JPH09283280A - Manufacture of organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To facilitate and secure the fine working so as to obtain an organic electroluminescent element, of which light emitting probability of an organic light emitting layer of non-selection part is small, by inclining a side surface of a film forming preventing layer, which is formed on an electrode film, to an over-hang side of the vertical line in relation to a plate surface of a base plate. SOLUTION: A film forming preventing layer 3 is formed on a conductive layer 2a provided on a board 1. A side surface 3A of this film forming preventing layer 3 is inclined to an over-hang side more than a right angle in relation to a plate surface 1A of the board 1. In the film forming preventing layer 3, which is extended long in one direction, a side surface 3A extended in the longitudinal direction is desirably inclined to the over-hang side. Angle θof this inclination formed by the side surface 3A of the film forming preventing layer 3 and the plate surface 1a of the board 1 is desirably set at 70-89 degree. A hole transferring layer 4, an organic light emitting layer 5 and a conductive layer (negative electrode) 2b are formed in the surface, which is not formed with the film forming preventing layer 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an organic electroluminescent device, and more particularly, to an organic device having an improved microfabrication process of a thin film type light emitting device which emits light by applying an electric field to a light emitting layer made of an organic compound. The present invention relates to a method for manufacturing an electroluminescent device.

[0002]

2. Description of the Related Art Conventionally, as a thin film type electroluminescent (EL) element, Zn, which is a group II-VI compound semiconductor of an inorganic material, is used.
In general, S, CaS, SrS, etc. are doped with Mn or a rare earth element (Eu, Ce, Tb, Sm, etc.), which is the emission center, but EL elements made from the above inorganic materials are Required (typically 50-1000)
Hz). High drive voltage (generally about 200V). It is difficult to make full color. In particular, there is a problem with blue. The cost of the peripheral drive circuit is high. There is a problem that.

However, in recent years, in order to improve the above problems,
Development of EL devices using organic thin films has been started. In particular, in order to improve the light emission efficiency, the electrode type is optimized for the purpose of improving the efficiency of carrier injection from the electrode, and the organic hole transport layer made of an aromatic diamine is used.
Of an organic electroluminescent device provided with an organic light emitting layer made of an aluminum complex of -hydroxyquinoline (Appl. P
hys. Lett. , 51, 913, 1987)
As a result, the luminous efficiency has been significantly improved as compared with the conventional electroluminescent device using a single crystal such as anthracene, and is approaching practical characteristics.

As a method of patterning such a method for manufacturing an organic electroluminescence device, the following method may be mentioned, for example.

First, an anode film (or a cathode film) is formed on a substrate, and then an organic light emitting layer is formed (at this time, an organic hole transport layer and the like are laminated and formed if necessary). Next, a cathode film (or an anode film) is formed in a pattern using a shadow mask by a vacuum vapor deposition method or the like. The organic electroluminescent device thus manufactured is sandwiched between the selected anode and cathode (hereinafter may be referred to as “selection part”).
The element emits light, and the other portion (hereinafter sometimes referred to as “non-selected portion”) does not emit light, so that the desired portion emits light.

In addition, a method of forming a wall (film formation preventing layer) to be a pattern in advance by using a resist and forming a light emitting layer by oblique vapor deposition has been attempted (Japanese Patent Laid-Open No. Hei 5 (1993) -58).
275172).

An important characteristic of the organic electroluminescent device is that only the selected portion emits light and the non-selected portion has a low emission probability. Therefore, in the manufacturing process of such an organic electroluminescent device, fine patterning is required. It is desired to surely perform the processing to obtain an organic electroluminescent device having excellent light emitting characteristics.

[0008]

Among the conventional microfabrication methods for organic electroluminescent devices, in the method using a shadow mask, the alignment between the substrate and the mask is accurately performed within a chamber in a vacuum apparatus with an accuracy of several μm. It has to be done and is not easy to operate. Further, there is a problem that the substance attached to the mask used for repeated vapor deposition becomes thick and the pattern of the mask is narrowed. On the other hand, patterning by oblique vapor deposition is an effective means when the element size is small,
In order to manufacture a large-sized element, it is necessary to occupy a large space on the substrate. Further, since a film thickness distribution appears between the source side and the opposite side of the substrate, good fine processing cannot be performed.

