JP2793373B2 - Method for patterning organic electroluminescent device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for patterning an organic electroluminescent device, and more particularly, to a completely new organic electroluminescent device which can be easily patterned by irradiating the organic electroluminescent device with ultraviolet rays. It relates to a patterning method.

[0002]

2. Description of the Related Art Electroluminescent devices (hereinafter referred to as EL devices) are characterized in that they have high visibility due to self-emission and excellent shock resistance because they are completely solid devices. Therefore, utilization of light emitting elements and the like in various display devices has been attempted. In particular, the organic EL elements are cathode / light-emitting layer / hole injection / transport layer / anode, cathode / electron injection / transport layer / light-emitting layer / anode, cathode / electron injection / transport layer / light-emitting layer / hole injection / transport layer / anode, anode / Structures such as a light emitting layer / cathode have been developed. These materials have excellent characteristics such as light emission only by applying a low voltage, high-luminance and high-efficiency light emission, and multi-color display. Light-emitting materials, charge injection / transport layers, electrodes Research on materials and the like has been actively conducted ("Applied Fixics Letters", vol. 51, p. 913 (1987).
Year); “Applied Fizzix Letters” No. 55
Volume, 1489 (1989); "Journal of
Applied Fixix, Vol. 65, p. 3610 (1
989). Conventionally, in order to easily pattern an organic EL element, a counter electrode of the element is patterned by a method in which a mask is placed on a substrate and an electrode is deposited on a light emitting element forming portion. There was a problem that the pattern accuracy deteriorated. In addition, since the mask for forming the organic layer and the mask for forming the counter electrode are different, in a normal vapor deposition apparatus having no mask exchange mechanism, the vacuum is broken once before forming the counter electrode, and the vacuum layer is broken. It is necessary to open the mask and replace it, or to install a mask, and the process is complicated. In this case, the interface between the organic layer and the counter electrode is contaminated, and E
It was difficult to obtain an L element. Further, in an organic EL device, an electrode of an alloy or a mixture of magnesium and a second metal is often formed and used for a cathode by a binary vapor deposition method. This causes dripping due to wraparound. For this reason, since the degree of wraparound between magnesium and the second metal system is different, the composition of this portion is shifted from the surface of the counter electrode, and there is a problem that the uniformity of light emission is impaired.

On the other hand, recently, a method of patterning an organic EL element with high definition has been disclosed (Japanese Patent Application Laid-Open No. 2-66873). In this, an acid etching method using photolithography is shown as a method for patterning a counter electrode. However, this method is a wet method, and there is a process of spreading the photoresist composition on the organic EL element with a solvent or washing away an unexposed portion with the same solvent. There is a restriction that a solvent that keeps the aluminum chelate complex intact must be selected. Also, there is a great limitation that the luminous medium itself must select a material that is resistant to the solvent. In the above-mentioned etching method, it is necessary to finally etch the metal with an acid (specifically, sulfuric acid solution 1 with respect to 100 of water) and then rinse with water. However, an organic material generally has higher water absorption than an inorganic material, and water permeates and absorbs from an edge portion of a patterned portion, so that it is considered that the function as an EL element is greatly reduced. Therefore, patterning of the opposing electrode using a mask and patterning using an acid using photolithography (wet method) have significant drawbacks. Therefore, the present inventors have intensively studied to solve the above problems.

[0004]

As a result, it has been found that an organic EL device can be efficiently obtained by performing etching using ultraviolet rays as a patterning method. The present invention has been completed based on such findings. That is, the present invention provides a method of patterning an organic EL device using an organic compound as a light-emitting material, wherein the method comprises patterning the irradiated portion with a non-light-emitting region by irradiating ultraviolet rays. Things.
The patterning method of the organic EL device of the present invention is roughly divided into the following two methods. One is a method of patterning before producing a counter electrode, and the other is a method of patterning after producing a counter electrode. (I) First, the method of patterning before producing the counter electrode is a method usually adopted to increase the effect of ultraviolet irradiation, and various organic EL element structures are conceivable.
The patterning of the organic EL device will be described below by taking as an example the organic EL device having a three-layer structure including the anode / light-emitting layer / cathode shown in FIG. (A) First, in FIG. 1, a light emitting layer 2 made of an organic compound is deposited on a glass substrate 1 with ITO. Next, in FIG. 2, the light emitting layer 2 is shielded by a UV (ultra violet) mask 3 having a specific slit, and ultraviolet light is irradiated from above. In FIG. 3, the light emitting layer 2 after irradiation with ultraviolet rays
Then, a counter electrode 4 is deposited, and a wiring 5 is provided. By performing such a patterning, it becomes possible to emit light only at a portion of the light emitting layer which is not irradiated with ultraviolet rays. (B) FIGS. 4 and 5 show a glass substrate 7 with ITO.
A method is shown in which a light emitting layer 8 made of an organic compound and an organic compound is placed on an XY stage (movable system) 6, and the element is moved on a plane while applying an ultraviolet spot 9 to perform patterning. Conversely, the spot 9 of the ultraviolet ray may be movably patterned. This method is performed by manufacturing an element in which a light emitting layer 2 made of an organic compound is vapor-deposited on a glass substrate 1 with ITO similarly to (A) and irradiating the element with ultraviolet rays on an XY stage. Patterning. An apparatus for performing such a process includes a laser processing apparatus, a resist exposure stepper, and the like, which are integrated with a computer, an XY stage, and an ultraviolet laser. Furthermore, the same method as in the above (A) and (B) can be used for patterning an organic EL element having a multilayer structure. For example, the patterning of an organic EL device having a multilayer structure of an anode / a hole injection / transport layer / a light emitting layer / a cathode and the hole injection / transport layer is an organic compound is performed as follows. In FIG. 6, a hole injection transport layer b is laminated on a glass substrate a with ITO. In FIG. 7, a UV injection mask c having a specific slit is used, through which a hole injection / transport layer b made of an organic compound is irradiated with ultraviolet light. In FIG. 8, the light emitting layer d is laminated on the hole injection transport layer b. In FIG. 9, a counter electrode e is deposited,
Wiring f is applied. In such a configuration in which the hole injecting and transporting layer and the light emitting layer are stacked, patterning may be performed on each of or one of the hole injecting and transporting layer and the light emitting layer. Further, the hole injection transport layer may be a hole injection transport light emitting layer.

