WO2010092797A1 - 発光素子、表示装置、および発光素子の製造方法 - Google Patents
発光素子、表示装置、および発光素子の製造方法 Download PDFInfo
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- WO2010092797A1 WO2010092797A1 PCT/JP2010/000783 JP2010000783W WO2010092797A1 WO 2010092797 A1 WO2010092797 A1 WO 2010092797A1 JP 2010000783 W JP2010000783 W JP 2010000783W WO 2010092797 A1 WO2010092797 A1 WO 2010092797A1
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
- H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
Definitions
- the present invention relates to a light emitting element, a display device, and a method for manufacturing the light emitting element, and more particularly to an organic EL element used for a flat display or the like.
- a light emitting layer is formed by patterning using an ink jet method.
- the ink jet method is a method suitable for forming a uniform thin film pattern in a minute region, and is a composition ink (hereinafter simply referred to as “ink”) containing an organic EL material in each pixel region defined by a bank. ) Is dropped and dried to form a uniform thin film pattern in these pixel regions.
- the bank surface is subjected to a liquid repellent treatment by fluorine plasma.
- the wettability of the bank surface with respect to the ink deteriorates, and the dropped ink does not easily flow out to the adjacent pixel region beyond the bank, so that high-definition patterning is possible.
- Patent Document 1 discloses that the bank has a two-layer structure of an upper layer portion made of a water-repellent material and a lower layer portion made of a lyophilic material, so that the upper layer portion of the bank has poor ink wettability.
- a technique for patterning a light emitting layer with higher definition so as to make it difficult for the ink to flow out, improve the wettability with respect to the ink in the lower layer portion of the bank, and make it easier for the ink to stay in the pixel region.
- the manufacturing cost of the organic EL element increases as the number of processes increases as compared with the case of a single-layer structure.
- an object of the present invention is to provide a light emitting element in which a light emitting layer is patterned with high definition and can be manufactured at low cost.
- a light-emitting element includes: A first electrode, a charge injecting and transporting layer, a light emitting layer, and a second electrode are laminated in this order, and at least the light emitting layer is defined by a bank, and the bank has at least a liquid repellent surface.
- the charge injecting and transporting layer is made of a metal compound having a lyophilic property compared with the surface of the bank, and the charge injecting and transporting layer has a level at the bottom of the bank in a region defined by the bank. It is characterized in that it is formed in a recessed structure that sinks more.
- the charge injecting and transporting layer is formed in a recessed structure that sinks below the level of the bank bottom surface in the region defined by the bank.
- the lower portion of the ink dropped on the remaining area can be stored in the recessed portion.
- the charge injection / transport layer is made of a lyophilic metal compound and has good wettability with respect to the ink, the inner surface of the recessed portion can keep the ink in the recessed portion stably. it can. Therefore, it is difficult for ink to flow out to the adjacent pixel region beyond the bank, and high-definition patterning of the light emitting layer is possible.
- the recessed portion can be easily formed by, for example, dissolving a part of the charge injecting and transporting layer with pure water, and the complicated structure for making the bank into a two-layer structure like the light emitting element of Patent Document 1. Since a process is unnecessary, it can be implemented at low cost.
- FIG. 1 It is a schematic diagram which shows the lamination
- FIG. 8 is a process diagram illustrating the method for manufacturing the light emitting element according to the first embodiment, following FIG. 7. It is a schematic diagram which shows the lamination
- a light-emitting element is a light-emitting element in which a first electrode, a charge injection transport layer, a light-emitting layer, and a second electrode are stacked in this order, and at least the light-emitting layer is defined by a bank, At least the surface of the bank is liquid repellent, while the charge injection transport layer is made of a metal compound having a lyophilic property compared to the surface of the bank, and the charge injection transport layer is The region defined by the above is characterized in that it is formed in a recessed structure that sinks below the level of the bank bottom surface.
- charge injection / transport layer is a generic term for a hole injection layer, a hole transport layer, a hole injection / transport layer, an electron injection layer, an electron transport layer, an electron injection / transport layer, and the like.
- the charge injection transport layer may be composed of a hole injection layer, may be composed of a hole transport layer, or may be composed of two layers, a hole injection layer and a hole transport layer.
- the hole injection / transport layer may be composed of an electron injection layer, an electron transport layer, or an electron injection layer and an electron transport layer. It may be comprised, and may be comprised by the electron injection transport layer.
- the terms “lyophilic” and “liquid repellency” are used in a relative sense. As described above, at least the surface of the bank is lyophobic. On the other hand, when the charge injecting and transporting layer is made of a lyophilic metal compound, the surface of the charge injecting and transporting layer is more parent than the surface of the bank. It is liquid and the surface of the bank is more liquid repellent than the surface of the charge injecting and transporting layer. The surface of the charge injection / transport layer that is lyophilic is relatively wettable with respect to the ink, and the surface of the bank that is liquid repellent is relatively poorly wettable with respect to the ink.
- the lyophilicity and liquid repellency can be defined by, for example, the contact angle of the ink with respect to the surface of the bank or the charge injecting and transporting layer. For example, when the contact angle is 10 ° or less, The case where the contact angle is 35 ° or more can be defined as liquid repellency.
