TW569463B - Method for forming a drying film, forming a drying film on a cover plate, and forming a drying film in an organic light emitting device - Google Patents

Abstract

A method for forming a drying film of an organic electroluminescent device, including providing a desiccant, and depositing the desiccant to form the drying film. Besides, this invention discloses a method for forming a drying film on a cover plate of an organic electroluminescent device. In this method, the desiccant is deposited on the cover plate to form the drying film. Furthermore, this invention also discloses a method for forming a drying film in an organic light emitting device. In this case, the desiccant is deposited above a substrate to form the drying film. A first electrode, an organic light-emitting layer, and a second electrode are formed on the substrate in turn.

Description

569463

V. Description of the Invention (1) [Field of Invention] The invention of i relates to a water-removing film (drying fi =, in particular, a method for forming a square film by using a depositionlon) to apply to organic light-emitting diodes ... 】 With the development of science and technology, the current thin, short, and small, and the materials used have many components or materials for the ring: 1 In fact, it is very easy to react with water molecules in the air. The result will affect the material used. Electronic components fail. Not only do various electronic components become lighter, but materials also change with each passing day. Among them, the water and gas are quite sensitive, that is, they cannot function normally due to the chemical or physical reactions caused by oxygen, which makes organic light-emitting diodes As an example, an organic light-emitting diode system uses an organic functional material (〇rganic functolonal self-luminescence) to achieve a display effect. As shown in FIG. 丨, the organic light-emitting diode element 1 includes a substrate. U, a first electrode 12, an organic light-emitting layer 13, a second electrode 14, and a cover plate 15. Among them, the substrate 11 and the first electrode 12 are transparent materials The first electrode 12 and the second electrode system serve as the anode and the cathode, respectively; when a current is applied to the organic light emitting diode element 1, holes are injected from the first electrode 12 while electrons are injected from the second electrode 1 4 "Injection" At this time, carriers move and meet in the organic light-emitting layer 13 due to the potential difference caused by the applied electric field, and recombination occurs. Exciton generated by the combination of electrons and holes can excite organic light emission. The luminescent molecules in layer 1 3, then the excited luminescent molecules are released in the form of light

569463 V. Description of the invention —— " --- --- Output energy. = μwherein, the organic light emitting layer 13 may have a single-layer structure, a double-layer structure, or a structure of more than two days, for example, the organic light-emitting layer 3 may include a 3: layer,-hole transfer, a light-emitting layer, a The electron transfer layer is a thunder-thousand injection layer. _ As mentioned on the electric circuit, the decay that occurs more often in organic light-emitting diodes and the system is the generation of dark spots, so the durability of organic and light-emitting diodes must be improved. ) Is how to reduce the generation of non-light emitting areas. The organic functional material in the organic light-emitting diode structure and the second electrode as the cathode are liable to react with moisture and oxygen in the air (especially moisture), resulting in the generation of non-luminous regions. Therefore, it is very important to completely remove the water. Therefore, generally, when manufacturing an organic light emitting diode device, coating is usually performed in a vacuum state, and then the semi-finished product is taken out by vacuum, and the organic light emitting diode device is sealed by packaging under normal pressure. However, in this way, it is still impossible to completely guarantee that the light-emitting diode elements of the machine will not be affected by moisture and cause the formation of non-light-emitting areas; and the vacuum process of the coating film does not match the pressure of the packaging process under normal pressure, which requires Breaking the vacuum will complicate the process, reduce the yield, and increase the manufacturing cost. In addition, moisture and oxygen in the atmosphere will invade the unfinished product, causing degradation of the organic light emitting diode element < '(degradation) 〇 As described above. The solution to completely prevent the formation of non-light-emitting areas, and further improve the life and stability of the organic light-emitting diode device is to remove the water inside the organic light-emitting diode device. A common formula> 2 = two

