| Publikationsnummer | USRE40531 E1 | | Typ av kungörelse | Beviljande | | Ansökningsnummer | 10/890,437 | | Publiceringsdatum | 7 okt 2008 | | Registreringsdatum | 12 jul 2004 | | Prioritetsdatum | 25 okt 1999 | | Även publicerat som | | |
| Uppfinnare | | | Ursprunglig innehavare | | |
| USA-klassificering | | | Internationell klassificering | | | Kooperativ klassning | | | Europeisk klassificering | H01L51/52C4B C23C14/08 B32B27/00 | |
| Hänvisningar | | | |
| Externa länkar | | |
Ultrabarrier substrates
US RE40531 E1 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.
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.
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.
| citerade patent | Registreringsdatum | Publiceringsdatum | Sökande | Titel |
|---|
| US2382432 | 2 aug 1940 | 14 aug 1945 | Crown Cork & Seal Company, Inc. | Method and apparatus for depositing vaporized metal coatings | | US2384500 | 8 jul 1942 | 11 sep 1945 | Crown Cork & Seal Company, Inc. | Apparatus and method of coating | | US3475307 | 4 feb 1965 | 28 okt 1969 | Continental Can Co. Inc. | Condensation of monomer vapors to increase polymerization rates in a glow discharge | | US3607365 | 12 maj 1969 | 21 sep 1971 | Minnesota Mining And Mfg. Co. | Vapor phase method of coating substrates with polymeric coating | | US3941630 | 29 apr 1974 | 2 mar 1976 | Rca Corporation | Method of fabricating a charged couple radiation sensing device | | US4061835 | 25 jun 1976 | 6 dec 1977 | Standard Oil Company (Indiana) | Process of forming a polypropylene coated substrate from an aqueous suspension of polypropylene particles | | US4098965 | 27 jun 1977 | 4 jul 1978 | Polaroid Corporation | Flat batteries and method of making the same | | US4266223 | 8 dec 1978 | 5 maj 1981 | W. H. Brady Co. | Thin panel display | | US4283482 | 25 mar 1980 | 11 aug 1981 | Nihon Shinku Gijutsu Kabushiki Kaisha | Dry Lithographic Process | | US4313254 | 4 aug 1980 | 2 feb 1982 | The Johns Hopkins University | Thin-film silicon solar cell with metal boride bottom electrode | | US4426275 | 27 nov 1981 | 17 jan 1984 | Deposition Technology, Inc. | Sputtering device adaptable for coating heat-sensitive substrates | | US4521458 | 1 apr 1983 | 4 jun 1985 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of National Defence | Process for coating material with water resistant composition | | US4537814 | 26 jan 1984 | 27 aug 1985 | Toyoda Gosei Co., Ltd. | Resin article having a ceramics coating layer | | US4555274 | 7 jun 1984 | 26 nov 1985 | Fuji Photo Film Co., Ltd. | Ion selective electrode and process of preparing the same | | US4557978 | 12 dec 1983 | 10 dec 1985 | Primary Energy Research Corporation | Electroactive polymeric thin films | | US4572842 | 24 aug 1984 | 25 feb 1986 | Leybold-Heraeus Gmbh | Method and apparatus for reactive vapor deposition of compounds of metal and semi-conductors | | US4581337 | 7 jul 1983 | 8 apr 1986 | E. I. Du Pont De Nemours And Company | Polyether polyamines as linking agents for particle reagents useful in immunoassays | | US4624867 | 21 mar 1985 | 25 nov 1986 | Nihon Shinku Gijutsu Kabushiki Kaisha | Process for forming a synthetic resin film on a substrate and apparatus therefor | | US4695618 | 23 maj 1986 | 22 sep 1987 | Ameron, Inc. | Solventless polyurethane spray compositions and method for applying them | | US4710426 | 28 nov 1983 | 1 dec 1987 | Polaroid Corporation, Patent Dept. | Solar radiation-control articles with protective overlayer | | US4722515 | 8 apr 1986 | 2 feb 1988 | Spectrum Control, Inc. | Atomizing device for vaporization | | US4768666 | 26 maj 1987 | 6 sep 1988 | Kessler; Milton | Tamper proof container closure | | US4842893 | 29 apr 1988 | 27 jun 1989 | Spectrum Control, Inc. | High speed process for coating substrates | | US4843036 | 29 jun 1987 | 27 jun 1989 | Eastman Kodak Company | Method for encapsulating electronic devices | | US4855186 | 23 feb 1988 | 8 aug 1989 | Hoechst Aktiengesellschaft | Coated plastic film and plastic laminate prepared therefrom | | US4889609 | 6 sep 1988 | 26 dec 1989 | Ovonic Imaging Systems, Inc. | Continuous dry etching system | | US4913090 | 20 sep 1988 | 3 apr 1990 | Mitsubishi Denki Kabushiki Kaisha | Chemical vapor deposition apparatus having cooling heads adjacent to gas dispersing heads in a single chamber | | US4931158 | 8 aug 1989 | 5 jun 1990 | The Regents Of The Univ. Of Calif. | Deposition of films onto large area substrates using modified reactive magnetron sputtering | | US4934315 | 19 okt 1988 | 19 jun 1990 | Alcatel N.V. | System for producing semicondutor layer structures by way of epitaxial growth | | US4954371 | 7 jul 1987 | 4 sep 1990 | Spectrum Control, Inc. | Flash evaporation of monomer fluids | | US4977013 | 3 jun 1988 | 11 dec 1990 | Andus Corporation | Tranparent conductive coatings | | US5032461 | 12 okt 1990 | 16 jul 1991 | Spectrum Control, Inc. | Method of making a multi-layered article | | US5036249 | 11 dec 1989 | 30 jul 1991 | Molex Incorporated | Electroluminescent lamp panel and method of fabricating same | | US5047131 | 8 nov 1989 | 10 sep 1991 | The Boc Group, Inc. | Method for coating substrates with silicon based compounds | | US5059861 | 26 jul 1990 | 22 okt 1991 | Eastman Kodak Company | Organic electroluminescent device with stabilizing cathode capping layer | | US5124204 | 29 mar 1991 | 23 jun 1992 | Sharp Kabushiki Kaisha | Thin film electroluminescent (EL) panel | | US5189405 | 23 dec 1991 | 23 feb 1993 | Sharp Kabushiki Kaisha | Thin film electroluminescent panel | | US5203898 | 16 dec 1991 | 20 apr 1993 | Corning Incorporated | Method of making fluorine/boron doped silica tubes | | US5204314 | 13 dec 1991 | 20 apr 1993 | Advanced Technology Materials, Inc. | Method for delivering an involatile reagent in vapor form to a CVD reactor | | US5237439 | 30 sep 1992 | 17 aug 1993 | Sharp Kabushiki Kaisha | Plastic-substrate liquid crystal display device with a hard coat containing boron or a buffer layer made of titanium oxide | | US5260095 | 21 aug 1992 | 9 nov 1993 | Battelle Memorial Institute | Vacuum deposition and curing of liquid monomers | | US5336324 | 4 dec 1991 | 9 aug 1994 | Emcore Corporation | Apparatus for depositing a coating on a substrate | | US5354497 | 19 apr 1993 | 11 okt 1994 | Sharp Kabushiki Kaisha | Liquid crystal display | | US5356947 | 29 okt 1992 | 18 okt 1994 | Minnesota Mining And Manufacturing Company | Controllable radiation curable photoiniferter prepared adhesives for attachment of microelectronic devices and a method of attaching microelectronic devices therewith | | US5393607 | 8 jan 1993 | 28 feb 1995 | Mitsui Toatsu Chemiclas, Inc. | Laminated transparent plastic material and polymerizable monomer | | US5395644 | 2 aug 1993 | 7 mar 1995 | Battelle Memorial Institute | Vacuum deposition and curing of liquid monomers | | US5402314 | 3 feb 1993 | 28 mar 1995 | Sony Corporation | Printed circuit board having through-hole stopped with photo-curable solder resist | | US5427638 | 3 dec 1993 | 27 jun 1995 | Alliedsignal Inc. | Low temperature reaction bonding | | US5440446 | 4 okt 1993 | 8 aug 1995 | Catalina Coatings, Inc. | Acrylate coating material | | US5451449 | 11 maj 1994 | 19 sep 1995 | The Mearl Corporation | Colored iridescent film | | US5461545 | 13 sep 1994 | 24 okt 1995 | Thomson-Csf | Process and device for hermetic encapsulation of electronic components | | US5464667 | 16 aug 1994 | 7 nov 1995 | Minnesota Mining And Manufacturing Company | Jet plasma process and apparatus | | US5510173 | 20 aug 1993 | 23 apr 1996 | Southwall Technologies Inc. | Multiple layer thin films with improved corrosion resistance | | US5512320 | 13 apr 1994 | 30 apr 1996 | Applied Materials, Inc. | Vacuum processing apparatus having improved throughput | | US5536323 | 25 jul 1994 | 16 jul 1996 | Advanced Technology Materials, Inc. | Apparatus for flash vaporization delivery of reagents | | US5547508 | 17 nov 1994 | 20 aug 1996 | Battelle Memorial Institute | Vacuum deposition and curing of liquid monomers apparatus | | US5554220 | 19 maj 1995 | 10 sep 1996 | The Trustees Of Princeton University | Method and apparatus using organic vapor phase deposition for the growth of organic thin films with large optical non-linearities | | US5576101 | 12 apr 1995 | 19 nov 1996 | Bridgestone Corporation | Gas barrier rubber laminate for minimizing refrigerant leakage | | US5578141 | 1 jul 1994 | 26 nov 1996 | Canon Kabushiki Kaisha | Solar cell module having excellent weather resistance | | US5607789 | 23 jan 1995 | 4 mar 1997 | Duracell Inc. | Light transparent multilayer moisture barrier for electrochemical cell tester and cell employing same | | US5620524 | 27 feb 1995 | 15 apr 1997 | Chen; J. James | Apparatus for fluid delivery in chemical vapor deposition systems | | US5629389 | 6 jun 1995 | 13 maj 1997 | Hewlett-Packard Company | Polymer-based electroluminescent device with improved stability | | US5652192 | 28 mar 1995 | 29 jul 1997 | Battelle Memorial Institute | Catalyst material and method of making | | US5654084 | 22 jul 1994 | 5 aug 1997 | Martin Marietta Energy Systems, Inc. | Protective coatings for sensitive materials | | US5660961 | 11 jan 1996 | 26 aug 1997 | Xerox Corporation | Electrophotographic imaging member having enhanced layer adhesion and freedom from reflection interference | | US5665280 | 2 okt 1996 | 9 sep 1997 | Tropsha; Yelena G. | Blood collection tube assembly | | US5681615 | 27 jul 1995 | 28 okt 1997 | Battelle Memorial Institute | Vacuum flash evaporated polymer composites | | US5681666 | 8 aug 1996 | 28 okt 1997 | Duracell Inc. | Light transparent multilayer moisture barrier for electrochemical celltester and cell employing same | | US5684084 | 21 dec 1995 | 4 nov 1997 | E. I. Du Pont De Nemours And Company | Coating containing acrylosilane polymer to improve mar and acid etch resistance | | US5686360 | 30 nov 1995 | 11 nov 1997 | Motorola | Passivation of organic devices | | US5693956 | 29 jul 1996 | 2 dec 1997 | Motorola | Inverted oleds on hard plastic substrate | | US5695564 | 3 aug 1995 | 9 dec 1997 | Tokyo Electron Limited | Semiconductor processing system | | US5711816 | 7 jun 1995 | 27 jan 1998 | Advanced Technolgy Materials, Inc. | Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same | | US5725909 | 9 feb 1996 | 10 mar 1998 | Catalina Coatings, Inc. | Acrylate composite barrier coating process | | US5731661 | 15 jul 1996 | 24 mar 1998 | Motorola, Inc. | Passivation of electroluminescent organic devices | | US5736207 | 27 okt 1995 | 7 apr 1998 | Schott Glaswerke | Vessel of plastic having a barrier coating and a method of producing the vessel | | US5747182 | 26 jul 1993 | 5 maj 1998 | Cambridge Display Technology Limited | Manufacture of electroluminescent devices | | US5757126 | 30 jun 1997 | 26 maj 1998 | Motorola, Inc. | Passivated organic device having alternating layers of polymer and dielectric | | US5759329 | 24 jun 1994 | 2 jun 1998 | Pilot Industries, Inc. | Fluoropolymer composite tube and method of preparation | | US5771177 | 16 maj 1994 | 23 jun 1998 | Kyoei Automatic Control Technology Co., Ltd. | Method and apparatus for measuring