CN1239396A - Organic electroluminescence device - Google Patents

Organic electroluminescence device Download PDF

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CN1239396A
CN1239396A CN 99107227 CN99107227A CN1239396A CN 1239396 A CN1239396 A CN 1239396A CN 99107227 CN99107227 CN 99107227 CN 99107227 A CN99107227 A CN 99107227A CN 1239396 A CN1239396 A CN 1239396A
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吴炯润
尹钟根
卓润兴
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Lg电子株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • H01L51/52Details of devices
    • H01L51/5237Passivation; Containers; Encapsulation, e.g. against humidity
    • H01L51/524Sealing arrangements having a self-supporting structure, e.g. containers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • H01L51/52Details of devices
    • H01L51/5237Passivation; Containers; Encapsulation, e.g. against humidity
    • H01L51/5259Passivation; Containers; Encapsulation, e.g. against humidity including getter material or desiccant

Abstract

一种具有叠层结构的有机电致发光装置,该叠层结构含有介于第一电极和第二电极之间的叠层有机薄膜,该装置含有与该叠层结构彼此隔开的吸收层,该吸收层由选自氧吸收剂、有机或无机吸湿剂以及装置抗氧化剂中的一种或一种以上材料形成,用于吸湿和吸氧,其中P Having a laminated structure of the organic electroluminescent device, the laminated structure including an organic thin film interposed between the laminated first and second electrodes, the apparatus comprising the absorbent layer and the laminated structure is spaced apart from each other, the absorbent layer is selected from oxygen absorber, inorganic or organic hygroscopic agents and antioxidants means one or more materials, for moisture and oxygen, wherein P

Description

有机电致发光装置 The organic electroluminescent device

本发明涉及显示装置,更具体地说,涉及一种有机电致发光装置。 The present invention relates to a display apparatus, and more particularly, relates to an organic electroluminescent device.

随着显示装置的尺寸变得更大,占用更少空间的平面显示装置的需求增加,作为其中之一的有机电致发光装置也引起了注意。 As the size of the display apparatus becomes larger, it takes up less space in the plane of the display device increased demand, as one of the organic electroluminescent device is also attracting attention. 根据其中使用的材料,分成无机电致发光装置和有机电致发光装置。 The material used therein, is divided into an inorganic electroluminescent device and an organic electroluminescent device. 在无机电致发光装置中,发光单元被施加高电场并且电子在此高电场中加速,撞击到其中的发光中心上,激发发光中心发光。 In the inorganic electroluminescent device, a high electric field is applied to the light emitting unit and the electrons accelerated in this high electric field, which impinges on the light emission center, light emission excited emission centers. 在有机电致发光装置中,从阴极和阳极分别将电子和空穴注射入发光单元中,这样注射的电子和空穴耦合成电子-空穴对(exiton),当电子-空穴对从受激状态落到基态时发射光。 In the organic electroluminescent device, the cathode and anode, respectively, from electrons and holes injected into the light emitting unit, such a coupling of electrons and holes injected into the electron - hole pairs (exiton), when the electron - hole pairs from the subject when the excited state emits light falls the ground state. 由于上述工作原理,要求大约100~200伏相对高的驱动电压故在无机电致发光装置要求强电场的时候,因为有机电致发光装置在5~20伏的低电压下能够工作的优势,对有机电致发光装置的研究已经活跃起来。 Due to the above principle, requires about 100 to 200 volts relatively high driving voltage it is caused when a light emitting device according strong electric field in inorganic as organic electroluminescent advantages emitting device capable of operating at a low voltage of 5 to 20 volts, for studies organic electroluminescent device has been active. 除了上述的优点之外,因为有机电致发光装置具有例如视角宽,响应速度快、高对比度的卓越特性,所以有机电致发光装置能够用作图形显示像素(pixel)、或者用作TV图像显示中的或表面光源中的像素,并且由于有机电致发光装置薄且轻以及色感好,所以有机电致发光装置适用于下一代的平面显示装置。 In addition to the above-mentioned advantages, because, for example, organic electroluminescent device having a wide viewing angle, fast response, high contrast outstanding features, the organic electroluminescence device emitting display pixels can be used as graphics (Pixel), or as an image display TV or a surface light source of the pixel, and an organic electroluminescent device since the thin and lightweight and good color sense, the organic electroluminescent device is suitable for next generation flat display device.

但是,有机电致发光装置实际应用于商业用途时的最大缺陷之一是使用寿命短。 However, one of the biggest drawback of the organic electroluminescent device at the time of the actual short life is used for commercial purposes. 决定装置寿命的因素有许多,其中主要的一些是,在有机材料中存在杂质、该有机材料与电极之间的界面状态、低结晶温度(Tg)以及装置被氧和湿气氧化。 Factors that determine the life of many devices, some of which is the main, the presence of impurities in the organic material, the interface state between the electrodes and the organic material, a low crystallization temperature (Tg) of oxygen and moisture and the device is oxidized. 有机材料中的杂质捕获空穴和电子,或者引起漏电,并且强化有机材料的结晶,从而缩短装置的寿命。 The organic impurities in the material capture holes and electrons, or cause leakage and reinforced crystalline organic material, thus shortening the life of the device. 如果该有机材料与该电极之间的界面状态不适合、将引起电荷(电子或者空穴)注射受阻或者电流过大,对有机材料带来损害。 If the organic material is not suitable for the state of the interface between the electrodes, would cause electric charge (electrons or holes) injected hindered or current is too large, the damage caused to the organic material. 除了该电极和该有机材料之间的界面状态不适合的情况之外,当有机材料之间的界面状态不良也会产生问题。 In addition to the state of the interface between the electrode and the organic material is not appropriate, when the failure state of the interface between the organic material can also cause problems. 即,由于材料从发光层(1ight emitting layer)(LEL)向空穴传递层(hole transport layer)(HTL)扩散和从空穴传递层向发光层扩散阻碍发光层中的电子运动,装置的发光效率恶化。 That is, since the movement of the electron emitting material is diffused and the light emitting layer hinder diffusion layer emitting layer, the transfer means from the light emitting layer from the hole (1ight emitting layer) (LEL) to the hole transport layer (hole transport layer) (HTL) efficiency deteriorates. 发光层和空穴传递层都由有机材料形成,扩散是发光层和空穴传递层之间的界面的内部扩散引起的。 A light emitting layer and a hole transport layer formed by an organic material, diffusion is diffused into the interface between the light emitting layer and a hole transport layer caused. 并且,低结晶温度的有机材料用作该装置材料的情况下,出射(exited)分子的传递由于该装置内的结晶而到了不发射光的程度,在发射光的级别上不发射光,降低发光效率并缩短装置的寿命。 Case where a low crystallization temperature the organic material is used as the apparatus material, passing the exit (the Exited) molecules by crystallization within the apparatus to the point of light is not emitted, no light is emitted at the level of the emitted light, reducing light emission efficiency and shorten the life of the device. 虽然可以通过提炼该有机材料、开发具有高结晶温度的材料以及引入提高有机材料和电极之间界面的粘合力的材料解决上述的问题,但是最难于解决的问题是除去氧和湿气。 Although the material may have a high crystallization temperature by rendering the organic material, and the material is introduced to improve the development of adhesion on the interface between the organic material and the electrode to solve the above problems, but the most difficult problem is the removal of oxygen and moisture. 湿气和氧或者在制造过程中已经存在于该装置中或者在制造该装置期间从外部渗透进入该装置中。 Moisture and oxygen during the manufacturing process or already present in the device or during the manufacture of the device penetrate into the device from the outside. 在后一种情况中,湿气和氧渗透到装置中的针孔内,氧化有机薄膜和金属、减少发光的面积,这意味着失去发光的功能。 In the latter case, the penetration of moisture and oxygen into the device a pinhole, a metal oxide and an organic thin film, reducing the light emitting area, which means that the loss of function of emitting light. 为了解决所述问题,提出了用聚合物保护薄膜覆盖该装置以阻挡湿气或氧的方法或者用一屏蔽玻璃并且在该屏蔽玻璃与该装置之间的空间填充硅油以阻挡湿气和氧的方法。 To solve the problem, a method with a polymer protective film covering the means to block moisture or oxygen, or by a glass shield and shield the space between the glass and the apparatus filled with silicone oil to block moisture and oxygen method.

图1显示相关技术装置的断面图。 Figure 1 shows a cross-sectional view of the related art apparatus. 该相关技术装置通过在具有玻璃1、第一电极2、有机多层(例如空穴注射层(injecting layer)、空穴传递层、电子注射层或者电子传递层)3和第二电极4的连续多层结构上形成保护薄膜5而阻挡湿气和氧。 By means of the related art 3 and the second electrode having a continuous glass 1, a first electrode 2, the organic multi-layer (e.g., a hole injection layer (injecting layer), a hole transport layer, electron injection layer or electron transport layer) 4 the multilayer structure is formed on the protective film 5 while blocking moisture and oxygen. 该保护膜5由聚合物形成。 The protective film 5 is formed of a polymer. 该聚合物为电绝缘的聚合化合物,主要是基于插烯物系的聚合物,具有聚乙烯、聚丙烯或者氟。 The polymerizable compound is electrically insulating polymer, polymer mainly based vinylogous system thereof, with polyethylene, polypropylene or fluorine. 然而在该层上真空共淀积该聚合物时,图1的装置发生困难并且不能够提供阻挡湿气和氧进入该装置的满意效果。 However vacuum co-deposition of the polymer on the layer, generating apparatus of FIG. 1 without difficulty and can provide a barrier to moisture and oxygen into the device is satisfactory results.

图2图示了美国专利5,505,985所提出的装置。 FIG 2 illustrates an apparatus set forth in U.S. Patent 5,505,985. 美国专利5,505,985显示了有机电致发光装置所提供的装置的结构,其具有一玻璃1、第一电极2、包括空穴注射层、空穴传递层、电子注射层或者电子传递层的有机多层3、第二电极4和保护层5、覆盖有机电致发光装置整个表面的屏蔽玻璃6、通过注射开口7在屏蔽玻璃和该装置之间注入的硅油8以及阻挡注射开口7的玻璃盖9。 U.S. Patent No. 5,505,985 shows a device structure of an organic electroluminescence light-emitting device is provided, which has a glass 1, a first electrode 2, comprising a hole injection layer, a hole transport layer, electron injection layer or the electron transport layer is an organic multilayer 3, the second electrode 4 and the protective layer 5 are covered with shielding the entire surface of the glass electroluminescent light-emitting device 6, 7 in the glass between the glass shield and the silicone oil injection apparatus 8 and the barrier injection opening 7 of the cover 9 through the injection opening.

