|Publication number||USRE40531 E1|
|Application number||US 10/890,437|
|Publication date||Oct 7, 2008|
|Filing date||Jul 12, 2004|
|Priority date||Oct 25, 1999|
|Also published as||US6413645, WO2001081649A1|
|Publication number||10890437, 890437, US RE40531 E1, US RE40531E1, US-E1-RE40531, USRE40531 E1, USRE40531E1|
|Inventors||Gordon Lee Graff, Mark Edward Gross, Ming Kun Shi, Michael Gene Hall, Peter Maclyn Martin, Eric Sidney Mast|
|Original Assignee||Battelle Memorial Institute|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (178), Non-Patent Citations (57), Referenced by (31), Classifications (22), Legal Events (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
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.
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.
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.
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 only one barrier stack is shown in
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.
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
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.
Native 7 mil PET
Teijin LCD film
*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.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2382432||Aug 2, 1940||Aug 14, 1945||Crown Cork & Seal Co||Method and apparatus for depositing vaporized metal coatings|
|US2384500||Jul 8, 1942||Sep 11, 1945||Crown Cork & Seal Co||Apparatus and method of coating|
|US3475307 *||Feb 4, 1965||Oct 28, 1969||Continental Can Co||Condensation of monomer vapors to increase polymerization rates in a glow discharge|
|US3607365 *||May 12, 1969||Sep 21, 1971||Minnesota Mining & Mfg||Vapor phase method of coating substrates with polymeric coating|
|US3941630 *||Apr 29, 1974||Mar 2, 1976||Rca Corporation||Method of fabricating a charged couple radiation sensing device|
|US4061835||Jun 25, 1976||Dec 6, 1977||Standard Oil Company (Indiana)||Process of forming a polypropylene coated substrate from an aqueous suspension of polypropylene particles|
|US4098965 *||Jun 27, 1977||Jul 4, 1978||Polaroid Corporation||Flat batteries and method of making the same|
|US4266223||Dec 8, 1978||May 5, 1981||W. H. Brady Co.||Thin panel display|
|US4283482 *||Mar 25, 1980||Aug 11, 1981||Nihon Shinku Gijutsu Kabushiki Kaisha||Dry Lithographic Process|
|US4313254||Aug 4, 1980||Feb 2, 1982||The Johns Hopkins University||Thin-film silicon solar cell with metal boride bottom electrode|
|US4426275||Nov 27, 1981||Jan 17, 1984||Deposition Technology, Inc.||Sputtering device adaptable for coating heat-sensitive substrates|
|US4521458||Apr 1, 1983||Jun 4, 1985||Nelson Richard C||Process for coating material with water resistant composition|
|US4537814||Jan 26, 1984||Aug 27, 1985||Toyoda Gosei Co., Ltd.||Resin article having a ceramics coating layer|
|US4555274||Jun 7, 1984||Nov 26, 1985||Fuji Photo Film Co., Ltd.||Ion selective electrode and process of preparing the same|
|US4557978||Dec 12, 1983||Dec 10, 1985||Primary Energy Research Corporation||Electroactive polymeric thin films|
|US4572842||Aug 24, 1984||Feb 25, 1986||Leybold-Heraeus Gmbh||Method and apparatus for reactive vapor deposition of compounds of metal and semi-conductors|
|US4581337 *||Jul 7, 1983||Apr 8, 1986||E. I. Du Pont De Nemours And Company||Polyether polyamines as linking agents for particle reagents useful in immunoassays|
