is exposed to a pressure gradient between two chambers or used as part of a pump, z. In that the film is moved and deformed by mechanical forces to move a medium (eg, a liquid) through a system.
  • a medium eg, a liquid
  • transition layers GSA or GSB or the layer A and the transition layer GAB Additional protection under thermal stress is provided by the transition layers GSA or GSB or the layer A and the transition layer GAB), since their composition, if possible, is chosen such that they have coefficients of thermal expansion of the order of the substrate used in each case.
  • the transition layers GSA and GSB presented here have coefficients of thermal expansion between 10 and 150 ppm / K, preferably between 15 and 100 ppm / K, in particular between 15 and 70 ppm / K in each case based on the volume.
  • the electrical resistance of the layer system is at least 10 18 ⁇ cm, preferably at least 10 14 ⁇ cm and in particular 10 17 ⁇ cm.
  • the layer system is particularly adapted to the transport of ions and other charge carriers in an applied electric field.
  • the layer system is chemically inert and consists predominantly of unipolar bonds and has the previously described arrangement of the individual components.
  • the presented here multifunctional layer system which restricts the diffusion of ions in aqueous solution even when applying an electric field gradient of at least 10 4 V / cm, preferably at least 10 5 V / cm and in particular of at least 10 7 V / cm, wherein the the currents measured are below 1 pA.
  • the breakdown voltage of the layer system presented here is at least 2 ⁇ 10 6 V / cm, preferably at least 4 ⁇ 10 6 V / cm, and in particular at least 10 7 V / cm.
  • the coating system is either completely based on biocompatible layers such.
  • amorphous carbon layers aC: H, ta-C: H, DLC, DLCH, PLCH, or amorphous carbon layers with foreign atoms (eg., N and / or Si and / or Ag and / or F and / or O or amorphous carbon films with functional groups, such as -NH 2, -NH, -COOH) are built up or terminated by such a layer on the body-facing side.
  • the biocompatibility of plasma-deposited carbon layers has already been investigated in numerous studies with different cell types (eg osteoblasts, Fibroblasts, keratinocytes) and body fluids (especially blood).
  • the coated substrate or component Due to the UV filter effect of either the final layer or the entire layer system, the coated substrate or component is protected from damage by UV radiation.
  • the layer system presented here filters out radiation with wavelengths smaller than 400 nm.
  • D diffusion-tight core layers
  • B amorphous carbon layers, aC: H and / or ta-C: H and / or ta-C and / or DLCH and / or AIO x and / or SiO x and / or ZrO x and / or TaO x and / or TiO x used.
  • aC H and / or PLCH and / or HC used polymers and / or plasma polymerized layers.
  • the lying in some applications under the layer system B insulating layer A is z.
  • terminating layer K aC: H and / or DLCH and / or PLCH are used.
  • aC: H and / or ta-C: H and / or ta-C and / or DLCH are used.
  • the top layer GBO used is amorphous carbon layers provided with functional groups and / or impurities.
  • Table 1 shows the elemental composition for different types of layers.
  • the number n of the diffusion-tight core layers (D) is at least 1 and is preferably between 2 and 200 and in particular between 3 and 9.
  • the number of elastic matrix layers E is n + 1.
  • the thickness of the diffusion-tight core layers (D) is between 3 and 150 nm, preferably between 3 and 75 nm and in particular between 3 and 30 nm.
  • the diffusion-tight core layers can be equidistant or random or with increasing towards the center of the layer system B density in the elastic Matrixschichen be distributed.
  • the thickness of the elastic matrix layers (E) is between 10 and 300 nm, preferably between 10 and 200 nm and in particular between 10 and 100 nm.
  • the elastic matrix layers E are between 2 and 100 times, preferably between 3 and 70 times and in particular at least ( YD / YE) 0 '5 SO thick, the diffusion-dense core layers D.
  • d un th and Y and ten than the thickness or the modulus of elasticity of the entire system below the layer region with a high density of diffusion-dense core layers, and d Obe n and Y Whether en than the thickness or the modulus of elasticity of the entire system above the layer region with a high density of diffusion-dense core layers can be selected to provide additional protection the thickness d at the top so that, in the order from
  • the transitions between the layers of different diffusion-tightness and elasticity are between 0.5 and 30 nm, preferably between 0.5 and 20 nm and in particular between 0.5 and 10 nm.
  • the thickness of the layer A is between 300 nm and 5 microns, preferably between
  • the thickness of the transition layers GSA and GSB are between 0.5 and 200 nm, preferably between 0.5 and 50 nm and in particular between 0.5 and 20 nm.
