There is a need for versatile visual display devices for electronic products of many different types. Many different display devices are presently being used, including liquid crystal displays (LCDs), light emitting diodes (LEDs), light emitting polymers (LEPs), electronic signage using electrophoretic inks, electroluminescent devices (EDs), and phosphorescent devices. Many of these display devices are environmentally sensitive. As used herein, the term environmentally sensitive display device means display devices 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 of the electronic product.

Although many current displays use glass substrates, there is a trend toward the use of plastic substrates. Plastic substrates are critical to future generations of electronic products and associated technologies because they are light weight, impact resistant, and cost effective. However, the gas and liquid permeation resistance of plastics is poor, often several orders of magnitude below what is required for sustained device performance. Barrier coatings are applied to substrates to decrease their gas and liquid permeability. Barrier coatings typically consist of single layer thin film inorganic materials, such as Al, SiO2, Al203, and Si3N4 vacuum deposited on polymeric substrates. The best single layer coatings reduce oxygen and water vapor permeability to levels of about 0. 1 to 1. 0 cc/m2/day and about 0. 1 to 1. 0 g/m2/day, respectively. (Conditions were not reported. The testing is believed to be at 23°C.) However, many displays require oxygen permeability levels of between about 10-6 and 10-5 cc/m2/day, and water vapor permeability levels between about 10-4 and 10-2 g/m2/day. The environmental sensitivity of the display devices limits the lifetime, reliability, and performance of devices constructed on plastics, which has retarded the development of display devices made with plastic substrates.

Thus, there is a need for an improved, lightweight, barrier construction which can be used to encapsulate environmentally sensitive display devices and prevent the deterioration caused by gas and liquid permeation, and for methods for making such encapsulated environmentally sensitive display devices.

The present invention meets these need by providing an encapsulated display device and a method for making such a device. The device includes a substrate, an environmentally sensitive display device adjacent to the substrate, and at least one first barrier stack adjacent to the environmentally sensitive display device. By adjacent, we mean next to, but not necessarily directly next to. There can be additional layers intervening between the adjacent layers. The barrier stack encapsulates the environmentally sensitive display device. It includes at least one first barrier layer and at least one first polymer layer. The encapsulated display device optionally includes at least one second barrier stack located between the substrate and the environmentally sensitive display device. The second barrier stack includes at least one second barrier layer and at least one second polymer layer.

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

Either one of the first and second barrier layers can be substantially opaque, if desired. The opaque barrier layers are preferably selected from opaque metals, opaque polymers, opaque ceramics, and opaque cermets.

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 glass), a metal, or a semiconductor.

The polymer layers of the first and second 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 in the first and/or the second barrier stacks can be the same or different.

The environmentally sensitive display device is preferably selected from liquid crystal displays, displays using electrophoretic inks, light emitting diodes, electroluminescent devices, and phosphorescent devices.

The encapsulated display device can include additional layers if desired, such as polymer smoothing layers, scratch resistant layers, or other functional layers.

The encapsulated display device can also include a lid adjacent to the at least one first barrier stack.

The present invention also involves a method of making the encapsulated display device. The method includes providing a substrate having an environmentally sensitive display device thereon, and placing at least one first barrier stack over the environmentally sensitive display device to encapsulate the environmentally sensitive display device. The barrier stack includes at least one first barrier layer and at least one first polymer layer.

The environmentally sensitive display device can be placed on the substrate by deposition or by lamination. The at least one first barrier stack can be placed over the environmentally sensitive display device 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, ultra sonic welding, pressure, or heat.

A second barrier stack can be placed on the substrate before the environmentally sensitive display device is placed there. The second barrier stack includes at least one second barrier layer and at least one second polymer layer.

The second barrier stack can be deposited on the substrate, preferably by vacuum deposition.

The substrate can be removed from the encapsulated environmentally sensitive display device, if desired.

Accordingly, it is an object of the present invention to provide an encapsulated display device, and to provide a method of making such as device.

Brief Description of the Drawings Fig. 1 is a cross-section of one embodiment of the encapsulated display device of the present invention.

Fig. 2 is a cross-section of an alternate embodiment of the encapsulated display device of the present invention.

One embodiment of the encapsulated display device of the present invention is shown in Fig. 1. The encapsulated display device 100 includes a substrate 105, an environmentally sensitive display device 110, and a first barrier stack 115. The first barrier stack 115 includes a barrier layer 120 and a polymer layer 125. The first barrier stack 115 encapsulates the environmentally sensitive display device 110, preventing environmental oxygen and water vapor from degrading the environmentally sensitive display device.

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 TransphanTM (a high glass transition temperature cyclic olefin polymer available from Lofo High Tech Film, GMBH of Weil am Rhein, Germany) ; metal ; paper ; fabric ; and combinations thereof. Rigid substrates are preferably ceramics, metals, or semicondutors.

