WO2004057920A1 - 表示装置及び表示装置の作製方法 - Google Patents
表示装置及び表示装置の作製方法 Download PDFInfo
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- WO2004057920A1 WO2004057920A1 PCT/JP2003/015764 JP0315764W WO2004057920A1 WO 2004057920 A1 WO2004057920 A1 WO 2004057920A1 JP 0315764 W JP0315764 W JP 0315764W WO 2004057920 A1 WO2004057920 A1 WO 2004057920A1
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- insulating layer
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/127—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
Definitions
- the present invention relates to a display device (hereinafter, referred to as a display device) having an element in which a light-emitting material is interposed between electrodes (hereinafter, referred to as a light-emitting element) and a method for manufacturing the display device.
- the present invention relates to a display device using a light-emitting material (hereinafter, referred to as an EL material) capable of obtaining EL (Electro-luminescence: E1ectroLuminescencce).
- EL display device using a light-emitting element utilizing the EL phenomenon of a light-emitting material (hereinafter, referred to as an EL element) has been developed.
- EL display devices have the advantage that they do not require a backlight like a liquid crystal display because the light emitting element itself has a light emitting capability, and that they have a wider viewing angle and higher contrast.
- an EL element by applying a voltage across an organic compound layer between a pair of electrodes, electrons injected from the cathode and holes injected from the anode recombine at the emission center in the organic compound layer. It is said that it forms a molecular exciton and emits energy when the molecular exciton returns to the ground state. Singlet excitation and triplet excitation are known as excited states, and light emission is possible through either excited state. It is believed that there is.
- Emissive materials used for EL devices include inorganic light-emitting materials and organic light-emitting materials, and organic light-emitting materials with low driving voltages are attracting attention.
- an organic EL element using an organic material for the EL element has a problem that, when driven for a certain period of time, the light emission characteristics such as light emission luminance and light emission uniformity are significantly deteriorated compared to the initial period. This low reliability is a factor that limits the practical application.
- a display device having a structure for preventing the EL element from deteriorating as described above has been developed.
- the EL element is housed in an airtight container, the EL element is confined in a sealed space to block it from outside air, and a desiccant is provided in the sealed space by separating the EL element from the EL element (for example, see Patent Document 1). .).
- a sealing material is formed on the insulator on which the EL element is formed, and the sealing material is there is also a method in which a closed space surrounded by a cover material and a seal material is filled with a filler material made of resin or the like, and is blocked from the outside (for example, see Patent Document 2).
- a sealing material is formed on an insulator on which an EL element is formed, and the sealing material is used to form a closed space surrounded by the cover material and the sealing material. Since this sealing step is performed in an inert gas atmosphere, a large amount of water or oxygen does not exist inside the display device from the beginning, and only a small amount of water or oxygen exists inside the display device immediately after sealing.
- moisture that causes deterioration mainly enters the display device after sealing.
- the insulator and the covering material are often made of metal or glass, water and oxygen mainly enter from the sealing material.
- FIG. 1 shows a top view of the EL display device described in Patent Document 2.
- Reference numeral 401 shown by a dotted line denotes a source side drive circuit
- 402 denotes a gate side drive circuit
- 403 denotes a pixel portion
- 409 denotes? ⁇ (Flexible Print Circuit).
- reference numeral 404 denotes a cover material
- reference numeral 405 denotes a first seal material
- reference numeral 406 denotes a second seal material.
- FIG. 27 A cross-sectional view of a conventional EL display device as shown in FIG. 1 is shown in FIG. 27 (the second sealing material 406 is not shown).
- the EL element is sealed inside with a sealing material in the region A of the sealing region.
- Patent Literature 1 and Patent Literature 2 described above in the region A in the sealing region in FIG. 27, the EL element and external moisture are blocked by the sealing material.
- the size of the EL display device is increased by the size of the container. Furthermore, since the desiccant (the protective layer containing the desiccant) is disposed separately from the EL element in order to prevent adverse effects caused by directly laminating the EL element, the airtight container becomes larger. However, although the size of the EL display device increases, the size of the light emitting portion does not change. In this case, the advantage of the thinness of the EL display device, which does not require a backlight, cannot be used. Furthermore, in the structure of Patent Document 1, moisture is adsorbed by the desiccant inside the airtight container, so that the moisture that has entered the inside of the airtight container may touch the EL element and cause deterioration of the EL element.
- Patent Document 2 the EL element is blocked from external moisture by a filler such as resin. However, since a sealing material is applied to the area A in FIG. It is inevitable that the display device will be larger.
- the display device As described above, if the area of the display device other than the pixel portion that emits light is large (region A in FIG. 27), the portion that does not emit light increases, and the display device must be enlarged to obtain a light-emitting portion of the same area. Have to be.
- FIG. 17 shows such an EL display device
- FIG. 2 shows an enlarged view of an end portion (edge) of a sealing region which is an end portion.
- 21 is a substrate
- 22 is a counter substrate
- 23 is a gate insulating film
- 24, 25 Is an interlayer film
- 26 is a wiring
- 27 is a seal material.
- the gate insulating film 23, the interlayer films 24, 25, and the wiring 26 on the substrate 21 are laminated, and the sealing material 27 is formed on the insulating layer (laminated film). Is applied.
- the region A in FIG. 27 where no light is emitted can be reduced.
- FIG. 2 is an example, and the materials of the films laminated on the TFT substrate side and the order of lamination are not limited to this example.
- the structure is such that a base film, a gate insulating film, a protective film and an interlayer film are laminated on a glass substrate, and wiring is laminated on the top.
- the sealing material for sealing is on the laminated film as shown in Fig. 2, all the laminated films come into direct contact with the atmosphere outside the panel. Water and oxygen enter the display device through the stacked films. Furthermore, when a material having high moisture permeability such as acrylic is used for the interlayer film, the amount of water and oxygen that penetrate further increases.
- the present invention provides a highly reliable EL display device that blocks invading moisture and oxygen, which is a cause of deteriorating the characteristics of an EL element, without increasing the size of the EL display device, and a method for manufacturing the EL display device.
- the task is to
- a sealing film that blocks the inside and the outside of a display device and protects a light-emitting element from contaminants is referred to as a sealing film.
- a display device of the present invention is a display device having a display portion formed by arranging light-emitting elements using an organic light-emitting material between a pair of substrates, wherein the display portion includes an insulating layer formed on one of the substrates.
- the pair of substrates are formed on a layer, and are formed on the outside of the display unit, surround the outer periphery, and are fixed by a sealing material formed on the insulating layer, and at least one layer of the insulating layer is an organic resin material.
- the outer end of the insulating layer located outside the sealing material is covered with a sealing film.
- a display device of the present invention is a display device having a display portion formed by arranging light-emitting elements using an organic light-emitting material between a pair of substrates, wherein the display portion includes an insulating layer formed on one of the substrates.
- the pair of substrates are formed on a layer, and are formed on the outside of the display unit, surround the outer periphery, and are fixed by a sealing material formed on the insulating layer, and at least one layer of the insulating layer is formed of an organic material. It is formed of a resin material, the insulating layer has an opening, the opening is covered with a sealing film, and the sealing material is formed in contact with the sealing film. .
- the display device of the present invention is a display device having a display portion formed by arranging a light-emitting element using an organic light-emitting material between a pair of substrates, wherein the display portion includes an insulating layer formed on one of the substrates. Formed on a layer, wherein the pair of substrates are outside the display unit. Formed around the outer periphery and fixed by a sealing material formed on the insulating layer, at least one of the insulating layers is formed of an organic resin material, the insulating layer has an opening, The opening is covered with a sealing film, and an outer end portion of the insulating layer located outside the sealing material is covered with the sealing film.
- the display device of the present invention is a display device having a display portion formed by arranging light emitting elements using an organic light emitting material between a pair of substrates, wherein the display portion is formed on one of the substrates.
- the pair of substrates are formed on a layer, and are formed on the outside of the display unit, surround the outer periphery, and are fixed by a sealing material formed on the insulating layer, and at least one layer of the insulating layer is an organic resin material.
- the insulating layer has a plurality of openings, the plurality of openings are covered with a sealing film, and the sealing material is formed in contact with the sealing film. .
- a display device of the present invention is a display device having a display portion formed by arranging light-emitting elements using an organic light-emitting material between a pair of substrates, wherein the display portion includes an insulating layer formed on one of the substrates.
