WO2004107468A2 - Flexible multilayer packaging material and electronic devices with the packaging material - Google Patents

Flexible multilayer packaging material and electronic devices with the packaging material Download PDF

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Publication number
WO2004107468A2
WO2004107468A2 PCT/EP2004/005842 EP2004005842W WO2004107468A2 WO 2004107468 A2 WO2004107468 A2 WO 2004107468A2 EP 2004005842 W EP2004005842 W EP 2004005842W WO 2004107468 A2 WO2004107468 A2 WO 2004107468A2
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WO
WIPO (PCT)
Prior art keywords
layer
barrier layer
organic
packaging material
electronic device
Prior art date
Application number
PCT/EP2004/005842
Other languages
French (fr)
Other versions
WO2004107468A8 (en
WO2004107468A3 (en
Inventor
Debora Henseler
Karsten Heuser
Ralph Pätzold
Georg Wittmann
Original Assignee
Osram Opto Semiconductors Gmbh
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 Osram Opto Semiconductors Gmbh filed Critical Osram Opto Semiconductors Gmbh
Priority to DE112004000938T priority Critical patent/DE112004000938B4/en
Priority to JP2006508230A priority patent/JP2007523800A/en
Priority to KR1020057022763A priority patent/KR101290134B1/en
Publication of WO2004107468A2 publication Critical patent/WO2004107468A2/en
Publication of WO2004107468A8 publication Critical patent/WO2004107468A8/en
Publication of WO2004107468A3 publication Critical patent/WO2004107468A3/en

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • H10K59/8731—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • An OLED device comprises a functional stack formed on a substrate.
  • the functional stack comprises at least one or more organic functional layers sandwiched between two conductive layers.
  • the conductive layers serve as electrodes (cathode and anode) .
  • When a voltage is applied to the electrodes charge carriers are injected through these electrodes into the functional layers and upon recombination of the charge carriers visible radiation can be emitted (electroluminescence) .
  • This functional stack of the OLED is very sensitive to moisture and oxidizing agents, which can cause, for example oxidation of the metals of the electrodes or deterioration of the organic functional layers.
  • flexible OLED devices can be built up on flexible substrates, like polymeric substrates.
  • polymeric substrates with a permeability for water or oxidizing agents below 10 "6 g/ (m 2 day) are needed.
  • the international patent application WO 01/81649 Al describes an environmentally sensitive display device, which is encapsulated by a barrier assembly consisting of a ceramic barrier layer and a polymeric layer (see Figure 1) . Due to the high permeability of the polymeric layer the barrier ability of this barrier stack is mainly attributed to the ceramic bar- rier layer. Therefore, the ceramic has to be of high quality and should have as less pinholes, grain boundaries, shadowing effects or other defects as possible. These defects can provide a continuos path for permeants for passing through the ceramic layer and therefore lead to a decreased ability of the ceramic barrier layer to function as a barrier. In order to reduce this problem the deposition conditions for the ceramic barrier layers have to be tightly controlled. Often several thin ceramic layers have to be deposited on top of each other in order to enhance the barrier abilities of the ceramic barrier layers. This leads to a complicated and therefore expensive production of flexible barrier layers.
  • the present invention meets these needs by providing a flexible multilayer packaging material according to the base claim 1.
  • Favourable embodiments of the invention and an electronic device with the packaging mate- rial are subjects of further dependent claims.
  • the main subject of the invention according to the base claim is a flexible multilayer packaging material for protection of articles, which are sensitive to moisture and oxidizing agents comprising at least one active polymeric barrier layer which is able to bind the moisture and oxidizing agents and at least one ceramic barrier layer.
  • the invention provides an active polymeric barrier layer which can actively bind and therefore neutralise permeants. This binding can take place by e . g. chemi- or physisorption of the permeants. Therefore, the active polymeric barrier layer exhibits an enhanced barrier ability in comparison to the conventional passive polymeric layers which are not able to bind permeants.
  • the multilayer packaging material of the invention an article can be sealed from the environment which can be, for example, food, pharmaceuticals or sensitive electronic de- vices.
  • the active polymeric layer binds the moisture and oxidizing agents chemically, and therefore permanently.
  • the required barrier capabilities of the ceramic barrier layers can be reduced, for example, by one order of magnitude from 5*10 "5 g/ (m 2 day) to 5*10 "4 g/ (m 2 day) .
  • the deposition conditions for the ceramic barrier layers do not have to be as tightly controlled as it would be the case with ceramic barrier layers of higher barrier abilities. Therefore the reduced requirements on the ceramic barrier layer result in an easier and therefore cheaper production of a multilayer packaging material of the invention.
  • the active polymeric barrier layer is preferably selected from a polymeric matrix with dispersed cyclodextrines, cyclic olefin copolymers, a polymeric matrix with anhydrides and mixtures thereof .
  • Cyclodextrines are cyclic oligomers of ⁇ -D-glucose formed by the action of certain enzymes such as cyclodextrin gluco- transferases .
  • the cyclodextrines consist of six, seven or eight ⁇ - 1,4 -linked glucose monomers and are known as ⁇ - , ⁇ - or ⁇ -cyclodextrines .
  • the cyclodextrine molecules are orientated in a special manner relative to each other so that con- tinuos channels are formed within the crystal lattice of the cyclodextrines. These channels have large hollow interiors of a specific volume and are therefore able to bind permeants e.g. gas molecules.
