TW200534744A - Electrode substrate and its production method - Google Patents

Abstract

To aim at a removal of a surface defect layer existing on the surface of an anode of a CCM board, protection of the anode surface, and, by extension, at prevention of rise of drive voltage of an organic EL element as well as maintenance of luminous uniformity. A CCM layer 14 is laminated on a board 12 for making wave-length change of light, and an anode 16 made of an IZO is formed on the CCM layer 14. A surface protection layer 18 made of an inorganic compound is laminated on the anode 16 by a sputtering process with a plasma-supporting magnetron sputter of an inductive coupling type. SiO2 is preferable as the inorganic compound. While removing the surface defect layer of the anode 16, the inorganic compound can maintain a state in which the surface defect is removed. As a result, electric stability of the anode 16 can be maintained for a long period of time to improve display image quality of an organic EL display device 100.

Description

200534744 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a substrate structure of an organic EL element and a manufacturing method thereof. In particular, it relates to an electrode substrate used in an organic EL device using the CCM method. More specifically, a color conversion (CCM) substrate is provided to counteract the deterioration of the transparent electrode surface of the substrate anode. [Prior art] A. [Technical background] In recent years, organic EL (electroluminescence) elements have attracted attention due to their application as light emitting devices and display devices. For example, color and full-color display devices used as data display devices, vehicle display devices, etc. have been developed. (1) Basic structure of organic EL elements Generally, organic EL elements use transparent electrodes as anodes, and A1 of counter electrodes Aluminum) as a cathode, and has a structure sandwiching an organic layer between the two electrodes. Such organic EL elements have been considered for various applications, but there is also great expectation for the application of color displays. (2) CCM method The present invention relates specifically to an organic EL element using a CCM (Color Changing Medium ') method. Here, the so-called CCM method is a method of coloring the instruction display device. Using organic EL elements -5- 200534744 (2) For a color display device, for example, ‘consider using organic materials that emit light in three primary colors (red, blue, and green). However, the use of three kinds of organic substances (hereinafter, simply referred to as organic substances) complicates the manufacturing steps, and it is desirable to make only one organic substance colorable. The CCM method is designed according to such requirements. It uses a fluorescent conversion layer that emits a monochromatic light (such as blue) of an organic substance, and can be converted into light of other wavelengths (such as red and green) by appropriate conversion into three primary colors. The way. This C CM method is one of the most promising methods to see the future from the viewpoint of high-definition (full-colorization) of manufacturing costs and patterns in the colorization of display devices. In addition, in this CCM method, not only the fluorescence conversion layer but also the use of a color filter to improve the purity of the emitted color is sometimes performed. That is, it is known to use a fluorescent conversion layer and / or a color filter layer to change the emission color of the organic EL. A model cross-sectional view showing the basic structure of the organic EL display device 10 using the CCM method is shown in Fig. 4. As shown in the figure, a CCM layer 14 is provided on a transparent glass substrate 12. The CCM layer 14 is a green CCM layer 14G that emits green fluorescence, a red CCM layer 14R that emits red fluorescence, and a blue color of a transparent material that allows blue light emitted by the organic layer 18 to pass through as it is. The CCM layer 14B, and one pixel on the screen of the display device is composed of a green CCM layer 14G, a red CCM layer 14R, and a blue CCM layer 14B. An anode 16 of a transparent electrode is laminated on the C CM layer 14. As the anode 16, ITO (Indium Tin Oxide) and IZO (Indium u Zinc Oxide) were used. On the anode 16, an organic material 200534744 (3) layer 18 and a cathode 20 (for example, aluminum (A 1)) are sequentially disposed. Since this organic substance layer 18 emits light by application of an electric field, it is called a light emitting layer. The organic EL display device 10 of the CCM type uses an organic substance-containing layer 18 which emits blue in many cases. The blue light is converted into green light through the green CCm layer 14 and converted into red light through the red CC M layer 14 R. On the other hand, the blue CCM layer MB allows the blue light emitted from the organic layer 18 to pass through as it is. With this structure, the three primary colors of red, blue, and green light can be obtained. In addition, in FIG. 4 and the present description, only the basic structure of the organic EL display device 10 of the CCM method is described, but in fact, when a color filter is included in the CCM layer 14 to improve color purity, many. In the organic layer 18, an electron injection layer and a hole injection layer are provided, and a structure in which electrons from the cathode 20 and holes from the anode 16 are efficiently supplied to the light emitting layer (organic layer 18) is widely used in practice. . The organic EL display device 10 is referred to as an "electrode substrate" in the sense that the substrate 12 to the anode 16 is constituted by a substrate with electrodes attached thereto. This electrode substrate is formed by laminating an organic substance constituting an EL element and a cathode, so that an organic EL display device 10 can be easily manufactured. Furthermore, when the CCM layer 14 is provided between the substrate 12 and the anode 16, a CCM-type organic EL display device 10 can be easily made. The electrode substrate in this case is particularly called a CCM substrate 24. That is, an electrode substrate composed of the substrate 12, the CCM layer 14, and the anode M is referred to as a CCM substrate 24. (3) Defective layer on the anode 200534744 (4) The organic EL element is formed on a substrate. When the CCM method is used, a fluorescent conversion layer and / or a color filter layer as described above is provided on the substrate. Next, an anode is provided on the fluorescent conversion layer and the like, and an organic EL element is formed on the substrate by laminating the organic layer and the cathode in this order. As described above, when the CCM method is used, the substrate, the fluorescent conversion layer and / or the color filter layer, and the anode laminated on the substrate are also referred to as a CCM substrate 24. As the anode 16 constituting the CCM substrate 24, a transparent electrode such as Indium Zinc Oxide can be used. The inventors of the present case investigated the formation of the surface defect layer of this anode and determined the following. ① When a CCM substrate is made, the number of manufacturing steps of the substrate is large, the substrate is easily contaminated, and a surface defect layer is easily formed on the anode surface. In particular, the surface of transparent electrodes such as IZO is susceptible to damage due to excessive cleaning steps or patterned etching residues. Furthermore, water is adsorbed on the electrode surface. The reason why a trace amount of impurity atoms contained in the volume of the electrode (the internal portion other than the surface portion) is deposited on the surface, etc., is that there is a tendency that a surface defect layer is formed on the anode. ② In addition, the CCM layer (fluorescence conversion layer) itself is mostly formed by a resin, and volatile gas components such as moisture from the resin may contaminate the anode surface slowly. (4) According to the investigation by the inventors of the present case, it is judged that the existence of such a surface defective layer causes the following phenomena. ① The driving voltage of the organic EL element is increased. That is, the so-called EL property -8- 200534744 (5) can be reduced. ② The light emitting uniformity of the organic EL element is reduced. Specifically, when forming a C C M panel (a display panel using an organic EL device using the C C M method), a phenomenon of downsizing of each pixel was observed. ③ When accelerating the CCM panel in a heated environment, it is observed that the pixel shrinking speed is accelerated (for example, using a heating environment of ~ 85 ° C). The above-mentioned problems are judged based on the investigation of the inventors and others of the present case. (5) Improvement of the previous anode In the past, various functions of improving the adhesion and conductivity of the anode 16 of the organic EL element and the organic substance laminated on the anode have been performed. One of the techniques is to insert an organic compound or a metal and a semiconductor inorganic substance in a buffer layer type between the anode 16 and the organic substance layer. This approach has been extensively studied in the past. However, the method of inserting this buffer layer is as shown in (3) and (4) above, and is not intended to improve the deterioration of the surface of the transparent electrode (anode). Therefore, the so-called method of inserting the buffer layer alone cannot improve the deterioration of the anode surface, so the effect itself can be said to have a limit. B. [Examples of prior art documents] Next, specific prior art documents are shown, the prior art is introduced, and its contents, disadvantages, and problem points are explained. -9- 200534744 (6) (1) Passivation film For example, WO 0072 63 7 A1 (hereinafter referred to as Document i) discloses a barrier film (passivation film) composed of oxidized sand. An organic EL display based on the CCM method. First, if according to this document 1, the substrate and the CCM layer (including the color filter layer) are covered with a planarized organic layer, and even under the planarization, an organic EL display device is laminated thereon. No "cut-off" etc. will occur. In the case where there is a step on the surface of the laminated organic EL element, a discontinuous portion may be generated on the film of the laminated organic EL element. This discontinuity is called "cut off". In addition, as an example of an organic layer for planarizing, an example of a thermosetting resin and an ultraviolet curing resin is shown in Document 1. Furthermore, in Document 1, it is pointed out that on the organic layer for planarization, if the organic EL element is directly laminated, the heat during the organic EL layering and driving causes the components of the organic layer for planarization to volatilize. And it has an adverse effect on the constituent materials of the organic EL. As a result, a non-light-emitting area where a so-called black spot is generated is pointed out in Document 1, and it is predicted that light emission of a predetermined quality cannot be maintained. Therefore, Document 1 shows that an organic layer and an organic EL element are used for planarization. A barrier layer (passivation film) composed of interlayered Si Ox ′ prevents the organic layer components used for planarization from diffusing into the materials of each layer of the organic EL element, and prevents deterioration of the element. However, although this barrier layer (passivation film) can effectively prevent the diffusion of volatile components in the organic layer and the CCM layer, it is considered that it is almost completely ineffective for mixing in moisture, etc. from the outside of the CCM layer 200534744 (7). The moisture mixed in the element is adsorbed between the anode 16 and the organic material layer, which reduces the adhesion and reduces the charge injection property. As a result, it is predicted that a so-called anode surface defect layer will be formed. The present invention is an invention to realize a method (surface protective layer) for suppressing the occurrence of such a surface-defective layer. (2) Lamination of a buffer layer on the anode The purpose of the buffer layer laminated on the anode is to improve adhesion, improve conductivity with inorganic materials, and use a thin film layer of an insulator to reversely sputter the anode surface. The following describes them in order. ① Insertion of the buffer layer for the purpose of improving the adhesion of the anode / organic material layer (adhesion of organic materials) Japanese Patent Application Laid-Open No. 1 0-2 1 46 8 (hereinafter referred to as Document 2) shows polycrystalline materials. ITO (Indium Tin Oxide) is different from the crystalline state of organic matter. Therefore, the anode and the organic matter layer will not be well bonded and part of the poor bonding will occur, sometimes dark sput will occur, and the heat generated in the poor bonding part will be Causes problems such as deterioration of the organic layer. In Document 2, in order to solve these problems, a conductive joint-improving layer (metals such as Αυ, Pt, MoOx, VOx, SnOx, InOx, BaOx, metal oxides, etc., and amorphous conjugated polymers, etc. (Plasma membrane) is set in a film thickness range of 1 to 500 μηι. Further, Japanese Patent Application Laid-Open No. 9-324176 (hereinafter referred to as Document 3) discloses a technique for improving the adhesion between an electrode and an organic film and preventing the occurrence of a non-light emitting portion, thereby improving long-term storage stability and continuous drive decay time. In order to achieve -11-200534744 (8), such a technique is disclosed in Document 3 to mediate the existence of a layer composed of a material that was previously replaced with a silane coupling agent as the terminal of a compound used as a hole injection transport material. Also, Japanese