- the pair of substrates are formed on a layer, and the pair of substrates are formed outside the display portion, surround the periphery, and are fixed by a sealing material formed on the insulating layer, and at least one of the insulating layers is formed of an organic material.
- the insulating layer is formed of a resin material, the insulating layer has a plurality of openings, the plurality of openings are covered with a sealing film, and an outer end of the insulating layer located outside the sealing material is It is characterized by being covered with a sealing film.
- the insulating layer may be provided with a plurality of openings and covered with a sealing film, or an opening may be provided in any part inside the display device. Pixel area And the peripheral drive circuit region, or may be sealed in a sealing region.
- the outer end of the insulating layer located outside the sealing material needs to be covered with a sealing film. Therefore, when the opening is located outside the sealing material, the outer end may be an opening as shown in FIG.
- the sealing film may be a film selected from one of a conductive thin film and an insulating thin film, or a film formed of a plurality of types.
- a film selected from the elements of A1, Ti, Mo, W, and Si, or a film including a plurality of types may be used.
- a film selected from a silicon nitride film, a silicon nitride oxide film, and a nitrogen-containing carbon film, or a film including a plurality of kinds may be used.
- the organic resin material may be a film selected from one of acrylic, polyamide, and polyimide, or a film including a plurality of types. Further, it may be formed of a material in which a skeleton structure is formed by a bond between silicon and oxygen.
- a material having a skeleton structure formed by a bond between silicon and oxygen includes a siloxane-based polymer. Specifically, a skeleton structure is formed by a bond between silicon and oxygen, and the substituent includes at least hydrogen.
- the method for manufacturing a display device of the present invention uses an organic light-emitting material between a pair of substrates.
- a method for manufacturing a display device of the present invention is a method for manufacturing a display device having a display portion formed by arranging light-emitting elements using an organic light-emitting material between a pair of substrates.
- the pair of substrates are formed around an outer periphery of the display unit, and are fixed by a sealing material formed on the insulating layer, and at least one layer of the insulating layer is formed on the insulating layer formed on the substrate.
- a method for manufacturing a display device of the present invention is a method for manufacturing a display device having a display portion formed by arranging light-emitting elements using an organic light-emitting material between a pair of substrates.
- the pair of substrates are formed around an outer periphery of the display unit, and are fixed by a sealant formed on the insulating layer; and at least one layer of the insulating layer is formed on the insulating layer.
- Is formed of an organic resin material an opening is formed in the insulating layer, the opening is covered with a sealing film, and an outer end of the insulating layer formed outside the sealing material is sealed. It is characterized by coating with a film.
- a method for manufacturing a display device of the present invention is a method for manufacturing a display device having a display portion formed by arranging light-emitting elements using an organic light-emitting material between a pair of substrates.
- the pair of substrates are formed around the outer periphery of the display unit, and are fixed with a sealing material formed on the insulating layer.
- At least one layer is formed of an organic resin material.
- a plurality of openings are formed in the insulating layer, the plurality of openings are respectively covered with a sealing film, and the sealing material is formed in contact with the sealing film.
- a method for manufacturing a display device of the present invention is a method for manufacturing a display device having a display portion formed by arranging light-emitting elements using an organic light-emitting material between a pair of substrates.
- the pair of substrates are formed around an outer periphery of the display unit, and are fixed by a sealing material formed on the insulating layer, and at least one of the insulating layers is formed on the insulating layer formed on the substrate.
- Is formed of an organic resin material a plurality of openings are formed in the insulating layer, the plurality of openings are respectively covered with a sealing film, and the insulating layer is formed outside the sealing material.
- the outer end is covered with a sealing film.
- the insulating layer may be provided with a plurality of openings and covered with a sealing film, or an opening may be provided in any part inside the display device. It may be sealed between the pixel region and the peripheral driving circuit region, or may be sealed with the sealing region.
- the outer end of the insulating layer located outside the seal material needs to be covered with a sealing film. Therefore, when the opening is located outside the sealing material, the outer end may be an opening as shown in FIG.
- the sealing film may be formed of one or more selected from a conductive thin film and an insulating thin film.
- the conductive thin film may be formed from one kind selected from the elements of A 1, T i, Mo, W or S i, or a plurality of kinds.
- the insulating thin film may be formed of a species selected from a silicon nitride film, a silicon nitride oxide film, or a nitrogen-containing carbon film, or a plurality of species.
- the organic resin material can be formed of one or more selected from acryl, polyamide, and polyimide. Further, it may be formed of a material in which a skeleton structure is formed by a bond between silicon and oxygen.
- a typical example of a material having a skeleton structure formed by a bond between silicon and oxygen is a siloxane-based polymer. More specifically, a material having a skeleton structure formed by a bond between silicon and oxygen and having at least hydrogen as a substituent Or a material having at least one of fluorine, an alkyl group, and an aromatic hydrocarbon as a substituent.
- the sealing film as in the present invention, the insulating layer containing the organic resin material of the display device does not come into direct contact with the atmosphere outside the display device (panel). For this reason, it is possible to prevent water and oxygen outside the display device from entering the display device through an insulating film containing a hygroscopic organic material. Therefore, it is possible to prevent various kinds of deterioration such as contamination of the inside of the display device caused by water or oxygen, deterioration of electrical characteristics, and dark spot shrinkage, thereby improving the reliability of the display device. . Further, since the present invention uses the film constituting the display device as a sealing film (protective film), a highly reliable display device can be manufactured without increasing the number of steps.
- the insulating layer containing the organic resin material of the display device does not come into direct contact with the outside air of the display device (panel).
- Absolute film containing organic material that has hygroscopic property Through the display device. Therefore, it is possible to prevent various kinds of deterioration such as contamination of the inside of the display device caused by water or oxygen, deterioration of electric characteristics, dark spot shrinkage, and the like, and improve reliability of the display device.
- the present invention forms a film of the same material as the film constituting the display device at the same time and uses it as a sealing film, a highly reliable display device can be manufactured without increasing the number of steps. Can be.
- the display device manufactured as described above has a structure for blocking contaminants in the sealing region at the end of the display device, the operation characteristics and reliability of the display device can be sufficient. . Further, an electronic device using the display device of the present invention can also have high reliability.
- FIG. 1 is a top view of a conventional display device.
- FIG. 2 is a diagram showing a conventional configuration.
- FIG. 3 is a diagram showing a configuration of the present invention.
- FIG. 4 is a diagram showing a configuration of the present invention.
- FIG. 5 is a diagram showing a configuration of the present invention.
- FIG. 6 is a cross-sectional view showing a manufacturing process of the active matrix matrix substrate.
- FIG. 7 is a cross-sectional view showing a step of manufacturing an active matrix substrate.
- FIG. 8 is a cross-sectional view showing a manufacturing process of an active matrix matrix substrate.
- FIG. 9 is a cross-sectional view of an active matrix substrate.
- FIG. 10 is a cross-sectional view of the display device of the present invention.
- FIG. 11 is a cross-sectional view of the display device of the present invention.
- FIG. 12 is a diagram illustrating an example of a display device.
- FIG. 13 is a diagram illustrating an example of a display device.
- FIG. 14 is a diagram illustrating an example of a display device.
- FIG. 15 is a diagram showing the result of reliability evaluation of a conventional display device.
- FIG. 16 is a diagram showing the results of the reliability evaluation of the display device of the present invention.
- FIG. 17 is a cross-sectional view of a conventional EL display device.
- FIG. 18 is a cross-sectional view of the display device of the present invention.
- FIG. 19 is a top view of a conventional display device.
- FIG. 20 is a cross-sectional view of the display device of the present invention.
- FIG. 21 is a cross-sectional view of the display device of the present invention.
- FIG. 22 is a top view of the display device of the present invention.
- FIG. 23 is a diagram showing the results of the reliability evaluation of the display device of the present invention.
- FIG. 24 is a diagram showing the result of the reliability evaluation of the display device of the present invention.
- FIG. 25 is a diagram showing the results of the reliability evaluation of the display device of the present invention.
- FIG. 26 is a diagram showing a display device of the present invention.
- FIG. 27 is a cross-sectional view of a conventional EL display device. BEST MODE FOR CARRYING OUT THE INVENTION
- a gate insulating film, an interlayer film, and wiring on a TFT substrate are laminated to form an insulating layer.