The present invention solves the above-mentioned conventional problems, and easily and surely performs fine processing in the manufacturing process of an organic electroluminescent device, so that the organic electroluminescent device of the non-selected portion has a significantly low emission probability. It aims at providing the method of manufacturing.

[0010]

A method for manufacturing an organic electroluminescent device according to the present invention comprises forming an electrode film of either an anode or a cathode on a substrate and then partially preventing film formation on the electrode film. A method for producing an organic electroluminescent device by forming a layer, and then sequentially stacking an organic light emitting layer and the other one of the electrode films on the surface on which the film formation preventing layer is not formed on the electrode film,
The side surface of the film formation prevention layer is inclined to the overhang side rather than perpendicular to the plate surface of the substrate.

If the side surface is a film formation preventing layer which is inclined to the overhang side from the vertical with respect to the plate surface of the substrate, patterning is performed more reliably to form the organic light emitting layer formed on the film forming prevention layer. It is possible to more reliably insulate and significantly reduce the light emission probability of the non-selected portion.

In the present invention, in particular, the side surface extending in the longitudinal direction of the film formation preventing layer extending long in one direction on the substrate is inclined toward the overhang side, and particularly, the side surface of the film forming prevention layer. The maximum angle between the board surface and the board surface is 70 ° to 8
It is preferably 9 °.

This film formation preventing layer can be formed of a dry film resist.

In the following, the shape of the film formation preventing layer according to the present invention, that is, the shape whose side surface is inclined to the overhang side rather than perpendicular to the plate surface of the substrate may be referred to as "inverse taper shape". is there.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for manufacturing an organic electroluminescent device of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing an embodiment of a machine electroluminescent device manufactured by the present invention. 1 is a substrate, 2a is a conductive layer as an anode, 3 is a film formation preventing layer, Reference numeral 4 denotes a hole transport layer, 5 denotes an organic light emitting layer, and 2b denotes a conductive layer as a cathode.

In the organic electroluminescent device of this embodiment, the conductive layer 2a on the substrate side serves as an anode for injecting holes.

The substrate 1 serves as a support for the organic electroluminescent device according to the present invention, and a plate of quartz or glass, a metal plate or metal foil, a plastic film or sheet, etc. is used, but a glass plate or polyester. A transparent synthetic resin substrate such as polymethacrylate, polycarbonate, or polysulfone is preferable.

A conductive layer 2a is provided on the substrate 1. This conductive layer 2a is usually made of aluminum, gold, silver,
It is composed of a metal such as nickel, palladium, tellurium, a metal oxide such as an oxide of indium and / or tin, copper iodide, carbon black, or a conductive polymer such as poly (3-methylthiophene). . The conductive layer 2a as an anode is usually formed by a sputtering method, a vacuum deposition method or the like, but metal fine particles such as silver, copper iodide, carbon black, conductive metal oxide fine particles, and conductive metal particles are used. When using fine polymer powder, etc., disperse them in an appropriate binder resin solution,
It can also be formed by coating on a substrate. Furthermore, when a conductive polymer is used, a thin film can be directly formed on the substrate by electrolytic polymerization, or can be formed by coating on the substrate (Appl. Phys. Let.
t. , 60, 2711, 1992). This conductive layer can also have a laminated structure of two or more layers of different materials. The thickness of the conductive layer 2a depends on the required transparency, and when the transparency is required, it is desirable that the visible light transmittance is 60% or more, preferably 80% or more. The thickness of the layer 2a is usually 5 to 10
It is about 00 nm, preferably about 10 to 500 nm.

When the conductive layer as the anode 2a may be opaque, the conductive layer 2a may be the same as the substrate 1. It is also possible to stack the conductive layers with different substances.