dynamic load | | US5771562 | 2 maj 1995 | 30 jun 1998 | Motorola, Inc. | Passivation of organic devices | | US5782355 | 12 nov 1997 | 21 jul 1998 | Fuji Photo Film Co., Ltd. | Cassette case | | US5792550 | 28 apr 1995 | 11 aug 1998 | Flex Products, Inc. | Barrier film having high colorless transparency and method | | US5795399 | 29 jun 1995 | 18 aug 1998 | Kabushiki Kaisha Toshiba | Semiconductor device manufacturing apparatus, method for removing reaction product, and method of suppressing deposition of reaction product | | US5811177 | 30 nov 1995 | 22 sep 1998 | Motorola, Inc. | Passivation of electroluminescent organic devices | | US5811183 | 11 aug 1995 | 22 sep 1998 | 3M Innovative Properties Company | Acrylate polymer release coated sheet materials and method of production thereof | | US5821692 | 26 nov 1996 | 13 okt 1998 | Motorola, Inc. | Organic electroluminescent device hermetic encapsulation package | | US5844363 | 23 jan 1997 | 1 dec 1998 | The Trustees Of Princeton Univ. | Vacuum deposited, non-polymeric flexible organic light emitting devices | | US5869791 | 1 mar 1996 | 9 feb 1999 | U.S. Philips Corporation | Method and apparatus for a touch sensing device having a thin film insulation layer about the periphery of each sensing element | | US5872355 | 9 apr 1997 | 16 feb 1999 | Hewlett-Packard Company | Electroluminescent device and fabrication method for a light detection system | | US5891554 | 15 sep 1997 | 6 apr 1999 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device | | US5895228 | 20 mar 1997 | 20 apr 1999 | International Business Machines Corporation | Encapsulation of organic light emitting devices using Siloxane or Siloxane derivatives | | US5902641 | 29 sep 1997 | 11 maj 1999 | Battelle Memorial Institute | Flash evaporation of liquid monomer particle mixture | | US5902688 | 16 jul 1996 | 11 maj 1999 | Hewlett-Packard Company | Electroluminescent display device | | US5904958 | 20 mar 1998 | 18 maj 1999 | Rexam Industries Corp. | Adjustable nozzle for evaporation or organic monomers | | US5912069 | 19 dec 1996 | 15 jun 1999 | Sigma Laboratories Of Arizona | Metal nanolaminate composite | | US5919328 | 18 jun 1997 | 6 jul 1999 | Becton Dickinson And Company | Blood collection tube assembly | | US5920080 | 8 maj 1998 | 6 jul 1999 | Fed Corporation | Emissive display using organic light emitting diodes | | US5922161 | 28 jun 1996 | 13 jul 1999 | Commonwealth Scientific And Industrial Research Organisation | Surface treatment of polymers | | US5929562 | 18 apr 1996 | 27 jul 1999 | Cambridge Display Technology Limited | Organic light-emitting devices | | US5934856 | 28 apr 1997 | 10 aug 1999 | Tokyo Electron Limited | Multi-chamber treatment system | | US5945174 | 1 jul 1998 | 31 aug 1999 | Delta V Technologies, Inc. | Acrylate polymer release coated sheet materials and method of production thereof | | US5948552 | 27 aug 1996 | 7 sep 1999 | Hewlett-Packard Company | Heat-resistant organic electroluminescent device | | US5952778 | 18 mar 1997 | 14 sep 1999 | International Business Machines Corporation | Encapsulated organic light emitting device | | US5955161 | 30 jan 1996 | 21 sep 1999 | Becton Dickinson And Company | Blood collection tube assembly | | US5965907 | 29 sep 1997 | 12 okt 1999 | Motorola, Inc. | Full color organic light emitting backlight device for liquid crystal display applications | | US5968620 | 22 okt 1997 | 19 okt 1999 | Becton Dickinson And Company | Blood collection tube assembly | | US5994174 | 29 sep 1997 | 30 nov 1999 | The Regents Of The University Of California | Method of fabrication of display pixels driven by silicon thin film transistors | | US5996498 | 24 jul 1998 | 7 dec 1999 | Presstek, Inc. | Method