- the recessed structure is cup-shaped.
- the recessed structure is a structure that sinks from a portion corresponding to a lower edge of the bank.
- the metal compound is a metal oxide, a metal nitride, or a metal oxynitride.
- the light emitting layer includes a layer made of a polymer material.
- the charge injecting and transporting layer extends in the direction of an adjacent pixel along the bank bottom surface.
- a light-emitting element is a light-emitting element in which a first electrode, a charge injection transport layer, a light-emitting layer, and a second electrode are stacked in this order, and at least the light-emitting layer is defined by a bank.
- the charge injection / transport layer includes a metal compound that is soluble in a predetermined solvent, and has a recessed portion formed by being dissolved by the predetermined solvent, and the recessed portion of the charge injection / transport layer.
- the charge injecting and transporting layer has a lyophilic property
- the bank has a lyophobic property
- the predetermined solvent is a developer for removing a part of the resist film when forming the bank, and / or a resist residue remaining after the bank is formed. It is a cleaning liquid for cleaning.
- the charge injection transport layer is a hole injection layer containing a metal oxide.
- the metal oxide is tungsten or molybdenum oxide.
- a display device includes any of the light-emitting elements described above.
- a method for manufacturing a light-emitting element includes a first step of forming a first electrode on a substrate, and a metal compound that is soluble in a predetermined solvent above the first electrode.
- the adhering resist residue is cleaned using a cleaning liquid, and a part of the thin film is dissolved by the cleaning liquid to form a charge injection transport layer having a recessed portion having an inner bottom surface and an inner side surface continuous to the inner bottom surface.
- a method for manufacturing a light-emitting element in which a first step of forming a first electrode on a substrate and dissolution in a predetermined solvent above the first electrode are possible.
- a second step of forming a thin film containing a metal compound, and forming a resist film containing a resist material on the thin film, etching with a developer, forming a bank, and adhering to the surface of the thin film with the developer A third step of cleaning a resist residue and dissolving a part of the thin film to form a charge injection transport layer having a recessed portion having an inner bottom surface and an inner surface continuous to the inner bottom surface;
- a fourth step of forming a light emitting layer by dropping ink into a defined region, applying the ink along the inner bottom surface and the inner side surface of the charge injection transport layer, and drying, and above the light emitting layer, Form the second electrode And 5 steps, and having a.
- FIG. 1 is a schematic diagram illustrating a stacked state of each layer of the light emitting device according to the first embodiment
- FIG. 2 is an enlarged view of a portion surrounded by a one-dot chain line in FIG.
- the light emitting device is a top emission type organic EL device in which RGB pixels are arranged in a matrix or a line, and each pixel is formed on a substrate 1. It has a laminated structure in which each layer is laminated.
- a first electrode 2 as an anode is formed in a matrix shape or a line shape, and an ITO (indium tin oxide) layer 3 is formed on the first electrode 2.
- the hole injection layer 4 as a charge injection transport layer is laminated
- the ITO layer 3 is laminated only on the first electrode 2, whereas the hole injection layer 4 is formed not only above the first electrode 2 but also over the entire upper surface side of the substrate 1.
- a bank 5 that defines pixels is formed, and a light emitting layer 6 is laminated in a region defined by the bank 5. Further, on the light emitting layer 6, the electron injection layer 7, the second electrode 8 serving as a cathode, and the sealing layer 9 are respectively connected to the adjacent pixels beyond the region defined by the bank 5. Is formed.
- the area defined by the bank 5 has a multilayer laminated structure in which the ITO layer 3, the hole injection layer 4, the light emitting layer 6, and the electron injection layer 7 are laminated in that order. It is configured.
- the functional layer may include other layers such as a hole transport layer and an electron transport layer.
- the substrate 1 is, for example, soda glass, non-fluorescent glass, phosphate glass, borate glass, quartz, acrylic resin, styrene resin, polycarbonate resin, epoxy resin, polyethylene, polyester, silicone resin, or alumina. It is made of an insulating material.
- the first electrode 2 is made of Ag (silver).
- the first electrode 2 is, for example, APC (silver, palladium, copper alloy), ARA (silver, rubidium, gold alloy), MoCr (molybdenum and chromium alloy), NiCr (nickel and chromium alloy), etc. It may be formed by. In the case of a top emission type light emitting element, it is preferably formed of a light reflective material.
- the ITO layer 3 is interposed between the first electrode 2 and the hole injection layer 4 and has a function of improving the bonding property between the layers.
- the hole injection layer 4 contains a metal compound that can be dissolved in a predetermined solvent, and is specifically formed of WOx (tungsten oxide) or MoWOx (molybdenum-tungsten oxide).
- the hole injection layer 4 may be formed of a metal compound having a lyophilic property compared to the surface of the bank 5, and examples of the metal compound having a lyophilic property include metal oxides and metal nitrides. Or metal oxynitride is mentioned.
- the hole injection layer 4 When the hole injection layer 4 is formed of a metal oxide, holes can be easily injected, and electrons can effectively contribute to light emission in the light emitting layer 6, so that good light emission characteristics can be obtained.