(II) The method of patterning after fabricating the counter electrode is a method adopted because the EL element must emit light outside, and one or both electrodes are often transparent or translucent. Yes, various organic EL element structures are conceivable. As a specific example, after the light emitting layer / charge injection / transport layer / cathode is laminated and sealed on a glass substrate with ITO, the layer is optionally formed by the method described in the above (I) (UV mask or ultraviolet beam) through ITO. Can be patterned. In this case, care must be taken when the transparent electrode is supported by the substrate. In this case, the supporting substrate also needs to transmit ultraviolet rays. Generally, compared to an electrode having a thickness of about 0.1 μm, the substrate is as thick as about 0.1 to 10 mm, so that it can easily absorb ultraviolet rays. Therefore, it is desirable to use quartz, white plate glass (non-alkali glass), or the like, which hardly absorbs ultraviolet rays from various substrates. However, blue glass (alkali glass) and polymer substrates (polyethylene terephthalate,
(Polyether sulfone, polycarbonate) even if the thickness of the substrate is about 0.1 to 1 mm, 350 to 400 nm
If the near ultraviolet transmittance is about 10% or more and the output of ultraviolet is strong, or if the irradiation time is lengthened, patterning is possible. Further, patterning is possible by a method other than the present invention, and patterning can be performed by burning off or evaporating the organic material using a powerful ultraviolet laser beam. However, in such a method, the processed portion becomes uneven, or a powerful laser is required, which does not reach the efficiency of the method of the present invention.

The ultraviolet light used in the present invention has a wavelength of 400
Those falling within the range of 10 nm to 10 nm are preferred. Specific examples of the ultraviolet light source include a high-pressure mercury lamp, a low-pressure mercury lamp, a hydrogen (deuterium) lamp, a rare gas (xenon, argon, helium, neon, etc.) discharge lamp, a nitrogen laser, and an excimer laser (eg, XeCl, XeF, Kr
F, KrCl, etc.), hydrogen lasers, halogen lasers, and harmonics of various visible-infrared lasers (eg, THG (third harmonic gen of YAG laser)
eration) light, etc.). Further, there are various organic materials for the organic EL device used in the present invention. For example, the organic compound that can be used as a light-emitting material is not particularly limited, but may be a benzothiazole-based compound,
Examples thereof include fluorescent whitening agents such as benzimidazole compounds and benzoxazole compounds, metal chelated oxinoid compounds, and styrylbenzene compounds. Specific examples of the compound name include those described in JP-A-59-194393. As a typical example,
2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) -1,3,4-thiadiazole; 4,
4'-bis (5,7-t-pentyl-2-benzooxazolyl) stilbene; 4,4'-bis [5,7-di-
(2-methyl-2-butyl) -2-benzoxazolyl] stilbene; 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) thiophene; 2,5-
Bis [5-α, α-dimethylbenzyl] -2-benzoxazolyl) thiophene; 2,5-bis [5,7-di-
(2-methyl-2-butyl) -2-benzoxazolyl] -3,4-diphenylthiophene; 2,5-bis (5-methyl-2-benzooxazolyl) thiophene;
4,4'-bis (2-benzoxazolyl) biphenyl; 5-methyl-2- [2- [4- (5-methyl-2-
Benzoxazoles such as benzoxazolyl) phenyl] vinyl] benzoxazolyl; 2- [2- (4-chlorophenyl) vinyl] naphtho [1,2-d] oxazole and 2,2 ′-(p-phenyl Benzothiazoles such as range vinylene) -bisbenzothiazole, 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole; 2- [2- (4-
And benzoimidazole-based fluorescent whitening agents such as [carboxyphenyl) vinyl] benzimidazole. Still other useful compounds are the Chemistry of
Synthetic soybeans 1971, pp. 628-637 and 640. Examples of the metal chelated oxinoid compound include, for example, JP-A-63-2956
No. 95 can be used. Representative examples thereof include tris (8-quinolinol) aluminum; bis (8-quinolinol) magnesium; bis (benzo [f] -8-quinolinol) zinc; bis (2-methyl-8-quinolinolate) aluminum oxide; 8-quinolinol) indium; tris (5-methyl-8-quinolinol) aluminum; lithium quinolinol; tris (5-chloro-8-quinolinol)
Gallium; bis (5-chloro-8-quinolinol) calcium; poly [zinc (II) -bis (8-hydroxy-
5-quinolinonyl) methane] and dilithium epindridione. In addition, as styrylbenzene compounds,
For example, European Patent No. 0319881 and European Patent No. 037
No. 3582 can be used. Representative examples thereof include 1,4-bis (2-methylstyryl) benzene; 1,4- (3-methylstyryl) benzene;
1,4-bis- (4-methylstyryl) benzene; distyrylbenzene; 1,4-bis (2-ethylstyryl)
Benzene; 1,4-bis (3-ethylstyryl) benzene; 1,4-bis (2-methylstyryl) 2-methylbenzene; 1,4-bis (2-methylstyryl) -2-ethylbenzene and the like. . Further, compounds represented by the following formula can also be mentioned.

