Recherche Images Maps Play YouTube Actualités Gmail Drive Plus »
Connexion
Les utilisateurs de lecteurs d'écran peuvent cliquer sur ce lien pour activer le mode d'accessibilité. Celui-ci propose les mêmes fonctionnalités principales, mais il est optimisé pour votre lecteur d'écran.

Brevets

  1. Recherche avancée dans les brevets
Numéro de publicationUSRE40531 E1
Type de publicationOctroi
Numéro de demandeUS 10/890,437
Date de publication7 oct. 2008
Date de dépôt12 juil. 2004
Date de priorité25 oct. 1999
État de paiement des fraisPayé
Autre référence de publicationUS6413645, WO2001081649A1
Numéro de publication10890437, 890437, US RE40531 E1, US RE40531E1, US-E1-RE40531, USRE40531 E1, USRE40531E1
InventeursGordon Lee Graff, Mark Edward Gross, Ming Kun Shi, Michael Gene Hall, Peter Maclyn Martin, Eric Sidney Mast
Cessionnaire d'origineBattelle Memorial Institute
Exporter la citationBiBTeX, EndNote, RefMan
Liens externes: USPTO, Cession USPTO, Espacenet
Ultrabarrier substrates
US RE40531 E1
Résumé
A barrier assembly. The barrier assembly includes at least one barrier stack having at least one barrier layer and at least one polymer layer. The barrier stack has an oxygen transmission rate of less than 0.005 cc/m2/day at 23° C. and 0% relative humidity, and an oxygen transmission rate of less than 0.005 cc/m2/day at 38° C. and 90% relative humidity. The barrier stack also has a water vapor transmission rate of less than 0.005 g/m2/day at 38° C. and 100% relative humidity. A method for making a barrier assembly is also disclosed.
Images(1)
Previous page
Next page
Revendications(25)
1. A barrier assembly comprising:
at least one barrier stack comprising at least one barrier layer and at least one polymer layer, wherein the at least one barrier stack has an oxygen transmission rate of less than 0.005 cc/m2/day at 23° C. and 0% relative humidity.
2. The barrier assembly of claim 1 wherein the at least one barrier stack has an oxygen transmission rate of less than 0.005 cc/m2/day at 38° C. and 90% relative humidity.
3. The barrier assembly of claim 1 wherein the at least one barrier stack has a water vapor transmission rate of less than 0.005 g/m2/day at 38° C. and 100% relative humidity.
4. The barrier assembly of claim 1 further comprising a substrate adjacent to the at least one barrier stack.
5. The barrier assembly of claim 1 wherein the at least one barrier layer is substantially transparent.
6. The barrier assembly of claim 1 wherein at least one of the at least one barrier layer comprises a material selected from metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxyborides, and combinations thereof.
7. The barrier assembly of claim 6 wherein the metal oxides are selected from silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide, tantalum oxide, zirconium oxide, niobium oxide, and combinations thereof.
8. The barrier assembly of claim 6 wherein the metal nitrides are selected from aluminum nitride, silicon nitride, boron nitride, and combinations thereof.
9. The barrier assembly of claim 6 wherein the metal oxynitrides are selected from aluminum oxynitride, silicon oxynitride, boron oxynitride, and combinations thereof.
10. The barrier assembly of claim 1 wherein the at least one barrier layer is substantially opaque.
11. The barrier assembly of claim 1 wherein at least one of the at least one barrier layers is selected from opaque metals, opaque polymers, opaque ceramics, and opaque cermets.
12. The barrier assembly of claim 4 wherein the substrate comprises a flexible substrate material.
13. The barrier assembly of claim 12 wherein the flexible substrate material is selected from polymers, metals, paper, fabric, and combinations thereof.
14. The barrier assembly of claim 4 wherein the substrate comprises a rigid substrate material.
15. The barrier assembly of claim 14 wherein the rigid substrate material is selected from ceramics, metals, and semiconductors.
16. The barrier assembly of claim 1 wherein at least one of the at least one polymer layers comprises an acrylate-containing polymer.
17. The barrier assembly of claim 4 further comprising a polymer smoothing layer adjacent to the substrate.
18. The barrier assembly of claim 4 further comprising a scratch resistant layer adjacent to the substrate.
19. The barrier assembly of claim 4 further comprising an anti-reflective coating adjacent to the substrate.
20. The barrier assembly of claim 4 further comprising an anti-fingerprint coating adjacent to the substrate.
21. The barrier assembly of claim 4 further comprising an anti-static coating adjacent to the substrate.
22. The barrier assembly of claim 1 wherein the at least one barrier layer comprises two barrier layers.
23. The barrier assembly of claim 22 wherein the two barrier layers are made of the same barrier material.
24. The barrier assembly of claim 22 wherein the two barrier layers are made of different barrier materials.
25. The barrier assembly of claim 11 wherein at least one of the at least one barrier layers is opaque cermet selected from zirconium nitride, titanium nitride, hafnium nitride, tantalum nitride, niobium nitride, tungsten disilicide, titanium diboride, and zirconium diboride.
Description

This application is a continuation-in-part of U.S. patent application Ser. No. 09/427,138, filed Oct. 25, 1999, entitled “Environmental Barrier Material For Organic Light Emitting Device and Method Of Making,” now U.S. Pat. No. 6,522,067, issued Feb. 18, 2003.

BACKGROUND OF THE INVENTION

The present invention relates generally to barrier coatings, and more particularly to barrier coatings having improved barrier properties.

Many different types of products are sensitive to gas and liquids, which can cause deterioration of the product or render it useless, including electronics, medical devices, and pharmaceuticals. Barrier coatings have been included in the packaging for these environmentally sensitive products to protect them from gas and liquid transmission. As used herein, the term environmentally sensitive means products which are subject to degradation caused by permeation of environmental gases or liquids, such as oxygen and water vapor in the atmosphere or chemicals used in the processing, handling, storage, and use of the product.

Plastics are often used in product packaging. However, the gas and liquid permeation resistance of plastics is poor, often several orders of magnitude below what is required for product performance. For example, the oxygen transmission rates for materials such polyethylene terephthalate (PET) are as high as 1550 cc/m2/day/micron of thickness (or 8.7 cc/m2/day for 7 mil thickness PET), and the water vapor transmission rates are also in this range. Certain display applications using environmentally sensitive display devices, such as organic light emitting devices, require encapsulation that has a maximum oxygen transmission rate of 10−4 to 10−2 cc/m2/day, and a maximum water vapor transmission rate of 10−5 to 10−6 g/m2/day.

Barrier coatings have been applied to plastic substrates to decrease their gas and liquid permeability. Barrier coatings typically consist of single layer thin film inorganic materials, such as Al, SiOx, AlOx, an Si3N4 vacuum deposited on polymeric substrates. A single layer coating on PET reduces oxygen permeability to levels of about 0.1 to 1.0 cc/m2/day, and water vapor permeability to about 0.1 to 1.0 g/m2/day, which is insufficient for many display devices.

Barrier coatings which include alternating barrier layers and polymeric layers have been developed. For example, U.S. Pat. Nos. 5,607,789 and 5,681,666 disclose a moisture barrier for an electrochemical cell tester. However, the claimed moisture barrier ranges from 2 to 15 micrograms/in2/day which corresponds to a rate of 0.003 to 0.023 g/m2/day. U.S. Pat. No. 5,725,909 to Shaw et al. discloses a coating for packaging materials which has an acrylate layer and an oxygen barrier layer. The oxygen transmission rate for the coating was reported to be 0.1 cc/m2/day at 23° C. and the water vapor transmission rate was reported to be 0.01 g/m2/day in D. G. Shaw and M. G. Langlois, Society of Vacuum Coaters, 37th Annual Technical Conference Proceedings, p. 240-244, 1994. The oxygen transmission rates for these coatings are inadequate for many display devices.

Thus, there is a need for an improved, lightweight, barrier coating, and for methods for making such a barrier coating.

