JP5569023B2 - Organic electroluminescence device and method for manufacturing the same - Google Patents

Description

  The present invention relates to an organic electroluminescence element (hereinafter referred to as an organic EL element) expected to be used for a display such as an information display terminal, and a method for producing the same.

  An organic EL element is one in which an organic light emitting layer made of an organic light emitting material is formed between two opposing electrodes, and light is emitted by passing a current through the organic light emitting layer. The film thickness is important, and it is necessary to form a thin film of about 100 nm. Furthermore, in order to make this a display, it is necessary to pattern the organic light emitting layer with high definition so that each pixel becomes red (R), green (G), and blue (B).

  Organic light-emitting materials that form the organic light-emitting layer include low-molecular materials and high-molecular materials. Generally, low-molecular materials are formed into a thin film by a dry film-forming method such as resistance heating vapor deposition, and a fine pattern mask is used at this time. However, this method has a problem that the patterning accuracy is less likely as the substrate becomes larger.

  Therefore, recently, a method of forming a thin film by a wet film forming method using a polymer material as an organic light emitting material and dispersing or dissolving the organic light emitting material in a solvent to form a coating liquid has been tried. . Examples of the wet film forming method for forming a thin film include a spin coating method, a bar coating method, a protruding coating method, a dip coating method, and the like. It is difficult to apply the coating method, and it is considered that the thin film formation by the printing method which is good at coating and patterning is most effective.

  Further, among various printing methods, in organic EL elements and displays using glass as a substrate, a method using a hard plate such as a metal printing plate such as a gravure printing method is unsuitable, and an elastic rubber blanket. An offset printing method using, and a relief printing method using an elastic rubber plate or resin plate are also suitable. Actually, as an attempt by these printing methods, a method by offset printing (Patent Document 1), a method by letterpress printing (Patent Document 2) and the like have been proposed.

  The organic light-emitting material, which is a material for forming the organic light-emitting layer, has poor solubility in water and alcohol solvents, and it is necessary to dissolve and disperse using an organic solvent in order to form a coating liquid (hereinafter referred to as ink). Among them, organic solvents such as toluene and xylene are preferable. Therefore, the ink of organic light emitting material (hereinafter referred to as organic light emitting ink) is an ink of organic solvent.

  However, the rubber blanket used for offset printing has a problem that it is easily swelled or deformed by toluene or xylene organic solvent. The types of rubber used in blankets vary from olefin rubber to silicon rubber, but none of these rubbers are resistant to toluene, xylene or other solvents, and are prone to swelling and deformation, so organic It is not suitable for printing luminescent ink.

  In addition, the relief printing method using an elastic relief plate includes a flexographic printing method using a rubber plate and a resin relief plate method using a resinous plate. Among these, a method using a water development type resin relief plate is used. If present, it has high resistance to organic solvents such as toluene and xylene, and can be used for printing organic light-emitting inks.

JP 2001-93668 A JP 2001-155858 A

  In general, when an organic light-emitting layer is formed on an active matrix substrate using a relief printing method, the convex portion of a resin relief plate having a line pattern is continuously applied with ink so as to straddle the partition between the first electrodes. Supplied and printed. Accordingly, the organic light emitting ink is supplied to both the patterned first electrode and the partition wall. In such a case, the ink supplied on the partition between the first electrodes flows onto the first electrode, so that the thickness of the organic light emitting layer in the vicinity of the partition on the first electrode becomes the center of the first electrode. It becomes thick compared with the film thickness of an organic light emitting layer (FIG. 5). In addition, when an organic light-emitting layer is formed on a pixel surrounded by a partition wall having a conventional height by a relief printing method, the contact between the relief plate and the substrate is hindered by the partition wall height, and the amount of ink supplied for each pixel. In other words, there is a problem that unevenness of light emission occurs in the pixels (e.g. unevenness of the light emitting region) and unevenness of light emission between pixels (the variation of the light emission area between pixels) occurs.

  The present invention has been made in view of the above, and an object of the present invention is to eliminate light emission unevenness and color mixing within a pixel and light emission unevenness between pixels by devising the arrangement of partition walls having different heights. An organic EL element having high optical characteristics is provided.