|US4624867 *||Mar 21, 1985||Nov 25, 1986||Nihon Shinku Gijutsu Kabushiki Kaisha||Process for forming a synthetic resin film on a substrate and apparatus therefor|
|US4695618 *||May 23, 1986||Sep 22, 1987||Ameron, Inc.||Solventless polyurethane spray compositions and method for applying them|
|US4710426||Nov 28, 1983||Dec 1, 1987||Polaroid Corporation, Patent Dept.||Solar radiation-control articles with protective overlayer|
|US4722515||Apr 8, 1986||Feb 2, 1988||Spectrum Control, Inc.||Atomizing device for vaporization|
|US4768666||May 26, 1987||Sep 6, 1988||Milton Kessler||Tamper proof container closure|
|US4842893 *||Apr 29, 1988||Jun 27, 1989||Spectrum Control, Inc.||High speed process for coating substrates|
|US4843036||Jun 29, 1987||Jun 27, 1989||Eastman Kodak Company||Method for encapsulating electronic devices|
|US4855186||Feb 23, 1988||Aug 8, 1989||Hoechst Aktiengesellschaft||Coated plastic film and plastic laminate prepared therefrom|
|US4889609||Sep 6, 1988||Dec 26, 1989||Ovonic Imaging Systems, Inc.||Continuous dry etching system|
|US4913090||Sep 20, 1988||Apr 3, 1990||Mitsubishi Denki Kabushiki Kaisha||Chemical vapor deposition apparatus having cooling heads adjacent to gas dispersing heads in a single chamber|
|US4931158||Aug 8, 1989||Jun 5, 1990||The Regents Of The Univ. Of Calif.||Deposition of films onto large area substrates using modified reactive magnetron sputtering|
|US4934315||Oct 19, 1988||Jun 19, 1990||Alcatel N.V.||System for producing semicondutor layer structures by way of epitaxial growth|
|US4954371 *||Jul 7, 1987||Sep 4, 1990||Spectrum Control, Inc.||Flash evaporation of monomer fluids|
|US4977013||Jun 3, 1988||Dec 11, 1990||Andus Corporation||Tranparent conductive coatings|
|US5032461 *||Oct 12, 1990||Jul 16, 1991||Spectrum Control, Inc.||Method of making a multi-layered article|
|US5036249 *||Dec 11, 1989||Jul 30, 1991||Molex Incorporated||Electroluminescent lamp panel and method of fabricating same|
|US5047131||Nov 8, 1989||Sep 10, 1991||The Boc Group, Inc.||Method for coating substrates with silicon based compounds|
|US5059861||Jul 26, 1990||Oct 22, 1991||Eastman Kodak Company||Organic electroluminescent device with stabilizing cathode capping layer|
|US5124204 *||Mar 29, 1991||Jun 23, 1992||Sharp Kabushiki Kaisha||Thin film electroluminescent (EL) panel|
|US5189405 *||Dec 23, 1991||Feb 23, 1993||Sharp Kabushiki Kaisha||Thin film electroluminescent panel|
|US5203898||Dec 16, 1991||Apr 20, 1993||Corning Incorporated||Method of making fluorine/boron doped silica tubes|
|US5204314||Dec 13, 1991||Apr 20, 1993||Advanced Technology Materials, Inc.||Method for delivering an involatile reagent in vapor form to a CVD reactor|
|US5237439 *||Sep 30, 1992||Aug 17, 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 *||Aug 21, 1992||Nov 9, 1993||Battelle Memorial Institute||Vacuum deposition and curing of liquid monomers|
|US5336324||Dec 4, 1991||Aug 9, 1994||Emcore Corporation||Apparatus for depositing a coating on a substrate|
|US5354497 *||Apr 19, 1993||Oct 11, 1994||Sharp Kabushiki Kaisha||Liquid crystal display|
|US5356947||Oct 29, 1992||Oct 18, 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||Jan 8, 1993||Feb 28, 1995||Mitsui Toatsu Chemiclas, Inc.||Laminated transparent plastic material and polymerizable monomer|
|US5395644 *||Aug 2, 1993||Mar 7, 1995||Battelle Memorial Institute||Vacuum deposition and curing of liquid monomers|
|US5402314||Feb 3, 1993||Mar 28, 1995||Sony Corporation||Printed circuit board having through-hole stopped with photo-curable solder resist|