Patent Application Laid-Open No. 9-2 04 9 8 5 (hereinafter referred to as Document 4) discloses a technique for surface-treating the IT0 electrode itself with a titanate-based coupling agent from the same viewpoint as Document 3. ② The application of inorganic materials (semiconductors, conductors) for the purpose of improving conductivity, etc. JP-A-Hei 3-1 05 89 8 (hereinafter referred to as "Document 5") discloses the transport of holes normally composed of organic substances. A layer or an electron transport layer is formed by a P-type or an N-type of an amorphous semiconductor having a good film formation state, and a technology for improving light emitting performance. In addition, Japanese Patent Application Laid-Open No. 10-260062 (hereinafter referred to as Document 6) discloses a structure that does not use an expensive hole injection transport material instead of forming a mixed layer of ITO and an inorganic semiconductor and has a resistivity of 20 Ω · cm or less. This structure is to directly connect the organic substance with ITO at a low cost. Therefore, from the viewpoint of improving the adhesion described above, good results can also be obtained, and an element that suppresses the occurrence of black spots can be formed. In Japanese Unexamined Patent Publication No. 9-63 77 1 (hereinafter, referred to as Document 7), a metal function (RuO, RuO, which has a work function of 5 to 30 nm, which is larger than that of ITO, is formed between the anode ITO and the hole transport layer. MoO, VOD, etc.), can reduce the energy barrier between the anode and the hole transport layer, and improve the luminous efficiency. Further, Japanese Patent Application Laid-Open No. 08-03 1 5 7 3 (hereinafter referred to as Document 8) discloses a configuration in which a part of the anode is formed of a carbon thin film or the entire anode. -12- 200534744 (9) In addition, JP 03-2 1 07 9 1, JP 03-262 1 70, JP 06- 1 1 9973 disclose that P-type semiconductor applications are short Cavity Conveying Material. ③ The formation of an insulator thin film layer between the anode and the organic substance layer is described in USP No. 5 8 5 3 905 (hereinafter referred to as Document 9) to improve the adhesion between the transparent electrode and the organic substance or actively form a charge barrier, and Proposal for the use of new components of the tunnel injection mechanism. Furthermore, in Japanese Patent Application Laid-Open No. 0 8-2 8 8 069 (hereinafter referred to as Document 10), it is disclosed that in order to avoid electric leakage that occurs during continuous driving, about 50 A of nitrogen is provided between the anode and the organic layer. Structure of nitride films such as aluminum oxide ④A person who reverse-sputtered the anode surface in advance JP-A No. 1 1-12626689 (hereinafter referred to as Document 1 1) determined that the occurrence of leakage current or black spots was due to the anode In order to avoid the unevenness of the surface, it is proposed to treat the surface of the anode with a shovel. [Summary of the Invention] The problems to be solved by the disclosure of the invention are in the prior art described in items (1) to (3) of "(2) for the anode laminated buffer layer" in the above "B. The purpose is to improve the bonding characteristics such as the adhesion between the anode and the organic layer, and to improve the hole injection characteristics of the organic layer from the anode. However, as described in the above (A. [Technical Background] "" (3) Surface Defective Layer on Anode "and the same as (4), the transparent electrode surface on ITO etc. exists originally through -13-200534744 (10) The existence of a defective surface layer causes various discomforts. For example, the existence of a surface defect layer increases the driving voltage during continuous driving, which may cause a short life. In addition, it is difficult to ensure heat resistance, and it is expected that this will become a problem especially when applied to various display devices for vehicles. Furthermore, especially in the case of a high-definition CCM panel, the problem of shrinking the luminescent pixels is caused by the generation and increase of the surface defect layer. Its characteristics are remarkable in high temperature environments. With this in mind, examples of countermeasures are still unknown. In item (4) of the above (2) For anode laminated buffer layer, although the anode surface has been proposed to be treated by reverse plating, it is considered insufficient for the following reasons. That is, since the inorganic compound is not laminated after the reverse sputtering, the possibility of contamination in a vacuum is high, and the moisture and the like existing in the vacuum tank may also be restored to the original surface state, which is considered as an effect Not enough. In view of these problems, the present invention has the following objects. (1) Remove the surface defect layer existing on the anode surface of the CCM substrate, and protect the anode surface for its purpose. (2) Stabilize the performance of organic EL elements, especially CCM panels, specifically. The purpose is to prevent the driving voltage from increasing, maintain the uniformity of light emission, and improve the heat resistance. Means for Solving the Problem In order to solve the above-mentioned problem, the present invention proposes a new structure different from the past in which an inorganic compound is laminated after removing the surface defective layer. By laminating the inorganic compound, it is possible to prevent the formation of a new surface defective layer. Prior Art-14-200534744 (11) The effect of the technique. The existence of the surface protective layer of the present invention can prevent the formation of a surface defect layer on the anode. For example, in a state where a barrier layer for cathode separation is formed on the anode of a CCM substrate for a full-color panel, it is not necessary to store or move it without particularly worrying about contamination. In the case of forming a panel (in the case of forming an organic EL film), it may be carried out in accordance with the original manufacturing procedure specified previously. Specifically, the present invention adopts the following constitutions. In order to solve the above-mentioned problem, the present invention includes an electrode composed of a substrate, a compound containing an In atom, and a layer between the electrode and the substrate, and used to convert the wavelength of light incident on the layer. The layered electrode substrate is characterized in that a surface protection layer made of an inorganic compound is formed on the surface of the electrode opposite to the surface of the fluorescent conversion layer. With such a structure, formation of a surface defect layer can be prevented. Specifically, it can effectively prevent the formation of a surface defect layer due to exposure to the atmosphere or the like. The present invention is also characterized in that the substrate of the electrode substrate and / or the constituent material of the electrode is a transparent material. By using such a transparent material, an electrode substrate can be obtained which can be used for display means. The present invention is also characterized in that the electrode surface is subjected to a reverse sputtering process. With such a structure, the surface defect layer on the electrode surface can be effectively reduced, and the electrode surface and the inside can be made homogeneous. Further, the present invention is characterized in that the above-mentioned reverse sputtering process is a reverse sputtering process using an induction bonding type RF plasma supporting magnetron sputtering apparatus. According to such a structure, the discharge gas ions that just remove the kinetic energy of the surface defect layer on the anode surface can be easily obtained, so the electrode will not be damaged and the surface defect layer of Table -15- 200534744 (12) can be removed. The present invention is characterized in that the inorganic compound constituting the surface protective layer is made of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, K, Cd, Mg, Si, Ta, Ge, Sb, Zn. , Cs, Eu, Y, Ce, W, Zr, La, Sc, Rb, Lu, Ti, Cr, Ho, Cu, Er, Sm, W, Co, Se, Hf, Tm, Fe, Nb At least one or more metal oxides, or any of nitrides, composite oxides, sulfides, and fluorides. With this structure, a dense surface protective layer can be formed on the electrode surface. In addition, the present invention is characterized in that the surface protective layer is formed by a plating method. With such a configuration, the surface defect layer of the electrode can be removed and a surface protective layer can be formed. In addition, the present invention is characterized in that the surface protective layer is formed by a sputtering method using an induction bonding type RF plasma to support a magnetron sputtering device. With such a structure, a surface protective layer can be effectively formed. In addition, the present invention is characterized in that the film thickness of the surface protective layer is within a range of 5 to 100A. With such a structure, it is possible to prevent recurrence of the surface defect layer, and to ensure a specified light transmittance. The present invention is characterized in that the electrode is made of tin oxide (ITO) or indium zinc oxide (IZO). With such a structure, excellent light transmittance can be obtained. The present invention is characterized in that the electrode is an amorphous oxide. With such a structure, excellent etching characteristics can be obtained. In addition, ITO is usually crystalline ', but it becomes a moisture ambient gas during film formation, and it can be made amorphous by mixing trace elements, etc. in 200534744 (13). Furthermore, the present invention is characterized by including a driving element for driving the electrode. In recent years, a liquid crystal display device and an organic EL display element each including a thin film transistor (TFT) and improving display performance have been widely used. Therefore, by providing an electrode substrate in which a driving element such as a TFT is provided in advance, a liquid crystal display device and an organic el display device of the TFT type as described above can be easily manufactured. Hereinafter, the manufacturing method of an electrode substrate is demonstrated. Secondly, in order to solve the above-mentioned problem, the present invention is an electrode composed of a substrate and a compound containing ϊ η atoms, and a layer located between the electricity and the substrate, and is used for measuring the wavelength of light incident on the layer. The manufacturing method of an electrode substrate for a converted fluorescent conversion layer includes a step of forming the fluorescent conversion layer on the substrate, a step of forming the electrode on the formed fluorescent conversion layer, and applying the electrode surface. A step of performing a reverse sputtering process, and in a step of applying a reverse sputtering process to the electrode surface, a surface made of an inorganic compound is formed after the reverse sputtering process is performed, or when the reverse sputtering process is performed. A protective layer is a method for manufacturing an electrode substrate. With such a structure, an electrode substrate capable of reducing a surface defect layer on an electrode can be manufactured. Through the surface protective layer of the inorganic compound, the state in which the defective surface layer is removed can be maintained, and the formation of the defective surface layer can be effectively prevented. Further, the present invention is characterized in that the reverse sputtering process is performed using an induction bonding type RF plasma supporting magnetron sputtering apparatus. According to such a structure, it is possible to easily obtain the energy of the discharge electrode body -17- 200534744 (14) which just removes the surface defect layer on the anode surface, so it will not damage the electrode and prevent the surface defect layer. The present invention is also characterized in that in the reverse sputtering process, a high frequency of 50 to 200 W and a frequency of 1 3.56 to 100 MHz is applied to the spiral coil of the induction-coupled RF plasma supporting magnetron, and The induction-coupled RF plasma supports the anode of the magnetron sputtering device, and the high frequency of 200 ~ 500W's 13.56 ~ 100MHz is used to cause the plasma to discharge. This makes the induction-coupled RF plasma support the magnetron sputtering. The manufacturing method characterized by the magnetic field strength of the magnetron of the plater in the range of 200 ~ 300 Gauss. With such a structure, the surface defect layer on the electrode surface can be removed more effectively. In particular, if the electrode substrate of the present invention is specified by the measurement of XPS, it is as follows. In order to solve the above problem, the present invention is an electrode composed of a substrate and a compound containing I η atoms, and a layer between the electrode and the substrate, and used to convert the wavelength of light incident on the layer. An electrode substrate of a fluorescent conversion layer is formed on the surface of the electrode opposite to the surface of the fluorescent conversion layer. An electrode substrate having a surface protection layer composed of an inorganic compound as a feature is formed on the surface of the electrode. X-rays on the electrode surface The measurement results of the photoelectron spectroscopy method were as follows. That is, according to the X-ray photoelectron spectroscopy method, the peak half-width 半 of the 3d% orbital spectrum of the In atom measured on the electrode surface is expressed by [In 3 d5 / 2] h, and according to the X-ray photoelectron spectroscopy method, Let the peak half-width of the 3d5 / 2 orbital spectrum of the In atom measured on the electrode surface be reduced by -18- 200534744 (15)

