WO2014073534A1 - Organic electroluminescent display device and production method for same - Google Patents

Organic electroluminescent display device and production method for same Download PDF

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Publication number
WO2014073534A1
WO2014073534A1 PCT/JP2013/079905 JP2013079905W WO2014073534A1 WO 2014073534 A1 WO2014073534 A1 WO 2014073534A1 JP 2013079905 W JP2013079905 W JP 2013079905W WO 2014073534 A1 WO2014073534 A1 WO 2014073534A1
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Prior art keywords
layer
organic electroluminescent
substrate
resin
liquid repellent
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PCT/JP2013/079905
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French (fr)
Japanese (ja)
Inventor
剛 平瀬
通 園田
岡本　哲也
亨 妹尾
有希 安田
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シャープ株式会社
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to an organic electroluminescent display device and a method for manufacturing the same, and more particularly to a technique for imparting moisture resistance to an organic electroluminescent display device.
  • Organic electroluminescence device is a self-luminous element, excellent in viewing angle, contrast, etc., and does not require a backlight, so it can be reduced in weight and thickness, and is advantageous from the viewpoint of power consumption. .
  • it since it has a high response speed and consists entirely of individuals, it is strong against external impact, has a wide operating temperature range, and has a merit that the manufacturing method is simple and inexpensive.
  • the organic light emitting element used in the organic electroluminescence device is made of an organic material and is vulnerable to moisture resistance.
  • the frit sealing is a technique in which a frit material is disposed as a sealing material around the upper and lower substrates constituting the organic electroluminescent device, and the frit material is locally heated and solidified by a laser to be sealed.
  • a configuration using an epoxy resin with low hygroscopicity as a sealing material is employed.
  • the gas barrier property is considerably inferior to that of the inorganic material only by the resin.
  • a desiccant is arranged between the upper and lower substrates constituting the organic electroluminescent device to improve the moisture resistance.
  • ODF Open Drop Fill
  • ODF was developed as a liquid crystal panel manufacturing technology, specifically, a method in which liquid crystal is dropped on a substrate before laminating the glass substrate, and another glass is laminated and bonded.
  • the ODF resin method is a sealing technique for an organic electroluminescence device, and is a method similar to ODF.
  • FIG. 4 is a cross-sectional view of a conventional organic electroluminescent device filled with resin by the ODF resin method.
  • the manufacturing process of the organic electroluminescent device 100 shown in FIG. 4 is roughly as follows. First, the light emitting layer 15 including the organic light emitting element is provided on the first substrate 12. Next, the sealing material 13 is disposed around the first substrate 12 and the second substrate 14. Thereafter, the resin material 16 is dropped, the second substrate 14 is overlaid on the first substrate 12, the sealing material 13 and the resin material 16 are cured by UV or thermosetting, and the substrates 12 and 14 are bonded together.
  • Patent Document 1 listed below describes a structure for forming a protective film (inorganic film or organic protective film, or a double layer thereof) for protecting an organic light emitting element in an organic electroluminescent device.
  • Patent Document 2 listed below discloses a frit sealing technique in which a glass frit for sealing a substrate is applied to the outer periphery and irradiated with a laser when sealing the substrate of an organic electroluminescence device.
  • Japanese Patent Publication Japanese Patent Laid-Open No. 2006-12785 (published on January 12, 2006)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2007-200890 (published on August 9, 2007)”
  • none of the above conventional techniques can sufficiently improve the moisture resistance of the organic electroluminescent device with a simple configuration.
  • FIG. 5 is a cross-sectional view of a conventional organic electroluminescent device 101 in which an inorganic film 19 is formed on the light emitting layer 15 that is a layer of an organic light emitting element.
  • the inorganic film 19 may be damaged (element degradation) 17 to the internal elements due to the occurrence of film stress due to temperature changes and the occurrence of cracks 20 or the like.
  • moisture penetrates from pinholes, cracks, or bulk of the seal portion generated in the inorganic film, thereby reducing the performance.
  • the desiccant 18 is disposed between the upper and lower substrates constituting the organic electroluminescent device, a process for disposing the desiccant 18 is required, and it is difficult to reduce the thickness of the device.
  • an object of the present invention is to provide a technique capable of improving the moisture resistance of an organic electroluminescent device with a simple configuration.
  • an organic electroluminescent device includes: (1) a first substrate; (2) In an organic electroluminescent device comprising: a light emitting element layer including at least one organic electroluminescent element located on the first substrate; and (3) a protective layer formed on the light emitting element layer. , (4) a liquid repellent layer formed so as to cover the protective layer; (5) a second substrate for sealing the first substrate; It is characterized by including.
  • FIGS. 1 to 3 An embodiment of the organic electroluminescent device of the present invention will be described with reference to FIGS. 1 to 3 as follows.
  • FIG. 1 is a cross-sectional view showing an example of an organic electroluminescent device according to the present invention.
  • the organic electroluminescent device 1 includes a first substrate 2 and a second substrate 4, a light emitting element layer 5 provided on the upper surface of the first substrate 2, and a position on the light emitting element layer 5.
  • a sealing material 3 for sealing the substrate 4 is included.
  • the light emitting element layer 5 includes at least one organic electroluminescent element (for example, an organic EL element).
  • the protective layer 6 may be an inorganic film or an organic film (parylene layer) and then an inorganic film.
  • the protective layer 6 has a role of protecting the light emitting element layer 5 so as not to be damaged by a plurality of steps performed after the light emitting element layer 5 is provided on the first substrate 2.
  • the inorganic film can be made of a combination of substances using materials such as SiN, SiON, and Al 2 O 3 . By using the above material, an effect of easily forming an inorganic film can be obtained.
  • the organic film can be a parylene film. Since the organic film is formed of a parylene film, the upper and side portions of the light emitting element layer 5 are also protected, and thus the effect of protecting the light emitting element layer 5 with high hydrophobicity, solvent resistance, and chemical resistance. Will improve. In addition, it is a material that is evenly coated on fine pinholes and cracks regardless of the shape of the object to be coated and has excellent insulation properties, so that the organic light emitting device can be protected more stably in the subsequent process. be able to.
  • the liquid repellent layer 7 may be a double layer of a resin layer formed so as to cover the protective layer 6 and a water repellent layer (liquid repellent film) formed so as to cover the resin layer.
  • the liquid repellent film may be a liquid repellent film formed by laminating a liquid repellent material on a resin layer, or the resin layer is subjected to plasma wave treatment or microwave treatment with fluorine gas or the like to impart liquid repellency.
  • a liquid film may be used.
  • the resin layer may be a combination of one or more substances selected from the group consisting of epoxy resin, acrylic resin, and silicon resin.
  • An epoxy resin is a very excellent resin, and is a resin that is easy to handle because it emits less volatile organic compounds (VOC) and has low toxicity and flammability. Further, since almost no volatile substances are produced, the curing shrinkage rate is small, and the heat resistance, moisture resistance, water resistance, chemical resistance and weather resistance are excellent. Moreover, in terms of curability, the composition can be cured at room temperature while being one-component, and can be cured in a short time because the usable energy level of ultraviolet rays is extremely high.
  • VOC volatile organic compounds
  • acrylic Since acrylic has excellent fluidity, it has an effect that it can be formed flat on the entire substrate.
  • Silicone resin is a resin excellent in water repellency and heat resistance.
  • a layer of an inorganic film such as SiN / SiON / Al 2 O 3 is formed by sputtering or CVD.
  • the entire surface of the inorganic film is filled with an epoxy resin, acrylic, or silicon material to form a resin layer, and the surface of the resin layer is subjected to a liquid repellent treatment.
  • the resin material for forming the resin layer covering the upper part of the inorganic layer By using the resin material for forming the resin layer covering the upper part of the inorganic layer, cracks in the inorganic film due to thermal expansion can be prevented. As a result, it is possible to block the slight residual moisture inside the apparatus or the intrusion of moisture attached to the glass surface, and the moisture-proof property is improved.
  • the water repellency can be further increased by using a resin layer covering the top of the inorganic layer as a resin layer having liquid repellency.
  • the barrier property is dramatically improved, damage to the organic light emitting device is reduced, and the life of the organic light emitting device is increased. Eventually, non-light emitting portions called dark spots are reduced, and as a result, dark defects are also reduced.
  • the organic electroluminescent device 1 can be divided into a pixel region I and a non-pixel region II provided around the pixel region I.
  • a pixel region I a plurality of pixels are arranged in a matrix, and each pixel is provided with an organic film layer 31 that emits light according to an image signal.
  • the organic film layer 31 is sandwiched between a first electrode 32 as an anode and a second electrode 33 as a cathode.