|US5427638 *||Dec 3, 1993||Jun 27, 1995||Alliedsignal Inc.||Low temperature reaction bonding|
|US5440446 *||Oct 4, 1993||Aug 8, 1995||Catalina Coatings, Inc.||Acrylate coating material|
|US5451449||May 11, 1994||Sep 19, 1995||The Mearl Corporation||Colored iridescent film|
|US5461545||Sep 13, 1994||Oct 24, 1995||Thomson-Csf||Process and device for hermetic encapsulation of electronic components|
|US5464667||Aug 16, 1994||Nov 7, 1995||Minnesota Mining And Manufacturing Company||Jet plasma process and apparatus|
|US5510173||Aug 20, 1993||Apr 23, 1996||Southwall Technologies Inc.||Multiple layer thin films with improved corrosion resistance|
|US5512320||Apr 13, 1994||Apr 30, 1996||Applied Materials, Inc.||Vacuum processing apparatus having improved throughput|
|US5536323 *||Jul 25, 1994||Jul 16, 1996||Advanced Technology Materials, Inc.||Apparatus for flash vaporization delivery of reagents|
|US5547508 *||Nov 17, 1994||Aug 20, 1996||Battelle Memorial Institute||Vacuum deposition and curing of liquid monomers apparatus|
|US5554220 *||May 19, 1995||Sep 10, 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 *||Apr 12, 1995||Nov 19, 1996||Bridgestone Corporation||Gas barrier rubber laminate for minimizing refrigerant leakage|
|US5578141||Jul 1, 1994||Nov 26, 1996||Canon Kabushiki Kaisha||Solar cell module having excellent weather resistance|
|US5607789 *||Jan 23, 1995||Mar 4, 1997||Duracell Inc.||Light transparent multilayer moisture barrier for electrochemical cell tester and cell employing same|
|US5620524 *||Feb 27, 1995||Apr 15, 1997||Fan; Chiko||Apparatus for fluid delivery in chemical vapor deposition systems|
|US5629389 *||Jun 6, 1995||May 13, 1997||Hewlett-Packard Company||Polymer-based electroluminescent device with improved stability|
|US5652192||Mar 28, 1995||Jul 29, 1997||Battelle Memorial Institute||Catalyst material and method of making|
|US5654084 *||Jul 22, 1994||Aug 5, 1997||Martin Marietta Energy Systems, Inc.||Protective coatings for sensitive materials|
|US5660961||Jan 11, 1996||Aug 26, 1997||Xerox Corporation||Electrophotographic imaging member having enhanced layer adhesion and freedom from reflection interference|
|US5665280||Oct 2, 1996||Sep 9, 1997||Becton Dickinson Co||Blood collection tube assembly|
|US5681615 *||Jul 27, 1995||Oct 28, 1997||Battelle Memorial Institute||Vacuum flash evaporated polymer composites|
|US5681666 *||Aug 8, 1996||Oct 28, 1997||Duracell Inc.||Light transparent multilayer moisture barrier for electrochemical celltester and cell employing same|
|US5684084 *||Dec 21, 1995||Nov 4, 1997||E. I. Du Pont De Nemours And Company||Coating containing acrylosilane polymer to improve mar and acid etch resistance|
|US5686360 *||Nov 30, 1995||Nov 11, 1997||Motorola||Passivation of organic devices|
|US5693956 *||Jul 29, 1996||Dec 2, 1997||Motorola||Inverted oleds on hard plastic substrate|
|US5695564||Aug 3, 1995||Dec 9, 1997||Tokyo Electron Limited||Semiconductor processing system|
|US5711816 *||Jun 7, 1995||Jan 27, 1998||Advanced Technolgy Materials, Inc.||Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same|
|US5725909||Feb 9, 1996||Mar 10, 1998||Catalina Coatings, Inc.||Acrylate composite barrier coating process|
|US5731661 *||Jul 15, 1996||Mar 24, 1998||Motorola, Inc.||Passivation of electroluminescent organic devices|
|US5736207||Oct 27, 1995||Apr 7, 1998||Schott Glaswerke||Vessel of plastic having a barrier coating and a method of producing the vessel|