When In3d5 / 2] n is expressed, the ratio of each half-width 値 ([In3d5 / 2] h / [In3d5 / 2] n) 値 is an electrode substrate whose characteristic is in the range of 0.9 to 1.2. With such a structure, the half-width width of the In3d5 / 2 orbital spectral peak of the electrode "inside" and the ratio of the half-width width of the "surface" of the electrode to the specified range are limited to form a non-surface defective layer on the electrode In addition, in the present invention, the “measurement on the surface” means that the measurement is performed on a part of the surface or a point on the surface. The present invention is an electrode composed of a substrate and an In atom-containing compound, and a layer between the electrode and the substrate. The electrode substrate of the fluorescent conversion layer for converting the wavelength of the light incident on the layer, on the surface of the electrode, forms a surface protection made of an inorganic compound on the surface opposite to the surface of the fluorescent conversion layer. The electrode substrate with its layer as its characteristic. The result measured by X-ray photoelectron spectroscopy is the following measurement. That is, 'The present invention is based on X-ray photoelectron spectroscopy, so that 3 d 5 / The peaks of the 2 orbital spectrum are represented by Inpeak, and according to the X-ray photoelectron spectroscopy, the 3d5 / 2 orbital spectral peaks of the Sn atoms measured by the electrode are represented by Sn peak, and the peak ratios measured inside the electrode When represented by (In peak / Sn peak) n, it is an electrode substrate characterized by ((Sn peak / In peak) h / (Sn peak / In peak) n) < 1.5. With such a configuration, the ratio of the peak 値 of the In atom to the peak 値 of the S η atom can be measured inside and outside the electrode, and the ratio between the inside and outside of the electrode can be limited to a specified range -19- 200534744 (16). An electrode substrate having no surface defect layer on the electrode. The "measured on the surface" as used herein means that it is measured on a part of the surface or a point on the surface, and is the same as the present invention. Effects of the Invention As described above, according to the electrode substrate of the present invention, since an electrode with a reduced surface defect layer is used, electrical stability can be improved. Therefore, if this electrode substrate is used as an anode of an organic EL element, for example, the effect of extending the life of the element can be achieved. Furthermore, the effect of suppressing the increase in driving voltage of the organic EL element can be achieved. Furthermore, the heat resistance of this organic EL element can be improved. Further, according to the present invention, since a driving element for driving electrodes on the electrode substrate is provided, it is possible to provide an electrode substrate suitable for manufacturing a display device such as a TFT system. In addition, if the electrode substrate of the present invention is used as an electrode of an organic EL element, and the organic EL element is configured, an organic EL display device with reduced emission spots and brightness variation and improved image quality can be obtained. Furthermore, it is possible to improve the image quality of the organic EL display device over time. Furthermore, according to the electrode substrate manufacturing method of the present invention, an electrode substrate capable of achieving the above-mentioned effects can be manufactured. Best Mode for Carrying Out the Invention The most suitable embodiment of the present invention will be described below with reference to the drawings. -20- 200534744 (17) A. Basic structure This embodiment proposes a structure in which an inorganic compound layer is laminated on the anode of a color conversion (C CM) substrate, and an organic substance layer is laminated thereon. A model diagram of the structure of such an organic EL display device 100 is shown in FIG. 1. As shown in the figure, this embodiment is characterized in that the anode 16 is provided with a surface protective layer 102 made of an inorganic compound or an organic compound. The organic material layer 18 is laminated on the surface protection layer 102. The organic layer 18 is also referred to as a light-emitting layer because it is a part that emits light. In addition, since organic matter is a compound in many cases, it is sometimes referred to as an organic compound layer. The organic material layer 18 has at least a recombination region and a light emitting region. The organic material layer 18 may also be referred to as an organic EL element layer. Regarding the organic material layer 18, in addition to the organic material layer 18 (light emitting layer), layers such as a hole injection layer, an electron injection layer, an organic semiconductor layer, an electron barrier layer, and an adhesion improving layer may be provided, if necessary. In this case, a plurality of layers containing these hole injection layers are generally referred to as organic layers 18. Next, a cathode 20 is formed on the organic layer 18 composed of the plurality of layers. In this embodiment, an example of an organic EL display device 100 is shown. This organic EL display device is equivalent to an example of a "light emitting device" in the scope of patent application. Since the organic EL element is a light-emitting element, a light-emitting device having a light-emitting function is configured. Although the present embodiment is described as an example of the light-emitting device, the organic EL display device 100 is not limited to the organic EL element. A typical configuration example (modified example) of the organic EL element shown in this embodiment is shown. Of course, it is not limited to this. 200534744 (18) The basic layer structure of the organic EL display device 100 is as follows. Substrate / Color Conversion Film (CCM Layer) / Passivation Film / Organic EL Element Here, the organic EL element 122 has the following modifications. (1) Transparent electrode (anode) / surface protection layer / light-emitting layer / electrode (cathode) (2) Transparent electrode (anode) / surface protection layer / hole-injection layer / light-emitting layer / electrode (cathode) (3) Transparent electrode (Anode) / Surface protection layer / Light-emitting layer / Electron injection layer / Electrode (Cathode) (4) Transparent electrode (Anode) / Surface protection layer / Hole injection layer / Light-emitting layer / Electron injection layer / Electrode (cathode) (5) ) Anode / Surface Protective Layer / Organic Semiconductor Layer / Light-Emitting Layer / Cathode (6) Anode / Surface Protective Layer / .Organic Semiconductor Layer / Electronic Barrier Layer / Light-Emitting Layer / Cathode (7) Anode / Surface Protective Layer / Hole Injection Layer The / light emitting layer / adhesion improving layer / cathode is structured as described above. Among them, Tongdang is preferably used with the structure of (4). This embodiment is characterized by a surface protection layer 102 included in the organic EL element 122. B. Defective layer on the surface of a transparent electrode such as ITO Here, an explanation will be given on a surface defect layer of an electrode. As described in (4) of "A. Background Technology" of the prior art, the transparent electrode surface of ITO or the like is damaged due to excessive cleaning or patterned etching residues in the cleaning step. In addition, due to reasons such as adsorption of water on the surface and precipitation of trace impurity atoms of -22-200534744 (19) contained in the volume, a so-called surface defect layer is formed as described below. An example focusing on the problem of this defective surface layer and trying to improve is still unknown. As a result, the conventional organic EL device was laminated with an organic substance in a state in which the anode was accompanied by the surface defect layer, and the charge injection property of the interface was reduced. (1) Surface protection layer The surface defect layer in this embodiment is, for example, one of the following requirements-* 〇 ① Dopant Sn is deposited on the surface. In the case of IZO, defects of Zn can be listed. ② The same blend is missing on the surface of the oxidized pores (that is, too many oxygen atoms). ③ The surface absorbs moisture. ④ Trace impurities (nitrogen, etc.) contained in the volume are deposited on the surface. In the presence of such a surface defect layer, a decrease in conductivity (hole-injection property) is observed, a region where the adherence of the organic substance laminated above is reduced, and a diffusion of impurities in the surface defect layer into the organic substance layer is observed. . The existence of such a surface-defective layer can be judged to cause the following problems. ① When the constant current is continuously driven, the voltage rises greatly and the life is short. ② The adhesion to the organic matter laminated on the surface defect layer is reduced, and as a result, the light emission is not uniform when driven at high temperature, and the light emission is not uniform after storage at high temperature. In the same way, the current injection properties and luminous efficiency at high temperatures are reduced. -23- 200534744 (20) etc. reduce the so-called heat resistance. (2) The detection method of the surface defect layer is analytically detected by X-ray photoelectron spectroscopy (XPS: X-ray Photoelectron Spectroscopy). ① Calculate the spectra of I n atoms In3d5 / 2 ( The peak size (combined energy 444.4 eV) (hereinafter, referred to as ιη peak), and the peak size of Sn 3d5 / 2 (combined energy 486.2eV) (hereinafter, f peak is Sn peak) 'and according to its ratio 値 Sn peak / In The peak is larger near the surface than inside the electrode (volume), and the presence of a surface defect layer is detected. Here, the calculation of In peak and Sn peak is actually to correct the obtained 値 with atomic sensitivity and obtain the final 値. Approximately Sn peak / In peak is 0.1 to 0.2 値. If the surface 考虑 is more than 1.5 times the volume 値, it is considered that S η is deposited on the surface and the presence of a surface defect layer is observed. That is, if Sn peak / In peak 値 on the electrode surface is represented by (Sn peak / In peak) h, and Sn peak / In peak 値 inside the electrode is represented by (Sn peak / In peak) n, then (Sn peak / ln peak) h / (Sn peak / In peak) n > = 1.5, the presence of a surface defect layer was observed. Conversely, if an electrode of (Sn peak / In peak) h / (Sn peak / In peak) n < 1.5 is produced, it is observed that there is virtually no surface defect layer. The measurement of xps on the electrode surface is generally performed on a part of the surface or a point on the surface. Therefore, the above measurement also refers to a part of the electrode surface or a point on the surface. -24- 200534744 (21) ② The peak half-width of In3d5 / 2 (FWHM: Full-Width Half-Maximum) in the spectrum of In atom reflecting the rotation of In atom. The atomic composition is different and the surface defect layer is formed below. An example and the model diagram of Fig. 2 will be described. This model diagram shows the spectral intensity (the unit is arbitrary) on the vertical axis, and the model diagram of the binding energy on the horizontal axis. For example, ' The electrode (installed on the substrate) that has been cleaned with ordinary organic solvents and UV cleaned is put into the XPS measurement cell as soon as possible and observed. The half-width above is 1.7eV (indicated by A in Figure 2). This is the surface. The half-width of the peak of In3d5 / 2. If it is sputtered with an argon ion gun for 30 seconds, and the surface controlled by about 50 people is observed, the half-width is 1.2 eV (indicated by B in FIG. 2). The half-width of the latter is the ITO half-width of the volume. If the surface of the half-width of the peak of In3d5 / 2 is represented by [In3d5 / 2] h 'and the volume (internal) of the half-width of the peak of In3d5 / 2 is represented by [In3d5 / 2] h means that if the ratio ([In3d5 / 2] h / [In3d5 / 2] n) 値 is in the range of 0.9 ~ 1.2 'The atomic composition of the electrode surface is different from the interior, and the presence of a surface defect layer is observed. For example, if the 値 is calculated using the above example, it is obtained] · 7/1 · 2 = 1.42, because it is not 0.9 ~ 1.2 Range, it is judged that there is a surface defect layer. For the example shown in this ②, for the electrode formed with Si02 on the ITO electrode, after washing the same as above, if the half width of In3d5 / 2 on the surface is observed, it is 1 .2eV, which is the same as the volume of ITO. From this result, it can be seen that the surface of the substrate on which Si02 is formed is to remove the surface defect layer. Since ([In3d5 / 2]) i / nn3d5 / 2] n) is 値] .0 , In the range of 0.9 to 1.2. There is also 200534744 (22), and the film formation of this SiO2 is performed using a rotary sputtering device. That is, this film-forming step is to remove the surface defect layer by plating, and form SiO 2 as a surface protection layer on the electrode surface. The induction-coupled RF plasma-supported magnetron sputtering device is referred to as a "rotary sputtering device". In addition, if the discharge gas flow rate during the film formation of the rotary sputtering device is changed, it can be seen that the In3d5 / 2 peak half-width of the substrate surface where the Si02 is formed is changed. Specifically, as the discharge gas flow rate becomes larger, the half width becomes narrower, and it is determined that the surface defect layer tends to be more removed. From the above, the surface defect layer on the surface of the ITO electrode can be removed by the sputtering effect of the discharge gas, which was observed by the inventors and others of the present case. A characteristic feature in the present invention is that a surface protective layer made of an inorganic compound such as SiO 2 is formed on the electrode surface by a sputtering method. By this sputtering, the surface defect layer on the electrode surface can be removed, and a protective layer for protecting the surface can be provided. ③ The film thickness of the surface protective layer is selected from a film thickness of about 5 to 100A. It is preferably 10 to 50 A, and more preferably 20 to 40 A. Generally, when the film thickness is 5 to 20A, the film becomes an island structure, and it is difficult to form the same interface. However, with a film thickness of 5A or more, the reproducibility of the effect can be obtained, and a film thickness of 20A can be at least uniformly formed. The system was confirmed by the inventors and others through the observation of a transmission electron microscope, and the sputtered film has been confirmed, especially Spin-sputtered films can form stable, dense films. On the other hand, if the film thickness is too thick (100A or more), since inorganic compounds such as 3 丨 02 (200534744 (23)) have many insulators and low electrical conductivity, they often become barriers for injection between the anode and the organic layer. Problems, and the components are not electrified due to high electrification. C. Structure of each layer The following describes the layers constituting the organic EL display device 100. As described above, the organic EL display device 100 has a substrate, a color conversion film (CCM layer), a passivation film, and an organic EL element. The organic EL element 122 is a configuration example having a transparent electrode (anode) / surface protection layer / hole injection layer / light-emitting layer / electron injection layer / electrode (cathode), and each layer will be described below. (1) Regarding the surface protection layer 102-an inorganic compound layer First, the surface protection layer 102 made of an inorganic compound according to the present invention will be described. The surface protection layer 102 is made of Ba, Ca, Sr, Yb, Al, Ga,