  • the permeants can even be linked cova- lently to the cyclodextrine molecules, for example, by the primary hydroxyl groups at the six-carbon positions of the glucose moiety and the secondary hydroxyl group in the t,wo- and three-carbon positions of the molecule.
  • These hydroxyl groups can also be replaced by other groups in order to change the solubility, compatibility and the thermostability of the cyclodextrines.
  • the substitution of the hydroxyl groups can also be used to adjust the binding strength to a value lying between the binding strength of cyclodextrines and of potential permeants. Therefore the cyclodextrines are able to permanently neutralize, for example, moisture or oxi- dizing agents.
  • cyclodextrines are dispersed in a polymeric matrix like polypropylene.
  • the cyclic olefin copolymers can, for example, comprise two components which are blended by extrusion.
  • One component can, for example, be an oxidizable polymer, like poly (ethylene/methylacrylate/cyclohexenyl-methylacrylate) (EMCM) .
  • the second component can for example, consist of a photoinitiator and a catalyst, for example of a transition metal catalyst. Both components can form a so-called oxygen scavenging system which can be activated, for example upon exposure to UV-radiation.
  • the cyclic olefin groups of these polymers are then able to chemically react with e.g. oxygen molecules via ring opening reactions or aromatization reactions .
  • the active polymeric barrier layer can also be a polymeric matrix with anhydrides.
  • the anhydrides are preferably carbonic acid anhydrides which can be formed by removing water from the respective free acids. Therefore, these anhydrides are able to bind moisture, e.g. water molecules very effectively.
  • Preferred examples for acid anhy- drides are acid anhydrides of organic acids like maleic anhydride.
  • the acid anhydrides are preferably bound covalently to the polymeric matrix e.g. polystyrene. It is also possible to use a mixture of cyclodextrines, cyclic olefin copolymers and anhydrides to ensure an optimal barrier performance for dif- ferent types of oxidizing agents or moisture.
  • liquid crystal polymers as an active polymeric barrier layer. These polymers exhibit the same properties as liquid crystals and are often synthesized by the polycondensation of aromatic dicarboxylic acids and aromatic diamines or phenols.
  • the ceramic barrier layer is selected from metalnitrides, metaloxides and metaloxynitrides .
  • the metal components of these metalnitrides, metaloxides or metaloxynitrides are preferably selected from aluminum and silicon.
  • These ceramic barrier layers provide a physical barrier for the permeation of gases or liquids. Apart from these materials other ceramic materials, which comprise predominantly inorganic and non-metallic compounds or elements can be used.
  • the at least one active polymeric barrier layer and the at least one ce- ramie barrier layer are transparent.
  • Transparent, flexible, multilayer packaging materials are preferred materials for, for example, organo-optical devices like the above-mentioned OLEDs, because these materials are transparent for the light emitted by the OLEDs.
  • a further object of the invention is a containment for the protection of articles which comprises a multilayer flexible packaging material of the invention.
  • this containment comprises an alternating assembly of polymeric barrier layers and ceramic barrier layers.
  • An assembly of alternating ceramic barrier layers and polymeric barrier layers exhibits very high barrier abilities and for example just shows permeation rates of up to 10 "6 g/ (m 2 day) for several thousand hours .
  • one of the ceramic barrier layers of the assembly faces towards the outside of the containment.
  • This ceramic barrier layer is then able to prevent most of the moisture and oxidizing agents from permeating into the interior of the containment.
  • the few molecules which are nevertheless able to permeate through this outside ceramic barrier layer are then absorbed by the active polymeric barrier layer, which preferably faces the interior of the containment and is arranged on the ceramic barrier layer.
  • a l ⁇ m thick active polymeric barrier layer which is arranged on a ceramic barrier layer with a diffusion rate of 10 "3 g/ (m 2 day) leads to 10,000 hours before the first permeating molecule can reach an article packed in the containment of the invention.
  • first and a second barrier layer on top of each other, the first ceramic barrier layer facing towards the outside of the containment. Going from the outside of the containment to the interior of the containment these two ceramic barrier layers might be fol- lowed by an active polymeric barrier layer, which is able to absorb the residual molecules permeating through the two ceramic barrier layers.
  • the barrier abilities of the two ceramic barrier layers can be enhanced by decoupling the defects of the first and second ceramic barrier layers. This can be done for example by changing the deposition parameters and growth conditions during the deposition of the two ceramic barrier layers.
  • first ceramic barrier layer on the active polymeric barrier layer, then modify the surface of the first ceramic barrier layer to in- troduce new nucleation sites on the surface of this first ceramic barrier layer and subsequently form a second ceramic barrier layer on the first ceramic barrier layer using the new nucleation sites. This method can also lead to mismatched subsequent ceramic barrier layers leading to enhanced barrier abilities of an assembly of two ceramic barrier layers.
  • the surface of the containment facing towards the outside of the containment entirely consists of a ceramic barrier layer.
  • an organic electronic device which is sensitive to moisture or oxidizing agents and comprises a flexible substrate, an organic functional area on the substrate, a cap encapsulating the organic functional area and additionally a flexible multilayer packaging material consisting of a ceramic barrier layer and an active polymeric barrier layer for protection of the organic functional area.
  • a flexible multilayer packaging material consisting of a ceramic barrier layer and an active polymeric barrier layer for protection of the organic functional area.
  • Such an organic electronic device exhibits an prolonged shelf life due to the enhanced barrier abilities which are attributed mainly to the flexible multilayer packaging material and the cap.
