• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The flexible composite barrier structure of the present invention is used to improve resistance to oxygen and moisture degradation of organic electronic devices comprising one or more active layers containing organic materials.
    公开号:KR20020011392A
    申请号:KR1020017013800
    申请日:2000-04-27
    公开日:2002-02-08
    发明作者:피터 프란시스 카르시아；로버트 스콧 맥클린
    申请人:메리 이. 보울러；이 아이 듀폰 디 네모아 앤드 캄파니；
    IPC主号:
    专利说明:

    Flexible Organic Electronic Device with Improved Resistance to Oxygen and Moisture Degradation}
    [2] Organic electronic devices include devices that emit light (eg, light emitting diodes that make displays) or devices that respond to radiation (eg, photodetectors). The display may contain active matrix addressing or passive matrix addressing. Passive matrix displays have an array of electrode lines that address individual pixels arranged in rows and columns, and energize the pixels by corresponding addresses by applying a voltage between specific rows and columns. Inferred from an active matrix liquid crystal display, the polymer electronics (display) can be addressed at individual pixels using thin film transistor (TFT) devices that turn the pixels on and off. In this configuration, each TFT is electrically connected to a "gate busline" and to a "data busline", which also need to be connected to an electric driver circuit, and thus outside of the activator area. Is sealed in.
    [3] In all these devices, the organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is light transmissive to allow light rays to pass through the electrical contact layer. The organic active layer may generate an electrical signal in response to the light passing through the one or more light transmissive electrical contacts, or may emit light through the light transmissive electrical contact layer upon application of electricity across the electrical contact layer. . In the latter case, the organic active layer contains an electroluminescent material.
    [4] It is well known to use organic electroluminescent materials as active materials in light emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives and coumarin derivatives are known to exhibit electroluminescence. Semiconductor conjugated polymers are also described, for example, in US Pat. No. 5,247,190 (Friend et al.), US Pat. No. 5,408,109 (Heeger et al.) And published European Patent Application No. 443 861 (Nakano et al.). As has been used it has been used as an electroluminescent material. Organic materials can be modified to provide emission at various wavelengths. However, they are mainly degraded by atmospheric gases, in particular oxygen and water vapor. This sensitivity can severely limit the working life of the device if the materials are not properly sealed.
    [5] Generally, the device is fabricated on a glass substrate and then welded to another glass sheet by epoxy to seal it. In US Pat. No. 5,427,858 (Nakamura et al.), The electroluminescent device has a protective layer of fluorine-containing polymer optionally covered by a glass barrier layer. US Pat. No. 5,482,896 (Tang) used a material such as an epoxy or hot melt adhesive to seal the edge of the electroluminescent device between a rigid support and a thin (25-50 micron) glass substrate. In US Pat. No. 5,073,446 (Scozzafava et al.), An electroluminescent device comprising a glass substrate comprises an outer capping layer composed of fused metal particles containing at least 80% indium to prevent oxidation of the second electrical contact layer. Have However, using glass as the substrate greatly increases the fragility of the device. Moreover, devices with glass substrates are not flexible at room temperature or below, and thus may not be suitable for curved surfaces.
    [6] Therefore, there is a need to improve the chemical stability of layers in organic electronic devices that are sensitive to environmental factors. In addition, there is a need to improve the durability as well as the flexibility of such devices.
    [7] Summary of the Invention
    [8] The present invention relates to a method for improving the resistance to oxygen and moisture degradation of a flexible organic electronic device and to a flexible organic electronic device having significantly improved resistance and improved durability against environmental degradation, in particular oxygen and moisture degradation. will be. The device includes an organic active layer sandwiched between two electrical contact layers, which sandwich is sealed between two flexible composite barrier structures. The flexible composite barrier structure preferably has an oxygen and water vapor transport rate of less than 1.0 kPa / m 2/24 hours / atm.
    [9] In one embodiment of the present invention, an apparatus comprises: (a) a first flexible composite barrier structure comprising at least one layer of a first polymer film and at least one layer of a first barrier material; (b) at least one first electrical contact layer; (c) one or more active layers containing organic active material and having dimensions defined in length and width; (d) at least one second electrical contact layer; (e) a second flexible composite barrier structure comprising at least one layer of a second polymer film and at least one layer of a second barrier material, in the order described, wherein at least one of the first and second composite barrier structures Is light transmissive and the first and second composite barrier structures are sealed together to enclose the active layer.
    [10] In a second embodiment, the device includes a portion of the first electrical contact layer and a portion of the second electrical contact layer extending beyond the dimensions of the active layer, wherein the first and second composite barrier structures also extend beyond the dimensions of the active layer. It is further sealed against a portion of the first electrical contact layer and a portion of the second electrical contact layer.
    [1] The present invention relates to an organic electronic device in which the active layer is an organic material. More particularly, the present invention relates to electronic devices covered by a flexible composite barrier structure.
    [11] 1 is a schematic diagram of a top view of an organic electronic device of the present invention.
    [12] 2 is a schematic view of the cross section at line 2-2 of the device of FIG. 1 before sealing the device.
    [13] 3 is a schematic representation of a top view at line 3-3 of the apparatus shown in FIG.
    [14] 4 is a schematic view of the cross section at line 2-2 of the apparatus of FIG. 1 after sealing.
    [15] FIG. 5 is a plot of peel strength versus distance when peeling off the composite barrier structure of the invention sealed against a pattern of electrodes on a polymer support.
    [16] 6 is a schematic diagram of a composite barrier structure peeled off from a support and an electrode material.
    [17] Figure 7 (a) is a plot of the light emission of the polymer light emitting device of the present invention 50 days after storage at initial and ambient conditions.
    [18] FIG. 7 (b) is a plot of the light emission of the polymer light emitting device without the barrier structure of the present invention after 50 days of storage at initial and ambient conditions.
    [19] The present invention provides at least a first flexible composite barrier structure; A first electrical contact layer; A layer containing at least one organic active material; A second electrical contact layer; And a device having a second flexible composite barrier structure in the order described.
