JP2012074225A - Organic el element and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic EL element having high performance, long life, and high luminance at low cost with fewer processes, and provide a manufacturing method of the organic EL element.SOLUTION: An organic EL element 1 includes: a substrate 2; a plurality of first electrodes 4 formed so as to be patterned on the substrate 2; a barrier 6 formed on the substrate 2 and covering the side surface of each of the first electrodes 4; a light-emitting medium layer 8 formed on each of the first electrodes 4 and the barrier 6; and a second electrode 10 formed on the substrate 2 and the light-emitting medium layer 8. The organic EL element 1 further includes a liquid repellent layer 12 formed so as to be patterned on the barrier 6 between the light-emitting medium layer 8 and the second electrode 10, and the light-emitting medium layer 8 includes a carrier injection layer 14 formed so as to cover each of the first electrodes 4 and the barrier 6, and an organic light-emitting layer 16 formed so as to be patterned on each of the first electrodes 4 of a carrier injection layer 14. The liquid repellent layer 12 is formed between the carrier injection layer 14 and the second electrode 10.

Description

  The present invention relates to an organic EL element used for a wide range of applications, such as a display of an information display terminal, and a method for manufacturing the same.

In an organic EL (electroluminescence) element, 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.
In order to efficiently emit light from the organic EL element, the thickness of the organic light emitting layer is important.
Further, in order to make this organic EL element into a color display, it is necessary to pattern the organic light emitting layer with high definition.

Generally, as a substrate for a color display, a substrate in which a patterned photosensitive polyimide is formed in a partition shape so as to partition subpixels is used. In that case, the partition pattern is formed so as to cover the edge portion of the transparent electrode formed as an anode.
In addition, there are two types of methods for forming a carrier injection layer for injecting hole carriers: a dry film formation method and a wet film formation method. A polythiophene derivative dispersed in the aqueous ink is used, but the water-based ink is easily affected by the base, and it is very difficult to coat uniformly.

On the other hand, film formation by vacuum vapor deposition can easily perform uniform entire surface coating.
There are two methods for forming the organic light emitting layer, the dry film forming method and the wet film forming method, as in the method for forming the carrier injection layer. When the vapor deposition method is used, it is necessary to perform patterning using a fine pattern mask, which makes it very difficult to use a large substrate or fine patterning.
Therefore, recently, a method has been attempted in which a polymer material is dissolved in a solvent to form a coating liquid, and this coating liquid is formed into a thin film by a wet film forming method.

As described above, the layer structure in the case of forming the light emitting medium layer including the organic light emitting layer by the wet film forming method using the coating liquid of the polymer material includes the hole transport layer, the organic light emitting layer and the like from the anode side. A two-layer structure is generally laminated.
At this time, in order to make the organic light emitting layer into a color panel, the organic light emitting materials having respective emission colors of red (R), green (G), and blue (B) are dissolved in a solvent or stable. It is possible to paint separately using the organic light-emitting ink dispersed (see Patent Documents 1 and 2).
In addition to the organic light emitting layer, a carrier injection layer (carrier transport layer) is formed between the electrodes.

Here, the carrier injection layer means that when electrons are injected from the electrode into the organic light emitting layer, the amount of injected electrons is controlled or when holes are injected from the other electrode into the organic light emitting layer. It is a layer used to control the amount of holes injected, and is a layer inserted between the electrode and the organic light emitting layer.
As the electron injecting layer, an electron transporting organic material such as a metal complex of a quinolinol derivative, a relatively small work function such as Ca or Ba, such as an alkali metal, or the like is used. In some cases, a plurality of layers having the above functions are stacked.
As the carrier injection layer, TPD (triphenyleneamine derivative: see Patent Document 3), PEDOT: PSS (mixture of polythiophene and polystyrenesulfonic acid: see Patent Document 4), or a hole transport material of an inorganic material ( Patent Document 5) can be used.

JP 2001-93668 A JP 2001-155858 A Japanese Patent No. 2916098 Japanese Patent No. 2851185 JP-A-9-63771

Any of the above carrier injection layers has the purpose of increasing the light emission efficiency by controlling the injection amount of electrons and holes by inserting it between the electrode and the light emitting layer.
In this case, ideally, it is possible to draw out performance by using different carrier injection layers for the respective light emitting layers of RGB. However, when different carrier injection layers are used, the number of steps is increased in the mass production process, and patterning with high definition becomes difficult. Therefore, a solid film common to RGB is formed in the carrier transport layer. It is common.

However, when an attempt is made to form a pattern on a solid film, the organic light-emitting ink flows to cause unevenness and repelling. For this reason, there arise problems that a desired pattern cannot be obtained and a uniform film thickness cannot be obtained.
In particular, when RGB pattern formation is insufficient, color mixture occurs in adjacent pixels and the emission color changes, which is fatal for a display.

As a method of forming an RGB pattern, there are a printing method, an ink jet method, a nozzle print, and the like. In particular, the ink jet method and the nozzle print method adopt a low viscosity condition in order to ensure a stable discharge property. There are many problems, and the fluidity of the solution is high, so that there is a problem of further color mixing.
In the present invention, even on a solid carrier injection layer, there is no color mixing to adjacent pixels, patterning is stable and high-definition, high efficiency, long life, high brightness, low cost with few processes An object of the present invention is to provide an organic EL device and a method for manufacturing the same.

Among the present inventions, the invention described in claim 1 is a substrate, a plurality of first electrodes formed by patterning on the substrate, and a side surface of each first electrode formed on the substrate. An organic EL device comprising: a partition wall to cover; the first electrode and a light emitting medium layer formed on the partition; and a second electrode formed on the substrate and the light emitting medium layer,
The light emitting medium layer includes a carrier injection layer formed so as to cover the first electrodes and the partition walls, and an organic light emission formed by patterning the first electrode among the carrier injection layers. A layer, and
A liquid repellent layer formed by patterning on the partition is provided between the carrier injection layer and the second electrode.

Next, of the present invention, the invention described in claim 2 is the invention described in claim 1, wherein the carrier injection layer is an inorganic compound.
Next, of the present invention, the invention described in claim 3 is the invention described in claim 1, wherein the carrier injection layer is an organic compound.

Next, among the present inventions, the invention described in claim 4 includes a first electrode forming step of patterning and forming a plurality of first electrodes on a substrate, and a partition covering the side surfaces of the first electrodes. A barrier rib forming step formed on the substrate, a light emitting medium layer forming step for forming a light emitting medium layer on each of the first electrodes and the barrier ribs, and a second electrode for forming a second electrode on the substrate and the light emitting medium layer. An organic EL device manufacturing method including an electrode forming step,
A liquid repellent layer forming step of forming a liquid repellent layer by patterning on the partition wall between the carrier injection layer and the second electrode;
The light emitting medium layer forming step includes a carrier injection layer forming step of forming a carrier injection layer so as to cover the first electrodes and the partition walls, and an organic light emitting layer of the first of the carrier injection layers. An organic light emitting layer forming step formed by patterning on the electrode,
In the organic light emitting layer forming step, an organic light emitting material that is a material of the organic light emitting layer is dissolved or dispersed in a solvent on the carrier injection layer formed so as to cover the first electrodes and the partition walls. The organic light emitting ink is applied to form an organic light emitting layer by patterning.

Next, of the present invention, the invention described in claim 5 is the invention described in claim 4, wherein the organic light emitting layer forming step is performed by any one of a printing method, an inkjet method, and a nozzle printing method. It is characterized by being used.
Next, among the present inventions, the invention described in claim 6 is the invention described in claim 4 or 5, wherein the liquid repellent layer forming step is performed by using a laminate transfer method. It is what.