同时,图3表示了除了图3中在屏蔽玻璃6下方具有吸湿层10和在吸湿层10下方具有聚合物支撑层11之外与图2结构相似的总体示图。 Meanwhile, FIG. 3 shows a similar overall and 10 of FIG. 2 shows a configuration diagram of FIG 3 except that 11 beyond the absorbent layer under the shield having a glass 6 having a polymeric support layer under the absorbent layer 10. 吸湿层10由吸湿剂形成,例如氧化铝、硅胶或者沸石。 The absorbent layer 10 is formed of a moisture-absorbing agent, such as alumina, silica gel or zeolite. 根据支撑层11的聚合物性质,图3所示的装置可以包括该吸湿层10的活性落差,例如如果支撑层11的聚合物为不吸湿的材料,则吸湿层10的材料相反阻挡吸湿。 The nature of the polymer support layer 11, the apparatus shown in Figure 3 may include an active gap of the absorbent layer 10, for example if the supporting layer 11 is a polymer of non-hygroscopic material, the absorbent material 10 opposite the barrier layer absorbent. 并且用于图2和3中结构的硅油渗透进装置的内部可能缩短装置的寿命,因为渗透的硅油可能成为一种杂质,阻挡电子在该装置中的传递。 Internal and silicone oils. 2 and 3 for the structure of FIG penetrate apparatus may shorten the life of the device, because of the penetration of silicone oil may be an impurity, the electron transfer blocking means.

总之,在相关技术的有机电致发光装置中,用于阻挡湿气和氧的支撑层不能有效阻挡湿气和氧,并且用于阻挡湿气和氧的硅油渗透到该装置内,缩短装置的寿命。 In short, the related art organic electroluminescent device, the support layer for blocking moisture and oxygen can not effectively block moisture and oxygen, and for blocking moisture and oxygen penetration of silicone oil into the apparatus, shortening means life.

因此,本发明致力于基本上排除相关技术的局限和缺陷造成的几个问题。 Accordingly, the present invention is directed to the substantial exclusion of several questions related to technical limitations and defects caused.

本发明的目的之一是提供一种能够阻挡湿气和氧以延长装置的寿命的有机电致发光装置。 One object of the present invention is to provide a moisture and oxygen barrier means to extend the life of the organic electroluminescent device.

本发明另外的特征和优点将在下列的描述中陈述,并且部分将因这些描述而显而易见,或者可以通过本发明的实践得知。 Additional features and advantages of the invention will be set forth in the following description, and in part will be obvious from the description by these, or may be learned by practice of the invention. 通过文字描述和其权利要求以及附图中特别指出的结构,将实现和达到本发明的目的和其它优点。 The written description and claims hereof as well as the structure particularly pointed out in the drawings, it will be realized and attained objectives and other advantages of the present invention.

作为概括和更广地描述,为了实现根据本发明的这些目的和优点,该有机电致发光装置包括含有介于第一电极和第二电极之间的叠层有机薄膜的一叠层结构,以及与该叠层结构彼此隔开的,由选自氧吸收剂、有机或无机吸湿剂、装置抗氧化剂中的一种或一种以上材料和它们的混合物形成的、用于吸湿和吸氧的吸收层。 As described and broader generalization, To achieve these objects and advantages of the present invention, the organic electroluminescent device comprising a laminated structure comprising stacked between the organic thin film between the first electrode and the second electrode, and the laminated structure with spaced, selected from oxygen absorber, inorganic or organic hygroscopic agent, an anti-oxidant means one or more materials or a mixture thereof and is formed, for absorbing the moisture and oxygen Floor.

“装置抗氧化剂”是指能够阻止叠层有机薄膜和第二电极氧化的试剂。 "Means an anti-oxidant" refers to an organic thin film laminate can be prevented and a second electrode oxidation reagent. 此氧化是有机和无机吸湿剂吸收湿气时,这些吸收剂液化引起的。 This oxidation is an organic and inorganic moisture-absorbing agent absorbs moisture, these absorbents cause liquefaction. 因此在本发明中,在该有机或无机吸湿剂吸湿之前或者之后,该装置抗氧化剂适宜于与该叠层有机薄膜或者第二电极通过惰性气体等等接触,以阻止该叠层有机薄膜和该第二电极的氧化。 Therefore, in the present invention, before the organic or inorganic absorbent or after the moisture absorbent, an antioxidant adapted to the apparatus by an inert gas and the like in contact with the organic thin film laminate or the second electrode to prevent the organic film and the laminate oxidation of the second electrode.

该氧吸收剂可以是1,2,3-苯三酚或者连二亚硫酸钠(Na2S2O4)。 The oxygen absorber may be pyrogallol or sodium dithionite (Na2S2O4). 并且该无机吸湿剂可以是一种或者一种以上选自下列的材料:IA族、IIA族和IIIA族的金属氧化物、氧化铝、硅胶、沸石和P2O5。 And inorganic hygroscopic agent may be one or more than one material selected from the group consisting of: Group IA metal oxides, IIA and IIIA of the Group, alumina, silica gel, zeolite, and P2O5. 并且,该金属氧化物优选为选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3中的一种。 And, the metal oxide is preferably selected from BaO, one kind of Li2O, Na2O, K2O, BeO, MgO, CaO, and B2O3 in. 有机吸湿剂可以是一种聚合物,该聚合物选自基于丙烯酰基的聚合物、聚脲、聚酰胺和聚酰亚胺,具有结构式-(CHX1-CHX2)n-(X1和X2的至少一个亲水基团)的化合物,其中X1或X2可以是选自羟基、氢、烷基、链烯基、酯基、醚基和氨基中的任一种,并且该聚合物优选为聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)以及它们的共聚物。 The organic hygroscopic agent may be a polymer, the polymer is selected from acryl-based polymer, polyurea, polyamide and polyimide having a structural formula - (CHX1-CHX2) n- (at least one of X1 and X2 compound having a hydrophilic group), wherein X1 or X2 may be selected from hydroxyl, hydrogen, an alkyl group, an alkenyl group, an ester group, an ether group, and any amino group, and the polymer is preferably a poly (vinyl alcohol ), poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) and copolymers thereof. 与此同时,该装置抗氧化剂可以是碱金属盐、金属或者它们的混合物,其中该碱金属盐优选为选自磷酸盐、硫酸盐或者碳酸盐中的一种或者一种以上的混合物,并且该金属可以优选为选自碱金属、碱土金属和电离度高于氢的金属。 At the same time, the apparatus may be an alkali metal salt of an anti-oxidant, metal or mixtures thereof, wherein the alkali metal salt is preferably selected from a phosphate, a sulfate or a carbonate or a mixture of more than one, and the metal may preferably be selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen. 该碱金属盐可以更优选为选自磷酸盐中的Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种或者一种以上的混合物,并且该金属可以更优选为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn中的一种粉末状材料。 The alkali metal salt may be more preferably Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 one kind or a mixture of one or more selected from the group of phosphates, and the metal may be more preferably selected from Na, K , Mg, Ca, Al, Cr, Mn, Fe, Co, Ni, Cu and Zn in a powdery material. 可以将惰性气体填充在该叠层结构和该吸收层之间的空间中。 Inert gas may be filled in a space between the laminated structure and the absorber layer.

该有机电致发光装置可以进一步包括用于支撑该吸收层的、形成于与该叠层结构相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 The organic electroluminescent device may further comprise a support for the absorber layer, is formed, a porous support layer of a polymer or glass on the bottom surface opposite to the absorbent layer of the laminated structure. 该聚合物可以是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种或者一种以上。 The polymer may be selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (the PET), poly (methyl methacrylate) (PMMA ), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, nylon, polyurethane, poly (chlorotrifluoroethylene ethylene), polyolefins, polycarbonates, polysulfones and polyacetal of one or more than one. 用于吸湿的吸收层的材料最优选为P2O5。 A layer of absorbent material for absorbing most preferably P2O5.

本发明提供一种具有叠层结构的有机电致发光装置,该叠层结构含有介于第一电极和第二电极之间的叠层有机薄膜,在该叠层结构上方形成以覆盖该叠层结构整个表面的屏蔽板,以及由选自氧吸收剂、有机或无机吸湿剂、装置抗氧化剂中的一种或一种以上材料以及它们的混合物在该屏蔽板的底表面上形成的用于吸湿和吸氧的吸收层。 The present invention provides a laminated structure of the organic electroluminescent device, the laminated structure including an organic thin film interposed between the laminated first electrode and a second electrode formed to cover the top of the stack in the laminate structure structure of the entire surface of the shielding plate, and selected from oxygen absorber, inorganic or organic hygroscopic agent, an anti-oxidant means one or more materials, and mixtures thereof is formed on the bottom surface of the shield plate for absorbent and an oxygen absorbing layer. 该氧吸收剂可以是1,2,3-苯三酚或者连二亚硫酸钠(Na2S2O4)。 The oxygen absorber may be pyrogallol or sodium dithionite (Na2S2O4). 并且该无机吸湿剂可以是一种或者一种以上选自下列的材料:选自IA族、IIA族和IIIA族的金属氧化物、氧化铝、硅胶、沸石和P2O5。 And inorganic hygroscopic agent may be one or more than one material selected from the group consisting of: a metal oxide selected from Group IA, IIA and IIIA of the Group, alumina, silica gel, zeolite, and P2O5. 并且,该无机吸湿剂中的金属氧化物优选为选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3中的一种。 Further, the metal oxide is preferably an inorganic hygroscopic agent is selected from BaO, one kind of Li2O, Na2O, K2O, BeO, MgO, CaO, and B2O3 in. 该有机吸湿剂可以是一种聚合物,该聚合物选自基于丙烯酰基的聚合物、聚脲、聚酰胺和聚酰亚胺,或者具有结构式-(CHX1-CHX2)n-(X1和X2的至少一个是亲水基团)的化合物,其中X1或X2可以是选自氢、烷基、链烯基、酯基、醚基和氨基中的任一种,并且该有机吸湿剂优选为选自聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)以及它们的共聚物中的一种。 The moisture absorbent may be an organic polymer, the polymer is selected from acryl-based polymer, polyurea, polyamide and polyimide, or having the structural formula - (CHX1-CHX2) n- (X1 and X2 at least one hydrophilic group) with a compound, wherein X1 or X2 may be selected from hydrogen, an alkyl group, an alkenyl group, an ester group, an ether group, and any amino group, and the organic hygroscopic agent is preferably selected from poly (vinyl alcohol), poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) and copolymers of one. 可以将惰性气体填充在该叠层结构和该吸收层之间的空间中。 Inert gas may be filled in a space between the laminated structure and the absorber layer.