    [20] It is understood that it is necessary to be able to connect the electrical contact layer of the device to an external circuit in order for the device to function. In most cases this circuit connection can be made by extending the electrical contact layer beyond the dimensions of the active layer for the connection. The composite barrier structure then seals together against an extension of the electrical contact layer, and the electrical contact layer extends out of the seal. However, it is also possible to connect the electrical contact layer to an external circuit using a conductive path known as a via. The via opening may be formed in each layer when the device is assembled, or may be formed by punching out all layers after the device is assembled. The openings are then fully plated using well known techniques, for example described in Sinnadurai, Handbook of Microelectronic Packaging and Interconnection Technologies (Electrochemical Publications Ltd., 1985). If vias are used, the opening must be completely sealed around the connecting wire to protect the active layer from exposure to the external environment.
    [21] The term "flexible" as used herein means that the planar sheet of material is less hard than glass having a thickness of 1 millimeter at room temperature, and preferably can be bent at an angle of at least 10 ° from the plane without breaking. It is. The term "light transmissive" means that the material transmits at least 50% of the light rays in the visible spectrum (400-700 nm). The term "barrier" means low permeability to oxygen and water vapor. The term "essentially X" means that the composition of a particular substance is primarily X and may also contain other substances which do not adversely affect the functional properties of the substance to the extent that the substance can no longer fulfill its intended purpose. Used to mean that there is.
    [22] If layer A is referred to as "adjacent" to the first surface of layer B, this is closer to the first surface of layer B than to the second surface of layer B where layer A is located opposite the first surface. Means that. The term "adjacent" as used herein does not mean that layer A is located immediately after the first surface of layer B. That is, it is entirely possible for layer C to be arranged between layer A and layer B, which also likewise corresponds to layer A being adjacent to the first surface of layer B.
    [23] 1 to 4 show one example of the organic electronic device 10 according to the present invention. As best seen in FIGS. 2 and 4, the device 10 includes a first flexible composite barrier structure 20, a first electrical contact layer 30, an active layer 40, a second electrical contact layer 50. ) And a second flexible composite barrier structure 60. Depending on the desired application, the device 10 may be connected directly to the electricity sources 100, 120 as best seen in FIGS. 1 and 3. Alternatively, device 10 may be connected to one or more external circuits (not shown), thereby becoming part of the overall electronic system (not shown).
    [24] As best seen in FIGS. 2 and 4, the first composite barrier structure 20 has an inner surface 24, and two polymer layers 21A on either side of the layer 22 of barrier material and It consists of 21B. The patterned first electrical contact layer 30 is located adjacent the inner surface 24 of the first composite barrier structure 20. As best seen in FIGS. 1 and 3, the first electrical contact layer pattern consists of lines that span the width 44 of the active layer and extend beyond the edge 43A of the active layer 40. The first electrical contact layer 30 extends beyond the dimensions of the active layer 40 in the region 31. As best seen in FIGS. 2 and 4, the patterned second electrical contact layer 50 is positioned opposite the active layer 40 relative to the surface 46 adjacent to the first electrical contact layer 30. Adjacent to the second surface 48 of the active layer 40 is sandwiched between the second electrical contact layer 50 and the first electrical contact layer 30. As best seen in FIGS. 1, 2 and 4, the second electrical contact layer pattern is in lines extending across the length 42 of the active layer and beyond the other edges 45A, 44 of the active layer 40. It is composed. As best seen in FIGS. 1 and 2, the second electrical contact layer extends beyond the dimensions of the active layer in region 52. As best seen in FIGS. 2 and 4, the second flexible composite barrier structure 60 consists of two polymer layers 61A and 61B on either side of the layer 62 of barrier material. An adhesive layer 70 is located on the inner surface 64 of the second barrier structure.
    [25] It is understood that the electrical contact layers 30, 50 may extend beyond any one or more of the active layer edges 43A, 43B, 45A, 45B, depending on the design of the device 10.
    [26] 1-4 are shown to exaggerate the separation of layers and show their relative order, and are not understood to accurately depict their relative dimensions.
    [27] As best shown in FIGS. 1, 2 and 4, the dimensions 65, 66 of the second composite barrier structure 60 may be smaller than the dimensions 26, 27 of the first composite barrier structure 20. In the illustrated embodiment, the dimensions 65, 66 of the second composite structure 60 are larger than the dimensions 42, 44 of the active layer 40 (not shown) to effectively seal the active layer 40. In embodiments where one or more electrical contact layers are also susceptible to environmental degradation (not shown), the dimensions of the composite barrier structure must be adjusted to effectively seal the sensitive electrical contact layer (s) as well. Thus, the relative dimensions 65, 66 of the second composite barrier structure 60 and the dimensions 26, 27 of the first composite barrier structure 20 are such that the composite barrier structures 20, 60 are relative to the device 10. It is understood that various changes can be made as long as an effective seal can be provided.
    [28] As best shown in FIG. 4, the first and second flexible composite barrier structures 20 and 60 are sealed together using an adhesive layer 70 outside of the dimensions of the active layer 40 in zone 102. do. Although not exactly shown in the figures, the first and second flexible composite barrier structures 20 and 60 are sealed at all edges such that the active layer 40 is completely contained within the sealed edges. Preferably, the first and second flexible composite barrier structures 20 and 60 define an area 31 of the first electrical contact layer 30 and an area 52 of the second electrical contact layer 50. It is sealed in such a way as to also include all parts of the first and second electrical contact layers 30, 50 except as well.
    [29] In embodiments where device 10 is a light emitting diode, layer 30 may be a cathode (or an anode), and layer 40 is a light emitting layer containing an electroluminescent material, and the layer 50 is each counter electrode, ie the anode (or cathode) in each case.
    [30] 1. Flexible composite barrier structure
    [31] Flexible composite barrier structures 20 and 60 are composites of one or more polymer film layers and one or more barrier material layers. The two composite barrier structures can be made of the same or different materials. At least one of the two composite layers should preferably be light transmissive, transmitting at least 80% in the visible region.
    [32] Polymer films 21A, 21B, 61A, 61B useful in the present invention are dimensionally and physically stable under the operating conditions of the device. Examples of suitable polymers include essentially polyolefins such as polyethylene and polypropylene; Polyesters such as polyethylene terephthalate and polyethylene naphthalate; Polyimide; Polyamides; Polyacrylonitrile and polymethacrylonitrile; Perfluorinated and partially fluorinated polymers such as polytetrafluoroethylene and copolymers of tetrafluoroethylene and 2,2-dimethyl-1,3-diosol; polystyrene; Polycarbonate; Polyvinyl chloride; Polyurethane; Polyacrylic resins including homopolymers and copolymers of esters of acrylic acid and / or methacrylic acid; Epoxy resins; And materials containing novolak resins. One or more layers of polymer film may be used, and combinations of films having different compositions may be used. Multiple layers may also be joined together using a suitable adhesive or by conventional layer-generating methods such as known coating and / or coextrusion methods. Polymer films generally have a thickness in the range of about 0.5-10 mils (12.7-254 microns). If more than one film layer is present, each thickness may be much smaller.
