Ultrabarrier substrates

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.

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Description

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

BACKGROUND OF THE INVENTION

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

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

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

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

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

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

SUMMARY OF THE INVENTION

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

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

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

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

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

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

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

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

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

BRIEF DESCRIPTION OF THE DRAWINGS

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

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

 DESCRIPTION OF THE INVENTION

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Claims

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.

Referenced Cited
U.S. Patent Documents
2382432 August 1945 McManus et al.
2384500 September 1945 Stoll
3475307 October 1969 Teumer et al.
3607365 September 1971 Lindlof
3941630 March 2, 1976 Larrabee
4061835 December 6, 1977 Poppe et al.
4098965 July 4, 1978 Kinsman
4266223 May 5, 1981 Frame
4283482 August 11, 1981 Hattori et al.
4313254 February 2, 1982 Feldman et al.
4426275 January 17, 1984 Meckel et al.
4521458 June 4, 1985 Nelson
4537814 August 27, 1985 Itoh et al.
4555274 November 26, 1985 Kitajima et al.
4557978 December 10, 1985 Mason
4572842 February 25, 1986 Dietrich et al.
4581337 April 8, 1986 Frey et al.
4624867 November 25, 1986 Iijima et al.
4695618 September 22, 1987 Mowrer
4710426 December 1, 1987 Stephens
4722515 February 2, 1988 Ham
4768666 September 6, 1988 Kessler
4842893 June 27, 1989 Yializis et al.
4843036 June 27, 1989 Schmidt et al.
4855186 August 8, 1989 Grolig et al.
4889609 December 26, 1989 Cannella
4913090 April 3, 1990 Harada et al.
4931158 June 5, 1990 Bunshah et al.
4934315 June 19, 1990 Linnebach et al.
4954371 September 4, 1990 Yializis
4977013 December 11, 1990 Ritchie et al.
5032461 July 16, 1991 Shaw et al.
5036249 July 30, 1991 Pike-Biegunski et al.
5047131 September 10, 1991 Wolfe et al.
5059861 October 22, 1991 Littman et al.
5124204 June 23, 1992 Yamashita et al.
5189405 February 23, 1993 Yamashita et al.
5203898 April 20, 1993 Carpenter et al.
5204314 April 20, 1993 Kirlin et al.
5237439 August 17, 1993 Misono et al.
5260095 November 9, 1993 Affinito
5336324 August 9, 1994 Stall et al.
5354497 October 11, 1994 Fukuchi et al.
5356947 October 18, 1994 Ali et al.
5393607 February 28, 1995 Kawasaki et al.
5395644 March 7, 1995 Affinito
5402314 March 28, 1995 Amago et al.
5427638 June 27, 1995 Goetz et al.
5440446 August 8, 1995 Shaw et al.
5451449 September 19, 1995 Shetty et al.
5461545 October 24, 1995 Leroy et al.
5464667 November 7, 1995 Kohler et al.
5510173 April 23, 1996 Pass et al.
5512320 April 30, 1996 Turner et al.
5536323 July 16, 1996 Kirlin et al.
5547508 August 20, 1996 Affinito
5554220 September 10, 1996 Forrest et al.