  • the flexible multilayer packaging material comprising an assembly of the ceramic barrier layer and the active polymeric barrier between the substrate an the organic functional area (see for example figures 3 and 4) .
  • polymeric substrates like poly-ethylenetherepthalate (PET) or polyethersulfones (PES) are preferably used.
  • PET poly-ethylenetherepthalate
  • PES polyethersulfones
  • the polymeric substrates of these flexible organic electric devices are much thicker than the ceramic barrier layers (thickness of ceramic barrier layers between 1 and 250 nm) or the thickness of the active polymeric barrier layers (around 1 to lO ⁇ m) .
  • Flexible polymeric substrates normally have a thickness of around 100 to 200 ⁇ m.
  • the moisture and oxidizing agent scavenging materials for example the cyclodextrines, the cyclic olefin copolymers or the anhydrides are preferably co-extruded into the polymeric substrate so that the polymeric substrate itself can serve as an active polymeric barrier layer.
  • Such a substrate can exhibit very high barrier abilities due to its large thickness (see e.g. figure 5) .
  • a cap encapsulating the organic functional stack can com- prise, for example a material like polymers, metals and glass or combinations thereof. It is also possible that the cap comprises a flexible multilayer packaging material consisting of ceramic barrier layers and active polymeric barrier layers (see, for example, Figure 4) .
  • the substrate comprises an alternating assembly of active polymeric barrier layers and ceramic barrier layers.
  • This alternating assembly results in very good bar- rier abilities of the substrate and therefore leads to a prolonged shelf life of the organic electric device.
  • the surface of the substrate facing towards the out- side environment consists of a ceramic barrier layer, which physically blocks the gases and liquid molecules from permeating into the device.
  • the organic functional area can consist of a stack of a first electrically conductive layer, an organic functional layer on the first conductive layer and a second electrically conductive layer on the functional layer, wherein the organic functional layer comprises at least one organic, electrolumines- cent layer.
  • An electronic device with such an organic functional stack forms an organic electroluminescent device (OLED) .
  • the organic functional layer between the first electrically conductive and the second electrically conductive layer can also be an organic, radiation detecting layer, so that the electronic device provides an organic radiation detecting device, for example, an organic solar cell.
  • the organic functional area can also form a so-called integrated plastic cir- cuit comprising organic electrically conductive materials.
  • Figure 1 shows a conventional electronic device.
  • Figure 2 shows a containment of the invention encapsulating an article.
  • FIG. 3 shows one embodiment of an organic electroluminescent device of the invention.
  • Figure 4 shows another embodiment of an organic electroluminescent device of the invention.
  • Figure 5 shows yet another embodiment of an organic electroluminescent device of the invention.
  • Figure 1 depicts a conventional environmentally sensitive display device as for example disclosed in the document WO 01/81649 Al .
  • a device 25 is arranged on a substrate 5.
  • the device 25 is encapsulated by a barrier stack consisting of a barrier layer 20, which can be a ceramic barrier layer and a passive polymeric layer 15. Due to the high permeability of the polymeric layer 15 most of the barrier abilities of the barrier stack are attributed to the ceramic barrier layer 20.
  • This ceramic barrier layer has to exhibit a very high quality concerning defects so that for example tightly controlled conditions for the deposition of this ceramic barrier layer are necessary.
  • FIG. 2 is a cross-sectional view of a containment 39 ac- cording to the invention, which encapsulates an environmentally sensitive article 40.
  • the containment 39 consists of a ceramic barrier layer 45 and an active polymeric barrier layer 50.
  • the active polymeric barrier layer is able to absorb the residual oxygen and moisture permeating to the ce- ramie barrier layer 45, so that a containment with enhanced barrier abilities results.
  • For higher barrier abilities more ceramic barrier layers and active polymeric barrier layers can be arranged on this containment leading e.g. to alternating arrangements of ceramic barrier layers and active poly- meric barrier layers.
  • FIG. 3 depicts a cross-sectional view of one embodiment of an organic electronic device of the invention.
  • An organic functional stack is arranged on a substrate 100.
  • An assembly 106 of different ceramic barrier layers and active polymeric barrier layers is arranged between the substrate 100 and the organic functional stack to function as a flexible multilayer packaging material.
  • the assembly 106 consists of an alternating assembly of a ceramic barrier layer 110 facing the substrate 100, an active polymeric barrier layer 120 and again a ceramic barrier layer 130 and an active polymeric barrier layer 140.
  • the active polymeric barrier layer 120 is able to bind the residual moisture and oxygen permeating in the substrate 100, as well as the molecules passing through the ceramic barrier layer 110.
  • On top of the active polymeric barrier layers 120 a ceramic barrier layer 130 is arranged.
  • This ceramic barrier layer 130 serves to block gases and moisture permeating through the active polymeric barrier layer 120.
  • the additional active polymeric barrier layer 140 is arranged on the ceramic barrier layers and can bind molecules permeating through the two ce- ramie barrier layers 110 and 130.
  • the organic functional stack consists of at least one organic functional layer 160 sandwiched between a first electrically conductive layer 150 and a second electrically conductive layer 170.
  • the at least one organic functional layer 160 comprises at least one organic electroluminescent layer.
  • the environmentally sensitive organic functional stack is encapsulated by a cap 180 which, for example, can comprise polymers, metals and glass.