该有机电致发光装置可以进一步包括用于支撑该吸收层的、形成于与该叠层结构相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 The organic electroluminescent device may further comprise a support for the absorber layer, is formed, a porous support layer of a polymer or glass on the bottom surface opposite to the absorbent layer of the laminated structure. 该聚合物可以是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种或者一种以上。 The polymer may be selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (the PET), poly (methyl methacrylate) (PMMA ), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, nylon, polyurethane, poly (chlorotrifluoroethylene ethylene), polyolefins, polycarbonates, polysulfones and polyacetal of one or more than one. P2O5为最优选用于吸湿的材料。 P2O5 is the most preferred material for the absorbent. 与此同时,该装置抗氧化剂可以是碱金属盐、金属或者它们的混合物,其中该碱金属盐优选为选自磷酸盐、硫酸盐或者碳酸盐中的一种或者一种以上的混合物,该磷酸盐可以更优选为选自Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种或者一种以上的混合物。 At the same time, the apparatus may be an alkali metal salt of an anti-oxidant, metal or mixtures thereof, wherein the alkali metal salt is preferably selected from a phosphate, a sulfate or a carbonate or a mixture of one or more of the more preferably selected from phosphate Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 one kind or a mixture of more than one. 用作该装置抗氧化材料的金属可以是选自碱金属、碱土金属和电离度高于氢的金属,优选为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn的一种粉末状材料。 As an anti-oxidizing material of the device may be a metal selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen, preferably selected from Na, K, Mg, Ca, Al, Cr, Mn, Fe, Co, Ni , Cu and Zn in a powdered material.

本发明提(a)在一种基片上形成的第一电极,(b)在该第一电极上形成的叠层有机薄膜,(c)在该叠层有机薄膜上形成的第二电极,(d)在该第二电极上方形成的以覆盖该第二电极和该叠层有机薄膜整个表面的屏蔽板;以及(e)在该屏蔽板底表面上形成的吸收层,该吸收层由下述材料组成,选自1,2,3-苯三酚和连二亚硫酸钠(Na2S2O4)的第一种材料,选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3、氧化铝、硅胶、沸石和P2O5中的一种或者一种以上的混合物的第二种材料,选自聚(乙烯醇)、聚乙烯吡咯烷酮、聚甲基丙烯酸、聚(乙烯基对苯二酚)和它们的共聚物的第三种材料,选自磷酸盐、硫酸盐和碳酸盐中的一种或者一种以上的混合物的第四种材料,选自碱金属、碱土金属和电离度高于氢的金属的第五种材料,或者从第一至第五种材料中选择两种材料的或者两种以上材料 A first electrode present tora (a) formed on one kind of substrate, (b) an organic laminated thin film formed on the first electrode, (c) a second electrode formed on the organic thin film laminate, ( d) to cover the second electrode and the organic thin film laminated surface of the entire shield plate is formed in the second upper electrode; and (e) absorbing layer formed on the bottom surface of the shielding plate, the absorbent layer by the following material selected from pyrogallol and sodium dithionite (of Na2S2O4) of a first material selected from BaO, Li2O, Na2O, K2O, BeO, MgO, CaO, and of B2O3, alumina, silica gel, P2O5 and zeolite in one or more second material or mixture, selected from poly (vinyl alcohol), polyvinylpyrrolidone, polymethacrylic acid, poly (vinyl hydroquinone) and copolymers thereof a third material, selected from phosphates, sulfates and carbonates of one kind or more than one fourth material mixture, selected from alkali metals, alkaline earth metals and the ionization degree higher than the first metal hydrogen five kinds of material, or two materials selected from the first to fifth material or two or more materials 合的第六种材料。 Sixth bonding material. 在此种情况下,可以在该第二电极和该吸收层之间的空间中填充一种惰性气体,并且该有机电致发光装置可以进一步包括用于支撑该吸收层的、形成于与该第二电极相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 In this case, an inert gas may be filled in the space between the second electrode and the absorber layer, and the organic electroluminescence light emitting device may further comprise a support for the absorber layer, is formed on the first and , porous support layer of a polymer or glass two electrodes on the bottom surface of the absorbent layer opposite. 该支撑层的聚合物可以优选为选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种或者一种以上。 The polymeric support layer may preferably be selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (the PET), poly (methyl methacrylate ester) (of PMMA), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, nylon, polyurethane , poly (vinyl chloride), polyolefins, polycarbonates, polysulfones and polyacetal of one or more than one. 作为第二种材料P2O5是最优选的,并且可以进一步将一种以上的装置抗氧化剂,如碱金属盐、金属或者它们的混合物加入其中。 P2O5 as the second material is most preferred, and may further be more than one apparatus antioxidants, such as alkali metal salts, metal or mixtures thereof added thereto. 与此同时,优选作为该装置抗氧化剂的碱金属盐可以是一种磷酸盐,其为选自Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种或者一种以上的混合物,硫酸盐或者碳酸盐,并且用作该装置抗氧化材料的金属可以是选自碱金属、碱土金属和电离度高于氢的金属,优选为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn的一种粉末状材料。 At the same time, an antioxidant is preferably an alkali metal salt of the apparatus may be a phosphate, which is selected Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 one kind or more than one in a mixture of sulfuric acid salts or carbonates, and used as the metal material in the oxidation means may be selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen, preferably selected from Na, K, Mg, Ca, Al, Cr, mn, Fe, Co, Ni, Cu and Zn in a powdered material.

根据本发明优选实施方案的有机电致发光装置,具有含有介于第一电极和第二电极之间的叠层有机薄膜的叠层结构,包括P2O5吸收层和一种以上装置抗氧化剂。 According to a preferred embodiment of the present invention is an organic electroluminescent device having a stacked-layer structure laminate comprising an organic thin film interposed between the first electrode and the second electrode, and the absorbent layer comprises P2O5 means one or more antioxidants. Na3PO4为优选的装置抗氧化剂。 Na3PO4 preferred apparatus antioxidant.

上述的一般描述和以下的详细描述均应当被理解为示例和解释,并且试图给本发明的权利要求提供进一步的说明。 General description and the following detailed description of the above are to be understood as exemplary and explanatory, and attempt to claim the present invention to provide further explanation.

为了进一步理解本发明,此说明书包括附图,并且将其合并作为说明书的组成部分,附图图示了本发明的实施方案并和文字说明部分一起用来阐述本发明的原理。 For a further understanding of the present invention, this specification including the drawings, and which is incorporated as part of the specification, illustrate embodiments of the invention, and text portions and serve to explain the principles of the present invention.

附图中:图1~3各显示了一种背景技术装置的断面图解;且图4和5分别显示根据本发明优选实施方案的有机电致发光装置的断面图解。 In the drawings: Figures 1 to 3 each show a cross-sectional illustration of one context art device; and Figures 4 and 5 show a diagrammatic cross section has an organic electroluminescent device according to a preferred embodiment of the invention.

现在详细论述本发明的优选实施方案,在附图中图解其实施例。 Is now discussed in detail preferred embodiments of the invention, illustrated in the accompanying drawings embodiments thereof. 为了提高装置的稳定性并延长装置的寿命,本发明的有机电致发光装置用氧吸收剂、有机或无机吸湿剂、装置抗氧化剂或者它们的混合物作为保护薄膜的材料,该保护薄膜阻挡对该装置产生致命影响的湿气和氧。 In order to improve the stability of the device and extend the life of the device, the present invention is an organic electroluminescent device with a material with oxygen absorbing agent, an organic or inorganic moisture-absorbing agent, an antioxidant or a mixture thereof means as a protective film, the protective film of the barrier It means lethal effect of moisture and oxygen. 即,不仅为了提高装置的寿命,而且为了简化装置的结构,本发明避开了背景技术中灌入硅油的复杂结构,使用具有出色吸湿和吸氧能力的吸收剂代替背景技术中对湿气和氧阻挡能力低的保护材料。 That is, not only in order to improve the life of the device, and in order to simplify the structure of the apparatus, the present invention avoids the complex structure of the background art poured into the silicone oil, instead of using an absorbent with excellent absorption background art and the moisture absorbing ability and low ability to protect the oxygen barrier material.