  • the first electrode 32 is electrically connected to the thin film transistor 34.
  • the thin film transistor 34 includes a source electrode 34a connected to a source wiring for supplying an image signal, a drain electrode 34b connected to the first electrode 32, and a gate electrode 34c to which a gate signal for controlling on / off of the thin film transistor 34 is supplied.
  • a semiconductor layer 34d connected to the source electrode 34a and the drain electrode 34b.
  • the thin film transistor 34 is covered with a planarizing film 41 such as an acrylic resin or a polyimide resin.
  • the first electrode 32, the organic film layer 31, and the second electrode 33 are formed on the planarizing film 41.
  • a pixel definition film 42 is stacked on the planarization film 41, and the second electrode 33 covers the pixel definition film 42.
  • a first metal wiring 51 is provided on the substrate 2 via a buffer layer 43 and a gate insulating film 44, and an insulating film 45 is provided on the first metal wiring 51.
  • Second metal wiring 52 is provided.
  • the first metal wiring 51 is used as a common power supply line
  • the second metal wiring 52 is electrically connected to the second electrode 33 and used as a power supply line for the second electrode 33.
  • the light emitting element layer 5 is formed on the upper surface of the first substrate 2.
  • the first substrate 2 can use glass.
  • a protective layer 6 is formed on the upper surface of the light emitting element layer 5.
  • the protective layer 6 may form an inorganic film after providing an inorganic film or an organic film (parylene layer).
  • the inorganic film may be made of a combination of substances using materials such as SiN / SiON / Al 2 O 3 .
  • the layer of the inorganic film such as SiN / SiON / Al 2 O 3 is provided by sputtering or CVD.
  • the CVD method refers to a method of obtaining at least one kind of solid reactive organism by supplying a raw material in a gas state and reacting it on the solid surface.
  • a mixed gas of a gas (which may be a plurality) containing a product element and a carrier gas (which may not be used) is used.
  • the organic film can be a parylene film.
  • the parylene can easily form a thin film on a normal temperature substrate by vapor deposition.
  • a liquid repellent layer 7 is formed on the protective layer 6.
  • the liquid repellent layer 7 is formed from a resin layer having liquid repellency so as to cover the protective layer 6.
  • the resin layer is provided with liquid repellency by laminating a liquid repellent material on the resin layer or by subjecting the resin layer to plasma wave treatment or microwave treatment with fluorine gas or the like.
  • the resin layer is preferably formed with a thickness of 1 ⁇ m to 50 ⁇ m.
  • liquid repellent layer 7 made of a resin layer on the protective layer 6
  • film stress due to thermal expansion does not occur, cracks can be prevented, and internal elements are not damaged and sealed.
  • the sealing material 3 is applied to the peripheral portion of the first substrate 2, and the first substrate 2 and the second substrate 4 are opposed to each other and bonded.
  • the second substrate 4 is irradiated with ultraviolet rays (UV) or the organic electroluminescent device 1 is heated to form the sealing material 3 and the liquid repellent layer 7 and / or the liquid repellent layer 8. Is cured. Thereby, the first substrate 2 is sealed by the second substrate 4 through the sealing material 3.
  • UV ultraviolet rays
  • the UV curing is performed at 0.5 to 10 J, preferably 1 to 6 J, particularly for the resin area.
  • baking is performed in the air in the range of 60 ° C. to 120 ° C. or 70 ° C. to 120 ° C. for 10 minutes to 2 hours and cured.
  • the bonding process of the first substrate 2 and the second substrate 4 is desirably performed in a dry atmosphere (dew point temperature of ⁇ 30 ° C. or lower, preferably ⁇ 70 ° C. or lower) or a vacuum atmosphere. It is because there exists an effect of degassing contained in antioxidant and a resin agent.
  • the liquid repellent layer 7 is formed by forming, for example, a Teflon (registered trademark) coating film as a fluororesin coating film on the surface of the resin layer.
  • the liquid repellent layer 7 may be formed by an adhesive layer having excellent liquid repellency.
  • the adhesive layer may be provided on the first substrate 2 by dropping a liquid adhesive onto the first substrate 2 by the ODF resin method described above, and the second substrate 4 may be bonded thereon.
  • the first substrate 2 on which the light emitting element layer 5 and the protective layer 6 have been formed may be bonded to the second substrate 4 by dropping a liquid adhesive onto the second substrate 4.
  • FIG. 1 shows a state in which there is a gap around the liquid repellent layer 7, but when the liquid repellent layer 7 is formed of an adhesive layer having excellent liquid repellency, the gap is eliminated.
  • the adhesive may be filled between the first substrate 2 and the second substrate 4. At that time, the first substrate 2 and the second substrate 4 are bonded together in a vacuum atmosphere (100 Pa or less), and pressure is applied in a vacuum environment while uniformly spreading the adhesive (or resin) to be filled.
  • an organic electroluminescent device (1) includes: (1) the first substrate (2); (2) a light emitting element layer (5) located on the first substrate (2) and including at least one organic electroluminescent element; (3) In an organic electroluminescent device (1) comprising a protective layer (6) formed on the light emitting element layer (5), (4) a liquid repellent layer (7) formed so as to cover the protective layer (6); (5) a second substrate (4) for sealing the first substrate (2); It is characterized by including.
  • the liquid repellent layer that covers the protective layer on the light emitting element layer
  • the liquid repellent layer improves the barrier property to block the ingress of moisture.
  • the protective layer is covered with the liquid repellent layer, the protective layer is less susceptible to the influence of the temperature change as compared with the case where the protective layer is not covered with the liquid repellent layer. Therefore, the generation of cracks in the protective layer is suppressed. As a result, since the intrusion of moisture through the crack as in the conventional case is prevented, the barrier property due to the provision of the liquid repellent layer is further improved.
  • the liquid repellent layer (7) is preferably composed of a resin layer and a liquid repellent film (liquid repellent layer 8) formed so as to cover the resin layer.
  • the “liquid-repellent film formed so as to cover the resin layer” may be a liquid-repellent film formed by laminating a liquid-repellent material on the resin layer, or the resin layer is subjected to plasma treatment with fluorine gas etc. It may be a liquid-repellent film having properties.
  • the liquid repellent layer is composed of a resin layer and a liquid repellent film formed so as to cover the resin layer, so that the intrusion of moisture is blocked and acid and alkali that adversely affect the organic light emitting element can be blocked.
  • the damage given to the organic light emitting device is reduced, which contributes to the extension of the lifetime of the organic light emitting device.
  • non-light emitting portions called dark spots are reduced, and as a result, dark defects are also reduced.
  • the liquid repellent layer is preferably composed of a resin layer having liquid repellency.
  • the liquid repellent layer is made of a resin layer having liquid repellency, so that the manufacturing process is simplified as compared with the configuration in which the liquid repellent material is laminated on the resin layer.
  • the intrusion of moisture is blocked, and it is possible to block acids and alkalis that adversely affect the organic light emitting device.
  • the damage given to the organic light emitting device is reduced, which contributes to the extension of the lifetime of the organic light emitting device.
  • non-light emitting portions called dark spots are reduced, and as a result, dark defects are also reduced.
  • the liquid repellent layer is composed of a resin layer and a liquid repellent film
  • the resin layer covered with the liquid repellent film is a resin layer having liquid repellency
  • the liquid repellent resin layer and the liquid repellent film are repelled. Since the protective layer can be double protected by the liquid film, the moisture resistance of the organic electroluminescent device can be further enhanced.
  • the resin layer is preferably made of one substance selected from the group consisting of epoxy resin, acrylic resin, and silicon resin, or a combination of these substances.
  • the resin layer is made of one substance selected from the group consisting of epoxy / acrylic / silicon materials or a combination of these substances, the resin layer is excellent in heat resistance, fluidity, etc., so that the resin layer can be easily formed. There is a further effect.
  • the epoxy resin is a resin excellent in heat resistance, moisture resistance, adhesiveness, and ease of handling. Moreover, in terms of curability, the composition can be cured at room temperature while being one-component, and can be cured in a short time because the usable energy level of ultraviolet rays is extremely high. Since the acrylic resin is excellent in fluidity, the entire substrate can be formed flat. Silicon resin is a resin excellent in water repellency and heat resistance.
  • the resin layer is preferably formed with a thickness of 1 ⁇ m to 50 ⁇ m.
  • the thickness of the resin layer is desirably set to 1 ⁇ m or more and 50 ⁇ m or less in consideration of the above points.
  • the particle suppression effect is about 1 ⁇ m or more and about 5 ⁇ m, it is considered that there is a sufficient effect.