- the metal oxide include Cr (chromium), Mo (molybdenum), W (tungsten), V (vanadium), Nb (niobium), Ta (tantalum), Ti (titanium), Zr (zirconium), and Hf ( Hafnium), Sc (scandium), Y (yttrium), Th (thorium), Mn (manganese), Fe (iron), Ru (ruthenium), Os (osmium), Co (cobalt), Ni (nickel), Cu ( Copper), Zn (zinc), Cd (cadmium), Al (aluminum), Ga (gallium), In (indium), Si (silicon), Ge (germanium), Sn (tin), Pb (lead), Sb ( Antimony), Bi (bismuth), and oxides such
- the metal constituting the metal compound is preferably a transition metal. Since the transition metal takes a plurality of oxidation numbers, it can take a plurality of potential levels. As a result, hole injection is facilitated and the driving voltage can be reduced.
- the hole injection layer 4 extends in the direction of the adjacent pixel along the bottom surface of the bank 5, and in a region defined by the bank 5, a depression recessed below the level of the bottom surface of the bank 5. It is formed in a structure and includes a recessed portion 4a (a portion indicated by mesh hatching in FIG. 2) formed by being dissolved by a predetermined solvent. In the hole injection layer 4, only the region defined by the bank 5 is thinner than the other regions, and the film thickness of the other regions is substantially uniform throughout. Since the hole injection layer 4 is made of a lyophilic metal compound, the inner surface 4b of the recessed portion 4a has good wettability with respect to ink. Therefore, the ink dropped on the area defined by the bank 5 tends to adhere to the inner surface 4b of the recessed portion 4a, and the ink tends to stay in the area defined by the bank 5.
- the hole injection layer 4 only needs to have a recessed structure that sinks below the level of the edge 5a at least on the bottom surface of the bank 5, and does not need to have a recessed structure that sinks below the level of the entire bottom surface.
- the structure is depressed from the level of the edge 5a on the bottom surface, but is not depressed from the level of the central portion 5b on the bottom surface.
- FIG. As shown by 5c, the level of the central portion 5b is aligned with the end edge portion 5a, and the bottom surface of the bank 5 may be flattened, for example, so that a recessed structure that sinks below the level of the entire bottom surface of the bank 5 may be used.
- the hole injection layer 4 has a recessed structure that sinks from a portion corresponding to the lower end edge 5d of the bank. Specifically, the region defined by the bank 5 on the upper surface of the hole injection layer 4 is formed from the portion corresponding to the lower end edge 5d. It sinks substantially vertically downward with respect to the upper surface of 1. As described above, in the case of the recessed structure that sinks from the portion corresponding to the lower end edge 5d of the bank 5, the film thickness of the light emitting layer 6 can be made uniform over a wide range, and luminance unevenness hardly occurs in the light emitting layer 6. .
- the hole injection layer 4 is not limited to the recessed structure that sinks from the portion corresponding to the lower end edge 5d of the bank 5, but, for example, as illustrated in FIG. It is good also as a structure which sank from the approached part. Further, a concave structure may be adopted that sinks from a portion closer to the center of the pixel than the portion corresponding to the lower end edge 5d of the bank 5. In this case, the contour of the concave portion 4a is indicated by a two-dot chain line 10 in FIG. Shape.
- the recessed structure of the hole injection layer 4 is cup-shaped. More specifically, the inner surface 4b of the recessed portion 4a is substantially parallel to the upper surface of the substrate 1 and is flat on the bottom surface 6a of the light emitting layer 6. The inner bottom surface 4c is in contact with the inner bottom surface 4c, and the inner side surface 4d extends from the edge of the inner bottom surface 4c in a direction substantially perpendicular to the upper surface of the substrate 1 and contacts the side surface 6b of the light emitting layer 6.
- the recessed structure when the recessed structure is cup-shaped, the presence of the inner side surface 4d makes it difficult for the ink in the recessed portion 4a to move in a direction parallel to the upper surface of the substrate 1, and thus the region defined by the bank 5 Ink can be kept more stable.
- the area of the inner surface 4b of the recessed portion 4a is increased, and the area where the ink and the hole injection layer 4 are in close contact with each other is increased. You can stay stable. Therefore, high-definition patterning of the light emitting layer 6 is possible.
- the recessed structure of the hole injection layer 4 is not limited to a cup shape, and as shown in FIG. 4, for example, the sectional shape of the recessed portion 4a (the portion indicated by hatching in FIG. 4) is a substantially sector shape or a substantially inverted triangle. It may be a dish-like shape.
- the average depth t of the recessed portion 4a is not particularly specified in the present invention, but can be set to 5 to 100 nm, for example. If the average depth t of the recessed portion 4a is 5 nm or more, a sufficient amount of ink can be stored in the recessed portion 4a, and the ink can be stably retained in the region defined by the bank 5. Further, since the light emitting layer 6 is formed without being repelled to the end of the bank 5, a short circuit between the electrodes 2 and 8 can be prevented.
- the average depth t of the recessed portion 4a is determined by measuring the surface contour of the hole injection layer 4 with a stylus profilometer or AFM (atomic force microscope), and calculating the average height of the portion that becomes a peak from the surface contour. The difference from the average height of the valley portion can be obtained and obtained.