参照图4,根据本发明优选实施方案的有机电致发光装置包括在带有第一电极23的叠层结构表面上形成的保护薄膜29,叠层有机薄膜(具有空穴注射层或者空穴传递层、有机发光层和电子传递层或者电子注射层)25,以及在透明基片21上形成的第二电极27,以及带有形成在叠层结构的上方的吸收层35的屏蔽板37,以覆盖保护薄膜29。 4, there is according to a preferred embodiment with reference to FIG embodiment of the present invention, organic electroluminescent devices comprising a protective film formed on the surface of the laminated structure 29 with a first electrode 23, an organic thin film laminate (having a hole injection layer or hole transport layer, an organic light-emitting layer and an electron transport layer or electron injection layer) 25, and a second electrode formed on the transparent substrate 2127, and an absorbent layer having a laminated structure is formed over the shield 37 of plate 35, to covering the protective film 29. 该保护薄膜29和具有吸收层35的该屏蔽板37之间的空间中填充一种惰性气体31。 The protective film 29 and the absorbent layer having the shielding plate 35 between the space 37 is filled with an inert gas 31. 该保护薄膜29保护该装置内免于湿气和氧的渗入以及其它外部影响,并且视情况要求可以将其省略。 The protective film 29 is protected from the penetration of moisture and oxygen, and other external influences within the device, and which can optionally be omitted claims. 本发明提供一种含有叠层结构和吸收层的有机电致发光装置,该叠层结构具有介于第一电极和第二电极之间的叠层有机薄膜;该吸收层由选自氧吸收剂、有机或无机吸湿剂和装置抗氧化剂中的一种或一种以上材料以及它们的混合物形成,与该叠层结构彼此隔开、用于吸收湿气和氧。 The present invention provides a laminated structure comprising the absorbent layer and the organic electroluminescent device, the organic thin film laminate having a laminated structure between the first electrode and the second electrode is interposed; the absorbent layer is selected from oxygen absorber , hygroscopic agent and an organic or inorganic anti-oxidant means one or more materials, and mixtures thereof are formed, spaced from the laminated structure to one another, for absorbing moisture and oxygen. 在本发明的说明书中,“装置抗氧化剂”是指能够阻止叠层有机薄膜和第二电极氧化的试剂。 In the present specification, the "device antioxidant" refers to an organic thin film stack to prevent the second electrode and the oxidizing reagent. 此氧化是有机或无机吸湿剂吸收湿气时,这些吸收剂液化引起的。 This oxidation is an organic or inorganic moisture-absorbing agent absorbs moisture, these absorbents cause liquefaction. 因此在本发明中,在该有机或无机吸湿剂吸湿之前或者之后,该装置抗氧化剂适宜于与该叠层有机薄膜或者第二电极通过惰性气体等等接触,以阻止该叠层有机薄膜和第二电极的氧化。 Therefore, in the present invention, before the organic or inorganic absorbent or after the moisture absorbent, an antioxidant adapted to the apparatus by an inert gas and the like in contact with the organic thin film laminate or the second electrode to prevent the organic film and the laminated oxide electrode.

该氧吸收剂可以是1,2,3-苯三酚或者连二亚硫酸钠(Na2S2O4)。 The oxygen absorber may be pyrogallol or sodium dithionite (Na2S2O4). 并且该无机吸湿剂可以是一种或者一种以上选自下列的材料:选自IA族、IIA族和IIIA族的金属氧化物、氧化铝、硅胶、沸石和P2O5。 And inorganic hygroscopic agent may be one or more than one material selected from the group consisting of: a metal oxide selected from Group IA, IIA and IIIA of the Group, alumina, silica gel, zeolite, and P2O5. 并且,该金属氧化物优选为选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3中的一种。 And, the metal oxide is preferably selected from BaO, one kind of Li2O, Na2O, K2O, BeO, MgO, CaO, and B2O3 in. 有机吸湿剂可以是一种聚合物,该聚合物选自基于丙烯酰基的聚合物、聚脲、聚酰胺和聚酰亚胺,具有结构式-(CHX1-CHX2)n-(X1和X2的至少一个是亲水基团)的化合物,其中X1或X2可以是选自羟基、氢、烷基、链烯基、酯基、醚基和氨基中的任一种,并且该聚合物优选为聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)以及它们的共聚物。 The organic hygroscopic agent may be a polymer, the polymer is selected from acryl-based polymer, polyurea, polyamide and polyimide having a structural formula - (CHX1-CHX2) n- (at least one of X1 and X2 is a compound having a hydrophilic group), wherein X1 or X2 may be selected from hydroxyl, hydrogen, an alkyl group, an alkenyl group, an ester group, an ether group and any amino group, and the polymer is preferably poly (ethylene alcohol), poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) and copolymers thereof. 与此同时,该装置抗氧化剂可以是碱金属盐、金属或者它们的混合物,其中该碱金属盐优选为选自磷酸盐、硫酸盐或者碳酸盐中的一种或者一种以上的混合物,并且该金属可以优选为选自碱金属、碱土金属和电离度高于氢的金属。 At the same time, the apparatus may be an alkali metal salt of an anti-oxidant, metal or mixtures thereof, wherein the alkali metal salt is preferably selected from a phosphate, a sulfate or a carbonate or a mixture of more than one, and the metal may preferably be selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen. 该碱金属盐可以更优选为选自磷酸盐中的Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种或者一种以上的混合物,并且该金属可以更优选为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn中的一种粉末状材料。 The alkali metal salt may be more preferably Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 one kind or a mixture of one or more selected from the group of phosphates, and the metal may be more preferably selected from Na, K , Mg, Ca, Al, Cr, Mn, Fe, Co, Ni, Cu and Zn in a powdery material. 可以将惰性气体填充在该叠层结构和该吸收层之间的空间中。 Inert gas may be filled in a space between the laminated structure and the absorber layer.

该有机电致发光装置可以进一步包括用于支撑该吸收层的、形成于与该叠层结构相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 The organic electroluminescent device may further comprise a support for the absorber layer, is formed, a porous support layer of a polymer or glass on the bottom surface opposite to the absorbent layer of the laminated structure. 该聚合物可以是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种或者一种以上。 The polymer may be selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (the PET), poly (methyl methacrylate) (PMMA ), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, nylon, polyurethane, poly (chlorotrifluoroethylene ethylene), polyolefins, polycarbonates, polysulfones and polyacetal of one or more than one. 用于吸湿的吸收层的材料最优选为P2O5。 A layer of absorbent material for absorbing most preferably P2O5.

本发明提供一种具有叠层结构的有机电致发光装置,该叠层结构含有介于第一电极和第二电极之间的叠层有机薄膜,该装置包括在该叠层结构上方形成以覆盖该叠层结构整个表面的屏蔽板,以及由选自氧吸收剂、有机或无机吸湿剂、装置抗氧化剂中的一种或一种以上材料以及它们的混合物在该屏蔽板的底表面上形成的用于吸湿和吸氧的吸收层。 The present invention there is provided a laminated structure having organic electroluminescent device, the laminated structure including an organic thin film interposed between the laminated first and second electrodes, the apparatus comprising a laminate is formed over the structure to cover the the laminate structure of the entire surface of the shielding plate, and selected from oxygen absorber, inorganic or organic hygroscopic agent, means against one or more oxidant materials and mixtures thereof is formed on the bottom surface of the shield plate and an oxygen absorbent for absorbing layer. 该氧吸收剂可以是1,2,3-苯三酚或者连二亚硫酸钠(Na2S2O4)。 The oxygen absorber may be pyrogallol or sodium dithionite (Na2S2O4). 并且该无机吸湿剂可以是一种或者一种以上选自下列的材料:选自IA族、IIA族和IIIA族的金属氧化物、氧化铝、硅胶、沸石和P2O5。 And inorganic hygroscopic agent may be one or more than one material selected from the group consisting of: a metal oxide selected from Group IA, IIA and IIIA of the Group, alumina, silica gel, zeolite, and P2O5. 并且,该无机吸湿剂中的金属氧化物优选为选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3中的一种。 Further, the metal oxide is preferably an inorganic hygroscopic agent is selected from BaO, one kind of Li2O, Na2O, K2O, BeO, MgO, CaO, and B2O3 in. 该有机吸湿剂可以是一种聚合物,该聚合物选自基于丙烯酰基的聚合物、聚脲、聚酰胺和聚酰亚胺,或者具有结构式-(CHX1-CHX2)n-(X1和X2的至少一个是亲水基团)的化合物,其中X1或X2可以是选自氢、烷基、链烯基、酯基、醚基和氨基中的任一种,并且该有机吸湿剂优选为选自聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)以及它们的共聚物中的一种。 The moisture absorbent may be an organic polymer, the polymer is selected from acryl-based polymer, polyurea, polyamide and polyimide, or having the structural formula - (CHX1-CHX2) n- (X1 and X2 at least one hydrophilic group) with a compound, wherein X1 or X2 may be selected from hydrogen, an alkyl group, an alkenyl group, an ester group, an ether group, and any amino group, and the organic hygroscopic agent is preferably selected from poly (vinyl alcohol), poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) and copolymers of one. 可以将惰性气体填充在该叠层结构和该吸收层之间的空间中。 Inert gas may be filled in a space between the laminated structure and the absorber layer.

该有机电致发光装置可以进一步包括用于支撑该吸收层的、形成于和该叠层结构相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 The organic electroluminescent device may further comprise a support for the absorber layer, is formed, a porous support layer of a polymer or glass on the bottom surface of the laminated structure and to the absorbent layer opposite. 该聚合物可以是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种或者一种以上。 The polymer may be selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (the PET), poly (methyl methacrylate) (PMMA ), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, nylon, polyurethane, poly (chlorotrifluoroethylene ethylene), polyolefins, polycarbonates, polysulfones and polyacetal of one or more than one. P2O5为最优选用于吸湿的材料。 P2O5 is the most preferred material for the absorbent. 与此同时,该装置抗氧化剂可以是碱金属盐、金属或者它们的混合物,其中该碱金属盐优选为选自磷酸盐、硫酸盐或者碳酸盐中的一种或者一种以上的混合物,该磷酸盐可以更优选为选自Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种或者一种以上的混合物。 At the same time, the apparatus may be an alkali metal salt of an anti-oxidant, metal or mixtures thereof, wherein the alkali metal salt is preferably selected from a phosphate, a sulfate or a carbonate or a mixture of one or more of the more preferably selected from phosphate Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 one kind or a mixture of more than one. 用作该装置抗氧化材料的金属可以是选自碱金属、碱土金属和电离度高于氢的金属,优选为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn的一种粉末状材料。 As an anti-oxidizing material of the device may be a metal selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen, preferably selected from Na, K, Mg, Ca, Al, Cr, Mn, Fe, Co, Ni , Cu and Zn in a powdered material.