On the other hand, the conductive layer 2b serves as a cathode to inject electrons into the organic light emitting layer 5. As the material used for the conductive layer 2b, the same material as the conductive layer 2a can be used, but a metal having a low work function is preferable for efficient electron injection, and tin, magnesium, Appropriate metals such as indium, aluminum, silver or alloys thereof are used. Conductive layer 2b
Also, a laminated structure of two or more layers of different substances may be used. The thickness of the conductive layer 2b is usually about the same as that of the conductive layer 2a. However, since at least one of the conductive layer 2a and the conductive layer 2b is required to have good transparency as an electroluminescent element, one or both of the conductive layer 2a and the conductive layer 2b have a thickness of about 10 to 500 nm. It is desired that the film thickness is excellent in transparency.

The film formation preventing layer 3 formed on the conductive layer 2a as the anode may be any non-conductive film, but the film forming prevention layer 3 according to the present invention has its side surface. Three
A is inclined to the overhang side rather than perpendicular to the plate surface 1A of the substrate 1. In particular, in the film formation preventing layer 3 extending in one direction, the side surface 3 extending in the longitudinal direction of the film forming prevention layer 3.
It is preferable that A is inclined to the overhang side, and the degree of this inclination is such that the maximum value of the angle (crossing angle) θ formed by the side surface 3A of the film formation prevention layer 3 and the plate surface 1A of the substrate 1 (in FIG. ,
The angle between the side surface 3A of the film formation prevention layer 3 and the surface of the conductive layer (anode) 2a is shown as θ, which is equivalent to the crossing angle of the plate surface 1A of the substrate 1. ) Is preferably 70 ° to 89 °.

Such a film formation preventing layer 3 is formed, for example, by a resist process capable of forming an inverse taper shape by using a photochemical reaction, or by forming a resist pattern on an inorganic material layer which becomes a film forming prevention layer. The inorganic material layer is etched, and the side surface lower part of the inorganic material layer is over-etched (the resist may be removed or left as it is).

Specifically, it can be formed by forming a photoreactive resist film on a substrate, exposing the pattern, and then developing, as described below.

In this case, the manufacturing conditions vary greatly depending on the resist material used. For example, AZ5 manufactured by Hoechst Co.
When the resist of 214 is used, it is as follows.

The film thickness is usually 0.1 to 100 μm, and the exposure dose depends on the film thickness, but is usually 5 to 500 mJ.
/ Cm ² . Inversion baking is performed to make the exposed portion insoluble in the developing solution, and the temperature at this time is usually 100 to 150 ° C. The reverse bake time is usually about 7 to 15 minutes. Further, exposure is performed in order to make the portion other than the pattern soluble in the developing solution (hereinafter referred to as "flood exposure"), and the flood exposure amount at this time is usually 50 to 5000 mJ / cm ² . As the developer, a 1 to 5 wt% aqueous solution of TMAH (tetramethylammonium hydroxide) or the like is usually used, and the developing time is usually 30 seconds to 3 minutes.

Since these conditions are strongly related to each other in forming the shape, it is not possible to form the tapered shape according to the present invention within the above-mentioned conditions. Under the conditions shown in Experimental Example 1 described later, the maximum value of the crossing angle is 83.7.
However, it was 89.5 ° under the conditions shown in Comparative Experimental Example 1.

The film formation prevention layer 3 can also be formed by using a dry film resist.

The dry film resist is a film-like resist that can be patterned by changing the properties of a region irradiated with light or the like, and has a feature that it does not require a solvent and is excellent in workability.

The dry film resist generally contains a polymer binder, an addition-polymerizable unsaturated compound and a photopolymerization initiator as essential components. Among these components, the polymer binder is a component that imparts film property to the resist, and an acrylic copolymer or the like is used. The polymer binder is usually copolymerized with a carboxyl group-containing monomer such as acrylic acid, methacrylic acid or itaconic acid in order to have alkali developability. Other copolymerizable components include various monofunctional vinyl compounds such as acrylic acid alkyl ester and methacrylic acid alkyl ester.

The addition-polymerizable unsaturated compound is a compound which is polymerized by irradiation with radiation such as light, and examples thereof include (meth) acrylic acid esters of polyols such as ethylene glycol di (meth) acrylate and methylenebis (meth).
(Meth) acrylamides such as acrylamide, di (2)
-Methacryloxyethyl) -2,4-tolylene diurethane and other urethane group-containing compounds, bisphenol A
-(Meth) acrylic acid esters modified and induced from bisphenol A such as a reaction product of a prepolymer of epichlorohydrin-based epoxy resin and (meth) acrylic acid can be exemplified (“(meth) acrylate” means “acrylate”). And / or methacrylate ”and“ (meth) acrylic ”means“ acrylic and / or methacrylic ”).