5576101 November 19, 1996 Saitoh et al.
5578141 November 26, 1996 Mori et al.
5607789 March 4, 1997 Treger et al.
5620524 April 15, 1997 Fan et al.
5629389 May 13, 1997 Roitman et al.
5652192 July 29, 1997 Matson et al.
5654084 August 5, 1997 Egert
5660961 August 26, 1997 Yu
5665280 September 9, 1997 Tropsha
5681615 October 28, 1997 Affinito et al.
5681666 October 28, 1997 Treger et al.
5684084 November 4, 1997 Lewin et al.
5686360 November 11, 1997 Harvey et al.
5693956 December 2, 1997 Shi et al.
5695564 December 9, 1997 Imahashi
5711816 January 27, 1998 Kirlin et al.
5725909 March 10, 1998 Shaw et al.
5731661 March 24, 1998 So et al.
5736207 April 7, 1998 Walther et al.
5747182 May 5, 1998 Friend et al.
5757126 May 26, 1998 Harvey et al.
5759329 June 2, 1998 Krause et al.
5771177 June 23, 1998 Tada et al.
5771562 June 30, 1998 Harvey, III et al.
5782355 July 21, 1998 Katagiri et al.
5792550 August 11, 1998 Phillips et al.
5795399 August 18, 1998 Hasegawa et al.
5811177 September 22, 1998 Shi et al.
5811183 September 22, 1998 Shaw et al.
5821692 October 13, 1998 Rogers et al.
5844363 December 1, 1998 Gu et al.
5869791 February 9, 1999 Young
5872355 February 16, 1999 Hueschen
5891554 April 6, 1999 Hosokawa et al.
5895228 April 20, 1999 Biebuyck et al.
5902641 May 11, 1999 Affinito et al.
5902688 May 11, 1999 Antoniadis et al.
5904958 May 18, 1999 Dick et al.
5912069 June 15, 1999 Yializis et al.
5919328 July 6, 1999 Tropsha et al.
5920080 July 6, 1999 Jones
5922161 July 13, 1999 Wu et al.
5929562 July 27, 1999 Pichler
5934856 August 10, 1999 Asakawa et al.
5945174 August 31, 1999 Shaw et al.
5948552 September 7, 1999 Antoniadis et al.
5952778 September 14, 1999 Haskal et al.
5955161 September 21, 1999 Tropsha
5965907 October 12, 1999 Huang et al.
5968620 October 19, 1999 Harvey et al.
5994174 November 30, 1999 Carey et al.
5996498 December 7, 1999 Lewis
6013337 January 11, 2000 Knors
6040017 March 21, 2000 Mikhael et al.
6045864 April 4, 2000 Lyons et al.
6066826 May 23, 2000 Yializis
6083313 July 4, 2000 Venkatraman et al.
6083628 July 4, 2000 Yializis
6084702 July 4, 2000 Byker et al.
6087007 July 11, 2000 Fujii et al.
6092269 July 25, 2000 Yializis et al.
6106627 August 22, 2000 Yializis et al.
6117266 September 12, 2000 Horzel et al.
6118218 September 12, 2000 Yializis et al.
6137221 October 24, 2000 Roitman et al.
6146225 November 14, 2000 Sheets et al.
6146462 November 14, 2000 Yializis et al.
6150187 November 21, 2000 Zyung et al.
6165566 December 26, 2000 Tropsha
6178082 January 23, 2001 Farooq et al.
6195142 February 27, 2001 Gyotoku et al.
6198217 March 6, 2001 Suzuki et al.
6198220 March 6, 2001 Jones et al.
6203898 March 20, 2001 Kohler et al.
6207238 March 27, 2001 Affinito
6207239 March 27, 2001 Affinito
6214422 April 10, 2001 Yializis
6217947 April 17, 2001 Affinito
6224948 May 1, 2001 Affinito
6228434 May 8, 2001 Affinito
6228436 May 8, 2001 Affinito
6231939 May 15, 2001 Shaw et al.
6264747 July 24, 2001 Shaw et al.
6268695 July 31, 2001 Affinito
6274204 August 14, 2001 Affinito
6322860 November 27, 2001 Stein et al.
6333065 December 25, 2001 Arai et al.
6348237 February 19, 2002 Kohler et al.
6350034 February 26, 2002 Fleming et al.
6352777 March 5, 2002 Bulovic et al.
6358570 March 19, 2002 Affinito
6361885 March 26, 2002 Chou
6387732 May 14, 2002 Akram
6397776 June 4, 2002 Yang et al.
6413645 July 2, 2002 Graff et al.
6416872 July 9, 2002 Maschwitz
6420003 July 16, 2002 Shaw et al.
6436544 August 20, 2002 Veyrat et al.