According to the present invention, the liquid-repellent layer is formed on the partition by patterning on the first electrode and on the carrier injection layer formed so as to cover the partition, and formed on the first electrode. The carrier injection layer can be flattened.
As a result, the film thickness of each pixel can be made uniform, and the organic light-emitting layer formed by patterning on the carrier injection layer can be patterned stably and with high resolution without color mixing with adjacent pixels. It becomes possible to do.
For this reason, it is possible to provide an organic EL element and a method for manufacturing the organic EL element that have high efficiency, long life, and high brightness, and can be provided at low cost with a small number of processes.

It is sectional drawing which shows schematic structure of the organic EL element in 1st embodiment of this invention. It is sectional drawing which shows the detailed structure of a board | substrate. It is a figure which shows schematic structure of the relief printing apparatus used for a relief printing method. It is sectional drawing which shows schematic structure of the modification in 1st embodiment of this invention.

(First embodiment)
Hereinafter, a configuration of an organic EL element according to the present embodiment and a method for manufacturing the organic EL element according to the first embodiment of the present invention (hereinafter referred to as “this embodiment”) will be described with reference to the drawings. .
(Constitution)
First, the structure of the organic EL element 1 of this embodiment is demonstrated using FIG.
FIG. 1 is a cross-sectional view showing a schematic configuration of an organic EL element 1 in the present embodiment.
As shown in FIG. 1, the organic EL element 1 includes a substrate 2, a plurality of first electrodes 4, a partition wall 6, a light emitting medium layer 8, a second electrode 10, and a liquid repellent layer 12. .
In this embodiment, as an example, a case where the organic EL element 1 is an active matrix driving type organic EL element in which the first electrode 4 is an anode and the second electrode 10 is a cathode will be described.

In this case, the first electrode 4 is formed as a pixel electrode partitioned by the partition wall 6 for each pixel, and the second electrode 10 is formed as a counter electrode formed on the entire surface of the element. Further, the carrier injection layer 14 described later is a hole transporting hole injection layer.
The configuration of the organic EL element 1 is not limited to the above configuration. For example, a passive matrix driving type in which each electrode (first electrode 4 and second electrode 10) is formed in a stripe shape orthogonal to each other. It may be an organic EL element.
Alternatively, the first electrode 4 may be a cathode and the second electrode 10 may be an anode. In this case, the carrier injection layer 14 is an electron transporting electron injection layer.

(Detailed configuration of substrate 2)
Hereinafter, a detailed configuration of the substrate 2 will be described with reference to FIG. 1 and FIG. 2.
FIG. 2 is a cross-sectional view showing a detailed configuration of the substrate 2.
In the present embodiment, a case where a TFT substrate provided with the first electrode 4 and the partition 6 is used as the substrate 2 will be described as an example.
As shown in FIG. 2, the substrate 2 provided in the organic EL element 1 of the present embodiment is provided with a thin film transistor 20 (TFT) and a first electrode 4 (pixel electrode).
The thin film transistor 20 and the first electrode 4 are electrically connected.

The thin film transistor 20 is supported by the substrate 2 (support).
As the substrate 2, any material can be used as long as it has mechanical strength and insulation and is excellent in dimensional stability.
Here, examples of the material of the substrate 2 include plastic films and sheets such as glass, quartz, polypropylene, polyethersulfone, polycarbonate, cycloolefin polymer, polyarylate, polyamide, polymethyl methacrylate, polyethylene terephthalate, and polyethylene naphthalate. Can be used.

  The material of the substrate 2 is, for example, a metal oxide such as silicon oxide or aluminum oxide, a metal fluoride such as aluminum fluoride or magnesium fluoride, silicon nitride, aluminum nitride, etc. Translucent substrate made of metal nitride, silicon oxynitride such as silicon oxynitride, polymer resin film such as acrylic resin, epoxy resin, silicone resin, polyester resin, etc., aluminum, stainless steel, etc. It is possible to use a metal foil, a sheet, a plate, or the like.

Furthermore, as the material of the substrate 2, for example, a non-translucent base material in which a metal film such as aluminum, copper, nickel, stainless steel or the like is laminated on the above-described plastic film or sheet can be used.
Here, the translucency of the substrate 2 may be selected according to which surface the light is extracted from.
The substrate 2 made of the above material has been subjected to moisture-proofing treatment or hydrophobic treatment by forming an inorganic film or applying a fluororesin in order to avoid intrusion of moisture into the organic EL element 1. Is preferred. In particular, in order to avoid intrusion of moisture into the light emitting medium layer 8, it is preferable to reduce the moisture content and gas permeability coefficient in the substrate 2.
As the thin film transistor 20, a known thin film transistor can be used.

Specifically, a thin film transistor composed mainly of an active layer 22 in which a source / drain region and a channel region are formed, a gate insulating film 24, and a gate electrode 26 can be given.
Here, the structure of the thin film transistor 20 is not particularly limited, and examples thereof include a staggered type, an inverted staggered type, a top gate type, and a coplanar type.

The configuration of the active layer 22 is not particularly limited, and for example, an inorganic semiconductor material such as amorphous silicon, polycrystalline silicon, microcrystalline silicon, cadmium selenide, thiophene oligomer, poly (p-ferri), or the like. It can be formed of an organic semiconductor material such as (lenvinylene).
The active layer 22 is formed by using, for example, a method of laminating amorphous silicon by plasma CVD and ion doping.

As a method of laminating amorphous silicon by plasma CVD and performing ion doping, for example, amorphous silicon is formed by LPCVD using SiH ₄ gas, and amorphous silicon is crystallized by solid phase growth to form polysilicon. After obtaining the above, there may be mentioned a method of ion doping by ion implantation.
As a method of laminating amorphous silicon by plasma CVD and ion doping, for example, amorphous silicon is formed by LPCVD using Si ₂ H ₆ gas and PECVD using SiH ₄ gas. In addition, there is a method (low temperature process) in which annealing is performed by a laser such as an excimer laser, and amorphous silicon is crystallized to obtain polysilicon, and then ion doping is performed by an ion doping method.

  As a method of laminating amorphous silicon by plasma CVD and performing ion doping, for example, polysilicon is laminated by low pressure CVD or LPCVD, and thermally oxidized at 1000 [° C.] or higher to form a gate insulating film. A method (high temperature process) of forming an n + polysilicon gate electrode 8 thereon and then performing ion doping by an ion implantation method can be used.

As the gate insulating film 24, what is generally used as a gate insulating film can be used. That is, as the gate insulating film 24, for example, SiO ₂ formed by PECVD, LPCVD, or the like, or SiO ₂ obtained by thermally oxidizing a polysilicon film can be used.
As the gate electrode 26, what is generally used as a gate electrode can be used. That is, examples of the material of the gate electrode 26 include metals such as aluminum and copper (refractory metals such as titanium, tantalum, and tungsten), polysilicon, silicides of refractory metals, polycides, and the like.

Note that the structure of the thin film transistor 20 may be 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.
Moreover, the organic EL element 1 of this embodiment needs to be connected so that the thin film transistor 20 functions as a switching element of the organic EL element 1. For this reason, the drain electrode 28 of the thin film transistor 20 and the first electrode 4 are electrically connected. In FIG. 2, reference numeral 30 is assigned to the source electrode, and reference numeral 32 is assigned to the scanning line.