  • Contacts 155 and 175 are present, which contact the first 150 and second 170 electrically conductive layers and can provide contact pads. Due to the enhanced barrier abilities of the substrate 105 which is mainly conferred by the barrier assembly 106, such an organic electronic device ex- hibits a prolonged shelf life.
  • Figure 4 shows a cross-sectional view of yet another embodiment of an organic electronic device of the invention.
  • a barrier assembly 206 is arranged between an organic functional stack and a substrate 200.
  • the barrier assembly 206 consists of an alternating assembly of a ceramic barrier layer 210 followed by an active polymeric barrier layer 220 on which another ceramic barrier layer 230 and a second active polymeric barrier layer 240 are deposited.
  • the organic functional stack consists of at least one organic functional layer 260 sandwiched between a first electrically conductive layer 250 and a second electrically conductive layer 270.
  • an alternating barrier assembly of ceramic barrier layers and active polymeric barrier layers is arranged on top of the functional stack encapsulating the organic functional stack.
  • the barrier assembly consists of an alternating sequence of an active polymeric barrier layer 280, a ceramic barrier layer 290, an active polymeric barrier layer 300 and a ceramic barrier layer 310.
  • the substrate 200 and the ceramic barrier layers and polymeric barrier layers are preferably transparent in order to enable the light to pass through the different layers.
  • Figure 5 depicts an organic electronic device of the invention, where the substrate 300 itself provides an active polymeric barrier layer.
  • a ceramic barrier layer 310 is arranged, completely covering the substrate 300, in order to prevent moisture and oxidizing agents from permeating into the substrate and the organic functional stack.
  • the organic functional stack comprises at least one organic functional layer 330 sandwiched between a first electrically conductive layer 320 and a second electrically conductive layer 340.
  • the functional stack is encapsulated by a cap 350.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Wrappers (AREA)
  • Packaging Frangible Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Packages (AREA)

Abstract

The invention discloses a flexible multilayer packaging material for protection of articles which are sensitive to moisture and oxidizing agents which comprises at least one active polymeric barrier layer (120, 140) which is able to bind the moisture and oxidizing agents and at least one ceramic barrier layer (110, 130). The combination of the active polymeric barrier layer and the ceramic barrier layer significantly enhances the barrier abilities of the multilayer packaging material.

Description

TITLE OF THE INVENTION
FLEXIBLE MULTILAYER PACKAGING MATERIAL AND ELECTRONIC DEVICES WITH THE PACKAGING MATERIAL
BACKGROUND OF THE INVENTION
Many articles, for example food, electronic devices or pharmaceuticals, are very sensitive to moisture and/or oxidizing agents. Many of these products rapidly degrade upon exposure to water, oxidizing agents or other gases or liquids. Polymeric substrates, like polymeric foils, are often used to package these products. These foils frequently exhibit a permeability for water vapor and for oxidizing agents in the range of more than 1 g/ (m2day) . This high degree of permeability is unacceptable for most of the products packaged by- polymeric foils.
One major field of application for packaging by polymeric substances are organic electroluminescent devices (OLEDs) . An OLED device comprises a functional stack formed on a substrate. The functional stack comprises at least one or more organic functional layers sandwiched between two conductive layers. The conductive layers serve as electrodes (cathode and anode) . When a voltage is applied to the electrodes, charge carriers are injected through these electrodes into the functional layers and upon recombination of the charge carriers visible radiation can be emitted (electroluminescence) . This functional stack of the OLED is very sensitive to moisture and oxidizing agents, which can cause, for example oxidation of the metals of the electrodes or deterioration of the organic functional layers.
Due to the intrinsic properties of the organic functional layers, flexible OLED devices can be built up on flexible substrates, like polymeric substrates. For sufficient life- time of the OLEDs polymeric substrates with a permeability for water or oxidizing agents below 10"6g/ (m2day) are needed.
The international patent application WO 01/81649 Al describes an environmentally sensitive display device, which is encapsulated by a barrier assembly consisting of a ceramic barrier layer and a polymeric layer (see Figure 1) . Due to the high permeability of the polymeric layer the barrier ability of this barrier stack is mainly attributed to the ceramic bar- rier layer. Therefore, the ceramic has to be of high quality and should have as less pinholes, grain boundaries, shadowing effects or other defects as possible. These defects can provide a continuos path for permeants for passing through the ceramic layer and therefore lead to a decreased ability of the ceramic barrier layer to function as a barrier. In order to reduce this problem the deposition conditions for the ceramic barrier layers have to be tightly controlled. Often several thin ceramic layers have to be deposited on top of each other in order to enhance the barrier abilities of the ceramic barrier layers. This leads to a complicated and therefore expensive production of flexible barrier layers.
SUMMARY OF THE INVENTION
Therefore, there is a need for polymeric substrates with improved barrier abilities. The present invention meets these needs by providing a flexible multilayer packaging material according to the base claim 1. Favourable embodiments of the invention and an electronic device with the packaging mate- rial are subjects of further dependent claims.
The main subject of the invention according to the base claim is a flexible multilayer packaging material for protection of articles, which are sensitive to moisture and oxidizing agents comprising at least one active polymeric barrier layer which is able to bind the moisture and oxidizing agents and at least one ceramic barrier layer.
In contrast to conventional multilayer packaging materials the invention provides an active polymeric barrier layer which can actively bind and therefore neutralise permeants. This binding can take place by e . g. chemi- or physisorption of the permeants. Therefore, the active polymeric barrier layer exhibits an enhanced barrier ability in comparison to the conventional passive polymeric layers which are not able to bind permeants.