  • the manufacturing method of the organic electroluminescent device (1) includes: (1) Organic electroluminescence comprising a first substrate, a light emitting element layer located on the first substrate and including at least one organic electroluminescent element, and a protective layer formed on the light emitting element layer In the device manufacturing method, (2) forming a liquid repellent layer so as to cover the protective layer; (3) sealing the first substrate with a second substrate; It is characterized by including.
  • the step of forming the liquid repellent layer (7) (2) forming a resin layer so as to cover the protective layer; (3) performing a plasma wave treatment or a microwave treatment on the resin layer in an atmosphere of a liquid repellent treatment gas; May be included.
  • liquid repellency can be obtained by performing liquid repellency treatment with plasma waves. Further excellent liquid repellency can be obtained by applying liquid repellency treatment with microwaves. No damage is observed in the OLED material by any liquid repellent treatment.
  • the present invention can be applied to all organic electroluminescent devices.

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Abstract

An organic electroluminescent display device provided with: a first substrate (2); a light-emitting element layer (5) that is positioned upon the first substrate (2) and contains an organic electroluminescent element; a protective layer (6) that is formed over the light-emitting element layer (5); a liquid repellent layer (7) that is formed so as to cover the protective layer (6); and a second substrate (4) that seals the first substrate (2).

Description

有機電界発光表示装置及びその製造方法Organic electroluminescent display device and manufacturing method thereof
　本発明は、有機電界発光表示装置及びその製造方法に関し、より詳細には、有機電界発光表示装置に耐湿性を持たせる技術に関する。 The present invention relates to an organic electroluminescent display device and a method for manufacturing the same, and more particularly to a technique for imparting moisture resistance to an organic electroluminescent display device.
　有機電界発光装置（Ｏｒｇａｎｉｃ　ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｃｅ　ｄｅｖｉｃｅ）は、自発光素子であり、視野角、コントラストなどに優れ、バックライトが不要なので、軽量化と薄型化が可能であり、消費電力の観点からも有利である。また、応答速度が速く、全て個体からなるため外部衝撃に強く、使用温度範囲も広く、製造方法が簡易で安価であるという長所を有する。 Organic electroluminescence device is a self-luminous element, excellent in viewing angle, contrast, etc., and does not require a backlight, so it can be reduced in weight and thickness, and is advantageous from the viewpoint of power consumption. . In addition, since it has a high response speed and consists entirely of individuals, it is strong against external impact, has a wide operating temperature range, and has a merit that the manufacturing method is simple and inexpensive.
　消費電力がブラウン管（ＣＲＴ）より低く、液晶（ＬＣＤ）と同程度で、高画質、広視野角といった特徴があり、次世代フラット・ディスプレイの本命とされている。しかし、すでに一部の携帯電話で製品化されてはいるが、耐久性の向上という課題が残されている。 Power consumption is lower than cathode ray tube (CRT), comparable to liquid crystal (LCD), with high image quality and wide viewing angle, making it the favorite of next-generation flat displays. However, although it has already been commercialized on some mobile phones, the problem of improving durability remains.
　有機電界発光装置に使われている有機発光素子は有機物で作られているため、耐湿性に対して脆弱である。 The organic light emitting element used in the organic electroluminescence device is made of an organic material and is vulnerable to moisture resistance.
　現在、耐湿性を向上させるために採用されている方式は、フリット封止等である。フリット封止とは、有機電界発光装置を構成する上下の基板の周辺部にシール材としてフリット材を配置し、レーザーでフリット材を局所加熱して固化させることによって封止する技術である。 Currently, the method employed to improve moisture resistance is frit sealing. The frit sealing is a technique in which a frit material is disposed as a sealing material around the upper and lower substrates constituting the organic electroluminescent device, and the frit material is locally heated and solidified by a laser to be sealed.
　また、シール材として、吸湿性の低いエポキシ系樹脂を用いる構成も採用されている。しかし、吸湿性が低いといっても樹脂だけに、そのガスバリア性は無機材料よりかなり劣っている。このため、シール材に樹脂を用いた構成では、有機電界発光装置を構成する上下の基板間に乾燥剤を配置し、耐湿性の向上を図っている。 Also, a configuration using an epoxy resin with low hygroscopicity as a sealing material is employed. However, even if the hygroscopicity is low, the gas barrier property is considerably inferior to that of the inorganic material only by the resin. For this reason, in the structure using resin as the sealing material, a desiccant is arranged between the upper and lower substrates constituting the organic electroluminescent device to improve the moisture resistance.
　また、有機電界発光装置の封止技術としてＯＤＦ（Ｏｐｅｎ　Ｄｒｏｐ　Ｆｉｌｌ）樹脂方式というコスト競争力のある技術がある。 In addition, as an organic electroluminescence device sealing technology, there is a cost competitive technology called ODF (Open Drop Fill) resin method.
　ＯＤＦは、液晶パネル製造技術として開発され、具体的にはガラス基板貼り合わせ前に基板上に液晶を滴下したうえで、もう一枚のガラスを重ねて接着する方式である。 ODF was developed as a liquid crystal panel manufacturing technology, specifically, a method in which liquid crystal is dropped on a substrate before laminating the glass substrate, and another glass is laminated and bonded.
　ＯＤＦ樹脂方式とは、有機電界発光装置の封止技術であって、ＯＤＦに類似した方式である。 The ODF resin method is a sealing technique for an organic electroluminescence device, and is a method similar to ODF.
　図４は、ＯＤＦ樹脂方式により樹脂を充填された従来の有機電界発光装置の断面図である。図４に示す有機電界発光装置１００の製造工程は、概略次のとおりである。まず、第１基板１２の上側に、有機発光素子を備えた発光層１５を設ける。次に、第１基板１２と第２基板１４の周辺部に、シール材１３を配置する。その後、樹脂材１６を滴下し、第１基板１２に第２基板１４を重ね、ＵＶ又は熱硬化により、シール材１３および樹脂材１６を硬化させ、両基板１２，１４を張り合わせる。 FIG. 4 is a cross-sectional view of a conventional organic electroluminescent device filled with resin by the ODF resin method. The manufacturing process of the organic electroluminescent device 100 shown in FIG. 4 is roughly as follows. First, the light emitting layer 15 including the organic light emitting element is provided on the first substrate 12. Next, the sealing material 13 is disposed around the first substrate 12 and the second substrate 14. Thereafter, the resin material 16 is dropped, the second substrate 14 is overlaid on the first substrate 12, the sealing material 13 and the resin material 16 are cured by UV or thermosetting, and the substrates 12 and 14 are bonded together.
　下掲の特許文献１には、有機電界発光装置において有機発光素子を保護する保護膜（無機膜または有機保護膜、またはこれらの二重層）を形成する構造が記載されている。 Patent Document 1 listed below describes a structure for forming a protective film (inorganic film or organic protective film, or a double layer thereof) for protecting an organic light emitting element in an organic electroluminescent device.
　また、下掲の特許文献２には、有機電界発光装置の基板を封止する際、外周に基板を封止するガラスフリットを塗布しレーザーで照射するフリット封止の技術が開示されている。 Further, Patent Document 2 listed below discloses a frit sealing technique in which a glass frit for sealing a substrate is applied to the outer periphery and irradiated with a laser when sealing the substrate of an organic electroluminescence device.
日本国公開特許公報「特開２００６－１２７８５号（２００６年１月１２日公開）」Japanese Patent Publication “Japanese Patent Laid-Open No. 2006-12785 (published on January 12, 2006)” 日本国公開特許公報「特開２００７－２００８９０号（２００７年８月９日公開）」Japanese Patent Publication “Japanese Patent Laid-Open No. 2007-200890 (published on August 9, 2007)”
　しかしながら、上記従来の技術では、いずれについても、簡易な構成で、有機電界発光装置の耐湿性を十分に高めることができない。 However, none of the above conventional techniques can sufficiently improve the moisture resistance of the organic electroluminescent device with a simple configuration.
　例えば、特許文献１に開示された構成では、有機発光素子の層の上側に無機膜を厚く形成しても、加速試験などでは耐久性が向上したとはいえない結果になる。図５は、有機発光素子の層である発光層１５の上側に無機膜１９を形成した従来の有機電界発光装置１０１の断面図である。無機膜１９は、温度変化によって膜応力が発生し、クラック２０などが入ることによって、内部素子にダメージ（素子劣化）１７を与えるおそれがある。さらに、無機膜に発生するピンホール、クラック、またはシール部バルクなどから水分が侵入し性能を低下させる。 For example, in the configuration disclosed in Patent Document 1, even if an inorganic film is formed thick above the layer of the organic light emitting element, it cannot be said that the durability is improved in an acceleration test or the like. FIG. 5 is a cross-sectional view of a conventional organic electroluminescent device 101 in which an inorganic film 19 is formed on the light emitting layer 15 that is a layer of an organic light emitting element. The inorganic film 19 may be damaged (element degradation) 17 to the internal elements due to the occurrence of film stress due to temperature changes and the occurrence of cracks 20 or the like. In addition, moisture penetrates from pinholes, cracks, or bulk of the seal portion generated in the inorganic film, thereby reducing the performance.