(Detailed configuration of the first electrode 4)
Hereinafter, the detailed configuration of the first electrode 4 will be described with reference to FIGS. 1 and 2.
Each first electrode 4 is formed in a pattern on the substrate 2 and is partitioned by a partition wall 6 to form a pixel electrode corresponding to each pixel.
Examples of the material of the first electrode 4 include metal composite oxides such as ITO (indium tin composite oxide), indium zinc composite oxide, and zinc aluminum composite oxide, metal materials such as gold and platinum, and these metal oxides. In addition, it is possible to use either a single layer or a laminate of a fine particle dispersion film in which fine particles of a metal material are dispersed in an epoxy resin, an acrylic resin or the like.

  Here, when the first electrode 4 is used as an anode, it is preferable to select a material having a high work function such as ITO. In the case of a so-called bottom emission structure in which light is extracted from below, it is necessary to select a light-transmitting material. Further, if necessary, a metal material such as copper or aluminum may be provided as an auxiliary electrode in order to reduce the wiring resistance of the first electrode 4.

(Detailed configuration of partition wall 6)
Hereinafter, with reference to FIG.1 and FIG.2, the detailed structure of the partition 6 is demonstrated.
The partition wall 6 is formed on the substrate 2 and is formed so as to partition the light emitting region corresponding to the pixel by covering the side surface of each first electrode 4.
Here, in general, in the active matrix driving type organic EL element 1, the first electrode 4 is formed for each pixel (sub-pixel), and each pixel tries to occupy as wide an area as possible. Therefore, the most preferable shape of the partition wall 6 formed so as to cover the end portion (side surface) of the first electrode 4 is basically a lattice shape that divides each first electrode 4 by the shortest distance.

Moreover, the material of the partition 6 contains an ethylenically unsaturated compound, a photoinitiator, and an alkali-soluble binder at least. Furthermore, the material of the partition wall 6 preferably contains a surfactant or the like, and also contains a solvent.
The suitable height of the partition wall 6 is in the range of 0.1 [μm] to 10 [μm], and more preferably in the range of 0.5 [μm] to 2 [μm]. It is. The reason is that if the height of the partition wall 6 is too high, the formation and sealing of the second electrode 10 (counter electrode) is hindered. If the height of the partition wall 6 is too low, the end of the first electrode 4 is completely covered. This is because there is no color mixing with adjacent pixels when the light emitting medium layer 8 is formed.

Examples of the cross-sectional shape of the partition wall 6 include a trapezoidal shape such as a forward taper shape and a reverse taper shape, a semicircular shape, and the like, and may have a multistage shape.
Here, when the cross-sectional shape of the partition wall 6 is a multi-stage shape, even if the lower stage on the lower substrate side and the upper stage on the upper substrate side are different materials / formation methods, the same material / formation method is used. Also good. In this case, for example, the lower stage is made of an inorganic material such as SiN, and the upper stage is made of the above-described material.

(Detailed structure of the light emitting medium layer 8)
Hereinafter, the detailed configuration of the light emitting medium layer 8 will be described with reference to FIGS. 1 and 2.
The light emitting medium layer 8 is formed on each of the first electrodes 4 and the partition walls 6 and includes a carrier injection layer 14, an organic light emitting layer 16, and an interlayer layer 18.
The carrier injection layer 14 is formed so as to cover the first electrodes 4 and the partition walls 6, specifically, the first electrodes 4 and the entire surface of the partition walls 6. As a result, the film shape in the pixel region becomes flat, and the film thickness for each pixel can be made uniform.

The detailed configuration of the carrier injection layer 14 will be described later.
The organic light emitting layer 16 is formed in a pattern on each first electrode 4 on the carrier injection layer 14. The detailed configuration of the organic light emitting layer 16 will be described later.
The interlayer layer 18 is formed between the carrier injection layer 14 and the organic light emitting layer 16 and laminated with the carrier injection layer 14 and the organic light emitting layer 16. In addition, the interlayer layer 18 forms an electron injection layer, a hole injection layer, and an electron block layer.

(Detailed configuration of carrier injection layer 14)
Hereinafter, the detailed configuration of the carrier injection layer 14 will be described with reference to FIGS. 1 and 2.
The carrier injection layer 14 has a shape along the partition wall 6, and an organic light emitting layer 16 formed on the carrier injection layer 14 by forming the liquid repellent layer 12 on the top (upper surface of the uppermost step). Is formed outside the region of the liquid repellent layer 12 without color mixing.
As a result, the organic EL elements 1 can be arranged as pixels (subpixels), and an image display device can be obtained. That is, a full-color display panel is produced by, for example, separately applying R (red), G (green), and B (blue) colors without mixing the organic light-emitting layer 16 constituting each pixel. Is possible.

The thickness of the carrier injection layer 14 is preferably in the range of 20 [nm] to 100 [nm]. This is because short defects are likely to occur when the thickness of the carrier injection layer 14 is thinner than 20 [nm], and when the thickness of the carrier injection layer 14 exceeds 100 [nm], the resistance is increased. This is because current is generated.
Any material can be used as the material of the carrier injection layer 14. For example, a material having a resistivity of 10 ⁴ [Ω · cm] or more is preferably used to prevent a short circuit between pixels. It is. In this case, by providing a step in the shape of the partition wall 6, the film thickness of the carrier injection layer 14 may be changed to suppress a short circuit between pixels.

Examples of the material of the carrier injection layer 14 include Cu ₂ O, Cr ₂ O ₃ , Mn ₂ O ₃ , FeOx, NiO, CoO, Pr ₂ O ₃ , Ag ₂ O, MoO ₂ , Bi ₂ O ₃ , One kind of transition metal oxides such as ZnO, TiO ₂ , SnO ₂ , ThO ₂ , V ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ , MoO ₃ , WO ₃ , MnO ₂ , and nitrides and sulfides thereof. The inorganic compound contained above is mentioned.

  Examples of the material for the carrier injection layer 14 include polyaniline derivatives, oligoaniline derivatives, quinonediimine derivatives, polythiophene derivatives, polyvinylcarbazole (PVK) derivatives, poly (3,4-ethylenedioxythiophene) (PEDOT), and pyrrole derivatives. , Aromatic amines, (triphenylamine) dimer derivative (TPD), (α-naphthyldiphenylamine) dimer (α-NPD), [(triphenylamine) dimer] spiro dimer (Spiro-TAD) 4,4 ′, 4 ″ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4 ′, 4 ″ -tris [1-naphthyl (phenyl) amino] tri Starburst amines such as phenylamine (1-TNATA) and 5, Oligothiophenes such as' -α-bis- {4- [bis (4-methylphenyl) amino] phenyl} -2,2 ': 5', 2'-α-terthiophene (BMA-3T), aromatic Examples include amine-containing polymers, aromatic diamine-containing polymers, fluorene-containing aromatic amine polymers, triazole-based, oxazole-based, oxadiazole-based, silole-based, and boron-based organic compounds.

  In particular, as described above, when the carrier injection layer 14 is a hole transporting hole injection layer, examples of the material of the carrier injection layer 14 include polyaniline derivatives, oligoaniline derivatives, quinonediimine derivatives, and polythiophene derivatives. , Polyvinylcarbazole (PVK) derivative, poly (3,4-ethylenedioxythiophene) (PEDOT), pyrrole derivative, aromatic amine, (triphenylamine) dimer derivative (TPD), (α-naphthyldiphenylamine) dimer (α -NPD), [(triphenylamine) dimer] spiro dimer (Spiro-TAD) and the like triarylamines, 4,4 ′, 4 ″ -tris [3-methylphenyl (phenyl) amino] triphenylamine ( m-MTDATA), 4,4 ′, 4 ″ -Tris [1-naphthyl (pheny ) Starburst amines such as amino] triphenylamine (1-TNATA) and 5,5′-α-bis- {4- [bis (4-methylphenyl) amino] phenyl} -2,2 ′: 5 ′ , 2′-α terthiophene (BMA-3T), aromatic amine-containing polymers, aromatic diamine-containing polymers, fluorene-containing aromatic amine polymers, and the like.