In, Li, Na, K, Cd, Mg, Si, Ta, Ge, Sb, Zn, Cs, Ευ, Y, C e, W, Zr, La, S c, Rb, Lu, Ti, Cr, Ηo, Cu 'Er, Sm, W, Co, Se, Hf, Tm, Fe, Nb and other metal oxides, nitrides, composite oxides, sulfides, and fluorides are suitable. In this example, Si Ox (x is an atomic ratio) is effective. For more specific examples, LiOx, LiNx, NaOx, KOx, RbOx, CsOx, BeOx, M g 0 x j MgNx, CaOx, CaNx, 200534744 (24)

SrOx, BaOx, ScOx, YOx, Ynx, LaOx, LaNx, CeOx, PrOx, NdOx, SmOx, EuOx, G d ox, T b O x, D y ox, ο ο O x, ErOx, TmOx, YbOx, LuOx, TiOx, TiNx, ZrOx, ZrNx, HfOx, HfNx, ThOx, V Ox, VNx, NbOx, NbNx, TaOx, TaNx, CrOx, CrNx, MoOx, MoNx, WOx, WNx, MnOx, ReOx, Fe Ox 5 FeN 5N RuOx? OsOx, CoOx, RhOx, IrOx, NiOx, PdOx, PtOx, CuOx, CuNx, AgOx, AuOx, ZnOx, CdOx, HgOx, BOx, BNx, AlOx, AINx, GaOx, GaNx, InOx, SiNxSnx Metal oxides or metal oxides such as PbOx, PO x 5 PNx, AsOx, SbOx, ScOx, TeOx are also preferred. Furthermore, it can also be LiA102, Li2Si03, Li2Ti03, Na2Al 2 2 0 3 4, NaFe02, Na 4 S i 0 4, K2 S i Ο 3, K 2 T i O 3, K2 W04, Rb2Cr〇4, Cs2Cr04, MgAi204, MgFe2O4, MgTi03, CaTi〇3, CaW04, CaZr03, SrFe12〇19 »SrTi03, SrZr〇3, B a A 12 〇4 ^ BaFe] 2〇i9, B a T i Ο 3, Y 3 A15 〇 12 5 Y3Fe50] 2, La F e 0 3, La a3 F e 5 0] 2, La2Ti2 0 7, C e S n 0 4, CeTi04, S m 3 F e 5 0: 12, E u F e 0 3, Eu3Fe5〇12, G d F e 0 3, G d 3 F e 5 0 1 2, D y F e 0 3, Dy3Fe 5 0] 2, H 0 F e 0 3, H 0 3 F e 5 0 ] 2, E r F e 0 3, Er3Fe5〇i2, Tm 3 F e 5〇12 5 Lu Fe 0 3, Lu 3 F e 5 0 j 2 5 NiTi03, Al2Ti〇3, FeTi03, B aZr 0 3, L i Z r 〇3, MgZr〇3, HfTi04, NH4VO3 5 Ag Y O3, L1VO3, B aN b 2 0 6 5 N aN b 0 3 5 SrNb2 0 6, KTa03 'N aT a 0 3, S r Ta2 〇'6 5 CuCr2 〇4, Ag2 C r 0, BaCr04, K2M0O4, Na2Mo04, NiMo〇4, BaW04, 200534744 (25)

Na2W04, SrW04, MnCr2O4, MnFe2O4, MnTi03, MnW04, CoFe204, ZnFe204, FeW04, coMo04, CoTi03, C0WO4, NiFe2O4, NiW04, CuFe2O4, CuMoCU, CuTi03, Cu W04, Ag2Mo04 , Ag2W04, Z n A12 〇4, ZnMo04, ZnW〇4, CdSn03, CdTi〇3, CdMo〇4, C d W 0 4, Na A 1 0 2,

MgAl2O4, SrAl2O4, Gd3Ga5012, InFe03, Mgln2O4, Al2Ti05, FeTi03, MgTi03, Na2Si03, CaSi03, ZrSiCU, K2Ge03, Li2Ge03, Na2Ge03, Bl2Sn3 09, MgSn03, SrMoSnSn 〇4, PbTi〇3, Sn02-Sb203, CuSc04, Na2Se03, ZnSe03, K2Te03, K2Te09, Na2Te03, Na2Te04 and other metal composite oxides.

Also, sulfides such as FeS, AI2S3, MgS, ZnS, fluorides such as LiF, MgF2, SmF3, chlorides such as HgCl, FeCl2, CrCl3, bromides such as AgBr, CuBr, MnBi * 2, Pb 1 2, Suitable materials are iodides such as Cul and Fel2, and metal oxides such as Si AI ON. Among them, oxides are preferable, and particularly good oxides having a Gibbs energy of -520 kJmr] are preferred as stable oxides. Examples thereof include Si02 (-8 5 5 kJmor1), Ge02 (-497 kJmol ·]), CeO2 (-1025 kJmor1), and Al203 (] 58 1 .9 kJmol ·]). Other compounds, such as AIN, sic, and CaS, are also stable compounds and are therefore preferred. Next, a procedure for forming the upper surface protective film 102 on the electrode will be described. -29- 200534744 (26) Main points of film formation procedure Step 1: Wet clean the substrate with anode (transparent electrode). The _ is the same as the substrate cleaning performed before the film formation of a general device. Specifically, _ a combination of ultrasonic cleaning using an organic solvent such as dipropanol and washing with pure water is effective. Further, it is preferable to perform ultrasonic cleaning using neutral cleaning or the like according to the degree of contamination on the anode surface. Step 2: The inorganic oxide is formed by a sputtering method such as spin sputtering. Here, the reason why an inorganic compound is formed by a sputtering method is as follows. φ • First, the temperature required for oxide or nitride deposition is generally high, which makes it difficult to deposit by electric heating. • Moreover, although film formation can be performed according to the electron beam deposition method, unlike sputtering, there is no modification effect on the surface defect layer of ITO. • Therefore, the improvement effect of the ITO surface defect layer by the sputtering method is because the discharge gas ions generated by the plasma are accelerated by the self-biased electric field generated by the plasma, and the surface defect layer is driven away and the ore is sputtered. Rinse (so-called reverse sputtering). φ • Rotary spatter is particularly preferred in sputtering. The reason for this is that, because of the large distance between substrates in general spin sputtering, the usual sputtering provides excessive energy to the substrate and causes damage to the substrate. On the other hand, it is experimentally confirmed that the spin sputtering is performed to remove the anode. Movement energy of the surface bad layer: (about 0.1 ~ lev). ’Specific example of film formation procedure Steps: Confirm that the degree of vacuum before introducing gas into the vacuum chamber is 10-3Pa -30- 200534744 (27) The first half. Step 2: Introduce a discharge gas such as Ar into the vacuum chamber. The vacuum degree at this time is lx10 GPa to lxl (T2Pa or so. It is not excessively low pressure, for example, 0.3 Pa to 1.0 Pa is preferred. It is reduced under low pressure due to the removal effect of the surface defective layer. Discharge The type of gas can be selected from rare gases such as Ar, Xe, Kr, etc. In terms of cost, Ar is preferred. Step 3: Sequentially, add 50 ~ 200W to the rotating coil (coil for induction combination), and external force to the cathode □ 200 ~ 500V, high frequency of 13.56MHz ~ 100MHz each, causing plasma discharge. At this time, the strength of the magnetron's magnetic field is about 200 ~ 300 Gauss. Step 4: After sufficient pre-plating (pre- sputter) to remove the target surface. The minimum time is more than 5 minutes, especially for the initial return after the target is replaced for more than 10 minutes. Step 5: Secondly, open the main shutter of the sputtering device to form the inorganic compound to the specified film Thick (5 ~ 100 A). (2) Substrate 12 The substrate used in this embodiment is transparent, and it is preferably a sufficiently rigid material that can support the color display device B. In this embodiment, SSW is used to enhance the color display. Install and mention Mechanical strength such as impact resistance. Examples of materials include glass plates, ceramic plates, and plastic plates (polycarbonate, citric acid, vinyl chloride, polyethylene terephthalate, polyimide, Polyester resin, etc.), etc. -31-200534744 (28) (3) CCM layer 1 4 CCM layer 14 (also known as color transfer loss layer) absorbs the light emitted by the organic EL element 122 and emits longer wavelength fluorescent light For example, it converts blue light into green light or red light. In addition to the CCM layer 14, a color filter may be included for better color reproducibility.

Each CCM layer 14 is preferably arranged corresponding to the light-emitting area of the organic EL element 122, for example, the position of the intersection of the anode 16 and the anode 20. The anode 16 and the anode 20 are arranged in a stripe shape for the opposite display surface, and they are arranged in a vertical direction on the display plane. The organic material layer 18 where the cathode 16 and the anode 20 are superposed (crossed) on a plane emits light. This overlap position (cross position) is equivalent to "one pixel" on the display plane. With this configuration, when the organic layer 18 (organic EL light-emitting layer) at the intersection of the anode 16 and the cathode 20 emits light, the CCM layer 14 receives light and emits light of different colors (wavelengths) to the outside.