    [33] While the polymer films 21A, 21B, 61A, 61B essentially contain the polymers described above, it is understood that these films may also include conventional additives. For example, many polymer films that are commercially available contain a slip agent or a matte agent to prevent the layers of the film from adhering when stored in large rolls. In some cases, the dimensions of these additives can cause irregularities and defects in adjacent layers of the barrier material, which can adversely affect the barrier properties of the composite barrier structure. Where the additives have a deleterious effect on the composite barrier structure, polymer films that are free of slips and mats or that have small or minor amounts of these components relative to the desired thickness of the layers 22 and 62 of the barrier material are preferred. In some cases, slip coating may be used.
    [34] In the composite structures 20, 60 of the present invention, one or more of the barrier materials 22, 62 sandwiched between at least two layers of the polymer films 21A, 21B, 61A, 61B as best shown in FIG. It is preferable to have a layer. This composite structure 20, 60 makes a very thin and flexible layer of barrier material, which is then protected from damage by the outer layer of the polymer film. There may be one or more layers of barrier material (not shown), each of which may be located between two polymer layers. The barrier layer can be applied to the first layer of the polymer film by one of the methods described below. The second layer of polymer film can then be applied by a lamination or coating, casting or extrusion method. The second polymer film layer can have the same or different composition as the first layer. For example, a 1-2 mil (25.4-50.8 micron) thick polyester film may be coated with a 2-500 nm thick silicon nitride (SiN x ) layer using plasma enhanced chemical vapor deposition. Can be. This layer can then be overcoated with a solution of acrylic resin and then dried, or overcoated with epoxy or novolac resin and then cured. Alternatively, the silicon nitride coated polyester film can be laminated to the second layer of the polyester film. The overall thickness of the composite structure is generally in the range of about 0.5-10 mils (12.3-254 microns), preferably 1-8 mils (25.4-203.2 microns). This overall thickness is affected by the method used to apply or laminate the composite structure.
    [35] As best shown in FIGS. 2 and 4, the adhesive 70 is generally applied to one or more surfaces of the composite structure 20, 60. The composite barrier structures 20, 60 are sealed by an adhesive by joining the inner surfaces 24, 64 of the structures 20, 60 together. The adhesive 70 should not only seal the two composite structures together, but should also be able to seal at least a portion of the electrical contact layers 31, 52 that extend beyond the dimensions of the active layer 40. An adhesive layer (not shown) may be disposed after the inner surface 24 of the first composite barrier structure 20 in addition to or instead of the adhesive layer 70.
    [36] In another embodiment, the adhesive component may be incorporated into at least one of the polymer films 21A, 61B adjacent to the active layer 40 instead of or in addition to the separate adhesive layer 70. In such a case, separate adhesive layers 70 may be unnecessary to seal the composite barrier structures 20 and 60 together.
    [37] Suitable adhesives useful as separate layers (eg, layer 70) and / or as components of one of the polymer film layers 21A, 61B are essentially polymer adhesives, amorphous polyesters, copolyesters, polyesters. Blends, nylons, polyurethanes and polyethylene, polypropylene, polyethylene vinylalcohol, ethylene vinylacetate copolymers, polyolefins including polyolefins, including copolymers of ionomers and acids. If the adhesive layer is adjacent to the light transmissive layer, it is understood that the adhesive layer should also be light transmissive. Likewise, the adhesive component to be incorporated into the light transmissive polymer film layer should not adversely affect the light-transmitting properties of the polymer film layer.
    [38] Barrier materials useful for the barrier layers 22 and 62 of the present invention are less than 1.0 kPa / m 2/24 hours / atm, preferably less than 0.2 kPa / m 2/24 hour / atm when molded into a continuous film having a thickness of 1000 kPa. It may be a material having oxygen and water vapor transport rates. Suitable barrier materials include materials that can be bent and are malleable and crack resistant. Examples of such materials essentially include materials containing metals and alloys such as aluminum, nickel, copper, tin, and stainless steel. The barrier material is also any inorganic chemically stable to water and oxygen, including inorganic oxides such as compounds of silicon, aluminum, indium, titanium, magnesium, hafnium, tantalum and zirconium, nitrides, fluorides and carbides, and combinations thereof. It can be a substance.
    [39] Each of the barrier layers 22, 62 should be a continuous layer containing a minimum number of defects that increase the oxygen and water vapor transmission properties of the material so that they cannot act for a long time as a barrier. Thus, for example, defects such as pinholes or cracks are undesirable. In addition to the dimensions of the defects, it is understood that the area density of the defects (ie, number of defects per unit area) may also affect the functional properties of the barrier material. In order to maintain flexibility, the layer of barrier material generally has a thickness of 1 micron or less, preferably 500 nm or less. In general, the barrier layer can have a thickness in the range of 2-500 nm. However, for some flexible metal films such as Al foils, barrier layers thicker than the preferred range may be used.
    [40] The barrier layer of the present invention is a composite containing a very thin layer of material with very low permeability.
    [41] The particular choice of polymer film and barrier material depends on the process conditions and light transmission requirements to which the composite structure will be exposed. When the composite structure 20 or 60 is used as a support having additional layers assembled thereon, it can withstand a variety of process conditions, including deposition and / or wet chemical etching. . In some cases, the polymer film can be the outer layer of the composite structure exposed to further processing. When they are subjected to chemical corrosion conditions, materials such as polyesters, polyimides and fluorinated polymers are preferred polymeric materials. If the process comprises a deposition step, the polymer film is a polyimide, or polyester, more preferably polyethylene naphthalate, having a high glass transition temperature (Tg) (e.g., Tg between 100 ° C and 350 ° C). It is preferable. In some cases, the barrier material may be the outer layer of the composite structure that is exposed to further processing. The barrier material should be chosen to withstand these conditions. If composite structure 20 or 60 is added as the final layer, this often does not undergo any further processing. Thus, the range of choices for the composition of the components in the composite barrier structure 20 or 60 disposed as the final layer is much broader.