As described above, when an inorganic material is used as the material for the hole injection layer, examples of the inorganic material include Cu ₂ O, Cr ₂ O ₃ , Mn ₂ O ₃ , FeOx, NiO, CoO, and Pr ₂ O. ₃ , Ag ₂ O, MoO ₂ , Bi ₂ O ₃ , ZnO, TiO ₂ , SnO ₂ , ThO ₂ , V ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ , MoO ₃ , WO ₃ , MnO _2, etc. Transition metal oxides and inorganic compounds containing one or more of these nitrides and sulfides can be used.

However, the above materials are not limited to these. In other words, inorganic materials are suitable because many materials are excellent in heat resistance and electrochemical stability, but these materials should be formed as a single layer or a laminated structure of a plurality of layers or a mixed layer. Is possible. In this case, the preferable film thickness is 5 [nm] or more, and more preferably about 15 [nm] or more.
On the other hand, as described above, when the carrier injection layer 14 is an electron transporting electron injection layer, the material of the carrier injection layer 14 is, for example, generally used as an electron transport material. Low molecular materials such as triazole, oxazole, oxadiazole, silole, and boron, alkali metals such as lithium fluoride and lithium oxide, salts of alkaline earth metals, oxides, etc. It is possible to use.

(Detailed structure of the organic light emitting layer 16)
Hereinafter, with reference to FIG.1 and FIG.2, the detailed structure of the organic light emitting layer 16 is demonstrated.
The organic light emitting layer 16 emits light by recombining holes and electrons. When the display light emitted from the organic light emitting layer 16 is monochromatic, it is formed so as to cover the interlayer layer 18. In order to obtain multicolor display light, it can be suitably used by performing patterning as necessary.

  Examples of the organic light emitting material for forming the organic light emitting layer 16 include coumarin, perylene, pyran, anthrone, porphyrene, quinacridone, N, N′-dialkyl-substituted quinacridone, naphthalimide, N, N ′. -Diaryl substituted pyrrolopyrrole, iridium complex and other luminescent dyes dispersed in polymers such as polystyrene, polymethyl methacrylate, polyvinylcarbazole, polyarylene, polyarylene vinylene and polyfluorene Although polymeric materials are mentioned, in this embodiment, it is not necessarily limited to these materials.

Said organic luminescent material becomes organic luminescent ink by melt | dissolving or disperse | distributing stably to a solvent.
Here, examples of the solvent for dissolving or dispersing the organic light emitting material include toluene, xylene, acetone, anisole, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like, or a mixed solvent thereof. In particular, aromatic organic solvents such as toluene, xylene, and anisole are preferable from the viewpoint of the solubility of the organic light emitting material. Moreover, surfactant, antioxidant, a viscosity modifier, a ultraviolet absorber, etc. may be added to said organic luminescent ink as needed.

  Examples of the organic light emitting material for forming the organic light emitting layer 16 include 9,10-diarylanthracene derivatives, pyrene, coronene, perylene, rubrene, 1,1,4,4-tetra, in addition to the polymer materials described above. Phenylbutadiene, tris (8-quinolato) aluminum complex, tris (4-methyl-8-quinolato) aluminum complex, bis (8-quinolato) zinc complex, tris (4-methyl-5-trifluoromethyl-8-quinolate) 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-sia Phenyl) phenolate] aluminum complex, tris (8-quinolinolato) scandium complex, bis [8- (para-tosyl) aminoquinoline] zinc complex and cadmium complex, 1,2,3,4-tetraphenylcyclopentadiene, poly-2 , 5-diheptyloxy-para-phenylene vinylene and other low molecular weight light emitting materials can be used.

(Detailed configuration of the second electrode 10)
Hereinafter, the detailed configuration of the second electrode 10 will be described with reference to FIGS. 1 and 2.
The second electrode 10 is formed on the substrate 2 and the light emitting medium layer 8 and faces each first electrode 4.
As a material of the second electrode 10, when the second electrode 10 is a cathode, for example, a substance having a high electron injection efficiency into the organic light emitting layer 16 and a low work function is used. In this case, specifically, a simple metal such as Mg, Al, or Yb may be used, and a compound such as Li, oxidized Li, or LiF is sandwiched by about 1 [nm] at the interface contacting the light emitting medium layer 8. Therefore, Al or Cu having high stability and conductivity may be laminated.

  The material of the second electrode 10 is, for example, Li, Mg, Ca, Sr, La, Ce, Er, Eu, which is a substance having a low work function in order to achieve both electron injection efficiency and stability. An alloy system of one or more metals such as Sc, Y, and Yb and a stable metal element such as Ag, Al, or Cu may be used. In this case, specifically, an alloy such as MgAg, AlLi, or CuLi can be used.

(Detailed configuration of the liquid repellent layer 12)
Hereinafter, the detailed configuration of the liquid repellent layer 12 will be described with reference to FIGS. 1 and 2.
The liquid repellent layer 12 is formed in a pattern on the partition 6 between the light emitting medium layer 8 and the second electrode 10, specifically, between the carrier injection layer 14 and the second electrode 10.
Examples of the material of the liquid repellent layer 12 include a silicon-containing compound and a fluorine compound, but a fluorine compound is preferable.
In the material of the liquid repellent layer 12, the molecular weight of the liquid repellent is not particularly limited, and may be a low molecular weight compound or a high molecular weight body.

  As the fluorine-based compound, a compound containing a perfluoroalkyl group (perfluoroalkyl group-containing compound) is suitable. For example, JP-A-7-35916, JP-A-11-281815, and International Publication 2004- In addition to the liquid repellent compounds disclosed in pamphlet No. 042474, JP-A 2005-60515, JP-A 2005-315984, JP-A 2006-71086, etc., “BYK-340” manufactured by Big Chemie, “Modiper F200”, “Modiper F600”, “Modiper F3035” manufactured by NOF Corporation, “Furgent M series, S series, F series, G series, D series, oligomer series” manufactured by Neos, Daikin Industries “Unidyne” manufactured by Shin-Etsu Silicone Co., Ltd. “Trifluoropropyl” Rikuroroshiran ", commercially available products and the like AGC Seimi Chemical Co., Ltd.," Surflon S-386 ", a resin obtained by copolymerizing perfluoro group-containing acrylic monomer as a component and the like can also be mentioned.

Furthermore, a compound containing a perfluoropolyether group or the like capable of avoiding a perfluoroalkyl group exceeding C6, which is concerned about safety, is also effective.
Moreover, as said fluorine-type compound, it is also possible to use a fluorinated epoxy resin, a fluorinated polyimide resin, a fluorinated polyamide resin, a fluorinated polyurethane resin, a fluorinated siloxane resin, and modified resins thereof.
As the liquid repellent, it is effective to use a liquid repellent resin, but besides this, as the liquid repellent, for example, a compound having a crosslinkable group capable of undergoing a cross-linking reaction at the time of exposure (hereinafter referred to as “liquid repellent”). , Which may be described as “cross-linkable group-containing liquid repellent”.