of lithographic imaging with reduced debris-generated performance degradation and related constructions | | US6013337 | 25 mar 1997 | 11 jan 2000 | Becton Dickinson And Company | Blood collection tube assembly | | US6040017 | 2 okt 1998 | 21 mar 2000 | Sigma Laboratories, Inc. | Formation of multilayered photonic polymer composites | | US6045864 | 1 dec 1997 | 4 apr 2000 | 3M Innovative Properties Company | Vapor coating method | | US6066826 | 16 mar 1998 | 23 maj 2000 | Sigma Laboratories Of Arizona, Llc | Apparatus for plasma treatment of moving webs | | US6083313 | 27 jul 1999 | 4 jul 2000 | Advanced Refractory Technologies, Inc. | Hardcoats for flat panel display substrates | | US6083628 | 4 apr 1996 | 4 jul 2000 | Sigma Laboratories Of Arizona, Inc. | Hybrid polymer film | | US6084702 | 15 okt 1998 | 4 jul 2000 | Pleotint, L.L.C. | Thermochromic devices | | US6087007 | 30 sep 1994 | 11 jul 2000 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Heat-Resistant optical plastic laminated sheet and its producing method | | US6092269 | 20 mar 1998 | 25 jul 2000 | Sigma Laboratories Of Arizona, Inc. | High energy density capacitor | | US6106627 | 4 apr 1996 | 22 aug 2000 | Sigma Laboratories Of Arizona, Inc. | Apparatus for producing metal coated polymers | | US6117266 | 22 apr 1998 | 12 sep 2000 | Interuniversifair Micro-Elektronica Cenirum (Imec Vzw) | Furnace for continuous, high throughput diffusion processes from various diffusion sources | | US6118218 | 1 feb 1999 | 12 sep 2000 | Sigma Technologies International, Inc. | Steady-state glow-discharge plasma at atmospheric pressure | | US6137221 | 8 jul 1998 | 24 okt 2000 | Agilent Technologies, Inc. | Organic electroluminescent device with full color characteristics | | US6146225 | 30 jul 1998 | 14 nov 2000 | Agilent Technologies, Inc. | Transparent, flexible permeability barrier for organic electroluminescent devices | | US6146462 | 7 maj 1999 | 14 nov 2000 | Astenjohnson, Inc. | Structures and components thereof having a desired surface characteristic together with methods and apparatuses for producing the same | | US6150187 | 27 jul 1998 | 21 nov 2000 | Electronics And Telecommunications Research Institute | Encapsulation method of a polymer or organic light emitting device | | US6165566 | 10 jun 1999 | 26 dec 2000 | Becton Dickinson And Company | Method for depositing a multilayer barrier coating on a plastic substrate | | US6178082 | 26 feb 1998 | 23 jan 2001 | International Business Machines Corporation | High temperature, conductive thin film diffusion barrier for ceramic/metal systems | | US6195142 | 24 dec 1996 | 27 feb 2001 | Matsushita Electrical Industrial Company, Ltd. | Organic electroluminescence element, its manufacturing method, and display device using organic electroluminescence element | | US6198217 | 8 maj 1998 | 6 mar 2001 | Matsushita Electric Industrial Co., Ltd. | Organic electroluminescent device having a protective covering comprising organic and inorganic layers | | US6198220 | 8 maj 1998 | 6 mar 2001 | Emagin Corporation | Sealing structure for organic light emitting devices | | US6203898 | 29 aug 1997 | 20 mar 2001 | 3M Innovatave Properties Company | Article comprising a substrate having a silicone coating | | US6207238 | 16 dec 1998 | 27 mar 2001 | Battelle Memorial Institute | Plasma enhanced chemical deposition for high and/or low index of refraction polymers | | US6207239 | 16 dec 1998 | 27 mar 2001 | Battelle Memorial Institute | Plasma enhanced chemical deposition of conjugated polymer | | US6214422 | 8 okt 1998 | 10 apr 2001 | Sigma Laboratories Of Arizona, Inc. | Method of forming a hybrid polymer film | | US6217947 | 16 dec 1998 | 17 apr 2001 | Battelle Memorial Institute | Plasma enhanced polymer deposition onto fixtures | | US6224948 | 29 sep 1997 | 1 maj 2001 | Battelle Memorial Institute | Plasma enhanced chemical deposition with low vapor pressure compounds | | US6228434 | 16 dec 1998 | 8 maj 2001 | Battelle Memorial Institute | Method of making a conformal coating of a microtextured surface | | US6228436 | 16 dec 1998 | 8 maj 2001 | Battelle Memorial Institute | Method of making light emitting polymer composite material | | US6231939 | 30 aug 1996 | 15 maj 2001 | Presstek, Inc. | Acrylate composite barrier coating | | US6264747 | 4 aug 1999 | 24 jul 2001 | 3M Innovative Properties Company | Apparatus for forming multicolor interference coating | | US6268695 | 16 dec 1998 | 31 jul 2001 | Battelle Memorial Institute | Environmental barrier material for organic light emitting device and method of making | | US6274204 | 16 dec 1998 | 14 aug 2001 | Battelle Memorial Institute | Method of making non-linear optical polymer | | US6322860 | 2 nov 1998 | 27 nov 2001 | Rohm And Haas Company | Plastic substrates for electronic display applications | | US6333065 | 17 jul 1998 | 25 dec 2001 | Tdk Corporation | Process for the production of an organic electroluminescent device | | US6348237 | 12 jan 2001 | 19 feb 2002 | 3M Innovative Properties Company | Jet plasma process for deposition of coatings | | US6350034 | 10 apr 2000 | 26 feb 2002 | 3M Innovative Properties Company | Retroreflective articles having polymer multilayer reflective coatings | | US6352777 | 19 aug 1998 | 5 mar 2002 | The Trustees Of Princeton University | Organic photosensitive optoelectronic devices with transparent electrodes | | US6358570 | 31 mar 1999 | 19 mar 2002 | Battelle Memorial Institute | Vacuum deposition and curing of oligomers and resins | | US6361885 | 19 nov 1998 | 26 mar 2002 | Organic Display Technology | Organic electroluminescent materials and device made from such materials | | US6387732 | 18 jun 1999 | 14 maj 2002 | Micron 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 | | US6397776 | 11 jun 2001 | 4 jun 2002 | General Electric Company | Apparatus for large area chemical vapor deposition using multiple expanding thermal plasma generators | | US6413645 | 20 apr 2000 | 2 jul 2002 | Battelle Memorial Institute | Ultrabarrier substrates | | US6416872 | 30 aug 2000 | 9 jul 2002 | Cp Films, Inc. | Heat reflecting film with low visible reflectance | | US6420003 | 20 dec 2000 | 16 jul 2002 | 3M Innovative Properties Company | Acrylate composite barrier coating | | US6436544 | 14 jul 1998 | 20 aug 2002 | Toray Plastics Europe S.A. | Composite metal-coated polyester films with barrier properties | | US6460369 | 3 jan 2001 | 8 okt 2002 | Applied Materials, Inc. | Consecutive deposition system | | US6465953 | 12 jun 2000 | 15 okt 2002 | General Electric Company | Plastic substrates with improved barrier properties for devices sensitive to water and/or oxygen, such as organic electroluminescent devices | | US6468595 | 13 feb 2001 | 22 okt 2002 | Sigma Technologies International, Inc. | Vaccum deposition of cationic polymer systems | | US6492026 | 20 apr 2000 | 10 dec 2002 | Battelle Memorial Institute | Smoothing and barrier layers on high Tg substrates | | US6548912 | 15 maj 2000 | 15 apr 2003 | Battelle Memorial Institute | Semicoductor passivation using barrier coatings | | US6570325 | 22 jun 2001 | 27 maj 2003 | Battelle Memorial Institute | Environmental barrier material for organic light emitting device and method of making | | US6573652 | 20 apr 2000 | 3 jun 2003 | Battelle Memorial Institute | Encapsulated display devices | | US6720203 | 26 feb 2003 | 13 apr 2004 | E. I. Du Pont De Nemours And Company | Flexible organic electronic device with