The invention according to claim 1 for solving the above-described problems includes at least a substrate, a first electrode formed on the substrate, an organic light emitting medium layer formed on the first electrode, and the organic light emission. An organic electroluminescence device comprising a second electrode provided so as to face the first electrode across a medium layer, the first partition formed around the end of the first electrode; a second barrier rib formed to surround spaced the first electrode and the first partition wall, have a, and an ink reservoir that is surrounded by the first partition wall and the second partition wall, high in the second partition Is higher than the height of the first partition, the height of the first partition is 0.1 μm or more and 0.5 μm or less, and the height of the second partition is 1.0 μm or more and 1.5 μm or less, and wherein the width of the ink reservoir is 10μm or more 15μm or less That is an organic electroluminescence element.
According to a second aspect of the present invention, the second partition is formed in a lattice shape, and the first partition and the first electrode are formed in a region surrounded by the lattice-shaped second partition. an organic electroluminescence device according to claim 1, wherein.
According to a third aspect of the present invention, the second partition is formed so as to surround the plurality of first electrodes and the first partition, and the plurality of first electrodes surrounded by the second partition are made of the same material. The organic electroluminescent element according to claim 1, wherein an organic light emitting medium layer is formed.
According to a fourth aspect of the present invention, there is provided the step of forming the first electrode on the substrate, the step of forming the first partition around the end of the first electrode, and the first partition separated from the first partition. Forming a second partition so as to surround the first partition, forming an ink reservoir surrounded by the first partition and the second partition, and forming an organic light emitting medium layer on the first electrode; And a step of forming a second electrode so as to face the first electrode across the organic light emitting medium layer, wherein the method of manufacturing an organic electroluminescence element comprises: The height is higher than the height of the first partition, the height of the first partition is 0.1 μm or more and 0.5 μm or less, and the height of the second partition is 1.0 μm or more and 1.5 μm or less. the width of said ink reservoir is formed to be a 10μm or 15μm or less, Forming a serial organic light emitting medium layer is a method of manufacturing an organic electroluminescent device which is a wet film formation method.
The invention according to claim 5 is the method for producing an organic electroluminescence element according to claim 4 , wherein the wet film forming method is a relief printing method.

  According to the present invention, since the first partition, the second partition, and the ink reservoir are formed, there is no color mixing between pixels, and the flatness of the organic light emitting layer on the first electrode is improved. A luminescence element and a manufacturing method thereof can be provided.

Sectional drawing which shows the structure of the organic EL element of this invention. The bird's-eye view of one Example of the organic EL element of this invention. The bird's-eye view of the other Example of the organic EL element of this invention. Schematic of the relief printing apparatus used for manufacture of the organic EL element of this invention. Sectional drawing which shows the structure of the conventional organic EL element.

  Below, although the organic EL element in this invention is demonstrated based on figures, it is not restricted to this.

  FIG. 1 is a view showing a cross section of the organic EL element 9 of the present invention taken along line AB in FIG. The present invention is applicable to both passive matrix organic EL elements and active matrix organic EL elements.

  As shown in FIG. 1, the organic EL element of the present invention has a first electrode 2 on a glass substrate 1. In the case of the passive matrix system, the first electrode 2 has a stripe pattern. In the case of the active matrix method, the first electrode 2 has a pattern for each pixel.

  The organic EL element of the present invention has an organic light emitting medium layer on the first electrode 2 and in a region (pixel portion) partitioned by the first partition 51. The organic light emitting medium layer may be composed of an organic light emitting layer alone, or may be composed of a laminated structure of an organic light emitting layer and a light emission auxiliary layer. FIG. 1 shows an organic light emitting medium layer composed of a laminated structure of a hole transport layer 3 which is a light emission auxiliary layer and organic light emitting layers (41, 42, 43). A hole transport layer 3 is provided on the first electrode 2, and an organic light emitting layer 41 (red), an organic light emitting layer 42 (green), and an organic light emitting layer 43 (blue) are provided on the hole transport layer 3. Yes. In addition, an ink reservoir 44 (a portion surrounded by a broken line in FIG. 1) is provided between the pixel partition wall 51 and the second partition wall 52.

  A second electrode 6 is disposed on the organic light emitting layer. In the case of the passive matrix system, the second electrode 6 is provided in a stripe shape so as to be orthogonal to the first electrode 2 having a stripe shape. In the case of the active matrix method, the second electrode 6 is formed on the entire surface of the organic EL element. A sealing resin 7 and a sealing substrate 8 are formed on the second electrode 6.

  FIGS. 2 and 3 show an overview of the organic EL element of the present invention in the case of the active matrix system (the second electrode 6, the sealing resin 7 and the sealing substrate 8 are omitted). In the active matrix organic EL element, the first electrode 2 is formed for each pixel. When an organic light emitting layer is formed by a relief printing method using organic light emitting inks having different emission colors such as red, green, and blue, the resin plate used in the relief printing method is striped, and also between the first electrodes. Ink is supplied. The printing direction in the relief printing method is indicated by an arrow Y. At this time, unnecessary rows of ink flow to the ink reservoir 44 by providing three rows of partition walls between the first electrodes in the printing direction Y as shown in FIG.

  Next, the manufacturing method of the organic EL element according to the present invention will be described. As the substrate according to the present invention, any substrate can be used as long as it has an insulating property. In the case of a bottom emission type organic EL element that emits light from the substrate side, it is necessary to use a transparent substrate.