  Specific examples of the fluorine-containing compound as the crosslinkable group-containing liquid repellent include, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt, Oligomers containing fluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and new oil groups, urethanes containing perfluoroalkyl and hydrophilic groups, perfluoroalkyls Fluorine-containing organic compounds such as esters and perfluoroalkyl phosphate esters can be mentioned.

  Commercially available products of these fluorine-containing compounds include, for example, “Megafac F116”, “Megafac F120”, “Megafac F142D”, “Megafac F144D”, “Megafac F150” manufactured by Dainippon Ink and Chemicals, Inc. ”,“ Mega Fuck F160 ”,“ Mega Fuck F171 ”,“ Mega Fuck F172 ”,“ Mega Fuck F173 ”,“ Mega Fuck F177 ”,“ Mega Fuck F178A ”,“ Mega Fuck F178K ”,“ Mega Fuck F179 ”, “Megafuck F183”, “Megafuck F184”, “Megafuck F191”, “Megafuck F812”, “Megafuck F815”, “Megafuck F824”, “Megafuck F833”, “DEFENSAMCF300”, “Megafuck MCF310” " “Megafuck MCF312”, “Megafuck MCF323”, “Megafuck RS304”, “Megafuck RS202”, “Megafuck RS201”, “Megafuck RS102”, “Megafuck RS101”, “Megafuck RS105”, “Mega Use fluorine-containing organic compounds commercially available under trade names such as "Fuck RS401", "MegaFuck RS402", "MegaFuck RS501", "MegaFuck RS502", "MegaFuck RS301", "MegaFuck RS303", etc. Is possible.

In addition to the above-mentioned commercial products of fluorine-containing compounds, for example, “Florard FC430”, “Megafac FC431” manufactured by Sumitomo 3M, “Asahi Guard AG710”, “Surflon S-” manufactured by Asahi Glass Co., Ltd. 382 "," Megafuck SC-101 "," Megafuck SC-102 "," Megafuck SC-103 "," Megafuck SC-104 "," Megafuck SC-105 "," Megafuck SC-106 " Alternatively, it is possible to use a fluorine-containing organic compound marketed under a trade name such as “Obtool DAC” manufactured by Daikin Industries, Ltd.
As a more preferable crosslinkable group-containing liquid repellent, for example, a resin having a fluorine atom-substituted substituent introduced into a resin having an epoxy resin, a phenol resin, a phenoxy resin, or an acrylate resin as a main skeleton can be mentioned.

  Hereinafter, such a crosslinkable group-containing liquid repellent, in particular, an epoxy resin type crosslinkable group-containing liquid repellent that is obtained by introducing a fluorine atom-substituted substituent into a resin having an epoxy resin as a main skeleton, and a phenol resin. The phenol resin type crosslinkable group-containing liquid repellent, in which a fluorine atom-substituted substituent is introduced into the resin having the main skeleton, will be specifically described.

(Description of epoxy resin type crosslinkable group-containing liquid repellent)
As an epoxy resin type crosslinkable group-containing liquid repellent, a fluorine atom-substituted alkyl group or a carboxylic acid having an aromatic ring (for example, fluorine-substituted carboxylic acid) added to an epoxy resin (for example, fluorine-substituted acid-modified) Epoxy resin) can be used. Here, the addition of an α, β-unsaturated group-containing carboxylic acid to an epoxy resin is preferable because it is cross-linked by light or heat treatment to prevent elution from the partition wall 6.

In addition, as the epoxy resin type crosslinkable group-containing liquid repellent, in order to improve the solubility of the photosensitive composition in an alkaline aqueous solution that is a solvent or a developer, the above α, β-insoluble liquid may be added as necessary. An unsaturated group and carboxyl group-containing epoxy resin in which a polyvalent carboxylic acid (anhydride) is added to a hydroxyl group generated by addition of a saturated group-containing carboxylic acid can be mentioned.
Examples of the fluorine atom-substituted carboxylic acid include perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, and the like.

Moreover, as an epoxy resin, (alpha), (beta)-unsaturated group containing carboxylic acid, and polyhydric carboxylic acid (anhydride), what is used in the unsaturated group and carboxyl group-containing epoxy resin mentioned above is used, and the alkali solubility mentioned above is used. By using the same synthesis method as the unsaturated group- and carboxyl group-containing epoxy resin in the binder, it is possible to obtain a fluorine-substituted acid-modified epoxy resin.
Here, the molar ratio of addition of fluorine atom-substituted carboxylic acid and α, β-unsaturated monocarboxylic acid to the epoxy resin is preferably in the range of 1: 0 to 0.1: 0.9.

In addition, the fluorine atom-substituted carboxylic acid and the α, β-unsaturated monocarboxylic acid are generally added within the range of 0.5 to 1 chemical equivalent to 1 chemical equivalent of the epoxy group of the epoxy resin. Is preferable.
The temperature during the addition reaction described above is usually in the range of 60 [° C.] to 150 [° C.], preferably in the range of 80 [° C.] to 120 [° C.]. Is possible.
Furthermore, the addition amount of the polyvalent carboxylic acid (anhydride) can usually be in the range of 0 to 1 chemical equivalent with respect to 1 chemical equivalent of the hydroxyl group generated by the above addition reaction.

(Description of phenolic resin type crosslinkable group-containing liquid repellent)
Examples of the phenol resin type crosslinkable group-containing liquid repellent include, for example, an epoxy compound having a fluorine atom-substituted alkyl group or an aromatic ring (for example, a fluorine-substituted epoxy compound) or a carboxylic acid (for example, a fluorine-substituted carboxylic acid). ) Or an isocyanate compound (for example, a fluorine-substituted isocyanate compound) added (for example, a fluorine-substituted epoxy, an acid, or an isocyanate-modified phenol resin) can be used. Here, more preferably, an α, β-unsaturated monoglycidyl compound, an α, β-unsaturated monocarboxylic acid, or an α, β-unsaturated monoisocyanate compound added to a phenol resin, It is suitable because it is cross-linked by light or heat treatment to prevent elution from the partition wall.

In addition, as the phenol resin type crosslinkable group-containing liquid repellent, if necessary, in order to improve the solubility of the photosensitive composition in an alkaline aqueous solution as a solvent or a developer, a polyvalent carboxylic acid is further added. An unsaturated group- and carboxyl group-containing phenol resin to which an acid (anhydride) is added may be mentioned.
Here, examples of the phenol resin include bisphenol A type novolak resin, bisphenol F type novolak resin, bisphenol S type novolak resin, phenol novolak resin, cresol novolak resin, trisphenol type novolak resin, phenol and dicyclopentane, Polymerization type novolak resin, dihydroxyoxyfluorene type novolak resin, dihydroxyalkyleneoxylfluorene type novolak resin, and the like.

In particular, the phenol resin is preferably a phenol novolac resin, a cresol novolac resin, or a polymer resin of phenol and dicyclopentadiene from the viewpoint of high cured film strength.
Examples of the glycidyl compound having a fluorine-substituted alkyl group include perfluorohexyl glycidyl ether, perfluorooctyl glycidyl ether, perfluorohexyl glycidyl thioether, and perfluorooctyl glycidyl thioether.

  Examples of the α, β-unsaturated monoglycidyl compound include acryloyloxyethyl glycidyl ether, methacryloyloxyethyl glycidyl ether, epoxy acrylate, epoxy methacrylate, and the like, fluorine atom-substituted carboxylic acid, and α The .beta.-unsaturated monocarboxylic acid can be appropriately selected from those exemplified in the description of the epoxy resin type crosslinkable group-containing liquid repellent.