The photopolymerization initiator is a component that generates an active radical by absorbing radiation such as light, and is roughly classified into an intramolecular cleavage type and a charge transfer complex type. this house,
The intramolecular cleavage type is a type in which radicals are generated by cleavage in the molecule due to light energy, and 1-phenyl-
Examples thereof include 1,2-propanedione-o-benzoyloxime and 2,2-diethoxyacetophenone. The charge-transfer complex type is a type in which an electron donor and an electron acceptor form a complex in an excited state, and finally a radical is generated by a hydrogen abstraction reaction.
-Bis (diethylamino) benzophenone (DEAB
P), dimethylaminobenzoic acid alkyl ester, methyldiethanolamine, triethylamine, and other amines, and the electron acceptor is benzophenone (B
P), thioxanthone, etc. can be illustrated. A typical combination of an electron donor and an electron acceptor is DEABP and B.
A combination of P and the like can be mentioned.

Such dry film resists are trade names; Liston 4720, Liston 4713 (manufactured by DuPont), Audil AP-938, Audil AF-7.
25 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), Nigo ALPHOW105
0, Nigo ALPHO15G251 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

For example, the film forming conditions when a dry film resist (ALPHO15G251) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. is used are as follows.

The film thickness of the dry film resist is usually 1
The exposure dose is usually from 5 to 5000 mJ / cm ² , although it depends on the film thickness. For development, an aqueous solution of calcium carbonate is used. The concentration at this time is usually 0.1 to 1
It is 0% by weight, and the liquid temperature is usually 10 to 40 ° C. The developing time is usually 5 seconds to 5 minutes.

Since these conditions are strongly related to each other in forming the shape, it is not possible to form the tapered shape according to the present invention within the above conditions. Under the conditions shown in Experimental Example 2 described later, the maximum value of the intersection angle was 84 °.

The maximum value of the crossing angle between the side surface 3A of the film formation preventing layer 3 and the plate surface of the substrate 1 can be measured, for example, as follows. That is, first, a cross section of a sample is made flat, a photograph obtained by observation with an SEM is captured by a computer with a scanner, and after producing this two-dimensional differential image, only the uppermost surface is used to extract a boundary. The angle is obtained from the edge portion of this boundary, and the angle is calculated by correcting this with the inclination of the pedestal at the time of SEM observation.

The film thickness of the film formation preventing layer 3 varies depending on the layer structure of the organic electroluminescent element, but is usually 0.1.
Is about 300 μm to about 300 μm, which is about 0.5 to 50 μm thicker than the total thickness of the layers formed on the conductive layer 2a, the hole transport layer 4, the organic light emitting layer 5, and the conductive layer 2b in this embodiment. Is preferred.

As a material of the hole transport layer 4 formed on the conductive layer 2a and the film formation preventing layer 3, the conductive layer 2 as an anode is used.
It is necessary that the material has a high hole injection efficiency from a and can efficiently transport the injected holes. For that, the ionization potential is small,
In addition, it is required that the hole mobility be large, the stability be excellent, and that impurities that serve as traps are unlikely to be generated during manufacturing or use.

Examples of such hole transport compounds include those disclosed in JP-A-59-194393 and US Pat.
175,960, U.S. Pat. No. 4,923,774 and U.S. Pat. No. 5,047,687, N,
N'-diphenyl-N, N '-(3-methylphenyl)
-1,1'-biphenyl-4,4'-diamine: 1,
Aromatic amine compounds such as 1'-bis (4-di-p-tolylaminophenyl) cyclohexane: 4,4'-bis (phenylamino) quadrophenyl, JP-A 2-3
The hydrazone compound shown in 11591 gazette, the silazane compound shown by US Patent 4,950,950, a quinacridone compound, etc. are mentioned. These compounds may be used alone, or may be used by mixing two or more kinds as necessary. In addition to the above compounds, polyvinylcarbazole and polysilane (Appl.Phy.
s. Lett. , 59, page 2760, 1991).