At this time, especially the organic EL element 122 emits blue light, and if it is converted into green and red light emission through the CCM layer 14, it is possible to obtain even an organic EL element 1 2 2 composed of one organic layer 18 The three primary colors of blue, green and red light are suitable for full color display. (3-1) Material The material of the C CM layer 14 is not particularly limited. For example, it is made of fluorescent pigment, or fluorescent pigment and adhesive resin. Among them, typical examples of the CCM layer 14 composed of a fluorescent pigment and a binder resin include solid state in which the fluorescent color -32- 200534744 (29) is dissolved or dispersed in the pigment resin and / or the binder resin. 〇 If a specific fluorescent pigment is described, in the organic EL element 122, a fluorescent pigment that converts purple light emission from near-ultraviolet light into blue light emission may include I · 4 · bis (2-methylstyryl) benzene. (Bis-MBS), trans-4,4, -diphenylstilbene (DPS) and other stilbene pigments, and 7-hydroxymethylcoumarin (coumarin 4) and other coumarin pigments. In addition, as the fluorescent dye when blue, cyan, or white light emission is converted into green light emission in the organic EL element 122, for example, 2, 3, 5, 6-1H, 4H-tetrahydro-8-trifluoro may be mentioned. Methyl walolino (9,9a, 1-gh) coumarin (coumarin 153), 3- (2, · benzothiazolyl) -7-diethylaminocoumarin (coumarin 6 ), 3- (2'-benzimidamido) -7_N, N-diethylamine coumarin (coumarin 7) and other coumarin pigments, and other basic coumarin pigment dyes yellow 51 Or Solvent Yellow 1 1, Solvent Yellow 1 1 6 and the like. Further, as the fluorescent dye when the blue light is converted to green or the white light is changed from orange to red in the organic EL element 122, for example, 4-dicyanomethylene-2- Anthocyanin pigments such as methyl-6- (p-dimethylaminostyryl) -4Hpyran (D CM), 1 · ethyl-2- (4-p-dimethylaminephenyl)- Pyridine-based pigments such as 13-phthaladienylpyridine p-chromate (pyridine 1), rhodamine-based pigments such as rhodamine B, rhodamine 6 G, and other humor-based pigments. Moreover, if various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) are fluorescent, they can also be selected as fluorescent dyes. In addition, fluorescent pigments were added to polymethacrylate, polyvinyl chloride, vinyl chloride-33 · 200534744 (30) vinyl acetate copolymer, alkyd resin, aromatic sulfonamide resin, urea resin, and melamine resin. Pigment resins, such as benzoguanamine resin, may be mixed in advance to be pigmented. On the other hand, it is preferable that the adhesive resin is transparent (the light transmittance in visible light is 50% or more). Examples thereof include transparent resins (polymers) such as polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, and carboxymethyl cellulose. In order to arrange the fluorescent media in a planar manner, a photosensitive resin using a photolithography method can be selected. Examples of the photocurable photoresist material include a reactive vinyl group, such as acrylic, methacrylic, polyvinylcinnamate, and cyclic rubber. When a printing method is used, a printing ink (medium) using a transparent resin is selected. For example, monomers such as polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, and polyamide resin can be used, Oligomer, polymer, or transparent resin such as polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, etc. (3-2) Forming method When the CCM layer 14 is mainly composed of a fluorescent pigment, it is preferable to form a film by vacuum deposition or sputtering method through a mask that obtains a desired pattern of the CCM layer 14. On the other hand, the CCM layer 14 When composed of a fluorescent pigment and a resin, the fluorescent pigment and the resin are mixed, dispersed or dissolved with an appropriate solvent to form -34- 200534744 (31) a liquid substance, and the liquid substance is spin-coated, roller The film is formed by coating, casting, etc., and then the desired pattern of the CCM layer 14 is patterned by photolithography, and the desired pattern is patterned by screen printing or the like to form the CCM layer 14 Better. (3-3) Thickness The thickness of the CCM layer 14 is not particularly limited as long as the thickness of the CCM layer 14 sufficiently receives (absorbs) light from the organic EL element 122 and does not hinder the light-emitting function of the fluorescent light. It is better, and more preferably 0. Ιμιη to 500 μιυ, and more preferably 5 μηι to 100 μπι. The reason for this is that if the thickness of the CCM layer 14 is less than 10 nm, the mechanical strength is reduced and lamination is difficult. On the other hand, if the thickness of the CCM layer 14 exceeds 1 mm, the light transmittance is significantly reduced, and the amount of external light is reduced, or the thickness of the organic EL light-emitting device becomes difficult. (4) Passivation film The passivation film is used to block the volatile components of the resin film such as the CCM layer 14 below it from contacting the organic EL element 122, and the material is not particularly limited if it is transparent in the visible light region. Specific materials include transparent inorganic substances. More specifically, Si02, SiOx, SiOxNy, Si3N4, A 1 203, AlOxNy, Ti02, TiOx, I but O (I n 2 0 3-S n 0 2), IZ0 (In2 03 -Zn0), Sn02 ZnO, ZnO, indium copper (Culn), gold, platinum, palladium, etc. alone or in combination of two or more kinds of transparent inorganic-35-200534744 (32). When using a transparent inorganic material as described above, the CCM layer 14 is preferably formed at a low temperature (below 200 ° C) and at a low temperature (less than 200 ° C), and the film formation is preferably performed. Specifically, sputtering, deposition, CVD, A method such as ion plating is preferred. Here, the thickness of the passivation film varies according to the fineness of the organic EL element 122, but may be selected from the range of 0.01 μm to 100 μm, preferably 0.05 μm to 10 μm, and more preferably 0.ΐ μm to 1 μm. . If the film thickness is less than 0.0 1 μm, the volatile components cannot be blocked sufficiently. If it is larger than 100 μm, the light of the organic EL element 122 is diffused, preventing the incidence of the desired C CM layer 14 and reducing visibility (bleeding). (5) Organic EL element 122 The organic EL display device 100 in this embodiment is formed on the cathode 16 included in the CCM substrate 124 by forming the above-mentioned inorganic compound layer (surface protection layer 102). ), And the center material organic material layer] 8 (also referred to as an organic compound layer) of the organic EL element 122 is laminated thereon. This organic material layer 18 is a one having at least a recombination region and a light emitting region. Most of the dynamic and light-emitting regions exist in the light-emitting layer having a light-emitting function. Therefore, in this embodiment, only the light-emitting layer can be used as the organic layer 18, and if necessary, in addition to the light-emitting layer, the organic layer 18 can also be used. For example, it contains a hole injection layer, an electron injection layer, an organic semiconductor layer, an electron barrier layer, an adhesion improving layer, etc. A cathode 20 is formed on these organic layers 18. 200534744 (33) In this embodiment, The anode 16 (transparent electrode) up to the cathode 20 is referred to as an organic EL element 122. That is, in a nutshell, the organic EL display device 100 includes an organic EL element 122 on a substrate 12 such as glass. This embodiment In the following, the following structure of the organic EL element has been described as an example, and the layers will be described below. Transparent electrode (anode) / surface protection layer / hole injection layer / light emitting layer / electron injection layer / electrode (cathode) That is, Here, the organic material layer 18 is used as an example of the configuration of the hole injection layer / light emitting layer / electron injection layer. Of course, it is also possible to use the organic material layer 18 composed of a single light emitting layer. (6) Anode 16 (transparent (Electrode) Typical anode 16 materials include ITO (indium tin oxide) and IZ 0, which have large work functions (more than 4 eV). The anode 16 is formed by depositing these electrode materials by a deposition method, a beach plating method, or the like. The thin film can be made. When the light emitted from the light emitting layer is released from the anode 16, the transmittance of the light emitted from the anode 16 is preferably greater than 10%. In addition, the sheet resistance of the anode is hundreds of holes per port (0/1112). The following is preferred. The thickness of the anode] 6 varies depending on the material However, the range of 10 nm to 1 μm and 10 nm to 200 nm is generally preferred. In this embodiment, a gauge electrode is used as the anode 16. Here, the material of the anode 16 is Amorphous oxide is used, and good contact characteristics are obtained. The above ITO is usually crystalline, and becomes a moisture ambient gas during film formation, and can be made amorphous by the blending of trace elements -37- 200534744 (34) (7) Light-emitting layer The light-emitting layer in this embodiment uses the general formula (1)

Y Y

= CH-Ar-CH = C

m m m

Y Y (I)

The illustrated distyryl arylidene compound is used as a light emitting material (host material). This compound is disclosed in, for example, Japanese Patent Application Laid-Open No. 2-2 4727 8. In the above general formula, Y1 to Y4 represent hydrogen molecules, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aralkyl groups having 7 to 8 carbon atoms, substituted or unsubstituted An aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Here, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, Carbonyl group of 1 to 6 carbon atoms] Carbonyl group of 6 to 6 carbon atoms, carboxyl group, styryl group, arylcarbonyl group of 6 to 20 carbon atoms, aryloxycarbonyl group of 6 to 20 carbon atoms, carbon 1 to 6 alkoxycarbonyl, vinyl, aniline carbonyl, carbamoyl, phenyl, nitro, hydroxyl, or halogen. Such substituents may be singular or plural. In addition, Y1 to γ4 are the same or different from each other, and Y1 and Y2 and Y3 and Y4 are combined with a substituent to form a substituted or unsubstituted saturated penta-negative ring or a substituted or unsubstituted saturation | -38- 200534744 (35) Hex ring. Ar is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, which may be single substituted or plural substituted, and the bonding portion may be any of ortho, para, and inter. However, when Ar is unsubstituted phenylene, γ1 to γ4 are respectively alkoxy groups having 1 to 6 carbon atoms, aralkyl groups having 7 to 8 carbon atoms, substituted or unsubstituted naphthyl groups, and biphenyl groups. , Cyclohexyl, aryloxy. Examples of such distyryl arylidene compounds include the following.

Ox < 〇K

C = CH

NO)

[DPVB1]

ch3〇h ^ K

C = CH

CH = C

OCHs OCHa

CHa CH3_0 > c = ch-^ H〇 > -ch = c

< 〇K

C = CH

CH = C

t — Bu [t-Bu: third butyl] -39- 200534744 (36) < 0 ^

C = CH

CH = C N〇M〇)

HaC CHa

C = CH

CH = C HsC ^ 〇 > -CH3 N〇 > -CH3 ^ > c = 〇h-0-0 ^ 〇) -ch = c ^ β

C = CH -CH = C d \ 〇 > β c = ch -0 ~ cH ^ ch = c (\ 〇 ^ CH3〇-0v y0-〇CHc > = CH-0-CH0 ~ CH = C CH3〇 h ^ / \ 〇 ^ 〇ch3 -40-200534744 (37) Another 'other preferable light-emitting materials (co-host materials) can be mentioned 8_ metal complexes of quinololine or its derivatives. Specific and In other words, it is a metal chimera oxa compound which is a chimera of a metal quinoline. Such a compound exhibits a high level of performance and can easily form a thin film. Examples of this oxa compound are as follows The structural person.

Here, in the formula, Mt is a metal, ^ is an integer of 1 to 3, and z is an independent position of each position, and it represents an atom necessary to complete at least two or more condensed aromatic rings.

Here, the metal shown by 'Mt' is a monovalent, divalent, or trivalent metal, such as an alkali metal such as bell, sodium, succinyl, alkaline earth metal such as magnesium and calcium, or an earth metal such as boron or indium. Generally, monovalent, divalent, or trivalent metals known as useful chimeric compounds can be used. Also, in the above formula, Z is an atom that shows that at least two or more condensed aromatic rings are a heterocyclic ring formed by beer sitting or plowing. In addition, in order to avoid bulky molecules that have not yet improved their functions, it is better to keep the number of atoms shown in Z to 18 or less. Furthermore, if specific examples of the chimeric oxa compounds are exemplified, they are bis (8-hydroxyd-quinine) aluminum, bis (8-hydroxyquinoline) magnesium, bis (benzo-8-hydroxyquinoline) zinc, Bis (2-methylphosphonate) alumina, tris (8_ -41-200534744 (38) hydroxyquinoline) indium, tris (5-methyl-8-hydroxyDquinoline) aluminum, 8-hydroxyDquino Lithium phosphonate'bis (5-chloro · 8-hydroxyDquinoline) gallium, calcium bis (5 · chloro-8_hydroxyfluoroline), 5,7-dichloro · 8-hydroxyDquinoline aluminum, tris (5 , 7 _ dibromo-8 · hydroxyzanline) aluminum. Furthermore, the metal complex compound substituted with phenate and substituted with 8-acyl dark phthaloline described in Japanese Patent Application Laid-Open No. 5-298378 is preferably used as a blue light-emitting material. Specific examples of the metal complex of phenoxide-substituted 8-hydroxyquinoline include bis (2-methyl-8-quinolinate) (phenate) aluminum (in) and bis (2-methyl- 8_D quinolinate) (o-cresol salt) aluminum (III), bis (2-methyl-8-D quinolinate) (m-cresol salt) aluminum (111), bis (2-methyl -8-D quinolinate) (p-cresol) aluminum (II), bis (2-methyl-8-quinolinate) (o-phenylphenate) aluminum (II), bis (2-Methyl-8_D quinolinate) (m-phenylphenolate) aluminum (II), bis (2-methyl-8-D quinolinate) (p-phenylphosphonium salt) aluminum ( 111), bis (2-methyl-8-D quinolinate) (2,3-dimethylphenate) aluminum (III), bis (2-methyl-8-D quinolinate) ( 2,6-dimethylphenate) aluminum (ill), bis (2-methyl-8-quinolinate) (3,4-dimethylphenate) aluminum (III), bis (2-formyl) -8- [i quinolinate) (3, dimethylphenate) aluminum (ΙΠ), bis (2-methyl-8-naolinate) (3,5-di-third-butyl) Phenate) aluminum (II), bis (2 • methyl-8-D quinolinate) (2,6-diphenylphenate) aluminum (m), bis (2-methyl · 8 · Quinolinate) (2,4,6-triphenylphenolate) Aluminum (III) and the like. These light-emitting materials may be used singly or in combination of two or more kinds. Hereinafter, the light emitting layer will be described more specifically. In general, when a white light is emitted, the 'light-emitting layer is composed of two layers. This is called a first light emitting layer and a second light emitting layer. Various known light-emitting materials can be used as the first light-emitting layer used in this embodiment, and it is preferable to add a slight amount of 0.2 to 3 weights to the above-mentioned oxo compound. 42-200534744 (39)% green fluorescence The pigment is used as the first light-emitting layer. The green fluorescent pigments added here are coumarin-based and D-quinacridone-based. An element that retains the first light-emitting layer by adding these pigments can achieve high-efficiency green light emission of 5 to 20 (lw / w). On the other hand, if yellow or orange is to be released from the first light-emitting layer with high efficiency, 0.2 to 3 weight of rubrene and its derivative, tricyanopyran derivative, and phenanthrene can be added to the oxa compound. Derivatives. These devices can emit light at high efficiency of 3 to 10 (1 w / w). The green fluorescent pigment and the red fluorescent pigment can be added to orange at the same time. For example, coumarin and dicyanopyran pigments, acrylone and osmium pigments, coumarin and osmium pigments can also be preferably used simultaneously. Other particularly preferred first light emitting layers are polyarylene vinylidene derivatives. It can output green or orange with high efficiency. As the second light-emitting layer used in this embodiment, various known blue light-emitting materials can be used. For example, a distyryl arylidene derivative, a tristylenyl arylate derivative, and an allyloxylated quinolinate metal complex are high-efficiency blue light-emitting materials with high purity below. Examples of the polymer include polyparaphenylene derivatives. The method for forming the light-emitting layer in the organic EL element used in this embodiment can be formed by thinning it according to a known method such as a deposition method, a spin coating method, a casting method, or a LB method, and a molecular deposition film is particularly preferred. Here, the molecular deposition film refers to a thin film formed by precipitation of the compound in a gas phase state, and a film formed by solidification of the compound in a molten state or a liquid phase state. Generally, this molecular deposition film is a thin film (molecular accumulation film) formed according to the L B method and an agglomerated structure, a high-level structure, and a difference in a function caused by the structure. In addition, this light-emitting layer can be formed by dissolving a junction material with a resin, etc. -43- 200534744 (40). The junction material can be dissolved in a solvent to make a solution, and then formed into a thin film by spin coating or the like. There is no particular limitation on the film thickness of the light-emitting layer formed in this way, and it can be selected according to appropriate conditions, but it is preferably in the range of 1 nm to 10 μm, and particularly preferably in the range of 5 nm to 5 μm. (8) Hole injection layer Secondly, although the hole injection layer is not a necessary structure for the organic EL display device 100, it is generally used to improve the light emitting performance. Therefore, an example of using the hole injection layer is described in this embodiment. . This hole injecting layer is a layer that assists injecting holes into the light emitting layer. The hole mobility is large, and the ionization energy is usually as small as 5.5 ev or less. This type of hole injection layer is preferably a material that transports holes to the light-emitting layer with a lower electric field, and the mobility of the holes is, for example, at least 1 (T6Cni2 when an electric field of 104 ~ 106V / cm is applied. / V · second ~ (that is, l (T6Cm2 / V · second or more) is more preferable. Such hole injection materials are not particularly limited as long as they have the above-mentioned preferred properties. In the past, they were used in light-conducting materials. Among them, any one that is conventionally used as a hole-transporting charge transporting material and a well-known material used in the hole injection layer of an EL element can be selected. Specific examples include triazole derivatives (refer to US Pat. 11 2,197, etc.), humadiazole derivatives (refer to US Pat. No. 3,18,44,7, etc.), imidazole derivatives (refer to Japanese Patent Publication No. 3 7-1 6096, etc.), polyaryl chains Alkane derivatives (refer to U.S. Patent Nos. 3,6 1 5,4 02, same as 3,820,98 No. 9, same as 3,542,544, Japanese Patent Publication No. 45-555, Japanese Patent Publication No. 51-10983, Japanese Patent Publication No. 55 -] 5 6 9 5 3, same as 56- 3 665 6), pyrazoline derivatives and 20 0534744 (41) Pyrazolone derivatives (refer to U.S. Patent No. 3,18 0,72 No.9, the same as No. 4,278,746, JP 55-88064, No. 55-88065, No. 4 9 -1 05 5 3 7; same as 5 5-5 1 0 8 6; same as 56-80051; same as 56-88141; same as 57-45545; same as 54-112637; 55-74546, etc.).