The molar ratio of the fluorine atom-substituted compound and the α, β-unsaturated group-containing compound to be added to the phenol resin is preferably in the range of 1: 0 to 0.1: 0.9. Moreover, it is preferable to add these normally in the range of 0.5-1 chemical equivalent with respect to 1 chemical equivalent of the hydroxyl group of a phenol resin.
The temperature during the above addition reaction is usually in the range of 60 [° C.] to 150 [° C.], and preferably in the range of 80 [° C.] to 120 [° C.]. be able to. Furthermore, the addition amount of the polyvalent carboxylic acid (anhydride) can usually be in the range of 0 to 1 chemical equivalent with respect to 1 chemical equivalent of the hydroxyl group generated by the above addition reaction.

(About sealed body)
The organic EL element 1 can emit light by sandwiching a light emitting material (light emitting medium layer 8) between electrodes (first electrode 4 and second electrode 10) and passing an electric current. The organic light emitting material as a material is easily deteriorated by moisture and oxygen in the atmosphere.
For this reason, normally, the organic EL element 1 is provided with a sealing body (not shown) for shielding from the outside. Such a sealing body can be formed by providing a resin layer on a sealing material, for example.

As a material for the sealing material, it is necessary to use a base material having low moisture and oxygen permeability.
Examples of the material for the sealing material include ceramics such as alumina, silicon nitride, and boron nitride, glass such as alkali-free glass and alkali glass, quartz, and moisture resistant film.
Examples of the moisture-resistant film include a film in which SiOx is formed on both surfaces of a plastic substrate by a CVD method, a film having a low permeability and a water absorption property, or a polymer film coated with a water absorbing agent. Here, the moisture permeability of the moisture-resistant film is preferably 10 ⁻⁶ [g / m ² / day] or less.

  Examples of the material for the resin layer include a photo-curing adhesive resin, a thermosetting adhesive resin, a two-component curable adhesive resin, and an ethylene ethyl acrylate (EEA) made of an epoxy resin, an acrylic resin, a silicone resin, or the like. ) 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. .

Examples of the method for forming the resin layer on the sealing material include a solvent solution method, an extrusion lamination method, a melt / hot melt method, a calendar method, a nozzle coating method, a screen printing method, a vacuum laminating method, and a hot roll. The laminating method etc. can be mentioned.
In this case, it is possible to contain a hygroscopic or oxygen-absorbing material as necessary. Here, the thickness of the resin layer formed on the sealing material is arbitrarily determined depending on the size and shape of the organic EL display device to be sealed, but is in the range of 5 [μm] to 500 [μm]. Is preferred.

In the above description, the sealing body is formed as a resin layer on the sealing material. However, the sealing body can be directly formed on the organic EL element 1 side.
The organic EL element 1 and the sealing body are bonded together in a sealing chamber.
Here, when the sealing body has a two-layer structure of a sealing material and a resin layer, and a thermoplastic resin is used for the resin layer, it is preferable to perform only pressure bonding with a heated roll. On the other hand, when a thermosetting adhesive resin is used for the resin layer, it is preferable to perform heat curing at a curing temperature after pressure bonding with a heated roll. Moreover, when using a photocurable adhesive resin for a resin layer, after crimping | bonding with a roll, it can harden | cure by further irradiating light.

(Method for producing organic EL element 1)
Hereinafter, the manufacturing method of the organic EL element 1 will be described with reference to FIGS. 1 and 2 and FIG.
When manufacturing the organic EL element 1, first, a first electrode forming process is performed in which a plurality of first electrodes 4 are formed by patterning on the substrate 2. That is, the manufacturing method of the organic EL element 1 includes a first electrode forming step.
In the first electrode forming step, the first electrode 4 is formed by a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, a sputtering method, depending on the material of the first electrode 4. It is possible to use a dry film forming method such as. Moreover, as a method of forming the first electrode 4, it is possible to use a gravure printing method, a wet film forming method such as a screen printing method, or the like other than the dry film forming method.

  Here, as a patterning method for the first electrode 4, an existing patterning method such as a mask vapor deposition method, a photolithography method, a wet etching method, or a dry etching method is used according to the material of the first electrode 4 and the film forming method. It is possible. Note that in the case where a substrate on which a TFT is formed (see FIG. 2) is used as the substrate 2, the substrate 2 is formed so as to be conductive corresponding to the lower pixel.

And after forming each 1st electrode 4 on the board | substrate 2, the partition 6 formation process which forms the partition 6 which covers the side surface of each 1st electrode 4 on the board | substrate 2 is performed. That is, the method for manufacturing the organic EL element 1 includes a partition wall forming step.
In the partition formation step, as a method of forming the partition 6 on the substrate 2 on which each first electrode 4 is formed, for example, an inorganic film is uniformly formed on the substrate 2 on which each first electrode 4 is formed, and a resist is formed. And a method of performing dry etching, and a method of laminating a photosensitive resin on the substrate 2 on which each first electrode 4 is formed and forming a predetermined pattern by a photolithography method.

After the partition wall 6 is formed on the substrate 2 by the partition wall forming step, the light emitting medium layer forming step of forming the light emitting medium layer 8 on each first electrode 4 and the partition wall 6 is performed. That is, the method for manufacturing the organic EL element 1 includes a light emitting medium layer forming step.
The light emitting medium layer forming step includes a carrier injection layer forming step for forming the carrier injection layer 14 so as to cover the first electrodes 4 and the partition walls 6, and an organic light emitting layer 16 for each first of the carrier injection layers 14. An organic light emitting layer forming step of forming a pattern on the electrode 4 is included.

In the carrier injection layer forming step, depending on the material of the carrier injection layer 14, a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, a dry film forming method such as a sputtering method, a spin coating method, or the like. An existing film formation method such as a wet film formation method such as a sol-gel method is used. In addition to these methods, a general film forming method may be used.
Here, when the carrier injection layer 14 is the hole injection layer described above, in the carrier injection layer forming step, as a method of forming the carrier injection layer 14, the material of the carrier injection layer 14 is dissolved in a solvent or Various coating methods using a spin coater or the like, a method of forming by a slit coating method, a spray coating method, a bar coating method, a dip coating method, a letterpress printing method, or a method of forming by a resistance heating vapor deposition method are used.

  On the other hand, when the carrier injection layer 14 is the above-described electron injection layer, a vacuum deposition method can be used as a method for forming the carrier injection layer 14 in the carrier injection layer forming step. In addition, the electron transporting material of the electron injection layer, and these electron transporting materials are dissolved in a polymer such as polystyrene, polymethyl methacrylate, polyvinyl carbazole, etc., and toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol It is also possible to use a method of forming a film by a printing method by dissolving or dispersing in ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, water or the like alone or in a mixed solvent to form an electron injection coating solution.

  In addition, in the organic light emitting layer forming step, existing film forming methods such as an ink jet printing method, a nozzle print printing method, a relief printing method, a gravure printing method, a screen printing method and the like are used depending on the material of the organic light emitting layer 16. A membrane method is used. In particular, when the organic light emitting layer 16 is applied to each light emitting color using an organic light emitting ink in which an organic light emitting material is dissolved or stably dispersed in a solvent, the ink is transferred between the partition walls 6 and patterned. An ink jet method, a nozzle printing method, and a relief printing method that can be used are suitable.