The hole transport layer 4 is laminated on the conductive layer 2a and the film formation prevention layer 3 by depositing the above organic hole transport material generally by a coating method or a vacuum deposition method. In the case of formation by a coating method, it is one of organic hole transport compounds.
One kind or two or more kinds, if necessary, a binder resin that does not become a hole trap, and additives such as a leveling agent and other coating property improving agents are added to prepare a dissolved coating solution, which is then subjected to a spin coating method or the like for conductivity. The organic hole transport layer 4 is formed by coating on the layer 2a and drying. In this case, as the binder resin, polycarbonate, polyarylate,
Polyester or the like can be used. The addition amount of the binder resin decreases the hole mobility when it is added in a large amount. Therefore, the binder resin is preferably added in a small amount, and the concentration of the coating solution is preferably 50% by weight or less.

In the case of the vacuum deposition method, the organic hole transporting material is placed in a crucible installed in a vacuum container, the interior of the vacuum container is evacuated by a suitable vacuum pump to 10 ⁻⁶ Torr, and then the crucible is opened. By heating, the hole transport material is evaporated, and the hole transport layer 4 is formed on the conductive layer 2a of the substrate 1 placed facing the crucible.

The thickness of the hole transport layer 4 thus formed is usually 10 to 300 nm, preferably 30 to 10 nm.
0 nm. A vacuum deposition method is often used to uniformly form such a thin film.

As the material of the hole transport layer 4, it is possible to use an inorganic material instead of the organic compound. The conditions required for the inorganic material are the same as those for the organic hole transport compound. As the inorganic material used for the hole transport layer 4, p-type hydrogenated amorphous silicon, p-type hydrogenated amorphous silicon carbide, p-type hydrogenated microcrystalline silicon carbide, or
Examples thereof include p-type zinc sulfide and p-type zinc selenide. The inorganic hole transport layer made of these materials is formed by the CVD method, the plasma CDV method, the vacuum deposition method, the sputtering method, or the like.

The thickness of the inorganic hole transporting layer is usually 10 to 300 nm, preferably 30 to 100, like the organic hole transporting layer.
nm.

The organic light emitting layer 5 formed on the hole transport layer 4 efficiently transports the electrons from the conductive layer 2b as the cathode between the electrodes to which the electric field is applied in the direction of the hole transport layer 4. Is formed from a compound capable of.

The compound used for the organic light emitting layer 5 needs to be a compound which has a high electron injection efficiency from the conductive layer 2b as a cathode and which can efficiently transport the injected electrons. . For that purpose, it is required that the compound has a high electron affinity, a high electron mobility, an excellent stability, and an impurity that becomes a trap is hard to be generated during the production or the use. Further, a role of causing light emission upon recombination of holes and electrons is also required. Further, it is important to provide a uniform thin film shape in terms of device stability.

As a material of such an organic light emitting layer 5,
Aromatic compounds such as tetraphenylbutadiene (JP-A-57-51781), metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP-A-59-194).
393, US Pat. No. 5,151,629, US Pat. No. 5,141,671), cyclopentadiene derivative (JP-A-2-289675), perinone derivative (JP-A-2-289676), Oxadiazole derivative (JP-A-2-216791), bis-styrylbenzene derivative (JP-A-1-245087,
JP-A-2-222484), perylene derivatives (JP-A-2-189890 and JP-A-3-791), and coumarin compounds (JP-A-2-191694 and JP-3-7).
92), rare earth complexes (JP-A-1-256584), and distyrylpyrazine derivatives (JP-A-2-252).
793), a p-phenylene compound (JP-A-3-3)
3183), thiadiazolopyridine derivative (JP-A-3-37293), pyrrolopyridine derivative (JP-A-3-37293), naphthyridine derivative (JP-A-3-203982), and the like. In particular, a metal complex formed from 8-hydroxyquinoline and its derivative is preferable. As the central metal of the metal complex, Al, Ga, In, Sc, Y, Zn, Be, M
g and Ca are preferable. These metal complexes may be used alone, or may be used by mixing two or more kinds as necessary.