Specific examples include phenylenediamine derivatives (refer to US Pat. No. 3,6 1 5,4 04, JP 51-10105, JP 4 6-3 7 1 2, JP 4 7-2 5 3 3 6, Japanese Patent Laid-Open No. 5 4-5 3 4 3 5, Japanese Patent Publication No. 54-110536, Japanese Patent Publication No. 54-119925, etc., and arylamine derivatives (refer to US Patent No. 3,5 Instruction No. 67,45, Instruction No. 3, 1 0 0,703, Instruction No. 3,240,5 97, Instruction No. 3,65 8,5 2 0, Instruction No. 4,23 2,103, Same as No. 4, 1 7 5, 96 No. 1, Same as No. 4, 0 1 2, 3, 76, Japanese Patent Publication No. 49-3 5 702, Japanese Patent Publication No. 39-275 77, Japanese Patent Publication No. 5- No. 1 44250, same as 5 6- 1 1 9 1 3 2, same as 5 6-224 37, West German Patent No. 151 10,518, etc.), alkane derivatives substituted with amine groups (refer to the United States Patent No. 3,526,501 No. 1), Sudazole derivatives (disclosed in US Patent No. 3,2 5 7,203, etc.), fluorenone derivatives (see Japanese Patent Laid-Open No. Sho 5 4-1 1 0 8 3 7 Bulletin, etc.), fluorene derivatives (refer to US Patent No. 3) , 7 1 7,4 62, JP 54-59143, JP 55-52063, JP 55-52064, JP 55-46760, JP 55- 8 5 495, JP 57- 1 1 3 5 0, same as 57-148749, JP-A Hei 2-31 1591, etc.), styrene anthracene derivatives (refer to JP-A 5-6-4 6 2 3 4), Stilbene derivatives (see JP 6 1 2 0 3 6 3, 6 2 2 8 4 5 1, 61-45- 200534744 (42) 14642, 61-72255 Gazette, same as Gazette 62-47646, Gazette 62-3 6674, Gazette 62- 1 0 6 5 2, Gazette 62-3 02 5 5, Gazette 6-93 44 5, Gazette 60 -94462, same as 60-1 7 4 7 4 9 and same 60_ 1 7 5 0 52, etc.), silazane derivatives (refer to US Patent No. 4,95 0,95 0 Specification), polysilane (Japanese Patent Application Laid-Open No. 2 204204), aniline copolymer (Japanese Patent Application Laid-open No. 2-2 822 63), and electrical conductivity disclosed in Japanese Patent Application Laid-Open No. 1-2 1 1 3 9 Polymer oligomers (particularly thiophene oligomers), etc. As the material of the φ hole injection layer, the above materials can be used, but a porphyrin compound (as disclosed in JP 6 3-2 9 5 6 9 65), an aromatic tertiary amine compound, and styrene are used. Amine compounds (refer to U.S. Patent No. 4,127,4 12, JP-A No. 5 3 -2 70 3 3, same as 5'4-5 8445, same as 54-149634, and same as 54-64299 Gazette, same as Gazette 55-79450, Gazette 55-144250, Gazette 56-119132, Gazette 6 295 5 58, Gazette 6 1-9 83 5 3, Gazette 63 -295 695 It is particularly preferred to use an aromatic tertiary amine compound in the bulletin. · Representative examples of the above porphyrin compounds include porphyrin, 1 '10, 15, 20-tetraphenyl-21H, and 23H-pyrrolidone ( II), 1,01,15,20-tetraphenyl-21H, 23H-oxomorpholine zinc (II), 5,10,15,20-tetrakis (pentafluorophenyl) -21H, 23Η-IIoline , Silicon phthalocyanine oxide, aluminum phthalocyanine chloride, metal phthalocyanine (metal-free), dilithium cyanocyanine, tetramethyl cyanocyanone, copper cyanocyanine, cyanocyanine, cyanocyanine, lead phthalocyanine, phthalocyanine oxidation Titanium, magnesium phthalocyanine, octamethyl phthalocyanine, etc. In addition, representative examples of the aforementioned aromatic tertiary amine compound and styrylamine compound include >],] ^, 1 ^, 1 ^ '-tetraphenyl-4,4'-diaminephenyl, 1 ^, -46-200534744 (43) N′-biphenyl-N, N′bis- (3-methylphenyl) _ [ι, 1, biphenylphenyl 4,4, -diamine (hereinafter referred to as TPD ), 2,2-bis (4-di-p-toluidinephenyl) propanate, 1'bubis (4-di-p-toluidinephenyl) cyclohexane, n, N, N ,, N , · Tetra-p-tolyl-4,4, diaminephenyl, 1,4-bis (4-di-p-toluidinephenyl) -4-phenylcyclohexane, bis (4-dimethylamine 2-methylphenyl) phenylmethane, bis (4-di-p-toluidinephenyl) phenylmethane, n, N'-biphenyl · N,: hTbis-bis (4-methyl Oxyphenyl) -4,4, -diaminobiphenyl, N, N, N,, N'-tetraphenyl-4,4'-diaminophenyl ether, 4,4, bis (benzidine) ) Bi-tetraphenyl, Ν, Ν, Ν-tri (p-tolyl) amine, 4 • (di · p-tolylaminob 4, _ [4 (di-p-tolyl) styryl]]; g, 4, N-diphenylamino- (2-distyryl) benzene, 3-methoxy-4,- , N, -benzidine styrene benzene, N-phenyl group, as described in U.S. Patent Table No. 5,06,59,9 having two condensed aromatic rings in the molecule such as 4,4,- Bis [N-(1-naphthyl) -N -anilino] biphenyl (hereinafter abbreviated as NPD), or the triphenylamine unit described in JP-A-4-3 08 6 8 8 is three star bursts Type-linked 4,4,, 4 " _tri [N_ (h methylphenyl) aniline] triphenylamine (hereinafter referred to as MTDATA) and the like. As the material of the light-emitting layer, in addition to the aforementioned aromatic secondary methyl-based compound, inorganic compounds such as p-Si and p-SiC can be used as the material of the hole injection layer. The hole injection layer is formed by thinning the compound described above, for example, by a known method such as a vacuum deposition method, a spin coating method, a casting method, or a LB method. The thickness of the hole injection layer is not particularly limited, but it is usually 5 nm to 5 μm. The hole injection layer is composed of one layer of one or two or more of the above materials. Alternatively, the hole injection layer may be laminated with a hole injection layer made of another compound. The organic semi-47-200534744 (44) conductive layer is a layer that facilitates the injection of holes or electrons into the light-emitting layer, and has a conductivity of 1 (T1 () S / Cm or more). Such organic semiconductor layers may be Use of thiophene-containing oligomers and arylamine-containing oligomers, which have low conductivity, and arylamine-containing dendrimers, etc. (9) Electron injection layer, adhesion improvement layer On the other hand, The electron injection layer is a layer that facilitates the injection of electrons into the light-emitting layer and has a large electron movement, and the adhesion improvement layer is a layer composed of a material that is not adhered to the cathode in the electron injection layer. The materials used for the electron injection layer include, for example, 8 -A metal complex of hydroxyquinoline or a derivative thereof, preferably a diazole derivative. The material used for the adhesion improving layer is particularly preferably a metal complex of oxoline or a derivative thereof. The 8-hydroxy group described above Specific examples of the metal complex of a derivative thereof or a derivative thereof include a metal chimeric oxo compound containing a chimera of 8-hydroxy group. On the other hand, crocodile organisms include the following general formula (II), (III) and (IV) ... (Π) • · αα The other layer, or the mouth of the timber 8-hydroxyquinoline Laid port Kui Kui morpholine morpholine oxazole derivatives D

Ν—Ν Ar12— 〇Ar A ~ t

Ar (IV) In this formula, Ar1G ~ Ar] 3 represents substituted or unsubstituted, respectively, Ar1G and Ar11 and Ar12 and Ar13 may be the same or different from each other, respectively, and the aryl group Ar1 '200534744 (45) is used to represent Substituted or unsubstituted arylene. Examples of the triazole derivative include electron-transporting compounds represented by these formulae. Here, examples of the aryl group include phenyl, biphenyl, anthryl, fluorenyl, and fluorenyl. Examples of the arylene include phenyl, naphthyl, phenyl, anthryl, and phenanthryl. Shen Yanji and others. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyano group. The electron-transporting compound is preferably a film-forming compound. Specific examples of the electron-transporting compound include compounds represented by the following formula. (PBD) C (CH3) 3