569463 V. Description of the invention (3) A water-trapping agent or a drying agent is added inside the organic light emitting diode element. In order to solve the generation of non-light emitting regions inside organic light emitting diode elements, there have been several related patent applications: as proposed by Kawami et al. In European patent case EP0 776 1 47, the organic light emitting diode elements are sealed in In an airtight container containing a solid material with chemical water absorption properties, such compounds with chemical water absorption properties include metal oxides such as calcium oxide and barium oxide7. In British patent case GB2 368 1 92, Hisisaniitsu used organic A metal compound (organoujetalhc compound) is used as a water-absorbing material. This organic metal compound can effectively adsorb water inside the organic light-emitting diode element, and can also adsorb other chemical drying agents and physical drying agents. In order to prevent the occurrence of non-light emitting areas. In U.S. Patent No. 1,136,226,890, 80105011 and others proposed that a desiccant be mixed with a binder having a good water vapor transmission rate. In order to form a thin film in the organic light-emitting element, it can have a better water absorption effect than the solid desiccant. More specifically, the water-absorbing material is generally filled in the organic light-emitting diode. There are two ways in the body element; please refer to FIG. 2, the first is to fill the absorbent material 26 in a cover plate 25 with a groove 251, and then add a layer of water permeable above the groove “I The film 27 is then filled with the water-absorbing material 26 and the prepared organic light-emitting diode element (not shown), and sealed with a sealant to make it a sealed element. But use The

Page 8 569463 V. Description of the invention (4) technology, because the groove 2 5 1 needs to be filled with the water-absorbing material 26, and a layer of water-permeable film 27 is needed. This will increase the complexity of the process and make the production of Yield reduction and manufacturing cost increase. In addition, please refer to FIG. 3, the second is to mix the water-absorbing material 36 in a water-based polymer solution, and form a film 37 containing the water-absorbing material 36 on the cover plate 35 by coating. Then, the solvent is removed, and then the cover plate 35 and the prepared organic light emitting diode element (not shown in the figure) are stacked on top of each other, and sealed with a sealant to make it a sealed element process. ΐ Γί ϊ ί is close to the packaging process in the manufacturing process, and reduces the heterogeneity of the manufacturing process. However, after the coating process, baking must be performed to maintain iron residues. ζ elimination 'results often cause organic light-emitting diodes. Element inner body: solvent, which may cause the prepared organic light-emitting diode 7 " to peel off from the fascia board, causing damage to the element. High scores ::: Utilizing coating ... and using organic light-emitting diodes = b: dlngGa " fixed the water-absorbing material in the ancient parts of the light-emitting diodes to form a water-repellent layer; however The organic layer, the benefit layer and the second electrode, use the vacuum deposition force, and need to break the process under the guidance of the integration of the same operating pressure increase; further ,; The reduction of the production rate and the production cost are called the formation of the cloth and the title. The water-removing layer will also have holes. (PM cannot effectively reduce the thickness of the water-repellent layer when the water-absorbing material is fixed with 2 binders. In particular, the thickness of the organic light-emitting diode element is limited. 疋 The organic light-emitting diode has a simple structure and is formed on page 9. 569463 V. Description of the invention (5) The flat display of _ can absorb water than the liquid crystal display. The water removal efficiency of the material is not good, so p is limited to the water-absorbing material at the time of packaging, which increases the thickness of the organic s photodiode = a large number of: shell: the device can be thinner; in addition, when ":", only fixed Water absorption on the surface of the dewatering layer = The water molecules inside the photodiode element, so σ b solid-the water-absorbing material that touches the organic hair surface can achieve the effect of adsorbing the molecules 丨 the water layer surface absorbs the water-absorbing material's adsorption capacity. How to provide a method that can integrate the deposition process and the environment to reduce the manufacturing process * 'Reduce the chance of organic light-emitting elements in the process of the process to improve the yield in the atmospheric environment Putianbei electronics industry is one of the important issues. [Summary of the invention] The purpose of the underwater sound 10 pairs of the above "2 inventions is to provide a method of forming a water removal film capable of reducing the thickness of the water removal layer. In order to provide a method for forming a water-removing film capable of exerting the adsorption ability of the water-removing film, another object of the present invention is to provide an operating environment capable of integrating a deposition process and a sealing process, thereby reducing the organic light-emitting element in the packaging process. A method for forming a water-removing film when the front road is under the atmosphere. * In order to achieve the above purpose, the present invention uses a deposition method to form a water-removing film for absorption. The water and oxygen of the industry can be tightly sloped 569463 V. Description of the invention (6) Covering the organic light-emitting element, blocking the penetration of subsequent moisture and oxygen, the method of forming a water-removing film including providing a A method for forming a water-removing film by absorbing water in a deposition method. A method for forming a water-removing film for a cover plate includes a water-absorbing material, and forming a water-removing film by depositing the water-absorbing material in a deposition method. A substrate is provided, a water-absorbing material is provided, and water is absorbed on the substrate to form a water-removing film. A first electrode, an organic light-emitting diode are formed in advance in the present invention, and the material is also prefabricated. The cover plate is formed on the cover plate in addition to the original method, which includes: a method for depositing materials: Mingzhong, on the substrate / and a first electrode. The method of forming a water-removing film according to the present invention uses a combined deposition process and a sealing film, so the organic light-emitting process environment can be reduced during the formation of the water-removing film. Reduce the manufacturing cost, and further improve the yield. The problem of residual organic solvents exposed to the atmosphere before the 7 ° package process is possible. The operating environment of the deposition process can be used to avoid the effects of water and soil. Reduce the thickness of the water-removing film, and have the ability to find the adsorption of the film. [Preferred embodiment] The following will describe the method of forming a thin water film: f ', which is divided by the preferred embodiment of the present invention. The same elements will be added with the same reference symbols on page 11. 569463 V. Description of the invention (7) Please refer to FIG. 4. A method 4 for forming a water removal film according to a preferred embodiment of the present invention includes the following steps: First, Step 41 1 First provide a water-absorbing material. In this embodiment, the water-absorbing material is a material that can be used as a deposition source, that is, it can be used in a deposition process, and it is a material having the ability to adsorb water molecules. Organomet al ic complex compound, metal test compound, metal test compound, metal test compound, metal test compound, metal test compound, metal test compound (alkaline earth metal oxide compound), sulfur compound, metal halide compound, perchlorate compound, or organic compound. Next, step 4 2 is to deposit a water-absorbing material by a deposition method to form a water-removing film. In this embodiment, the water-removing film may be formed by using a conventional deposition method, such as vapor deposition (va ρ 〇 rd ρ 〇 siti ο η), physical vapor deposition (physica 1 vap〇rdep〇siti. η), chemical vapor deposition, or evaporation M. To make the content of the present invention easier to understand, two examples will be given below to illustrate the water removal film according to the preferred embodiment of the present invention. Application of formation method 4. Referring to FIG. 5, this embodiment shows that the method 4 for forming a water-removing film is applied to a cover 51. In this embodiment, the cover plate 51 is used for sealing.