By the multilayer packaging material of the invention an article can be sealed from the environment which can be, for example, food, pharmaceuticals or sensitive electronic de- vices. Preferably, the active polymeric layer binds the moisture and oxidizing agents chemically, and therefore permanently.
Due to the enhanced barrier abilities of active polymeric barrier layers in comparison to passive polymeric layers, the required barrier capabilities of the ceramic barrier layers can be reduced, for example, by one order of magnitude from 5*10"5g/ (m2day) to 5*10"4g/ (m2day) . Moreover, the deposition conditions for the ceramic barrier layers do not have to be as tightly controlled as it would be the case with ceramic barrier layers of higher barrier abilities. Therefore the reduced requirements on the ceramic barrier layer result in an easier and therefore cheaper production of a multilayer packaging material of the invention.
The active polymeric barrier layer is preferably selected from a polymeric matrix with dispersed cyclodextrines, cyclic olefin copolymers, a polymeric matrix with anhydrides and mixtures thereof .
Cyclodextrines are cyclic oligomers of α-D-glucose formed by the action of certain enzymes such as cyclodextrin gluco- transferases . The cyclodextrines consist of six, seven or eight α- 1,4 -linked glucose monomers and are known as α- , β- or γ-cyclodextrines . The cyclodextrine molecules are orientated in a special manner relative to each other so that con- tinuos channels are formed within the crystal lattice of the cyclodextrines. These channels have large hollow interiors of a specific volume and are therefore able to bind permeants e.g. gas molecules. The permeants can even be linked cova- lently to the cyclodextrine molecules, for example, by the primary hydroxyl groups at the six-carbon positions of the glucose moiety and the secondary hydroxyl group in the t,wo- and three-carbon positions of the molecule. These hydroxyl groups can also be replaced by other groups in order to change the solubility, compatibility and the thermostability of the cyclodextrines. The substitution of the hydroxyl groups can also be used to adjust the binding strength to a value lying between the binding strength of cyclodextrines and of potential permeants. Therefore the cyclodextrines are able to permanently neutralize, for example, moisture or oxi- dizing agents. Preferably cyclodextrines are dispersed in a polymeric matrix like polypropylene.
The cyclic olefin copolymers can, for example, comprise two components which are blended by extrusion. One component can, for example, be an oxidizable polymer, like poly (ethylene/methylacrylate/cyclohexenyl-methylacrylate) (EMCM) . The second component can for example, consist of a photoinitiator and a catalyst, for example of a transition metal catalyst. Both components can form a so-called oxygen scavenging system which can be activated, for example upon exposure to UV-radiation. The cyclic olefin groups of these polymers are then able to chemically react with e.g. oxygen molecules via ring opening reactions or aromatization reactions .
In another embodiment the active polymeric barrier layer can also be a polymeric matrix with anhydrides. The anhydrides are preferably carbonic acid anhydrides which can be formed by removing water from the respective free acids. Therefore, these anhydrides are able to bind moisture, e.g. water molecules very effectively. Preferred examples for acid anhy- drides are acid anhydrides of organic acids like maleic anhydride. The acid anhydrides are preferably bound covalently to the polymeric matrix e.g. polystyrene. It is also possible to use a mixture of cyclodextrines, cyclic olefin copolymers and anhydrides to ensure an optimal barrier performance for dif- ferent types of oxidizing agents or moisture.
It is also possible to use liquid crystal polymers as an active polymeric barrier layer. These polymers exhibit the same properties as liquid crystals and are often synthesized by the polycondensation of aromatic dicarboxylic acids and aromatic diamines or phenols.
In a preferred embodiment of the invention the ceramic barrier layer is selected from metalnitrides, metaloxides and metaloxynitrides . The metal components of these metalnitrides, metaloxides or metaloxynitrides are preferably selected from aluminum and silicon. These ceramic barrier layers provide a physical barrier for the permeation of gases or liquids. Apart from these materials other ceramic materials, which comprise predominantly inorganic and non-metallic compounds or elements can be used.
In an advantageous embodiment of the invention the at least one active polymeric barrier layer and the at least one ce- ramie barrier layer are transparent. Transparent, flexible, multilayer packaging materials are preferred materials for, for example, organo-optical devices like the above-mentioned OLEDs, because these materials are transparent for the light emitted by the OLEDs.
A further object of the invention is a containment for the protection of articles which comprises a multilayer flexible packaging material of the invention. Preferably this containment comprises an alternating assembly of polymeric barrier layers and ceramic barrier layers. An assembly of alternating ceramic barrier layers and polymeric barrier layers exhibits very high barrier abilities and for example just shows permeation rates of up to 10"6g/ (m2day) for several thousand hours .
Preferably one of the ceramic barrier layers of the assembly faces towards the outside of the containment. This ceramic barrier layer is then able to prevent most of the moisture and oxidizing agents from permeating into the interior of the containment. The few molecules which are nevertheless able to permeate through this outside ceramic barrier layer are then absorbed by the active polymeric barrier layer, which preferably faces the interior of the containment and is arranged on the ceramic barrier layer. A lμm thick active polymeric barrier layer which is arranged on a ceramic barrier layer with a diffusion rate of 10"3g/ (m2 day) leads to 10,000 hours before the first permeating molecule can reach an article packed in the containment of the invention.