The organic light emitting layer 5 is formed of these materials in the same manner as the organic hole transport layer 4, but is preferably formed by a vacuum vapor deposition method, and the film thickness thereof is usually 10 to 10. 200 nm, preferably 30 to 100 nm.

For the purpose of improving the luminous efficiency of the device and changing the luminescent color of the organic luminescent layer 5, for example, a fluorescent dye for laser such as coumarin is used as a host material of aluminum complex of 8-hydroxyquinoline. Doping (J. Appl. Phys., Volume 65, 361)
Page 0, 1989). Also in the present invention, an organic phosphor such as a laser dye is added to the organic light emitting layer 5 at a concentration of 10 ^−3.
By doping in an amount of 10 to 10 mol%, the emission characteristics of the device can be further improved. When the organic light emitting layer 5 is doped with these fluorescent dyes, the stability of the device is further improved by setting the substrate temperature in the range of 60 ° C to 150 ° C.

The organic electroluminescent device shown in FIG. 1 is an example of the organic electroluminescent device of the present invention, and the present invention is not limited to the illustrated device unless it exceeds the gist. Absent.

For example, as the layer constitution formed on the substrate, the following (1) to (3) can be adopted.

Anode / organic hole transport layer / organic light emitting layer /
Cathode Anode / Inorganic hole transport layer / Organic light emitting layer / Cathode Anode / Organic light emitting layer / Electron transport layer / Cathode Anode / Organic hole transport layer / Organic light emitting layer / Electron transport layer /
Cathode Anode / Organic hole transport layer / Organic light emitting layer / Interface layer / Cathode Anode / Organic hole transport layer / Organic light emitting layer / Electron transport layer /
Interface Layer / Cathode In the above layer structure, the electric transport layer is for further improving the efficiency of the device, and is laminated on the organic light emitting layer. The compound used for the electron transport layer is required to be capable of easily injecting electrons from the cathode and further having an electron transporting ability. Examples of such an electron transport material include oxadiazole derivatives (Appl. Phys. Lett., Vol. 55, 1) shown in the following [Chemical formula 1] and [Chemical formula 2].
489, 1989; Jpn. J. Appl. Phys
s. , 31, 1812, 1992) and P
Systems dispersed in a resin such as MMA (polymethylmethacrylate) (Appl. Phys. Lett., 61, 27
93, 1992), or n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, and the like. The thickness of the electron transport layer is usually 5 to 200 nm, preferably 10 to 100 nm.

[0054]

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[0055]

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In the above layer structure, the interface layer is for improving the contact between the cathode and the organic layer. The aromatic diamine compound (JP-A-6-267658),
Quinacridone compound (JP-A-6-330031), naphthacene derivative (JP-A-6-330032), organic silicon compound (JP-A-6-325871), organic phosphorus compound (JP-A-6-325872), etc. Is mentioned. The thickness of the interface layer is usually 2 to 1
00 nm, preferably 5 to 30 nm.

In the present invention, instead of providing such an interface layer, a region containing 50 mol% or more of the above interface layer material may be provided in the vicinity of the cathode interface of the organic light emitting layer and the electron transport layer.

Although not shown in FIG. 1, a substrate similar to the substrate 1 may be further provided on the conductive layer 2b as the cathode. In this case, at least one of the two substrates needs to have high transparency.

Further, the structure opposite to that shown in FIG. 1, that is, the conductive layer (cathode) 2b, the organic light emitting layer 5, the hole transport layer 4, is formed on the substrate 1.
It is also possible to stack the conductive layer (anode) 2a in this order,
It is also possible to stack the above layer structures in the reverse structure. Further, as described above, it is also possible to provide the layer structure of the organic electroluminescent element as described above between two substrates, at least one of which is highly transparent.

[0060]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Experimental Examples, Examples, Comparative Experimental Examples, and Comparative Examples. However, the present invention is limited to the following Examples unless the gist thereof is exceeded. It is not something that will be done.

Experimental Example 1 An experiment was conducted to examine the side surface shape of the film formation prevention layer according to the present invention.