- 31 is a substrate
- 32 is an opposing substrate
- 33 is an insulating film
- 34 and 35 are interlayer films
- 36 is a sealing film as a protective film
- 37 is a sealing material.
- the example of lamination in FIG. 3 is an example, and the materials of the films laminated on the TFT substrate side and the order of lamination are not limited to this example.
- the structure is such that a base film (not shown), a gate insulating film, a protective film and an interlayer film, and a sealing film are laminated on a glass substrate.
- the sealing film laminated on the top is formed of the same material as the wiring at the same time as the wiring, and a base film (not shown) laminated before that It has a structure that covers insulating films, interlayer films, and protective films.
- the sealing film With this sealing film, a film such as an interlayer film does not come into direct contact with the atmosphere outside the display device. Therefore, it is possible to prevent water or oxygen outside the display device from entering the display device through an interlayer film or the like or a gap between the films. Therefore, it is possible to prevent various kinds of deterioration such as contamination of the inside of the display device caused by water and oxygen, deterioration of electric characteristics, dark spot shrinkage, and the like, and improve reliability of the display device. Further, the present invention constitutes a display device. Since a film made of the same material as the film used as the sealing film is used as the sealing film, a highly reliable display device can be manufactured without increasing the number of steps.
- the sealing film Since a sealing film that blocks water, oxygen, and the like functions as a protective film, it is preferable that the sealing film has a dense structure.
- a film selected from a conductive thin film and an insulating thin film, or a film formed from a plurality of types may be used.
- a film such as one selected from the elements of A 1, T i, Mo, W, or S i, or an alloy film of a plurality of types may be used.
- the insulating thin film one or a plurality of films selected from a silicon nitride film, a silicon nitride oxide film, and a nitrogen-containing carbon film can be used.
- an organic resin material used for the insulating layer acrylic, polyimide, polyimide, or the like can be used, and there is no limitation on the material.
- a material in which a skeleton structure is formed by a bond between silicon and oxygen may be used.
- a typical example of a material having a skeletal structure formed by a bond between silicon and oxygen is a siloxane-based polymer. More specifically, a skeleton structure is formed by a bond between silicon and oxygen, and at least a substituent is present.
- not only one sealing film but also two or more sealing films may be provided.
- a conductive film in order to avoid a short circuit inside the display device, as shown in Fig. 5 (B), it is separated from the display device internal region and only the sealing region. Need to be laminated.
- the end portions of the display device are stacked and blocked in this way, the blocking effect of the contaminants is further enhanced as compared with a single layer of the sealing film.
- the shape of the film of the lower layer to be covered is such that the slope surface has a shape in which the radius of curvature changes continuously (smoothly).
- the thin film is formed without disconnection. If the film surface of the lower layer is not smooth, the thickness of the sealing film on the surface of the lower layer becomes thinner, and the inclined surface of the lower layer film is destroyed. The destroyed film cannot sufficiently block the contaminants, and the effect of the present invention is reduced. The better the flatness of the surface of the lower film to be covered, the better the coverage of the sealing film formed in a stack, and the effect of the present invention is further improved. Therefore, it is preferable to perform the wet etching using a photosensitive material as the lower layer film since the film surface is less rough and the flatness is improved.
- an insulating film, an interlayer film, and wiring on the TFT substrate are laminated to form an insulating layer.
- 41 is a substrate
- 42 is a counter substrate
- 43 is an insulating film
- 44 and 45 are interlayer films
- 46 is a sealing film as a protective film
- 47 is a sealing material.
- the stacking example in FIG. 4 is an example, and the materials of the films stacked on the TFT substrate side and the order of stacking are not limited to this example.
- the structure is such that a base film (not shown), an insulating film, a protective film and an interlayer film are laminated on a glass substrate, and a sealing film is laminated on the top.
- a sealing agent is applied on the laminated insulating layer, and adheres to the substrate including the insulating layer and the counter substrate.
- an opening is provided in a laminated base film (not shown), an insulating film, an interlayer film, a protective film, and the like, and a sealing film is laminated in the opening.
- the structure is formed so as to cover the film.
- This sealing film is formed simultaneously with the same material as the wiring.
- the insulating layer including the organic resin material below the sealing film is separated into an inner region and an outer region in the display device. Those films in the area inside the display device do not come into direct contact with the atmosphere outside the display device. For this reason, the outer insulating layer in the separated display device is exposed to the atmosphere, and water or oxygen outside the display device is discharged from the interlayer film or the gap between the films, and the interlayer film or the film in the outer region. Even if it enters the panel through the gap, it is blocked by the sealing film and cannot enter the display device.
- the sealing film since the sealing film is formed at the same time using the same material as the film forming the display device, the reliability of the display device manufactured without increasing the number of steps can be improved. Since a sealing film that blocks water, oxygen, and the like functions as a protective film, it is preferable that the sealing film has a dense structure.
- a film selected from a conductive thin film and an insulating thin film, or a film formed from a plurality of types may be used.
- the conductive thin film may be a film selected from the group consisting of A1, Ti, Mo, W, or Si, or an alloy film of a plurality of types. May be used.
- As the insulating thin film one or a plurality of films selected from a silicon nitride film, a silicon nitride oxide film, and a nitrogen-containing carbon film can be used.
- an organic resin material used for the insulating layer acrylic, polyimide, polyimide, or the like can be used, and there is no limitation on the material. Further, it may be formed of a material in which a skeleton structure is formed by a bond between silicon and oxygen.
- a typical example of a material having a skeletal structure formed by a bond between silicon and oxygen is a siloxane-based polymer. Specifically, a skeletal structure is formed by a bond between silicon and oxygen, and at least hydrogen is used as a substituent.
- the multilayer film may be divided a plurality of times, or may be divided at any part inside the display device. That is, it may be divided between the pixel region and the peripheral drive circuit region, or may be divided in the sealing region.
- the insulating layer may be provided with a plurality of openings and covered with a sealing film, or an opening may be provided at any portion inside the display device. It may be sealed between the pixel region and the peripheral driving circuit region, or may be sealed with a sealing region. However, the outer end of the insulating layer located outside the sealing material needs to be covered with a sealing film. Therefore, when the opening is located outside the sealing material, the outer end may be an opening as shown in FIG.
- the opening is formed so as to reach the glass substrate.
- the structure of the present invention is not limited to this. In other words, it is only necessary that the insulating film containing an organic material having hygroscopicity can be covered with the sealing film. Therefore, an opening is formed until a film that can be used as a sealing film such as a silicon nitride film is formed. It may be covered with a film.
- FIG. 5A not only one sealing film but also two or more sealing films may be provided.
- 501 is a substrate
- 502 is a counter substrate
- 503 is an insulating film
- 504 and 505 are interlayer films
- 506 and 508 are protective films.
- a sealing film, 507 is a sealing material.
- 511 is a substrate
- 512 is a counter substrate
- 513 is an insulating film
- 514 and 515 are interlayer films
- 516 and 518 are protective films.
- the sealing film, 5 17, is a sealing material. In this way, if the number of divisions inside the display device is increased, combined with a structure that covers the edges, or the edges of the display device are laminated and blocked, the effect of blocking contaminants is even greater than a single layer of the sealing film. Rises.
- Embodiment 1 can be freely combined with Embodiment 1.
- FIGS. 6 to 9 show the fabrication method of the active matrix substrate. It will be described using FIG. Although the active matrix substrate includes a plurality of TFTs, a case will be described in which the active matrix substrate includes a driving circuit unit having an n-channel TFT and a p-channel TFT, and a pixel unit.
- a silicon nitride oxide film having a thickness of 10 to 200 nm (preferably 50 to: LOO nm) is formed as a base film 300 on a substrate 200 having an insulating surface by a plasma CVD method.
- a silicon oxynitride film is stacked in a thickness of 50 to 200 nm (preferably 100 to 150 nm).
- a silicon nitride oxide film is formed to a thickness of 50 nm and a silicon oxynitride film is formed to a thickness of 100 nm by a plasma CVD method.
- the substrate 200 is a glass substrate, a quartz substrate, a silicon substrate, a metal substrate or a stainless steel substrate. May have an insulating film formed on the surface thereof.
- a plastic substrate having heat resistance enough to withstand the processing temperature of this embodiment may be used, or a flexible substrate may be used.
- a two-layer structure may be used as the base film, or a single-layer film of the base (insulating) film or a structure in which two or more layers are stacked may be used.
- a semiconductor film 301 is formed over the base film (FIG. 6A).