It is also possible to change the sequence of the different ceramic barrier layers and active polymeric barrier layers. For example, it is possible to arrange a first and a second barrier layer on top of each other, the first ceramic barrier layer facing towards the outside of the containment. Going from the outside of the containment to the interior of the containment these two ceramic barrier layers might be fol- lowed by an active polymeric barrier layer, which is able to absorb the residual molecules permeating through the two ceramic barrier layers. The barrier abilities of the two ceramic barrier layers can be enhanced by decoupling the defects of the first and second ceramic barrier layers. This can be done for example by changing the deposition parameters and growth conditions during the deposition of the two ceramic barrier layers. For example, it is possible to deposit two aluminum oxide ceramic barrier layers on top of each other, having different modifications, for example α- aluminumoxide and γ-aluminumoxide . This should lead to mismatched subsequent ceramic barrier layers which exhibit dif- ferent microstructures and therefore enhance the path for gases and water vapor permeation, leading to enhanced barrier abilities. It is also possible to deposit a first ceramic barrier layer on the active polymeric barrier layer, then modify the surface of the first ceramic barrier layer to in- troduce new nucleation sites on the surface of this first ceramic barrier layer and subsequently form a second ceramic barrier layer on the first ceramic barrier layer using the new nucleation sites. This method can also lead to mismatched subsequent ceramic barrier layers leading to enhanced barrier abilities of an assembly of two ceramic barrier layers. Methods for forming an arrangement of two subsequent barrier layers on polymeric substrates are described in detail in the copending European patent application, application No. 03 005 270.8, title: "Method for Forming an Arrangement of Barrier Layers on a Polymeric Substrate", which is hereby incorporated by reference in its entirety. In a preferred embodiment of the invention, the surface of the containment facing towards the outside of the containment entirely consists of a ceramic barrier layer.
Yet a further object of the invention is an organic electronic device, which is sensitive to moisture or oxidizing agents and comprises a flexible substrate, an organic functional area on the substrate, a cap encapsulating the organic functional area and additionally a flexible multilayer packaging material consisting of a ceramic barrier layer and an active polymeric barrier layer for protection of the organic functional area. Such an organic electronic device exhibits an prolonged shelf life due to the enhanced barrier abilities which are attributed mainly to the flexible multilayer packaging material and the cap. For example, it is possible to arrange the flexible multilayer packaging material comprising an assembly of the ceramic barrier layer and the active polymeric barrier between the substrate an the organic functional area (see for example figures 3 and 4) . It is also possible to integrate the flexible multilayer packaging of the invention directly into the substrate. For example, for flexible organic electronic devices, polymeric substrates like poly-ethylenetherepthalate (PET) or polyethersulfones (PES) are preferably used. Nor- mally the polymeric substrates of these flexible organic electric devices are much thicker than the ceramic barrier layers (thickness of ceramic barrier layers between 1 and 250 nm) or the thickness of the active polymeric barrier layers (around 1 to lOμm) . Flexible polymeric substrates normally have a thickness of around 100 to 200 μm. Therefore the moisture and oxidizing agent scavenging materials, for example the cyclodextrines, the cyclic olefin copolymers or the anhydrides are preferably co-extruded into the polymeric substrate so that the polymeric substrate itself can serve as an active polymeric barrier layer. Such a substrate can exhibit very high barrier abilities due to its large thickness (see e.g. figure 5) .
A cap encapsulating the organic functional stack can com- prise, for example a material like polymers, metals and glass or combinations thereof. It is also possible that the cap comprises a flexible multilayer packaging material consisting of ceramic barrier layers and active polymeric barrier layers (see, for example, Figure 4) .
In a preferred embodiment of the organic electric device of the invention, the substrate comprises an alternating assembly of active polymeric barrier layers and ceramic barrier layers. This alternating assembly results in very good bar- rier abilities of the substrate and therefore leads to a prolonged shelf life of the organic electric device. Advantageously the surface of the substrate facing towards the out- side environment consists of a ceramic barrier layer, which physically blocks the gases and liquid molecules from permeating into the device.
The organic functional area can consist of a stack of a first electrically conductive layer, an organic functional layer on the first conductive layer and a second electrically conductive layer on the functional layer, wherein the organic functional layer comprises at least one organic, electrolumines- cent layer. An electronic device with such an organic functional stack forms an organic electroluminescent device (OLED) .
The organic functional layer between the first electrically conductive and the second electrically conductive layer can also be an organic, radiation detecting layer, so that the electronic device provides an organic radiation detecting device, for example, an organic solar cell. The organic functional area can also form a so-called integrated plastic cir- cuit comprising organic electrically conductive materials.
In the following the invention will be explained in more detail by the figures.
DESCRIPTION OF THE DRAWINGS
Figure 1 shows a conventional electronic device.
Figure 2 shows a containment of the invention encapsulating an article.
Figure 3 shows one embodiment of an organic electroluminescent device of the invention.
Figure 4 shows another embodiment of an organic electroluminescent device of the invention. Figure 5 shows yet another embodiment of an organic electroluminescent device of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Figure 1 depicts a conventional environmentally sensitive display device as for example disclosed in the document WO 01/81649 Al . A device 25 is arranged on a substrate 5. The device 25 is encapsulated by a barrier stack consisting of a barrier layer 20, which can be a ceramic barrier layer and a passive polymeric layer 15. Due to the high permeability of the polymeric layer 15 most of the barrier abilities of the barrier stack are attributed to the ceramic barrier layer 20. This ceramic barrier layer has to exhibit a very high quality concerning defects so that for example tightly controlled conditions for the deposition of this ceramic barrier layer are necessary.