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Further, a distyrylpyrazine derivative described in JP-A-2-252793 can be used as a light emitting material. A typical example is 2,5-bis (4
-Methylstyryl) pyrazine; 2,5-bis (4-ethylstyryl) pyrazine; 2,5-bis [2- (1-naphthyl) vinyl] pyrazine; 2,5-bis (4-methoxystyryl) pyrazine; , 5-bis [2- (4-biphenyl) vinyl] pyrazine; and 2,5-bis [2- (1-pyrenyl) vinyl] pyrazine. As other materials, for example, a polyphenyl-based compound described in European Patent No. 0388715 can also be used as a light-emitting material. Specific examples thereof include a compound represented by the following formula.

[0032]

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Further, in addition to the above compounds, for example, 12-
Phthaloperinone [Journal of Applied Physics, Vol. 27, L713 (1988)
Year)]; 1,4-diphenyl-1,3-butadiene;
1,1,4,4-tetraphenyl-1,3-butadiene [“Applied Physics Letters (Appl. Phys.
Lett.) Vol. 56, 799 (1990)], naphthalimide derivatives (JP-A-2-305886), perylene derivatives (JP-A-2-189890), and oxadiazole derivatives (JP-A-2-216791). Gazette), aldazine derivatives (JP-A-2-220393), pyrazirine derivatives (JP-A-2-220394), cyclopentadiene derivatives (JP-A-2-289675), and pyrrolopyrrole derivatives (JP-A-2-29691).
Publication), styrylamine derivatives (Applied Physics Letter (Appl. Phys. Lett.) Vol. 56, 799 (1990)), or coumarin-based compounds (JP-A-2-191694). . The following compounds are mentioned as typical examples.

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And the like. In addition, those described in aromatic dimethylidin compounds (European Patent No. 0388768) can be used.

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And the like. Further, as a light emitting material, Japanese Patent Application No. 2-248949 and Japanese Patent Application No. 2-27
The following general formula (I) shown in JP 9304

[0051]

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[X and Y each represent a fluorescent compound having an electroluminescence element function, which may be the same or different. Q represents a divalent group that cuts a conjugated system. ] The compound represented by these is mentioned. The light-emitting material represented by X and Y in the general formula (I) means a visible light region (400 to 700 n) when excited with various energies.
m) is a fluorescent organic compound. Some luminescent materials used in the present invention include near ultraviolet (330 to 380 nm)
In the short wavelength region of the visible region (400 to 450 n
m) may also contain a fluorescent whitening agent which emits purple to blue fluorescent light. Q is a divalent group that cuts a conjugated system. Here, conjugatedness is due to nonpolarity of π electrons, and includes conjugated double bonds, unpaired electrons, or lone electron pairs.
Specifically, a divalent group obtained by removing one H atom from a straight-chain alkane, for example,

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And so on. The reason for using the divalent group that cuts the conjugated system in this way is that the luminescent material X or Y having the above-described EL element capability is used alone as the organic EL element of the present invention to obtain an EL emission color. And the EL emission color obtained when the compound represented by the general formula (I) is used as the organic EL device of the present invention. That is, it is to prevent the wavelength from becoming shorter or longer. When connected by a divalent group that cuts the conjugated system, the glass transition temperature (Tg)
Was confirmed to increase, and it was clarified that a uniform pinhole-free microcrystalline or amorphous thin film could be obtained. Further, since the compound is bonded by a divalent group that cuts a conjugated system, the EL emission does not have a longer wavelength, and has an advantage that synthesis or purification can be easily performed. Note that having an EL element capability means that, for example, when a compound is thinned by a known method such as an evaporation method, a spin coating method, a casting method, and an LB method, and this is used as a light emitting layer, an anode or a positive electrode is applied when an electric field is applied. An injection function capable of injecting holes from the hole injection transport layer and injecting electrons from the cathode or the electron injection transport layer, and a transport function of moving the injected charges (electrons and holes) by an electric field. In addition, it has a light-emitting function or the like that provides a field for recombination of electrons and holes and connects it to light emission. Specific examples of the fluorescent compound having the EL element function represented by X and Y include the above-mentioned organic compounds that can be used as various light emitting materials.
Specific examples of the compound represented by the general formula (I) include the following.

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The light emitting layer can be formed by thinning it by a known method such as a vapor deposition method, a spin coating method, a casting method, and an LB method. Is more preferred. Here, the molecular deposition film refers to a thin film formed by depositing the compound from a gaseous state or a film formed by solidifying the compound from a solution state or a liquid phase state. Can be distinguished from a thin film (molecule cumulative film) formed by the LB method by differences in the aggregated structure and higher-order structure and functional differences caused by the difference. Further, as disclosed in JP-A-59-194393, a light-emitting layer is obtained by dissolving a binder such as a resin and the compound in a solvent to form a solution, and then spin-coating the solution. Can be formed into a thin film. The thickness of the light emitting layer thus formed is not particularly limited and can be appropriately selected depending on the situation.
Is preferable. The light-emitting layer in the EL element of the present invention has an injection function capable of injecting holes from an anode or a hole injection transport layer and applying electrons from a cathode or an electron injection transport layer when an electric field is applied. It has a transport function of moving the generated charges (electrons and holes) by the force of an electric field, a light-emitting function of providing a field for the recombination of electrons and holes, and connecting it to light emission. Note that there may be a difference between the ease of hole injection and the ease of electron injection. In addition, although the transport function represented by the mobility of holes and electrons may be large or small, it is preferable to move one of them.