    [42] If the composite structure 20 or 60 is adjacent to the light transmissive electrical contact layer, the composite barrier structure must also be light transmissive in order to transmit light into the device or to transmit light generated by the device. In this case, any light transmissive layer of barrier material, including inorganic oxides, nitrides, fluorides and carbides having a glass and a band gap of 2.5 eV or more can be used. Particularly preferred light-transmissive barrier materials include silicon nitride having the formula (I); Silicon oxide having the formula II; Aluminum oxide having the formula III; A glass such as a material consisting essentially of aluminum nitride having the general formula (IV):
    [43] SiN w
    [44] SiO x
    [45] AlO y
    [46] AlN 2
    [47] In the above formula,
    [48] w is 0.8 to 1.2,
    [49] x is 1.5 to 2.0,
    [50] y is 1 to 1.5,
    [51] z is 0.8 to 1.2.
    [52] Combinations of suitable materials may also be used.
    [53] If the composite structure is adjacent to the opaque electrical contact layer, no light transmissive composite barrier structure is required.
    [54] In summary, there are four types of composite barrier structures that can be used depending on the arrangement of the structure in the device: (i) The composite barrier structure is used as a support on which additional layers are to be processed, Adjacent to; (ii) the composite barrier structure is used as a support on which additional layers are to be processed, and is adjacent to the opaque electrical contact layer; (iii) the composite barrier structure is the final layer applied and is adjacent to the light transmissive electrical contact layer; (iv) The composite barrier structure is the final layer applied and is adjacent to the opaque electrical contact layer. The choice of materials used in the component layers of the composite barrier structure depends in part on the shape of the composite structure.
    [55] The polymer film layers 21A, 21B, 61A, 61B and the barrier materials 22, 62 may be coated with desired coating thicknesses, such as spin coating and spray coating, extrusion coating, casting, screen printing, and deposition methods. Any known application technique can be used together to provide the properties. The preferred method is to apply the barrier materials 22 and 62 to the polymer film 21A or 21B, 61A or 61B, respectively, by the deposition method. Such methods include chemical vapor deposition and plasma enhanced chemical vapor deposition, and physical deposition methods such as evaporation, ion-plating, and sputtering. Plasma enhanced chemical vapor deposition is particularly preferred because this method results in less heating of the substrate (in this case polymer film 21A, 21B, 61A or 61B), and the coating flux is more uniform. . This provides an essentially defect free layer.
    [56] 2. First electrical contact layer
    [57] The first electrical contact layer 30 is applied to one side of the first flexible composite barrier structure. This electrical contact layer may comprise any material capable of injecting (or collecting) charge carriers into the active layer 40 (or, optionally, from the active layer).
    [58] Although not shown in the figures, the first electrical contact layer may consist of one single layer of material, or may be a composite of multiple layers of first electrical contact layer material. If the first electrical contact layer is an anode (ie, an electrode that is particularly efficient for injecting or collecting positive charge carriers), it may be a material containing, for example, metal, mixed metal, alloy, metal oxide or mixed-metal oxide Or it may be a conductive polymer. Suitable metals include Group IB metals, Group IV, V and VI metals, and Group VIII transition metals. If the first electrical contact layer is light transmissive, a mixed-metal oxide of Group II, III and IV metals such as indium-tin oxide, or a conductive polymer such as polyaniline can be used.
    [59] Although the first electrical contact layer 30 is shown having an elongated portion 31 for connecting the device to an external circuit, the device (not shown) incorporating other circuit connecting means (eg, vias) is shown. It is understood that this may not require this extended portion 31. It is also understood that the composition of the first electrical contact layer 30 can vary over the dimensions 26, 65 of the composite barrier layers 20, 60. For example, where the first electrical contact layer 30 includes an extended portion 31, a portion of the extended portion disposed outside of the sealed composite barrier layer 20, 60 is essentially environmental It may contain a material (eg, aluminum) that is more resistant to deterioration or is a better conductor than the first electrical contact layer composition present over the same length as the active layer 40. That is, the first electrical contact layer composition present over the same length as the active layer 40 can be selected to provide better electron band-gap matching. At the same time, the first electrical contact layer composition in the extended portion 31 may be selected to provide greater conductivity and increased resistance to environmental degradation outside of the sealed device. The changed composition can be provided by using a separate layer of first electrical contact layer material, or by adjusting the alloy composition in the first electrical contact layer.
    [60] The first electrical contact layer 30 is typically applied by a physical vapor deposition method. The term "physical deposition" refers to various deposition means performed in vacuo. That is, for example, physical deposition methods include all forms of sputtering, including ion beam sputtering, and all forms of deposition, such as e-beam evaporation. A particular type of physical vapor deposition method useful in the present invention is rf magentron sputtering.
    [61] Generally, the first electrical contact layer is patterned. It is understood that the pattern can be changed as desired. The first electrical contact layer can be applied in a pattern, for example, by placing a patterned mask or photoresist on the first flexible composite barrier structure prior to applying the first electrical contact layer material. Alternatively, the first electrical contact layer may be applied as an entire layer and then patterned using, for example, photoresist or wet chemical corrosion. The first electrical contact layer generally has a thickness in the range of 50-500 nm. As the first electrical contact layer material and patterning method, those well known in the art may be used.
    [62] 3. Organic active layer
    [63] Depending on the application of the device 10, the active layer 40 may be a light emitting layer (e.g. in the case of a light emitting diode) activated by an applied voltage, or an applied bias in response to radiant energy. ) A layer of material that generates a signal in the presence or absence of a voltage (eg for a photodetector). Examples of photodetectors include photoconductive cells, photoresistors, photoswitches, phototransistors and phototubes, and wet photovoltaic cells, which are described in Markus, John, Electronics and Nucleonics Dictionary , 470 and 476 (McGraw-Hill, Inc., 1966).
    [64] If the active layer is light emitting, the layer emits light when a sufficient bias voltage is applied to the electrical contact layer. The light emitting active layer may contain any of an organic electroluminescent material or other organic light emitting material. Such materials are small molecule materials, such as those described, for example, in US Pat. No. 4,356,429 (Tang) and US Pat. No. 4,539,507 (Van Slyke et al., The relevant portions of which are incorporated herein by reference). Can be. Alternatively, such materials are described in US Pat. No. 5,247,190 (Friend et al.), US Pat. No. 5,408,109 (Heeger et al.) And US Pat. No. 5,317,169 (Nakano et al. Polymer material, such as described in the specification). Preferred electroluminescent materials are semiconductor conjugated polymers. An example of such a polymer is poly (p-phenylenevinylene) called PPV. The light emitting material can be dispersed in a matrix of another material in the presence and absence of additives, but preferably forms a layer alone. The active organic layer generally has a thickness in the range of 50-500 nm.