- the film thickness of the light emitting layer 6 is not particularly specified.
- the average film thickness h after drying of the light emitting layer 6 is 100 nm or more
- the average depth t of the recessed portions 4a is 100 nm or less.
- the film thickness of the light emitting layer 6 in the region defined by the bank 5 can be made uniform.
- the difference between the average film thickness h of the light emitting layer 6 and the average depth t of the recessed portions 4a is preferably 20 nm or less.
- the average film thickness h of the light emitting layer 6 is too smaller than the average depth t of the recessed portion 4a (for example, when th> 20 nm), as shown in FIG. A portion not in contact with the light emitting layer 6 (a portion where the light emitting layer 6 is not applied) is formed on the inner side surface 4d, and there is a possibility that a short circuit between the electrodes 2 and 8 may occur in that portion.
- the average film thickness h of the light emitting layer 6 is too larger than the average depth t of the recessed portion 4a (for example, when ht> 20 nm), as shown in FIG. Due to the liquid repellency, the film thickness of the bank vicinity portion 6c of the light emitting layer 6 becomes thinner than other portions, the cross-sectional shape of the light emitting layer 6 becomes substantially convex, and uneven light emission due to the difference in film thickness occurs. May occur.
- the inner side surface 4d of the recessed portion 4a only needs to be in contact with at least a part of the side surface 6b of the light emitting layer 6.
- the light emitting layer The inner side surface 4d of the recessed portion 4a comes into contact only with the lower side, which is at least part of the side surface 6b.
- the entire side surface 6b of the light emitting layer 6 includes the inside of the recessed portion 4a. The side surface 4d contacts.
- a lyophilic layer 12 such as an IL layer (intermediate layer) may be formed below the light emitting layer 6 in the recessed portion 4 a of the hole injection layer 4.
- ink is dropped on the upper surface 12a of the lyophilic layer 12 instead of the inner bottom surface 4c of the recessed portion 4a.
- the upper surface 12a is still lyophilic, it is defined by the bank 5. Ink can be kept stable in the area.
- the inner surface 4d of the recessed portion 4a will not come into contact with the ink, so the average film thickness g of the lyophilic layer 12 is the recessed portion. It is preferably thinner than the average depth t of 4a.
- the bank 5 is formed of an organic material such as a resin or an inorganic material such as glass, and has an insulating property.
- organic materials include acrylic resins, polyimide resins, novolac type phenol resins, and examples of inorganic materials include SiO 2 (silicon oxide), Si 3 N 4 (silicon nitride), and the like. It is done.
- the bank 5 preferably has organic solvent resistance, and preferably transmits visible light to a certain degree. Furthermore, since the bank 5 may be subjected to an etching process, a baking process, or the like, it is preferable that the bank 5 be formed of a material having high resistance to these processes.
- Bank 5 has at least a surface having liquid repellency. Therefore, when the bank 5 is formed of a lyophilic material, it is necessary to make the surface lyophobic by performing a water repellency treatment or the like.
- the bank 5 may be a pixel bank or a line bank.
- the bank 5 is formed so as to surround the entire circumference of the light emitting layer 6 for each pixel.
- a bank 5 is formed so as to divide a plurality of pixels into columns or rows, and the bank 5 exists only on both sides in the row direction or both sides in the column direction of the light emitting layer 6. Or the thing of the bank becomes a continuous structure.
- the light emitting layer 6 includes, for example, an oxinoid compound, a perylene compound, a coumarin compound, an azacoumarin compound, an oxazole compound, an oxadiazole compound, a perinone compound, a pyrrolopyrrole compound, a naphthalene compound, an anthracene compound described in JP-A-5-163488.
- the light emitting layer 6 includes a layer made of a polymer material
- the light emitting layer 6 can be formed by a printing technique such as an ink jet method or a nozzle coating method. Compared to the above, there is an effect that it is possible to easily cope with cost reduction for large format.
- the electron injection layer 7 has a function of transporting electrons injected from the second electrode 8 to the light emitting layer 6, and is preferably formed of, for example, barium, phthalocyanine, lithium fluoride, or a combination thereof.
- the second electrode 8 is made of, for example, ITO, IZO (indium zinc oxide) or the like. In the case of a top emission type light emitting element, it is preferably formed of a light transmissive material.
- the sealing layer 9 has a function of preventing the light emitting layer 6 and the like from being exposed to moisture or air, and is made of, for example, a material such as SiN (silicon nitride) or SiON (silicon oxynitride). It is formed. In the case of a top emission type light emitting element, it is preferably formed of a light transmissive material.
- FIG. 7 is a process diagram illustrating a method for manufacturing a light emitting device according to the first embodiment
- FIG. 8 is a process diagram illustrating a method for manufacturing the light emitting device according to the first embodiment following FIG. is there.
- an Ag thin film is formed on a glass substrate 1 by sputtering, for example, and the Ag thin film is formed by photolithography, for example.
- the first electrode 2 is formed in a matrix shape or a line shape by patterning.
- the Ag thin film may be formed by vacuum deposition or the like.