  For example, a glass substrate or a quartz substrate can be used. Further, it may be a plastic film or sheet such as polypropylene, polyethersulfone, polycarbonate, cycloolefin polymer, polyarylate, polyamide, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate. In addition, for the purpose of preventing moisture from entering the organic light-emitting medium layer, a metal oxide thin film, a metal fluoride thin film, a metal nitride thin film, a metal oxynitride thin film, or a polymer resin is added to the film or sheet of the above material. A laminate of films may be used as the substrate.

  In addition, it is more preferable to reduce the moisture adsorbed on the inside or the surface of the substrate as much as possible by performing a heat treatment on these substrates in advance. Further, in order to improve the adhesion depending on the material to be laminated on the substrate, it is preferable to use after performing surface treatment such as ultrasonic cleaning treatment, corona discharge treatment, plasma treatment, UV ozone treatment.

  Further, a thin film transistor (TFT) can be formed on the above substrate to form a substrate for an active matrix type organic EL element. A known thin film transistor can be used as the thin film transistor. Specifically, a thin film transistor mainly including an active layer in which a source / drain region and a channel region are formed, a gate insulating film, and a gate electrode can be given. The structure of the thin film transistor is not particularly limited, and examples thereof include a staggered type, an inverted staggered type, a top gate type, and a coplanar type.

  The active layer is not particularly limited, and examples thereof include inorganic semiconductor materials such as amorphous silicon, polycrystalline silicon, microcrystalline silicon, cadmium selenide, thiophene oligomers, poly (p-ferylene vinylene), and the like. It can be formed of an organic semiconductor material.

These active layers are formed by, for example, laminating amorphous silicon by plasma CVD, ion doping, forming amorphous silicon by LPCVD using SiH ₄ gas, and crystallizing amorphous silicon by solid phase growth. After obtaining silicon, ion doping is performed by ion implantation, LPCVD using Si ₂ H ₆ gas, and amorphous silicon is formed by PECVD using SiH ₄ gas, and laser such as excimer laser is used. After annealing and crystallizing amorphous silicon to obtain polysilicon, polysilicon is laminated by ion doping (low temperature process), low pressure CVD or LPCVD, and thermally oxidized at 1000 ° C. or higher. Gate break Film is formed, a gate electrode of the n ⁺ polysilicon is formed thereon, then, a method of ion doping (high temperature process), and the like by an ion implantation method.

As the gate insulating film, typically, it can be used that is used as a gate insulating film, for example, PECVD method, SiO formed by the LPCVD method or the like _2; SiO obtained polysilicon film was thermally oxidized ₂ Etc. can be used.

  As a gate electrode, what is normally used as a gate electrode can be used, for example, metals, such as aluminum and copper, refractory metals, such as titanium, tantalum, and tungsten, polysilicon, silicide of a refractory metal, Polycide etc. are mentioned.

  The thin film transistor may have a single gate structure, a double gate structure, or a multi-gate structure having three or more gate electrodes. Moreover, you may have a LDD structure and an offset structure. Further, two or more thin film transistors may be arranged in one pixel. The organic EL element of the present invention needs to be connected so that the thin film transistor functions as a switching element of the organic EL element, and the drain electrode of the transistor and the first electrode 2 of the organic EL element are electrically connected. The thin film transistor, the drain electrode, and the first electrode 2 of the organic EL element are connected through a connection wiring formed in a contact hole that penetrates the planarization film.

  A first electrode 2 is provided on the substrate. When the first electrode 2 is used as an anode, the material is a metal such as ITO (indium tin composite oxide), IZO (indium zinc composite oxide), tin oxide, zinc oxide, indium oxide, zinc aluminum composite oxide, etc. A single layer or laminated layer of metal materials such as composite oxide, gold, platinum, and chromium can be used. The first electrode 2 can be formed by a dry film forming method such as a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method depending on the material.

  In addition, ITO is preferably used because of its low resistance, solvent resistance, and high transparency when the bottom mission method is adopted. ITO is formed on the glass substrate 1 by a sputtering method, and is patterned by the photolithography method to form the first electrode 2.

After the first electrode 2 is formed, a first partition 51 and a second partition 52 are formed so as to cover the first electrode edge. The first partition 51 and the second partition 52 need to have insulating properties, and a photosensitive material or the like can be used. The photosensitive material may be a positive type or a negative type, a photo-curing resin of a photo radical polymerization system, a photo cationic polymerization system, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol. , Novolac resin, polyimide resin, cyanoethyl pullulan, and the like can be used. Further, as a partition wall forming _material, it is also possible to use SiO 2, TiO ₂ or the like. If necessary, a water repellent can be added, or plasma or UV can be irradiated to impart liquid repellency to the ink after formation.

When the partition wall forming material is a photosensitive material, the entire surface of the forming material solution is coated by a slit coating method or a spin coating method, and then patterning is performed by a photolithography method such as exposure and development. In the case of the spin coating method, the height of the partition wall can be controlled by conditions such as the number of rotations when spin coating, but there is a limit height in one coating, and if it is higher than that, multiple spin coatings are performed. Use an iterative approach. Further, when the partition wall forming material is SiO ₂ or TiO ₂ , it can be formed by a dry film forming method such as a sputtering method or a CVD method. The patterning of the partition walls can be performed by a photolithography method using a photomask.