That is, in the organic light emitting layer forming step, the organic light emitting material as the material of the organic light emitting layer 16 is dissolved or dispersed in the solvent on the carrier injection layer 14 formed so as to cover the first electrodes 4 and the partition walls 6. The organic light emitting ink thus applied is applied to form the organic light emitting layer 16 in a pattern.
In addition, the organic light emitting layer forming step is performed using any one of a printing method, an ink jet method, and a nozzle printing method.
In addition, you may form the organic light emitting layer 16 using methods other than the film-forming method mentioned above.

Here, the procedure for forming the organic light emitting layer 16 by the above-described relief printing method will be described with reference to FIG.
FIG. 3 is a diagram showing a schematic configuration of the relief printing apparatus 34 used in the relief printing method.
As shown in FIG. 3, the relief printing apparatus 34 performs pattern printing of organic light emitting ink made of an organic light emitting material on the substrate 2 on which the first electrode 4, the carrier injection layer 14, and the interlayer layer 18 are formed. And an ink tank 36, an ink chamber 38, an anilox roll 40, and a plate cylinder 44 on which a relief plate 42 provided with projections is mounted.

The ink tank 36 contains organic luminescent ink diluted with a solvent, and the organic luminescent ink is fed into the ink chamber 38 from the ink tank 36.
The anilox roll 40 is rotatably supported by the ink chamber 38 in contact with the ink supply unit of the ink chamber 38.
When the pattern printing is performed, the ink layer 46 of the organic light-emitting ink supplied to the surface of the anilox roll 40 is formed with a uniform film thickness as the anilox roll 40 rotates. The ink in the ink layer 46 is transferred to the convex portion of the relief plate 42 mounted on the plate cylinder 44 that is driven to rotate in the vicinity of the anilox roll 40.

On the stage 48, the substrate 2 to be printed is installed, the ink on the convex portion of the relief plate 42 is printed on the substrate 2, and if necessary, a drying process is performed, and an organic light emitting layer is formed on the substrate 2. 16 will be formed. In FIG. 3, reference numeral 50 is assigned to the doctor.
In addition, also about the case where other luminescent medium layers (for example, interlayer layer 18) are made into ink and applied, it is possible to form a layer on the substrate 2 using the same formation method as described above.

Here, in the organic EL element 1 of the present embodiment, the light emitting medium layer 8 includes the carrier injection layer 14, the organic light emitting layer 16, and the interlayer layer 18.
For this reason, in this embodiment, the interlayer layer formation process which forms the interlayer layer 18 is performed as a post process of an organic light emitting layer formation process. That is, in this embodiment, the light emitting medium layer forming step includes an interlayer layer forming step for forming the interlayer layer 18.

  In forming the interlayer layer 18 in the interlayer layer forming step, the material of the interlayer layer 18 is polyvinylcarbazole, or a derivative thereof, a polyarylene derivative having an aromatic amine in the side chain or main chain, an arylamine. Derivatives, polymers containing aromatic amines such as triphenyldiamine derivatives, etc., these materials are dissolved or dispersed in a solvent, and various coating methods using a spin coater, ink jet method, nozzle printing method, letterpress printing It is formed using a method, a slit coat method, and a bar coat method.

After the light emitting medium layer 8 is formed by the above-described light emitting medium layer forming step, the liquid repellent layer 12 is formed by patterning on the partition wall 6 between the carrier injection layer 14 and the second electrode 10. A formation process is performed. That is, the method for manufacturing the organic EL element 1 includes a liquid repellent layer forming step.
Here, “on the partition wall 6” means on the carrier injection layer 14 formed on the partition wall 6, and the interlayer layer 18 and the organic light emitting layer 16 are also formed on the carrier injection layer 14. A portion other than the portion is shown, and the vicinity of the apex immediately above the partition wall 6 is shown.

In the liquid repellent layer forming step, as a method of forming the liquid repellent layer 12, there are a method of forming a pattern by a wet process such as a printing method, a method of forming a pattern by a dry process such as a shadow mask and vacuum deposition, plasma CVD, Any of these can be selected.
In the present embodiment, a laminate transfer method is used in which the damage to the carrier injection layer 14 is small, the pattern forming property is excellent, and the surface liquid repellent pattern having excellent liquid repellency can be formed only on the pattern surface by a simple method. Use.

Here, it is preferable that the conditions for performing the laminate transfer method (laminate conditions) are appropriately selected so that a desired transfer region and film thickness can be obtained. Moreover, it is suitable for the liquid repellent on a film to exist in the range whose thickness is 5 [nm]-150 [nm].
The roll temperature is preferably in the range of 100 [° C.] to 150 [° C.]. Furthermore, the conveyance speed is preferably in the range of 100 [mm / min] to 200 [mm / min]. The pressing pressure is preferably in the range of 0.2 [MPa] to 1 [MPa].

The film thickness of the liquid repellent layer 12 obtained by the above method is preferably in the range of 5 [nm] to 100 [nm] in order to achieve both sufficient liquid repellency and suppression of cathode disconnection. It is.
After the liquid repellent layer 12 is formed by the liquid repellent layer forming process, a second electrode forming process is performed in which the second electrode 10 is formed on the substrate 2 and the light emitting medium layer 8. That is, the method for manufacturing the organic EL element 1 includes a second electrode forming step.
In the second electrode forming step, the second electrode 10 is formed by a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, a sputtering method, depending on the material of the second electrode 10. It is possible to use a dry film forming method such as.
After forming the 2nd electrode 10, the sealing body mentioned above is formed and manufacture of the organic EL element 1 is complete | finished.

(Effects of the first embodiment)
Hereinafter, effects of the first embodiment will be described.
In the organic EL element 1 and the manufacturing method thereof according to this embodiment, the liquid repellent layer 12 is formed on the partition wall 6 among the carrier injection layers 14 formed so as to cover the first electrodes 4 and the partition walls 6. By forming the pattern, the carrier injection layer 14 formed on the first electrode 4 can be flattened.
For this reason, it becomes possible to make the film thickness of each pixel uniform, and the organic light-emitting layer 16 formed by patterning on the carrier injection layer 14 has no color mixing with adjacent pixels and is stably high-definition. It becomes possible to perform patterning.
As a result, it is possible to provide the organic EL element 1 and a method for manufacturing the organic EL element 1 that have high efficiency, long life, and high luminance, and can be provided at low cost with few processes.

(Modification)
Hereinafter, modifications of the first embodiment will be listed.
(1) In the organic EL element 1 of the present embodiment, the configuration of the light emitting medium layer 8 is configured to include the carrier injection layer 14, the organic light emitting layer 16, and the interlayer layer 18, but is limited to this. Instead, as shown in FIG. 4, the configuration of the light emitting medium layer 8 may not include the interlayer layer 18. FIG. 4 is a cross-sectional view showing a schematic configuration of a modified example of the present embodiment.
(2) In the manufacturing method of the organic EL element 1 of the present embodiment, the light emitting medium layer forming step includes the interlayer layer forming step of forming the interlayer layer 18, but the present invention is not limited to this. The medium layer forming step may not include the interlayer layer forming step (see FIG. 4).

(Example)
Hereinafter, the results of manufacturing the organic EL element 1 of the first embodiment described above and the organic EL element of the comparative example and evaluating the physical properties of both will be described with reference to FIGS.
In the following description, the organic EL element 1 of the first embodiment is referred to as “organic EL element of the present invention example”. Similarly, in the following description, the organic EL element of the comparative example is described as “organic EL element of comparative example”.