SUMMARY OF THE INVENTION

The present invention meets these needs by providing a barrier assembly and a method for making such an assembly. The barrier assembly includes at least one barrier stack having at least one barrier layer and at least one polymer layer. The barrier stack has an oxygen transmission rate of less than 0.005 cc/m2/day at 23° C. and 0% relative humidity, and an oxygen transmission rate of less than 0.005 cc/m2/day at 38° C. and 90% relative humidity. It also preferably has a water vapor transmission rate of less than 0.005 g/m2/day at 38° C. and 100% relative humidity.

Preferably, the barrier layers of the barrier stacks are substantially transparent. At least one of the barrier layers preferably comprises a material selected from metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxyborides, and combinations thereof.

The barrier layers can be substantially opaque, if desired. The opaque barrier layers are preferably selected from opaque metals, opaque polymers, and opaque ceramics.

The barrier assembly can include a substrate adjacent to the at least one barrier stack. By adjacent, we mean next to, but not necessarily directly next to. There can be additional layers intervening between the adjacent layers. The substrate can either be flexible or rigid. It is preferably made of a flexible substrate material, such as polymers, metals, paper, fabric, and combinations thereof. If a rigid substrate is used, it is preferably a ceramic (including glasses), a metal, or a semiconductor.

The polymer layers of the barrier stacks are preferably acrylate-containing polymers. As used herein, the term acrylate-containing polymers includes acrylate-containing polymers, methacrylate-containing polymers, and combinations thereof The polymer layers can be the same or different.

The barrier assembly can include additional layers if desired, such as polymer smoothing layers, scratch resistant layers, antireflective coatings, or other functional layers.

The present invention also involves a method of making the barrier assembly. The method includes providing a substrate, and placing at least one barrier stack on the substrate. The barrier stack includes at least one barrier layer and at least one polymer layer.

The at least one barrier stack can be placed on the substrate by deposition, preferably vacuum deposition, or by laminating the barrier stack over the environmentally sensitive device. The lamination can be performed using an adhesive, solder, ultrasonic welding, pressure, or heat.

Accordingly, it is an object of the present invention to provide a barrier assembly, and to provide a method of making such a barrier assembly.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-section of one embodiment of the barrier assembly of the present invention.

FIG. 2 is a cross-section of an encapsulated device made using the barrier assembly of the present invention.

DESCRIPTION OF THE INVENTION

One embodiment of the barrier assembly of the present invention is shown in FIG. 1. The barrier assembly is supported by a substrate 105. The substrate 105 can be either rigid or flexible. A flexible substrate can be any flexible material, including, but not limited to: polymers, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or high temperature polymers, such as polyether sulfone (PES), polyimides, or Transphan™ (a high glass transition temperature cyclic olefin polymer available from Lofo High Tech Film, GMBH or Weil am Rhein, Germany); metal; paper; fabric; and combinations thereof. Rigid substrates are preferably glass, metal, or silicon.

There are scratch resistant layers 110 on either side of the substrate 105 to protect it. When a scratch resistant layer is included, it is preferred that both sides of the substrate have a scratch resistant layer. This helps to balance stresses and prevent deformation of a flexible substrate during processing and use.

On top of the scratch resistant layer 110, there is a polymer smoothing layer 115. The polymer smoothing layer decreases surface roughness, and encapsulates surface defects, such as pits, scratches, and digs. This produces a planarized surface which is ideal for subsequent deposition of layers. Depending on the desired application, there can be additional layers deposited on the substrate 105, such as organic or inorganic layers, planarizing layers, electrode layers, antireflective coatings, and other functional layers. In this way, the substrate can be specifically tailored to different applications.

The first barrier stack 120 is adjacent to the polymer smoothing layer 115. The first barrier stack 120 includes a barrier layer 125 and a polymer layer 130. The first barrier layer 125 includes barrier layers 135 and 140. Barrier layers 135 and 140 can be made of the same barrier material or of different barrier materials.

Although FIG. 1 shows a barrier stack with two barrier layers and one polymer layer, the barrier stacks can have one or more polymer layers and one or more barrier layers. There could be one polymer layer and one barrier layer, there could be one or more polymer layers on one side of one or more barrier layers, or there could be one or more polymer layers on both sides of one or more barrier layers. The important feature is that the barrier stack have at least one polymer layer and at least one barrier layer. The barrier layers and polymer layers in the barrier stack can be made of the same material or of a different material. The barrier layers are typically about 100-400 Å thick, and the polymer layers are typically about 1000-10,000 Å thick.

Although only one barrier stack is shown in FIG. 1, the number of barrier stacks is not limited. The number of barrier stacks needed depends on the substrate material used and the level of permeation resistance needed for the particular application. One or two barrier stacks should provide sufficient barrier properties for some applications. The most stringent applications may require five or more barrier stacks.

There is a transparent conductor 145, such as an indium tin oxide layer, adjacent to the first barrier stack 120. There can be additional overcoat layers on top of the barrier stack, such as organic or inorganic layers, planarizing layers, transparent conductors, antireflective coatings, or other functional layers, if desired. This allows the barrier assembly to be tailored to the application.

FIG. 2 shows a barrier assembly being used to encapsulate an environmentally sensitive display device. The substrate 205 has an environmentally sensitive display device 210 on it. There is a barrier stack 215 over the environmentally sensitive display device 210 encapsulating it. The barrier stack 215 includes a barrier layer 220 and a polymer layer 225.

The environmentally sensitive display device 210 can be any display device which is environmentally sensitive. Examples of environmentally sensitive display devices include, but are not limited to liquid crystal displays (LCDs), light emitting diodes (LEDs), light emitting polymers (LEPs), electronic signage using electrophoretic inks, electroluminescent devices (EDs), and phosphorescent devices. These display devices can be made using known techniques, such as those described in U.S. Pat. Nos. 6,025,899, 5,995,191, 5,994,174, 5,956,112 (LCDs); U.S. Pat. Nos. 6,005,692, 5,821,688, 5,747,928 (LEDs); U.S. Pat. Nos. 5,969,711, 5,961,804, 4,026,713 (E Ink); U.S. Pat. Nos. 6,023,373, 6,023,124, 6,023,125 (LEPs); and U.S. Pat. Nos. 6,023,073, 6,040,812, 6,019,654, 6,018,237, 6,014,119, 6,010,796 (EDs), which are incorporated herein by reference.

The method of making the barrier assembly will be described with reference to FIGS. 1 and 2. Any initial layers which are desired, such as scratch resistant layers, planarizing layers, electrically conductive layers, etc., can be coated, deposited, or otherwise placed on the substrate. A polymer smoothing layer is preferably included to provide a smooth base for the remaining layers. It can be formed by depositing a layer of polymer, for example, an acrylate-containing polymer, onto the substrate or previous layer. The polymer layer can be deposited in vacuum or by using atmospheric processes such as spin coating and/or spraying. Preferably, an acrylate-containing monomer, oligomer, or resin is deposited and then polymerized in situ to form the polymer layer. As used herein, the term acrylate-containing monomer, oligomer, or resin includes acrylate-containing monomers, oligomers, and resins, methacrylate-containing monomers, oligomers, and resins, and combinations thereof.

The barrier stack is then placed on the substrate. The barrier stack includes at least one barrier layer and at least one polymer layer. The barrier stacks are preferably made by vacuum deposition. The barrier layer can be vacuum deposited onto the polymer smoothing layer, the substrate, or the previous layer. The polymer layer is then deposited on the barrier layer, preferably by flash evaporating acrylate-containing monomers, oligomers, or resins, condensing on the barrier layer, and polymerizing in situ in a vacuum chamber. U.S. Pat. Nos. 5,440,446 and 5,725,909, which are incorporated herein by reference, describe methods of depositing thin film, barrier stacks.

Vacuum deposition includes flash evaporation of acrylate-containing monomer, oligomer, or resin with in situ polymerization under vacuum, plasma deposition and polymerization of acrylate-containing monomer, oligomer, or resin, as well as vacuum deposition of the barrier layers by sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma enhanced vapor deposition (ECR-PECVD), and combinations thereof.