本发明提供(a)在一种基片上形成的第一电极,(b)在该第一电极上形成的叠层有机薄膜,(c)在该叠层有机薄膜上形成的第二电极,(d)在该第二电极上方形成的以覆盖该叠层有机薄膜和该第二电极整个表面的屏蔽板;以及(e)由下述材料组成的吸收层,选自1,2,3-苯三酚和连二亚硫酸钠(Na2S2O4)的第一种材料,选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3、氧化铝、硅胶、沸石和P2O5中的一种或者一种以上的混合物的第二种材料,选自聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)和它们的共聚物的第三种材料,选自磷酸盐、硫酸盐和碳酸盐中的一种或者一种以上的混合物的第四种材料,选自碱金属、碱土金属和电离度高于氢的金属的第五种材料,或者从第一至第五种材料中选择两种材料的或者两种以上材料混合的第六种材料。 The present invention provides (a) a first electrode formed on one kind of substrate, (b) an organic laminated thin film formed on the first electrode, (c) a second electrode formed on the organic thin film laminate, ( d) so as to cover the organic film and the second stack electrode is formed throughout the surface of the shield plate in the second upper electrode; and (e) absorbing layer is composed of the following materials selected from 1,2,3-benzenetricarboxylic trisphenol and sodium dithionite (of Na2S2O4) of a first material selected from BaO, Li2O, Na2O, K2O, BeO, MgO, CaO, and of B2O3, an alumina, silica gel, zeolite, and P2O5, or in one or more the second material mixture, selected from poly (vinyl alcohol), poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) and the third material a copolymer thereof, is selected from a phosphate, sulfate, and carbonate, or a mixture of more than one fourth of a material, selected from alkali metals, alkaline earth metals and the ionization degree is higher than a fifth of the material of the metal hydrogen or from the first materials selected to fifth or sixth of the two materials of two or more materials of mixed materials. 在此例中,可以在该第二电极和该吸收层之间的空间中填充一种惰性气体,并且该有机电致发光装置可以进一步包括用于支撑该吸收层的、形成于和该第二电极相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 In this embodiment, an inert gas may be filled in the space between the second electrode and the absorber layer, and the organic electroluminescence light emitting device may further comprise a support for the absorber layer, is formed on the second and , porous support layer of a polymer or glass electrode on the bottom surface of the absorbent layer opposite. 该支撑层的聚合物可以优选为选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种或者一种以上。 The polymeric support layer may preferably be selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (the PET), poly (methyl methacrylate ester) (of PMMA), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, nylon, polyurethane , poly (vinyl chloride), polyolefins, polycarbonates, polysulfones and polyacetal of one or more than one. 作为第二种材料P2O5是最优选的,并且可以进一步将一种以上的装置抗氧化剂,如碱金属盐、金属或者它们的混合物加入其中。 P2O5 as the second material is most preferred, and may further be more than one apparatus antioxidants, such as alkali metal salts, metal or mixtures thereof added thereto. 与此同时,优选作为该装置抗氧化剂的碱金属盐可以是一种磷酸盐,其为选自Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种或者一种以上的混合物,硫酸盐或者碳酸盐,并且用作该装置抗氧化材料的金属可以是选自碱金属、碱土金属和电离度高于氢的金属,优选为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn的一种粉末状材料。 At the same time, an antioxidant is preferably an alkali metal salt of the apparatus may be a phosphate, which is selected Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 one kind or more than one in a mixture of sulfuric acid salts or carbonates, and used as the metal material in the oxidation means may be selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen, preferably selected from Na, K, Mg, Ca, Al, Cr, mn, Fe, Co, Ni, Cu and Zn in a powdered material.

根据本发明优选实施方案的具有在第一电极和第二电极之间带叠层有机薄膜的叠层结构的有机电致发光装置,含有P2O5吸收层和一种以上装置抗氧化剂。 According to a preferred embodiment of the present invention has a laminated structure between the first electrode and the second electrode strips stacked organic thin film organic electroluminescent device, the absorbent layer containing P2O5 and one or more antioxidants apparatus. P2O5易于发生化学反应而产生H3PO4-一种滴到叠层有机薄膜上的液体,导致第二电极金属氧化,从而缩短该装置的寿命。 H3PO4- produce one kind of liquid is dropped onto the organic thin film laminate P2O5 chemical reaction is liable to occur, resulting in a second metal oxide electrode, thereby shortening the life of the device. 因此,本发明中最后将一种抗氧化剂,优选如Na3PO4、Na2HPO4或NaH2PO4的磷酸盐,加入该吸收层以阻止P2O5液化从而阻止该装置的氧化。 Accordingly, the present invention finally an antioxidant, preferably as a phosphate Na3PO4, Na2HPO4 or NaH2PO4, adding absorption layer to prevent the liquefaction P2O5 to prevent oxidation of the device. 可以由选自氧吸收剂、有机或无机吸湿剂、装置抗氧化剂中一种以上的混合物形成吸收层35。 May be selected from oxygen absorber, organic or inorganic moisture-absorbing agent, an antioxidant means a mixture of more than one absorbent layer 35 is formed. 即,视情况要求,可以由包括全部氧吸收剂、有机或无机吸湿剂、装置抗氧化剂的,它们中的两种的混合物或者仅它们中的一种形成吸收层35。 That is, as the case requires, may include all the oxygen absorber, inorganic or organic hygroscopic agents, antioxidants apparatus, a mixture of two of them or only one of them absorbing layer 35 is formed. 通过使用一种非活性溶剂使吸收层35的材料流动性良好并且分散等等可以将该材料装填入该屏蔽板37的底部表面。 By using a non-reactive solvent so that the absorbent material layer 35 is good fluidity and dispersion, etc. The material can be filled into a bottom surface of the shielding plate 37. 根据该吸收层材料的性能,该吸收层材料的活化条件不同,并且在氧化铝或者硅胶的情形下,它们或者在大约100~400℃真空下或者在向其中吹氮气的条件下干燥。 The properties of the absorbent material layer, different activation conditions of the absorbent material layer, and in the case of alumina or silica gel, which was dried under vacuum or or about 100 ~ 400 ℃ under conditions wherein the nitrogen blowing. 干燥的时间为10~24个小时或者更长时间。 The drying time is 10 to 24 hours or more. 作为另一实施例,P2O5可以用作该材料而无需活化过程。 As another example, P2O5 can be used as the material without activation process. 并且能够被用作该吸收层材料的所有材料可以不使用溶剂,而以粉末状装填使用。 And all materials can be used as the absorbent layer of material without using a solvent, and to the use of powder filling. 与此同时,可以用不锈钢、铝或者玻璃、或者玻璃化转变温度Tg高的聚合物形成屏蔽板37,并且如此形成的屏蔽板37用环氧或者UV粘合剂39,例如基于丙烯醛基的化合物粘结在透明基片21上。 At the same time, it can be used stainless steel, aluminum or glass, or glass transition temperature Tg of the polymer forming the shielding plate 37, and thus the shield plate 37 is formed with an epoxy or a UV adhesive 39, for example based on acrolein group on the transparent substrate 21 bonded compound. 粘结屏蔽板37后,形成两个或者两个以上的开口,在真空下除去内部的气体,填充惰性气体并密封开口,或者在氮气氛下整个装置不形成开口而被密封,从而省去了装填的过程。 Adhesive shield 37, formed of two or more than two openings, the interior of the gas removal, an inert gas is filled and sealed in an opening under vacuum or under a nitrogen atmosphere and the whole apparatus is sealed without forming the opening, thereby eliminating the need the filling process. 这样,能够阻挡影响该装置的湿气和氧的吸收层的形成可以完成,并且如图5所示,在和该第二电极相对的该吸收层的底表面上可以进一步形成用于支撑该吸收层的支撑层33。 In this manner, the barrier affect the formation of moisture and oxygen absorbing layer of the device can be completed, and 5, may be further formed on a bottom surface for supporting the second electrode and the absorbent layer opposite the absorbent support layer 33 layer. 此外,该装置进一步包括位于第二电极上的保护薄膜29。 In addition, the apparatus 29 further comprises a protective film on the second electrode.

如图5所示,在和该第二电极相对的屏蔽板37之下的吸收层35的底表面上形成支撑层33,用于支撑该吸收层。 5, the support layer 33 is formed on the bottom surface and the second opposing electrode shield plate 37 under the absorbent layer 35, for supporting the absorber layer. 以只能够通过湿气的、和该吸收层的材料不同的多孔聚合物或者玻璃形成支撑层33,以使支撑层33能够阻止吸收层35的材料落下,而不影响吸收层35吸湿。 In only can be formed by moisture, and a layer of absorbent material of the porous polymer or a different glass support layer 33, so that the support layer 33 can prevent the absorption layer material 35 is dropped, without affecting the absorber layer 35 of the absorbent. 支撑层33的聚合物可以是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种或者一种以上的混合物。 The polymeric support layer 33 may be selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (the PET), poly (methyl methacrylate ) (of PMMA), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, nylon, polyurethane, poly (vinyl chloride), polyolefins, polycarbonates, polysulfones and polyacetal of one or a mixture of more than one. 该支撑层优选具有大约0.01~10μm的孔尺寸。 The support layer preferably has a pore size of about 0.01 ~ 10μm.

本发明能够解决当有机电致发光装置中使用P2O5作为强吸湿剂时发生的问题,在此情况下,鉴于纯磷酸熔点为42.35℃,由于P2O5吸收许多湿气,因为H3PO4在室温下以液态存在,当P2O5吸收许多湿气而变为H3PO4液体。 The present invention can solve the problem when an organic electroluminescent device using P2O5 as a strong moisture-absorbing agent occurs, in this case, in view of the melting point of pure phosphoric acid is 42.35 deg.] C, since a lot of moisture absorption P2O5 as H3PO4 present in the liquid at room temperature when moisture becomes P2O5 H3PO4 absorbing many liquids. 一般地,由于酸通过氧化腐蚀电离度高于氢的材料,所以液体磷酸影响该装置,如当磷酸通过支撑层33时,因氧化该有机电致发光装置尤其是第二电极,Al、Mg、Ag等等而缩短该装置的寿命。 Generally, since the degree of ionization of the acid by oxidation etching materials than hydrogen, so the influence of the liquid phosphoric acid apparatus, such as when the support layer 33 by the phosphoric acid, by oxidation of the organic electroluminescent device, especially the second electrode, Al, Mg, Ag, etc. to shorten the life of the device. 此外,当该有机电致发光装置被抛弃时,P2O5的酸性会成为问题。 Further, when the organic electroluminescent device is abandoned, P2O5 acid can be a problem. 本发明的有机电致发光装置中,在有氧吸收剂、吸湿剂和聚合物中的一种或者有它们的混合物材料的吸收层中包含了一种或者一种以上的装置抗氧化材料,以阻止该有机电致发光装置被氧化和腐蚀。 The present invention is an organic electroluminescent device, an aerobic absorbent, moisture absorbent and a polymer or a mixture thereof with a layer of absorbent material comprises one or more than one device antioxidant material to preventing the organic electroluminescent device is oxidation and corrosion.