The silicon substrate was ultrasonically cleaned with acetone and isopropyl alcohol for 10 minutes, dried in a drying chamber, and further dried in a clean oven at 120 ° C. for 30 minutes. A film formation preventing layer was formed on this substrate by the following method.

Image reversal resist AZ5 on the substrate
214 (manufactured by Hoechst) was formed into a film having a thickness of about 1 μm by a spin coating method, and the film was formed in a clean oven at 85 ° C. for 25 minutes.
Heat dried for minutes. This substrate was subjected to pattern exposure at 11.9 mJ / cm ² and then baked in a clean oven at 120 ° C. for 9 minutes. Furthermore, after taking out this substrate, 1
After exposure with an exposure dose of 46 mJ / cm ² , TM of 2.38%
Development was performed for 90 seconds using AH (23 ° C.). The width of the stripe pattern thus manufactured is about 200.
The pitch (space width) was about 200 μm.

This substrate was cleaved to prepare a smooth cut surface. This was observed by SEM, and the maximum value of the crossing angle θ between the side surface of the film formation prevention layer and the plate surface of the substrate was obtained by the above-mentioned image processing. The same material was measured at three different points, and the average thereof was 83.7 °. FIG. 2 shows a SEM photograph of a cross section of the film formation preventing layer taken at this time.

Example 1 A transparent conductive film of indium tin oxide (ITO) deposited to a thickness of 120 nm on a glass substrate was used to form a pattern using a normal resist process, and then HCl6N was used.
Etching was performed for 10 minutes using an (50 ° C.) etching solution to process the ITO film into a stripe pattern having a width of 80 μm and a pitch of 80 μm. This substrate was ultrasonically cleaned with acetone and isopropyl alcohol, dried with dry nitrogen, and further dried in a clean oven at 120 ° C. for 30 minutes.

A width of 2 is applied to this substrate in the same manner as in Experimental Example 1.
A film formation preventing layer having a stripe pattern of 00 μm and a pitch of 200 μm was formed so as to be orthogonal to the stripe of the ITO film.

After this substrate was washed with UV / ozone, it was placed in a vacuum vapor deposition apparatus and the degree of vacuum in the apparatus was 2 × 10 ⁻⁶ T.
After evacuating using an oil diffusion pump equipped with a liquid nitrogen trap to a value of orr or lower, copper phthalocyanine shown in the following [Chemical Formula 3] was used as an organic hole injection layer material on the substrate.
A film was formed to a thickness of 0 nm. The deposition rate at this time is 0.3n
It was m / sec.

[0068]

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Next, as an organic hole transport layer material, N, N'-diphenyl-N, N'-di (1-
Naphthyl) -1,1′-biphenyl-4,4′-diamine was placed in a ceramic crucible and heated by a tantalum wire heater around the crucible to perform vapor deposition. The temperature of the crucible at this time was controlled in the range of 160 to 170 ° C. The degree of vacuum during vapor deposition was 2 × 10 ⁻⁶ Torr, and the organic hole transport layer 3 having a film thickness of 60 nm was obtained with the vapor deposition time of 3 minutes and 10 seconds.

[0070]

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Next, aluminum 8-hydroxyquinoline complex Al (C ₉ H ₆ NO) ₃ shown in the following [Chemical formula 5] was used as a material for the organic light emitting layer, and the same process was performed on the organic hole transport layer. It was vapor-deposited on. The temperature of the crucible at this time is 2
The temperature was controlled in the range of 30 to 270 ° C. The degree of vacuum during evaporation is 2
× 10 ^-6 Torr, evaporation time 3 minutes 30 seconds, film thickness 75
was nm.

[0072]

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The cathode is an alloy of magnesium and silver (Mg:
An electrode of Ag = 10: 1.5 (atomic ratio) was formed by vapor deposition by a binary simultaneous vapor deposition method so as to have a film thickness of 40 nm. Vapor deposition uses a molybdenum boat and the degree of vacuum is 4 ×
It was carried out at 10 ⁻⁶ Torr and vapor deposition time of 4 minutes and 20 seconds to obtain a glossy film. Furthermore, 40n of aluminum is used as a protective layer.
m was deposited.