(Example of the present invention)
When manufacturing the organic EL element 1 of the present invention example, as the substrate 2, a thin film transistor 20 functioning as a switching element provided on the substrate 2, and a first electrode 4 (pixel electrode) formed thereabove. An active matrix substrate provided with
The size of the active matrix substrate (substrate 2) is 200 [mm] × 200 [mm]. Further, the above active matrix substrate has a diagonal of 5 inches and a display having 320 × 240 pixels arranged in the center. The active matrix substrate has an extraction electrode and a contact portion at the substrate end.
And the partition 6 was formed in the shape which coat | covers the edge part of the 1st electrode 4 provided on said active matrix substrate, and partitions a pixel.

  Here, when the partition wall 6 is formed, “positive resist ZWD6216-6” manufactured by ZEON Corporation is formed on the entire surface of the active matrix substrate with a thickness of 2 [μm] by a spin coater, and then photolithography is performed. Thus, the partition wall 6 having a width of 40 [μm] was formed. As a result, the number of subpixels was 960 × 240 dots, and pixel areas with a pitch of 0.12 [mm] × 0.36 [mm] were partitioned.

The active matrix substrate on which the partition walls 6 are formed as described above is set in a sputtering film forming apparatus in which a molybdenum target is set, and a hole injection layer (on the display region is formed so as not to be formed on the extraction electrode or the contact portion). The carrier injection layer 14) was patterned and formed.
The sputtering conditions at this time were a pressure of 1 [Pa], a power of 1 [kW], and a flow rate ratio of oxygen to argon gas of 30 [%]. The film thickness of the hole injection layer was 50 [nm].

Thereafter, the film on which the liquid repellent having a thickness of 30 [nm] is formed is laminated at a roll temperature of 120 [° C.] and a pressing pressure of 0.6 [MPa] at a speed of 150 [mm] per minute, On the hole injection layer formed on the partition wall 6, the liquid repellent layer 12 was patterned and formed so as to have a thickness of 10 [nm].
Then, using the ink in which the polyvinyl carbazole derivative, which is the material of the interlayer layer 18, is dissolved in toluene so that the concentration is 0.5 [%], the above active matrix substrate is set in a printing machine, Printing was performed by a relief printing method on the first electrode 4 sandwiched between the insulating layers according to the line pattern.

At this time, an anilox roll of 300 lines / inch and a photosensitive resin plate were used. As a result, the thickness of the interlayer layer 18 after printing and drying was 20 [nm].
Next, the above active matrix substrate is set in a printing machine using an organic light emitting ink in which a polyphenylene vinylene derivative, which is an organic light emitting material, is dissolved in toluene so that its concentration is 1 [%], and an insulating layer is formed. The organic light emitting layer 16 was printed by a relief printing method in accordance with the line pattern directly above the first electrode 4 sandwiched between the layers.

At this time, a photosensitive resin plate corresponding to an anilox roll of 150 lines / inch and a pixel pitch was used. As a result, the film thickness of the organic light emitting layer 16 after printing and drying was 80 [nm].
The above steps were repeated a total of three times to form organic light emitting layers 16 corresponding to the emission colors of R (red), G (green), and B (blue) in each pixel.
Thereafter, as an electron injection layer (carrier injection layer 14), calcium is formed to have a thickness of 10 [nm] by using a vacuum deposition method, and an aluminum film is formed as the second electrode 10 to a thickness. The film was formed to have a thickness of 150 [nm].

Then, on the active matrix substrate on which the second electrode 10 is formed as described above, a glass plate as a sealing material is placed so as to cover the entire light emitting region, and then at about 90 [° C.] for about one hour. The adhesive was thermally cured and sealed.
When the display device provided with the active matrix driving type organic EL element 1 of the present invention obtained by the above-described procedure was driven, it was confirmed that the driving could be performed satisfactorily.

(Comparative example)
After the active matrix substrate similar to the organic EL element 1 of the present invention example was used and the partition wall 6 was formed, the hole transport layer was formed in a film thickness of 50 [ nm] was formed.
Thereafter, without forming a liquid repellent layer, an interlayer layer was formed by the same method as in the examples of the present invention. As a result, the ink got over the convex shape and a uniform film thickness could not be obtained between pixels.

Similar to the formation of the interlayer layer, color mixing with other pixels occurred during the formation of the organic light emitting layer. After that, a glass plate as a sealing material is placed on the active matrix substrate so as to cover the entire light emitting region, and then the adhesive is thermally cured at about 90 [deg.] C. for about one hour for sealing. It was.
When a display device provided with the active matrix driving type organic EL element of the comparative example obtained by the above procedure is driven, normal RGB emission color cannot be obtained, and the luminous efficiency and luminance half-life are significantly reduced. It was confirmed that
As described above, the organic EL element 1 of the present invention can obtain a normal RGB emission color as compared with the organic EL element of the comparative example, and can improve the luminous efficiency and extend the luminance half-life. I got a result.

DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Board | substrate 4 1st electrode 6 Partition 8 Light emission medium layer 10 2nd electrode 12 Liquid repellent layer 14 Carrier injection layer 16 Organic light emitting layer 18 Interlayer layer 20 Thin-film transistor 22 Active layer 24 Gate insulating film 26 Gate electrode 28 Drain Electrode 30 Source electrode 32 Scan line 34 Letterpress printing device 36 Ink tank 38 Ink chamber 40 Anilox roll 42 Letterpress 44 Plate cylinder 46 Ink layer 48 Stage 50 Doctor

Claims (6)

A substrate, a plurality of first electrodes patterned on the substrate, a partition formed on the substrate and covering a side surface of each first electrode, and on each of the first electrode and the partition An organic EL device comprising: a formed light emitting medium layer; and a second electrode formed on the substrate and the light emitting medium layer,
The light emitting medium layer includes a carrier injection layer formed so as to cover the first electrodes and the partition walls, and an organic light emission formed by patterning the first electrode among the carrier injection layers. A layer, and
An organic EL device comprising a liquid repellent layer formed by patterning on the partition between the carrier injection layer and the second electrode.   The organic EL device according to claim 1, wherein the carrier injection layer is an inorganic compound.   The organic EL device according to claim 1, wherein the carrier injection layer is an organic compound. A first electrode forming step of patterning and forming a plurality of first electrodes on the substrate; a barrier rib forming step of forming a partition wall covering the side surface of each first electrode on the substrate; and a light emitting medium layer A method for producing an organic EL device, comprising: a light emitting medium layer forming step formed on one electrode and the partition; and a second electrode forming step forming a second electrode on the substrate and the light emitting medium layer,
A liquid repellent layer forming step of forming a liquid repellent layer by patterning on the partition wall between the carrier injection layer and the second electrode;
The light emitting medium layer forming step includes a carrier injection layer forming step of forming a carrier injection layer so as to cover the first electrodes and the partition walls, and an organic light emitting layer of the first of the carrier injection layers. An organic light emitting layer forming step formed by patterning on the electrode,
In the organic light emitting layer forming step, an organic light emitting material that is a material of the organic light emitting layer is dissolved or dispersed in a solvent on the carrier injection layer formed so as to cover the first electrodes and the partition walls. A method for producing an organic EL device, comprising: forming an organic light emitting layer by applying an organic light emitting ink.   The method for producing an organic EL element according to claim 4, wherein the organic light emitting layer forming step is performed using any one of a printing method, an inkjet method, and a nozzle printing method.   6. The method of manufacturing an organic EL element according to claim 4, wherein the liquid repellent layer forming step is performed using a laminate transfer method.

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