- an ITO thin film is formed by, for example, sputtering, and the ITO layer 3 is formed by patterning the ITO thin film by, for example, photolithography.
- a thin film 11 containing a metal compound that can be dissolved in a predetermined solvent is formed.
- the thin film 11 of WOx or MoWOx is formed by a vacuum deposition method, a sputtering method, or the like so as to have a uniform film thickness over the entire upper surface side of the substrate 1.
- the bank 5 is formed so as to surround each pixel region (region where the first electrode 2 is disposed), for example, by photolithography.
- a resist film for example, a resin film
- a resist pattern is further formed on the resist film, and then an etching process is performed with a developing solution.
- a desired portion is removed to form a bank 5 pattern.
- a CVD method or the like is used. Resist residue adhering to the surface of the thin film 11 remaining after the etching is removed with, for example, hydrofluoric acid.
- a liquid repellent treatment is performed on the surface of the bank 5 as necessary.
- the hole injection layer 4 has a structure in which only the region defined by the bank 5 is thinner than the other regions.
- the concave portion 4a is formed by, for example, the bank 5 on the upper surface of the thin film 11 with pure water at the time of pure water cleaning in which impurities such as hydrofluoric acid remaining on the surface of the bank 5 after resist residue removal is cleaned with pure water. This is done by melting the area that has been made.
- the predetermined solvent is pure water, and the depth and shape of the recessed portion 4a can be adjusted as appropriate by changing the condition of pure water cleaning.
- the substrate 1 is rotated by a spin coater, and pure water (for example, room temperature) is dropped on the rotating substrate 1 for cleaning. Thereafter, the pure water is stopped from dripping while the substrate 1 is kept rotating, and the water is drained.
- the depth and shape of the recessed portion 4a can be adjusted according to the time for which pure water is dropped. Further, since the dissolution rate of the thin film 11 also changes depending on the temperature of pure water, the depth and shape of the recessed portion 4a can be adjusted by the temperature of pure water.
- the formation method of the recessed part 4a is not limited to the above.
- the resist residue adhering to the surface of the thin film 11 is cleaned with a cleaning liquid such as pure water, and a part of the thin film 11 is dissolved with the cleaning liquid to form the recessed portion 4a.
- the predetermined solvent is a cleaning liquid.
- the resist film is etched with a developer to form the bank 5, the resist residue adhering to the surface of the thin film 11 is washed with the developer, and a part of the thin film 11 is dissolved to form the recess 4 a. May be formed.
- the developer is a predetermined solvent.
- the hole injection layer 4 is formed by dissolving the thin film 11 using a solvent such as a cleaning solution or a developing solution used in the bank formation process, it is necessary to use a predetermined solvent separately to form the recessed portion 4a. In addition, since it is not necessary to carry out an additional step for forming the recessed portion 4a, the production efficiency is good.
- a solvent such as a cleaning solution or a developing solution used in the bank formation process
- the formation of the recessed portion 4a is not limited to the case where the above-mentioned predetermined solvent is used.
- WOx or MoWOx is formed in all regions except the region where the first electrode 2 is disposed by using sputtering and photolithography.
- a thin film is formed, and a WOx or MoWOx thin film is formed in all regions from above to form a concave hole injection layer 4 in the region where the first electrode 2 is disposed. good.
- ink is dropped into the region defined by the bank 5 by, for example, an ink jet method, and the ink is applied along the inner bottom surface 4 c and the inner side surface 4 d of the hole injection layer 4. Then, the luminescent layer 6 is formed by drying.
- the ink may be dropped by a dispenser method, a nozzle coating method, a spin coating method, intaglio printing, letterpress printing, or the like.
- a barium thin film that becomes the electron injection layer 7 is formed by, for example, vacuum deposition, and an ITO thin film that becomes the second electrode 8 by, for example, sputtering, as shown in FIG. 8 (g).
- a sealing layer 9 is further formed as shown in FIG.
- the light emitting device is related to the first embodiment in that the ITO layer is not formed below the hole injection layer and the protective film is formed on the hole injection layer. It is very different from the light emitting element.
- points different from the first embodiment will be mainly described, and the same points as in the first embodiment will be simplified or omitted to avoid duplication.
- FIG. 9 is a schematic diagram illustrating a stacked state of each layer of the light emitting device according to the second embodiment.
- a first electrode 102 which is an anode is formed on a substrate 101
- a hole injection layer 104 as a charge injection transport layer and a protective layer are formed thereon.
- Layers 110 are stacked in that order.
- the hole injection layer 104 is formed over the entire upper surface side of the substrate 101, whereas the protective layer 110 is not formed above the first electrode 102. Further, no ITO layer is interposed between the first electrode 102 and the hole injection layer 104.
- a bank 105 for partitioning pixels is formed on the hole injection layer 104, and a light emitting layer 106 is stacked in a region partitioned by the bank 105.
- An electron injection layer 107 and a cathode are formed on the light emitting layer 106.
- a certain second electrode 108 and sealing layer 109 are formed so as to be continuous with those of the adjacent pixels beyond the area partitioned by the bank 105.