In order to protect the integrity of the barrier layer, the formation of defects and/or microcracks in the deposited layer subsequent to deposition and prior to downstream processing should be avoided. The barrier assembly is preferably manufactured so that the barrier layers are not directly contacted by any equipment, such as rollers in a web coating system, to avoid defects that may be caused by abrasion over a roll or roller. This can be accomplished by designing the deposition system such that the barrier layers are always covered by polymer layers prior to contacting or touching any handling equipment.

When the barrier stack is being used to encapsulate an environmentally sensitive display device, the substrate can be prepared as described above, and the environmentally sensitive display device placed on the substrate. Alternatively, the environmentally sensitive display device can be placed directly on a substrate (or on a substrate with functional layers, such as planarizing layers, scratch resistant layers, etc.).

The environmentally sensitive display device can be placed on the substrate by deposition, such as vacuum deposition. Alternatively it can be placed on the substrate by lamination. The lamination can use an adhesive, glue, or the like, or heat to seal the environmentally sensitive display device to the substrate.

A barrier stack is then placed over the environmentally sensitive display device to encapsulate it. The second barrier stack can be placed over the environmentally sensitive display device by deposition or lamination.

The barrier layers in the first and second barrier stacks may be any barrier material. The barrier layers in the first and second barrier stacks can be made of the same material or a different material. In addition, multiple barrier layers of the same or different barrier materials can be used in a barrier stack.

The barrier layers can be transparent or opaque, depending on the design of the packaging, and application for which it is to be used. Preferred transparent barrier materials include, but are not limited to, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxyborides, and combinations thereof. The metal oxides are preferably selected from silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide, tantalum oxide, zirconium oxide, niobium oxide, and combinations thereof. The metal nitrides are preferably selected from aluminum nitride, silicon nitride, boron nitride, and combinations thereof. The metal oxynitrides are preferably selected from aluminum oxynitride, silicon oxynitride, boron oxynitride, and combinations thereof.

Opaque barrier layers can be also be used in some barrier stacks. Opaque barrier materials include, but are not limited to, metals, ceramics, polymers, and cermets. Examples of opaque cermets include, but are not limited to, zirconium nitride, titanium nitride, hafnium nitride, tantalum nitride, niobium nitride, tungsten disilicide, titanium diboride, and zirconium diboride.

The polymer layers of the first and second barrier stacks are preferably acrylate-containing monomers, oligomers, or resins. The polymer layers in the first and second barrier stacks can be the same or different. In addition, the polymer layers within each barrier stack can be the same or different.

In a preferred embodiment, the barrier stack includes a polymer layer and two barrier layers. The two barrier layers can be made from the same barrier material or from different barrier materials. The thickness of each barrier layer in this embodiment is about one half the thickness of the single barrier layer, or about 50 to 200 Å. There are no limitations on the thickness, however.

When the barrier layers are made of the same material, they can be deposited either by sequential deposition using two sources or by the same source using two passes. If two deposition sources are used, deposition conditions can be different for each source, leading to differences in microstructure and defect dimensions. Any type of deposition source can be used. Different types of deposition processes, such as magnetron sputtering and electron beam evaporation, can be used to deposit the two barrier layers.

The microstructures of the two barrier layers are mismatched as a result of the differing deposition sources/parameters. The barrier layers can even have different crystal structure. For example, Al2O3 can exist in different phases (alpha, gamma) with different crystal orientations. The mismatched microstructure can help decouple defects in the adjacent barrier layers, enhancing the tortuous path for gases and water vapor permeation.

When the barrier layers are made of different materials, two deposition sources are needed. This can be accomplished by a variety of techniques. For example, if the materials are deposited by sputtering, sputtering targets of different compositions could be used to obtain thin films of different compositions. Alternatively, two sputtering targets of the same composition could be used but with different reactive gases. Two different types of deposition sources could also be used. In this arrangement, the lattices of the two layers are even more mismatched by the different microstructures and lattice parameters of the two materials.

A single pass, roll-to-roll, vacuum deposition of a three layer combination on a PET substrate, i.e., PET substrate/polymer layer/barrier layer/polymer layer, can be more than five orders of magnitude less permeable to oxygen and water vapor than a single oxide layer on PET alone. See J. D. Afinito, M. E. Gross, C. A. Coronado, G. L. Graff, E. N. Greenwell, and P. M. Martin, Polymer-Oxide Transparent Barrier Layers Produced Using PML Process, 39th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, Vacuum Web Coating Session, 1996, pages 392-397; J. D. Affinito, S. Eufinger, M. E. Gross, G. L. Graff, and P. M. Martin, PML/Oxide/PML Barrier Layer Performance Difference Arising From Use of UV or Electron Beam Polymerization of the PML Layers, Thin Solid Films, Vol. 308, 1997, pages 19-25. This is in spite of the fact that the effect on the permeation rate of the polymer multilayers (PML) layers alone, without the barrier layer (oxide, metal, nitride, oxynitride) layer, is barely measurable. It is believed that the improvement in barrier properties is due to two factors. First, permeation rates in the roll-to-roll coated oxide-only layers were found to be conductance limited by defects in the oxide layer that arose during deposition and when the coated substrate was wound up over system idlers/rollers. Asperities (high points) in the underlying substrate are replicated in the deposited inorganic barrier layer. These features are subject to mechanical damage during web handling/take-up, and can lead to the formation of defects in the deposited film. These defects seriously limit the ultimate barrier performance of the films. In the single pass, polymer/barrier/polymer process, the first acrylic layer planarizes the substrate and provides an ideal surface for subsequent deposition of the inorganic barrier thin film. The second polymer layer provides a robust “protective” film that minimizes damage to the barrier layer and also planarizes the structure for subsequent barrier layer (or environmentally sensitive display device) deposition. The intermediate polymer layers also decouple defects that exist in adjacent inorganic barrier layers, thus creating a tortuous path for gas diffusion.

The permeability of the barrier stacks used in the present invention is shown in Table 1. The barrier stacks of the present invention on polymeric substrates, such as PET, have measured oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) values well below the detection limits of current industrial instrumentation used for permeation measurements (Mocon OxTran 2/20L and Permatran). Table 1 shows the OTR and WVTR values (measured according to ASTM F 1927-98 and ASTM F 1249-90, respectively) measured at Mocon (Minneapolis, Minn.) for several barrier stacks on 7 mil PET, along with reported values for other materials.

TABLE 1
Oxygen Water Vapor
Permeation Rate Permeation
(cc/m2/day) (g/m2/day)*
Sample 23° C. 38° C. 23° C. 38° C.
Native 7 mil PET 7.62
1-barrier stack <0.005 <0.005* 0.46*
1-barrier stack <0.005 <0.005* 0.011*
with ITO
2-barrier stacks <0.005 <0.005* <0.005*
2-barrier stacks <0.005 <0.005* <0.005*
with ITO
5-barrier stacks <0.005 <0.005* <0.005*
5-barrier stacks <0.005 <0.005* <0.005*
with ITO
DuPont film1 0.3
(PET/Si3N4 or
PEN/Si3N4)
Polaroid3 <1.0
PET/Al2 0.6 0.17
PET/silicon 0.7-1.5 0.15-0.9
oxide2
Teijin LCD film <2 <5
(HA grade-
TN/STN)3
*38° C., 90% RH, 100% O2
*38° C., 100% RH
1P. F. Carcia, 46th International Symposium of the American Vacuum Society, October 1999
2Langowski, H. C., 39th Annual Technical Conference Proceedings, SVC, pp. 398-401 (1996)
3Technical Data Sheet

As the data in Table 1 shows, the barrier stacks of the present invention provide oxygen and water vapor permeation rates several orders of magnitude better than PET coated with aluminum, silicon oxide, or aluminum oxide. Typical oxygen permeation rates for other barrier coatings range from 1 to about 0.1 cc/m2/day. The oxygen transmission rate for the barrier stacks of the present invention is less than 0.005 cc/m2/day at 23° C. and 0% relative humidity, and at 38° C. and 90% relative humidity. The water vapor transmission rate is less than 0.005 g/m2/day at 38° C. and 100% relative humidity. The actual transmission rates are lower, but cannot be measured with existing equipment.