　このほか、有機電界発光装置を構成する上下の基板間に乾燥剤１８を配置する構成では、乾燥剤１８を配置するためのプロセスが必要になる上、装置を薄型化することが困難である。 In addition, in the configuration in which the desiccant 18 is disposed between the upper and lower substrates constituting the organic electroluminescent device, a process for disposing the desiccant 18 is required, and it is difficult to reduce the thickness of the device.
　発光層を覆うように樹脂材を滴下するＯＤＦ樹脂方式では、樹脂材の脱泡処理が必要である。さらに、ノズル詰りに対するケアや、滴下した樹脂材を位置決めする枠が必要なので、プロセスが多く装着工程が煩雑で、コストが掛かるという問題がある。 In the ODF resin method in which a resin material is dropped so as to cover the light emitting layer, it is necessary to defoam the resin material. Furthermore, since care for nozzle clogging and a frame for positioning the dropped resin material are necessary, there are problems that the process is complicated and the mounting process is complicated and costly.
　また、シール材の樹脂に代えてガラスを用いた手法もあるが、２００度という高温の焼成が必要で好ましくない。 Also, there is a method using glass instead of the resin of the sealing material, but it is not preferable because firing at a high temperature of 200 degrees is necessary.
　特許文献２に開示されたレーザーを用いたフリット封止の技術では、レーザー波長のコントロールが困難なため、３インチサイズ程度の小型装置でしか量産の歩留まりを見込めない。 In the frit sealing technique using a laser disclosed in Patent Document 2, it is difficult to control the wavelength of the laser, so the yield of mass production can be expected only with a small device of about 3 inches.
　本発明は、上記の課題に鑑みて、簡易な構成で、有機電界発光装置の耐湿性を高めることができる技術を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a technique capable of improving the moisture resistance of an organic electroluminescent device with a simple configuration.
　上記の課題を解決するために、本発明の一態様に係る有機電界発光装置は、
 (1)第一基板と、
 (2)上記第一基板上に位置し、少なくとも１つの有機電界発光素子を含む発光素子層と、 (3)上記発光素子層の上に形成された保護層とを備えた有機電界発光装置において、
 (4)上記保護層を覆うように形成された撥液層と、
 (5)上記第一基板を封止する第二基板と、
を含むことを特徴としている。 In order to solve the above-described problem, an organic electroluminescent device according to one embodiment of the present invention includes:
(1) a first substrate;
(2) In an organic electroluminescent device comprising: a light emitting element layer including at least one organic electroluminescent element located on the first substrate; and (3) a protective layer formed on the light emitting element layer. ,
(4) a liquid repellent layer formed so as to cover the protective layer;
(5) a second substrate for sealing the first substrate;
It is characterized by including.
　本発明の一態様によれば、有機電界発光装置の製造工程において、有機発光素子の劣化を防止するために、湿気などの侵入を低減する封止技術を提供することができるという効果を奏する。 According to one embodiment of the present invention, in the manufacturing process of an organic electroluminescent device, there is an effect that it is possible to provide a sealing technique that reduces intrusion of moisture and the like in order to prevent deterioration of the organic light emitting element.
本発明に係る有機電界発光装置の断面図である。It is sectional drawing of the organic electroluminescent apparatus which concerns on this invention. 本発明に係る有機電界発光装置の製造方法を説明するための断面図である。It is sectional drawing for demonstrating the manufacturing method of the organic electroluminescent apparatus which concerns on this invention. 本発明に係る有機電界発光装置における発光素子層の詳細な構成を示す断面図である。It is sectional drawing which shows the detailed structure of the light emitting element layer in the organic electroluminescent apparatus which concerns on this invention. 従来技術に係る有機電界発光装置を示す断面図である。It is sectional drawing which shows the organic electroluminescent apparatus which concerns on a prior art. 従来技術に係る有機電界発光装置を示す断面図である。It is sectional drawing which shows the organic electroluminescent apparatus which concerns on a prior art.
　　本発明の有機電界発光装置に関する実施の一形態について図１～図３に基づいて説明すれば以下のとおりである。 An embodiment of the organic electroluminescent device of the present invention will be described with reference to FIGS. 1 to 3 as follows.
　（実施形態１）
　（有機電界発光装置の基本構成）
　図１は、本発明に係る有機電界発光装置の一例を示す断面図である。図１に示すように、有機電界発光装置１は、第一基板２と、第二基板４とを含み、第一基板２の上面に設けられた発光素子層５と、その上に位置し、発光層３を被覆する保護層６と、その上に位置し、保護層６を被覆する撥液層７と、上記第一基板２の周縁部に配置され、上記第一基板２と上記第二基板４とを封止するシール材３とを含んでいる。 (Embodiment 1)
(Basic configuration of organic electroluminescence device)
FIG. 1 is a cross-sectional view showing an example of an organic electroluminescent device according to the present invention. As shown in FIG. 1, the organic electroluminescent device 1 includes a first substrate 2 and a second substrate 4, a light emitting element layer 5 provided on the upper surface of the first substrate 2, and a position on the light emitting element layer 5. A protective layer 6 for covering the light emitting layer 3; a liquid repellent layer 7 for covering the protective layer 6; and a peripheral edge of the first substrate 2; A sealing material 3 for sealing the substrate 4 is included.
　（各部の具体的な構成）
　上記発光素子層５は、少なくとも１つの有機電界発光素子（例えば、有機ＥＬ素子）を含んでいる。 (Specific configuration of each part)
The light emitting element layer 5 includes at least one organic electroluminescent element (for example, an organic EL element).
　上記保護層６は、無機膜、または有機膜（パリレン層）を設けた後、無機膜を形成するものであってもよい。上記保護層６は、第一基板２上に発光素子層５を設けた後で実施される複数の工程によって損傷を受けないように、発光素子層５を保護する役割を有する。 The protective layer 6 may be an inorganic film or an organic film (parylene layer) and then an inorganic film. The protective layer 6 has a role of protecting the light emitting element layer 5 so as not to be damaged by a plurality of steps performed after the light emitting element layer 5 is provided on the first substrate 2.
　上記無機膜は、ＳｉＮ、ＳｉＯＮ、およびＡｌ２Ｏ３等の材料を用いた物質の組み合わせからなり得る。上記の材料を用いることにより、無機膜を成膜しやすいという効果を奏する。 The inorganic film can be made of a combination of substances using materials such as SiN, SiON, and Al 2 O 3 . By using the above material, an effect of easily forming an inorganic film can be obtained.
　上記有機膜は、パリレン膜で形成され得る。上記有機膜は、パリレン膜で形成されることにより、発光素子層５の上部及び側部も保護されるため、高い疎水性、耐溶剤性、および耐化学性により発光素子層５を保護する効果が向上する。また、コーティングしようとする物体の形状に関係なく微細ピンホールやクラックにも均一にコーティングされ、絶縁性も優れた物質であるので、後の工程に対してさらに安定的に有機発光素子を保護することができる。 The organic film can be a parylene film. Since the organic film is formed of a parylene film, the upper and side portions of the light emitting element layer 5 are also protected, and thus the effect of protecting the light emitting element layer 5 with high hydrophobicity, solvent resistance, and chemical resistance. Will improve. In addition, it is a material that is evenly coated on fine pinholes and cracks regardless of the shape of the object to be coated and has excellent insulation properties, so that the organic light emitting device can be protected more stably in the subsequent process. be able to.
　上記撥液層７は、上記保護層６を覆うように形成された樹脂層と、上記樹脂層を覆うように形成された撥水層（撥液膜）の二重層であってもよい。 The liquid repellent layer 7 may be a double layer of a resin layer formed so as to cover the protective layer 6 and a water repellent layer (liquid repellent film) formed so as to cover the resin layer.
　上記撥液膜は、樹脂層上に撥液材料を積層させて形成した撥液膜でもよいし、樹脂層にフッ素ガスなどでプラズマ波処理またはマイクロ波処理を施し撥液性を持たせた撥液膜でもよい。 The liquid repellent film may be a liquid repellent film formed by laminating a liquid repellent material on a resin layer, or the resin layer is subjected to plasma wave treatment or microwave treatment with fluorine gas or the like to impart liquid repellency. A liquid film may be used.