  • the thickness of the outer layers E, K 1 and V are between 10 and 300 nm, preferably between 10 and 200 nm and in particular between 10 and 100 nm.
  • the thickness of the cover layer GBO is between 0.5 and 30 nm, preferably between 0.5 and 20 nm and in particular between 0.5 and 10 nm.
  • the material grows by addition of atomic or small molecular building blocks.
  • the layer building blocks eg atoms, molecules, ions
  • these particles adhere to the point where they arrive by chance, they form a relatively open structure. If, on the other hand, their mobility is sufficient to find a place with as many bonding partners as possible before they are restricted in their ability to move by the atoms that will subsequently arrive, a compact network is created which hardly allows any diffusion.
  • the mobility of the atoms at the surface is made possible mainly by the thermal movement.
  • the ratio of the growth temperature T A to the melting temperature T s plays an important role. Since the plastics are generally destroyed even at temperatures well below 100 ° C, the strong heating of the substrates prohibits increasing the mobility. However, the mobility can also be significantly increased by ion bombardment. Therefore, plasma-physical methods (such as PECVD-plasma-enhanced chemical vapor deposition, ECWR-electron-cyclotron-wave-resonance, ECR-electron-cyclotron-resonance, magnetron sputtering, rf-glow discharge) are used to deposit the diffusion-tight layer system presented here.
  • DBD - dielectric barrier discharge ICP - inductively-coupled plasma, arc method, FCVA, filtered cathodic vacuum arc, remote plasma deposition
  • a high density of the layer materials of the diffusion-tight core layers D must be achieved.
  • Only intensive bombardment of the growing layers with ions of medium energy ensures that micro cavities are reliably avoided. Since the ion bombardment is associated with an energy input, one must strive for only moderate growth rates in the coating of plastics. Moreover, it is advantageous if the ion energy is not significantly higher than is required to trigger the necessary change of location processes. Since the binding energies are on the order of a few eV, ion energies of a few 10 eV are optimal.
  • the proposed layer system is produced in a single coating process. This eliminates time-consuming changes of equipment and repeated surface preparation. Seamless transitions from the diffusion-tight core layers to the elastic matrix layers are achieved by gradually changing the process parameters (e.g., process gas or precursor flow, pressure, rf power, magnetic field strength, DC bias, target material, cathode voltage).
  • process parameters e.g., process gas or precursor flow, pressure, rf power, magnetic field strength, DC bias, target material, cathode voltage.
  • the following is an example of a layer system based on carbon compounds.
  • the amorphous carbons are characterized by particularly diverse properties, which are easily adjustable depending on the deposition conditions. High hardness, low coefficient of friction, optical transparency and good body compatibility are the best known properties of these materials.
  • the primarily chemically inert, electrical insulating layers are composed of low molecular weight carbon compounds, which arrange themselves with a certain close order in an otherwise disorderly amorphous matrix.
  • H layers (ellipse with a red-dashed line) come into question. They may have more polymer-like (PLCH) or diamond-like (DLCH) properties.
  • the diffusion-tight "core layers” consist of very thin, extremely dense carbon layers (eg a-C: H, DLC, DLCH). They are deposited alternately with thicker, elastic and less dense carbon layers (eg a-C: H, PLCH, HC polymers).
  • the amorphous carbon diffusion-resistant core layers (D) already effectively suppress diffusion due to solubility.
  • the network must be strongly networked by a relatively high density of C-C bonds. In this way, the movement of foreign atoms, ions or molecules in the layer is almost completely suppressed.
  • the deposition conditions are selected so that no cracks or other passage possibilities, for example in the form of microscopic channels (pinholes) form during layer growth.
  • the gas permeability is drastically reduced several orders of magnitude.
  • FIG. 6 shows the helium flow through a 30 nm thick diffusion-tight core layer D made of amorphous carbon (applied to a 130 ⁇ m thick layer) Polyethylene film).
  • a single diffusion-proof core layer can achieve a significant reduction in helium flow over the uncoated film.
  • FIG. 6 shows the helium flow through coated and uncoated 130 ⁇ m thick polyethylene (PE) films as a function of the helium pressure. The mean flux values measured for the coated films are indicated by boxes (PE coated), those for the uncoated films are indicated by diamonds (PE uncoated).
  • the un-coated film is approximately 40,000 times more permeable to He gas than that coated with a 30 nm thick diffusion-tight core layer D of amorphous carbon.
  • these diffusion-tight core layers are embedded in elastic matrix layers (E) which also consist of carbon compounds.
  • the elasticity of carbon layers is generally determined by their proportion of CC-sp 3 bonds, their density depends essentially on the C concentration.