  The shape of the first partition 51 is formed so as to cover the end portions of the first electrode 2 so that the plurality of first electrodes 2 on the substrate become light emitting regions corresponding to the pixels. Therefore, as shown in FIG. 2, the same number of first partition walls 51 as the number of first electrodes 2 on the substrate are formed. As shown in FIG. 2, the shape of the second partition 52 is formed in a lattice shape covering the first partition 51 between the adjacent first electrodes 2, and the first partition 51 and the second partition 52 are separated from each other. The ink reservoir 44 prevents the ink supplied on the first partition wall from flowing into the pixel. Moreover, the cross-sectional shape of the 1st partition 51 and the 2nd partition may be shapes, such as a taper shape, a reverse taper shape, a square, a semicircle.

  Since the second partition 52 is provided to prevent color mixing of different organic light emitting medium layer inks, the second partition 52 is formed between the first electrodes 2 that supply the same organic light emitting medium layer ink as shown in FIG. Alternatively, the ink reservoir 44 may be formed only by the first partition 51, and the second partition 52 may be formed only between the first electrodes 2 that supply different organic light emitting medium layer inks. In this case, the second partition 52 is formed as a rectangle surrounding the first partition 51 on which the same organic light emitting medium layer is formed.

  When the organic light emitting medium layer is formed by printing, the height of each of the first partition walls 51 and the second partition walls 52 is an important point for preventing color mixing of the organic light emitting medium layer ink. In the conventional organic EL device as shown in FIG. 5, the partition walls are made high in order to prevent color mixing of the ink between the pixels, the general partition wall height is higher than 0.5 μm, and the flatness of the organic light emitting layer. There was a problem. On the other hand, in the present invention, since the color mixing of the ink is prevented by the second partition 52 and the ink reservoir, the height of the first partition 51 can be lowered to improve the flatness of the organic light emitting layer. Therefore, the height of the first partition is preferably 0.5 μm or less, and may be 0.1 μm or more for patterning the ink on the pixel.

  The height of the second partition 52 is preferably in the range of 1.0 μm to 1.5 μm. The height of the second partition 52 is preferably high in order to prevent color mixing. However, when the organic light-emitting layer is formed by a relief printing method, if the height of the second partition exceeds 1.5 μm, the convex portion of the plate and the substrate The second partition wall 52 prevents the ink from being transferred from the plate to the pixels. On the other hand, when the thickness is less than 1.0 μm, the ink supplied to the adjacent ink reservoir 44 across the second partition 52 is mixed beyond the second partition, and the mixed ink flows onto the first electrode in the pixel. There is a risk of color mixing.

  If the width of the ink reservoir 44 is 10 μm or more and 15 μm or less, a sufficient area can be secured for the ink on the partition wall to flow into the pixel. If the width is less than 10 μm, the ink on the partition wall may flow into the pixel. The opening of the pixel becomes small for use as a display.

  Therefore, when forming the first partition wall 51 having a low height, it is sufficient to perform the coating once. However, when forming the second partition wall 52 having a higher height, the coating is performed a plurality of times. There is a need to. As a method of forming the first partition 51 and the second partition 52 having different heights, for example, a portion that becomes the first partition 51 and the second partition 52 is coated, and only a portion that becomes the first partition 51 is exposed and cured, A portion to be the second partition wall 52 is coated thereon, and a portion to be the second partition wall 52 is exposed and cured, and then developed to form the first partition wall 51 and the second partition wall 52 having different heights. . Note that the method is not limited to the above method as long as the first partition 51 can be formed to have a height of 0.1 μm to 0.5 μm and the second partition 52 has a height of 1.0 μm to 1.5 μm. Absent.

  Next, an organic light emitting medium layer is formed. The organic light emitting medium layer may be composed of the organic light emitting layers 41, 42, 43 alone, or the organic light emitting layers 41, 42, 43 and the hole transport layer 3, other hole injection layers, electron transport layers, electrons. A laminated structure with a light emission auxiliary layer for assisting light emission such as an injection layer may be used. The hole transport layer, hole injection layer, electron transport layer, and electron injection layer are appropriately selected as necessary.