　上記樹脂層は、エポキシ樹脂、アクリル樹脂、シリコン樹脂よりなる群から選択された１種又はそれ以上の物質の組み合わせであってもよい。 The resin layer may be a combination of one or more substances selected from the group consisting of epoxy resin, acrylic resin, and silicon resin.
　エポキシ樹脂とは、非常に優れた樹脂であって、揮発性有機化合物（ＶＯＣ）の発散が少なく、毒性および引火性が小さいので扱いやすい樹脂である。また、揮発性物質がほとんど出ないので硬化収縮率が小さく、耐熱、耐湿、耐水、耐薬品、耐候性が優れている。また、硬化性においては、一液性でありながら、室温で硬化させることができ、かつ、使用可能な紫外線のエネルギーレベルがきわめて高いため、短時間で硬化が可能となる。 An epoxy resin is a very excellent resin, and is a resin that is easy to handle because it emits less volatile organic compounds (VOC) and has low toxicity and flammability. Further, since almost no volatile substances are produced, the curing shrinkage rate is small, and the heat resistance, moisture resistance, water resistance, chemical resistance and weather resistance are excellent. Moreover, in terms of curability, the composition can be cured at room temperature while being one-component, and can be cured in a short time because the usable energy level of ultraviolet rays is extremely high.
　アクリルは、流動性に優れているので基板全体に平坦に形成できるという効果を奏する。 Since acrylic has excellent fluidity, it has an effect that it can be formed flat on the entire substrate.
　シリコン樹脂は、撥水性や、耐熱性に優れている樹脂である。 Silicone resin is a resin excellent in water repellency and heat resistance.
　一般に、発光素子層上に陰極との表面を無機膜ＳｉＯＮなどで保護膜を形成しただけでは、厚みが薄く、温度変化などにより膜応力が働きクラックなどが入る。その結果、外部から侵入する水分は封止ガラスにより遮断できるが、装置内部のわずかな残留水分、またはガラス表面に付着した水分、または封止材料に含まれる水分が内部で揮発し、有機発光素子にダメージを与え有機発光素子の特性が著しく低下し、有機発光素子の寿命に大きく影響する。最終的にはダークスポットと呼ばれる非発光部が生じ、暗欠陥となる。そのため、パネル内部では、水分を所定量以下に抑えなければならない。 Generally, simply forming a protective film on the surface of the light emitting element layer with an inorganic film SiON or the like on the light emitting element layer results in a thin thickness, which causes film stress due to temperature changes and cracks. As a result, moisture entering from the outside can be blocked by the sealing glass, but slight residual moisture inside the device, moisture attached to the glass surface, or moisture contained in the sealing material volatilizes inside, and the organic light emitting device The characteristics of the organic light emitting device are significantly deteriorated and the life of the organic light emitting device is greatly affected. Eventually, a non-light-emitting portion called a dark spot occurs, resulting in a dark defect. Therefore, moisture must be kept below a predetermined amount inside the panel.
　一方、発光素子層上の無機膜を厚くすると無機膜の形成に莫大な時間が必要であり、コスト面および材料効率も悪い。 On the other hand, if the inorganic film on the light emitting element layer is made thick, enormous time is required to form the inorganic film, and the cost and material efficiency are also poor.
　これに対して、本発明では、スパッタまたはＣＶＤ法でＳｉＮ／ＳｉＯＮ／Ａｌ２Ｏ３等の無機膜の層を形成している。この無機膜の上部を覆うようにエポキシ樹脂やアクリル、シリコン材料を用いて全面充填し樹脂層を形成し、樹脂層の表面に撥液処理を施している。 In contrast, in the present invention, a layer of an inorganic film such as SiN / SiON / Al 2 O 3 is formed by sputtering or CVD. The entire surface of the inorganic film is filled with an epoxy resin, acrylic, or silicon material to form a resin layer, and the surface of the resin layer is subjected to a liquid repellent treatment.
　無機層の上部を覆う樹脂層の形成に上記樹脂材を用いることにより、熱膨張による無機膜のクラックを防ぐことができる。その結果、装置内部のわずかな残留水分またはガラス表面に付着した水分の侵入を遮断することができ、防湿性が高くなる。また、無機層の上部を覆う樹脂層を、撥液性を持たせた樹脂層とすることにより撥水性がさらに高くなる。その結果、飛躍的にバリア性が向上し、有機発光素子に与えるダメージが低下され、有機発光素子の高寿命化に寄与する。最終的にはダークスポットと呼ばれる非発光部が減少し、その結果、暗欠陥も減少するという効果を奏する。 By using the resin material for forming the resin layer covering the upper part of the inorganic layer, cracks in the inorganic film due to thermal expansion can be prevented. As a result, it is possible to block the slight residual moisture inside the apparatus or the intrusion of moisture attached to the glass surface, and the moisture-proof property is improved. In addition, the water repellency can be further increased by using a resin layer covering the top of the inorganic layer as a resin layer having liquid repellency. As a result, the barrier property is dramatically improved, damage to the organic light emitting device is reduced, and the life of the organic light emitting device is increased. Eventually, non-light emitting portions called dark spots are reduced, and as a result, dark defects are also reduced.
　（有機電界発光素子の詳細な構成）
　ここで、図３を参照して、上記発光素子層５の詳細な構成を説明する。なお、図１に示す構成と同一の構成には、同じ符号を付して、その説明を省略する。 (Detailed configuration of organic electroluminescence device)
Here, with reference to FIG. 3, the detailed structure of the said light emitting element layer 5 is demonstrated. In addition, the same code | symbol is attached | subjected to the structure same as the structure shown in FIG. 1, and the description is abbreviate | omitted.
　図３に示すように、有機電界発光装置１は、画素領域Ｉと、画素領域Ｉの周囲に設けられた非画素領域IIとに分けることができる。画素領域Ｉには、複数の画素がマトリクス状に配置され、各画素には、画像信号に応じて発光する有機膜層３１が設けられている。 As shown in FIG. 3, the organic electroluminescent device 1 can be divided into a pixel region I and a non-pixel region II provided around the pixel region I. In the pixel region I, a plurality of pixels are arranged in a matrix, and each pixel is provided with an organic film layer 31 that emits light according to an image signal.
　上記有機膜層３１は、アノードとしての第１電極３２と、カソードとしての第２電極３３とに挟まれている。第１電極３２は、薄膜トランジスタ３４に電気的に接続されている。 The organic film layer 31 is sandwiched between a first electrode 32 as an anode and a second electrode 33 as a cathode. The first electrode 32 is electrically connected to the thin film transistor 34.
　薄膜トランジスタ３４は、画像信号を供給するソース配線に接続されたソース電極３４ａと、第１電極３２に接続されたドレイン電極３４ｂと、薄膜トランジスタ３４のオンオフを制御するゲート信号が供給されるゲート電極３４ｃと、ソース電極３４ａおよびドレイン電極３４ｂに接続された半導体層３４ｄとを備えている。 The thin film transistor 34 includes a source electrode 34a connected to a source wiring for supplying an image signal, a drain electrode 34b connected to the first electrode 32, and a gate electrode 34c to which a gate signal for controlling on / off of the thin film transistor 34 is supplied. A semiconductor layer 34d connected to the source electrode 34a and the drain electrode 34b.
　薄膜トランジスタ３４は、アクリル系樹脂またはポリイミド系樹脂などの平坦化膜４１によって覆われている。上記第１電極３２、有機膜層３１および第２電極３３は、平坦化膜４１上に形成されている。さらに、平坦化膜４１上に画素定義膜４２が積層され、画素定義膜４２上を第２電極３３が覆っている。 The thin film transistor 34 is covered with a planarizing film 41 such as an acrylic resin or a polyimide resin. The first electrode 32, the organic film layer 31, and the second electrode 33 are formed on the planarizing film 41. Further, a pixel definition film 42 is stacked on the planarization film 41, and the second electrode 33 covers the pixel definition film 42.
　一方、非画素領域IIには、基板２上に、バッファ層４３およびゲート絶縁膜４４を介して、第１メタル配線５１が設けられ、第１メタル配線５１の上に、絶縁膜４５を介して、第２メタル配線５２が設けられている。第１メタル配線５１は、共通電源供給線として使用され、第２メタル配線５２は、第２電極３３と電気的に接続され、第２電極３３に対する電源供給線として使用される。 On the other hand, in the non-pixel region II, a first metal wiring 51 is provided on the substrate 2 via a buffer layer 43 and a gate insulating film 44, and an insulating film 45 is provided on the first metal wiring 51. Second metal wiring 52 is provided. The first metal wiring 51 is used as a common power supply line, and the second metal wiring 52 is electrically connected to the second electrode 33 and used as a power supply line for the second electrode 33.