(CH3) 3C

(CH3) (10) Cathode 20 Cathode 20 uses metals, alloys, and conductive materials with a small work function (below 4 eV). 200534744 (46) Electrical compounds and mixtures are used as electrode materials. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium-silver alloy, aluminum / aluminum oxide (Al203), aluminum-lithium alloy, indium, and rare-earth metals. The cathode 20 is formed by depositing, depositing, and sputtering such electrode materials, and can be formed by forming a thin film. The sheet resistance of the cathode is preferably several hundreds Ω / □ or less, and the film thickness is usually selected from 10 nm to 1 μm, and particularly preferably in a range of 50 to 200 nm. Furthermore, the organic material used in this embodiment is In the EL element, it is preferable that either the anode 16 or the anode 20 is transparent or translucent. If it is transparent or translucent, the light can be transmitted, so the light emission efficiency is good. (11) Laminating method of the layers constituting the organic EL element 122 a. Anode 16 (substrate electrode) An electrode in which the substrate 12 is laminated on the side is referred to as a substrate electrode. Therefore, the anode 16 as described above is a substrate electrode. The method of laminating the substrate electrodes is not particularly limited. For example, a deposition method, a sputtering method, an ion plating method, an electron beam deposition method, a DVD method (CVD method (CVD: Chemical Vapor Deposition)), Dry film-forming methods such as MOCVD (MOCVD: Metalorganic CVD) and plasma CVD are preferred. The anode 16 is also laminated in this way. B. Organic layer 18 The method described in the "(7) Light-emitting layer" above is laminated in the same way. -50- 200534744 (47) c. Counter electrode The electrode opposing the substrate electrode is called the counter electrode. Therefore, the cathode as described above 20 is a counter electrode. The counter electrode is also laminated in the same manner as the above-mentioned substrate electrode. [Embodiment] Hereinafter, the CCM electrode substrate of this embodiment and an organic EL display device when an organic EL element is constructed thereon will be described. (CCM panel), enumerating specific data to explain the embodiment. [Embodiment 1] In this embodiment 1, a surface protection layer 02 is provided on the anode 16 on the CCM substrate 124 (also referred to as a CCM electrode substrate). This CC When the M substrate 124 is made into an organic EL element 122 (also referred to as a CCM panel), it is proved that the organic EL element 122 has higher performance. ① One of the CCM layer 124 (color conversion substrate) is produced (until a color conversion film is formed) 102mmxl33nmxl.lmm support substrate (〇A2 glass: manufactured by Nippon Electric Glass Co., Ltd.) was spin-coated with black matrix (BM) material V259BK (manufactured by Nippon Steel Chemical Co., Ltd.) and exposed to ultraviolet light to form a small grid After being developed with a 2 ° / 〇 sodium carbonate aqueous solution, it was baked at 200 t (bake: calcined) to form a black matrix (film thickness υμη ^). -51-200534744 (48) Next, the blue color V2 5 9 B (manufactured by Nippon Steel Chemical Co., Ltd.) of the color filter material was spin-coated, and a mask was obtained by obtaining stripe patterns of 3 20 rectangular (90 μηι lines, 240 μπι pitch) strips, and ultraviolet exposure was performed with the BM position. After being developed with a 2% sodium carbonate aqueous solution, it is baked (calcined) at 200 ° C to form a pattern of a blue color filter (film thickness 1.5 μm). Next, the green color filter material V25 9G ( (Produced by Nippon Steel Chemical Co., Ltd.) Coating, through a mask with 3, 20 stripe patterns of rectangular (90 μπι lines, 2 40 μιυ gaps), UV exposure with BM position, development with 2% sodium carbonate ice solution, and baking at 200 ° C (Calcination), forming a pattern of a green color filter (film thickness 1 · 5 μιη) next to the blue color filter. Next, V25 9R (manufactured by Nippon Steel Chemical Co., Ltd.) with red color and filter material was spin-coated, and a mask with 320 stripe patterns (90 μπι lines and 240 μιη gaps) was obtained by matching the BM position. By ultraviolet exposure, a pattern of a red color filter (film thickness 1.5 μΐΏ) was formed between the blue color filter and the green color filter. Next, the material of the green CCM layer 14G was prepared at a concentration of 0.04 mol / kg (counter solid content) of coumarin 6 to dissolve in acrylic negative photoresist (V2 5 9R, solid content concentration 50%: New Nikkei Chemical Co., Ltd.). This ink was spin-coated on a previous substrate, and exposed to ultraviolet light on a green color filter. After being developed with a 2% sodium carbonate aqueous solution, it was baked (calcined) at 200 ° C and applied to the green color filter. A pattern (film thickness 10 μm) of a green conversion film was formed thereon. -52- 200534744 (49) Next, the coumarin 6 of the material of the red CCM layer 14R: 0.53 grams of basic violet 1 1: 1.5 grams, rhodamine 6G: 1.5 grams are used in acrylic negative photoresist (V25 9R, solid content concentration 50%: manufactured by Nippon Steel Chemical Co., Ltd.) · 100 g of dissolved ink. This ink was spin-coated on the previous substrate, and exposed to ultraviolet light on a red color filter. After being developed with a 2% sodium carbonate aqueous solution, it was baked (calcined) at 180 ° C and applied to the red color filter. A pattern (film thickness 10 μm) of a red conversion film was formed thereon to obtain a color conversion substrate. ② Second production of CCM layer 124 (color conversion substrate) (until planarization film ~ anode 16 ~ formation of partition walls) Second, acrylic thermosetting resin (V2 5 9R: Nippon Steel) as the planarization film (Manufactured by Chemical Co., Ltd.) was spin-coated on a previous substrate and baked (calcined) at 180 ° C to form a flattened film (film thickness: 5 μm). Secondly, a transparent inorganic film SiOxNy (O / O + N = 50%: atomic ratio) as an oxygen blocking layer is formed at a low temperature of C VD to a thickness of 200 nm. The moisture permeability is less than 0.1 g / m2 · day. Next, IZO (indium zinc oxide) was sputtered to a thickness of 200 nm. Next, on this substrate, a mask with a stripe pattern of 90 μm lines and a gap of 20 μm is passed through a positive-type photoresist (HP R2 04: manufactured by Fujifilm Arch), and the position is overlapped with the CCM layer or the color filter pattern. It was exposed to ultraviolet light and developed with a developing solution of TIMA (tetramethylammonium hydroxide), and baked (calcined) at 130 ° C to obtain a photoresist pattern. Secondly, the IZO etched product composed of 5% oxalic acid aqueous solution was used to etch the IZO part exposed from 200534744 (50). Next, the photoresist was stripped with ethanolamine as the main component (N 3 0 · · Nagase Industry Co., Ltd.) to obtain an IZO pattern (lower electrode: anode 16 and wire number 960).

Next, a negative photoresist (V2 5 9P A: manufactured by Nippon Steel Chemical Co., Ltd.) as the first interlayer insulating film was spin-coated, exposed to UV light, and displayed with TMAH (tetramethylammonium hydroxide). Image development. Secondly, it is baked (calcined) at 180 ° C and covers the edge of ITO, so that the opening of IZO is 70 μπι X 2 9 0 μηι 〇 Secondly, it will be used as the negative photoresistor of the second interlayer insulating film (partition wall) (ZPN1100: manufactured by Japan Zoon) was spin-coated and passed through a mask with a stripe pattern of 20 μm lines and a gap of 3 10 μm, exposed to ultraviolet light, and then baked and baked (calcined) after exposure. Secondly, a negative photoresist is developed with a developing solution of TMAH (tetramethylammonium hydroxide) to form an interlayer insulating film (partition wall) of an organic film with vertical IZO stripes. ③ Fabrication of CCM substrate 124 (color conversion substrate). Third (form a surface protective layer 102 on the anode 16) on the substrate provided with an interlayer insulating film as described above to induce a combined RF electric award to support magnetron sputtering. The method (hereinafter referred to as the spin-excitation plating method) forms SiO 2 into 20A. The detailed procedures are as follows. After the substrates are cleaned, the cleaned substrates are mounted in a sputtering chamber 'and evacuated. In addition, the device used in the experiment was a distance of 30 cm from the target of 5 2 to the substrate. After confirming that the degree of vacuum was 2.0 × 1 × 4 + pa or less, the discharge gas Ar • 54-200534744 (51) was introduced into 80 ° cm with a shielded flow controller. The degree of vacuum at this time was 0.38 Pa. When the main shutter directly above the target is closed, 50W is applied to the induction coupling coil with a frequency of 13.56MHz, and high frequency with a frequency of 13.5 6 MHZ50 0 W is applied to Si02, causing plasma discharge. At this time, the reflection of each coil is 5 W or less. With the main shutter closed, the above discharge was continued for 5 minutes, and the surface of the Si02 target was washed. After that, the main shutter was opened, and the film formation rate 値, which was measured in advance, was estimated, and the film was formed by a plasma discharge of 6 minutes and 20 seconds. As a result, Si02 having a film thickness of 20 A was formed on IZO. ④ An organic EL element and a panel are formed on the CCM substrate 124 (color conversion substrate): Sealing The substrate thus treated is ultrasonically washed in pure water and isopropyl alcohol, and dried by purging with dry nitrogen. The substrate was moved inside an organic MEMS device (manufactured by Japan Vacuum Technology), and the substrate was fixed to a substrate holder. There is a heating tank made of molybdenum in the organic deposition apparatus. Each heating tank made of molybdenum is filled with various materials in advance. Specifically, 4,4,, 4 ,,-tri [N- (3-methylphenyl, N-anilino] triphenylamine (MTDATA), 4,4'-bis [N- (l- Naphthyl) · N-aniline] Biphenyl (NPD) as a hole injection material. The main material of the light-emitting material is 4,4 * -bis (2,2-distyryl) biphenyl (DPVBi) .The blend is charged with 1,4-bis [4- (N, N-benzylaminostyryl)] (DPAVB). Electron-55- 200534744 (52) The injection material is charged with tris (8-hydroxyl D quinoline) aluminum (person 1 (}) and Li. In addition, the cathode 20 is filled with A1 a. Thereafter, the vacuum tank is decompressed to 5 X l (up to T7 torr), and the following procedures are followed. The hole injection layer is laminated to the cathode 20. Also, during the lamination step, the layers are sequentially laminated under a vacuum so as not to temporarily break the vacuum. First, the hole injection layer will be used as the hole injection layer. MTDATA was deposited at a deposition rate of 0.1 to 0.3 nm / sec to obtain a film thickness of 60 nm. Furthermore, NPD φ was deposited at a deposition rate of 0.1 to 0.3 nm / sec to obtain a film 20nm thick. DPVBi and DPAVB will be used as the light-emitting layer at a deposition rate of 0.1 ~ 0.3nm / The deposition rate is from 0.03 to 0.05 nm / second, and the film thickness is 50 nm. A 1 q and L · i, which are used as the electron injection layer, are set at 0.1 to 0.3 nm / second, respectively. It was co-deposited into a film with a thickness of 0.05 nm / second to obtain a film thickness of 20 nm. Finally, A1 of the cathode 20 was formed at a deposition rate of 0.1 to 0.3 nm / second to form a cathode having a film thickness of 150 nm. 20. Prepare an organic EL device in this way. Φ Next, move the substrate in a spherical box with a dry nitrogen (dew point-5 (TC)) cycle, and cover the display section with blue glass of 102nmxl33nmxl.lnm, and the periphery of the display section The part is made of a cation-curing adhesive (TB3102: 3 Bond) and is light-cured and bonded to produce a passive organic EL display device. ⑤ The driving evaluation of the seal of the color conversion panel consists of the lower electrode (cathode 16: IZ0) and The upper electrode (anode 20: -56- 200534744 (53) A1) with Duty = 1 /: 120, and a voltage of 15V (the lower electrode: (+), the upper electrode: (-), the cross section of each electrode (drawing (E.g.) is the luminescence. The luminous brightness is based on the color difference meter (CS100, manufactured by Minolta), which is obtained in the monitor color. The luminous light section (monitor pixel) is 16 cd / m2 and the CIE chromaticity coordinate is X = 0.15 and Υ = 0 · 16. The light is emitted in the green CCM layer / green color filter section (green picture). Green) is 45cd / m2 and the CIE chromaticity coordinates are X = 0 · 27, Υ = 〇 · 67 for green emission, the red C CM layer / red color filter section (red pixels) is 45cd / m2 and CIE The chromaticity coordinates are red with X = 0.64 and Υ = 0.35, and the three primary colors of light are obtained. In addition, the light emitting luminance of the organic EL element at this time was 200 cd / m2 (equivalent to full-pixel light emission), and the CIE chromaticity coordinates were blue light emission of X = 0.17 and y = 0.28. Secondly, under these driving conditions, when driven at room temperature 2 2 ° C for 100 hours, the blue pixel is 100 cd / m2 (if the initial value is 1, the ratio is 0.67), and the green pixel is It was 27 cd / m2 (when the initial 値 was 1, the ratio was 0.60). The red pixel is 9 cd / m2 (if the initial value is 1, the ratio is 0.60). The organic EL element has a brightness of 126 cd / m2 (if the initial value is 1, the ratio is 0.63). In addition, when the organic EL element manufactured without the CCM and produced by the above-mentioned film formation process is sealed with an inert gas such as ordinary dry nitrogen, the brightness of the organic EL element is deteriorated to the same driving conditions as the above driving conditions. If the initial 値 is 1, the ratio is 0.6 5. [Comparative Example 1] In Example 1, ③ the production of the CCM substrate 124 (film formation on the anode 16 200534744 (54) out of the surface protection layer 102) did not perform the Si 02 film formation step as the surface protection layer 102, immediately The process of forming the organic EL element layer and sealing the panel on the CCM substrate 124 is performed in exactly the same manner, and an organic EL display device (organic EL panel) is produced. In the same manner as in Example 1, the driving evaluation of the sealing of the color conversion panel was performed, and the following results were obtained.