  • the elastic matrix layers are characterized by a lower density and a small modulus of elasticity.
  • the modulus of elasticity of various layers generally decreases with decreasing degree of crosslinking of the layer-forming molecules. High cross-linking is achieved by ionized precursor molecules impinging on the surface with a certain energy, breaking up there and dividing the energy between the daughter atoms.
  • the densest (highly crosslinked) layers are obtained at ion energies corresponding to 100 eV per C atom.
  • the deposited layer material is less dense and softer.
  • plasma-polymerized layers are then obtained, plasma polymerization generally being used for the deposition of high molecular weight compounds in electrical discharges, to which amorphous carbon layers, also known as polymer-like ones, are not counted.
  • the elastic matrix layers can also be deposited from low molecular weight hydrocarbons.
  • the deposition conditions are chosen so that predominantly sp 3- bonded amorphous carbon layers with a high hydrogen content (40-60 atom%) are formed, with most of the sp 3 bonds of the carbon atoms going to hydrogen atoms.
  • These bound H atoms have an inhibitory effect on the sp 2 clusters (olefin chains or aromatic rings) that otherwise form in amorphous carbon layers, resulting in a weakly crosslinked "polymer-like" amorphous carbon network (PLCH). This happens z. B.
  • a corresponding doping of the amorphous carbon layers with suitable foreign atoms reduces their modulus of elasticity.
  • oxygen, fluorine and vanadium are used in the elastic matrix layers.
  • the values for the elastic modulus of the elastic matrix layers E are between 1 and 70 GPa, preferably between 3 and 50 GPa and in particular between 3 and 20 GPa.
  • the layer system based on carbon compounds described here already has all the properties of a biocompatible layer.
  • the transition layer to the surface therefore does not need to be made extra biocompatible.
  • the coating system - in addition to its elasticity and diffusion-tightness - still has the option of coupling active ingredients to its surface.
  • a loading with functional amino groups of at least 2.5 / nm 2 preferably of at least 5 / nm 2 and in particular of at least 10 / nm 2 is achieved.
  • the layer system described here is z. B. with a falling in the class of PECVD (Plasma Enhanced Chemical Vapor Deposition) method method.
  • An inductively coupled high frequency plasma jet source is used to excite the process gases and precursors used.
  • process gases z. B. hydrocarbon gases such.
  • methane acetylene used individually or mixed with each other and / or mixed with nitrogen-containing process gases (such as nitrogen, ammonia) and / or in mixture with fluorine-containing process gases (such as, for example, carbon tetrafluorocarbon) used.
  • nitrogen-containing process gases such as nitrogen, ammonia
  • fluorine-containing process gases such as, for example, carbon tetrafluorocarbon
  • vaporized liquid precursors such as, for example, allylamine
  • organic and / or organometallic precursors such as, for example, para-xylene, HMDSO
  • the properties of the layer-forming particle flow can be varied independently of one another via a large number of process parameters (such as pressure, precursor gas flow, and rf power) such that amorphous carbon layers with very different properties deposit.
  • process parameters such as pressure, precursor gas flow, and rf power
  • process pressures in the range of I x IO "4 mbar - 9 ⁇ 10 " 3 mbar
  • I x IO "4 mbar - 9 ⁇ 10 " 3 mbar reduced the residence time of the gas molecules in the source to a minimum, so that predominantly ionized and / or simply dissociated Precursorgasteilchen arise (eg 02H 2 + , C2H + in the case of Acetylenprecursorgas).
  • the particle flow thus generated is under appropriate geometry (direct or indirect or oblique incidence or diffused or semi-directed secondary plasma) on the
  • Substrate directed so that the deposition rates and thus the energy input and the associated increase in temperature of the substrate remain limited.
  • the carbon-based diffusion-tight core layers D are made from predominantly hydrocarbon-containing gaseous precursors (eg acetylene) at a process gas pressure between 3.0 ⁇ 10 -5 mbar and 3.0 ⁇ 10 -3 mbar, preferably between 5.0 ⁇ 10 -5 mbar and 2.0 x 10 -3 mbar and in particular between 7.0 x 10 "4 mbar and 1, 0 x 10 -3 mbar deposited.
  • the fed into the plasma RF power is between 70 and 350 W, preferably between 100 and 300 W and in particular between 200 and 250 W.
  • the geometric arrangement is selected such that the deposition rates are between 0.5 and 100 nm / min, preferably between 5 and 50 nm / min and in particular between 10 and 20 nm / min
  • Ions at the layer-forming particle flux is between 5 and 70%, preferably between 5 and 40% and in particular between 10 and 20%
  • the ion energies are between 8 and 100 eV / C-atom, preferably between 10 and 30 eV / C-atom and in particular between 10 and 20 eV / C atom.