6460369 October 8, 2002 Hosokawa
6465953 October 15, 2002 Duggal
6468595 October 22, 2002 Mikhael et al.
6469437 October 22, 2002 Parthasarathy et al.
6492026 December 10, 2002 Graff et al.
6497598 December 24, 2002 Affinito
6497924 December 24, 2002 Affinito et al.
6509065 January 21, 2003 Affinito
6512561 January 28, 2003 Terashita et al.
6522067 February 18, 2003 Graff et al.
6537688 March 25, 2003 Silvernail et al.
6544600 April 8, 2003 Affinito et al.
6548912 April 15, 2003 Graff et al.
6569515 May 27, 2003 Hebrink et al.
6570325 May 27, 2003 Graff et al.
6573652 June 3, 2003 Graff et al.
6576351 June 10, 2003 Silvernail
6592969 July 15, 2003 Burroughes et al.
6597111 July 22, 2003 Silvernail et al.
6613395 September 2, 2003 Affinito et al.
6614057 September 2, 2003 Silvernail et al.
6624568 September 23, 2003 Silvernail
6627267 September 30, 2003 Affinito
6628071 September 30, 2003 Su
6653780 November 25, 2003 Sugimoto et al.
6656537 December 2, 2003 Affinito et al.
6664137 December 16, 2003 Weaver
6681716 January 27, 2004 Schaepkens
6720203 April 13, 2004 Carcia et al.
6734625 May 11, 2004 Vong et al.
6743524 June 1, 2004 Schaepkens
6749940 June 15, 2004 Terasaki et al.
6765351 July 20, 2004 Forrest et al.
6811829 November 2, 2004 Affinito et al.
6815887 November 9, 2004 Lee et al.
6818291 November 16, 2004 Funkenbusch et al.
6835950 December 28, 2004 Brown et al.
6836070 December 28, 2004 Chung et al.
6837950 January 4, 2005 Berard
6864629 March 8, 2005 Miyaguchi et al.
6866901 March 15, 2005 Burrows et al.
6867539 March 15, 2005 McCormick et al.
6872114 March 29, 2005 Chung et al.
6872248 March 29, 2005 Mizutani et al.
6872428 March 29, 2005 Yang et al.
6878467 April 12, 2005 Chung et al.
6888305 May 3, 2005 Weaver
6888307 May 3, 2005 Silvernail et al.
6891330 May 10, 2005 Duggal et al.
6897474 May 24, 2005 Brown et al.
6897607 May 24, 2005 Sugimoto et al.
6905769 June 14, 2005 Komada
6923702 August 2, 2005 Graff et al.
6936131 August 30, 2005 McCormick et al.
6975067 December 13, 2005 McCormick et al.
6994933 February 7, 2006 Bates
6998648 February 14, 2006 Silvernail
7002294 February 21, 2006 Forrest et al.
7012363 March 14, 2006 Weaver et al.
7015640 March 21, 2006 Schaepkens et al.
7018713 March 28, 2006 Padiyath et al.
7029765 April 18, 2006 Kwong et al.
7033850 April 25, 2006 Tyan et al.
7056584 June 6, 2006 Iacovangelo
7086918 August 8, 2006 Hsiao et al.
7156942 January 2, 2007 McCormick et al.
7183197 February 27, 2007 Won et al.
20010015074 August 23, 2001 Hosokawa
20010015620 August 23, 2001 Affinito
20020022156 February 21, 2002 Bright
20020025444 February 28, 2002 Hebgrink et al.
20020068143 June 6, 2002 Silvernail
20020069826 June 13, 2002 Hunt et al.
20020102363 August 1, 2002 Affinitio et al.
20020102818 August 1, 2002 Sandhu et al.
20020125822 September 12, 2002 Graff et al.
20020139303 October 3, 2002 Yamazaki et al.
20020140347 October 3, 2002 Weaver
20030038590 February 27, 2003 Silvernail et al.
20030085652 May 8, 2003 Weaver
20030098647 May 29, 2003 Silvernail et al.
20030124392 July 3, 2003 Bright
20030127973 July 10, 2003 Weaver et al.
20030184222 October 2, 2003 Nilsson
20030197197 October 23, 2003 Brown et al.
20030218422 November 27, 2003 Park et al.
20030235648 December 25, 2003 Affinito et al.
20040029334 February 12, 2004 Bijker et al.
20040046497 March 11, 2004 Schaepkens et al.
20040071971 April 15, 2004 Lacovangelo
20040113542 June 17, 2004 Hsiao et al.
20040115402 June 17, 2004 Schaepkens