    [65] When the active layer 40 is integrated into the photodetector, the layer responds to radiant energy and generates a signal in the presence or absence of a biased voltage. Substances that respond to radiation and are capable of generating signals by biased voltages (e.g. in the case of photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes) include, for example, many conjugated polymers Electroluminescent materials are included. Substances that are responsive to radiant energy and capable of generating signals in the absence of biased voltages (eg, in the case of photoconductive cells or wet photovoltaics) include chemically reacting to light rays and thus generating signals do. Such photosensitive chemically reactive materials include, for example, a number of conjugated polymers and electro- and photo-luminescent materials. Specific examples include MEH-PPV (“Optocoupler made from semiconducting polymers”, G. Yu, K. Pakbaz, and AJ Heeger, Journal of Electronic Materials , Vol. 23, pp 925-928 (1994)); And MEH-PPV complexes with CN-PPV (“Efficient Photodiodes from Interpenetrating Polymer Networks”. JJM Halls et al. (Cambridge group) Nature Vol. 376, pp. 498-500, 1995). no.
    [66] The layer 40 containing the active organic material may be applied to the first electrical contact layer 30 from solution by any of conventional means, including spin-coating, casting and printing. The active organic material can be applied directly by the deposition method depending on the nature of the material. In addition, after the active polymer precursor has been applied, it may also be converted into a polymer by heating in general.
    [67] The active layer 40 is applied on the first electrical contact layer 30 but generally does not cover the entire layer. As best seen in FIG. 2, there is a portion 31 of the first electrical contact layer extending beyond the dimensions of the active layer to enable connection with the drive and / or detection circuits in the fabricated device. do.
    [68] 4. Second electrical contact layer
    [69] The second electrical contact layer 50 is applied to the other side of the active layer 40. Although not shown in the figures, the second electrical contact layer may consist of one single layer of material, or may be a composite of multiple layers of material.
    [70] The second electrical contact layer can be essentially a material containing a metal or nonmetal capable of injecting (or collecting) charge carriers into the active layer 40 (or, optionally, from the active layer). Generally, when the second electrical contact layer is a cathode (ie an electrode that is particularly efficient for injecting or collecting electrons or negative charge carriers), the cathode has a lower working function than the first electrical contact layer (in this case the anode). It can be metal or nonmetal. The material for the second electrical contact layer can be selected from alkali metals of Group I (eg Li, Cs), Group IIA (alkaline earth) metals, Group II metals, including rare earth and lanthanide elements and actinium elements. have. Materials such as aluminum, indium, calcium, barium and magnesium and combinations thereof can be used.
    [71] Although the second electrical contact layer 50 is shown having an elongated portion 52 for connecting the device to an external circuit, the device (not shown) incorporating other circuit connection means (eg, vias). It is understood that this extension portion 52 may not be required. It is also understood that the composition of the second electrical contact layer 50 can vary over the dimensions 27, 66 of the composite barrier layers 20, 60. For example, where the second electrical contact layer 50 includes an extended portion 52, a portion of the extended portion disposed outside of the sealed composite barrier layer 20, 60 is essentially environmental It may contain a material (eg, aluminum) that is more resistant to deterioration and / or is a better conductor than the second electrical contact layer composition present over the same length as the active layer 40. That is, the second electrical contact layer composition present over the same length as the active layer 40 can be selected to provide better electron band-gap matching. At the same time, the second electrical contact layer composition in the extended portion 52 can be selected to provide greater conductivity and increased resistance to environmental degradation outside of the sealed device. The changed composition may be provided by a separate layer of the second electrical contact layer material, or may be alloyed in one second electrical contact layer.
    [72] The second electrical contact layer is typically applied by a physical vapor deposition method. In general, the second electrical contact layer is patterned as mentioned above in connection with the first electrical contact layer 30. Similar processing techniques can be used to pattern the second electrical contact layer. The second electrical contact layer generally has a thickness in the range of 50-500 nm. As the second electrical contact layer material and patterning method, those well known in the art may be used.
    [73] The portion 52 of the second electrical contact layer extends beyond the dimensions of the light emitting layer 40. As in the first electrical contact layer 30, this extended portion 52 enables connection to the drive and / or detection circuits in the manufactured device.
    [74] 5. Any other layer
    [75] It is known to have different layers in organic electronic devices. For example, to facilitate electrical charge transport and / or electron band-gap matching of layers 30 and 40, or to reduce chemical reactivity between active layer 40 and first electrical contact layer 30. There may be a layer (not shown) between the first electrical contact layer 30 and the active layer 40. Likewise, a layer (not shown) facilitates electrical charge transport and / or electron band-gap matching between layers 40, 50, or chemically reactive between active layer 40 and second electrical contact layer 50. It may be disposed between the active layer 40 and the second electrical contact layer 50 to reduce this. Layers known in the art can be used. In addition, any of the above-described layers may consist of multiple layers. Alternatively, any of the first electrical contact layer 30, the active layer 40, and the second electrical contact layer 50 can all be surface treated to increase the charge carrier transport efficiency. Moreover, additional barrier layers (not shown) may also be disposed between one of the multiple sets of layers 20, 30, 40, 50, 60 to protect them from bad process conditions.
    [76] The choice of material for each of the component layers 21A, 22, 22B, 30, 40, 50, 61A, 62, 61B can preferably be determined to balance the purpose of providing a device with high electro-optic efficiency. .
    [77] In most cases, the organic electronic device of the invention can be fabricated by first applying a first electrical contact layer and assembling the device from it. It is also possible to assemble the layers from the second electrical contact layer.
    [78] The following examples illustrate certain features and advantages of the present invention.
    [79] The following examples illustrate the invention and do not limit it.