在本发明的该有机电致发光装置中,装置抗氧化材料有以下功能。 In the present invention, the organic electroluminescent device, the device has the following functions oxidation resistant material.

在本发明的电致发光装置中作为吸湿剂的P2O5吸收湿气并变为磷酸。 In the present invention, the electrical electroluminescent device as P2O5 moisture absorbent absorbs moisture and becomes phosphorylated. 在此情况下,磷酸氧化添加在吸收层中选自碱金属、碱土金属或者电离度高于氢的金属的材料,其为靠近磷酸的金属,以使磷酸氧化叠层有机薄膜或者该装置中金属之前就失去磷酸的活性。 In this case, oxidative phosphorylation is added in the absorption layer is selected from alkali metal, alkaline earth metal or metallic material is higher than the ionization of hydrogen, which is close to a metal phosphate, phosphoric acid so that the oxide film or the stacked organic metal apparatus prior to the loss of activity of phosphoric acid. 该金属可以优选为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn的一种粉末状材料。 The metal may be preferably selected from Na, K, Mg, Ca, Al, Cr, Mn, Fe, Co, Ni, Cu and Zn in a powdered material. 同时,不同于前述金属,存在可以用作装置抗氧化材料的碱金属盐。 Meanwhile, unlike the metal, the presence of an alkali metal salt may be used as an anti-oxidation means material. 当该碱金属盐在水中电离时,碱金属盐呈碱性(pH值7以上)。 When the alkali metal salt in water ionizing alkali metal salt alkaline (pH value above 7). 该碱金属盐与吸湿剂有关的反应如下。 The alkali metal salt of the following reactions associated moisture absorbent. P2O5吸湿转变为酸性的磷酸。 P2O5 phosphoric acid into the absorbent. 在此情况下,在转变为磷酸的过程中,均来自碱金属盐的碱金属离子和碱土金属离子与邻近的磷酸或者与在变为磷酸的P2O5反应转变为磷酸盐。 In this case, the transformation process is phosphoric acid, both alkali metal ions and alkaline earth metal ions from the alkali metal salt of phosphoric acid, or with adjacent transition P2O5 reaction becomes acid phosphate. 该碱金属盐可以是选自磷酸盐、硫酸盐和碳酸盐的一种或者一种以上的混合物。 The alkali metal salt may be selected from phosphates, carbonates and sulfates of one kind or a mixture of more than one. 该磷酸盐可以是选自Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种或者一种以上的混合物。 The phosphates may be selected Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 one kind or a mixture of more than one. 当装置抗氧化材料被包括在该吸湿剂中的情况下,通过调节碱金属盐的量容易地将pH值保持在5~8的范围内,能够解决废弃的该装置的酸性问题。 If the unit antioxidant material be included in the absorbent agent, easily by adjusting the amount of alkali metal salt maintaining the pH in the range of 5 to 8, the apparatus capable of solving the problem of acidic waste. 因为当磷酸变为磷酸盐时熔点变高,所以碱金属盐用作装置抗氧化允许将吸湿剂控制在该吸收层中,从而能够阻止支撑层和屏蔽板被腐蚀。 Because when a phosphate acid becomes high melting point, the alkali metal peroxide is used as an anti-moisture absorbent means allow the control of the absorber layer, thereby preventing the support layer and the shield plate corrosion. 此外,由于该碱金属盐具有出色的吸湿能力,该碱金属盐对吸湿剂的吸湿能力影响不大。 Further, since the alkali metal salt has excellent absorption capacity, the alkali metal salt has little effect on the absorption capacity of the absorbent agent. 如前面的解释,当将P2O5用作吸收层中的吸湿剂时,金属或者碱金属盐、或者它们的混合物可以与P2O5一起使用。 As previously explained, when used as P2O5 moisture absorbent absorbing layer, the metal or alkali metal salt, or a mixture thereof may be used in conjunction with the P2O5. 另外,可以进一步向P2O5的附加量或者P2O5与上述加入吸收层的装置抗氧化剂中添加UV硬化剂。 Further, P2O5 or may be further added to the above-described absorbent layer means adding an antioxidant agent to the UV curable additional amount of P2O5. 该UV硬化剂能够解决将例如P2O5的吸湿剂引入该吸收层的过程中,粉末状的颗粒被吹落的问题。 The UV curing agent is capable of resolution procedure e.g. P2O5 absorbent agent into the absorbing layer, the powdered particles are blown problem. 该UV硬化剂可以是聚硅氧烷、丙烯酰基(acryl)、环氧或者氨基甲酸乙酯类。 The agent may be a UV curable silicone, acryl (Acryl), epoxy or urethane. 最后,用如环氧类粘合剂的密封剂(sealers)39将屏蔽板37粘结在基片上。 Finally, as with an epoxy adhesive sealant (sealers) 39 adhered to the shielding plate 37 on the substrate.

根据本发明优选实施方案制造有机电致发光装置的方法将参照图4说明。 According to a preferred embodiment of the present invention is method of manufacturing an organic electroluminescent device will be described with reference to FIG.

在具有ITO(铟锡氧化物)的透明基片21上淀积出厚15纳米的铜酞菁(CuPc)层作为空穴注射层,在其上涂布的厚140纳米的透明电极作为第一电极。 Deposited to a thickness of 15 nm of copper phthalocyanine (CuPc) layer on a transparent substrate having ITO (indium tin oxide) as a hole injection layer 21, in which a transparent electrode 140 nm thick coated on the first electrode. 然后,淀积TPD[N,N′-二苯基-N,N′-双(3-甲基苯基)-(1,1′-联二苯)-4,4′-二胺]至厚度大约30纳米作为空穴传递层,并且真空淀积Alq3(8-羟基喹啉铝)至厚度大约50纳米作为绿光发射层。 Then, depositing TPD [N, N'- diphenyl -N, N'- bis (3-methylphenyl) - (1,1'-biphenyl) -4,4'-diamine] to a thickness of about 30 nm as a hole transport layer, and the vacuum deposition of Alq3 (8- hydroxyquinoline aluminum) to a thickness of about 50 nm as green light emitting layer. 然后可以或者可以不形成电子注射层或者电子注射传递层。 It may then be injected or the electron transfer layer or electron injection layer may not be formed. 在如有机电致发光装置中那样形成的叠层有机薄膜25上涂布薄碱金属氧化物薄膜和薄金属薄膜以形成第二电极层27。 If the thin organic electroluminescent alkali metal oxide coated thin films and metal thin film stacked organic light emitting device 25 formed as a second electrode layer 27 is formed. 该第二电极层可以由Li2O或者Al形成,厚度为大约50纳米。 The second electrode layer may be formed of Li2O or Al, having a thickness of about 50 nm. 在第二电极层29上形成保护薄膜29。 A protective film 29 is formed on the second electrode layer 29. 保护薄膜29可以通过化学汽相淀积有机金属化合物或聚合物形成,或者可以被省略。 The protective film 29 may be deposited by chemical vapor phase organometallic compound or polymer, or may be omitted. 图4所示的装置具有保护薄膜。 Apparatus shown in Figure 4 with a protective film. 接着,形成屏蔽板37以覆盖和保护按前述工艺形成的基片。 Next, the shield plate 37 is formed to cover and protect the substrate formed by the foregoing process. 将屏蔽板37的玻璃的、塑料的或者涂层金属的板凹进以在其中引入吸湿剂并形成吸收层35,其中,虽然屏蔽板的可用的塑料材料的范围取决于厚度,但是一般可以优选使用PET、PBT、尼龙、聚碳酸酯,并且通过在这些聚合物上涂布金属,能够取得更好的效果。 The shielding plate 37 of glass, plastic or coated metal plate is introduced therein is recessed to form a moisture-absorbing agent and the absorbent layer 35, wherein the range of available plastic material, although depending on the thickness of the shielding plate, but generally preferably using PET, PBT, nylon, polycarbonate, and by coating a metal on these polymers, it is possible to achieve better results. 在其中形成吸收层35的屏蔽板37的金属板可以由铝、铁或者铜形成。 Wherein the shielding plate is formed in the absorbent layer 35 a metal plate 37 may be formed of aluminum, iron or copper.

在屏蔽板37中的吸湿剂的吸收层35的形成方法将详细说明如下。 The method of forming the absorbent layer of the absorbent agent 35 in the shield plate 37 will be described in detail below. P2O5作为吸湿剂,当P2O5用作吸湿剂时,将装置抗氧化剂加入其中。 P2O5 as a moisture absorbent, moisture-absorbing agent when used as P2O5, wherein the device is added an antioxidant. 装置抗氧化剂和以前的相同并且优选为Na3PO4或者K3PO4形成的。 Antioxidants and previous apparatus and is preferably the same as or K3PO4 Na3PO4 formed. 然后具有如此形成的吸收层35的屏蔽板37被粘结在基材上。 Then thus formed with the shielding plate 37 of the absorbent layer 35 is bonded to the substrate. 环氧类的粘合剂用作粘结该屏蔽板的密封剂。 Epoxy-based adhesives as the adhesive sealant of the shielding plate.

根据本发明的另一个实施方案制造有机电致发光装置的方法将参照图5陈述。 According to another embodiment of the present invention, a method of manufacturing an organic electroluminescent device will be set forth with reference to FIG.