- the semiconductor film may be formed to a thickness of 25 to 200 nm (preferably 30 to L50 nm) by a known means (such as a sputtering method, an LPCVD method, or a plasma CVD method).
- a known means such as a sputtering method, an LPCVD method, or a plasma CVD method.
- silicon or a silicon germanium (SiGe) alloy it is preferable to use silicon or a silicon germanium (SiGe) alloy.
- a thermal crystallization method and a laser crystallization method using a metal element that promotes crystallization are performed on the amorphous silicon film.
- an amorphous silicon film of 54 nm was formed as a semiconductor film by a plasma CVD method.
- Nickel is used as a metal element, and is introduced on the amorphous silicon film by a solution coating method.
- the method of introducing the metal element into the amorphous silicon film is as follows. There is no particular limitation as long as the metal element can be present on or in the surface of the amorphous silicon film. Examples thereof include a sputtering method, a CVD method, a plasma processing method (including a plasma CVD method), an adsorption method, and a metal salt. Can be used. Among them, the method using a solution is simple and useful in that the concentration of the metal element can be easily adjusted.
- the first crystalline silicon film 303 is irradiated with a laser beam to promote crystallization, and a second crystalline silicon film 304 is obtained.
- Laser crystallization irradiates a semiconductor film with laser light.
- the laser used is preferably a continuous wave solid state laser, a gas laser or a metal laser.
- the a r continuous wave laser as a gas, single tHE, K r, single the property has C0 2 laser, or the like, the metal helium force continuous wave as the laser Domiumureza, copper vapor laser, gold vapor laser and the like.
- continuous emission excimer The can also be applied.
- the laser beam may be converted into a harmonic by a non-linear optical element.
- the crystal used for the nonlinear optical element is excellent in conversion efficiency when, for example, a crystal called LB0, BB0, KDP, KTP, KB5, or CLB0 is used. By placing these nonlinear optical elements in the laser cavity, the conversion efficiency can be greatly increased.
- Nd, Yb, Cr, and the like are doped in the laser of the harmonic, and these are excited and the laser oscillates.
- the type of the dopant may be appropriately selected by the practitioner.
- the semiconductor film include an amorphous semiconductor film, a microcrystalline semiconductor film, and a crystalline semiconductor film. An amorphous structure such as an amorphous silicon germanium film and an amorphous silicon film is used. May be applied.
- the crystalline semiconductor film 304 obtained as described above is patterned by photolithography to form semiconductor layers 305 to 308.
- a small amount of impurity element (boron or phosphorus) may be doped in order to control the threshold value of TFT.
- the gate insulating film 309 is formed of an insulating film containing silicon with a thickness of 40 to 150 nm by using a plasma CVD method or a sputtering method.
- a silicon oxynitride film having a thickness of 115 nm was formed by a plasma CVD method.
- the gate insulating film is not limited to the silicon oxynitride film, and another insulating film may be used as a single layer or a laminated structure.
- a first conductive film having a thickness of 20 to 10 O rnn is formed on the gate insulating film, It is formed by laminating a second conductive film of 100 to 40 Onm.
- the first conductive film and the second conductive film are formed of an element selected from Ta, W, Ti, Mo, Al, and Cu, or an alloy material or a compound material containing the aforementioned element as a main component.
- a semiconductor film typified by a polycrystalline silicon film doped with an impurity element such as phosphorus or an AgPdCu alloy may be used as the first conductive film and the second conductive film.
- the structure is not limited to a two-layer structure.
- a 50-nm-thick tungsten film, a 500-nm-thick aluminum-silicon alloy (A 1 —S i) film, and a 3-onm-thick titanium nitride film May be sequentially laminated to form a three-layer structure.
- tungsten nitride may be used instead of tungsten for the first conductive film, or an alloy of aluminum and silicon (A11-Si) film for the second conductive film.
- an alloy film of aluminum and titanium (A 1 —T i) may be used, or a titanium film may be used instead of the titanium nitride film of the third conductive film.
- it may have a single-layer structure.
- a 3 Onm-thick tantalum nitride film 3110 and a 37-Onm-thick tungsten film 311 were sequentially laminated on the gate insulating film 309 (FIG. 7A). ⁇ .
- a resist mask 312 to 316 is formed by using a photolithography method, and a first etching process is performed to form an electrode and a wiring.
- ICP Inductively Coupled Plasma: ICP
- the first conductivity is adjusted by appropriately adjusting the etching conditions (the amount of power applied to the coil-type electrode, the amount of power applied to the electrode on the substrate side, the temperature of the electrode on the substrate side, etc.) by using an etching method.
- the film and the second conductive film can be etched into a desired tapered shape.
- etching gas As an etching gas, C 1 2, BC 1 S i C 1 4 Or it can be used chlorine-based gas typified by CC 1 4, a fluorine-based gas or ⁇ 2, typified by CF 4, SF 6 or NF 3 as appropriate.
- the first shape conductive layer 3 17 to 3 2 1 composed of the first conductive layer and the second conductive layer (the first conductive layers 3 17 a to 3 21 a and the Two conductive layers 3 17b to 32 1b) were formed (Fig. 7 (B)).
- a second etching process is performed without removing the resist mask.
- the W film is selectively etched.
- the second conductive layers 322b to 326b are formed by a second etching process.
- the first conductive layers 32 2 a to 32 26 a are hardly etched, and form the second shape conductive layers 32 2 to 32 6.
- a first doping process is performed without removing the resist mask, and an impurity element imparting n-type is added to the semiconductor layer at a low concentration.
- the doping treatment may be performed by an ion doping method or an ion implantation method.
- An element belonging to Group 15 such as phosphorus (P) or arsenic (A s) is used as an impurity element for imparting n-type, but phosphorus (P) is used here.
- conductive layers 32 22 to 32 26 serve as a mask for the impurity element imparting n-type, and impurity regions 327 to 330 are formed in a self-aligned manner.
- An impurity element imparting n-type is added to the impurity regions 32 to 330 in the concentration range of 1 ⁇ 10 ′ 8 to 1 ⁇ 10 2 Vcm 3 (FIG. 7 (0)).
- a new resist mask 3311a to 3311c is formed, and the second doping process is performed at an acceleration voltage higher than that of the first doping process.
- the doping process is performed on the second conductive layer 323 b, 3 Using 26b as a mask for the impurity element, doping is performed so that the impurity element is added to the semiconductor layer below the tapered portion of the first conductive layer.
- a third doping process is performed by lowering the accelerating voltage from the second doping process to obtain a state shown in FIG.
- the second doping process and the third doping processing first overlapping with the conductive layer low-concentration impurity regions 3 3 5, in 34 1 in a concentration range of IX 1 0 18 ⁇ 5 X 1 0 19 / cm 3
- the n-type impurity element is added, and the high-concentration impurity regions 334, 337, and 340 have an n-type impurity element in a concentration range of 1 ⁇ 10 19 to 5 ⁇ 10 2 i / cm 3. Is added.
- the second doping process and the third doping process can form a low-concentration impurity region and a high-concentration impurity region by one doping process.
- a fourth doping process is performed.
- an impurity region in which an impurity element imparting a conductivity type opposite to the one conductivity type is added to a semiconductor layer serving as an active layer of a p-channel TFT.
- the impurity regions 343, 344, 347, 348 are formed. Using the first and second conductive layers 322 and 326 as a mask for the impurity element, an impurity element imparting a P-type is added to form an impurity region in a self-aligned manner.
- the impurity regions 343, 344, 347, and 348 are formed by an ion doping method using dipolane (B 2 H 6 ) (FIG. 8B).
- the semiconductor layer forming the n-channel TFT is covered with masks 342a and 342b made of a resist.
- Impurity regions 3 Phosphorus is added at different concentrations to 32, 340, and 341, respectively.In each of the regions, the concentration of the impurity element imparting p-type is set to 1 ⁇ 10 19 to 5 ⁇ 10 2 I atoms / By performing the doping treatment so as to have a size of cm, there is no problem in functioning as the source region and the drain region of the p-channel TFT.
- impurity regions are formed in the respective semiconductor layers.
- the first interlayer insulating film 349 is formed of an insulating film containing silicon with a thickness of 100 to 200 nm using a plasma CVD method or a sputtering method (FIG. 8 (0).