　（有機電界発光装置の製造方法）
　図２の（ａ）に示すように、第一基板２の上面には発光素子層５が形成される。上記第一基板２は、ガラスを使用し得る。 (Method for manufacturing organic electroluminescent device)
As shown in FIG. 2A, the light emitting element layer 5 is formed on the upper surface of the first substrate 2. The first substrate 2 can use glass.
　次に、図２の（ｂ）に示すように、上記発光素子層５の上面に保護層６を形成する。保護層６は、無機膜、または有機膜（パリレン層）を設けた後、無機膜を形成するものであってもよい。 Next, as shown in FIG. 2B, a protective layer 6 is formed on the upper surface of the light emitting element layer 5. The protective layer 6 may form an inorganic film after providing an inorganic film or an organic film (parylene layer).
　上記無機膜は、ＳｉＮ／ＳｉＯＮ／Ａｌ２Ｏ３等の材料を用いた物質の組み合わせからなり得る。ＳｉＮ／ＳｉＯＮ／Ａｌ２Ｏ３等の無機膜の層は、スパッタまたはＣＶＤ法によって設ける。 The inorganic film may be made of a combination of substances using materials such as SiN / SiON / Al 2 O 3 . The layer of the inorganic film such as SiN / SiON / Al 2 O 3 is provided by sputtering or CVD.
　なお、ＣＶＤ法とは、原料となる物質をガス状態で供給し、これを固体表面で反応させることにより少なくとも１種類の固体反応性生物を得る手法をいう。原料ガスには生成物元素を含むガス（複数のことがある）とキャリアガス（用いられないこともある）の混合ガスが使用される。 The CVD method refers to a method of obtaining at least one kind of solid reactive organism by supplying a raw material in a gas state and reacting it on the solid surface. As the source gas, a mixed gas of a gas (which may be a plurality) containing a product element and a carrier gas (which may not be used) is used.
　上記有機膜は、パリレン膜で形成され得る。上記パリレンは常温の基板に気相蒸着で容易に薄膜を形成することができる。 The organic film can be a parylene film. The parylene can easily form a thin film on a normal temperature substrate by vapor deposition.
　次に、図２の（ｃ）に示すように、保護層６の上に撥液層７を形成する。上記撥液層７は、上記保護層６を覆うように撥液性を備えた樹脂層から形成される。樹脂層上に撥液材料を積層させたり、樹脂層にフッ素ガスなどでプラズマ波処理またはマイクロ波処理を施したりすることにより、樹脂層に撥液性を備える。上記樹脂層は、１μｍ以上５０μｍ以下の厚さで形成することが好ましい。 Next, as shown in FIG. 2C, a liquid repellent layer 7 is formed on the protective layer 6. The liquid repellent layer 7 is formed from a resin layer having liquid repellency so as to cover the protective layer 6. The resin layer is provided with liquid repellency by laminating a liquid repellent material on the resin layer or by subjecting the resin layer to plasma wave treatment or microwave treatment with fluorine gas or the like. The resin layer is preferably formed with a thickness of 1 μm to 50 μm.
　このように、保護層６の上に樹脂層からなる撥液層７を形成することで、熱膨張による膜応力が発生せず、クラックが防止でき、内部素子にダメージを与えなることなく、封止を構成することができる。撥液層７は樹脂層から構成されるため、ピンホールが発生せず、さらに樹脂層に撥液性持たせることにより、耐湿性を向上させることができる。 Thus, by forming the liquid repellent layer 7 made of a resin layer on the protective layer 6, film stress due to thermal expansion does not occur, cracks can be prevented, and internal elements are not damaged and sealed. Can be configured. Since the liquid repellent layer 7 is composed of a resin layer, no pinholes are generated, and the moisture resistance can be improved by providing the resin layer with liquid repellency.
　続いて、図２の（ｄ）に示すように、第一基板２の周縁部にシール材３を塗布し、第一基板２と第二基板４とを対向させ、接合する。 Subsequently, as shown in FIG. 2D, the sealing material 3 is applied to the peripheral portion of the first substrate 2, and the first substrate 2 and the second substrate 4 are opposed to each other and bonded.
　そして、上記第二基板４に、紫外線（ＵＶ）を照射するか、または有機電界発光装置１を加熱することによって、シール材３と、撥液層７および／または撥液層８を形成する樹脂を硬化させる。これにより、第一基板２は、シール材３を介して第二基板４によって封止される。 The second substrate 4 is irradiated with ultraviolet rays (UV) or the organic electroluminescent device 1 is heated to form the sealing material 3 and the liquid repellent layer 7 and / or the liquid repellent layer 8. Is cured. Thereby, the first substrate 2 is sealed by the second substrate 4 through the sealing material 3.
　なお、上記ＵＶ硬化は、特に樹脂エリアに対して０．５～１０Ｊ、望ましくは１～６Ｊで行う。熱硬化の場合は、大気中にて、６０℃～１２０℃または７０℃以上１２０℃以下の範囲で、１０分以上２時間以下の時間で焼成を行い硬化する。 The UV curing is performed at 0.5 to 10 J, preferably 1 to 6 J, particularly for the resin area. In the case of thermosetting, baking is performed in the air in the range of 60 ° C. to 120 ° C. or 70 ° C. to 120 ° C. for 10 minutes to 2 hours and cured.
　上記第一基板２および第二基板４の貼り合せ工程は、乾燥雰囲気（露点温度－３０℃以下のぞましくは－７０℃以下）もしくは真空雰囲気で行うことが望ましい。酸化防止および樹脂剤に含まれるガス抜きの効果があるからである。 The bonding process of the first substrate 2 and the second substrate 4 is desirably performed in a dry atmosphere (dew point temperature of −30 ° C. or lower, preferably −70 ° C. or lower) or a vacuum atmosphere. It is because there exists an effect of degassing contained in antioxidant and a resin agent.
　（実施形態２）
　図２の（ｃ）において、保護層６の上に撥液層７を形成する場合に、上記保護層６を覆うように形成された樹脂層と、当該樹脂層の表面に撥液処理を施すようにしてもよい。 (Embodiment 2)
In FIG. 2C, when the liquid repellent layer 7 is formed on the protective layer 6, the resin layer formed so as to cover the protective layer 6 and the surface of the resin layer are subjected to liquid repellent treatment. You may do it.
　具体的には、樹脂層の表面に、フッ素樹脂コーティング膜として、例えばテフロン（登録商標）コーティング膜を形成することにより、上記撥液層７が形成される。 Specifically, the liquid repellent layer 7 is formed by forming, for example, a Teflon (registered trademark) coating film as a fluororesin coating film on the surface of the resin layer.
　（実施形態３）
　図２の（ｃ）において、撥液層７を、撥液性に優れた接着剤層によって形成してもよい。接着剤層は、前述したＯＤＦ樹脂方式により、液状の接着剤を第一基板２上に滴下することによって、第一基板２上に設け、その上に第二基板４を接合してもよいし、液状の接着剤を第二基板４上に滴下することによって、発光素子層５および保護層６を形成済みの第一基板２を第二基板４に接合してもよい。 (Embodiment 3)
In FIG. 2C, the liquid repellent layer 7 may be formed by an adhesive layer having excellent liquid repellency. The adhesive layer may be provided on the first substrate 2 by dropping a liquid adhesive onto the first substrate 2 by the ODF resin method described above, and the second substrate 4 may be bonded thereon. The first substrate 2 on which the light emitting element layer 5 and the protective layer 6 have been formed may be bonded to the second substrate 4 by dropping a liquid adhesive onto the second substrate 4.
　さらに、図１には、撥液層７の周囲に空隙がある状態を示したが、撥液層７を撥液性に優れた接着剤層によって形成する場合には、上記空隙が無くなるように、第一基板２と第二基板４との間に、接着剤が充填されるようにしてもよい。その際は、第一基板２と第二基板４とを真空雰囲気中（１００Ｐａ以下）で貼り合せ、充填する接着剤（または樹脂）を均一に広げつつ、真空環境で圧力をかける。 Further, FIG. 1 shows a state in which there is a gap around the liquid repellent layer 7, but when the liquid repellent layer 7 is formed of an adhesive layer having excellent liquid repellency, the gap is eliminated. The adhesive may be filled between the first substrate 2 and the second substrate 4. At that time, the first substrate 2 and the second substrate 4 are bonded together in a vacuum atmosphere (100 Pa or less), and pressure is applied in a vacuum environment while uniformly spreading the adhesive (or resin) to be filled.