|US5747182 *||Jul 26, 1993||May 5, 1998||Cambridge Display Technology Limited||Manufacture of electroluminescent devices|
|US5757126 *||Jun 30, 1997||May 26, 1998||Motorola, Inc.||Passivated organic device having alternating layers of polymer and dielectric|
|US5759329 *||Jun 24, 1994||Jun 2, 1998||Pilot Industries, Inc.||Fluoropolymer composite tube and method of preparation|
|US5771177||May 16, 1994||Jun 23, 1998||Kyoei Automatic Control Technology Co., Ltd.||Method and apparatus for measuring dynamic load|
|US5771562 *||May 2, 1995||Jun 30, 1998||Motorola, Inc.||Passivation of organic devices|
|US5782355||Nov 12, 1997||Jul 21, 1998||Fuji Photo Film Co., Ltd.||Cassette case|
|US5792550 *||Apr 28, 1995||Aug 11, 1998||Flex Products, Inc.||Barrier film having high colorless transparency and method|
|US5795399||Jun 29, 1995||Aug 18, 1998||Kabushiki Kaisha Toshiba||Semiconductor device manufacturing apparatus, method for removing reaction product, and method of suppressing deposition of reaction product|
|US5811177 *||Nov 30, 1995||Sep 22, 1998||Motorola, Inc.||Passivation of electroluminescent organic devices|
|US5811183 *||Aug 11, 1995||Sep 22, 1998||Shaw; David G.||Acrylate polymer release coated sheet materials and method of production thereof|
|US5821692 *||Nov 26, 1996||Oct 13, 1998||Motorola, Inc.||Organic electroluminescent device hermetic encapsulation package|
|US5844363 *||Jan 23, 1997||Dec 1, 1998||The Trustees Of Princeton Univ.||Vacuum deposited, non-polymeric flexible organic light emitting devices|
|US5869791||Mar 1, 1996||Feb 9, 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 *||Apr 9, 1997||Feb 16, 1999||Hewlett-Packard Company||Electroluminescent device and fabrication method for a light detection system|
|US5891554||Sep 15, 1997||Apr 6, 1999||Idemitsu Kosan Co., Ltd.||Organic electroluminescence device|
|US5895228||Mar 20, 1997||Apr 20, 1999||International Business Machines Corporation||Encapsulation of organic light emitting devices using Siloxane or Siloxane derivatives|
|US5902641 *||Sep 29, 1997||May 11, 1999||Battelle Memorial Institute||Flash evaporation of liquid monomer particle mixture|
|US5902688 *||Jul 16, 1996||May 11, 1999||Hewlett-Packard Company||Electroluminescent display device|
|US5904958 *||Mar 20, 1998||May 18, 1999||Rexam Industries Corp.||Adjustable nozzle for evaporation or organic monomers|
|US5912069 *||Dec 19, 1996||Jun 15, 1999||Sigma Laboratories Of Arizona||Metal nanolaminate composite|
|US5919328||Jun 18, 1997||Jul 6, 1999||Becton Dickinson And Company||Blood collection tube assembly|
|US5920080||May 8, 1998||Jul 6, 1999||Fed Corporation||Emissive display using organic light emitting diodes|
|US5922161 *||Jun 28, 1996||Jul 13, 1999||Commonwealth Scientific And Industrial Research Organisation||Surface treatment of polymers|
|US5929562||Apr 18, 1996||Jul 27, 1999||Cambridge Display Technology Limited||Organic light-emitting devices|
|US5934856||Apr 28, 1997||Aug 10, 1999||Tokyo Electron Limited||Multi-chamber treatment system|
|US5945174 *||Jul 1, 1998||Aug 31, 1999||Delta V Technologies, Inc.||Acrylate polymer release coated sheet materials and method of production thereof|
|US5948552 *||Aug 27, 1996||Sep 7, 1999||Hewlett-Packard Company||Heat-resistant organic electroluminescent device|
|US5952778 *||Mar 18, 1997||Sep 14, 1999||International Business Machines Corporation||Encapsulated organic light emitting device|