The barrier assemblies were also tested by encapsulating organic light emitting devices using the barrier stacks of the present invention. The organic light emitting devices are extremely sensitive to water vapor, and they are completely destroyed in the presence of micromole quantities of water vapor. Experimentation and calculations suggest that the water vapor transmission rate through the encapsulation film must be on the order of about 10−6 to 10−5 g/m2/day to provide sufficient barrier protection for acceptable device lifetimes. The experiments/calculations are based on the detrimental hydrolysis reaction of water vapor with the extremely thin (less than 10 nm), low work function, cathode materials (Ca, Mg, Li, LiF). Hydrolysis of the cathode leads to the formation of non-conductive reaction products (such as hydroxides and oxides) that delaminate or blister away from the electron transport layers of the organic light emitting devices, resulting in the formation of dark spots on the device.

The organic light emitting devices encapsulated in the barrier stacks of the present invention have been in operation for over six months and without measurable degradation. The extrapolated lifetime for the encapsulated devices exceeds the required 10,000 hours necessary to satisfy industry standards. The barrier stacks are extremely effective in preventing oxygen and water penetration to the underlying components, substantially outperforming other thin-film barrier coatings on the market.

The preferred deposition process is compatible with a wide variety of substrates. Because the preferred process involves flash evaporation of a monomer and magnetron sputtering, deposition temperatures are well below 100° C., and stresses in the coating can be minimized. Multilayer coatings can be deposited at high deposition rates. No harsh gases or chemicals are used, and the process can be scaled up to large substrates and wide webs. The barrier properties of the coating can be tailored to the application by controlling the number of layers, the materials, and the layer design. Thus, the present invention provides a barrier stack with the exceptional barrier properties necessary for hermetic sealing of an environmentally sensitive display device, or other environmentally sensitive device. It permits the production of an encapsulated environmentally sensitive display device.

While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the compositions and methods disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims.