  • the carbon matrix-based elastic matrix layers E are made from predominantly hydrocarbon-containing gaseous precursors (eg methane and / or acetylene), possibly obtained by evaporation, at a process gas pressure of between 8.0 ⁇ 10 -4 mbar and 9.0 ⁇ 10 -3 mbar , preferably between 2.0 x 10 -3 mbar and 7.0 x 10 "3 mbar and in particular between 3.0 x 10" 4 mbar and 6.0 x 10 -3 mbar separated.
  • the RF power fed into the plasma is between 50 and 350 W, preferably between 70 and 200 W and in particular between 100 and 175 W.
  • the geometric arrangement is selected so that the deposition rates between 0.5 and 100 nm / min, preferably between 5 and 50 nm / min and in particular between 10 and 20 nm / min.
  • the proportion of ions in the layer-forming particle flux is between 5 and 25%, preferably between 5 and 20% and in particular between 5 and 15%.
  • the ion energies are between 8 and 50 eV / C atom, preferably between 8 and 30 eV / C atom and in particular between 8 and 15 eV / C atom.
  • a PLCH layer with a suitably adapted coefficient of thermal expansion and high elasticity is applied as layer A or substrate-near layer E of layer system B, which changes into a dense diffusion barrier layer (DLCH) by gradually changing the process parameters.
  • DLCH dense diffusion barrier layer
  • the boundary region to any subsequent polymer layers again has polymer-like properties and provides on the surface functional groups or reactive centers (eg -NH 2 , -NH, -COOH or N and / or Si and / or Ag and / or F and / or O) ready for good connection of the following layer.
  • surface functional groups or reactive centers eg -NH 2 , -NH, -COOH or N and / or Si and / or Ag and / or F and / or O
  • the amorphous carbon-based layer system already has good biocompatibility. If wear protection is to be achieved, a DLCH layer is applied as the finishing layer.
  • the amorphous carbon surface may be attached to any of the active ingredients required for the particular application or to achieve another functionality (eg to set a specific wettability or free surface energy or to set specific, eg bactericidal or cell-growth-promoting properties) functional groups and bonding centers equipped by the last - step
  • Precursorase obtained by evaporation eg, ammonia, carbon tetrachloride, organometallic precursors
  • the desired elements can be incorporated by cosputting solid-state targets.
  • transitions between the individual types of amorphous carbon layers ensure that, as described above, cracks do not form in the diffusion barrier layer due to movement of the workpiece or temperature-induced expansion of the material surrounding the layer, leaving a permeability to the species to be isolated (ions, gases, liquid molecules , Particles) would result.
  • species to be isolated ions, gases, liquid molecules , Particles
  • Oxidic layers are predominantly produced by means of sputtering processes.
  • sputtering process also cathode sputtering
  • gas ions are accelerated from a plasma to a target.
  • the target material is thereby atomized and the released (sputtered) material is then deposited on a substrate located near the target.
  • the sputtering is realized in a closed container, which is pumped off before the deposition of the best possible vacuum.
  • a process gas is admitted to a typical working pressure between 10 "3 and 5 x 10 " 2 mbar.
  • the target is set to an electrical potential (DC or rf). Due to natural cosmic radiation, there are always some ions and electrons which are accelerated in the electric field and lead to collective ionization through collisions in the gas.
  • the resulting plasma is compressed by suitable magnetic fields in such a way that the greatest intensity prevails directly on the target surface.
  • the resulting layer properties can be specifically determined by the plasma parameters, such as electron energy distribution function, electron density and plasma potential in different gas compositions.
  • a gas mixture of Ar (60% to 90%) and O 2 (40% to 10%) admitted into the process chamber.
  • an AC voltage having a frequency of 13.6 MHz is applied to the metallic sputtering target.
  • a low plasma power (100 W to 150 W) is set.
  • the materials AI, Si, Zr, Ta, and Ti are used.
  • Stoichiometry of the layer is determined by the gas ratios ArAD 2 , the sputtering power and the distance from the substrate to the ion source.
  • the described sputtering methods are combined with the previously described PECVD method in the layer system.
  • the layer system on z. B. oxidic base contains oxidic diffusion-tight core layers z. B. are embedded in deposited by the PECVD method elastic matrix layers.
  • Suitable elastic matrix layers are the elastic matrix layers described above, as well as polymer-type plasma-deposited layers deposited from evaporated organometallic precursors.
  • HMDSO offers as a corresponding organometallic precursor.