The environmentally sensitive display device 110 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. Patent Nos. 6, 025, 899, 5, 995, 191, 5, 994, 174, 5, 956, 112 (LCDs) ; U. S. Patent Nos. 6, 005, 692, 5, 821, 688, 5, 747, 928 (LEDs) ; U. S. Patent Nos.

5, 969, 711, 5, 961, 804, 4, 026, 713 (E Ink) ; U. S. Patent Nos. 6, 023, 373, 6, 023, 124, 6, 023, 125 (LEPs) ; and U. S. Patent 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.

In each barrier stack 115, there can be one or more barrier layers 120 and one or more polymer layers 125. 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 in the range of about 100-400 A thick, and the polymer layers are typically in the range of about 1000-10, 000 A thick.

Although Fig. 1 shows a barrier stack with a single barrier layer and a single 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.

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.

A second embodiment of the encapsulated display device of the present invention is shown in Fig. 2. The encapsulated display device 200 has a substrate 205. There are scratch resistant layers 210 on either side of the substrate 205 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 prevent curling of a flexible substrate.

On top of the scratch resistant layer 210, there is a polymer smoothing layer 220. 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 deposition of subsequent layers. Depending on the desired application, there can be additional layers deposited on the substrate 205, 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 230 is above the polymer smoothing layer 220. The first barrier stack 230 includes a first barrier layer 235 and a first polymer layer 240.

The first barrier layer 235 includes barrier layers 245 and 250. Barrier layers 245 and 250 can be made of the same barrier material or of different barrier materials.

The environmentally sensitive display device 255 is placed over the first barrier stack 230. There is a second barrier stack 260 placed over the environmentally sensitive display device 255 to encapsulate it. The second barrier stack has a barrier layer 265 and a polymer layer 270, although it can have one or more barrier layers and one or more polymer layers, as discussed above. The barrier layers and polymer layers in the first and second barrier stacks can be the same or they can be different.

Although only one first barrier stack and only one second barrier stack are shown in Fig. 2, 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 lid 280 over the second barrier stack 260. The lid can be can be rigid or flexible, and it can be made of the same types of materials as the substrate 205.

The method of making the encapsulated display device will be described with reference to the embodiment shown in Fig. 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 first barrier stack is then placed on the substrate. The first and second barrier stacks include 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, substrate, or 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. Patent 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 encapsulated display device 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.

The environmentally sensitive display device is then placed on the first barrier layer. 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.

The second 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.

When a liquid device, such as a liquid crystal display or an electrophoretic ink, is used, the barrier layers (and any other layers desired) are deposited on the substrates. The edges of the substrates are then sealed leaving a space between them, and an opening is left in the seal. The liquid is introduced into the opening in the seal, and the opening is sealed, producing the device.

The barrier layers can be transparent or opaque, depending on the design and application of the display device. 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 carbides are preferably boron carbide, tungsten carbide, silicon carbide, 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. The metal oxyborides are preferably zirconium oxyboride, titanium oxyboride, and combinations thereof.

For most devices, only one side of the device must be transparent.

Therefore, opaque barrier layers can be used in some barrier stacks depending on the design of the display device. Opaque barrier materials include, but are not limited to, metal, ceramic, 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 A. 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, Al203 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. Affinito, 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, 39"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 Differences 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 value (measured according to ASTM F 1927-98 and ASTM F 1249-90, respectively) measured at Mocon (Minneapolis, MN) for several barrier stacks on 7 mil PET along with reported values for other materials.

Table 1 Sample Oxygen Permeation Water Vapor Rate cc/m2/day) Permeation (g/m2/day)+ 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 with ITO <0. 005 <0. 005*-0. 011+ 2-barrier stacks <0. 005 <0. 005*-<0. 005+ 2-barrier stacks with ITO <0. 005 <0. 005*-<0. 005+ 5-barrier stacks <0. 005 <0. 005*-<0. 005+ 5-barrier stacks with ITO <0. 005 <0. 005*-<0. 005+ DuPont film'0. 3 (PET/Si3N4 or PEN/Si3N4) Polaroid film3 <1.0 - - - PET/AI2 0. 6 0. 17 PET/silicon oxide2 0. 7-1. 5-0. 15-0. 9 Teijin LCD film <2 <5 (HA grade-TN/STN) 3 (") 38°C, 90% RH, 100% O2 (+) 38°C, 100% RH 1-P. F. Carcia, 46"International Symposium of the American Vacuum society, Oct. 1999 2-Langowski, H. C., 39"Annual Technical Conference Proceedings, SVC, pp. 398-401 (1996) 3-Technical 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. The barrier stacks are extremely effective in preventing oxygen and water penetration to the underlying components, substantially outperforming other 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. 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.