569463 V. Description of the invention (8) Organic light-emitting diode element 6 (as shown in FIG. 6) The organic light-emitting diode element 6 includes a substrate 61, a), an organic light-emitting layer 63, and a first Two electrodes 64. Electrode 62, MoruoΪ In the example, the first electrode 62 is formed on the substrate 61; the ancient light-emitting layer 63 is formed on the first electrode 62_, and there is a factory-machined light-emitting layer 63. In general, the substrate 6 is the first; ^ =; plate, such as a glass substrate, a plastic substrate, or a flexible substrate; the first electrode 62 may be a sputtering method or It is formed by ion plating on the substrate 61. The first electrode 62 is usually used as an anode and the metal is usually a transparent conductive metal oxide, such as indium tin oxide, k ( ιτο), alumina zinc (AZ0) or indium oxide (IZ〇); the organic light emitting layer 63 usually includes a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer and an electron injection layer (Not shown in the figure), the main material of the hole injection layer is COPPER phthalocyanine (CuPc), and the material of the hole transport layer is mainly 4,4-bis [N- (1-naphthy 1) -N-pheny lamin. ] biphenyl (NPB) 'The material of the electron injection layer is mainly fluorinated chain (LiF), the material of the electron transport layer is mainly tris (8-quinolinato-N1, 08) —aluminum (Alq), and the organic light-emitting layer 63 Can be used for evaporation, spin coating, inkjet printing (Ink jet printing) or print (Printing) is formed over the first electrode 62, in addition, organic light-emitting layer 63 the light emitted can be a blue, green, red, white, or