|US5955161||Jan 30, 1996||Sep 21, 1999||Becton Dickinson And Company||Blood collection tube assembly|
|US5965907 *||Sep 29, 1997||Oct 12, 1999||Motorola, Inc.||Full color organic light emitting backlight device for liquid crystal display applications|
|US5968620||Oct 22, 1997||Oct 19, 1999||Becton Dickinson And Company||Blood collection tube assembly|
|US5994174||Sep 29, 1997||Nov 30, 1999||The Regents Of The University Of California||Method of fabrication of display pixels driven by silicon thin film transistors|
|US5996498 *||Jul 24, 1998||Dec 7, 1999||Presstek, Inc.||Method of lithographic imaging with reduced debris-generated performance degradation and related constructions|
|US6013337||Mar 25, 1997||Jan 11, 2000||Becton Dickinson And Company||Blood collection tube assembly|
|US6040017||Oct 2, 1998||Mar 21, 2000||Sigma Laboratories, Inc.||Formation of multilayered photonic polymer composites|
|US6045864 *||Dec 1, 1997||Apr 4, 2000||3M Innovative Properties Company||Vapor coating method|
|US6066826||Mar 16, 1998||May 23, 2000||Yializis; Angelo||Apparatus for plasma treatment of moving webs|
|US6083313||Jul 27, 1999||Jul 4, 2000||Advanced Refractory Technologies, Inc.||Hardcoats for flat panel display substrates|
|US6083628 *||Apr 4, 1996||Jul 4, 2000||Sigma Laboratories Of Arizona, Inc.||Hybrid polymer film|
|US6084702||Oct 15, 1998||Jul 4, 2000||Pleotint, L.L.C.||Thermochromic devices|
|US6087007||Sep 30, 1994||Jul 11, 2000||Kanegafuchi Kagaku Kogyo Kabushiki Kaisha||Heat-Resistant optical plastic laminated sheet and its producing method|
|US6092269||Mar 20, 1998||Jul 25, 2000||Sigma Laboratories Of Arizona, Inc.||High energy density capacitor|
|US6106627||Apr 4, 1996||Aug 22, 2000||Sigma Laboratories Of Arizona, Inc.||Apparatus for producing metal coated polymers|
|US6117266||Apr 22, 1998||Sep 12, 2000||Interuniversifair Micro-Elektronica Cenirum (Imec Vzw)||Furnace for continuous, high throughput diffusion processes from various diffusion sources|
|US6118218||Feb 1, 1999||Sep 12, 2000||Sigma Technologies International, Inc.||Steady-state glow-discharge plasma at atmospheric pressure|
|US6137221||Jul 8, 1998||Oct 24, 2000||Agilent Technologies, Inc.||Organic electroluminescent device with full color characteristics|
|US6146225 *||Jul 30, 1998||Nov 14, 2000||Agilent Technologies, Inc.||Transparent, flexible permeability barrier for organic electroluminescent devices|
|US6146462||May 7, 1999||Nov 14, 2000||Astenjohnson, Inc.||Structures and components thereof having a desired surface characteristic together with methods and apparatuses for producing the same|
|US6150187||Jul 27, 1998||Nov 21, 2000||Electronics And Telecommunications Research Institute||Encapsulation method of a polymer or organic light emitting device|
|US6165566||Jun 10, 1999||Dec 26, 2000||Becton Dickinson And Company||Method for depositing a multilayer barrier coating on a plastic substrate|
|US6178082 *||Feb 26, 1998||Jan 23, 2001||International Business Machines Corporation||High temperature, conductive thin film diffusion barrier for ceramic/metal systems|
|US6195142||Dec 24, 1996||Feb 27, 2001||Matsushita Electrical Industrial Company, Ltd.||Organic electroluminescence element, its manufacturing method, and display device using organic electroluminescence element|
|US6198217||May 8, 1998||Mar 6, 2001||Matsushita Electric Industrial Co., Ltd.||Organic electroluminescent device having a protective covering comprising organic and inorganic layers|