在基片21上形成第一电极23之后,在其上形成包含发光层的叠层有机薄膜25并在其上涂敷碱金属涂层,以形成第二电极层27。 Forming a first electrode 23 on the substrate 21 after forming the organic thin film comprising a laminated luminescent layer 25 thereon and an alkali metal coating applied thereon, to form a second electrode layer 27. 在第二电极层27上可以通过化学汽相淀积施加有机金属化合物或者聚合物的涂层形成第一保护薄膜29,或者可以不形成它。 Forming a first protective film coating on the second electrode layer 27 may be applied by chemical vapor deposition of an organometallic compound or a polymer 29, or it may not be formed. 图5所示的装置具有该保护薄膜。 Apparatus shown in FIG. 5 having the protective film. 形成屏蔽板37之后,在其内形成P2O5和装置抗氧化剂的吸收层35。 After the shield plate 37 is formed, and an antioxidant forming apparatus P2O5 absorption layer 35 therein. 在此未作陈述的作为装置抗氧化剂材料的化合物、材料或者部件的组装方法,与前述的那些一致。 It means compounds as an antioxidant materials have not been set forth herein or a method of assembling the component materials of those consistent with the foregoing. 与图4所示的有机电致发光装置相比,图5所示的有机电致发光装置的不同之处在于引入了支撑层33以阻止装置上吸收层中的P2O5落下,从而保护该装置。 There are shown in FIG. 4 as compared to the organic electroluminescent device, FIG. 5 are different from the organic electroluminescent device is the introduction of the support layer 33 to inhibit absorption layer falls P2O5 device, thereby protecting the apparatus shown in FIG. 调节支撑层33的孔尺寸以使水分子容易通过,而吸湿剂不能。 Adjusting the pore size of the supporting layer 33 so that water molecules are readily by, but not moisture absorbent. 支撑层33中的孔的尺寸范围优选调节到0.01~10μm。 Pore ​​size range of the supporting layer 33 is preferably adjusted to 0.01 ~ 10μm. 支撑层33还由多孔聚合物或者玻璃形成,聚合物的种类与前述相同。 The support layer 33 is also formed of a porous polymer, or glass, with the same type of polymer. 然后将支撑层33粘结并固定在具有形成于其上的吸收层35的屏蔽板37上。 The support layer 33 is then bonded and fixed in the absorbing layer formed thereon having a shielding plate 35 on the upper 37. 即,在支撑层33上施加热熔粘合剂涂层之后,将支撑层33压下并熔融粘结该支撑层到屏蔽板37上或者将该支撑层压下并在该支撑熔融而未施加粘合剂的温度下熔融,以粘结支撑层33到屏蔽板37上。 That is, after application of the hot melt adhesive coating 33 on the support layer, the support layer 33 is depressed and the support layer is fusion bonded to the shield plate 37 or the lower support and the laminate is applied on the support without melting the melting temperature of the adhesive to bond the support layer 33 to the shield plate 37. 或者可以在室温下,或向支撑层33或向屏蔽板37施加粘合剂以后将支撑层33和屏蔽板37粘结在一起。 Or it may be at room temperature, the adhesive layer 37 or the support 33 and the shield plate together with the support layer 33 or after the adhesive is applied to the shield plate 37. 并且最后将屏蔽板37粘结在基片21上。 And finally the shield plate 37 bonded to the substrate 21.

在根据本发明的优选实施方案制造有机电致发光装置的方法中,可以将UV硬化剂进一步包括在图5阐述的有机电致发光装置的吸收层35中。 In the method of manufacturing an organic electroluminescent device according to a preferred embodiment of the invention, a hardener may be UV absorbing layer further comprises an organic electroluminescent device 35 set forth in FIG. 5. 该UV硬化剂可以是聚硅氧烷、丙烯酰基(acryl)、环氧或者氨基甲酸乙酯类。 The agent may be a UV curable silicone, acryl (Acryl), epoxy or urethane.

本发明的有机电致发光装置仅以P2O5(A)、P2O5和碱性材料(B)以及氧化铝(C)进行的对比实验结果显示如下。 The present invention have comparative results for an organic electroluminescent device only P2O5 (A), P2O5, and basic material (B) and the alumina (C) are shown below. < <

>从上述实验结果能够得知,向P2O5中添加Na3PO4没有造成P2O5吸湿能力方面的差别。 > From the above experimental results that can be added to make the difference P2O5 P2O5 in Na3PO4 no moisture absorption capacity. 因此使用如Na3PO4的装置抗氧化剂能够阻止装置被腐蚀以及P2O5液化,从而显著提高了装置的稳定性。 Thus the use of antioxidants such as Na3PO4 apparatus can prevent corrosion and P2O5 liquefying apparatus, thereby significantly improving the stability of the device. 而且向具有前述吸湿功能的吸收层中添加UV硬化剂能够防止吹掉保护薄膜的粉末状组分。 And UV curing agent is added to the moisture absorbing layer having a function capable of preventing the blow off the powdery component of the protective film.

总之,根据本发明优选实施方案的具有P2O5吸收层和一种或者一种以上装置抗氧化剂的有机电致发光装置能够提供简单的制造方法并且既不氧化也不腐蚀装置,而吸湿力能够与使用强吸湿剂P2O5之前的保持相同。 In summary, according to a preferred embodiment of the present invention having a P2O5-absorbing layer and one or more than one device antioxidant organic electroluminescent device can provide a simple manufacturing method and apparatus neither oxidation nor corrosive, and can be used while the absorbent force maintaining the same strength before moisture absorbent P2O5.

在不背离本发明精神或者范围的情况下,对本发明的有机电致发光装置进行各种修改和变化将是本领域技术人员显而易见的。 Without departing from the spirit or scope of the present invention, the present invention has an organic electroluminescent device that various modifications and variations will be apparent to the skilled person. 因此本发明包括那些落入本发明权利要求以及它们的等同物的范围内的修改和变化。 Accordingly the present invention include modifications and variations that fall within the scope of the claims of the present invention and the equivalents thereof.

Claims (40)