The hole injecting / transporting material of the organic EL device used in the present invention is not particularly limited as long as it has the above-mentioned preferable properties. Any material can be selected from those commonly used as materials and known materials used in the hole injection / transport layer of the EL device. Examples of the charge transporting material include triazole derivatives (see U.S. Pat. No. 3,112,197), oxadiazole derivatives (see U.S. Pat. No. 3,189,447), and imidazole derivatives (see Japanese Patent Publication No. 37-16096). ), Polyarylalkane derivatives (US Pat. No. 3,615,
No. 402, No. 3,820,989, No. 3,542,544, Japanese Patent Publication No. 45-555, and No. 51-1098.
No. 3, JP-A-51-93224, JP-A-55-1
Nos. 7105, 56-4148 and 55-1
JP-A-86667, JP-A-55-16953, and 5-
No. 6,36,656), pyrazoline derivatives and pyrazolone derivatives (U.S. Pat. No. 3,180,729;
4,278,746, JP-A-55-88064,
JP-A-55-88065, JP-A-49-105537, JP-A-55-51086, JP-A-56-80051, JP-A-56-88141, and JP-A-57-45545.
JP-A-5-112637 and JP-A-55-745.
46, etc.), phenylenediamine derivatives (U.S. Pat. No. 3,615,404, JP-B-51-10105, JP-B-46-3712, JP-B-47-25336, JP-A-54-53435), Id 54-110
536, 54-119925, etc.),
Arylamine derivatives (U.S. Pat. Nos. 3,567,450, 3,180,703, 3,240,597,
3,658,520, 4,232,103, 4,175,
No. 961, No. 4,012,376, JP-B-49-3
Nos. 5702 and 39-27577, JP-A-5
JP-A-5-144250, JP-A-56-119132, JP-A-56-22437, West German Patent No. 1,110,518
), Amino-substituted chalcone derivatives (see US Pat. No. 3,526,501), oxazole derivatives (as described in US Pat. No. 3,257,203, etc.),
Styryl anthracene derivatives (JP-A-56-46234)
And fluorenone derivatives (JP-A-54-1).
No. 10837), hydrazone derivatives (U.S. Pat. No. 3,717,462, JP-A-54-59143, JP-A-55-52063, JP-A-55-52064, JP-A-55-46760, and JP-A-55-46060. -85495
Gazette, JP-A-57-1350, and JP-A-57-1487
No. 49, JP-A-2-311591 etc.),
Stilbene derivatives (JP-A-61-210363,
No. 61-228451, No. 61-14642, No. 61-72255, No. 62-47646, No. 62-36674, No. 62-10652.
JP-A-62-30255 and JP-A-60-9344.
No. 5, JP-A-60-94462, JP-A-60-174
749, 60-175052, etc.). Further, examples of the hole injecting and transporting material include silazane derivatives (U.S. Pat. No. 4,950,950), polysilanes (JP-A-2-204996), aniline-based copolymers (JP-A-2-282263), and Conductive polymer oligomers, particularly thiophene oligomers, described in Japanese Patent Application No. 1-211399 are exemplified.

In the present invention, these compounds can be used as a hole injecting / transporting material. However, the following porphyrin compounds (those described in JP-A-63-2956965) and aromatic tertiary compounds can be used. Secondary amine compounds and styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-53-27033, JP-A-54-5844).
No. 5, No. 54-149634, No. 54-64
Nos. 299 and 55-79450 and 55-1
Nos. 44250, 56-119132 and 6
Nos. 1-295558 and 61-98353,
It is particularly preferable to use the aromatic tertiary amine compound. Representative examples of the porphyrin compound include porphine, 1,10,
15,20-tetraphenyl-21H, 23H-porphine copper (II), 1,10,15,20-tetraphenyl21H, 23H-porphine cuprous (II), 5,10,1
5,20-tetrakis (pentafluorophenyl) -2
1H, 23H-porphine, silicon phthalocyanine oxide, aluminum phthalocyanine chloride, phthalocyanine (metal-free), dilithium phthalocyanine, copper tetramethyl phthalocyanine, copper phthalocyanine, chromium phthalocyanine, zinc phthalocyanine, lead phthalocyanine, titanium phthalocyanine oxide, magnesium phthalocyanine, copper octa Methyl phthalocyanine and the like. Representative examples of the aromatic tertiary amine compound and styrylamine compound include N, N, N ',
N'-tetraphenyl-4,4'-diaminophenyl,
N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diaminobiphenyl (TPDA),
2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-
p-tolyl-4,4'-diaminobiphenyl, 1,1-
Bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-
Methylphenyl) phenylmethane, bis (4-di-p-
Tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N'-di (4-methoxyphenyl)-
4,4'-diaminobiphenyl, N, N, N ', N'-
Tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl, N, N, N-tri (p-tolyl) amine, 4-
(Di-p-tolylamino) -4 ′-[4 (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-
Methoxy-4'-N, N-diphenylaminostilbenzene, N-phenylcarbazole and the like. Further, an aromatic dimethylidin compound shown as a hole injection / transport material or a light emitting material can also be used. The hole injection transport layer in the EL device of the present invention comprises the above compound,
For example, vacuum deposition, spin coating, casting, LB
It can be formed by forming a film by a known thinning method such as a method. The thickness of the hole injection / transport layer is not particularly limited, but is usually 5 nm to 5 μm. The hole injecting and transporting layer may be composed of one or more of these hole injecting and transporting materials, or may be a hole injecting and transporting material composed of a compound different from the hole injecting and transporting layer. Layered layers may be used. Further, the organic E used in the present invention
The electron injection / transport layer of the L element is made of an electron injection material, and has a function of transmitting electrons injected from the cathode to the light emitting layer. There is no particular limitation on such an electron injecting material, and any one of conventionally known compounds can be selected and used. Preferred examples of the electron injection material include:

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Nitro-substituted fluorenone derivatives, anthraquinodimethane derivatives described in JP-A-57-149259, JP-A-58-55450, JP-A-63-104061, etc .; Polymer Preprints, Japan Vol.
37, No. 3 (1988), p.

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Diphenylquinone derivatives such as

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Thiopyran dioxide derivatives such as

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And heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene and carbodiimide.
JJ APPl. Phys., 27, L269 (1988).

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A compound represented by the following formula:
No. 57, No. 61-143765, No. 61-14815
No. 9, JP-A-61-225151 and JP-A-61-2337.
No. 50, etc., anthraquinodimethane derivatives and anthrone derivatives, Appl. Phys. Lett. 55 (1
5) Oxadiazole derivatives described in 1489 etc.