  The organic light emitting layers 41, 42, and 43 are layers that emit light when a current is applied. Organic light-emitting materials formed by the organic light-emitting layers 41, 42, and 43 include 9,10-diarylanthracene derivatives, pyrene, coronene, perylene, rubrene, 1,1,4,4-tetraphenylbutadiene, tris (8-quinolate). ) Aluminum complex, tris (4-methyl-8-quinolato) aluminum complex, bis (8-quinolato) zinc complex, tris (4-methyl-5-trifluoromethyl-8-quinolato) aluminum complex, tris (4-methyl) -5-cyano-8-quinolato) aluminum complex, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) [4- (4-cyanophenyl) phenolate] aluminum complex, bis (2-methyl-5- Cyano-8-quinolinolato) [4- (4-cyanophenyl) phenolate] a Minium complex, tris (8-quinolinolato) scandium complex, bis [8- (paratosyl) aminoquinoline] zinc complex and cadmium complex, 1,2,3,4-tetraphenylcyclopentadiene, 2,5-diheptyloxy-para -A low molecular weight light emitting material such as phenylene vinylene can be used.

  Also, coumarin phosphors, perylene phosphors, pyran phosphors, anthrone phosphors, porphyrin phosphors, quinacridone phosphors, N, N′-dialkyl-substituted quinacridone phosphors, naphthalimide phosphors, A material obtained by dispersing a low molecular weight light emitting material such as an N, N′-diaryl-substituted pyrrolopyrrole-based fluorescent pair or a phosphorescent light emitter such as an Ir complex in a polymer can be used. As the polymer, polystyrene, polymethyl methacrylate, polyvinyl carbazole and the like can be used.

  Also, poly (2-decyloxy-1,4-phenylene) (DO-PPP), poly [2,5-bis- [2- (N, N, N-triethylammonium) ethoxy] -1,4-phenyl- Alt-1,4-phenyllene] dibromide (PPP-NEt3) poly [2- (2′-ethylhexyloxy) -5-methoxy-1,4-phenylenevinylene] (MEH-PPV), poly [5-methoxy -(2-propanoxysulfonide) -1,4-phenylenevinylene] (MPS-PPV), poly [2,5-bis- (hexyloxy) -1,4-phenylene- (1-cyanovinylene)] ( CN-PPV) and poly (9,9-dioctylfluorene) (PDAF) may be used. Examples thereof include polymer precursors such as PPV precursor, PNV precursor, and PPP precursor. Further, a material obtained by dispersing or copolymerizing the low-molecular light-emitting material in these polymer materials, or other existing light-emitting materials can also be used.

Examples of the hole transport material used for the hole transport layer include copper phthalocyanine and derivatives thereof, 1,1-bis (4-di-p-triaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-. Low molecular weight materials such as aromatic amines such as bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, polyaniline derivatives, polythiophene derivatives, polyvinylcarbazole derivatives, poly (3,4-ethylenedioxy) Thiophene) (hereinafter PEDOT), polymer materials such as PEDOT and polystyrene sulfonic acid (PSS) mixture (PEDOT / PSS), polythiophene oligomer material, Cu ₂ O, Mn ₂ O ₃ , NiO, Ag _{2 O, MoO 2, ZnO, TiO} , Ta 2 O 5, MoO 3, WO 3, MoO 3 which inorganic Such as fee compound, and the like.

  As a material for the electron transport layer, 2- (4-bifinylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (1-naphthyl)- 1,3,4-oxadiazole, an oxadiazole derivative, a bis (10-hydroxybenzo [h] quinolinolato) beryllium complex, a triazole compound, or the like can be used.

  Solvents that dissolve or disperse the organic light emitting material include toluene, xylene, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, 2-methyl- (t-butyl) Benzene, 1,2,3,4-tetramethylbenzene, pentylbenzene, 1,3,5-triethylbenzene, cyclohexylbenzene, 1,3,5-tri-isopropylbenzene and the like can be used alone or in combination. . Moreover, surfactant, antioxidant, a viscosity modifier, a ultraviolet absorber, etc. may be added to organic luminescent ink as needed.

  Solvents that dissolve or disperse the hole transport material and electron transport material include, for example, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, water, etc. Alternatively, a mixed solvent thereof can be used. In particular, water or alcohols are suitable when forming a hole transport material into an ink.

The organic light emitting medium layer is formed by a wet film forming method. As the wet film forming method, spin coating method, die coating method, dip coating method, discharge coating method, pre-coating method, roll coating method, bar coating method and the like, relief printing method, inkjet printing method, offset printing method, Examples of the printing method include a gravure printing method. In particular, when forming the organic light emitting layers 41, 42, and 43, it can be selectively applied to the pixel portion by a printing method. For this reason, it becomes possible to manufacture the organic EL element which can perform a color display by printing to each pixel the light emitting layer which light-emits in a mutually different color.
When the organic light emitting medium layer has a laminated structure, it is not necessary to form all of the layers by a wet film forming method. Particularly when a part of the laminated structure is made of an inorganic material, a known dry type is used. It can be formed by a film formation method, and examples thereof include a vacuum deposition method and a sputtering method.