Figure 2 is a cross-sectional view of a containment 39 ac- cording to the invention, which encapsulates an environmentally sensitive article 40. The containment 39 consists of a ceramic barrier layer 45 and an active polymeric barrier layer 50. The active polymeric barrier layer is able to absorb the residual oxygen and moisture permeating to the ce- ramie barrier layer 45, so that a containment with enhanced barrier abilities results. For higher barrier abilities more ceramic barrier layers and active polymeric barrier layers can be arranged on this containment leading e.g. to alternating arrangements of ceramic barrier layers and active poly- meric barrier layers.
Figure 3 depicts a cross-sectional view of one embodiment of an organic electronic device of the invention. An organic functional stack is arranged on a substrate 100. An assembly 106 of different ceramic barrier layers and active polymeric barrier layers is arranged between the substrate 100 and the organic functional stack to function as a flexible multilayer packaging material. The assembly 106 consists of an alternating assembly of a ceramic barrier layer 110 facing the substrate 100, an active polymeric barrier layer 120 and again a ceramic barrier layer 130 and an active polymeric barrier layer 140. The active polymeric barrier layer 120 is able to bind the residual moisture and oxygen permeating in the substrate 100, as well as the molecules passing through the ceramic barrier layer 110. On top of the active polymeric barrier layers 120 a ceramic barrier layer 130 is arranged. This ceramic barrier layer 130 serves to block gases and moisture permeating through the active polymeric barrier layer 120. To complete the barrier assembly 106 the additional active polymeric barrier layer 140 is arranged on the ceramic barrier layers and can bind molecules permeating through the two ce- ramie barrier layers 110 and 130.
The organic functional stack consists of at least one organic functional layer 160 sandwiched between a first electrically conductive layer 150 and a second electrically conductive layer 170. In the case of organic electroluminescent devices the at least one organic functional layer 160 comprises at least one organic electroluminescent layer. The environmentally sensitive organic functional stack is encapsulated by a cap 180 which, for example, can comprise polymers, metals and glass. Contacts 155 and 175 are present, which contact the first 150 and second 170 electrically conductive layers and can provide contact pads. Due to the enhanced barrier abilities of the substrate 105 which is mainly conferred by the barrier assembly 106, such an organic electronic device ex- hibits a prolonged shelf life.
Figure 4 shows a cross-sectional view of yet another embodiment of an organic electronic device of the invention. A barrier assembly 206 is arranged between an organic functional stack and a substrate 200. In contrast to Figure 3 the barrier assembly 206 consists of an alternating assembly of a ceramic barrier layer 210 followed by an active polymeric barrier layer 220 on which another ceramic barrier layer 230 and a second active polymeric barrier layer 240 are deposited.
The organic functional stack consists of at least one organic functional layer 260 sandwiched between a first electrically conductive layer 250 and a second electrically conductive layer 270. Instead of a cap, as shown in Figure 3, an alternating barrier assembly of ceramic barrier layers and active polymeric barrier layers is arranged on top of the functional stack encapsulating the organic functional stack. The barrier assembly consists of an alternating sequence of an active polymeric barrier layer 280, a ceramic barrier layer 290, an active polymeric barrier layer 300 and a ceramic barrier layer 310. In the case of an organic electroluminescent display or an organic radiation detecting device, the substrate 200 and the ceramic barrier layers and polymeric barrier layers are preferably transparent in order to enable the light to pass through the different layers.
Figure 5 depicts an organic electronic device of the invention, where the substrate 300 itself provides an active polymeric barrier layer. On the substrate 300 a ceramic barrier layer 310 is arranged, completely covering the substrate 300, in order to prevent moisture and oxidizing agents from permeating into the substrate and the organic functional stack. The organic functional stack comprises at least one organic functional layer 330 sandwiched between a first electrically conductive layer 320 and a second electrically conductive layer 340. The functional stack is encapsulated by a cap 350.
The scope of the invention is not limited to the embodiments shown in the figures. Indeed various variations, especially concerning the sequence of ceramic barrier layers and active polymeric barrier layers in barrier assemblies, are possible. The invention is embodied in each novel characteristic and each combination of characteristics, which includes every combination of any features which are stated in the claims, even if this combination of features is not explicitly stated in the claims.

Claims

Claims :
1. Flexible multilayer packaging material for protection of articles, which are sensitive to moisture and oxidizing agents, comprising: at least one active polymeric barrier layer, which is able to bind the moisture and oxidizing agents and at least one ceramic barrier layer.
2. Packaging material according to claim 1, wherein the active polymeric barrier layer is able to chemically bind the moisture and oxidizing agents.
3. Packaging material according to claim 1, - wherein the active polymeric barrier layer is selected from the following materials: a polymeric matrix with dispersed cyclodextrines, cyclic olefin copolymers and a polymeric matrix with anhydrides.
4. Packaging material according to claim 1, wherein the ceramic barrier layer is selected from metal - nitrides, metaloxides and metaloxynitrides.
5. Packaging material according to claim 3, wherein the ceramic barrier layer is selected from metal - nitrides, metaloxides and metaloxynitrides.
6. Packaging material according to claim 4, - wherein the metal is selected from Al and Si.
7. Packaging material according to claim 1, wherein the at least one active polymeric barrier layer and the at least one ceramic barrier layer are transpar- ent .