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And the like. JP-A-59-1
No. 94393, a series of electron-transporting compounds. In the above publication, the substance is disclosed as a material for forming a light emitting layer. However, as a result of investigation, it has been found that the substance can be used as a material for forming an electron injection / transport layer of the present invention. In particular, the following are desirable.

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Specific examples of metal complexes of 8-quinolinol derivatives include the following compounds: tris (8-quinolinol) aluminum, tris (5,7-dichloro-8-
(Quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, and complexes of magnesium, copper, gallium, tin and lead other than aluminum and indium. . Examples of the metal-free or metal phthalocyanine or those whose terminals are substituted with an alkyl group, a sulfonic acid group or the like are as follows.

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The distyrylpyrazine derivative shown as a light emitting material can also be mentioned as an electron injecting and transporting material. The electron injecting and transporting layer in the EL device of the present invention may be formed by applying the above compound to, for example, a vacuum evaporation method, a spin coating method, a casting method, or the like.
It can be formed by forming a film by a known thinning method such as the LB method. The thickness of the electron injecting and transporting layer is not particularly limited, but is usually 5 nm to 5 μm. The electron injecting and transporting layer may be composed of one or more layers of one or more of these electron injecting and transporting materials, or a layer obtained by laminating an electron injecting and transporting layer made of a compound different from the above-mentioned layer. There may be. Further, a hole injecting and transporting material using inorganic materials such as p-type Si and p-type SiC, and an electron injecting and transporting material using n-type α-Si and n-type α-SiC can be used as the electron injecting and transporting material. For example, International Publication WO90
And inorganic semiconductors disclosed in U.S. Pat. As the positive electrode in this EL element, a metal, an alloy, an electrically conductive compound and a mixture thereof having a large work function (4 eV or more) and an electrode material thereof are preferably used. Specific examples of such an electrode material include metals such as Au and dielectric transparent materials such as CuI, ITO, SnO ₂ and ZnO. The positive electrode can be manufactured by forming a thin film from these electrode substances by a method such as evaporation or sputtering. When light is extracted from this electrode, the transmittance is desirably greater than 10%, and the sheet resistance of the electrode is several hundred Ω.
/ □ or less is preferred. Further, the thickness depends on the material, but is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm. On the other hand, as the cathode, a metal, an alloy, an electrically conductive compound having a small work function (4 eV or less), and a mixture thereof as an electrode material are used. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, Al / Al ₂ O ₃ , and indium. The cathode can be manufactured by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. Further, the sheet resistance as an electrode is preferably several hundred Ω / □ or less, and the film thickness is usually 10 to 10Ω / □.
It is selected in the range of 500 nm, preferably 50 to 200 nm. In this EL device, it is convenient that one of the anode and the cathode is transparent or translucent because it transmits light, so that the efficiency of extracting light is good.
Next, a preferred example of manufacturing an EL element in the method of the present invention will be described. A method for manufacturing an EL device composed of the anode / hole injection / transport layer / light emitting layer / cathode will be described.
First, a thin film made of a desired electrode material, for example, a material for an anode, is formed on a suitable substrate in a thickness of 1 μm or less, preferably 10 to 20 μm.
An anode is formed so as to have a thickness of 0 nm by a method such as evaporation or sputtering. next,
A thin film made of a hole injection transport material is formed thereon, and a hole injection transport layer is provided. As a method of thinning the hole injecting / transporting material, there are spin coating method, casting method, vapor deposition method and the like as described above, but from the viewpoint that a uniform film is easily obtained and pinholes are hardly generated. Preferably, a vacuum deposition method is used. When this vapor deposition method is used for thinning the hole injection material, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, and the like. 50-450 ° C,
Vacuum degree 10 ^-5 to 10 ^-3 Pa, deposition rate 0.01 to 50 nm
/ Sec, substrate temperature -50 to 300 ° C, film thickness 5 nm to 5μ
It is desirable to select an appropriate value within the range of m. Next, after forming this light emitting layer, a thin film made of a material for a negative electrode is
A desired EL element can be obtained by forming the film to a thickness of 00 nm, preferably 50 to 200 nm, for example, by a method such as vapor deposition or sputtering and providing a cathode. In the production of this EL element,
The production order is reversed, and the cathode, the light emitting layer, the hole injecting and transporting layer,
It is also possible to produce in the order of the anode. The light emitting layer,
As described above, it is assumed that at least one of the hole injection transport layers and the like has been irradiated with ultraviolet rays. When a DC voltage is applied to the EL element obtained in this manner, light emission can be observed by applying a voltage of about 5 to 40 V with the positive electrode having a positive polarity and the negative electrode having a negative polarity. Also, even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the positive electrode becomes + and the negative electrode becomes-. The waveform of the applied alternating current may be arbitrary.

[0086]