　（まとめ）
　上記の課題を解決するために、本発明の一態様に係る有機電界発光装置（１）は、
 (1)第一基板（２）と、
 (2)上記第一基板（２）上に位置し、少なくとも１つの有機電界発光素子を含む発光素子層（５）と、
 (3)上記発光素子層（５）の上に形成された保護層（６）とを備えた有機電界発光装置（１）において、
 (4)上記保護層（６）を覆うように形成された撥液層（７）と、
 (5)上記第一基板（２）を封止する第二基板（４）と、
を含むことを特徴としている。 (Summary)
In order to solve the above problems, an organic electroluminescent device (1) according to one embodiment of the present invention includes:
(1) the first substrate (2);
(2) a light emitting element layer (5) located on the first substrate (2) and including at least one organic electroluminescent element;
(3) In an organic electroluminescent device (1) comprising a protective layer (6) formed on the light emitting element layer (5),
(4) a liquid repellent layer (7) formed so as to cover the protective layer (6);
(5) a second substrate (4) for sealing the first substrate (2);
It is characterized by including.
　上記の構成によれば、発光素子層の上の保護層を覆う撥液層が形成されていることにより、撥液層によって、水分の浸入を遮断するバリア性が向上する。また、保護層を撥液層で覆っていることにより、保護層を撥液層で覆わない形態と比較して、保護層が温度変化の影響を受けにくくなる。したがって、保護層にクラックが発生することが抑制される。この結果、従来のような、クラックを介した水分の浸入が防止されるので、撥液層を設けたことによるバリア性が一層向上する。 According to the above configuration, since the liquid repellent layer that covers the protective layer on the light emitting element layer is formed, the liquid repellent layer improves the barrier property to block the ingress of moisture. Further, since the protective layer is covered with the liquid repellent layer, the protective layer is less susceptible to the influence of the temperature change as compared with the case where the protective layer is not covered with the liquid repellent layer. Therefore, the generation of cracks in the protective layer is suppressed. As a result, since the intrusion of moisture through the crack as in the conventional case is prevented, the barrier property due to the provision of the liquid repellent layer is further improved.
　これにより、有機電界発光素子に与えるダメージが低下され、有機電界発光素子の高寿命化に寄与する。最終的にはダークスポットと呼ばれる非発光部が減少し、その結果、暗欠陥も減少する。 This reduces the damage to the organic electroluminescent element and contributes to a longer life of the organic electroluminescent element. Eventually, non-light emitting portions called dark spots are reduced, and as a result, dark defects are also reduced.
　以上のように、保護層を撥液層によって覆うという簡易な構成で、有機電界発光装置の耐湿性を高めることができるという効果を奏する。 As described above, it is possible to improve the moisture resistance of the organic electroluminescent device with a simple configuration in which the protective layer is covered with the liquid repellent layer.
　本発明の一態様に係る有機電界発光装置（１）における、
 (1)上記撥液層（７）は、樹脂層と樹脂層を覆うように形成された撥液膜（撥液層８）とからなることが好ましい。 In the organic electroluminescent device (1) according to one aspect of the present invention,
(1) The liquid repellent layer (7) is preferably composed of a resin layer and a liquid repellent film (liquid repellent layer 8) formed so as to cover the resin layer.
　上記「樹脂層を覆うように形成された撥液膜」は、樹脂層上に撥液材料を積層させて形成した撥液膜でもよいし、樹脂層にフッ素ガスなどでプラズマ処理を施し撥液性を持たせた撥液膜でもよい。 The “liquid-repellent film formed so as to cover the resin layer” may be a liquid-repellent film formed by laminating a liquid-repellent material on the resin layer, or the resin layer is subjected to plasma treatment with fluorine gas etc. It may be a liquid-repellent film having properties.
　上記撥液層は、樹脂層と樹脂層を覆うように形成された撥液膜とからなることにより、水分の侵入が遮断され、有機発光素子に悪影響を与える酸やアルカリを遮断できる。その結果、有機発光素子に与えるダメージが低下され、有機発光素子の高寿命化に寄与する。最終的にはダークスポットと呼ばれる非発光部が減少し、その結果、暗欠陥も減少するという効果を奏する。 The liquid repellent layer is composed of a resin layer and a liquid repellent film formed so as to cover the resin layer, so that the intrusion of moisture is blocked and acid and alkali that adversely affect the organic light emitting element can be blocked. As a result, the damage given to the organic light emitting device is reduced, which contributes to the extension of the lifetime of the organic light emitting device. Eventually, non-light emitting portions called dark spots are reduced, and as a result, dark defects are also reduced.
　本発明の一態様に係る有機電界発光装置（１）における、
 (1)上記撥液層は、撥液性を備えた樹脂層から成ることが好ましい。 In the organic electroluminescent device (1) according to one aspect of the present invention,
(1) The liquid repellent layer is preferably composed of a resin layer having liquid repellency.
　上記の構成によれば、撥液層は、撥液性を備えた樹脂層からなることにより、樹脂層上に撥液材料を積層させた構成よりも、製造プロセスが簡素化される。 According to the above configuration, the liquid repellent layer is made of a resin layer having liquid repellency, so that the manufacturing process is simplified as compared with the configuration in which the liquid repellent material is laminated on the resin layer.
　また、水分の侵入が遮断され、有機発光素子に悪影響を与える酸やアルカリを遮断できる。その結果、有機発光素子に与えるダメージが低下され、有機発光素子の高寿命化に寄与する。最終的にはダークスポットと呼ばれる非発光部が減少し、その結果、暗欠陥も減少するという効果を奏する。 Also, the intrusion of moisture is blocked, and it is possible to block acids and alkalis that adversely affect the organic light emitting device. As a result, the damage given to the organic light emitting device is reduced, which contributes to the extension of the lifetime of the organic light emitting device. Eventually, non-light emitting portions called dark spots are reduced, and as a result, dark defects are also reduced.
　なお、撥液層を樹脂層と撥液膜とで構成する場合に、撥液膜で覆われる樹脂層を撥液性を備えた樹脂層とすれば、撥液性を備えた樹脂層と撥液膜とによって、保護層を二重に保護することができるので、有機電界発光装置の耐湿性をさらに高めることができる。 When the liquid repellent layer is composed of a resin layer and a liquid repellent film, if the resin layer covered with the liquid repellent film is a resin layer having liquid repellency, the liquid repellent resin layer and the liquid repellent film are repelled. Since the protective layer can be double protected by the liquid film, the moisture resistance of the organic electroluminescent device can be further enhanced.
　本発明の一態様に係る有機電界発光装置（１）における、
 (1)上記樹脂層は、エポキシ樹脂、アクリル樹脂、およびシリコン樹脂よりなる群から選択された１つの物質またはこれらの物質の組み合わせからなることが好ましい。 In the organic electroluminescent device (1) according to one aspect of the present invention,
(1) The resin layer is preferably made of one substance selected from the group consisting of epoxy resin, acrylic resin, and silicon resin, or a combination of these substances.
　上記樹脂層がエポキシ／アクリル／シリコン材料よりなる群から選択された１つの物質またはこれらの物質の組み合わせからなることにより、耐熱性、流動性等に優れているため、樹脂層を形成しやすいというさらなる効果を奏する。 Since the resin layer is made of one substance selected from the group consisting of epoxy / acrylic / silicon materials or a combination of these substances, the resin layer is excellent in heat resistance, fluidity, etc., so that the resin layer can be easily formed. There is a further effect.
　ここで、エポキシ樹脂とは、耐熱性、耐湿性、接着性、取扱いの簡便さに優れている樹脂である。また、硬化性においては、一液性でありながら、室温で硬化させることができ、かつ、使用可能な紫外線のエネルギーレベルがきわめて高いため、短時間で硬化が可能となる。アクリル樹脂は、流動性に優れているので基板全体を平坦に形成できるという効果を奏する。シリコン樹脂は、撥水性や、耐熱性に優れている樹脂である。 Here, the epoxy resin is a resin excellent in heat resistance, moisture resistance, adhesiveness, and ease of handling. Moreover, in terms of curability, the composition can be cured at room temperature while being one-component, and can be cured in a short time because the usable energy level of ultraviolet rays is extremely high. Since the acrylic resin is excellent in fluidity, the entire substrate can be formed flat. Silicon resin is a resin excellent in water repellency and heat resistance.
　本発明の一態様に係る有機電界発光装置（１）における、
 (1)上記樹脂層は、１μｍ以上５０μｍ以下の厚さで形成することが好ましい。 In the organic electroluminescent device (1) according to one aspect of the present invention,
(1) The resin layer is preferably formed with a thickness of 1 μm to 50 μm.