Citations de brevets
Brevet cité Date de dépôt Date de publication Déposant Titre
US23824322 août 194014 août 1945Crown Cork & Seal CoMethod and apparatus for depositing vaporized metal coatings
US23845008 juil. 194211 sept. 1945Crown Cork & Seal CoApparatus and method of coating
US3475307 *4 févr. 196528 oct. 1969Continental Can CoCondensation of monomer vapors to increase polymerization rates in a glow discharge
US3607365 *12 mai 196921 sept. 1971Minnesota Mining & MfgVapor phase method of coating substrates with polymeric coating
US3941630 *29 avr. 19742 mars 1976Rca CorporationMethod of fabricating a charged couple radiation sensing device
US406183525 juin 19766 déc. 1977Standard Oil Company (Indiana)Process of forming a polypropylene coated substrate from an aqueous suspension of polypropylene particles
US4098965 *27 juin 19774 juil. 1978Polaroid CorporationFlat batteries and method of making the same
US42662238 déc. 19785 mai 1981W. H. Brady Co.Thin panel display
US4283482 *25 mars 198011 août 1981Nihon Shinku Gijutsu Kabushiki KaishaEtching a plasma polymerized film
US43132544 août 19802 févr. 1982The Johns Hopkins UniversityThin-film silicon solar cell with metal boride bottom electrode
US442627527 nov. 198117 janv. 1984Deposition Technology, Inc.Confining heated plasma
US45214581 avr. 19834 juin 1985Nelson Richard CProcess for coating material with water resistant composition
US453781426 janv. 198427 août 1985Toyoda Gosei Co., Ltd.Resin article having a ceramics coating layer
US45552747 juin 198426 nov. 1985Fuji Photo Film Co., Ltd.Ion selective electrode and process of preparing the same
US455797812 déc. 198310 déc. 1985Primary Energy Research CorporationPolymerizing an aromatic acene hydrocarbon and an acidic mononer; polyacenequinone radical type coating
US457284224 août 198425 févr. 1986Leybold-Heraeus GmbhMethod and apparatus for reactive vapor deposition of compounds of metal and semi-conductors
US4581337 *7 juil. 19838 avr. 1986E. I. Du Pont De Nemours And CompanyPolyether polyamines as linking agents for particle reagents useful in immunoassays
US4624867 *21 mars 198525 nov. 1986Nihon Shinku Gijutsu Kabushiki KaishaProcess for forming a synthetic resin film on a substrate and apparatus therefor
US4695618 *23 mai 198622 sept. 1987Ameron, Inc.Solventless polyurethane spray compositions and method for applying them
US471042628 nov. 19831 déc. 1987Polaroid Corporation, Patent Dept.Multilayer-transparent support, infrared radiation reflection layer and protective polymeric coating
US47225158 avr. 19862 févr. 1988Spectrum Control, Inc.Flash vaporizing monomeric resin for capacitor structures
US476866626 mai 19876 sept. 1988Milton KesslerTamper proof container closure
US4842893 *29 avr. 198827 juin 1989Spectrum Control, Inc.High speed process for coating substrates
US484303629 juin 198727 juin 1989Eastman Kodak CompanyMethod for encapsulating electronic devices
US485518623 févr. 19888 août 1989Hoechst AktiengesellschaftCoated plastic film and plastic laminate prepared therefrom
US48896096 sept. 198826 déc. 1989Ovonic Imaging Systems, Inc.Continuous dry etching system
US491309020 sept. 19883 avr. 1990Mitsubishi Denki Kabushiki KaishaChemical vapor deposition apparatus having cooling heads adjacent to gas dispersing heads in a single chamber
US49311588 août 19895 juin 1990The Regents Of The Univ. Of Calif.Deposition of films onto large area substrates using modified reactive magnetron sputtering
US493431519 oct. 198819 juin 1990Alcatel N.V.System for producing semicondutor layer structures by way of epitaxial growth
US4954371 *7 juil. 19874 sept. 1990Spectrum Control, Inc.Flash evaporation of monomer fluids
US49770133 juin 198811 déc. 1990Andus CorporationTranparent conductive coatings
US5032461 *12 oct. 199016 juil. 1991Spectrum Control, Inc.Method of making a multi-layered article
US5036249 *11 déc. 198930 juil. 1991Molex IncorporatedElectroluminescent lamp panel and method of fabricating same
US50471318 nov. 198910 sept. 1991The Boc Group, Inc.Method for coating substrates with silicon based compounds
US505986126 juil. 199022 oct. 1991Eastman Kodak CompanyOrganic electroluminescent device with stabilizing cathode capping layer
US5124204 *29 mars 199123 juin 1992Sharp Kabushiki KaishaThin film electroluminescent (EL) panel
US5189405 *23 déc. 199123 févr. 1993Sharp Kabushiki KaishaThin film electroluminescent panel
US520389816 déc. 199120 avr. 1993Corning IncorporatedHeating boron oxide doped porous glass preform, flowing fluorine containing gas and boron trifluoride through pores, consolidating; uniform doping of both boron and fluorine
US520431413 déc. 199120 avr. 1993Advanced Technology Materials, Inc.Flash vaporization of Group II beta-diketonate source material to form superconducting oxide and Group II fluorides
US5237439 *30 sept. 199217 août 1993Sharp Kabushiki KaishaAdhesion, noncracking
US5260095 *21 août 19929 nov. 1993Battelle Memorial InstituteVacuum deposition and curing of liquid monomers
US53363244 déc. 19919 août 1994Emcore CorporationApparatus for depositing a coating on a substrate
US5354497 *19 avr. 199311 oct. 1994Sharp Kabushiki KaishaPrevention of cracks in undercoat layer and electrode and of peeling
US535694729 oct. 199218 oct. 1994Minnesota Mining And Manufacturing CompanyControllable radiation curable photoiniferter prepared adhesives for attachment of microelectronic devices and a method of attaching microelectronic devices therewith
US53936078 janv. 199328 févr. 1995Mitsui Toatsu Chemiclas, Inc.Laminated transparent plastic material and polymerizable monomer
US5395644 *2 août 19937 mars 1995Battelle Memorial InstituteManufacturing a lithium/polymer battery
US54023143 févr. 199328 mars 1995Sony CorporationPrinted circuit board having through-hole stopped with photo-curable solder resist
US5427638 *3 déc. 199327 juin 1995Alliedsignal Inc.Polishing surface, cleaning, ion bombarding with oxygen and fluorine ions
US5440446 *4 oct. 19938 août 1995Catalina Coatings, Inc.Acrylate coating material
US545144911 mai 199419 sept. 1995The Mearl CorporationMultilayer laminate of thermoplastic resin containing soluble transparent dye
US546154513 sept. 199424 oct. 1995Thomson-CsfProcess and device for hermetic encapsulation of electronic components
US546466716 août 19947 nov. 1995Minnesota Mining And Manufacturing CompanyJet plasma process and apparatus
US551017320 août 199323 avr. 1996Southwall Technologies Inc.Durability, transparent
US551232013 avr. 199430 avr. 1996Applied Materials, Inc.Batch heating, cooling
US5536323 *25 juil. 199416 juil. 1996Advanced Technology Materials, Inc.Apparatus for flash vaporization delivery of reagents
US5547508 *17 nov. 199420 août 1996Battelle Memorial InstituteVacuum deposition and curing of liquid monomers apparatus
US5554220 *19 mai 199510 sept. 1996The Trustees Of Princeton UniversityMethod and apparatus using organic vapor phase deposition for the growth of organic thin films with large optical non-linearities
US5576101 *12 avr. 199519 nov. 1996Bridgestone CorporationPolyamide, cured siloxane, natural or synthetic rubber
US55781411 juil. 199426 nov. 1996Canon Kabushiki KaishaSolar cell module having excellent weather resistance
US5607789 *23 janv. 19954 mars 1997Duracell Inc.Light transparent multilayer moisture barrier for electrochemical cell tester and cell employing same
US5620524 *27 févr. 199515 avr. 1997Fan; ChikoApparatus for fluid delivery in chemical vapor deposition systems
US5629389 *6 juin 199513 mai 1997Hewlett-Packard CompanyPolymer-based electroluminescent device with improved stability
US565219228 mars 199529 juil. 1997Battelle Memorial InstituteMixture of catalytically active material and carrier materials which may themselves be active; achieved by combining active and carrier materials prior to or concurrent with crystallite formation
US5654084 *22 juil. 19945 août 1997Martin Marietta Energy Systems, Inc.Multilayer diffusion barrier to protect against environmental effects, physical barrier, getter material
US566096111 janv. 199626 août 1997Xerox CorporationElectrophotographic imaging member having enhanced layer adhesion and freedom from reflection interference
US56652802 oct. 19969 sept. 1997Becton Dickinson CoBlood collection tube assembly
US5681615 *27 juil. 199528 oct. 1997Battelle Memorial InstituteDissolving a salt in a monomer solution, vacuum flash evaporating the solution, condensing evaporated solution as a liquid film, and depositing the composite material on to a substrate in vacuum atomosphere
US5681666 *8 août 199628 oct. 1997Duracell Inc.Light transparent multilayer moisture barrier for electrochemical celltester and cell employing same