Next, the present invention will be described in more detail with reference to examples. Example 1 An ITO electrode having a thickness of 100 nm formed on a white glass substrate having a size of 25 mm × 75 mm × 1.1 mm by an area deposition method of 20 mm × 65 mm was used as a transparent electrode (HOY).
A). The substrate was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with ultrapure water for 5 minutes, impregnated with isopropyl alcohol, and dried with dry nitrogen gas. This transparent electrode substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Nippon Vacuum Engineering Co., Ltd.), and N, N'-diphenyl-N, N'-di (3-
Methylphenyl) -4,4'-diaminobiphenyl (T
PDA) and 200mg of tris (8-quinolinol) aluminum (Al)
The vacuum layer was evacuated to 1 × 10 ⁻⁴ Pa with 200 mg of q ₃ ). After that, the boat containing TPDA was
It heated to 220 degreeC and vapor-deposited on the transparent electrode substrate at the vapor deposition rate of 0.1-0.3 nm / sec, and formed the 60-nm-thick hole injection transport layer. The substrate humidity at this time was room temperature. This was taken out from the vacuum layer, and Alq ₃ was used as a light-emitting layer on another hole injection / transport layer from another boat.
nm. The deposition conditions were a boat temperature of 230 ° C., a deposition rate of 0.02 to 0.03 nm / sec, and a substrate temperature of room temperature. Next, this was taken out and 10 m above the center of the light emitting layer
Install a stainless steel plate of mx 20 mm
20 watt low pressure mercury lamp (mainly 185, 254 nm
UV light is generated in a UV ozone cleaning device (UV-300 manufactured by Samco International), and only the low-pressure mercury lamp is used without starting the ozone generator.
0 seconds, UV light from the light emitting layer side of the EL element being manufactured.
Light was applied for 20 seconds. Next, the substrate was returned to the vacuum layer again and fixed to the substrate holder. Then, 1 g of a magnesium ribbon was put in a molybdenum resistance heating boat, and 500 mg of a silver wire was attached to a different tungsten basket. Thereafter, the pressure in the vacuum layer was reduced to 2 × 10 ⁻⁴ Pa, and then silver was simultaneously deposited at a deposition rate of 0.1 nm / sec and magnesium at a deposition rate of 1.4 nm / sec to obtain a mixed metal of magnesium and silver. An electrode was laminated on the light emitting layer to a thickness of 150 nm to form a counter electrode. Organic EL patterned with this ultraviolet light
When a voltage of 4 V or more was applied using ITO of the element as an anode and a magnesium mixed electrode as a cathode, light emission was observed only from the central 10 mm × 20 mm area where no ultraviolet light was irradiated, and no light emission was observed from other parts. . The light emission performance of the light emitting region was a green light emission having a luminance of 250 cd / m ² when a current of 7 mA / cm ² flowed when a voltage of 7 V was applied.
This confirmed that patterning was possible by irradiation with ultraviolet light.

Example 2 An ITO electrode formed on a white glass substrate having a size of 25 mm × 75 mm × 1.1 mm by an area deposition method of 20 mm × 65 mm to a thickness of 100 nm was used as a transparent electrode (HOY).
A). The substrate was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with ultrapure water for 5 minutes, impregnated with isopropyl alcohol, and dried with dry nitrogen gas. This transparent electrode substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Nippon Vacuum Engineering Co., Ltd.), and N, N'-diphenyl-N, N'-di (3-
Methylphenyl) -4,4'-diaminobiphenyl (T
PDA) was placed in an amount of 200 mg, and the pressure in the vacuum layer was reduced to 1 × 10 ⁻⁴ Pa. After that, the boat containing TPDA was
It heated to 220 degreeC and vapor-deposited on the transparent electrode substrate at the vapor deposition rate of 0.1-0.3 nm / sec, and formed the 60-nm-thick hole injection transport layer. The substrate humidity at this time was room temperature. This is taken out from the vacuum layer, and 1 is placed on the center of the hole injection / transport layer.
A stainless steel plate of 0 mm × 20 mm was installed, and a 120 W low-pressure mercury lamp (mainly 185, 254 n)
m UV light is generated), and only the low-pressure mercury lamp is activated for 40 seconds without activating the ozone generator, and the positive polarity of the EL element being manufactured is started. UV light was irradiated for 40 seconds from the hole injection transport layer side. Next, the substrate was returned to the vacuum layer again and fixed to the substrate holder. Then, 200 mg of Alq ₃ was put into a molybdenum resistance heating boat, 1 g of magnesium ribbon was put into another molybdenum resistance heating boat, and 500 mg of silver wire was attached to another tungsten basket. Thereafter, the pressure of the vacuum layer was reduced to 2 × 10 ⁻⁴ Pa, and then Alq ₃ was first heated to 230 ° C. to form a 60 nm layer on the hole injection transport layer at a deposition rate of 0.02 to 0.03 nm / sec. Next, 0.1n of silver
Magnesium was simultaneously vapor-deposited at a vapor deposition rate of m / sec and a vapor deposition rate of 1.4 nm / sec, and a mixed metal electrode of magnesium and silver was laminated on the light-emitting layer by 150 nm to form a counter electrode. When a voltage of 4 V or more is applied using the ITO of the organic EL element patterned with the ultraviolet light as an anode and the magnesium mixed electrode as a cathode, the central 10 mm × 2 which is not irradiated with the ultraviolet light is applied.
Green light emission was observed only from the 0 mm region, and no light emission was confirmed from other portions. The luminous performance of the luminous region is such that a current of 6 mA / cm ² flows when a voltage of 7 V is applied.
It emitted green light with a luminance of 0 cd / m ² .

Example 3 The luminescent material was 4,4'-bis [2,2- (4-t-butylphenyl) vinyl] biphenyl (DTBPVBI), and DTBPVBI was heated to 345 ° C., and the deposition rate was 0.1 to 0.1%.
The same organic EL device as in Example 1 was patterned except that the light emitting layer was laminated on the hole injection transport layer at 0.3 nm / sec. The I of the organic EL element patterned with this ultraviolet light
When a voltage of 5 V or more is applied using TO as an anode and a magnesium mixed electrode as a cathode, the central 10 not irradiated with ultraviolet light is applied.
Blue light emission was observed only from the area of mm × 20 mm, and no light emission was confirmed from other portions. The light emission performance of the light emitting region was blue light emission with a luminance of 1000 cd / m ² when a current of 40 mA / cm ² flowed when a voltage of 12 V was applied.