20040115859 June 17, 2004 Murayama et al.
20040119028 June 24, 2004 McCormick et al.
20040175512 September 9, 2004 Schaepkens
20040175580 September 9, 2004 Schaepkens
20040209090 October 21, 2004 Iwanaga
20040219380 November 4, 2004 Naruse et al.
20040229051 November 18, 2004 Schaepkens et al.
20040241454 December 2, 2004 Shaw et al.
20040263038 December 30, 2004 Ribolzi et al.
20050003098 January 6, 2005 Kohler et al.
20050006786 January 13, 2005 Sawada
20050051094 March 10, 2005 Schaepkens et al.
20050079295 April 14, 2005 Schaepkens
20050079380 April 14, 2005 Iwanaga
20050093001 May 5, 2005 Liu et al.
20050093437 May 5, 2005 Ouyang
20050094394 May 5, 2005 Padiyath et al.
20050095736 May 5, 2005 Padiyath et al.
20050112378 May 26, 2005 Naruse et al.
20050122039 June 9, 2005 Satani
20050129841 June 16, 2005 McCormick et al.
20050133781 June 23, 2005 Yan et al.
20050140291 June 30, 2005 Hirakata et al.
20050146267 July 7, 2005 Lee et al.
20050174045 August 11, 2005 Lee et al.
20050212419 September 29, 2005 Vazan et al.
20050238846 October 27, 2005 Arakatsu et al.
20060003474 January 5, 2006 Tyan et al.
20060028128 February 9, 2006 Ohkubo
20060061272 March 23, 2006 McCormick et al.
20060062937 March 23, 2006 Padiyath et al.
20060063015 March 23, 2006 McCormick et al.
20060246811 November 2, 2006 Winters et al.
20060250084 November 9, 2006 Cok et al.
20070009674 January 11, 2007 Okubo et al.
Foreign Patent Documents
704297 February 1968 BE
704 297 February 1968 BE
2353506 May 2000 CA
196 03 746 April 1997 DE
19603746 April 1997 DE
696 15 510 May 2002 DE
0 147 696 July 1985 EP
0 299 753 January 1989 EP
0 299 753 January 1989 EP
0 340 935 November 1989 EP
0 340 935 November 1989 EP
0 390 540 March 1990 EP
0 390 540 October 1990 EP
0 468 440 January 1992 EP
0 547 550 June 1993 EP
0 547 550 June 1993 EP
0 590 467 April 1994 EP
0 590 467 April 1994 EP
0 722 787 July 1996 EP
0 722 787 July 1996 EP
0 777 280 June 1997 EP
0 777 280 June 1997 EP
0 777 281 June 1997 EP
0 787 824 August 1997 EP
0 787 826 August 1997 EP
0 787 826 August 1997 EP
0 915 105 May 1999 EP
0 916 394 May 1999 EP
0 916 394 May 1999 EP
0 931 850 July 1999 EP
0 931 850 July 1999 EP
0 977 469 February 2000 EP
0 977 469 February 2000 EP
1 021 070 July 2000 EP
1127 381 August 2001 EP
1 130 420 September 2001 EP
1 278 244 January 2003 EP
1 514 317 March 2005 EP
S63-96895 April 1988 JP
63136316 June 1988 JP
63136316 August 1988 JP
64-18441 January 1989 JP
S64-41192 February 1989 JP
2-183230 July 1990 JP
3-290375 December 1991 JP
4-48515 February 1992 JP
4-14440 April 1992 JP
H4-267097 September 1992 JP
H5-182759 July 1993 JP
06-136159 May 1994 JP
06158305 June 1994 JP
61-79644 June 1994 JP
6-234186 August 1994 JP
07-074378 March 1995 JP
H07-147189 June 1995 JP
H7-192866 July 1995 JP
8-72188 March 1996 JP
H8-171988 July 1996 JP
8-179292 July 1996 JP
08325713 October 1996 JP
08325713 December 1996 JP
09059763 April 1997 JP
H9-132774 May 1997 JP
09-161967 June 1997 JP
09-232553 September 1997 JP
10-013083 January 1998 JP
H10-41067 February 1998 JP
11-017106 January 1999 JP
11-040344 February 1999 JP
11-255928 September 1999 JP
2000-058258 February 2000 JP
2002/505969 February 2002 JP
10312883 March 2002 JP
3579556 October 2004 JP
2006-294780 October 2006 JP
WO 87/07848 December 1987 WO
WO 98/00337 January 1989 WO
WO 95/10117 April 1995 WO
WO 96/23217 August 1996 WO
WO 97/04885 February 1997 WO
WO 97/16053 May 1997 WO
WO 97/22631 June 1997 WO
WO 98/10116 March 1998 WO
WO 98/18852 May 1998 WO