  The organic light emitting layers 41, 42, and 43 are particularly preferably formed by a relief printing method. In the case of the relief printing method, the ink is transferred so that the convex portions of the plate and the substrate are in direct contact with each other. Therefore, it is desirable that the partition walls be lowered so that the convex portions and the substrate can be easily in contact with each other. When the organic EL element of the present invention is produced by the relief printing method, the relief plate to be used is preferably a water development type resin relief plate. As the water development type photosensitive resin constituting the resin relief plate, for example, a hydrophilic polymer is used. And a monomer containing an unsaturated bond, a so-called crosslinkable monomer, and a photopolymerization initiator. In this type, polyamide, polyvinyl alcohol, cellulose derivatives and the like are used as hydrophilic polymers. Examples of the crosslinkable monomer include methacrylates having a vinyl bond, and examples of the photopolymerization initiator include aromatic carbonyl compounds. Among these, a polyamide-based water-developable photosensitive resin is preferable from the viewpoint of printability.

  The printing apparatus used to form the organic light emitting layers 41, 42, and 43 can be any relief printing apparatus that prints on a flat plate, but the following printing apparatus is desirable. FIG. 4 shows a schematic diagram of a relief printing apparatus used for manufacturing the organic EL element of the present invention. This printing apparatus has a plate cylinder 14 to which an ink tank 10, an ink chamber 11, an anilox roll 12, and a resin relief plate 13 are attached. The ink tank 10 contains an organic light emitting ink diluted with a solvent, and the organic light emitting ink is fed into the ink chamber 11 from the ink tank 10. The anilox roll 12 rotates in contact with the ink supply unit of the ink chamber 11 and the plate cylinder 14.

  As the anilox roll 12 rotates, the organic light-emitting ink supplied from the ink chamber 11 is uniformly held on the surface of the anilox roll 12 and then has a uniform film thickness on the convex portion of the resin relief plate 13 attached to the plate cylinder 14. It will transfer at. Further, the substrate 15 to be printed is fixed on a slidable substrate fixing base, and is moved to the printing start position while adjusting the position by the position adjustment mechanism of the plate pattern and the substrate pattern, and the plate cylinder 14 is rotated. At the same time, the convex portion of the resin relief plate 13 further moves while being in contact with the substrate, and the ink is transferred by patterning to a predetermined position of the substrate 15 to be printed on the stage 16.

  Next, the second electrode 6 is formed. When the second electrode 6 is a cathode, a material having a high electron injection efficiency is used. Specifically, a single metal such as Mg, AL, or Yb is used, or a compound such as Li, oxidized Li, or LiF is sandwiched by about 1 nm at the interface in contact with the light emitting medium, and Al or Cu having high stability and conductivity is laminated. And use. Alternatively, in order to achieve both electron injection efficiency and stability, one or more metals such as Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, and Yb having a low work function and stable Ag, Al An alloy system with a metal element such as Cu is used. Specifically, alloys such as MgAg, AlLi, and CuLi can be used. Further, in the case of a top emission type organic EL device, the cathode needs to have transparency, and for example, transparency can be achieved by a combination of these metals and a transparent conductive layer such as ITO.

  As a method for forming the second electrode 6, a dry film forming method such as a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used. The thickness is preferably about 10 nm to 1 μm. In the present invention, the first electrode can be a cathode and the second electrode can be an anode.

  Since the organic light emitting material is easily deteriorated by moisture and oxygen in the atmosphere, the substrate 1 is sealed with the sealing substrate 8 through the sealing resin 7. The sealing resin 7 is preferably formed on the sealing substrate 8, but can also be directly formed on the substrate 1.

  The sealing substrate 8 needs to be a base material having low moisture and oxygen permeability. Moreover, ceramics such as alumina (aluminum oxide), silicon nitride and boron nitride, glass such as alkali-free glass and alkali glass, quartz, moisture-resistant film, and the like can be mentioned, but the present invention is not limited to these. Absent.

Examples of moisture-resistant films include films formed by CVD of SiOx on one or both sides of a plastic substrate, polymer films coated with a film with low permeability and a water-absorbing film, or a water-absorbing agent. The water vapor transmission rate of the conductive film is preferably 10 ⁻⁶ g / m ² day or less.

  Examples of the material of the sealing resin 7 include a photo-curing adhesive resin made of an epoxy resin, an acrylic resin, a silicone resin, a thermosetting adhesive resin, a two-component curable adhesive resin, and ethylene ethyl acrylate (EEA). ) Acrylic resins such as polymers, vinyl resins such as ethylene vinyl acetate (EVA), thermoplastic resins such as polyamide and synthetic rubber, and thermoplastic adhesive resins such as acid-modified products of polyethylene and polypropylene. However, the present invention is not limited to these.

  Methods for forming the sealing resin 7 on the sealing substrate 8 include solvent solution method, extrusion lamination method, melting / hot melt method, calendar method, nozzle coating method, screen printing method, vacuum laminating method, hot roll laminating. Law. A material having a hygroscopic property or an oxygen absorbing property may be contained as necessary. The thickness of the sealing resin 16 formed on the sealing substrate is arbitrarily determined depending on the size and shape of the organic EL display to be sealed, but is preferably about 5 μm to 500 μm.