569463

疋 For other monochromatic light, the second electrode W can be formed by the steamer method, the E-gun method or the SpUttering method, and the material can be aluminum, aluminum / lithium, and calcium. , A magnesium-silver alloy, or a conductive material such as silver, and the second electrode 64 is usually used as a cathode. As shown in FIG. 5, the deposition source 5 2 ′ is a water-absorbing material. In this embodiment, the deposition source 52 is deposited on the cover plate 51 by a deposition process to form a water-removing film 52. The system is as described above, so it will not be described further. In addition, please refer to FIG. 7. In another preferred embodiment of the present invention, the method 4 for forming a water-removing film is applied to a prefabricated organic light-emitting diode. 7 in. In this embodiment, the prefabricated organic light emitting diode element 7 includes a substrate 71, a first electrode 72, an organic light emitting layer 73, and a second electrode 74. The description about the prefabricated organic light emitting diode element 7 is as described above, so it will not be described again. As shown in the figure, the deposition source 75 is a water-absorbing material. This embodiment uses a deposition process to deposit the deposition source 75 onto a prefabricated organic light-emitting diode element 7 to form a water removal film 75. The method of forming the thin film is as described above, so it will not be described further. It should be noted that the water removal film 75 may cover the first electrode 72, the organic light emitting layer 73, and the second electrode 74, or it may be formed on the second electrode 74 (not shown in the figure). Then, a packaging process is performed to complete the fabrication of the organic light emitting diode device. As shown in FIG. 8A, the first electrode 72, the organic light-emitting layer 73, the second electrode 74, and the water-removing film 75 are enclosed in a sealed two room by a cover plate 76. The i-plate 76 is made of transparent A piece of glue 7 6 1 is stuck on the substrate 7 1

Page 14 569463 is described. The thickness of the coating during the coating process can be reduced by the formation method to avoid the thickness. The film is only described by Shen and Fan Fu's Shenjiao 7 6 1 series, such as epoxy resin. A protective layer (pass electrode 72, organic light-emitting layer 73, first and second steps in accordance with this method and a ring formed in addition to the previous process) is used to make solvent residues. In addition, it also has an exemplary domain, and please divide the patented film by the The operator does not make use of it and it is applied on the fifth, the description of the invention (ίο), and this cover is shown in Figure 8B. The water-repellent film covering the first electrical film 75 is integrated into the second seal by deposition. The electrode is used to build the execution platform, so that the water-removing film can be used to remove the water-removing film. The above-mentioned essence of the present invention should be included in the water-repellent light-emitting element water film of the later invention, the deposition process, so the manufacturing environment, and Buy this. In addition, the problem of leaving can avoid sticking 〇, and # is limited to the scope of its implementation. C epoxy) 〇i vat i on fi Two electrodes 7 4 to form a square water thin m to form in addition to the environment, must flower Coating prepared> product side can have redundant interference by compulsory. Any equivalent modification or in addition, such as) 77, and the method of forming a thin film of water, and the method of forming a cover plate, for example, a thin film is an extra cost process to form an effective reduction without effectively leaving the change.