8. Packaging material according to claim 5, wherein the at least one active polymeric barrier layer and the at least one ceramic barrier layer are transparent .
9. Containment for protection of articles, comprising a packaging material according to claim 1, wherein an active polymeric barrier layer and a ceramic barrier layer are integrated into the said containment.
10. Containment according to claim 9, further comprising an alternating assembly of at least two ceramic barrier layers and at least two active polymeric barrier layers.
11. Containment according to claim 10, - wherein the surface of the containment facing towards the outside consists of a ceramic barrier layer.
12. Organic electronic device, which is sensitive to moisture or oxidizing agents, comprising - a flexible substrate, an organic functional area on the substrate, comprising active elements, a cap encapsulating the organic functional area, and a flexible multilayer packaging material according to claim 1 for protection of the organic functional area.
13. Organic electronic device, which is sensitive to moisture or oxidizing agents, comprising - a flexible substrate, - an organic functional area on the substrate, comprising active elements, a cap encapsulating the organic functional area, a flexible multilayer packaging material according to claim 3 for protection of the organic functional area.
14. Organic electronic device according to claim 13, wherein the flexible multilayer packaging material is arranged between the functional area and the substrate.
15. Organic electronic device according to claim 12, - wherein the flexible multilayer packaging material is arranged between the functional area and the substrate.
16. Electronic device according to claim 12, wherein the cap comprises a flexible multilayer packaging material consisting of: at least one active polymeric barrier layer, which is able to bind the moisture and oxidizing agents and at least one ceramic barrier layer.
17. Electronic device according to claim 12, wherein the cap comprises a flexible multilayer packaging material consisting of: at least one active polymeric barrier layer, which is able to bind the moisture and oxidizing agents, and - at least one ceramic barrier layer, the active polymeric barrier layer being selected from the following materials: a polymeric matrix with dispersed cyclodextrines, cyclic olefin copolymers and - a polymeric matrix with anhydrides.
18. Electronic device according to claim 12, wherein the cap comprises a material selected from a group comprising : - polymers, metals and glass.
19. Electronic device according to claim 12, - wherein the substrate comprises an active polymeric barrier layer.
20. Electronic device according to claim 19, wherein the cap additionally comprises a flexible multilayer packaging material consisting of: at least one active polymeric barrier layer, which is able to bind the moisture and oxidizing agents and at least one ceramic barrier layer.
21. Electronic device according to claim 19,
- wherein the cap additionally comprises a flexible multi- layer packaging material consisting of: at least one active polymeric barrier layer, which is able to bind the moisture and oxidizing agents and at least one ceramic barrier layer, the active polymeric barrier layer being selected from the following materials: a polymeric matrix with dispersed cyclodextrines, cyclic olefin copolymers and a polymeric matrix with anhydrides.
22. Electronic device according to claim 19,
- wherein the substrate is an active polymeric barrier layer.
23. Electronic device according to claim 12, wherein the substrate comprises an assembly of active polymeric barrier layers and ceramic barrier layers.
24. Electronic device according to claim 23, wherein the surface of the substrate facing towards the outside environment consists of a ceramic barrier layer.
25. Electronic device according to claim 12, wherein the organic functional area comprises a stack consisting of a first electrically conductive layer, an organic, functional layer on the first conductive layer and a second electrically conductive layer on the functional layer, the organic, functional layer comprising at least one organic, electroluminescent layer forming an OLED.
26.Electronic device according to claim 13, - wherein the organic functional area comprises a stack, consisting of a first electrically conductive layer, an organic, functional layer on the first conductive layer and a second electrically conductive layer on the functional layer, - the organic, functional layer comprising at least one organic, electroluminescent layer forming an OLED.
27.Electronic device according to claim 12, wherein the organic functional area comprises a stack con- sisting of a first electrically conductive layer, an organic, functional layer on the first conductive layer and a second electrically conductive layer on the functional layer, the organic, functional layer comprising at least one or- ganic, radiation detecting layer forming an organic radiation sensor.
28. Electronic device according to claim 13, wherein the organic functional area comprises a stack con- sisting of a first electrically conductive layer, an organic, functional layer on the first conductive layer and a second electrically conductive layer on the functional layer, the organic, functional layer comprising at least one or- ganic, radiation detecting layer forming an organic radiation sensor.
29. Electronic device according to claim 12, wherein the organic functional area comprises an inte- grated plastic circuit.
30.Electronic device according to claim 13, wherein the organic functional area comprises an integrated plastic circuit .
PCT/EP2004/005842 2003-05-30 2004-05-28 Flexible multilayer packaging material and electronic devices with the packaging material WO2004107468A2 (en)

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JP2010514124A (en) * 2006-12-19 2010-04-30 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ Package to protect the device from surrounding materials
KR101407423B1 (en) * 2006-12-19 2014-06-17 코닌클리케 필립스 엔.브이. Package for protecting a device from ambient substances

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TWI247364B (en) 2006-01-11
KR101290134B1 (en) 2013-07-26
CN103325959A (en) 2013-09-25
TW200511448A (en) 2005-03-16
US20040239241A1 (en) 2004-12-02
KR20060010830A (en) 2006-02-02
WO2004107468A8 (en) 2005-05-26
WO2004107468A3 (en) 2008-01-10
JP2007523800A (en) 2007-08-23
US7535017B2 (en) 2009-05-19

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