WO 99/16557 April 1999 WO
WO 99/16931 April 1999 WO
WO 99/46120 September 1999 WO
WO 00/26973 May 2000 WO
WO 00/35603 June 2000 WO
WO 00/35604 June 2000 WO
WO 00/35993 June 2000 WO
WO 00/36661 June 2000 WO
WO 00/36665 June 2000 WO
WO 01/68360 September 2001 WO
WO 01/81649 November 2001 WO
WO 01/82336 November 2001 WO
WO 01/82389 November 2001 WO
WO 01/87825 November 2001 WO
WO 01/89006 November 2001 WO
WO 02/26978 April 2002 WO
WO 03/016589 February 2003 WO
WO 03/098716 November 2003 WO
WO 2004/006199 January 2004 WO
WO 2004/016992 February 2004 WO
WO 2004/070840 August 2004 WO
WO 2004/089620 October 2004 WO
WO 2005/015655 February 2005 WO
WO 2005/045947 May 2005 WO
WO 2005/048368 May 2005 WO
WO 2006/036492 April 2006 WO
Other references
  • Inoue et al., Proc. Jpn. Congr. Mater. Res., vol. 33, p. 177-9, 1990.
  • 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.
  • 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.
  • 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.
  • Chwang et al., “Thin Film encapsulated flexible organic electroluminescent displays”, American Institute of Physics, 2003.
  • 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.
  • De Gryse, R. et al., “Sputtered Transparent Barrier Layers,” Tenth International Conference on Vacuum Web Coating, Nov. 1996, pp. 190-198.
  • 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.
  • 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.
  • Affinito, J.D., Vacuum Deposited Conductive Polymer Films; The Eleventh International Conference on Vacuum Web Coatings, Nov. 9-11, 1997, pp. 1-13.
  • 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; 45th International Symposium of the American Vacuum Society; Nov. 2-6, 1998, pp. 0-26.
  • 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.
  • Yializis, A. et al., Ultra High Barrier Films; Denver, Apr. 15-20, 2000, pp. 404-407; Society of Vacuum Coaters.
  • 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.
  • Tropsha et al., Combinatorial Barrier Effect of the Multilayer SiOx Coatings on Polymer Substrates; 1997 Society of Vacuum Coaters, 40th Annual Technical Conferences Proceedings; Apr. 12-17, 1997; pp. 64-69.
  • 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.
  • 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 40th Annual Technical Conference, Apr. 12-17, 1997, 4 pages only.
  • 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.
  • Felts, J.T., Transparent Barrier Coatings Update: Flexible Substrates; Society of Vacuum Coaters; 36th Annual Technical Conference Proceedings; Apr. 25-30, 1993; pp. 324-331.
  • Affinito, J.D. et al., Molecularly Doped Polymer Composite Films for Light Emitting Polymer Application Fabricated by the PML Process; 41st Technical Conference of the Society of Vacuum Coaters; Apr. 1998; pp. 220-225.
  • 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.
  • Mahon, J.K. et al, Requirements of Flexible Substrates for Organic Light Emitting Devices in Flat Panel Display Applications, Society of Vacuum Coaters, 42nd Annual Technical Conference Proceedings, Apr. 1999, pp. 456-459.
  • 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.
  • Hibino, N. et al., Transparent Barrier Al203 Coating By Activated Reactive Evaporation; Thirteenth International Conference on Vacuum Web Coating; Oct. 17-19, 1999; pp. 234-246.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Bunshah, R. F. et al., “Deposition Technologies for Films and Coatings” Noyes Publications, Park Ridge, New Jersey, 1982, p. 339.