- a silicon oxynitride film with a thickness of 150 nm is formed by a plasma CVD method, and the first interlayer insulating film 349 is not limited to the silicon oxynitride film, but includes other silicon.
- the insulating film may have a single-layer structure or a stacked structure.
- heat treatment, intense light irradiation, or laser light irradiation is performed to activate the impurity element.
- the plasma damage to the gate insulating film and the plasma damage to the interface between the semiconductor layer and the semiconductor layer can be recovered simultaneously with the activation.
- a second interlayer insulating film 350 made of an inorganic insulating material or an organic insulating material is formed.
- an acrylic resin film having a thickness of 1.6 ⁇ 111 is formed, and one having a viscosity of 10 to 100 cp, preferably 40 to 200 cp is used.
- a material in which a skeleton structure is formed by a bond between silicon and oxygen may be used. Materials with a skeletal structure formed by the bond between silicon and oxygen As a typical example, a siloxane-based polymer is mentioned.
- a material having a skeleton structure formed by a bond between silicon and oxygen and containing at least hydrogen as a substituent, or a fluorine, alkyl, or aromatic substituent is used. It is a material that has at least one of the hydrocarbons.
- a passivation film 351 made of a nitride insulating film (typically, a silicon nitride film, a silicon nitride oxide film, or a nitrogen-containing carbon film (CN)) is formed on the second interlayer insulating film 350. .
- a metal film is formed, and the metal film is etched to form a source electrode and a drain electrode which are electrically connected to the respective impurity regions, and respective wirings (not shown).
- a film made of an element of aluminum (A l), titanium (T i), molybdenum (Mo), tungsten (W), or silicon (S i), or an alloy film using these elements may be used. .
- a titanium-aluminum alloy film / a titanium film (T i / A 1 —S i / T i) were laminated at 100/350/100 nm, respectively.
- a source electrode, a drain electrode 352 and respective wirings (not shown) are formed by patterning and etching into a desired shape. Accordingly, a p-channel TFT 11 and an n-channel TFT 12 are formed in the peripheral circuit section 1, and an n-channel TFT 13 and a p-channel TFT 14 are formed in the pixel section 2.
- a film of the same material as the wiring may be formed as a sealing film at the end of the substrate serving as a sealing region according to the present invention so as to cover a lower layer film. Since the light-emitting element does not need to come into contact with the outside air, the end sealing method may be used in Embodiment Mode 1 or 2, or a combination thereof.
- an electrode an anode or a cathode in the case of an EL display device, and a pixel electrode in the case of a liquid crystal display device
- the electrodes used ITS_ ⁇ of indium tin oxide and an acid of silicon, ITO, or a transparent conductive film such as S Ita_ ⁇ 2, a metal film such as A 1 in the case of reflection type liquid crystal display device Or you can.
- the electrode 353 is formed by depositing ITO and etching it into a desired shape (FIG. 9).
- an active matrix substrate provided with TFT is completed.
- the present invention is not limited to the method of manufacturing a top gate type (planar type) TFT shown in this embodiment, but may be a bottom gate type (inverted stagger type) or a gate insulating film provided above and below a channel region.
- the present invention can be applied to a dual gate type having two gate electrodes and other structures.
- a display device is a general term for a display panel in which a light emitting element formed on a substrate is sealed between the substrate and a cover material, and a display module including a TFT in the display panel. is there.
- the light-emitting element has a layer (light-emitting layer) containing an organic compound capable of obtaining luminescence generated by application of an electric field (light-emitting layer), an anode layer, and a cathode layer.
- the luminescence of an organic compound includes light emission (fluorescence) when returning from a singlet excited state to a ground state and light emission (phosphorescence) when returning from a triplet excited state to a ground state.
- EL materials that can be used in the present invention include all luminescent materials that emit light via singlet excitation or triplet excitation, or both.
- organic light-emitting layers specifically includes a light emitting layer, a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, and the like.
- a light-emitting element has a structure in which an anode layer, a light-emitting layer, and a cathode layer are sequentially stacked.
- an anode layer, a hole injection layer, a light-emitting layer, a cathode layer, anode layer, a hole injection layer, light emitting layer, electron transporting layer, c Figure 1 1 which is also to have a structure in which a cathode in that order layer such as a cross-sectional view of a display device of the present embodiment.
- the peripheral circuit section 6001 has a p-channel TFT 603, an n-channel TFT 604, and a pixel section 602 has an n-channel TFT 605 and a p-channel TFT.
- a TFT 600 is formed and sealed in a sealing region 600.
- a double gate structure in which two channel formation regions are formed is used, but a single gate structure in which one channel formation region is formed or a triple gate structure in which three channel formation regions are formed may be used.
- the drive circuit provided on the substrate 700 is formed using the CMOS circuit of FIG. Therefore, the description of the structure may be referred to the description of the n-channel TFT 11 and the p-channel TF 12.
- a single gate structure is used, but a double gate structure or a triple gate structure may be used.
- Reference numeral 711 denotes a pixel electrode (anode of a light-emitting element) made of a transparent conductive film ( transparent conductive films include compounds of indium oxide and tin oxide, compounds of indium oxide and zinc oxide, and zinc oxide
- transparent conductive films include compounds of indium oxide and tin oxide, compounds of indium oxide and zinc oxide, and zinc oxide
- the transparent conductive film to which gallium is added may be used
- the pixel electrode 711 may be a flat interlayer insulating film before the wiring is formed. It is effective to flatten the steps due to TFT using a flattening film made of resin The light emitting layer formed later is very thin, so the light emission is caused by the presence of the steps Therefore, it is desirable that the light emitting layer is planarized before forming the pixel electrode so that the light emitting layer can be formed on a flat surface as much as possible.
- a bank 712 is formed as shown in FIG.
- the bank 712 may be formed by patterning an insulating film containing 100 to 400 nm of silicon or an organic resin film.
- a material in which a skeleton structure is formed by a bond between silicon and oxygen may be used.
- a typical example of a material having a skeleton structure formed by a bond between silicon and oxygen is a siloxane-based polymer. More specifically, a material having a skeleton structure formed by a bond between silicon and oxygen and containing at least hydrogen as a substituent Or a material having at least one of fluorine, an alkyl group, and an aromatic hydrocarbon as a substituent.
- the banks 7 12 are insulating films, care must be taken to prevent electrostatic breakdown of elements during film formation.
- carbon particles or metal particles are added to the insulating film that is the material of the banks 7 12 to lower the resistivity and suppress the generation of static electricity.
- the added amount of the carbon particles and the metal particles is adjusted so that the resistivity becomes 1 ⁇ 10 6 to 1 ⁇ 10 12 ⁇ (preferably 1 ⁇ 10 8 to 1 ⁇ 10 10 Qm). Just adjust it.
- the light emitting layer 7 13 is formed on the pixel electrode 7 11. Although only one pixel is shown in FIG. 11, light emitting layers corresponding to R (red), G (green), and B (blue) are separately formed in this embodiment.
- a low molecular weight organic light emitting material is formed by a vapor deposition method. Specifically, a 2 O nm thick copper phthalocyanine (CuPc) film is provided as a hole injection layer, and a 70 nm thick tris-18-quinolinolato aluminum complex (A1 q 3 ) It has a laminated structure with a film. Kinakuri Dong A 1 d 3, it is possible to control the luminescent color by adding a fluorescent dye such as perylene or DCM 1.
- a fluorescent dye such as perylene or DCM 1.
- the above example is an example of the organic light emitting material that can be used as the light emitting layer, and there is no need to limit the present invention to this.
- the light-emitting layer (a layer for performing light emission and carrier movement therefor) may be formed by freely combining a light-emitting layer, a charge transport layer, or a charge injection layer.
- a low molecular organic light emitting material is used as the light emitting layer
- a medium molecular organic light emitting material or a high molecular organic light emitting material may be used.
- an organic light-emitting material having no sublimability and having a molecular number of 20 or less or a chain molecule having a length of 10 im or less is defined as a medium-molecular-weight organic light-emitting material.
- polymer organic light emitting materials As an example, a polythiophene (P ED OT) film of 20 nm is provided as a hole injection layer by a spin coating method, and a para- phenylene vinylene (P PV) film of about 100 nm is provided thereon as a light emitting layer. A laminated structure may be provided. If a 7T conjugated polymer of PPV is used, the emission wavelength can be selected from red to blue. It is also possible to use an inorganic material such as silicon carbide for the charge transport layer and the charge injection layer. Known materials can be used for these organic light emitting materials and inorganic materials.