  • the diffusion-tight SiO x layer can also be deposited from the organometallic precursor by a PECVD process with the addition of oxygen gas to set the appropriate stoichiometry (Table 1), a method which facilitates the deposition of the gradual transition layers GEB and GBE.
  • Table 1 a method which facilitates the deposition of the gradual transition layers GEB and GBE.
  • TaO x as diffusion-tight core layers tantalum tetraethoxy- dimethylaminoethoxide (TAT DMAE) or tantalumate (Ta (C 2 H 5 O) 5 ) or in the case of ZrO x zirconium acetate as an organometallic precursor, the corresponding with oxygen gas in the PECVD Method can be used.
  • the transition from oxide to polymer-like layers is when using organometallic precursor (MO) z.
  • MO organometallic precursor
  • the flow ratio (oxygen / MO) and the power fed into the plasma which ensures a corresponding dissociation of the MO molecules regulated.
  • the diffusion-tight core layers D are deposited at high oxygen / MO ratio and high power, the elastic matrix layers at low power (small Yasuda factor) from the organometallic precursor.
  • the plasma-deposited, electrically insulating, diffusion-tight, elastic body-compatible layer system presented here can be used in a multitude of fields of application because of its multifunctional properties. In principle, all applications in which a mass flow must be suppressed come into question.
  • z. As packaging films and containers, especially in the food industry for food and beverages, in the pharmaceutical industry for z.
  • drugs and in the chemical industry for z. As volatile solvents, gasolines, corrosive liquids, hygroscopic solids and powders. These are z. B. tanks for fuels such.
  • gasoline hydrocarbons and hydrogen.
  • the layer system can be incorporated into seals and covers and significantly improve their barrier function. Due to its great tolerance to deformation, it can also be extremely loaded by mechanical pressure components such. As O-rings, are used and provide an additional diffusion protection for sealing. It also adds new functionality to fabrics and garments.
  • the layer system gives plastics an elastic barrier layer, which prevents the outgassing of harmful additives, such.
  • the coating system protects flat screens (so-called FPD, flat panel displays, such as liquid crystal displays, LCDs) as well as organic light-emitting diodes (OLEDs) from diffusion and rapid aging processes and is suitable for Encapsulation of so-called MEMS (micro-electro-mechanical systems) as z. B. occur in printer heads of inkjet printers or in acceleration sensors for triggering airbags.
  • the layer system is used for the encapsulation of electrodes and electronic circuits, in particular against the ingress of moisture into
  • the layer system protects electrodes and electronic circuits against ion diffusion and prevents voltage breakthroughs. Due to the additional excellent body compatibility of the
  • Layer system is particularly suitable for the encapsulation of medical implants, on the one hand by keeping body fluids, ions, proteins and other molecules from the implant interior and on the other hand prevents a release (possibly harmful) implant components in the surrounding tissue. Thus, body compatibility and functionality of the implant are guaranteed even under the above-mentioned loads. The residence time of the implant in the body can thus be extended considerably.
  • the layer system is particularly suitable for the encapsulation of electrically active medical implants. These include z. For example, implants for functional electrostimulation (FES), implants with electrode systems for recording bioelectrical
  • implants for the electrical stimulation of individual nerve fibers altogether just so-called neuroprostheses, cardiac pacemakers, implants for dynamic myoplasty, implants for diaphragmatic or phrenic nerve stimulation) and for the encapsulation of electromechanical implants (such as, for example, artificial hearts , VAD (ventricular-assisted devices) systems, total artificial heart systems) and for the encapsulation of so-called BioMEMS (micro-implants based on micromechanical systems).
  • electromechanical implants such as, for example, artificial hearts , VAD (ventricular-assisted devices) systems, total artificial heart systems
  • BioMEMS micro-implants based on micromechanical systems

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Abstract

L'invention concerne un système multicouche appliqué sur un substrat, lequel système multicouche est appliqué sur le substrat par dépôt par plasma. L'invention se caractérise en ce que le système multicouche est conçu de sorte à présenter une grande étanchéité à la diffusion vis-à-vis d'ions en solution aqueuse, le courant IIon, engendré par la diffusion des ions en présence d'un gradient de champ électrique supérieur à 104V/m, de préférence supérieur à 105V/m, idéalement supérieur à 107V/m, étant < 6,5x10-8 A/cm2, de préférence < 6,5x10 -10 A/cm2, en particulier < 1x10-12 A/cm2.
EP08707792A 2007-02-23 2008-02-22 Système stratifié élastique, étanche à la diffusion, électriquement isolant et déposé par plasma Withdrawn EP2137337A2 (fr)

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