  • Affinito, J. D., Energy Res. Abstr. 18(6), #17171, 1993.
  • Graupner, W. et al.; “High Resolution Color Organic Light Emitting Diode Microdisplay Fabrication Method”, SPIE Proceedings; Nov. 6, 2000; pp. 1-9.
  • Czeremuszkin, G. et al.; Permeation Through Defects in Transparent Barrier Coated Plastic Films; 43rd Annual Technical Conference Proceedings; Apr. 15, 2000; pp. 408-413.
  • 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.
  • G. Gustafason, et al.; Flexible light-emitting diodes made from soluble conducting polymers; Letters to Nature; vol. 357; Jun. 11, 1992; pp. 477-479.
  • F.M. Penning; Electrical Discharges in Gases; 1965; pp. 1-51; Gordon and Breach, Science Publishers, New York-London-Paris.
  • Affinito, J.D., et al.; High Rate Vacuum Deposition of Polymer Electrolytes: Journal Vacuum Science Technology A 14(3), May/Jun. 1996.
  • Affinito, J.D. et al.; Vacuum Deposition of Polymer Electrolytes On Flexible Substrates, The Ninth International Conference on Vacuum Web Coating; pp. 20-37.
  • 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.
  • 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.
  • 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.
  • Affinito, J.D. et al.; Vacuum Deposited Polymer/Metal Multilayer Films for Optical Application; Thin Solid Films 270, 1995; pp. 43-48.
  • Felts, J.T.; Transparent Barrier Coatings Update: Flexible Substrates; pp. 324-331.
  • 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.
  • Yamada, Y. et al.; The Properties of a New Transparent and Colorless Barrier Film; 1995; pp. 28-31; Society of Vacuum Coaters.
  • Chahroudi, D.; Transparent Glass Barrier Coatings for Flexible Film Packaging; 1991; pp. 130-133; Society of Vacuum Coaters.
  • Krug, T. et al.; New Developments in Transparent Barrier Coatings; 1993; pp. 302-305; Society Vacuum Coaters.
  • 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.
  • Affinito, J.D. et al.; A new method for fabricating transparent barrier layers, Thin Solid Films 290-291; 1996; pp. 63-67.
  • Affinito, J.D. et al.; Polymer-Oxide Transparent Barrier Layers; SVC 39th Annual Technical Conference; Vacuum Web Coating Session; 1996; pp. 392-397.
  • Hoffmann, G. et al.; Transparent Barrier Coatings by Reactive Evaporation; 1994; pp. 155-160; Society of Vacuum Coaters.
  • Klemberg-Sapieha, J.E. et al.; Transparent Gas Barrier Coatings Produced by Dual-Frequency PECVD; 1993; pp. 445-449; Society of Vacuum Coaters.
  • Finson, E. et al.; Transparent SiO2 Barrier Coatings: Conversion and Production Status; 1994; pp. 139-143; Society of Vacuum Coaters.
  • 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.
  • 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.
  • Clark I. Bright, et al., Transparent Barrier Coatings Based on ITO for Flexible Plastic Displays, Oct. 17-19, 1999, pp. 247-264, Tucson, Arizona.
  • Notification of Transmittal of the International Search Report Or The Declaration, Mar. 3, 2000, PCT/US99/29853.
Patent History
Patent number: RE40531
Type: Grant
Filed: Jul 12, 2004
Date of Patent: Oct 7, 2008
Assignee: Battelle Memorial Institute (Columbus, OH)
Inventors: Gordon Lee Graff (West Richland, WA), Mark Edward Gross (Pasco, WA), Ming Kun Shi (Pleasanton, CA), Michael Gene Hall (West Richland, WA), Peter Maclyn Martin (Kennewick, WA), Eric Sidney Mast (Richland, WA)
Primary Examiner: Kuo-Liang Peng
Attorney: Dinsmore & Shohl LLP
Application Number: 10/890,437