　上記樹脂層は、シール部バルクを通して、側面から水分が侵入する場合、側面の面積が小さいほど、水分の侵入量が少なくなる。したがって、上記樹脂層は薄い方が、上記側面の面積が小さくなるので、水分の侵入量が少なくなり、有機電界発光装置の耐湿性能を向上させることができる。しかしながら、１μｍより薄くなると、樹脂層の下に有る下地層でのパーティクルの抑え込みが不十分になるため、樹脂層によって十分な撥液性が得られず、性能は著しく低下してしまう。そのため、樹脂層の厚さは、上記の点を考慮して、１μｍ以上５０μｍ以下に設置することが望ましい。なお、パーティクルの抑え込み効果は、１μｍ以上５μｍ程度であっても、十分効果はあると考えられる。 When the moisture enters from the side surface of the resin layer through the bulk of the seal portion, the amount of moisture penetration decreases as the area of the side surface decreases. Therefore, the thinner the resin layer, the smaller the area of the side surface, so that the amount of moisture intrusion is reduced and the moisture resistance performance of the organic electroluminescent device can be improved. However, if the thickness is less than 1 μm, particles are not sufficiently suppressed in the underlying layer under the resin layer, so that sufficient liquid repellency cannot be obtained by the resin layer, and the performance is significantly deteriorated. Therefore, the thickness of the resin layer is desirably set to 1 μm or more and 50 μm or less in consideration of the above points. In addition, even if the particle suppression effect is about 1 μm or more and about 5 μm, it is considered that there is a sufficient effect.
　本発明の一態様に係る有機電界発光装置（１）の製造方法は、
 (1)第一基板と、上記第一基板上に位置し、少なくとも１つの有機電界発光素子を含む発光素子層と、上記発光素子層の上に形成された保護層とを備えた有機電界発光装置の製造方法において、
 (2)上記保護層を覆うよう撥液層を形成する段階と、
 (3)上記第一基板を第二基板で封止する段階と、
を含むことを特徴としている。 The manufacturing method of the organic electroluminescent device (1) according to one aspect of the present invention includes:
(1) Organic electroluminescence comprising a first substrate, a light emitting element layer located on the first substrate and including at least one organic electroluminescent element, and a protective layer formed on the light emitting element layer In the device manufacturing method,
(2) forming a liquid repellent layer so as to cover the protective layer;
(3) sealing the first substrate with a second substrate;
It is characterized by including.
　上記の構成によれば、既に説明したように、保護層を撥液層によって覆うという簡易なプロセスを加えるだけで、有機電界発光装置の耐湿性を高めることができるという効果を奏する。 According to the above configuration, as described above, it is possible to improve the moisture resistance of the organic electroluminescent device only by adding a simple process of covering the protective layer with the liquid repellent layer.
　本発明の一態様に係る有機電界発光装置（１）の製造方法における、
 (1)上記撥液層（７）を形成する段階は、
 (2)保護層を覆うように樹脂層を形成する段階と、
 (3)上記樹脂層に対し、撥液処理用ガスの雰囲気中でプラズマ波処理またはマイクロ波処理を施す段階と、
を含んでいてもよい。 In the method for producing an organic electroluminescent device (1) according to one aspect of the present invention,
(1) The step of forming the liquid repellent layer (7)
(2) forming a resin layer so as to cover the protective layer;
(3) performing a plasma wave treatment or a microwave treatment on the resin layer in an atmosphere of a liquid repellent treatment gas;
May be included.
　上記の構成によれば、既に説明したように、保護層を撥液層によって覆うという簡易なプロセスを加えるだけで、有機電界発光装置の耐湿性を高めることができるという効果を奏する。 According to the above configuration, as described above, it is possible to improve the moisture resistance of the organic electroluminescent device only by adding a simple process of covering the protective layer with the liquid repellent layer.
　また、プラズマ波で撥液処理を施すことで、優れた撥液性が得られる。マイクロ波で撥液処理を施すことで、更に優れた撥液性が得られる。いずれの撥液処理によっても、ＯＬＥＤ材料にダメージは確認されない。 Moreover, excellent liquid repellency can be obtained by performing liquid repellency treatment with plasma waves. Further excellent liquid repellency can be obtained by applying liquid repellency treatment with microwaves. No damage is observed in the OLED material by any liquid repellent treatment.
　本発明は上述した実施形態および補足例に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、実施形態および補足例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。さらに、各実施形態にそれぞれ開示された技術的手段を組み合わせることにより、新しい技術的特徴を形成することができる。 The present invention is not limited to the above-described embodiments and supplementary examples, and various modifications are possible within the scope of the claims, and the technical means disclosed in the embodiments and supplemental examples are appropriately combined. The obtained embodiment is also included in the technical scope of the present invention. Furthermore, a new technical feature can be formed by combining the technical means disclosed in each embodiment.
　本発明は、有機電界発光装置全般に適用することができる。 The present invention can be applied to all organic electroluminescent devices.
　１　有機電界発光装置
　２、１２　第一基板
　３、１３　シール材
　４、１４　第二基板
　５、１５　発光層
　６、１６　保護層
　７　撥液層 DESCRIPTION OF SYMBOLS 1 Organic electroluminescent apparatus 2,12 1st board | substrate 3,13 Seal material 4,14 2nd board | substrate 5,15 Light emitting layer 6,16 Protective layer 7 Liquid repellent layer

Claims (7)

  1. 　第一基板と、
    　上記第一基板上に位置し、少なくとも１つの有機電界発光素子を含む発光素子層と、
    　上記発光素子層の上に形成された保護層とを備えた有機電界発光装置において、
    　上記保護層を覆うように形成された撥液層と、
    　上記第一基板を封止する第二基板と、
    を含むことを特徴とする有機電界発光装置。     A first substrate;
    A light emitting element layer located on the first substrate and including at least one organic electroluminescent element;
    In an organic electroluminescent device comprising a protective layer formed on the light emitting element layer,
    A liquid repellent layer formed so as to cover the protective layer;
    A second substrate for sealing the first substrate;
    An organic electroluminescent device comprising:
  2. 　上記撥液層は、樹脂層と当該樹脂層を覆うように形成された撥液膜とからなることを特徴とする請求項１に記載の有機電界発光装置。 The organic electroluminescent device according to claim 1, wherein the liquid repellent layer comprises a resin layer and a liquid repellent film formed so as to cover the resin layer.
  3. 　上記撥液層は、撥液性を備えた樹脂層からなることを特徴とする請求項１に記載の有機電界発光装置。 2. The organic electroluminescent device according to claim 1, wherein the liquid repellent layer comprises a resin layer having liquid repellency.
  4. 　上記樹脂層は、エポキシ樹脂、アクリル樹脂、およびシリコン樹脂よりなる群から選択された１つの物質またはこれらの物質の組み合わせからなることを特徴とする請求項２または３に記載の有機電界発光装置。 The organic electroluminescent device according to claim 2 or 3, wherein the resin layer is made of one substance selected from the group consisting of epoxy resin, acrylic resin, and silicon resin, or a combination of these substances.
  5. 　上記樹脂層は、１μｍ以上５０μｍ以下の厚さで形成することを特徴とする請求項２から４までの何れか１項に記載の有機電界発光装置。 The organic electroluminescent device according to any one of claims 2 to 4, wherein the resin layer is formed with a thickness of 1 µm to 50 µm.
  6. 　第一基板と、上記第一基板上に位置し、少なくとも１つの有機電界発光素子を含む発光素子層と、上記発光素子層の上に形成された保護層とを備えた有機電界発光装置の製造方法において、
    　上記保護層を覆うよう撥液層を形成する段階と、
    　上記第一基板を第二基板で封止する段階と
    を含むことを特徴とする有機電界発光装置の製造方法。     Production of an organic electroluminescent device comprising a first substrate, a light emitting element layer located on the first substrate and including at least one organic electroluminescent element, and a protective layer formed on the light emitting element layer In the method
    Forming a liquid repellent layer to cover the protective layer;
    Sealing the first substrate with a second substrate. A method for producing an organic electroluminescent device, comprising:
  7. 　上記撥液層を形成する段階は、
    　上記保護層を覆うように樹脂層を形成する段階と、
    　上記樹脂層に対し、撥液処理用ガスの雰囲気中でプラズマ波処理またはマイクロ波処理を施す段階と
    を含むことを特徴とする請求項６に記載の有機電界発光装置の製造方法。
          The step of forming the liquid repellent layer includes
    Forming a resin layer so as to cover the protective layer;
    The method of manufacturing an organic electroluminescence device according to claim 6, further comprising: performing plasma wave treatment or microwave treatment on the resin layer in an atmosphere of a liquid repellent treatment gas.
PCT/JP2013/079905 2012-11-12 2013-11-05 Organic electroluminescent display device and production method for same WO2014073534A1 (en)

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