569463 Schematic description [Schematic description] Schematic schematic diagram of a photodiode 'shows the conventional "intent ;, the cover of the organic light-emitting diode Figure 1 is / schematic diagram' shows the conventional organic diagram 2-- Schematic diagram of water absorbing material Figure 3 is a schematic diagram showing another—Xi 4 AA cover plate and a schematic diagram of water absorbing material; Figure 4 of an organic light emitting diode is a flowchart showing the flow of the method for forming a hair film according to the present invention; Fig. 5 is a schematic diagram of the water removal of the Jiaguan example, showing the use of Shiyang m to sacrifice Zangu 氺 荖 煸 l 叱 丄 叱 丄 using this & Ming preferred embodiment of the water removal film opening method 开Fig. 6 is a schematic diagram showing the formation of a water-removing thin film on the board. Fig. 6 is a schematic diagram showing the unintended appearance of an ancient film. A schematic diagram of a photodiode element with an organic hair film with a cover plate as shown in Fig. 5 shows that it is better to use the present invention. Example of forming a water-removing thin light emitting device on a water-removing prefabricated organic light-emitting diode element: having a prefabricated organic follow-up as shown in FIG. 7, a schematic diagram of a light-polarity element; organic light-emitting_ β M r two, song not another has as shown in Figure 7 Schematic diagram of organic light-emitting diode element with 7 pieces of system. [Explanation of Symbols] 1 Organic light-emitting diode 胄 + ^ U substrate body 7 " page 16 569463 Simple illustration of the diagram 12 First electrode 13 Organic light-emitting layer_ 14 Second electrode 15 Cover plate 2 5 Cover plate 251 Groove 2 6 Water absorbing material 2 7 Water permeable film 3 5 Cover plate 3 6 Water absorbing material 37 Film 4 Dewatering film formation method 4 1 ~ 4 2 Dewatering film Forming method flow 51 cover 5 2 water-removing film 5 2 'deposition source 6 prefabricated organic light emitting diode element 61 substrate 62 first electrode 63 organic light emitting layer 64 second electrode 7 prefabricated organic light emitting diode element 71 Substrate 72 first electrode

Page 17 569463

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Claims (1)