The luminous brightness is measured by chromatic aberration (CS100, manufactured by Minolta), obtained from the blue color filter section (blue pixels) is llcd / m2, and the CIE chromaticity coordinate is X = 〇 "5, Υ = 0 · 16 Blue light emission, green light emission in green CCM layer / green color filter section (green pixel) 33cd / m2 and CIE chromaticity coordinates of X = 0.27, Y = 0.67, in red CCM layer / The red color filter part (red part pixel) is 12 cd / m 2 and the CIE chromaticity coordinates are X = 0.64, Y = 0.36. The red light is emitted, and the three primary colors of light are obtained. Also, at this time, the EL element emits blue light with a luminance of 150 cd / m2 (equivalent to full pixel emission) and a CIE chromaticity coordinate of X = 0.17 and Υ = Ό.27.

Second, under these driving conditions, when driven at room temperature for 22 hours for 1,000 hours, the blue pixels are 6 cd / m2 (if the initial value is 1, the ratio is 0.55), and the green pixels are 16 cd / m2. (If the initial stage is set to 1, the ratio is 0,48), the red pixels are 6 cd / m2 (if the initial stage is set to 1, the ratio is 0.50), and the brightness of the organic EL element is 84 cd / m2 (if the initial stage is set to 1, then the ratio is 0.56). In addition, the brightness of the organic EL element when the organic EL element on the substrate without the CCM and the surface protective layer film-forming step is sealed with an inert gas such as ordinary dry nitrogen is deteriorated under these driving conditions. If the initial 値 is 1, the ratio is 0.58. -58- 200534744 (55) From the above results, it can be understood that if the surface protection layer 102 is formed on the CCIV [substrate 124 anode 16 IZO], then in the case of no film formation, the luminous brightness of each color increases to the same voltage. . That is, according to this embodiment, it can be confirmed that the luminous efficiency is improved. In addition, it can be understood that the case where the surface protective layer 10 02 is formed as compared with the case where the film is not formed during continuous driving can suppress the deterioration of the emission luminance. In this way, when the upper surface protective layer 102 is formed on the anode 16, it can be judged that the light emitting performance can be improved, and the stability (i.e., life) of the panel during continuous driving can be improved. An example in which the configuration of Embodiment 2 includes a TFT, and the example shown in FIG. 1 is an anode 16 shown on the CCM layer 14. Although the driving method of the anode 16 is not particularly shown in FIG. 1, for example, a TFT (Thin Film Transistor) is preferably used for driving. Such a structure is shown in FIG. 3. In FIG. 3, a cross-sectional view of one color portion in one pixel shown in FIG. 1 is shown. That is, in red, blue, and green in FIG. 1, any color portion is shown. As shown in the figure, in this embodiment, a CCM layer 14 is provided on the substrate 12. Next, a coating layer 2 10 and a passivation film 212 are provided on the CC layer 14. On the passivation film 212, a gate electrode 226 of the thin film transistor 220 is provided, and a laminated insulating film 230 is covered thereon. On the insulating film 230, an anode 16 and a drain 224 and a source 222 of the thin film transistor 220 driving the anode 16 are formed. Secondly, the drain electrode 224 is electrically connected to the anode electrode 16. -59- 200534744 (56) A characteristic feature in the second embodiment is that the anode 6 is driven by a thin film transistor (TFT). By applying a potential to the gate 226 of the thin film transistor 220, the power supply to the anode 16 can be controlled. The thin film transistor 220 is an example of a "driving element" corresponding to the scope of patent application. One of the characteristics of the present invention is that the anode 16 is provided with a surface protection 102. However, the anode and the same layer may be provided with the thin film transistor 2 2 0 as shown in the second embodiment. In other words, the second embodiment is substantially different from FIG. 2 only in that the anode 16 is driven by the thin film transistor 220. That is, a surface protection layer 102 is provided on the anode and the thin film transistor 220 as in FIG. 1. The surface protection layer is the same as the surface protection and protection layer 102 described above. As in Fig. 1, an organic substance layer 18 and an anode 20 are provided on the surface protective layer 102, and the organic EL display device 200 is constituted as a whole. In the second embodiment, a driving method using the thin film transistor 220 as the anode 16 is shown. Of course, various other driving elements may be used as appropriate. [Brief description of the drawings] Fig. 1 is a cross-sectional model diagram showing the structure of a suitable organic EL display device of the present invention. Fig. 2 is a model diagram showing a spectrum of an I? -Containing compound examined by XPS. Fig. 3 is a cross-sectional view showing the structure of an organic EL display device according to the second embodiment in a -60-200534744 (57) plane. FIG. 4 is a cross-sectional model diagram of a conventional CCM type organic EL display device. [Description of main component symbols] 1: Pixels 12: Substrate 〇14: CCM layer (+ passivation film) 16: Anode 18: Organic layer 2 0: cathode

100: Organic EL display device 102: Surface protection layer 122: Organic EL element 124: CCM substrate 200: Organic EL display device 2 1 0: Cover layer 2 1 2: Passive film 2 20: Thin film transistor 2 2 2: Source 2 2 4: Drain 2 2 6: Gate 2 3 0: Insulating film -61-

Claims (1)

200534744 (1) The scope of application and patent application 1. An electrode substrate characterized by containing an electrode composed of a substrate, a compound containing an In atom, and a layer between the electrode and the substrate, and used to transform the incident The wavelength of light of the layer enters the electrode substrate of the fluorescent conversion layer, and a surface protection layer composed of an inorganic compound is formed on the surface of the electrode opposite to the surface of the fluorescent conversion layer and the opposite surface. 2. The electrode substrate according to item 1 of the scope of patent application, wherein the substrate and / or the constituent material of the electrode is a transparent material. 3. If the electrode substrate of item 1 or item 2 of the scope of patent application, the electrode is an electrode subjected to reverse sputtering. 4 · The electrode substrate according to item 3 of the scope of patent application, wherein the reverse sputtering process is a reverse sputtering process using an induction bonding type RF plasma to support the magnetron sputtering device. 5. The electrode substrate according to any one of claims 1 to 4 in the scope of patent application, wherein the inorganic compound constituting the surface protective layer is made of Ba, Ca, Sr, Yb, A1, Ga, In, Li, Na, K, Cd, Mg, Si, Ta, Ge 'S b Zn' Cs' Eu, Y, Ce, W, Zr, La, Sc, Rb, L υ »Ti, Cr Ho 'Cu' Er, Sm, W, Among Co, Se, Hf, Tm, Fe, and Nb, at least one of oxides, or nitrides, composite oxides, sulfides, and fluorides of metals is selected. 6. The electrode substrate according to item 5 of the application, wherein the surface protection layer is formed by a sputtering method. 7 · If the electrode substrate of item 6 of the patent scope is requested, the surface protection-62- 200534744 (2) The protective layer is formed by a sputtering method using an induction bonding type RF plasma to support the magnetron sputtering device. 8. The electrode substrate according to any one of items 1 to 7 of the scope of patent application, wherein the film thickness of the surface protective layer is within a range of 5 to 100A. 9 · The electrode substrate according to any one of claims 1 to 8 in the scope of the patent application ′ wherein the electrode is made of tin oxide copper (ITO) or oxidized oxide (IZO). 10 · The electrode substrate according to item 9 of the patent application scope, wherein the electrode is an amorphous oxide. η The electrode substrate according to any one of the scope of claims 1 to 10 of the scope of patent application, which includes a driving element for driving the electrode. 12. A method for manufacturing an electrode substrate, which is characterized in that an electrode composed of a substrate, ..., thallium, and a compound containing an In atom, and a layer located between the electrode and the substrate are used to transform the incident substrate. The method of forming a layer of light wavelength fluorescent conversion layer and an electrode substrate includes a step of forming the fluorescent conversion layer on the substrate, a step of forming the electrode on the formed fluorescent conversion layer, and a step of forming the electrode. The electrode surface is subjected to a reverse sputtering process, and in the step of applying the reverse sputtering process to the electrode surface, after the reverse sputtering process is performed, or when the reverse sputtering process is performed, an inorganic compound is formed; Composition of a surface protective layer. 1 3 · The method for manufacturing an electrode substrate according to item I 2 of the scope of patent application, wherein the inverse source plating process is performed by using an induction-coupled RF electric generator supporting magnetron 200534744 (3) Sputterer. 14 · The method for manufacturing an electrode substrate according to item 13 of the scope of patent application, wherein in the reverse sputtering process, the induction coil-type RF plasma supports a rotating coil of a magnetron sputtering device, and an electric power of 50 ~ 200W, high frequency with a frequency of 13.56 ~ 100MHZ and the cathode of the magnetron sputter supported by the induction-coupled RF plasma, plus 200 ~ 500 ~, high frequency with a frequency of 13.56 ~ 1001 ^ 1 ^, causing the plasma to discharge In addition, the strength of the magnetic field of the magnetron of the induction-coupled RF plasma supporting magnetron sputtering device is set to be within a range of 200 to 300 Gauss. I5. The electrode substrate according to item 1 of the scope of patent application, wherein according to the X-ray photoelectron spectroscopy, the peak half-width of the 3d5 / 2 orbital spectrum of the 'I η atom measured on the surface of the surface protective layer is set to [In3d5 / 2] When h is expressed, the ratio ([In3d5 / 2] h / [In3d5 / 2] n) of each half-width is in the range of 0.9 to 1.2. 16 · If the electrode substrate of item 1 of the scope of patent application, according to the X-ray photoelectron spectroscopy method, the 3d5 / 2 orbital spectral peak of In atom measured by the electrode is represented by In peak, and according to the X-ray photoelectron spectroscopy method, Let the 3d5 / 2 orbital spectral peak value of the S η atom measured by the electrode be represented by Sn peak, and the ratio of each peak measured on the surface of the electrode is represented by (In peak / Sn peak) h, and each peak measured inside the electrode The ratio is expressed by (In peak / Sn peak) n 200534744 (4), ((Sn peak / In peak) h / (Sn peak / In peak) n) < 1.5 〇 J -65-