US5684084 *21 déc. 19954 nov. 1997E. I. Du Pont De Nemours And CompanyCoating containing acrylosilane polymer to improve mar and acid etch resistance
US5686360 *30 nov. 199511 nov. 1997MotorolaHermetic sealing of plastic substrate
US5693956 *29 juil. 19962 déc. 1997MotorolaInverted oleds on hard plastic substrate
US56955643 août 19959 déc. 1997Tokyo Electron LimitedMultichamber system wherein transfer units and desired number of process units each with separate inert gas supply and exhaust systems are connected via interconnection units
US5711816 *7 juin 199527 janv. 1998Advanced Technolgy Materials, Inc.Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same
US57259099 févr. 199610 mars 1998Catalina Coatings, Inc.Acrylate composite barrier coating process
US5731661 *15 juil. 199624 mars 1998Motorola, Inc.Passivation of electroluminescent organic devices
US573620727 oct. 19957 avr. 1998Schott GlaswerkeSequentially arranged barrier layers of polymer and inorganic oxides or oxynitrides
US5747182 *26 juil. 19935 mai 1998Cambridge Display Technology LimitedManufacture of electroluminescent devices
US5757126 *30 juin 199726 mai 1998Motorola, Inc.Organic light emitting diodes
US5759329 *24 juin 19942 juin 1998Pilot Industries, Inc.Continuously extruding the first thermoplastic fluoropolymer, chemically activating the outer surface of fluoropolymer by plasma treatment, continuously extruding a second layer of non-fluoropolymer on first layer to form chemical bonding
US577117716 mai 199423 juin 1998Kyoei Automatic Control Technology Co., Ltd.Method and apparatus for measuring dynamic load
US5771562 *2 mai 199530 juin 1998Motorola, Inc.Passivation of organic devices
US578235512 nov. 199721 juil. 1998Fuji Photo Film Co., Ltd.Cassette case
US5792550 *28 avr. 199511 août 1998Flex Products, Inc.Waterproofing, oxygen impervious food packaging
US579539929 juin 199518 août 1998Kabushiki Kaisha ToshibaSemiconductor device manufacturing apparatus, method for removing reaction product, and method of suppressing deposition of reaction product
US5811177 *30 nov. 199522 sept. 1998Motorola, Inc.Passivation of electroluminescent organic devices
US5811183 *11 août 199522 sept. 1998Shaw; David G.Acrylate polymer release coated sheet materials and method of production thereof
US5821692 *26 nov. 199613 oct. 1998Motorola, Inc.Organic electroluminescent device hermetic encapsulation package
US5844363 *23 janv. 19971 déc. 1998The Trustees Of Princeton Univ.Vacuum deposited, non-polymeric flexible organic light emitting devices
US58697911 mars 19969 févr. 1999U.S. Philips CorporationMethod and apparatus for a touch sensing device having a thin film insulation layer about the periphery of each sensing element
US5872355 *9 avr. 199716 févr. 1999Hewlett-Packard CompanyElectroluminescent device and fabrication method for a light detection system
US589155415 sept. 19976 avr. 1999Idemitsu Kosan Co., Ltd.Organic electroluminescence device
US589522820 mars 199720 avr. 1999International Business Machines CorporationApplying and inner buffer layer and an outer layer which adheres to buffer layer; for noncontamination, stability, oxidation resistance
US5902641 *29 sept. 199711 mai 1999Battelle Memorial InstituteMixing liquid monomer with insoluble particles; flash evaporating to form a composite vapor; continuously cryocondensing on a cool substrate and crosslinking to form solid composite polymer layer; electronic devices
US5902688 *16 juil. 199611 mai 1999Hewlett-Packard CompanyElectroluminescent display device
US5904958 *20 mars 199818 mai 1999Rexam Industries Corp.Coating a substrate, condensation and adjustment of apertures vacuum chamber;
US5912069 *19 déc. 199615 juin 1999Sigma Laboratories Of ArizonaFor use in explosives, propellants and pyrotechnics, radiation cross-linked multifunctional acrylate polymer materials
US591932818 juin 19976 juil. 1999Becton Dickinson And CompanyBlood collection tube assembly
US59200808 mai 19986 juil. 1999Fed CorporationEmissive display using organic light emitting diodes
US5922161 *28 juin 199613 juil. 1999Commonwealth Scientific And Industrial Research OrganisationSurface treatment of polymers
US592956218 avr. 199627 juil. 1999Cambridge Display Technology LimitedOrganic electroluminescent display,
US593485628 avr. 199710 août 1999Tokyo Electron LimitedMulti-chamber treatment system
US5945174 *1 juil. 199831 août 1999Delta V Technologies, Inc.Acrylate polymer release coated sheet materials and method of production thereof
US5948552 *27 août 19967 sept. 1999Hewlett-Packard CompanyHeat-resistant organic electroluminescent device
US5952778 *18 mars 199714 sept. 1999International Business Machines CorporationEncapsulated organic light emitting device
US595516130 janv. 199621 sept. 1999Becton Dickinson And CompanyBlood collection tube assembly
US5965907 *29 sept. 199712 oct. 1999Motorola, Inc.Full color organic light emitting backlight device for liquid crystal display applications
US596862022 oct. 199719 oct. 1999Becton Dickinson And CompanyBlood collection tube assembly
US599417429 sept. 199730 nov. 1999The Regents Of The University Of CaliforniaMethod of fabrication of display pixels driven by silicon thin film transistors
US5996498 *24 juil. 19987 déc. 1999Presstek, Inc.Method of lithographic imaging with reduced debris-generated performance degradation and related constructions
US601333725 mars 199711 janv. 2000Becton Dickinson And CompanyBlood collection tube assembly
US60400172 oct. 199821 mars 2000Sigma Laboratories, Inc.Forming a multilayer film polymer composites and evaporation, condensation, flash evaporation of mixtures, condensation and radiation curing
US6045864 *1 déc. 19974 avr. 20003M Innovative Properties CompanyVapor coating method
US606682616 mars 199823 mai 2000Yializis; AngeloApparatus for plasma treatment of moving webs
US608331327 juil. 19994 juil. 2000Advanced Refractory Technologies, Inc.Abrasive resistant, transparent barrier coating for plastic substrates comprised of carbon, hydrogen, silicon and oxygen in an amorphous structure
US6083628 *4 avr. 19964 juil. 2000Sigma Laboratories Of Arizona, Inc.Vacuum deposited, radiation polymerized acrylate monomer film; metallized packaging; heat, wear, and corrosion resistance
US608470215 oct. 19984 juil. 2000Pleotint, L.L.C.Thermochromic devices
US608700730 sept. 199411 juil. 2000Kanegafuchi Kagaku Kogyo Kabushiki KaishaHeat-Resistant optical plastic laminated sheet and its producing method
US609226920 mars 199825 juil. 2000Sigma Laboratories Of Arizona, Inc.High energy density capacitor
US61066274 avr. 199622 août 2000Sigma Laboratories Of Arizona, Inc.Multilayer; patterns; using a rotating drum, masking
US611726622 avr. 199812 sept. 2000Interuniversifair Micro-Elektronica Cenirum (Imec Vzw)Furnace for continuous, high throughput diffusion processes from various diffusion sources
US61182181 févr. 199912 sept. 2000Sigma Technologies International, Inc.Steady-state glow-discharge plasma at atmospheric pressure
US61372218 juil. 199824 oct. 2000Agilent Technologies, Inc.Organic electroluminescent device with full color characteristics
US6146225 *30 juil. 199814 nov. 2000Agilent Technologies, Inc.Transparent, flexible permeability barrier for organic electroluminescent devices
US61464627 mai 199914 nov. 2000Astenjohnson, Inc.Structures and components thereof having a desired surface characteristic together with methods and apparatuses for producing the same
US615018727 juil. 199821 nov. 2000Electronics And Telecommunications Research InstituteEncapsulation method of a polymer or organic light emitting device
US616556610 juin 199926 déc. 2000Becton Dickinson And CompanyUseful for providing an effective barrier against gas permeability in containers and for extending shelf-life of containers, especially plastic evacuated blood collection devices
US6178082 *26 févr. 199823 janv. 2001International Business Machines CorporationHigh temperature, conductive thin film diffusion barrier for ceramic/metal systems
US619514224 déc. 199627 févr. 2001Matsushita Electrical Industrial Company, Ltd.Organic electroluminescence element, its manufacturing method, and display device using organic electroluminescence element
US61982178 mai 19986 mars 2001Matsushita Electric Industrial Co., Ltd.Organic electroluminescent device having a protective covering comprising organic and inorganic layers
US61982208 mai 19986 mars 2001Emagin CorporationComprising a metal film overlying a dielectric film; metal layer may react with moisture or oxygen to seal off pin holes; low moisture and oxygen permeability, stress resistance
US620389829 août 199720 mars 20013M Innovatave Properties CompanyArticle comprising a substrate having a silicone coating