Example 4 An ITO electrode formed on a white glass substrate having a size of 25 mm × 75 mm × 1.1 mm by an area deposition method of 20 mm × 65 mm to a thickness of 100 nm was used as a transparent electrode (HOY).
A). The substrate was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with ultrapure water for 5 minutes, impregnated with isopropyl alcohol, and dried with dry nitrogen gas. This transparent electrode substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Nippon Vacuum Engineering Co., Ltd.), and N, N'-diphenyl-N, N'-di (3-
Methylphenyl) -4,4'-diaminobiphenyl (T
PDA) and 200mg of tris (8-quinolinol) aluminum (Al)
q ₃₎ was reduced to a vacuum chamber to 1 × 10 ^-4 Pa put 200 mg. After that, the boat containing TPDA was
It heated to 220 degreeC and vapor-deposited on the transparent electrode substrate at the vapor deposition rate of 0.1-0.3 nm / sec, and formed the 60-nm-thick hole injection transport layer. The substrate temperature at this time was room temperature. This was taken out from the vacuum chamber, and Alq ₃ was used as a light-emitting layer on another hole-injecting and transporting layer.
nm. The deposition conditions were a boat temperature of 230 ° C., a deposition rate of 0.02 to 0.03 nm / sec, and a substrate temperature of room temperature. Next, the substrate was returned to the vacuum chamber, and a stainless steel mask was placed on the light emitting layer and fixed to the substrate holder. Then, 1 g of a magnesium ribbon was put in a molybdenum resistance heating boat, and 500 mg of a silver wire was attached to a different tungsten basket. Thereafter, the pressure in the vacuum chamber was reduced to 2 × 10 ⁻⁴ Pa, and then the silver was reduced to 0.
At a deposition rate of 1 nm / sec and magnesium of 1.4 nm /
Simultaneous vapor deposition was performed at a vapor deposition rate of 2 seconds, and a mixed metal electrode of magnesium and silver was laminated on the light emitting layer to a thickness of 150 nm to form a counter electrode. 15mm x 50mm area of counter electrode by mask
And The organic EL device was taken out of the vacuum chamber and "EL" was written on the glass substrate with a black felt pen. In this state, ultraviolet light was irradiated from the glass substrate side with a 400 W high-pressure mercury lamp (UVL-400P, manufactured by Riko Kagaku Sangyo Co., Ltd., with a strong ultraviolet ray of 365 nm) for 20 minutes. Thereafter, the letter "EL" written on the glass substrate was wiped off using dichloromethane. In this state, a voltage was applied using ITO as an anode and a magnesium mixed metal electrode as a cathode, and the light emission state was observed from the glass substrate side. As a result, when a voltage of 8 V was applied, the character portion of “EL” showed strong green light emission, and its luminance was 1
000 cd / m ² . Light emission was not observed in portions other than the letters "EL" despite the application of a voltage of 8V. In addition, the non-light-emitting portion had a metal electrode on the back surface similarly to the light-emitting portion, and light emission of “EL” was clearly determined.

Example 5 An ITO electrode formed on a white glass substrate having a size of 25 mm × 75 mm × 1.1 mm by an area deposition method of 20 mm × 65 mm to a thickness of 100 nm was used as a transparent electrode (HOY).
A). The substrate was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with ultrapure water for 5 minutes, impregnated with isopropyl alcohol, and dried with dry nitrogen gas. This transparent electrode substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Nippon Vacuum Engineering Co., Ltd.), and N, N'-diphenyl-N, N'-di (3-
Methylphenyl) -4,4'-diaminobiphenyl (T
PDA) and 200mg of tris (8-quinolinol) aluminum (Al)
q ₃₎ was reduced to a vacuum chamber to 1 × 10 ^-4 Pa put 200 mg. After that, the boat containing TPDA was
It heated to 220 degreeC and vapor-deposited on the transparent electrode substrate at the vapor deposition rate of 0.1-0.3 nm / sec, and formed the 60-nm-thick hole injection transport layer. The substrate temperature at this time was room temperature. This was taken out from the vacuum chamber, and Alq ₃ was used as a light-emitting layer on another hole-injecting and transporting layer.
nm. The deposition conditions were a boat temperature of 230 ° C., a deposition rate of 0.02 to 0.03 nm / sec, and a substrate temperature of room temperature. Next, the substrate was returned to the vacuum chamber, and a stainless steel mask was placed on the light emitting layer and fixed to the substrate holder. Then, 1 g of a magnesium ribbon was put in a molybdenum resistance heating boat, and 500 mg of a silver wire was attached to a different tungsten basket. Thereafter, the pressure in the vacuum chamber was reduced to 2 × 10 ⁻⁴ Pa, and then the silver was reduced to 0.
At a deposition rate of 1 nm / sec and magnesium of 1.4 nm /
Simultaneous vapor deposition was performed at a vapor deposition rate of 2 seconds, and a mixed metal electrode of magnesium and silver was laminated on the light emitting layer to a thickness of 150 nm to form a counter electrode. 15mm x 50mm area of counter electrode by mask
And The organic EL element was taken out of the vacuum chamber, and irradiated with a nitrogen gas laser (VSL-337, manufactured by Laser Science) in an area of 3 mm × 8 mm from the glass substrate side. The laser output at this time was 10 mW / cm ² ,
The repetition frequency was 20 Hz. After irradiating UV light for 20 minutes in this state, a voltage of 7 V was applied using ITO as an anode and a magnesium mixed metal electrode as a cathode. As a result, green light emission with a luminance of 500 cd / m ² was observed in the non-irradiated part of the ultraviolet light, but the luminance of the part irradiated with the ultraviolet light was 1 cd / m ^2.
m ² or less.