- a cathode 714 made of a conductive film is provided on the light emitting layer 713.
- an alloy film of aluminum and lithium is used as the conductive film.
- a known MgAg film an alloy film of magnesium and silver
- a conductive film made of an element belonging to Group 1 or 2 of the periodic table or a conductive film to which those elements are added may be used.
- the light emitting element 715 is completed when the cathode 714 is formed.
- the light-emitting element 715 here refers to a diode formed by the pixel electrode (anode) 711, the luminescent layer 713, and the cathode 714.
- the passivation film is made of an insulating film including a carbon film, a silicon nitride film, a nitrogen-containing carbon film (CN), or a silicon nitride oxide film.
- the insulating film is used as a single layer or a laminated layer.
- the passivation film it is preferable to use a film having good coverage as the passivation film, and it is effective to use a carbon film, particularly a DLC film. Since the DLC film can be formed in a temperature range from room temperature to 100 ° C or less, the light-emitting layer has low heat resistance. A film can be easily formed above 13 as well. In addition, the DLC film has a high blocking effect against oxygen, and can suppress the oxidation of the light emitting layer 7 13. Therefore, it is possible to prevent the problem that the light emitting layer 7 13 is oxidized during the subsequent sealing step.
- a sealing material 7 17 is provided on a passivation film (not shown), and a power bar material 7 20 is bonded.
- An ultraviolet-curing resin may be used as the sealing material 717, and it is effective to provide a substance having a moisture absorbing effect or a substance having an antioxidant effect inside.
- the cover material 720 is formed of a glass substrate, a quartz substrate, a plastic substrate (including a plastic film), or a flexible substrate having a carbon film (preferably a DLC film) formed on both surfaces thereof.
- an aluminum film (A1ON, A1N, A1O, etc.), SiN, etc. can be used.
- a display device having a structure as shown in FIG. 11 is completed.
- the process from the formation of the puncture 712 to the formation of the passivation film (not shown) is continuously performed without releasing the air using a multi-chamber one-type (or in-line type) film forming apparatus. Is effective. Further, it is possible to further develop and continuously process up to the step of bonding the cover material 720 without releasing it to the atmosphere.
- an impurity region overlapping the gate electrode with an insulating film interposed therebetween an impurity region overlapping the gate electrode with an insulating film interposed therebetween. Therefore, an n-channel TFT that is resistant to deterioration due to the hot carrier effect can be formed. Therefore, a highly reliable display device can be realized.
- logic circuits such as a signal division circuit, a DZA converter, an op amp, and a correction circuit can be formed on the same insulator, and furthermore, a memory and a microprocessor can be formed. sell.
- a sealing film 718 using the same material as the wiring is formed at the end of the substrate serving as a sealing region according to the present invention.
- the sealing film is formed so as to cover (cover) the lower film. Since the insulating layer, especially the insulating film containing a hygroscopic organic material, does not need to come into contact with the outside atmosphere, the method for coating and blocking the edge may be used in Embodiment 1 or 2 or a combination thereof. It is not limited to the structure of FIG. Therefore, the end of the panel may be covered with a pixel electrode, a bank, a passivation film, a cathode, or the like stacked above the wiring, or may be covered with two or more layers, or any combination of films.
- a structure in which a sealing film is formed in the opening and the lower film is separated into an inner region and an outer region in the display device to prevent intrusion of contaminants may be employed.
- a structure in which the insulating layer at the end of the display device is covered with a sealing film made of the same material, and the opening formed in the insulating layer is covered with the sealing film See Figure 20. In Fig.
- 20 9000 is a sealed area
- 9001 is a peripheral circuit
- 9002 is a pixel
- 9003 and 9006 are p-channel TFTs
- 9004 and 9005 are n-channel TFTs
- 2000 is a substrate
- 2001 is a wiring
- 20 1 1 and 20 14 are electrodes (anode or cathode)
- 2012 is a bank
- 2013 is a light emitting layer
- 2015 is a light emitting element
- 2018 is an opening
- 2019 is a sealing film covering the opening 20 18 and side edges.
- 20 17 is a seal material. When covering with a conductive film, short circuit inside the display device, etc. In order to avoid this, it is necessary to separate from the internal area of the display device and laminate only in the sealed area as shown in FIG.
- FIG. 21 shows an example of using a laminated structure of a film of the same material as the wiring and a film of the same material as the ITO as the sealing film.
- 950 is a sealed region
- 950 1 is a peripheral circuit portion
- 950 is a pixel portion
- 950, 950 are p-channel TFTs
- 950, 95 0 5 is an ⁇ -channel type TFT
- 2 100 is a substrate
- 2 101 is a wiring
- 2 1 1 and 2 1 1 4 are electrodes (anode or cathode)
- 2 1 1 2 is a bank
- 2 1 1 3 Is a light-emitting layer
- 2 11 5 is a light-emitting element
- 2 11 8 is an opening
- 2 11 a, 21 9 b is an opening 2 11 18 and a sealing film (a protective film) covering a side end.
- 2 1 17 are sealing materials.
- a highly reliable display device can be manufactured without increasing the number of steps, regardless of which film is used as a sealing film in any combination of the films constituting the display device.
- the sealing film formed on the outermost side as the sealing film and exposed to the outside air containing external moisture and oxygen needs to be a dense film capable of blocking moisture and oxygen.
- the sealing material is formed on a part of the sealing film, but may be formed so as to cover the entire sealing film.
- FIG. 15 shows the state of light emission of the display device having the conventional structure
- FIG. 16 shows the state of light emission of the display device having the structure using the present embodiment 190 hours after storage under the above conditions.
- the photographs in FIGS. 15 and 16 show the state of light emission at nine locations in the pixel region where light is emitted.
- the non-light-emitting region extends from the edge of the display device toward the center. This is a deterioration called shrink, as described above, because contaminants such as water and oxygen have entered the inside of the display device. In comparison, Figure 16 shows little such degradation. This means that contaminants such as water and oxygen were blocked by the present invention and could not enter the display device.
- the sealing film prevents the film such as the interlayer film from coming into direct contact with the atmosphere outside the display device. For this reason, it was possible to prevent water and oxygen outside the display device from entering the display device through an interlayer film or the like or a gap between the films. Therefore, it was possible to prevent various deteriorations such as contamination of the inside of the display device caused by water and oxygen, deterioration of electric characteristics, dark spot shrinkage, etc., thereby improving the reliability of the display device. . Further, since the present invention uses a film of the same material as the film constituting the display device as a sealing film, a highly reliable display device can be manufactured without increasing the number of steps.
- the display device manufactured as described above has a structure for blocking contaminants in the sealing region at the end of the display device, the operation characteristics and reliability of the display device can be sufficient. . And such a display device is used for various electronic devices. W 200
- It can be used as a display unit of a container.
- a display device is manufactured by using the TFT manufacturing method for manufacturing the active matrix substrate shown in Embodiment 1.
- FIG. 10 is a cross-sectional view of the display device of this example.
- 50,000 is a sealed region
- 5001 is a peripheral circuit portion
- 5002 is a pixel portion
- 5003 and 506 are p-channel TFTs
- 5 is an ⁇ -channel type TF II
- 100 is a substrate
- 1001 is a wiring
- 1011, and 11014 are electrodes (anode or cathode)
- 1012 is a bank (partition)
- Reference numeral 13 denotes a light emitting layer
- reference numeral 101 denotes a light emitting element
- reference numeral 110 18 denotes an opening
- reference numeral 110 denotes a sealing film (protective film) that covers the opening 108 and side edges.
- 17 is a sealing material.
- the electrode 101 is made of a transparent conductive film.
- a compound of indium oxide and tin oxide a compound of indium oxide and zinc oxide, zinc oxide, tin oxide, or indium oxide can be used. Further, a material obtained by adding gallium to the transparent conductive film may be used.
- a film made of the same material as the electrode 101 may be formed as a sealing film on the source electrode and the drain electrode.
- a non-photosensitive acrylic, a photosensitive acrylic, or an inorganic material can be used for the interlayer insulating film below the source electrode and the drain electrode.
- Non-photosensitive acrylic or inorganic materials When opening a contact in an interlayer film, it is necessary to use dry etching. Etching by dry etching may cause unevenness in the etched cross section, which may degrade the film forming properties of the source electrode and the drain electrode. As shown in Fig.