|US6198220||May 8, 1998||Mar 6, 2001||Emagin Corporation||Sealing structure for organic light emitting devices|
|US6203898||Aug 29, 1997||Mar 20, 2001||3M Innovatave Properties Company||Article comprising a substrate having a silicone coating|
|US6207238||Dec 16, 1998||Mar 27, 2001||Battelle Memorial Institute||Plasma enhanced chemical deposition for high and/or low index of refraction polymers|
|US6207239||Dec 16, 1998||Mar 27, 2001||Battelle Memorial Institute||Plasma enhanced chemical deposition of conjugated polymer|
|US6214422||Oct 8, 1998||Apr 10, 2001||Sigma Laboratories Of Arizona, Inc.||Method of forming a hybrid polymer film|
|US6217947||Dec 16, 1998||Apr 17, 2001||Battelle Memorial Institute||Plasma enhanced polymer deposition onto fixtures|
|US6224948||Sep 29, 1997||May 1, 2001||Battelle Memorial Institute||Plasma enhanced chemical deposition with low vapor pressure compounds|
|US6228434||Dec 16, 1998||May 8, 2001||Battelle Memorial Institute||Method of making a conformal coating of a microtextured surface|
|US6228436||Dec 16, 1998||May 8, 2001||Battelle Memorial Institute||Method of making light emitting polymer composite material|
|US6231939||Aug 30, 1996||May 15, 2001||Presstek, Inc.||Acrylate composite barrier coating|
|US6264747||Aug 4, 1999||Jul 24, 2001||3M Innovative Properties Company||Apparatus for forming multicolor interference coating|
|US6268695||Dec 16, 1998||Jul 31, 2001||Battelle Memorial Institute||Environmental barrier material for organic light emitting device and method of making|
|US6274204||Dec 16, 1998||Aug 14, 2001||Battelle Memorial Institute||Method of making non-linear optical polymer|
|US6322860||Nov 2, 1998||Nov 27, 2001||Rohm And Haas Company||Plastic substrates for electronic display applications|
|US6333065||Jul 17, 1998||Dec 25, 2001||Tdk Corporation||Process for the production of an organic electroluminescent device|
|US6348237||Jan 12, 2001||Feb 19, 2002||3M Innovative Properties Company||Jet plasma process for deposition of coatings|
|US6350034||Apr 10, 2000||Feb 26, 2002||3M Innovative Properties Company||Retroreflective articles having polymer multilayer reflective coatings|
|US6352777||Aug 19, 1998||Mar 5, 2002||The Trustees Of Princeton University||Organic photosensitive optoelectronic devices with transparent electrodes|
|US6358570||Mar 31, 1999||Mar 19, 2002||Battelle Memorial Institute||Vacuum deposition and curing of oligomers and resins|
|US6361885||Nov 19, 1998||Mar 26, 2002||Organic Display Technology||Organic electroluminescent materials and device made from such materials|
|US6387732||Jun 18, 1999||May 14, 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||Jun 11, 2001||Jun 4, 2002||General Electric Company||Apparatus for large area chemical vapor deposition using multiple expanding thermal plasma generators|
|US6413645||Apr 20, 2000||Jul 2, 2002||Battelle Memorial Institute||Ultrabarrier substrates|
|US6416872||Aug 30, 2000||Jul 9, 2002||Cp Films, Inc.||Heat reflecting film with low visible reflectance|
|US6420003||Dec 20, 2000||Jul 16, 2002||3M Innovative Properties Company||Acrylate composite barrier coating|
|US6436544||Jul 14, 1998||Aug 20, 2002||Toray Plastics Europe S.A.||Composite metal-coated polyester films with barrier properties|
|US6460369||Jan 3, 2001||Oct 8, 2002||Applied Materials, Inc.||Consecutive deposition system|