  Finally, the substrate 1 and the sealing substrate 8 are bonded together. When a thermoplastic resin is used for the sealing resin 7, it is preferable to perform only the pressure bonding with a heated roll. When a thermosetting adhesive resin is used for the sealing resin 7, it is preferable to perform heat curing at a curing temperature after pressure bonding with a heated roll. When a photocurable adhesive resin is used for the sealing resin 7, it can be cured by further irradiating light after pressure bonding with a roll.

  The step of bonding the substrate 1 and the sealing substrate 8 through the sealing resin 7 is performed in a vacuum or in order not to include oxygen and moisture that cause deterioration of the organic EL display in the sealing resin 7. Perform in an active gas atmosphere. When an inert gas is used, a rare gas such as argon can be used, but nitrogen is preferably used for ease of handling and economical reasons.

  Next, although this invention is demonstrated according to an Example, it is not restricted to this.

(Example 1)
In order for the thin film transistor to function as a switching element, a top emission backplane formed so as to be connected to the first electrode 2 through a contact hole formed in the planarization film is used, and the number of pixels is 240 × 320 dots. The number of pixels was 720 × 320 dots. Then, chromium (Cr) was patterned by a sputtering method so that the space between the sub-pixels was 40 μm in length and 100 μm in width at a pitch of 120 μm × 360 μm, thereby forming the first electrode 2.

  Next, a positive photosensitive material TELR series (manufactured by Tokyo Ohka Co., Ltd.) was applied to the entire effective surface by a spin coating method. A plurality of first partition walls 51 having an arrangement as shown in FIG. The height of the obtained partition was 0.5 μm. In each first partition 51, the width of the overlapping portion with the first electrode 2 is 5 μm, covers the edge of the first electrode 2, and surrounds the four sides of the first electrode 2. Further, the same method was repeated to form the second partition wall 52 so that the height was 1.0 μm. Further, the width of the ink reservoir 44 surrounded by the first partition 51 and the second partition 52 is 10 μm.

  Next, a 0.1 μm-thick poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid mixture (hereinafter referred to as PEDOT / PSS) is dispersed in water as the hole transport layer 3 on the first electrode 2. Then, a film was formed by a spin coating method.

  Next, polyphenylene vinylene derivatives, which are organic light emitting materials having red, green, and blue emission colors, are performed for each color by a relief printing method using a water-developable photosensitive resin relief plate, and the organic light emitting layers 41, 42, 43 was formed. At this time, the film thickness of the obtained organic light emitting layers 41, 42, and 43 using an anilox roll of 150 lines / inch was 80 nm.

  Next, as the second electrode 6, Ba was deposited with a thickness of 5 nm by vacuum deposition, and Al was deposited thereon with a thickness of 20 nm. After that, an ITO film is formed using a sputtering method, and sealing is performed by sticking a glass plate with a thermosetting adhesive under nitrogen with a dew point of −80 degrees and an oxygen concentration of 1 ppm without exposure to the atmosphere. An EL element was obtained.

  When the obtained organic EL device is checked for lighting of the panel and the light emission state is checked, light emission unevenness such as a deviation of the light emission area within the pixel and a difference in luminance between pixels is confirmed, as well as color mixing. Was not. At this time, the pixel area was 100%, and the light emission area ratio was 93%.

(Comparative Example 1)
<When the first partition is high>
After forming the thin film transistor in the same manner as in Example 1, the height of the first barrier rib pattern is 1.5 μm, the vertical barrier rib width is 10 μm, the horizontal barrier rib width is 10 μm, and the overlapping portion with the first electrode 2 is 5 μm. Partitions having a grid pattern of one row at a time were formed between the first electrodes 2. Subsequent steps were performed in the same manner as in Example 1 to produce an organic EL device. When the display of the panel is checked for the obtained organic EL element and the light emission state is checked, the film in the vicinity of the partition wall is compared with the film thickness in the center of the electrode in the pixel composed of a part of the organic light emitting layer 41. Due to the increase in thickness, the flatness was poor, and light emission unevenness due to the uneven emission region was confirmed. At this time, the pixel area was 100%, and the light emission area ratio was 33%.

(Comparative Example 2)
<When there is no second partition>
After forming the thin film transistor in the same manner as in Example 1, the height of the first barrier rib pattern is 0.5 μm, the vertical barrier rib width is 10 μm, the horizontal barrier rib width is 10 μm, and the overlapping portion with the first electrode 2 is 5 μm. Partitions having a grid pattern of one row at a time were formed between the first electrodes 2. Subsequent steps were performed in the same manner as in Example 1 to produce an organic EL device. When the display of the panel was confirmed for the obtained organic EL element and the light emission state was checked, in the pixel composed of a part of the organic light emitting layer 41, there was no abnormality such as a deviation of the light emitting region, Color irregularity called color mixing has occurred.