569463 _ plug No. 911253 ^ [Month day __ VI. Patent application scope compound) ° 8. The method for forming a water-removing film as described in item 6 of the patent application scope, wherein the water-absorbing material is an alkaline metal compound) ° 9. The method for forming a water-removing film as described in item 8 of the scope of patent application, wherein the alkali metal compound is an alkali metal oxide compound 〇1 0, as in the scope of patent application item 6 The method for forming a water-removing film, wherein the water-absorbing material is an alkaline earth metal compound 〇11. The method for forming a water-removing film as described in item 10 of the Shen Jing patent scope, wherein the soil test The metal compound is alkaline earth metal oxide (compound). 1 2. The method for forming a water-removing film as described in item 6 of the scope of the patent application, in which the COSCO water-absorbing material is a sulfur compound. 1 3. The method for forming a water-removing film as described in item 6 of the scope of patent application, wherein the water-absorbing material is a metal halide compound 569463 ____ ^ 1 ^ 91125336 _ γ Month m__ A. Apply for IS s " i 4. The method for forming a water-removing film as described in item 6 of the patent application, wherein the water-absorbing material is a perchloric acid compound ( perchlrate compound) ° 15. The method for forming a water-removing film as described in item 6 of the scope of the patent application, wherein the water-absorbing material is an organic compound. 16. A method for forming a water-removing film of a cover plate, which is used to form a water-removing film of an organic light-emitting element, comprising: pre-forming a cover plate; providing a water-absorbing material; and forming the water-absorbing material on the surface by a deposition method. Cover to form the dewatering film. 17. The method for forming a water-removing film of a cover plate as described in item 16 of the Shen-Jin patent scope, wherein the deposition method is a vapor deposition method. 18. The method for forming a water-removing film of a cover plate according to item 丨 7 of the scope of the patent application, wherein the deposition method is a physical vapor deposition method. 19. The method for forming a water-removing film on a cover plate as described in item 7 of the patent application scope, wherein the deposition method is a chemical vapor deposition method. Page 21 569463 _ Case No. 91125336 _ year and month amend _ six, the scope of patent application 20, the method of forming a cover plate water removal film as described in the scope of patent application No. 16 method, wherein the deposition method is a vapor deposition the way. 2 1. The method for forming a water-removing film of a cover plate according to item 16 of the scope of patent application, wherein the water-absorbing material is a deposition source material. 2 2. The method for forming a water-removing film of a cover plate as described in item 21 of the scope of patent application, wherein the water-absorbing material is an organometallic compound. 2 3. The method for forming a water-removing film on a cover plate as described in item 21 of the scope of patent application, wherein the water-absorbing material is a metal compound. 24. The method for forming a water-removing film of a cover plate according to item 23 of the scope of the patent application, wherein the metal detection compound is an alkali metal oxide. 25. The method for forming a water-removing film on a cover plate as described in item 21 of the scope of the patent application, wherein the water-absorbing material is a soil test metal compound. 26. The method for forming a water-removing film of a cover plate according to item 25 of the scope of the patent application, wherein the soil test metal compound is a soil test metal oxide. 27. The method for forming a water-removing film of a cover plate as described in item 21 of the scope of patent application, wherein the water-absorbing material is a sulfur-containing metal compound. Page 22 569463 t #. 9U25336 6. Scope of patent application 28. The cover plate division method according to item 21 of the scope of patent application, wherein the water-absorbing material is a metal tooth compound. Film-forming party 2 ::; 1 Please "f" Item 21 for the method of forming a water-removing film for a cover sheet No. 8 No. 5 absorbent material is a perchloric acid compound. 30, ^ Patent range item 21 A thin water-removing method for a cover plate, wherein the water-absorbing material is an organic compound. A method for forming a water-removing thin film for an organic light-emitting element includes: prefabricating a substrate on which a first electrode is sequentially formed; A light layer and a second electrode; providing a water-absorbing material; and forming the water-absorbing material on the substrate in a deposition manner to form a water-removing film. 3 2. Organic light-emitting according to item 31 of the scope of patent application Method for forming a water-removing film of an element ', wherein the water-removing film is formed on the second electrode. 33. The method for forming a water-removing film of an organic light-emitting device according to item 31 of the scope of application for a patent, wherein the water-removing film is Cover the first electrode, the organic light-emitting layer and the second electrode. 3 4. The water-removing thin film of the organic light-emitting element according to item 3 丨 in the scope of patent application. Page 23 569463 _ j No. 9112Fi: ^ fi _ ^ __ ^ ~ --___ 6. Scope of Patent Application The film formation method, wherein the deposition method is a vapor deposition method. 35. The method for forming a water-removing film of an organic light-emitting element according to item 34 of the scope of the patent application, wherein the deposition method is a physical vapor deposition method. 36. The method for forming a water-removing film of an organic light-emitting device according to item 34 of the scope of the patent application, wherein the deposition method is a chemical vapor deposition method. 37. The method for forming a water-removing film of an organic light-emitting element according to item 31 of the scope of the patent application, wherein the deposition method is a steam-bonding method. 38. The method for forming a water-removing film of an organic light-emitting element according to item 31 of the scope of the patent application, wherein the water-absorbing material is / deposition source material. 39. The method for forming a water-removing film of an organic light-emitting element according to item 38 of the scope of application for a patent, wherein the water-absorbing material is an organometallic compound. 40. The method for forming a water-removing film of an organic light-emitting element according to item 38 of the scope of the patent application, wherein the water-absorbing material is a metal test compound. 4 1. The method for forming a water-removing film of an organic light-emitting element according to item 40 of the scope of the patent application, wherein the alkali metal compound is an alkali metal oxide. 4 2. Water removal thin film for organic light-emitting element as described in item 38 of the scope of patent application 569463 _Case No. 91125336_ Years and months Amendment_ VI. Scope of patent application Film formation method ’wherein the water-absorbing material is a test metal compound. 43. The method for forming a water-removing film of an organic light-emitting element according to item 42 of the scope of the patent application, wherein the soil test metal compound is a soil test metal oxide. 4 4. The method for forming a water-removing film of an organic light-emitting element according to item 38 of the scope of the patent application, wherein the water-absorbing material is a sulfur-containing metal compound. 45. The method for forming a water-removing film of an organic light-emitting device according to item 38 of the scope of the patent application, wherein the water-absorbing material is a metal compound. 46. The method for forming a water-removing film of an organic light-emitting device according to item 38 of the scope of the patent application, wherein the water-absorbing material is a perchloric acid compound. 47. The method for forming a water-removing film of an organic light-emitting element according to item 38 of the scope of the patent application, wherein the water-absorbing material is an organic compound. Page 25