- FIG. 10 is a process diagram illustrating the method for manufacturing the light emitting device according to the second embodiment.
- a first electrode 102 is formed of an Al (aluminum) material on a glass substrate 101.
- a thin film 111 of WOx or MoWOx that will later become the hole injection layer 104 is formed thereon, and a thin film 112 of WOx or MoWOx that will later become the protective layer 110 is formed thereon.
- the thin film 112 has a function of protecting the hole injection layer 104 during etching when the bank 105 is formed.
- a bank 105 is formed on the thin film 112. Specifically, a resist film containing a resist material is formed on the thin film 112, a resist pattern is further formed on the resin film, and then a desired portion of the resist film is removed by etching with a developing solution. 105 patterns are formed. Note that impurities such as hydrofluoric acid remaining on the surface of the bank 105 after formation are cleaned and removed with a cleaning solution such as pure water, but the region defined by the bank 105 on the upper surface of the thin film 112 is melted and settled by the cleaning solution.
- the entire region defined by the bank 105 of the thin film 112 is melted to be in the state of the protective layer 110. Then, since the thin film 111 is exposed when the thin film 112 is melted, the region defined by the bank 105 on the upper surface of the thin film 111 is melted and sinks, and the recessed portion 104a is formed. In this way, the hole injection layer 104 is formed.
- the light emitting layer 106 is formed in the region defined by the bank 105. Subsequent steps are the same as those according to the first embodiment, and thus are omitted.
- the light emitting device according to the third embodiment is greatly different from the light emitting device according to the second embodiment in the region where the hole injection layer is formed.
- points different from the second embodiment will be mainly described, and the same points as in the second embodiment will be simplified or omitted to avoid duplication.
- FIG. 11 is a schematic diagram illustrating a stacked state of each layer of the light emitting device according to the third embodiment.
- a first electrode 202 which is an anode is formed on a substrate 201, and a hole injection layer 204 as a charge injection transport layer and a protective layer are formed thereon.
- Layers 210 are stacked in that order.
- the hole injection layer 204 is not formed over the entire upper surface of the substrate 1, but is formed only on the first electrode 202 and the peripheral portion of the first electrode 202.
- the protective layer 210 is not formed above the first electrode 202.
- a bank 205 for dividing pixels is formed on the hole injection layer 204, and a light emitting layer 206 is stacked in a region partitioned by the bank 205.
- An electron injection layer 207 and a cathode are formed on the light emitting layer 206.
- a certain second electrode 208 and sealing layer 209 are formed so as to be continuous with those of the adjacent pixels beyond the area partitioned by the bank 205.
- FIG. 12 is a process diagram illustrating the method for manufacturing the light emitting element according to the third embodiment.
- a first electrode 102 is formed of an Al-based material on a glass substrate 101, and then, The exposed surface (upper surface and side surface) of one electrode 102 is oxidized to form an oxide film 211 that becomes the hole injection layer 204, and a WOx or MoWOx thin film 212 that later becomes the protective layer 210 is formed thereon.
- a bank 205 is formed on the thin film 212. Impurities such as hydrofluoric acid remaining on the surface of the bank 205 are cleaned and removed with a cleaning liquid such as pure water. The cleaning liquid dissolves and sinks a region defined by the bank 205 on the upper surface of the thin film 212.
- the thin film 212 is in the state of the protective layer 210 which is the final form by melting all the regions defined by the bank 205. Moreover, since the region defined by the bank 205 of the oxide film 211 is exposed when the thin film 212 is melted, the upper surface of the region is melted and sinks, and the recessed portion 204a is formed. In this way, the hole injection layer 204 is formed.
- the light emitting layer 206 is formed in the region defined by the bank 205. Subsequent steps are the same as those according to the first embodiment, and thus are omitted.
- FIG. 13 is a perspective view showing a display device and the like according to the fourth embodiment.
- a display device 300 according to one embodiment of the present invention includes an organic pixel in which pixels that emit R, G, or B light are regularly arranged in a matrix in the row direction and the column direction.
- each pixel includes the light-emitting element according to one embodiment of the present invention.
- the charge injection / transport layer is not limited to the hole injection layer, and may be a hole transport layer or a hole injection / transport layer.
- the first electrode may be a cathode and the second electrode may be an anode.
- the charge injection / transport layer may be an electron injection layer, an electron transport layer, or an electron injection / transport layer.
- the light emitting element is not limited to the top emission type, and may be a bottom emission type.
- the present invention is applicable to organic EL display devices used for flat light sources, flat displays, and the like.