- An electrode 104 made of a conductive film is provided on the light emitting layer 101.
- an alloy film of aluminum and lithium is used as the conductive film.
- a known Mg Ag film an alloy film of magnesium and silver
- a conductive film made of an element belonging to Group 1 or 2 of the periodic table or a conductive film to which these elements are added may be used.
- the sealing film 110 19 is formed of the same material as the electrode 110 14. An opening reaching the substrate is formed, and a sealing film is formed so as to cover the opening. A conductive film that functions as both an anode and a sealing film is continuously formed to the outside of the peripheral circuit. Even if moisture or oxygen enters through the interlayer film, they can be blocked by the sealing film of the present invention. Therefore, deterioration of the EL display device due to moisture or oxygen can be prevented.
- the electrode 110 14 and the sealing film 110 19 may be connected to each other, or may be formed separately using a mask or the like.
- a film made of the same material as the cathode is used as the sealing film.
- a passivation film is formed on the cathode (second electrode), and a sealing film is formed using the same material as the passivation film. May be.
- first and second embodiments and the first and second embodiments may be combined, or a plurality of them may be used in combination.
- connection structure between a pixel electrode and a source / drain electrode and the structure of a sealing film are different from each other in the display device manufactured in Embodiment 2 or Embodiment 3 will be described with reference to FIGS.
- 800 is a sealed region
- 8001 is a peripheral circuit portion
- 8002 is a pixel portion
- 8003 and 8006 are p-channel TFTs
- 8004 and 8005 are n.
- 110 1 is substrate, 110 1 is wiring, 1 1 1 1 and 1 1 1 4 are electrodes (anode or cathode), 1 1 2 is flattening layer, 1 1 3 is 1 Light-emitting layer, 1 1 1 5 is a light-emitting element, 1 1 1 6 is a bank, 1 1 1 8 is an opening, 1 1 1 9 is an opening 1 1 1 8 ), 1 1 1 7 are sealing materials.
- a flattening layer 1 1 1 2 is provided on the wiring 1 101 which is a source electrode and a drain electrode, and an electrode 1 1 1 1 is provided on the flattening layer 1 1 1 2.
- the planarizing layer 111 may be an inorganic insulating film or an organic insulating film.
- the use of a flattening layer is more effective in improving flatness.
- Non-photosensitive acrylic, photosensitive acrylic, inorganic material, and the like can be used for the flattening layer 111.
- a material in which a skeleton structure is formed by a bond between silicon and oxygen may be used.
- a typical example is a siloxane-based polymer. More specifically, a material having a skeleton structure formed by a bond between silicon and oxygen and having at least hydrogen as a substituent, or a fluorine, alkyl group, or aromatic hydrocarbon as a substituent It is a material with at least one of them.
- the light emitting layer is planarized before forming the electrode (pixel electrode) so that the light emitting layer can be formed as flat as possible.
- An electrode 111 made of a conductive film is provided on the light emitting layer 111.
- an alloy film of aluminum and lithium is used as the conductive film.
- a known Mg Ag film an alloy film of magnesium and silver
- a conductive film made of an element belonging to Group 1 or 2 of the periodic table or a conductive film to which these elements are added may be used.
- the sealing film 111 is formed of the same material as the electrode 111. An opening reaching the substrate is formed, and a sealing film is formed so as to cover the opening. A conductive film having the function of both a cathode and a sealing film is continuously formed to the outside of the peripheral circuit to protect the internal EL elements and TFTs. Even if moisture and oxygen enter through the interlayer film, they can be blocked by the sealing film of the present invention. Therefore, deterioration of the EL display device due to moisture and oxygen can be prevented. Further, the electrodes 111 and the sealing film 111 may be connected to each other, or may be separated by using a mask or the like. May be implemented.
- a film made of the same material as the cathode is used as the sealing film.
- a passivation film is formed on the cathode (second electrode), and a sealing film is formed using the same material as the passivation film. May be.
- the sealing structure is applied to the case of the EL display device.
- the sealing structure of the present invention can be applied to the liquid crystal display device having the structure using the flattening film of the first embodiment and the present embodiment.
- a display device using a liquid crystal instead of a light-emitting element for a display portion may be manufactured using the sealing structure of the present invention.
- This embodiment may be combined with the first or second embodiment and the first, second, and third embodiments, or may be used by combining a plurality of them.
- various display devices active matrix display devices
- the present invention can be applied to various electronic devices in which these display devices are incorporated in a display unit.
- Such electronic devices include video cameras, digital cameras, and projects. Yuichi, head-mounted display (goggle type display), car navigation, car stereo, personal computer, portable information terminal (mobile computer, mobile phone or electronic book, etc.). Examples of these are shown in Fig. 12, Fig. 13 and Fig. 14.
- FIG. 12A shows a personal computer, which includes a main body 3001, an image input section 3002, a display section 303, a keyboard 3004, and the like.
- the personal computer of the present invention is completed by applying the display device manufactured by the present invention to the display portion 3003.
- Fig. 12 (B) shows a video camera.
- the video camera of the present invention is completed by applying the display device manufactured by the present invention to the display section 3102.
- Fig. 12 (C) shows the mobile computer (mobile computer).
- the display device manufactured according to the present invention is referred to as a display unit 320.
- Fig. 1 2 (D) shows a goggle-type display.
- the display portion 3302 uses a flexible substrate as a substrate, and the display portion 3302 is curved to produce a goggle-type display. It also realizes a lightweight and thin goggle type display.
- the gordal display of the present invention is completed.
- Fig. 12 (E) shows a player using a recording medium on which a program is recorded (hereinafter referred to as a recording medium).
- the player can use a DVD (Digital Versatile Disc), CD, or the like as a recording medium, and can enjoy music, movies, games, and the Internet.
- the recording medium of the present invention is completed by applying the display device manufactured by the present invention to the display portion 3402.
- FIG. 12F shows a digital camera including a main body 3501, a display section 3502, an eyepiece section 3503, an operation switch 3504, an image receiving section (not shown), and the like.
- the digital camera of the present invention is completed by applying the display device manufactured by the present invention to the display portion 3502.
- FIG. 13A shows a front type projector 1 including a projection device 3601, a screen 3602, and the like.
- the display device manufactured by the present invention to the liquid crystal display device 388 that constitutes a part of the projection device 3601, and other drive circuits, the front type projector of the present invention is completed.
- FIG. 13B shows a rear-type projector, which includes a main body 3701, a projection device 3702, a mirror 3703, a screen 3704, and the like.
- FIG. 13 (C) is a diagram showing an example of the structure of the projection devices 3601 and 3702 in FIGS. 13 (A) and 13 (B).
- Projection device 360 1, 3702 is a light source optical system 3801, mirror 3802, 3804-3806, dichroic mirror 3803, prism 3807, liquid crystal display device 380, It is composed of a phase difference plate 38 09 and a projection optical system 38 10.
- the projection optical system 3810 is constituted by an optical system including a projection lens.
- the present embodiment shows an example of a three-plate type, it is not particularly limited, and may be a single-plate type, for example.
- the practitioner In the optical path indicated by the arrow in FIG. 13 (C), the practitioner appropriately places an optical system such as an optical lens, a film having a polarizing function, a film for adjusting a phase difference, and an IR film. It may be provided.
- FIG. 13D is a diagram showing an example of the structure of the light source optical system 3801 in FIG. 13C.
- the light source optical system 380 1 includes a reflector 381 1 1, a light source 380 1 2, a lens array 381 3, 3 814, a polarization conversion element 381 5, It consists of a lens 3 8 16.
- the light source optical system shown in FIG. 13 (D) is an example and is not particularly limited.
- the practitioner may appropriately provide an optical system such as an optical lens, a film having a polarizing function, a film for adjusting a phase difference, and an IR film in the light source optical system.
- FIG. 14 (A) shows a mobile phone, which is composed of the main body 3901, audio output section 3902, audio input section 3903, display section 3904, operation switch 3905, antenna 3906, etc. Including.
- the mobile phone of the present invention is completed by applying the display device manufactured by the present invention to the display portion 3904.
- FIG. 14B illustrates a portable book (electronic book), which includes a main body 401, display portions 4002 and 4003, a storage medium 4004, an operation switch 4005, an antenna 4006, and the like.
- the portable book of the present invention is completed.
- FIG. 14C illustrates a display, which includes a main body 4101, a support 4102, a display section 4103, and the like.