US620723816 déc. 199827 mars 2001Battelle Memorial InstituteFlash evaporating a crosslinkable monomer into a polymer with the selected index of refraction, forming an evaporate, passing it to a glow discharge electrode creating a monomer plasma, cryocondensing plasma on a substrate and
US620723916 déc. 199827 mars 2001Battelle Memorial InstitutePlasma enhanced chemical deposition of conjugated polymer
US62144228 oct. 199810 avr. 2001Sigma Laboratories Of Arizona, Inc.Method of forming a hybrid polymer film
US621794716 déc. 199817 avr. 2001Battelle Memorial InstituteVapor deposition of polymers in a vacuum
US622494829 sept. 19971 mai 2001Battelle Memorial InstitutePlasma enhanced chemical deposition with low vapor pressure compounds
US622843416 déc. 19988 mai 2001Battelle Memorial InstitutePlasma polymerized polymer films, enhanced chemical vapordeposition with a flash evaporated feed source of a low vapor pressure compound.
US622843616 déc. 19988 mai 2001Battelle Memorial InstitutePlasma polymerized polymer films, enhanced chemical vapordeposition with a flash evaporated feed source of a low vapor pressure compound.
US623193930 août 199615 mai 2001Presstek, Inc.Acrylate composite barrier coating
US62647474 août 199924 juil. 20013M Innovative Properties CompanyApparatus for forming multicolor interference coating
US626869516 déc. 199831 juil. 2001Battelle Memorial InstituteEnvironmental barrier material for organic light emitting device and method of making
US627420416 déc. 199814 août 2001Battelle Memorial InstituteMethod of making non-linear optical polymer
US63228602 nov. 199827 nov. 2001Rohm And Haas CompanyPlastic substrates for electronic display applications
US633306517 juil. 199825 déc. 2001Tdk CorporationProcess for the production of an organic electroluminescent device
US634823712 janv. 200119 févr. 20023M Innovative Properties CompanyJet plasma process for deposition of coatings
US635003410 avr. 200026 févr. 20023M Innovative Properties CompanyRetroreflective articles having polymer multilayer reflective coatings
US635277719 août 19985 mars 2002The Trustees Of Princeton UniversityOrganic photosensitive optoelectronic devices with transparent electrodes
US635857031 mars 199919 mars 2002Battelle Memorial InstitutePlacing moving substrate into a vacuum chamber, degassing first liquid material selected from oligomer, resin, oligomer and monomer, resin and monomer to form a degassed first liquid material, depositing thin layer of liquid; curing
US636188519 nov. 199826 mars 2002Organic Display TechnologyAnodes and cathodes for electroluminescent device
US638773218 juin 199914 mai 2002Micron Technology, Inc.Methods of attaching a semiconductor chip to a leadframe with a footprint of about the same size as the chip and packages formed thereby
US639777611 juin 20014 juin 2002General Electric CompanyApparatus for large area chemical vapor deposition using multiple expanding thermal plasma generators
US641364520 avr. 20002 juil. 2002Battelle Memorial InstituteUltrabarrier substrates
US641687230 août 20009 juil. 2002Cp Films, Inc.Heat reflecting film with low visible reflectance
US642000320 déc. 200016 juil. 20023M Innovative Properties CompanySheet including thermoplastic substrate, vapor deposited crosslinked acrylate layer, gas barrier material and second vapor deposited acrylate which was crosslinked before the gas barrier contacted any solid surface; low oxygen permeability
US643654414 juil. 199820 août 2002Toray Plastics Europe S.A.Metal layers on polyvinyl alcohol and polyesters
US64603693 janv. 20018 oct. 2002Applied Materials, Inc.Consecutive deposition system
US646595312 juin 200015 oct. 2002General Electric CompanyPlastic substrates with improved barrier properties for devices sensitive to water and/or oxygen, such as organic electroluminescent devices
US646859513 févr. 200122 oct. 2002Sigma Technologies International, Inc.Vaccum deposition of cationic polymer systems
US6492026 *20 avr. 200010 déc. 2002Battelle Memorial InstitutePolymer substrate having a high glass transition temperature (tg); and adjacent the substrate, a barrier stack of a barrier layer and polymer layer; for visual display devices; chemical resistance, wear resistance
US6548912 *15 mai 200015 avr. 2003Battelle Memorial InstituteSemicoductor passivation using barrier coatings
US6570325 *22 juin 200127 mai 2003Battelle Memorial InstituteEnvironmental barrier material for organic light emitting device and method of making
US6573652 *20 avr. 20003 juin 2003Battelle Memorial InstituteThe device includes a substrate, an environmentally sensitive display device adjacent to the substrate, and at least one first barrier stack adjacent to the environmentally sensitive display device. The barrier stack encapsulates the
US6720203 *26 févr. 200313 avr. 2004E. I. Du Pont De Nemours And CompanyFlexible organic electronic device with improved resistance to oxygen and moisture degradation
US6923702 *13 déc. 20022 août 2005Battelle Memorial InstituteMethod of making encapsulated display devices
BE704297A * Titre non disponible
DE19603746A1 *2 févr. 199624 avr. 1997Bosch Gmbh RobertElektrolumineszierendes Schichtsystem
EP0299753A2 *13 juil. 198818 janv. 1989The BOC Group, Inc.Controlled flow vaporizer
EP0340935A2 *17 avr. 19898 nov. 1989SPECTRUM CONTROL, INC. (a Delaware corporation)High speed process for coating substrates
EP0390540A2 *28 mars 19903 oct. 1990Sharp Kabushiki KaishaProcess for preparing an organic compound thin film for an optical device
EP0547550A1 *14 déc. 199223 juin 1993Matsushita Electric Industrial Co., Ltd.Method of manufacturing a chemically adsorbed film
EP0590467A1 *21 sept. 19936 avr. 1994Röhm GmbhProcess for forming scratch-resistant silicon oxide layers on plastics by plasma-coating
EP0722787A2 *4 oct. 199424 juil. 1996Catalina Coatings, Inc.Process for making an acrylate coating
EP0787826A1 *24 janv. 19976 août 1997Becton Dickinson and CompanyBlood collection tube assembly
EP0916394A2 *12 nov. 199819 mai 1999Sharp CorporationMethod of manufacturing modified particles and manufacturing device therefor
EP0931850A1 *13 nov. 199828 juil. 1999Leybold Systems GmbHMethod for treating the surfaces of plastic substrates
EP0977469A2 *30 juil. 19992 févr. 2000Hewlett-Packard CompanyImproved transparent, flexible permeability barrier for organic electroluminescent devices
JPH08325713A * Titre non disponible
JPS63136316A * Titre non disponible
Citations hors brevets
Référence
1Affinito, J. D. et al., "Molecularly Doped Polymer Composite Films for Light Emitting Polymer Applications Fabricated by the PML Process" 41st Technical Conference of Society of Vacuum Coaters, Apr. 1998, pp. 1-6.
2Affinito, J. D. et al., "Vacuum Deposited Conductive Polymer Films" The Eleventh International Conference on Vacuum Web Coating, no earlier than Feb. 1998, pp. 200-212.
3Affinito, J. D., Energy Res. Abstr. 18(6), #17171, 1993.
4Affinito, J.D. et al, Ultra High Rate, Wide Area, Plasma Polymerized Films from High Molecular Weight/Low Vapor Pressure Liquid or Solid Monomer Precursors; 45<SUP>th </SUP>International Symposium of the American Vacuum Society; Nov. 2-6, 1998, pp. 0-26.
5Affinito, J.D. et al., "Vacuum Deposition of Polymer Electrolytes on Flexible Susbtrates" The Ninth International Conference on Vacuum Web Coating, 1995, pp. 0-16.
6Affinito, J.D. et al., Molecularly Doped Polymer Composite Films for Light Emitting Polymer Application Fabricated by the PML Process; 41<SUP>st </SUP>Technical Conference of the Society of Vacuum Coaters; Apr. 1998; pp. 220-225.
7Affinito, J.D. et al., PML/Oxide/PML Barrier Layer Performance Differences Arising From Use Of UV Or Electron Beam Polymerization Of The PML Layers, SVC 40<SUP>th </SUP>Annual Technical Conference, Apr. 12-17, 1997, 4 pages only.
8Affinito, J.D. et al., Polymer/polymer, Polymer/Oxide, and Polymer/Metal Vacuum Deposited Interference Filters; Tenth International Vacuum Web Coating Conference; Nov. 1996; pp. 0-14.
9Affinito, J.D. et al., Vacuum Deposited Polymer/metal Multilayer Films for Optical Applications; Paper No. C1.13; International Conference on Metallurgical Coatings; Apr. 15-21, 1995, pp. 1-14.
10Affinito, J.D. et al.; A new method for fabricating transparent barrier layers, Thin Solid Films 290-291; 1996; pp. 63-67.
11Affinito, J.D. et al.; Molecularly Doped Polymer Composit Films for Light Emitting Polymer Application Fabricated by the PML Process; 41st Technical Conference of the Society of Vacuum Coaters; 1998; pp. 220-225.
12Affinito, J.D. et al.; PML/Oxide/PML Barrier Layer Performance Differences Arising From Use Of UV or Electron Beam Polymerization of the PML Layers; Thin Solid Films; Elsevier Science S.A.; vol. 308-309; Oct. 31, 1997; pp. 19-25.