- Second electrode 300 Display device
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Abstract
Description
第1電極、電荷注入輸送層、発光層、第2電極がこの順に積層され、少なくとも前記発光層がバンクにより規定されてなる発光素子であって、前記バンクは少なくともその表面が撥液性となっており、一方、前記電荷注入輸送層は前記バンクの表面と比較して親液性のある金属化合物からなり、且つ、前記電荷注入輸送層は、バンクで規定された領域においてはバンク底面のレベルよりも沈下した凹入構造に形成されていることを特徴とする。
本発明の一態様に係る発光素子は、第1電極、電荷注入輸送層、発光層、第2電極がこの順に積層され、少なくとも前記発光層がバンクにより規定されてなる発光素子であって、前記バンクは少なくともその表面が撥液性となっており、一方、前記電荷注入輸送層は前記バンクの表面と比較して親液性のある金属化合物からなり、且つ、前記電荷注入輸送層は、バンクで規定された領域においてはバンク底面のレベルよりも沈下した凹入構造に形成されていることを特徴とする。
<発光素子の概略構成>
図1は、第1の実施形態に係る発光素子の各層の積層状態を示す模式図であり、図2は、図1における一点鎖線で囲まれた部分の拡大図である。
基板1は、例えば、ソーダガラス、無蛍光ガラス、燐酸系ガラス、硼酸系ガラス、石英、アクリル系樹脂、スチレン系樹脂、ポリカーボネート系樹脂、エポキシ系樹脂、ポリエチレン、ポリエステル、シリコーン系樹脂、又はアルミナ等の絶縁性材料で形成されている。
図7は、第1の実施形態に係る発光素子の製造方法を説明する工程図であり、図8は、図7に続く第1の実施形態に係る発光素子の製造方法を説明する工程図である。
第2の実施形態に係る発光素子は、ホール注入層の下にITO層が形成されていない点、及び、ホール注入層の上に保護膜が形成される点が、第1の実施形態に係る発光素子とは大きく異なる。以下では、第1の実施形態と異なる点について重点的に説明し、第1の実施形態と同様の点ついては重複を避けるため説明を簡略若しくは省略する。
図9は、第2の実施形態に係る発光素子の各層の積層状態を示す模式図である。図9に示すように、第2の実施形態に係る発光素子は、基板101上に陽極である第1電極102が形成されており、その上に電荷注入輸送層としてのホール注入層104及び保護層110がその順で積層されている。なお、ホール注入層104が基板101の上面側全体に亘って形成されているのに対し、保護層110は第1電極102の上方には形成されていない。また、第1電極102とホール注入層104との間にITO層は介在していない。
図10は、第2の実施形態に係る発光素子の製造方法を説明する工程図である。第2の実施形態に係る発光素子の製造工程では、まず、図10(a)に示すように、ガラス製の基板101上にAl(アルミニウム)系の材料で第1電極102を形成し、その上に、後にホール注入層104となるWOx又はMoWOxの薄膜111を形成し、さらにその上に、後に保護層110となるWOx又はMoWOxの薄膜112を形成する。当該薄膜112はバンク105形成時のエッチングの際にホール注入層104を保護する機能を有する。
第3の実施形態に係る発光素子は、ホール注入層が形成されている領域が、第2の実施形態に係る発光素子とは大きく異なる。以下では、第2の実施形態と異なる点について重点的に説明し、第2の実施形態と同様の点ついては重複を避けるため説明を簡略若しくは省略する。
図11は、第3の実施形態に係る発光素子の各層の積層状態を示す模式図である。図11に示すように、第3の実施形態に係る発光素子は、基板201上に陽極である第1電極202が形成されており、その上に電荷注入輸送層としてのホール注入層204及び保護層210がその順で積層されている。ホール注入層204は、基板1の上面全体に亘って形成されておらず、第1電極202上及び当該第1電極202の周辺部のみに形成されている。一方、保護層210は第1電極202の上方には形成されていない。
図12は、第3の実施形態に係る発光素子の製造方法を説明する工程図である。第3の実施形態に係る発光素子の製造工程では、まず、図12(a)に示すように、ガラス製の基板101上にAl系の材料で第1電極102を形成し、次に、第1電極102の露出面(上面及び側面)を酸化させることによってホール注入層204となる酸化膜211を形成し、さらにその上に、後に保護層210となるWOx又はMoWOxの薄膜212を形成する。
図13は、第4の実施形態に係る表示装置等を示す斜視図である。図13に示すように、本発明の一態様に係る表示装置300は、R、G、又はBの光を出射する各ピクセルが行方向及び列方向にマトリックス状に規則的に配置されてなる有機ELディスプレイであって、各ピクセルが本発明の一態様に係る発光素子で構成されている。
以上、本実施の形態に係る発光素子、表示装置、および発光素子の製造方法を実施の形態に基づいて具体的に説明してきたが、本発明の一態様に係る発光素子、表示装置、および発光素子の製造方法は、上記の実施の形態に限定されない。
4,104,204 電荷注入輸送層
4a 凹入部
4c 凹入部の内底面
4d 凹入部の内側面
5,105,205 バンク
5a バンクの底面
5d バンクの下端縁
6,106,206 発光層
6a 発光層の底面
6b 発光層の側面
8,108,208 第2電極
300 表示装置
Claims (14)
- 第1電極、電荷注入輸送層、発光層、第2電極がこの順に積層され、少なくとも前記発光層がバンクにより規定されてなる発光素子であって、
前記バンクは少なくともその表面が撥液性となっており、一方、前記電荷注入輸送層は前記バンクの表面と比較して親液性のある金属化合物からなり、