|US6465953||Jun 12, 2000||Oct 15, 2002||General Electric Company||Plastic substrates with improved barrier properties for devices sensitive to water and/or oxygen, such as organic electroluminescent devices|
|US6468595||Feb 13, 2001||Oct 22, 2002||Sigma Technologies International, Inc.||Vaccum deposition of cationic polymer systems|
|US6492026 *||Apr 20, 2000||Dec 10, 2002||Battelle Memorial Institute||Smoothing and barrier layers on high Tg substrates|
|US6548912 *||May 15, 2000||Apr 15, 2003||Battelle Memorial Institute||Semicoductor passivation using barrier coatings|
|US6570325 *||Jun 22, 2001||May 27, 2003||Battelle Memorial Institute||Environmental barrier material for organic light emitting device and method of making|
|US6573652 *||Apr 20, 2000||Jun 3, 2003||Battelle Memorial Institute||Encapsulated display devices|
|US6720203 *||Feb 26, 2003||Apr 13, 2004||E. I. Du Pont De Nemours And Company||Flexible organic electronic device with improved resistance to oxygen and moisture degradation|
|US6923702 *||Dec 13, 2002||Aug 2, 2005||Battelle Memorial Institute||Method of making encapsulated display devices|
|BE704297A *||Title not available|
|DE19603746A1 *||Feb 2, 1996||Apr 24, 1997||Bosch Gmbh Robert||Elektrolumineszierendes Schichtsystem|
|EP0299753A2 *||Jul 13, 1988||Jan 18, 1989||The BOC Group, Inc.||Controlled flow vaporizer|
|EP0340935A2 *||Apr 17, 1989||Nov 8, 1989||SPECTRUM CONTROL, INC. (a Delaware corporation)||High speed process for coating substrates|
|EP0390540A2 *||Mar 28, 1990||Oct 3, 1990||Sharp Kabushiki Kaisha||Process for preparing an organic compound thin film for an optical device|
|EP0547550A1 *||Dec 14, 1992||Jun 23, 1993||Matsushita Electric Industrial Co., Ltd.||Method of manufacturing a chemically adsorbed film|
|EP0590467A1 *||Sep 21, 1993||Apr 6, 1994||Röhm Gmbh||Process for forming scratch-resistant silicon oxide layers on plastics by plasma-coating|
|EP0722787A2 *||Oct 4, 1994||Jul 24, 1996||Catalina Coatings, Inc.||Process for making an acrylate coating|
|EP0787826A1 *||Jan 24, 1997||Aug 6, 1997||Becton Dickinson and Company||Blood collection tube assembly|
|EP0916394A2 *||Nov 12, 1998||May 19, 1999||Sharp Corporation||Method of manufacturing modified particles and manufacturing device therefor|
|EP0931850A1 *||Nov 13, 1998||Jul 28, 1999||Leybold Systems GmbH||Method for treating the surfaces of plastic substrates|
|EP0977469A2 *||Jul 30, 1999||Feb 2, 2000||Hewlett-Packard Company||Improved transparent, flexible permeability barrier for organic electroluminescent devices|
|JPH08325713A *||Title not available|
|JPS63136316A *||Title not available|
|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.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US7675074||Jan 12, 2007||Mar 9, 2010||Semiconductor Energy Laboratory Co., Ltd.||Light emitting device including a lamination layer|
|US7959769||Jun 14, 2011||Infinite Power Solutions, Inc.||Deposition of LiCoO2|
|US7985188||May 12, 2010||Jul 26, 2011||Cv Holdings Llc||Vessel, coating, inspection and processing apparatus|
|US7993773||Aug 21, 2009||Aug 9, 2011||Infinite Power Solutions, Inc.||Electrochemical apparatus with barrier layer protected substrate|
|US8021778||Aug 23, 2005||Sep 20, 2011||Infinite Power Solutions, Inc.||Electrochemical apparatus with barrier layer protected substrate|
|US8062708||Sep 26, 2007||Nov 22, 2011||Infinite Power Solutions, Inc.||Masking of and material constraint for depositing battery layers on flexible substrates|