13Affinito, J.D. et al.; Polymer-Oxide Transparent Barrier Layers; SVC 39th Annual Technical Conference; Vacuum Web Coating Session; 1996; pp. 392-397.
14Affinito, J.D. et al.; Ultra High Rate, Wide Area, Plasma Polymerized Films from High Molecular Weight/Low Vapor Pressure Liquid or Liquid/Solid Suspension Monomer Precursors; MRS Conference; Nov. 29-Dec. 3, 1998; Paper No. Y12.1.
15Affinito, J.D. et al.; Ultrahigh Rate, Wide Area, Plasma Polymerized Films from High Molecular Weight/Low Vapor Pressure Liquid or Solid Monomer Precursors; Journal Vacuum Science Technology A 17(4); Jul./Aug. 1999; pp. 1974-1981; American Vacuum Society.
16Affinito, J.D. et al.; Vacuum Deposited Polymer/Metal Multilayer Films for Optical Application; Thin Solid Films 270, 1995; pp. 43-48.
17Affinito, J.D. et al.; Vacuum Deposition of Polymer Electrolytes On Flexible Substrates, The Ninth International Conference on Vacuum Web Coating; pp. 20-37.
18Affinito, J.D., et al.; High Rate Vacuum Deposition of Polymer Electrolytes: Journal Vacuum Science Technology A 14(3), May/Jun. 1996.
19Affinito, J.D., Vacuum Deposited Conductive Polymer Films; The Eleventh International Conference on Vacuum Web Coatings, Nov. 9-11, 1997, pp. 1-13.
20 *Affinito, J.F., et al., "Vacuum Deposition of Polymer Electrolytes On Flexible Substrates", "Proceedings of the Ninth International Conference on Vacuum Web Coating", Nov. 1995 ed R. Bakish, Bakish Press 1995, pp. 20-36.
21Akedo et al., "LP-5: Lake-News Poster: Plasma-CVD SiNx/Plasma-Polymerized CNx:H Multi-layer Passivation Films for Organic Light Emmitting Diods", SID 03 Digest.
22Bright, Clark I., Transparent Barrier Coatings Based on ITO for Flexible Plastic Displays; Thirteenth International Conference on Vacuum Web Coating; Oct. 17-19, 1999; pp. 247-255.
23Bunshah, R. F. et al., "Deposition Technologies for Films and Coatings" Noyes Publications, Park Ridge, New Jersey, 1982, p. 339.
24Chahroudi, D.; Transparent Glass Barrier Coatings for Flexible Film Packaging; 1991; pp. 130-133; Society of Vacuum Coaters.
25Chwang et al., "Thin Film encapsulated flexible organic electroluminescent displays", American Institute of Physics, 2003.
26Clark I. Bright, et al., Transparent Barrier Coatings Based on ITO for Flexible Plastic Displays, Oct. 17-19, 1999, pp. 247-264, Tucson, Arizona.
27Czeremuszkin, G. et al.; Permeation Through Defects in Transparent Barrier Coated Plastic Films; 43rd Annual Technical Conference Proceedings; Apr. 15, 2000; pp. 408-413.
28De Gryse, R. et al., "Sputtered Transparent Barrier Layers," Tenth International Conference on Vacuum Web Coating, Nov. 1996, pp. 190-198.
29F.M. Penning; Electrical Discharges in Gases; 1965; pp. 1-51; Gordon and Breach, Science Publishers, New York-London-Paris.
30Felts, J.T., Transparent Barrier Coatings Update: Flexible Substrates; Society of Vacuum Coaters; 36<SUP>th </SUP>Annual Technical Conference Proceedings; Apr. 25-30, 1993; pp. 324-331.
31Felts, J.T.; Transparent Barrier Coatings Update: Flexible Substrates; pp. 324-331.
32Finson, E. et al.; Transparent SiO2 Barrier Coatings: Conversion and Production Status; 1994; pp. 139-143; Society of Vacuum Coaters.
33G. Gustafason, et al.; Flexible light-emitting diodes made from soluble conducting polymers; Letters to Nature; vol. 357; Jun. 11, 1992; pp. 477-479.
34Graupner, W. et al.; "High Resolution Color Organic Light Emitting Diode Microdisplay Fabrication Method", SPIE Proceedings; Nov. 6, 2000; pp. 1-9.
35Henry, B.M. et al., Microstructural and Gas Barrier Properties of Transparent Aluminum Oxide and Indium Tin Oxide Films; Denver, Apr. 15-20, 2000; pp. 373-378; Society of Vacuum Coaters.
36Henry, B.M. et al., Microstructural Studies of Transparent Gas Barrier Coatings on Polymer Substrates; Thirteenth International Conference on Vacuum Web Coating; Oct. 17-19, 1999; pp. 265-273.
37Hibino, N. et al., Transparent Barrier Al<SUB>2</SUB>0<SUB>3 </SUB>Coating By Activated Reactive Evaporation; Thirteenth International Conference on Vacuum Web Coating; Oct. 17-19, 1999; pp. 234-246.
38Hoffmann, G. et al.; Transparent Barrier Coatings by Reactive Evaporation; 1994; pp. 155-160; Society of Vacuum Coaters.
39 *Inoue et al., Proc. Jpn. Congr. Mater. Res., vol. 33, p. 177-9, 1990.
40Klemberg-Sapieha, J.E. et al.; Transparent Gas Barrier Coatings Produced by Dual-Frequency PECVD; 1993; pp. 445-449; Society of Vacuum Coaters.
41Krug, T. et al.; New Developments in Transparent Barrier Coatings; 1993; pp. 302-305; Society Vacuum Coaters.
42Kukla, R. et al., Transparent Barrier Coatings with EB-Evaporation, an Update; Section Five; Transparent Barrier Coating Papers; Thirteenth International Conference on Vacuum Web Coating; Oct. 17-19, 1999 pp. 222-233.
43Mahon, J.K. et al, Requirements of Flexible Substrates for Organic Light Emitting Devices in Flat Panel Display Applications, Society of Vacuum Coaters, 42<SUP>nd </SUP>Annual Technical Conference Proceedings, Apr. 1999, pp. 456-459.
44Norenberg, H. et al., Comparative Study of Oxygen Permeation Through Polymers and Gas Barrier Films, Denver, Apr. 15-20, 2000; pp. 347-351; Society of Vacuum Coaters.
45 *Notification of Transmittal of the International Search Report Or The Declaration, Mar. 3, 2000, PCT/US99/29853.
46 *Penning, F.M., Electrical Discharges in Gasses, Gordon and Breach Science Publishers, 1965, Chapters 5-6, pp. 19-35, and Chapter 8, pp. 41-50.
47Phillips, R.W.; Evaporated Dielectric Colorless Films on PET and Opp Exhibiting High Barriers Toward Moisture and Oxygen; Society of Vacuum Coaters; 36th Annual Technical Conference Proceedings; 1993; pp. 293-300.
48Shaw, D.G. et al.; Use of Vapor Deposited Acrylate Coatings to Improve the Barrier Properties of Metallized Film; 1994; pp. 240-244; Society of Vacuum Coaters.
49Shi, M.K. et al.; In situ and real-time monitoring of plasma-induced etching PET and acrylic films, Plasmas and Polymers; Dec. 1999, 494); pp. 1-25.
50Shi, M.K., et al., Plasma treatment of PET and acrylic coating surfaces-I, In situ XPS measurements, Journal of Adhesion Science and Technology, Mar. 2000, 14(12), pp. 1-28.
51Tropsha et al., Activated Rate Theory Treatment of Oxygen and Water Transport through Silicon Oxide/Poly(ethylene terphthalate) Composite Barrier Structures; J. Phys. Chem B Mar. 1997; pp. 2259-2266.
52Tropsha et al., Combinatorial Barrier Effect of the Multilayer SiOx Coatings on Polymer Substrates; 1997 Society of Vacuum Coaters, 40<SUP>th </SUP>Annual Technical Conferences Proceedings; Apr. 12-17, 1997; pp. 64-69.
53Vossen, J.L. et al.; Thin Film Processes; Academic Press, 1978, Part II, Chapter II-1, Glow Discharge Sputter Deposition, pp. 12-63; Part IV, Chapter IV-1 Plasma Deposition of Inorganic Compounds and Chapter IV-2 Glow Discharge Polymerization, pp. 335-397.
54Wong, C.P., "Recent Advances in IC Passivation and Encapsulation: Process Techniques and Materials," Polymers for Electronic and Photonic Applications, AT&T Bell Laboratories, 1993, pp. 167-209.
55Yamada, Y. et al.; The Properties of a New Transparent and Colorless Barrier Film; 1995; pp. 28-31; Society of Vacuum Coaters.
56Yializis, A. et al., Ultra High Barrier Films; Denver, Apr. 15-20, 2000, pp. 404-407; Society of Vacuum Coaters.
57Yializis, A. et al.; High Oxygen Barrier Polypropylene Films Using Transparent Acrylate-A2O3 and Opaque Al-Acrylate Coatings; 1995; pp. 95-102; Society of Vacuum Coaters.
Référencé par
Brevet citant Date de dépôt Date de publication Déposant Titre
US767507412 janv. 20079 mars 2010Semiconductor Energy Laboratory Co., Ltd.Light emitting device including a lamination layer
US81297152 mars 20106 mars 2012Semiconductor Energy Labratory Co., Ltd.Light emitting device
US847662328 févr. 20122 juil. 2013Semiconductor Energy Laboratory Co., Ltd.Light emitting device
US86590121 juil. 201325 févr. 2014Semiconductor Energy Laboratory Co., Ltd.Light emitting device
Classifications
Classification aux États-Unis428/446, 428/688, 428/411.1, 428/500, 428/457, 428/469, 426/126, 428/690
Classification internationaleH01L51/52, C23C14/08, B32B27/00, B32B15/04
Classification coopérativeC23C14/08, B32B27/00, G02F2201/50, H01L51/5256
Classification européenneH01L51/52C4B, C23C14/08, B32B27/00
Événements juridiques
DateCodeÉvénementDescription
24 déc. 2013FPAYFee payment
Year of fee payment: 12
7 sept. 2012ASAssignment
Free format text: MERGER;ASSIGNOR:SAMSUNG MOBILE DISPLAY CO., LTD.;REEL/FRAME:028912/0083
Effective date: 20120702
Owner name: SAMSUNG DISPLAY CO., LTD., KOREA, REPUBLIC OF
17 déc. 2010ASAssignment
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BATTELLE MEMORIAL INSTITUTE;REEL/FRAME:025516/0773
Effective date: 20101028
Owner name: SAMSUNG MOBILE DISPLAY CO., LTD., KOREA, REPUBLIC