(Comparative Example 3)
<When the second partition is low>
After forming the thin film transistor in the same manner as in Example 1, the height of the first barrier rib pattern is 0.5 μm, the vertical barrier rib width is 10 μm, the horizontal barrier rib width is 10 μm, and the overlapping portion with the first electrode 2 is 5 μm. Partitions having a grid pattern of one row at a time were formed between the first electrodes 2. Furthermore, the 2nd partition 52 was created with the method and conditions similar to a 1st partition. At this time, the height of the second partition wall 52 is 0.8 μm, and the vertical partition wall width is 10 μm. The horizontal partition wall width was 10 μm. As a result, the ink reservoir 44 was provided with a width of 10 μm. Subsequent steps were performed in the same manner as in Example 1 to produce an organic EL device. When the display of the panel was confirmed with respect to the obtained organic EL element and the light emission state was checked, in the pixel composed of a part of the organic light emitting layer 41, a color unevenness abnormality called color mixture occurred.

(Comparative Example 4)
<When the second partition is high>
After forming the thin film transistor in the same manner as in Example 1, the height of the first barrier rib pattern is 0.5 μm, the vertical barrier rib width is 10 μm, the horizontal barrier rib width is 10 μm, and the overlapping portion with the first electrode 2 is 5 μm. Partitions having a grid pattern of one row at a time were formed between the first electrodes 2. Furthermore, the 2nd partition 52 was created with the method and conditions similar to a 1st partition. At this time, the height of the second partition wall 52 is 1.6 μm, and the vertical partition wall width is 10 μm. The horizontal partition wall width was 10 μm. As a result, the ink reservoir 44 was provided with a width of 10 μm. Subsequent steps were performed in the same manner as in Example 1 to produce an organic EL device. When the display of the panel is confirmed for the obtained organic EL element and the light emission state is checked, the transfer of ink caused by the second partition walls being too high in the pixel composed of a part of the organic light emitting layer 41. A defect occurred and the missing pixel was confirmed.

  According to the present invention, by having the second partition between the first electrodes, color mixing is prevented and the flatness of the organic light emitting layer surrounded by the partition on the edge of the first electrode is improved. An organic EL element having high optical characteristics free from uneven light emission and color mixing and free from uneven light emission between pixels can be obtained.

DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... 1st electrode 3 ... Hole transport layer 41 ... Red organic light emitting layer 42 ... Green organic light emitting layer 43 ... Blue organic light emitting layer 44 ... Ink reservoir 51 ... 1st partition 52 ... 2nd partition 6 ... 2nd electrode 7 ... Sealing resin 8 ... Sealing substrate 9 ... Organic EL element 10 ... Ink tank 11 .... Ink chamber 12 ... Anilox roll 13 ... Resin relief plate 14 ... Plate cylinder 15 ... Substrate 16 ... Stage

Claims (5)

At least a substrate, a first electrode formed on the substrate, an organic light emitting medium layer formed on the first electrode, and provided to face the first electrode across the organic light emitting medium layer An organic electroluminescence device comprising a second electrode,
A first partition formed around an end of the first electrode; a second partition formed so as to surround and separate the first electrode and the first partition; the first partition and the second partition It has a, and an ink reservoir which is surrounded by the,
The height of the second partition is higher than the height of the first partition,
The height of the first partition is 0.1 μm or more and 0.5 μm or less, the height of the second partition is 1.0 μm or more and 1.5 μm or less,
The width of the ink reservoir is 10 μm or more and 15 μm or less, and the organic electroluminescence element. 2. The organic electro luminescence device according to claim 1, wherein the second barrier rib is formed in a lattice shape, and the first barrier rib and the first electrode are formed in a region surrounded by the second lattice barrier rib. Luminescence element. The second barrier rib is formed so as to surround the plurality of first electrodes and the first barrier rib, and an organic light emitting medium layer made of the same material is formed on the plurality of first electrodes surrounded by the second barrier rib. The organic electroluminescent element according to claim 1 . Forming a first electrode on the substrate;
Forming a first partition around the end of the first electrode;
Forming a second partition so as to surround the first partition apart from the first partition, and forming an ink reservoir surrounded by the first partition and the second partition;
Forming an organic light emitting medium layer on the first electrode;
Forming a second electrode so as to face the first electrode across the organic light emitting medium layer;
It is a manufacturing method of an organic electroluminescence element characterized by consisting of:
The height of the second partition is higher than the height of the first partition,
The height of the first partition is 0.1 μm or more and 0.5 μm or less, the height of the second partition is 1.0 μm or more and 1.5 μm or less,
The ink reservoir is formed to have a width of 10 μm to 15 μm,
The method of forming an organic electroluminescent element is characterized in that the step of forming the organic light emitting medium layer is a wet film forming method. The method for producing an organic electroluminescence element according to claim 4 , wherein the wet film forming method is a relief printing method.

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