Example 6 An ITO electrode was formed on a white glass substrate having a size of 25 mm × 75 mm × 1.1 mm by an area evaporation method of 20 mm × 65 mm to a thickness of 100 nm to form a transparent electrode (HOY).
A). The substrate was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with ultrapure water for 5 minutes, impregnated with isopropyl alcohol, and dried with dry nitrogen gas. This transparent electrode substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Nippon Vacuum Engineering Co., Ltd.), and N, N'-diphenyl-N, N'-di (3-
Methylphenyl) -4,4'-diaminobiphenyl (T
PDA) and 200mg of tris (8-quinolinol) aluminum (Al)
q ₃₎ was reduced to a vacuum chamber to 1 × 10 ^-4 Pa put 200 mg. After that, the boat containing TPDA was
It heated to 220 degreeC and vapor-deposited on the transparent electrode substrate at the vapor deposition rate of 0.1-0.3 nm / sec, and formed the 60-nm-thick hole injection transport layer. The substrate temperature at this time was room temperature. This was taken out from the vacuum chamber, and Alq ₃ was used as a light-emitting layer on another hole-injecting and transporting layer.
nm. The deposition conditions were a boat temperature of 230 ° C., a deposition rate of 0.02 to 0.03 nm / sec, and a substrate temperature of room temperature. Next, the substrate was returned to the vacuum chamber, and a stainless steel mask was placed on the light emitting layer and fixed to the substrate holder. Then, 1 g of a magnesium ribbon was put in a molybdenum resistance heating boat, and 500 mg of a silver wire was attached to a different tungsten basket. Thereafter, the pressure in the vacuum chamber was reduced to 2 × 10 ⁻⁴ Pa, and then the silver was reduced to 0.
At a deposition rate of 1 nm / sec and magnesium of 1.4 nm /
Simultaneous vapor deposition was performed at a vapor deposition rate of 2 seconds, and a mixed metal electrode of magnesium and silver was laminated on the light emitting layer to a thickness of 150 nm to form a counter electrode. 15mm x 50mm area of counter electrode by mask
And The organic EL device was taken out of the vacuum chamber, and placed on a commercially available pulse stage (manufactured by XY Stage Obtec with a control system) with the glass substrate facing up. Next, an output beam of the same nitrogen gas laser as used in Example 5 was formed into a circular beam having a diameter of 1 mm by a lens and an aperture. The output intensity at this time was 120 mW / cm ² . This beam was irradiated on the EL element through the glass, and at the same time, the pulse stage was moved by 3 cm at a speed of 0.1 mm / sec. As a result of applying a voltage of 7 V to the EL element using ITO as an anode / magnesium mixed electrode as a cathode and confirming the light emission state, green light emission of 500 cd / m ² or more was observed on average.
It was confirmed that only the portion was in a non-light emitting state with a width of 1 mm. This showed that fine patterning using laser light was possible.

[0092]

As described above, according to the present invention, by patterning an organic EL element using ultraviolet rays, it is possible to efficiently pattern an organic EL element in a short time. Therefore, the present invention can be used in the chemical industry as an efficient method for manufacturing a light emitting material and a display element.

[Brief description of the drawings]

FIG. 1 is a diagram of one stage of patterning.

FIG. 2 shows two stages of patterning

FIG. 3 is a diagram of a patterned organic EL device.

FIG. 4 is a diagram of patterning an XY stage.

FIG. 5 is a view of FIG. 4 as viewed from above;

FIG. 6 is a diagram of one stage of patterning.

FIG. 7 shows two stages of patterning.

FIG. 8 shows three stages of patterning.

FIG. 9 is a diagram of a patterned organic EL element.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass substrate with ITO 2 Light emitting layer 3 UV mask 4 Counter electrode 5 Wiring 6 XY stage 7 Glass substrate with ITO 8 Light emitting layer 9 Spot of ultraviolet rays a Glass substrate with ITO b Hole injection transport layer c UV mask d Light emitting layer e Counter electrode f Wiring

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) H05B 33/10 H05B 33/14

Claims (8)

(57) [Claims] An organic electroluminescent device using an organic compound as a light emitting material is characterized by irradiating a light emitting layer made of a light emitting material with an ultraviolet ray to form a non-light emitting area when patterning an organic electroluminescent element using the organic compound as a light emitting material. A method for patterning a luminescence element. 2. The patterning method for an organic electroluminescence device according to claim 1, wherein the organic electroluminescence device is a stacked device with a charge injection / transport layer. 3. When patterning an organic electroluminescent element in which a light emitting material made of an organic compound is interposed between two electrodes facing each other, an arbitrary pattern is formed on the element being manufactured prior to manufacturing the counter electrode. 2. The method for patterning an organic electroluminescence device according to claim 1, wherein the step of irradiating the ultraviolet light is performed, and thereafter, a counter electrode is formed. 4. In patterning an organic electroluminescent element in which a light emitting material made of an organic compound is interposed between two opposing electrodes, at least one of which is transparent or translucent, the transparent or translucent electrode is used to pattern the organic electroluminescent element. 2. The patterning method for an organic electroluminescent device according to claim 1, wherein the pattern is irradiated with ultraviolet rays. 5. In patterning an organic electroluminescence device using an organic compound as a charge injection / transport material, a charge injection / transport layer made of the charge injection / transport material is irradiated with ultraviolet rays, and a portion corresponding to the irradiated portion is not illuminated. A method for patterning an organic electroluminescent element, wherein the pattern is a region. 6. The method for patterning an organic electroluminescent device according to claim 5, wherein the organic electroluminescent device is a laminated device with a charge injection / transport layer. 7. In patterning an organic electroluminescent element in which a light emitting material made of an organic compound is interposed between two electrodes facing each other, an arbitrary pattern is formed on the element being manufactured prior to manufacturing the counter electrode. 6. The method for patterning an organic electroluminescence device according to claim 5, wherein the step of irradiating the ultraviolet light is performed, and thereafter, a counter electrode is formed. 8. When patterning an organic electroluminescent element in which a light emitting material made of an organic compound is interposed between two opposing electrodes, at least one of which is transparent or translucent, any one of the transparent or translucent electrodes is used to pattern the organic electroluminescent element. 6. The patterning method for an organic electroluminescent device according to claim 5, wherein the pattern is irradiated with ultraviolet rays.