    [80] Example 1
    [81] A flexible composite barrier structure was formed using a polyester film and a thin film barrier of SiN x . SiN x is a polyethylene that is provided by Mylar ™ 200D (provided by EI du Pont de Nemours and Company, Inc. (Wilmington, DE)) using a microwave electron cyclotron resonance (ECR) plasma. It was coated on a 0.002 inch (50.8 micron) thick film of terephthalate (PET). Prior to deposition, the chamber was evacuated to a pressure of 1.5 × 10 −7 Torr using a turbo-molecular pump. During deposition, 2 sccm (standard cubic centimeters) of SiH 4 , 98 sccm of Ar and 20 sccm of N 2 were introduced into the chamber. While maintaining the plasma at 2.455 GHz using a microwave power of 150 W, the magnetic field was adjusted to about 900 gauss corresponding to the resonance conditions for electron motion in the plasma. One hour deposition resulted in a SiN x film about 840 mm thick as measured by atomic force microscopy (AFM). Chemical depth profiling by X-ray photoelectron spectroscopy (XPS) shows that the film is essentially incorporating some oxygen (~ 10%) and speculative hydrogen (not measurable by XPS). It was confirmed that it was SiN x (x-1.15). Oxygen transport rate (OTR) through the coated PET film at 50% relative humidity was evaluated using a commercial instrument (MOCON Oxtran 2/20; manufactured by Mocon, Minneapolis, MN), 0.012 ㏄ (O 2 ) / m 2 / It was measured to be work / atm. For reference, the uncoated film of Mylar ™ 200D has an OTR of about 24 kPa (O 2 ) / m 2 / day / atm. Thus, the SiN x coating provides a barrier improvement factor of 2000 ×.
    [82] Example 2
    [83] A second flexible composite barrier structure was formed using a 200 kHz thick SiN x film barrier. SiN x was coated on a 0.002 inch (50.8 micron) thick Mylar ™ 200D PET film using microwave ECR plasma. As gas flow conditions during deposition, 2 sccm of SiH 4 , 98 sccm of Ar, and 20 sccm of N 2 were used at a microwave power of 100 W. Deposition lasted for 30 minutes. The OTR of the SiN x coated PET was then determined to be 0.12 kPa (O 2 ) / m 2 / day / atm.
    [84] Example 3
    [85] This embodiment illustrates the OTR of a flexible composite barrier structure having a laminated structure. Lamination of SiN x coated PET protects the SiN x coating from mechanical damage, impairing barrier properties. A 0.002 inch (50.8 micron) thick PET with an about 1000 μs SiN x coating, produced by microwave plasma chemical vapor deposition (CVD), was also 0.002 inch using the commercial adhesive 3M 8142 (3M, St. Paul, MN). It was laminated to uncoated PET with a (50.8 micron) thickness. The laminator had a single rubber roll and was run at 48 ° C. and 35 psi. The final structure of the laminated film was PET / 1000 mm 3 / SiN x / adhesive / PET. Subsequently, the OTR of this laminated structure was measured at 0.00825 kPa (O 2 ) / m 2 / day / atm.
    [86] Example 4
    [87] This example illustrates a flexible composite barrier structure with two stacked SiN x layers. Two PET films, each coated with about 1000 mm SiN x by microwave plasma enhanced CVD, were laminated together using an adhesive to position the SiN x film inside the structure using the conditions of Example 3, and the OTR Was measured. That is, the structure was PET / SiN x / adhesive / SiN x / PET. Prior to lamination, each SiN x coated PET film was measured to have an OTR of about 0.0075 kPa (O 2 ) / m 2 / day / atm. The OTR of the laminated structure was less than 0.005 kPa (O 2 ) / m 2 / day / atm, which is the measurement lower limit of the MOCON mechanism.
    [88] Example 5
    [89] This example illustrates the formation of an opaque composite barrier structure using aluminum (a combination of a layer of deposited aluminum and a barrier polymer to provide an oxygen and moisture barrier) as the barrier material.
    [90] The first metallized film was prepared using polyvinylidene chloride copolymer-polyester-aluminum-polyvinylidene chloride copolymer. A roll of Mylar ™ LB biaxially oriented polyester film is placed in a vacuum chamber where it is unwrapped and exposed to evaporated aluminum to give aluminum a thickness of 400 kPa (or absorbance (OD) of 2.8) on the film surface. Condensation. The metallized film was then solvent coated on both sides of the film with a composition that was essentially a copolymer of vinylidene chloride / vinyl chloride / methylmethacrylate / acrylonitrile. The dry coating weight was 1.6 g / m 2 on both coated sides.
    [91] The second metallized film was prepared by coating a Mylar ™ LB film with a 1% solution of polyethyleneimine primer in water. The dried coating weight was 0.02 to 0.2 g / m 2. The primed polyester film was then finish coated with polyvinyl alcohol at the second coater location. Anhydrous polyvinyl alcohol was diluted with 10% solution using water and steam sparging at 95-98 ° C. to create a coating bath. After cooling, the coating was applied using reverse gravure coating techniques. The dry coating weight was 0.4-1.0 g / m 2. The product was then aluminum vacuum metallized to 400 mm thick (or OD of 2.8) on the polyvinyl alcohol side as described above.
    [92] A third "pure" or nonmetalized polyester film was coated on one side with a 17% solid tetrahydrofuran solution of a mixture of poly (terephthalic acid / azelnic acid / ethylene glycol) copolymers essentially. This was a heat sealable layer. The coating was applied at a dry coating weight of 6 g / m 2 by reverse metering coating.
    [93] The first and second metallized films were laminated together using a solvent based polyurethane adhesive such that the polyvinylidene chloride layer (located on aluminum) of the first film was adjacent to the aluminum layer of the second film. The third polyester film was then laminated to the combination of the first two films using a solvent based polyurethane adhesive such that the pure polyester surface of the first two films combined was adjacent to the pure polyester film surface of the third film. The basic overall lamination structure is missing the adhesive and primer layers: polyvinylidene chloride copolymer-polyester-aluminum-polyvinylidene chloride copolymer-aluminum-polyvinyl alcohol-polyester-polyester-solvent coated polyester thermal It was a sealing layer. OTR was measured by an external laboratory to be 0.00062 kPa / m 2/24 hours / atm.
    [94] Example 6
    [95] This example illustrates the bond strength of a heat-sealed composite barrier structure.