且つ、前記電荷注入輸送層は、バンクで規定された領域においてはバンク底面のレベルよりも沈下した凹入構造に形成されている
ことを特徴とする発光素子。 - 前記凹入構造はカップ状であることを特徴とする請求項1記載の発光素子。
- 前記凹入構造はバンクの下端縁相当部位から沈下した構造であることを特徴とする請求項1記載の発光素子。
- 前記金属化合物は、金属酸化物、金属窒化物または金属酸窒化物であることを特徴とする請求項1記載の発光素子。
- 前記発光層は、高分子材料からなる層を含むことを特徴とする請求項1記載の発光素子。
- 前記電荷注入輸送層は、バンク底面に沿って隣のピクセル方向に拡がっていることを特徴とする請求項1記載の発光素子。
- 第1電極、電荷注入輸送層、発光層、第2電極がこの順に積層され、少なくとも前記発光層がバンクにより規定されてなる発光素子であって、
前記電荷注入輸送層は、所定の溶剤に対して溶解可能である金属化合物を含み、前記所定の溶剤により溶解されて形成されている凹入部を有し、
前記電荷注入輸送層の前記凹入部は、
前記発光層の底面に接触する内底面と、
前記内底面に連続し、前記発光層の側面の少なくとも一部に接触する内側面と、
を有することを特徴とする発光素子。 - 前記電荷注入輸送層は親液性を有し、前記バンクは溌液性を有することを特徴とする請求項7記載の発光素子。
- 前記所定の溶剤は、前記バンクを形成の際にレジスト膜の一部を除去するための現像液、または/および、前記バンク形成後に残留するレジスト残渣を洗浄するための洗浄液であることを特徴とする請求項7記載の発光素子。
- 前記電荷注入輸送層は、金属酸化物を含むホール注入層であることを特徴とする請求項7記載の発光素子。
- 前記金属酸化物は、タングステンまたはモリブテンの酸化物であることを特徴とする請求項7記載の発光素子。
- 請求項1~11いずれかに記載の発光素子を含むことを特徴とする表示装置。
- 基板上に第1電極を形成する第1工程と、
前記第1電極の上方に、所定の溶剤に対して溶解可能である金属化合物を含む薄膜を形成する第2工程と、
前記薄膜上に、レジスト材料を含むレジスト膜を形成し、現像液によりエッチング処理し、バンクを形成する第3工程と、
前記バンクを形成後、前記薄膜表面に付着するレジスト残渣を洗浄液を用いて洗浄すると共に、前記洗浄液により前記薄膜の一部を溶解させ、内底面と前記内底面に連続する内側面とを備える凹入部を有する電荷注入輸送層を形成する第4工程と、
前記バンクにより規定された領域内にインクを滴下し、前記電荷注入輸送層の前記内底面および前記内側面に沿って塗布させて乾燥させ、発光層を形成する第5工程と、
前記発光層の上方に、第2電極を形成する第6工程と、
を有することを特徴とする発光素子の製造方法。 - 基板上に第1電極を形成する第1工程と、
前記第1電極の上方に、所定の溶剤に対して溶解可能である金属化合物を含む薄膜を形成する第2工程と、
前記薄膜上に、レジスト材料を含むレジスト膜を形成し、現像液によりエッチング処理し、バンクを形成すると共に、前記現像液により薄膜表面に付着するレジスト残渣を洗浄し、かつ、前記薄膜の一部を溶解させ、内底面と前記内底面に連続する内側面とを備える凹入部を有する電荷注入輸送層を形成する第3工程と、
前記バンクにより規定された領域内にインクを滴下し、前記電荷注入輸送層の前記内底面および前記内側面に沿って塗布させて乾燥させ、発光層を形成する第4工程と、
前記発光層の上方に、第2電極を形成する第5工程と、
を有することを特徴とする発光素子の製造方法。
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CN103646959A (zh) | 2014-03-19 |
KR101643018B1 (ko) | 2016-07-27 |
CN102308404A (zh) | 2012-01-04 |
KR101581989B1 (ko) | 2015-12-31 |
US8890173B2 (en) | 2014-11-18 |
JP2014146824A (ja) | 2014-08-14 |
CN102308405B (zh) | 2015-07-08 |
CN102308405A (zh) | 2012-01-04 |
JP5904471B2 (ja) | 2016-04-13 |
US8890174B2 (en) | 2014-11-18 |
KR20110124216A (ko) | 2011-11-16 |
JP5513415B2 (ja) | 2014-06-04 |
JP5904472B2 (ja) | 2016-04-13 |
EP2398083A1 (en) | 2011-12-21 |
EP2398085B1 (en) | 2018-06-27 |
JP2014160834A (ja) | 2014-09-04 |
US20110291128A1 (en) | 2011-12-01 |
JP5513414B2 (ja) | 2014-06-04 |
CN102308404B (zh) | 2016-01-20 |
KR20110124215A (ko) | 2011-11-16 |
JPWO2010092797A1 (ja) | 2012-08-16 |
WO2010092795A1 (ja) | 2010-08-19 |
CN103646959B (zh) | 2016-09-14 |
EP2398085A4 (en) | 2013-03-13 |
EP2398085A1 (en) | 2011-12-21 |
EP2398083B1 (en) | 2018-06-13 |
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