- the display portion 4103 is manufactured using a flexible substrate, and can realize a lightweight and thin display.
- the display section 4103 can be curved.
- the display of the present invention is completed by applying the display device manufactured by the present invention to the display portion 4103.
- the applicable range of the present invention is extremely wide, and can be applied to electronic devices in various fields.
- 2000 is a substrate, 200 is a wiring, 201 is an electrode (anode or cathode), 201 is a light emitting layer, 210 is an electrode (anode or cathode), Reference numeral 115 denotes a light emitting element, and reference numeral 210 denotes a sealing material.
- a sealing film 201 is formed by the same process and the same material as the wiring 200 1.
- An opening 208 reaching the substrate 200 is formed in the sealing region, and the opening 210 is covered with the sealing film 201, and the insulating layer at the end of the display device is exposed. It is a structure that covers the area marked with.
- reference numeral 210 denotes a substrate
- reference numeral 210 denotes a wiring
- reference numeral 211 denotes an electrode
- 201 13 is a light emitting layer
- 211 is an electrode (anode or cathode)
- 211 is a light emitting element
- 211 is a sealing material.
- a sealing film 2 119 a formed of the same material as the wiring 211 and a sealing film 211 b formed of the same material as the pixel electrode 211 are used. .
- the sealing films 211 a and 211 b can be formed simultaneously with the wiring 211 and the pixel electrode 211 in the same process.
- An opening 2 11 18 reaching the substrate 2 100 is formed in the sealing area, and the opening 2 11 18 is covered with the sealing films 2 1 1 9 a and 2 1 1 9 b, and a display device is provided. The extreme layer at the end covers the exposed part.
- the opening 211 of the sealing region is formed until the substrate reaches the substrate.
- a dense base film may be formed. Since the opening may be formed in a hydrophilic film through which moisture passes, the formation depth of the opening may be set as appropriate.
- This embodiment is an example of the present invention, and the present invention is not limited to this embodiment.
- the sealing material even if moisture or oxygen enters through the sealing material, an interlayer film such as acryl exposed to the outside, or the planarizing layer 201, moisture and oxygen are blocked by the sealing film.
- the EL element and the TFT inside the display device can be protected. Therefore, deterioration of the EL display device due to moisture or oxygen can be prevented.
- the ability to block contaminants such as moisture is further improved.
- FIG. 23 shows a display device having the structure shown in FIG. 20 of the present embodiment
- FIG. 24 shows a display device having the structure shown in FIG. 21. Show the situation.
- the photographs in Fig. 23 and Fig. 24 show the light emission at nine locations in the pixel area where light is emitted.
- the luminance starts to deteriorate slightly from the upper right and lower left corners, but no severe deterioration is observed.
- the sealing film in FIG. 24 was further formed into a laminated structure, such deterioration was hardly observed. This means that since the opening and the end were covered with the sealing film, moisture was cut off multiple times and could not enter the display device. In addition, it was confirmed that by stacking a plurality of sealing films, the blocking ability was improved and the deterioration of the display device could be prevented.
- the film such as the interlayer film is not in direct contact with the atmosphere outside the display device due to the sealing film. For this reason, it was possible to prevent water or oxygen outside the display device from entering the display device through an interlayer film or the like or a gap between the films.
- the sealing film can prevent various deteriorations such as contamination of the inside of the display device caused by water and oxygen, deterioration of electrical characteristics, dark spot shrinkage, etc., and improve the reliability of the display device I was able to do it.
- the present invention uses a film of the same material as the film forming the display device as a sealing film, a highly reliable display device can be manufactured without increasing the number of steps. .
- FIG. 1 a display device having a different wiring arrangement from the end portion of the display device will be described with reference to FIGS. 1, 19, 22, and 25.
- FIG. 1 a display device having a different wiring arrangement from the end portion of the display device will be described with reference to FIGS. 1, 19, 22, and 25.
- FIG. 1 a display device having a different wiring arrangement from the end portion of the display device will be described with reference to FIGS. 1, 19, 22, and 25.
- FIG. 19 shows an enlarged view of the section 4 11.
- Figure 19 shows the conventional wiring arrangement, 1901 is the cathode, 1902 is the first anode, 1903 is the 2nd anode, and 1904 is the 3rd anode .
- the cathode 1901 which is the outermost wiring, has an FPC connection portion inside. For this reason, the outermost wiring cannot completely cover the end of the display device. Therefore, moisture and the like enter through the gap, and the deterioration of the display device cannot be prevented.
- FIG. 22 shows the layout of the wiring of the display device of the present invention.
- the first anode 1902 which has the connection with the FPC most outside the device, is arranged outermost, and the cathode 1901 is arranged inside. Therefore, it is possible for the outermost wiring to completely cover the end of the display device without gaps other than the FPC connection portion, and it is possible to sufficiently block moisture.
- the wiring may be arranged such that the outermost wiring is connected to other wiring such as FPC on the outermost side, and the type, polarity and number of the wiring may be set as appropriate.
- FIG. 25 shows the state of light emission 500 hours after the display device having the structure of FIGS. 20 and 22 is stored under the above-described conditions.
- the inside of the display device caused by water, oxygen, etc.
- Various deteriorations such as contamination of the display, deterioration of electric characteristics, and dark spot shrinkage can be prevented, and the reliability of the display device can be further improved.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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AU2003288999A AU2003288999A1 (en) | 2002-12-19 | 2003-12-10 | Display unit and method of fabricating display unit |
KR1020057010889A KR100890957B1 (ko) | 2002-12-19 | 2003-12-10 | 표시장치 및 표시장치의 제작 방법 |
CN2003801067189A CN1729719B (zh) | 2002-12-19 | 2003-12-10 | 显示装置和显示装置的制作方法 |
JP2005502613A JP4906051B2 (ja) | 2002-12-19 | 2003-12-10 | 表示装置 |
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JP2002-368984 | 2002-12-19 | ||
JP2002368984 | 2002-12-19 | ||
JP2003139679 | 2003-05-16 | ||
JP2003-139679 | 2003-05-16 |
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WO2004057920A1 true WO2004057920A1 (ja) | 2004-07-08 |
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PCT/JP2003/015764 WO2004057920A1 (ja) | 2002-12-19 | 2003-12-10 | 表示装置及び表示装置の作製方法 |
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US (2) | US7190115B2 (ja) |
JP (11) | JP4906051B2 (ja) |
KR (1) | KR100890957B1 (ja) |
CN (2) | CN1729719B (ja) |
AU (1) | AU2003288999A1 (ja) |
TW (1) | TWI322455B (ja) |
WO (1) | WO2004057920A1 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
US20080116795A1 (en) | 2008-05-22 |
JP6391634B2 (ja) | 2018-09-19 |
CN1729719B (zh) | 2010-09-15 |
JP2012094524A (ja) | 2012-05-17 |
KR20050084297A (ko) | 2005-08-26 |
JP5921517B2 (ja) | 2016-05-24 |
JP2016001327A (ja) | 2016-01-07 |
AU2003288999A1 (en) | 2004-07-14 |
TW200415698A (en) | 2004-08-16 |
JP2016219433A (ja) | 2016-12-22 |
US8179040B2 (en) | 2012-05-15 |
TWI322455B (en) | 2010-03-21 |
JP2018036661A (ja) | 2018-03-08 |
JP5969203B2 (ja) | 2016-08-17 |
JP2019091705A (ja) | 2019-06-13 |
JP2020107610A (ja) | 2020-07-09 |
JP6085012B2 (ja) | 2017-02-22 |
CN101882668A (zh) | 2010-11-10 |
JP2017224616A (ja) | 2017-12-21 |
JP6553150B2 (ja) | 2019-07-31 |
JP2014063748A (ja) | 2014-04-10 |
JPWO2004057920A1 (ja) | 2006-04-27 |
JP2021185568A (ja) | 2021-12-09 |
US7190115B2 (en) | 2007-03-13 |
JP6691246B2 (ja) | 2020-04-28 |
JP2021192366A (ja) | 2021-12-16 |
KR100890957B1 (ko) | 2009-03-27 |
CN1729719A (zh) | 2006-02-01 |
JP4906051B2 (ja) | 2012-03-28 |
JP6491276B2 (ja) | 2019-03-27 |
US20040185301A1 (en) | 2004-09-23 |
CN101882668B (zh) | 2012-05-09 |
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