    [96] The composite barrier structure of Example 5 was heat sealed to the following second materials representing the second barrier structure:
    [97] Example 6-A: PET (400D) 0.004 inch (50.8 micron) thick
    [98] Example 6-B: 0.004 inch (50.8 micron) thick PET (400D) coated with an unpatterned electrically conductive ITO film having a thickness of 1500-2000 mm 3
    [99] Example 6-C: 0.004 inch (50.8 micron) thick PET (400D) coated with patterned ITO lines (1 mm line width / 0.75 mm spacing) with a thickness of 1500-2000 mm 3
    [100] The composite barrier structure and the second material were arranged such that the heat sealable layer was adjacent to the second material and, if present, the ITO layer of the second material. Two 4 × 4 inch (10.2 × 10.2 cm) pieces were cut and stacked together. They were heat sealed using a Sentinel Brand Machine (Model # 12A8-0; manufactured by Packaging Group Inc., Hyannis, MA) with adjustable temperature and timer adjustment. A 1-inch (2.54 cm) seal was obtained by applying a pressure of 30 psi at the temperature and dwell time indicated below.
    [101] In order to measure the bond strength after heat sealing, the sealed structure was cut into strips 1 inch (2.54 cm) wide. Depending on the film thickness, Scotch Red Colored Cellophane Tape (Type 650) was applied to the thinner of the sealed substrate to prevent breakage at the sealing line. Peel strength was then measured on an Instron Universal Testing Instrument (Model 1122; available from Instron Corp.). A 5 pound full scale load limit was used at a crosshead speed set to run at 2 inches (5.1 cm) per minute. Peel strength was reported as the average of four samples.
    [102] Adhesion tests on patterned ITO were measured both vertically and horizontally against the ITO line. Bond strength was measured after sealing at 120 ° C. or 140 ° C. for 0.5 or 1.0 seconds. The results are summarized in Table 1 below.
    [103] Example120 ℃140 ℃0.5 sec1.0 sec0.5 sec1.0 sec 6-A667 g / in.766 g / in.864 g / in.881 g / in. 6-B1276 g / in.913 g / in.515 g / in.358 g / in. 6-C (⊥)554 g / in.668 g / in.624 g / in.--- 6-C (//)659 g / in.923 g / in.916 g / in.998 g / in.
    [104] These peel tests suggest that the polyester heat sealable layer binds to the conductive ITO more strongly and transparent under certain conditions, equally well compared to the bond to PET alone.
    [105] Adhesion of the composite barrier structure to both the electrode material and the support is illustrated in FIGS. 5 and 6. As shown in FIG. 5, the peel strength was plotted against the distance by stripping Sample 6-C (P-VIII). Peel strength varies with regular peaks and valleys corresponding to different materials (electrode materials or polymer supports) that strip the barrier structure. As shown in FIG. 6, the composite barrier structure 300 was alternately stripped from the electrode material 200 and the polymer support 400. If the barrier structure 300 only bound to the support material 400, the plot of peel strength can be expected to have a single continuous value without peaks and valleys.
    [106] Example 7
    [107] This embodiment describes the polymer light emitting diode (PLED) device lifetime (sample 7) having a composite barrier structure with a silicon nitride barrier layer compared to the lifetime of a device without a silicon nitride barrier layer (comparative sample Y). Ten sample 7 devices and ten comparative Y devices were prepared and tested.
    [108] The basic PLED device structure of both Sample 7 and Comparative Sample Y included a glass substrate with a transparent conductive anode layer of indium-tin oxide and a yellow light emitting polymer layer, each overcoated with a polymer hole-injection layer of about 100 nm. It was then covered with a thin layer (-20 nm) of low workability metal and then covered with a 1 micron thick layer of aluminum.
    [109] Sample 7 was further prepared as follows: A about 6 in 2 monolayer of 2 mil thick PET (polyethylene terephthalate) was continuously coated on both sides with a silicon nitride barrier layer of about 80 nm thick. The silicon nitride layer was placed by microwave plasma-enhanced (electrocyclotron resonance (ECR)) chemical vapor deposition (CVD). Conditions upon deposition were 150 watt microwave power, 2.7 sccm of silane (SiH 4 ), about 100 sccm Ar and 20 sccm N 2 . The silicon nitride coated PET was then laminated to another 2 mil thick sheet of uncoated PET using a 2 mil thick commercial adhesive as described in Example 3 above to form a composite barrier structure. Thereafter, 35 mm x 25 mm sections of the laminated composite barrier structure were cut and used to seal PLED devices of approximately the same area using a commercially available ultraviolet curable epoxy. Good barriers can prevent deterioration of the device caused by atmospheric gases that infiltrate the device.
    [110] Comparative Sample Y devices were further prepared as follows: Similar PLED devices were also epoxy sealed with similar PET laminates without the barrier layer of silicon nitride.
    [111] The light emission of the Sample 7 and Comparative Sample Y devices was measured 4 days after device fabrication (storage at ambient conditions) and then again after storage of the device at ambient conditions for 50 days after device fabrication.
    [112] FIG. 7A shows a plot of the initial light emission 500 of the Sample 7 photodiode and the light emission 502 of Sample 7 50 days later. There was little change in the light emission of these devices here.
    [113] In contrast, the performance of the Comparative Sample Y apparatus was significantly different. FIG. 7B shows a plot of the initial light emission 600 of the comparative sample Y photodiode and the light emission 602 of Sample 7 50 days later. Light emission was significantly reduced after storage for 50 days at ambient conditions.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] a) a first flexible composite barrier structure 20 comprising at least one layer 21A, 21B of a first polymer film and at least one layer 22 of a first barrier material and having a first inner surface 24;
    b) at least one first electrical contact layer 30;
    c) at least one active layer 40 comprising an organic active material and having dimensions defined in length and width;
    d) at least one second electrical contact layer 50;
    e) a second flexible composite barrier structure 60 comprising at least one layer 61A, 61B of the second polymer film and at least one layer 62 of the second barrier material, the second flexible composite barrier structure 60 having a second inner surface 64. In the order listed,
    Wherein at least one of the first (20) and second (60) composite barrier structures is light transmissive, and the first (20) and second (60) composite barrier structures are sealed together to enclose at least one active layer (40). Flexible organic electronic devices (10).
    [2" claim-type="Currently amended] The method of claim 1, wherein a portion of the first electrical contact layer and a portion of the second electrical contact layer extend beyond the dimensions of the active layer, and the first and second composite barrier structures also extend from the first and second electrical contact layers. Sealed to the closed part.