1.一种具有叠层结构的有机电致发光装置,该叠层结构在第一电极和第二电极之间含有叠层有机薄膜,该装置包括:与该叠层结构彼此隔开,由选自氧吸收剂、有机或无机吸湿剂以及装置抗氧化剂中的一种或一种以上材料形成的吸收层。 A laminate structure having an organic electroluminescent device, the laminated structure between the first electrode and the second electrode stack comprising an organic thin film, the apparatus comprising: spaced apart from each other with the laminated structure selected from the group an oxygen-absorbing layer from absorbing agent, hygroscopic agent and an organic or inorganic antioxidants means of one or more materials.
2.如权利要求1所述的装置,其中氧吸收剂为1,2,3-苯三酚或者连二亚硫酸钠(Na2S2O4)。 2. The apparatus according to claim 1, wherein the oxygen absorbing agent is pyrogallol or sodium dithionite (Na2S2O4).
3.如权利要求1所述的装置,其中无机吸湿剂为一种或者一种以上选自下列的材料:选自IA族、IIA族和IIIA族的金属氧化物、氧化铝、硅胶、沸石和P2O5。 3. The apparatus according to claim 1, wherein the inorganic hygroscopic agent is one or more than one material selected from the group consisting of: a metal oxide selected from Group IA, IIA and IIIA of the Group, alumina, silica gel, zeolite, and P2O5.
4.如权利要求3所述的装置,其中金属氧化物为选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3中的一种。 4. The apparatus of claim 3, one kind of Li2O, Na2O, K2O, BeO, MgO, CaO, and B2O3 in claim, wherein the metal oxide is selected from BaO,.
5.如权利要求1所述的装置,其中有机吸湿剂为一种聚合物,该聚合物选自基于丙烯酰基的聚合物、聚脲、聚酰胺、聚酰亚胺或者具有结构式-(CHX1-CHX2)n-(X1和X2的至少一个是亲水基团)的化合物。 5. The apparatus according to claim 1, wherein the organic hygroscopic agent is a polymer, the polymer is selected from acryl-based polymer, polyurea, polyamide, polyimide, or having the structural formula - (CHX1- CHX2) n- (X1 and X2 is at least one hydrophilic group) compound.
6.如权利要求5所述的装置,其中X1或X2选自羟基、氢、烷基、链烯基、酯基、醚基和氨基中的任一种。 6. The apparatus according to claim 5, wherein X1 or X2 is selected from hydroxyl, hydrogen, an alkyl group, an alkenyl group, an ester group, an ether group and any amino group.
7.如权利要求5所述的装置,其中有机吸湿剂选自聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)以及它们的共聚物中的一种。 7. The apparatus of claim 5, wherein a copolymer thereof, wherein the organic hygroscopic agent is selected from poly (vinyl alcohol), poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) and in kind.
8.如权利要求1所述的装置,其中在该叠层结构和该吸收层之间的空间中填充一种惰性气体。 The apparatus as claimed in claim 1, wherein an inert gas is filled in a space between the laminated structure and the absorber layer.
9.如权利要求1所述的装置,进一步包括用于支撑吸收层的、形成于和该叠层结构相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 9. The apparatus according to claim 1, further comprising means for supporting the absorbent layer is formed, a porous support layer of a polymer or glass on the bottom surface of the laminated structure and to the absorbent layer opposite.
10.如权利要求9所述的装置,其中该聚合物是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种材料或者一种以上材料的混合物。 10. The apparatus according to claim 9, wherein the polymer is selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (PET) , poly (methyl methacrylate) (of PMMA), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene fluoride, poly tetrafluoroethylene, nylon, polyurethane, poly (vinyl chloride), polyolefins, polycarbonates, polyoxymethylene and mixtures of one material polysulfone or more than one material.
11.如权利要求3所述的装置,其中该无机吸湿剂是P2O5。 11. The apparatus according to claim 3, wherein the inorganic hygroscopic agent is P2O5.
12.如权利要求1所述的装置,其中的装置抗氧化剂为碱金属盐、金属或者该碱金属盐和该金属的混合物。 12. The apparatus according to claim 1, wherein the antioxidant means an alkali metal salt, or a mixture of a metal and the alkali metal salt of the metal.
13.如权利要求12所述的装置,其中该碱金属盐是选自磷酸盐、硫酸盐和碳酸盐中的一种材料或者一种以上材料的混合物。 13. The apparatus of claim 12, wherein the alkali metal salt is selected from phosphates, sulfates and carbonates mixture of one material or of more than one material.
14.如权利要求12所述的装置,其中该金属选自碱金属、碱土金属和电离度高于氢的金属。 14. The apparatus of claim 12, wherein the metal selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen.
15.如权利要求13所述的装置,其中磷酸盐是选自Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种材料或者一种以上材料的混合物。 15. The apparatus according to claim 13, wherein the phosphate is selected Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, and MgHPO4 CaHPO4 mixture of one material or of more than one material.
16.如权利要求14所述的装置,其中该金属为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn中的一种材料粉末。 16. The apparatus according to claim 14, wherein the metal is selected from Na, K, Mg, material powder Ca, Al, Cr, Mn, Fe, Co, Ni, Cu and Zn.
17.一种具有叠层结构的有机电致发光装置,该叠层结构含有介于第一电极和第二电极之间的叠层有机薄膜,该装置包括:在该叠层结构上方形成屏蔽板以覆盖该叠层结构的整个表面;以及由选自氧吸收剂、有机或无机吸湿剂以及装置抗氧化剂中的一种或一种以上材料在该屏蔽板的底表面上形成的吸收层。 17. A laminate structure of organic electroluminescent device, the laminated structure comprising an organic thin film interposed between the laminated first and second electrodes, the apparatus comprising: a shielding plate is formed over the structure and the laminate absorbing layer and selected from oxygen absorber, inorganic or organic hygroscopic agents and antioxidants means one or more material formed on the bottom surface of the shield plate; so as to cover the entire surface of the laminate structure.
18.如权利要求17所述的装置,其中该氧吸收剂为1,2,3-苯三酚或者连二亚硫酸钠(Na2S2O4)。 18. The apparatus according to claim 17, wherein the oxygen absorber is pyrogallol or sodium dithionite (Na2S2O4).
19.如权利要求17所述的装置,其中无机吸湿剂是一种或者一种以上的选自下列的材料:选自IA族、IIA族和IIIA族的金属氧化物、氧化铝、硅胶、沸石和P2O5。 19. The apparatus according to claim 17, wherein the inorganic moisture-absorbing agent is one or more than one material selected from the group consisting of: a metal oxide selected from Group IA, IIA and IIIA of the Group, alumina, silica gel, zeolite and P2O5.
20.如权利要求19所述的装置,其中金属氧化物为选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3中的一种。 20. The apparatus of claim 19, one kind of Li2O, Na2O, K2O, BeO, MgO, CaO, and B2O3 in claim, wherein the metal oxide is selected from BaO,.
21.如权利要求17所述的装置,其中有机吸湿剂为一种聚合物,该聚合物选自基于丙烯酰基的聚合物、聚脲、聚酰胺、聚酰亚胺或者分子式具有结构式-(CHX1-CHX2)n-(X1和X2的至少一个是亲水基团)的化合物。 21. The apparatus according to claim 17, wherein the organic hygroscopic agent is a polymer, the polymer is selected from acryl-based polymer, polyurea, polyamide, polyimide, or the formula having the formula - (CHX1 -CHX2) compound n- (X1 and X2 is at least one hydrophilic group).
22.如权利要求21所述的装置,其中X1或X2选自羟基、氢、烷基、链烯基、酯基、醚基和氨基中的任一种。 22. The apparatus according to claim 21, wherein X1 or X2 is selected from hydroxyl, hydrogen, an alkyl group, an alkenyl group, an ester group, an ether group and any amino group.
23.如权利要求21所述的装置,其中有机吸湿剂选自聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)和它们的共聚物中的一种。 23. The apparatus of claim 21, poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) and copolymers thereof, wherein the organic hygroscopic agent is selected from poly (vinyl alcohol), in kind.
24.如权利要求17所述的装置,其中在该叠层结构和该吸收层之间的空间中填充一种惰性气体。 24. The apparatus according to claim 17, wherein an inert gas is filled in a space between the laminated structure and the absorber layer.
25.如权利要求17所述的装置,进一步包括用于支撑吸收层的、形成于和该叠层结构相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 25. The apparatus according to claim 17, further comprising means for supporting the absorbent layer is formed, a porous support layer of a polymer or glass on the bottom surface of the laminated structure and to the absorbent layer opposite.
26.如权利要求25所述的装置,其中该聚合物是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种材料或者一种以上材料的混合物。 26. The apparatus according to claim 25, wherein the polymer is selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (PET) , poly (methyl methacrylate) (of PMMA), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene fluoride, poly tetrafluoroethylene, nylon, polyurethane, poly (vinyl chloride), polyolefins, polycarbonates, polyoxymethylene and mixtures of one material polysulfone or more than one material.
27.如权利要求19所述的装置,其中该无机吸湿剂是P2O5。 27. The apparatus according to claim 19, wherein the inorganic hygroscopic agent is P2O5.
28.如权利要求17所述的装置,其中的装置抗氧化剂为碱金属盐、金属或者该碱金属盐和该金属的混合物。 28. The apparatus according to claim 17, wherein the antioxidant means an alkali metal salt, or a mixture of a metal and the alkali metal salt of the metal.
29.如权利要求28所述的装置,其中该碱金属盐是选自磷酸盐、硫酸盐和碳酸盐中的一种材料或者一种以上材料的混合物。 29. The apparatus according to claim 28, wherein the alkali metal salt is selected from phosphates, sulfates and carbonates mixture of one material or of more than one material.
30.如权利要求28所述的装置,其中该金属选自碱金属、碱土金属和电离度高于氢的金属。 30. The apparatus according to claim 28, wherein the metal selected from alkali metals, alkaline earth metals and metal ionization degree than hydrogen.
31.如权利要求29所述的装置,其中磷酸盐是选自Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、CaHPO4和MgHPO4中的一种材料或者一种以上材料的混合物。 31. The apparatus according to claim 29, wherein the phosphate is selected, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, Na3PO4 mixture of one material and MgHPO4 CaHPO4, or in more than one material.
32.如权利要求30所述的装置,其中该金属为选自Na、K、Mg、Ca、Al、Cr、Mn、Fe、Co、Ni、Cu和Zn中的一种材料粉末。 32. The apparatus according to claim 30, wherein the metal is selected from Na, K, Mg, material powder Ca, Al, Cr, Mn, Fe, Co, Ni, Cu and Zn.
33.一种有机电致发光装置包括:(a)在一种基片上形成的第一电极,(b)在该第一电极上的叠层有机薄膜,(c)在该叠层有机薄膜上的第二电极,(d)在该第二电极上方形成的以覆盖该叠层有机薄膜和该第二电极整个表面的屏蔽板;以及,(e)在该屏蔽板的底表面上形成吸收层,所述吸收层由下述材料组成,选自1,2,3-苯三酚和连二亚硫酸钠(Na2S2O4)的第一种材料,选自BaO、Li2O、Na2O、K2O、BeO、MgO、CaO和B2O3、氧化铝、硅胶、沸石和P2O5中的一种材料或者一种以上的混合物的第二种材料,选自聚(乙烯醇)、聚(乙烯吡咯烷酮)、聚(甲基丙烯酸)、聚(乙烯基对苯二酚)和它们的共聚物的第三种材料,选自磷酸盐、硫酸盐和碳酸盐中的一种材料或者一种以上材料的混合物的第四种材料,选自碱金属、碱土金属和电离度高于氢的金属的第五种材料,或者从第一至第五种材料中 33. An organic electroluminescent device comprising: (a) a first electrode formed on one kind of substrate, (b) an organic film laminated on the first electrode, (c) an organic film laminated on the a second electrode, (d) formed in the second upper electrode covering the organic film and the second stack electrode the entire surface of the shield plate; and, (e) forming an absorption layer on the bottom surface of the shield plate the absorbing layer is composed of the following materials selected from pyrogallol and sodium dithionite (of Na2S2O4) of a first material selected from BaO, Li2O, Na2O, K2O, BeO, MgO, CaO and a second material or material mixture of one or more of B2O3, alumina, silica gel, zeolite, and P2O5 is selected from poly (vinyl alcohol), poly (vinyl pyrrolidone), poly (methacrylic acid), poly (vinyl hydroquinone) third material and their copolymers, are selected from phosphate, a fourth material mixture of one material and carbonates or sulfates of one or more materials selected from alkali metals, alkaline earth metals and the ionization degree is higher than a fifth of the material of the metal hydrogen or from the first to fifth material 选择两种材料的或者两种以上材料混合的第六种材料。 Sixth selection of the two materials or two or more kinds of materials mixed material.
34.如权利要求33所述的装置,其中在该第二电极和该吸收层之间的空间中填充一种惰性气体。 34. The apparatus according to claim 33, wherein an inert gas is filled in the space between the second electrode and the absorber layer.
35.如权利要求33所述的装置,进一步包括用于支撑该吸收层的、形成于和该第二电极相对的该吸收层的底表面上的、聚合物的或者玻璃的多孔支撑层。 35. The apparatus according to claim 33, further comprising means for supporting the absorbent layer, formed on the porous support layer of a polymer or glass on the bottom surface and the second electrode layer opposite to the absorber.
36.如权利要求35所述的装置,其中该聚合物是选自聚苯乙烯、聚酰亚胺、聚酰胺、纤维素、聚乙烯、聚(对苯二甲酸乙二醇酯)(PET)、聚(甲基丙烯酸甲酯)(PMMA)、聚丙烯、聚氯乙烯、聚二氯乙烯、聚三氯乙烯、聚四氯乙烯、聚氟乙烯、聚二氟乙烯、聚三氟乙烯、聚四氟乙烯、尼龙、聚氨酯、聚(氯乙烯)、聚烯烃、聚碳酸酯、聚甲醛和聚砜中的一种材料或者一种以上材料的混合物。 36. The apparatus according to claim 35, wherein the polymer is selected from polystyrene, polyimide, polyamide, cellulose, polyethylene, poly (ethylene terephthalate) (PET) , poly (methyl methacrylate) (of PMMA), polypropylene, polyvinyl chloride, polyvinylidene chloride, trichlorethylene polyethylene, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene fluoride, poly tetrafluoroethylene, nylon, polyurethane, poly (vinyl chloride), polyolefins, polycarbonates, polyoxymethylene and mixtures of one material polysulfone or more than one material.
37.如权利要求33所述的装置,其中第二种材料是P2O5。 37. The apparatus according to claim 33, wherein the second material is P2O5.
38.如权利要求33所述的装置,进一步包括位于第二电极上的保护薄膜。 38. The apparatus according to claim 33, further comprising a protective film on the second electrode.
39.一种具有叠层结构的有机电致发光装置,该叠层结构含有介于第一电极和第二电极之间的叠层有机薄膜,该装置包括:与该叠层结构彼此隔开、由P2O5和一种或一种以上装置抗氧化剂形成的吸收层。 39. A laminated structure having an organic electroluminescent device, the laminated structure including an organic thin film interposed between the laminated first and second electrodes, the apparatus comprising: the laminated structure and spaced from each other, the absorbent layer is formed of P2O5 and one or more antioxidants device.
40.如权利要求39所述的装置,其中该装置抗氧化剂为Na3PO4。 40. The apparatus according to claim 39, wherein the antioxidant is means Na3PO4.
CN 99107227 1998-04-08 1999-04-08 Organic electroluminescence device CN1239396A (en)

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