|US8129715||Mar 2, 2010||Mar 6, 2012||Semiconductor Energy Labratory Co., Ltd.||Light emitting device|
|US8197781||Nov 5, 2007||Jun 12, 2012||Infinite Power Solutions, Inc.||Sputtering target of Li3PO4 and method for producing same|
|US8236443||Mar 16, 2007||Aug 7, 2012||Infinite Power Solutions, Inc.||Metal film encapsulation|
|US8260203||Sep 10, 2009||Sep 4, 2012||Infinite Power Solutions, Inc.||Energy device with integral conductive surface for data communication via electromagnetic energy and method thereof|
|US8268488||Jan 23, 2009||Sep 18, 2012||Infinite Power Solutions, Inc.||Thin film electrolyte for thin film batteries|
|US8350519||Apr 2, 2009||Jan 8, 2013||Infinite Power Solutions, Inc||Passive over/under voltage control and protection for energy storage devices associated with energy harvesting|
|US8394522||Apr 29, 2008||Mar 12, 2013||Infinite Power Solutions, Inc.||Robust metal film encapsulation|
|US8404376||Apr 21, 2010||Mar 26, 2013||Infinite Power Solutions, Inc.||Metal film encapsulation|
|US8431264||Jul 25, 2008||Apr 30, 2013||Infinite Power Solutions, Inc.||Hybrid thin-film battery|
|US8445130||Nov 17, 2006||May 21, 2013||Infinite Power Solutions, Inc.||Hybrid thin-film battery|
|US8476623||Feb 28, 2012||Jul 2, 2013||Semiconductor Energy Laboratory Co., Ltd.||Light emitting device|
|US8508193||Oct 7, 2009||Aug 13, 2013||Infinite Power Solutions, Inc.||Environmentally-powered wireless sensor module|
|US8512796||Jun 27, 2011||Aug 20, 2013||Si02 Medical Products, Inc.||Vessel inspection apparatus and methods|
|US8518581||Jan 9, 2009||Aug 27, 2013||Inifinite Power Solutions, Inc.||Thin film encapsulation for thin film batteries and other devices|
|US8535396||Aug 21, 2009||Sep 17, 2013||Infinite Power Solutions, Inc.||Electrochemical apparatus with barrier layer protected substrate|
|US8599572||Sep 1, 2010||Dec 3, 2013||Infinite Power Solutions, Inc.||Printed circuit board with integrated thin film battery|
|US8636876||Dec 7, 2005||Jan 28, 2014||R. Ernest Demaray||Deposition of LiCoO2|
|US8659012||Jul 1, 2013||Feb 25, 2014||Semiconductor Energy Laboratory Co., Ltd.||Light emitting device|
|US8728285||May 20, 2004||May 20, 2014||Demaray, Llc||Transparent conductive oxides|
|US8834954||Jul 12, 2013||Sep 16, 2014||Sio2 Medical Products, Inc.||Vessel inspection apparatus and methods|
|US8906523||Aug 11, 2009||Dec 9, 2014||Infinite Power Solutions, Inc.||Energy device with integral collector surface for electromagnetic energy harvesting and method thereof|
|US9118025||Jan 29, 2014||Aug 25, 2015||Semiconductor Energy Laboratory Co., Ltd.||Light emitting device|
|US20080305360 *||Jun 5, 2008||Dec 11, 2008||Dong-Won Han||Organic light emitting device and method of manufacturing the same|
|US20100156287 *||Mar 2, 2010||Jun 24, 2010||Semiconductor Energy Laboratory Co., Ltd.||Light emitting device|
|US20150158762 *||Dec 5, 2013||Jun 11, 2015||Intermolecular Inc.||Simplified Protection Layer for Abrasion Resistant Glass Coatings and Methods for Forming the Same|
|U.S. Classification||428/446, 428/688, 428/411.1, 428/500, 428/457, 428/469, 426/126, 428/690|
|International Classification||H01L51/52, C23C14/08, B32B27/00, B32B15/04|
|Cooperative Classification||H01L51/5256, G02F2201/50, Y10T428/31678, Y10T428/31855, Y10T428/31504, C23C14/08, B32B27/00|
|European Classification||H01L51/52C4B, C23C14/08, B32B27/00|
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