    [3" claim-type="Currently amended] The method of claim 1, wherein the first and second polymer films of the first and second composite barrier structures comprise polyolefins, polyesters, polyimides, polyamides, polyacrylonitriles and polymethacrylonitriles; A device selected from perfluorinated and partially fluorinated polymers, polycarbonates, polyvinylchlorides, polyurethanes, polyacrylic resins, epoxy resins, and novolac resins.
    [4" claim-type="Currently amended] The device of claim 1, wherein the first and second barrier materials are independently selected from metals, metal alloys, inorganic oxides, inorganic nitrides, inorganic carbides, inorganic fluorides, and combinations thereof.
    [5" claim-type="Currently amended] The method of claim 1, wherein the first flexible composite barrier structure and the first electrical contact layer are light transmissive; The first and second polymer films in the first composite barrier material are selected from polyethylene terephthalate, polyethylene naphthalate, polyimide, and combinations thereof.
    [6" claim-type="Currently amended] The apparatus of claim 1 wherein the barrier material is selected from aluminum, nickel, chromium, copper, tin, stainless steel, alloys thereof, inorganic oxides, inorganic nitrides, inorganic fluorides, inorganic carbides, and combinations thereof.
    [7" claim-type="Currently amended] 7. The device of any one of the preceding claims, wherein the active layer comprises a conjugated polymer.
    [8" claim-type="Currently amended] An electroluminescent display comprising the device of claim 1.
    [9" claim-type="Currently amended] A photodetector comprising the device of claim 1.
    [10" claim-type="Currently amended] A first flexible composite barrier structure containing at least one layer of the first polymer film and at least one layer of the first barrier material and having a first inner surface is disposed adjacent to the at least one first electrical contact layer outer surface;
    A second flexible composite barrier structure containing at least one layer of the second polymer film and at least one layer of the second barrier material and having a second inner surface is disposed adjacent to the outer surface of the at least one second electrical contact layer (where At least one of the first and second composite barrier structures is light transmissive);
    Characterized by obtaining the device of any one of claims 1 to 6 by sealing the first inner surface and the second inner surface together outside of the dimensions of the active layer so that the active layer is wrapped.
    At least one first electrical contact layer having a first electrical contact layer outer surface and an opposing first electrical contact layer inner surface, the organic active material being adjacent to the first electrical contact layer inner surface and having a set of dimensions At least one active layer, and at least one second electrical contact layer having a second electrical contact layer outer surface and an opposing second electrical contact layer inner surface, wherein the second electrical contact layer inner surface is adjacent to the active layer. To improve the resistance to oxygen and moisture degradation of the flexible organic electronic device.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR101964038B1|2019-04-02|Adhesive Film
    US10752814B2|2020-08-25|Pressure sensitive adhesive composition, pressure sensitive adhesive film, and method of manufacturing organic electronic device using the same
    EP3142164B1|2020-08-12|Encapsulation film
    KR101589374B1|2016-01-28|Encapsulation Film and Encapsulation Method of Organic Electronic Device Using the Same
    JP5991789B2|2016-09-14|Adhesive film
    JP5367531B2|2013-12-11|Smooth layer and barrier layer on Tg substrate
    Burrows et al.2001|Ultra barrier flexible substrates for flat panel displays
    JP6001595B2|2016-10-05|Organic electroluminescence device
    US7951726B2|2011-05-31|Organic/inorganic hybrid thin film passivation layer for blocking moisture/oxygen transmission and improving gas barrier property
    US6878467B2|2005-04-12|Organic electro-luminescence element used in a display device
    Weaver et al.2002|Organic light-emitting devices with extended operating lifetimes on plastic substrates
    US6624568B2|2003-09-23|Multilayer barrier region containing moisture- and oxygen-absorbing material for optoelectronic devices
    US20190019987A1|2019-01-17|Encapsulation film and organic electronic device comprising the same
    US7368659B2|2008-05-06|Electrodes mitigating effects of defects in organic electronic devices
    US7015639B2|2006-03-21|Electroluminescent devices and method of making transparent cathodes
    US8445937B2|2013-05-21|Barrier films for plastic substrates fabricated by atomic layer deposition
    US6592969B1|2003-07-15|Flexible substrates for organic devices
    US6617052B2|2003-09-09|Organic EL element and method of manufacturing the same
    JP5410000B2|2014-02-05|Organic electro-optical device and manufacturing method thereof
    US7075103B2|2006-07-11|Multilayer device and method of making
    US6083635A|2000-07-04|Conductive coatings
    US6818924B2|2004-11-16|Pulsed laser deposition of transparent conducting thin films on flexible substrates
    JP4383077B2|2009-12-16|Gas barrier substrate
    US6872473B2|2005-03-29|Panel display device and method for forming protective layer within the same
    US8637147B2|2014-01-28|Barrier laminate, gas barrier film and device using the same
    同族专利:
    公开号 | 公开日
    NZ514372A|2003-07-25|
    HK1043664A1|2002-09-20|
    EP1186065A1|2002-03-13|
    IL145317D0|2002-06-30|
    HU0200536A2|2002-06-29|
    US6720203B2|2004-04-13|
    US20040217348A1|2004-11-04|
    BR0011205A|2002-02-19|
    US20030207488A1|2003-11-06|
    AU4807500A|2000-11-10|
    US20030164497A1|2003-09-04|
    MXPA01010917A|2002-07-30|
    CN1348609A|2002-05-08|
    CA2367465A1|2000-11-02|
    WO2000065670A1|2000-11-02|
    US7005798B2|2006-02-28|
    AU768085B2|2003-12-04|
    JP2002543563A|2002-12-17|
    ID30404A|2001-11-29|
    TW543341B|2003-07-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-04-28|Priority to US13141699P
    1999-04-28|Priority to US60/131,416
    1999-06-07|Priority to US13792899P
    1999-06-07|Priority to US60/137,928
    2000-04-27|Application filed by 메리 이. 보울러, 이 아이 듀폰 디 네모아 앤드 캄파니
    2000-04-27|Priority to PCT/US2000/011534
    2002-02-08|Publication of KR20020011392A
    优先权:
    申请号 | 申请日 | 专利标题
    US13141699P| true| 1999-04-28|1999-04-28|
    US60/131,416|1999-04-28|
    US13792899P| true| 1999-06-07|1999-06-07|
    US60/137,928|1999-06-07|
    PCT/US2000/011534|WO2000065670A1|1999-04-28|2000-04-27|Flexible organic electronic device with improved resistance to oxygen and moisture degradation|
    [返回顶部]