improved resistance to oxygen and moisture degradation | | US6923702 | 13 dec 2002 | 2 aug 2005 | Battelle Memorial Institute | Method of making encapsulated display devices | | BE704297A | | | | Ingen titel tillgänglig | | DE19603746A1 | | | | Ingen titel tillgänglig | | EP0299753A2 | 13 jul 1988 | 18 jan 1989 | The BOC Group, Inc. | Controlled flow vaporizer | | EP0340935A2 | 17 apr 1989 | 8 nov 1989 | SPECTRUM CONTROL, INC. (a Delaware corporation) | High speed process for coating substrates | | EP0390540A2 | 28 mar 1990 | 3 okt 1990 | Sharp Kabushiki Kaisha | Process for preparing an organic compound thin film for an optical device | | EP0547550A1 | 14 dec 1992 | 23 jun 1993 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing a chemically adsorbed film | | EP0590467A1 | 21 sep 1993 | 6 apr 1994 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Process for forming scratch-resistant silicon oxide layers on plastics by plasma-coating | | EP0722787A2 | 4 okt 1994 | 24 jul 1996 | Catalina Coatings, Inc. | Process for making an acrylate coating | | EP0787826A1 | 24 jan 1997 | 6 aug 1997 | Becton Dickinson and Company | Blood collection tube assembly | | EP0916394A2 | 12 nov 1998 | 19 maj 1999 | Sharp Corporation | Method of manufacturing modified particles and manufacturing device therefor | | EP0931850A1 | 13 nov 1998 | 28 jul 1999 | Leybold Systems GmbH | Method for treating the surfaces of plastic substrates | | EP0977469A2 | 30 jul 1999 | 2 feb 2000 | Hewlett-Packard Company | Improved transparent, flexible permeability barrier for organic electroluminescent devices | | JP8325713A | | | | Ingen titel tillgänglig | | JP63136316A | | | | Ingen titel tillgänglig |
| Hänvisning |
|---|
| 1 | Affinito, 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. | | 2 | Affinito, 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. | | 3 | Affinito, J. D., Energy Res. Abstr. 18(6), #17171, 1993. | | 4 | Affinito, 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. | | 5 | Affinito, J.D. et al., "Vacuum Deposition of Polymer Electrolytes on Flexible Susbtrates" The Ninth International Conference on Vacuum Web Coating, 1995, pp. 0-16. | | 6 | Affinito, 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. | | 7 | Affinito, 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. | | 8 | Affinito, 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. | | 9 | Affinito, 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. | | 10 | Affinito, J.D. et al.; A new method for fabricating transparent barrier layers, Thin Solid Films 290-291; 1996; pp. 63-67. | | 11 | Affinito, 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. | | 12 | Affinito, 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. | | 13 | Affinito, J.D. et al.; Polymer-Oxide Transparent Barrier Layers; SVC 39th Annual Technical Conference; Vacuum Web Coating Session; 1996; pp. 392-397. | | 14 | Affinito, 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. | | 15 | Affinito, 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. | | 16 | Affinito, J.D. et al.; Vacuum Deposited Polymer/Metal Multilayer Films for Optical Application; Thin Solid Films 270, 1995; pp. 43-48. | | 17 | Affinito, J.D. et al.; Vacuum Deposition of Polymer Electrolytes On Flexible Substrates, The Ninth International Conference on Vacuum Web Coating; pp. 20-37. | | 18 | Affinito, J.D., et al.; High Rate Vacuum Deposition of Polymer Electrolytes: Journal Vacuum Science Technology A 14(3), May/Jun. 1996. | | 19 | Affinito, 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. | | 21 | Akedo 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. | | 22 | Bright, 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. | | 23 | Bunshah, R. F. et al., "Deposition Technologies for Films and Coatings" Noyes Publications, Park Ridge, New Jersey, 1982, p. 339. | | 24 | Chahroudi, D.; Transparent Glass Barrier Coatings for Flexible Film Packaging; 1991; pp. 130-133; Society of Vacuum Coaters. | | 25 | Chwang et al., "Thin Film encapsulated flexible organic electroluminescent displays", American Institute of Physics, 2003. | | 26 | Clark I. Bright, et al., Transparent Barrier Coatings Based on ITO for Flexible Plastic Displays, Oct. 17-19, 1999, pp. 247-264, Tucson, Arizona. | | 27 | Czeremuszkin, G. et al.; Permeation Through Defects in Transparent Barrier Coated Plastic Films; 43rd Annual Technical Conference Proceedings; Apr. 15, 2000; pp. 408-413. | | 28 | De Gryse, R. et al., "Sputtered Transparent Barrier Layers," Tenth International Conference on Vacuum Web Coating, Nov. 1996, pp. 190-198. | | 29 | F.M. Penning; Electrical Discharges in Gases; 1965; pp. 1-51; Gordon and Breach, Science Publishers, New York-London-Paris. | | 30 | Felts, 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. | | 31 | Felts, J.T.; Transparent Barrier Coatings Update: Flexible Substrates; pp. 324-331. | | 32 | Finson, E. et al.; Transparent SiO2 Barrier Coatings: Conversion and Production Status; 1994; pp. 139-143; Society of Vacuum Coaters. | | 33 | G. Gustafason, et al.; Flexible light-emitting diodes made from soluble conducting polymers; Letters to Nature; vol. 357; Jun. 11, 1992; pp. 477-479. | | 34 | Graupner, W. et al.; "High Resolution Color Organic Light Emitting Diode Microdisplay Fabrication Method", SPIE Proceedings; Nov. 6, 2000; pp. 1-9. | | 35 | Henry, 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. | | 36 | Henry, 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. | | 37 | Hibino, 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. | | 38 | Hoffmann, 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. | | 40 | Klemberg-Sapieha, J.E. et al.; Transparent Gas Barrier Coatings Produced by Dual-Frequency PECVD; 1993; pp. 445-449; Society of Vacuum Coaters. | | 41 | Krug, T. et al.; New Developments in Transparent Barrier Coatings; 1993; pp. 302-305; Society Vacuum Coaters. | | 42 | Kukla, 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. | | 43 | Mahon, 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. | | 44 | Norenberg, 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. | | 47 | Phillips, 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. | | 48 | Shaw, 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. | | 49 | Shi, 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. | | 50 | Shi, 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. | | 51 | Tropsha 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. | | 52 | Tropsha 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. | | 53 | Vossen, 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. | | 54 | Wong, 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. | | 55 | Yamada, Y. et al.; The Properties of a New Transparent and Colorless Barrier Film; 1995; pp. 28-31; Society of Vacuum Coaters. | | 56 | Yializis, A. et al., Ultra High Barrier Films; Denver, Apr. 15-20, 2000, pp. 404-407; Society of Vacuum Coaters. | | 57 | Yializis, 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. |
| citeras i | Registreringsdatum | Publiceringsdatum | Sökande | Titel |
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| US7675074 | 12 jan 2007 | 9 mar 2010 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device including a lamination layer | | US8129715 | 2 mar 2010 | 6 mar 2012 | Semiconductor Energy Labratory Co., Ltd. | Light emitting device |
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