When a voltage of 10 V was applied with the ITO side of the device thus manufactured as a positive electrode and the MgAg alloy side as a negative electrode, the organic light emitting layer in the non-selected portion where the film formation preventing layer was formed emitted light at a ratio of 7 %Met.

Comparative Experimental Example 1 A film formation preventing layer was prepared in the same manner as in Experimental Example 1 except that the exposure amount during pattern exposure was 8.6 mJ / cm ^2, and the maximum value of the crossing angle was set in the same manner. The average of three points was calculated and found to be 89.5 °.

Comparative Example 1 An element was produced in the same manner as in Example 1 except that the film formation preventing layer was formed in the same manner as in Comparative Experimental Example 1.

When a voltage of 10 V was applied with the ITO side of the device thus manufactured as a positive electrode and the MgAg alloy side as a negative electrode, the ratio of light emission from the organic light emitting layer in the non-selected portion where the film formation preventing layer was formed was 20. %Met.

Experimental Example 2 As a material for the film formation prevention layer, a dry film resist Nigo ALPHO15G251 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Was laminated on the ITO substrate prepared in the same manner as in Example 1. The same dry film resist was further laminated on this substrate to prevent the formation of pinholes.

Next, using an ultra high pressure mercury lamp, 250 mJ
This substrate was exposed with an exposure amount of / cm ² and then developed for 21 seconds using a 1 wt% calcium carbonate aqueous solution (solution temperature 30 ° C.), width 50 μm, pitch (space width) 280 μm
A film formation preventing layer having a stripe pattern was formed so as to be orthogonal to the stripe of the ITO film.

This substrate was cut to form a smooth cut surface, which was observed with an SEM, and the maximum value of the crossing angle was obtained by the image processing described above, and the average of three positions was obtained.
0 °.

Example 2 An organic light emitting layer and a cathode were formed in the same manner as in Example 1 on a substrate on which a film formation preventing layer was produced in the same manner as in Experimental Example 2. When a voltage of 10 V was applied with the ITO side of the device thus manufactured as a positive electrode and the MgAg alloy side as a negative electrode, the non-selected portion of the organic light emitting layer on which the film formation preventing layer was formed emitted 0% light. there were.

[0082]

As described above in detail, according to the method for manufacturing an organic electroluminescent device of the present invention, fine processing in the manufacturing process of the organic electroluminescent device is easily and surely performed, and the organic light emitting layer of the non-selected portion is manufactured. It is possible to provide an organic electroluminescent device having a significantly low emission probability.

Therefore, the organic electroluminescent element according to the present invention can be applied to flat panel displays (for example, for OA computers and wall-mounted televisions), display boards, and marker lights, and its industrial utility is extremely large.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic electroluminescent device of the present invention.

FIG. 2 is an SEM of a cross section of the film formation prevention layer obtained in Experimental Example 1.
It is a photograph.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2a Conductive layer (anode) 2b Conductive layer (cathode) 3 Film formation prevention layer 4 Hole transport layer 5 Organic light emitting layer

Claims (4)

[Claims] 1. A film formation preventing layer is partially formed on the electrode film after forming an electrode film of either one of an anode and a cathode on a substrate, and then the film forming prevention on the electrode film. A method for manufacturing an organic electroluminescent device by sequentially forming an organic light emitting layer and one of the other electrode films on a non-layer-formed surface, wherein a side surface of the film formation prevention layer is perpendicular to a plate surface of the substrate. A method for manufacturing an organic electroluminescent device, which is inclined to the overhang side rather than. 2. The film formation prevention layer according to claim 1, wherein the film formation prevention layer extends long in one direction on the substrate, and a side surface extending in the longitudinal direction of the film formation prevention layer is inclined toward the overhang side. A method for manufacturing an organic electroluminescent device, characterized in that 3. The maximum value of an angle formed by the side surface of the film formation preventing layer and the plate surface of the substrate is 70 ° according to claim 1 or 2.
The method for manufacturing an organic electroluminescence device is characterized in that the angle is ~ 89 °. 4. The method for manufacturing an organic electroluminescence device according to claim 1, wherein the film formation prevention layer is made of a dry film resist.