CN1418041A - Organic electrofluorescent element - Google Patents
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- CN1418041A CN1418041A CN 01136897 CN01136897A CN1418041A CN 1418041 A CN1418041 A CN 1418041A CN 01136897 CN01136897 CN 01136897 CN 01136897 A CN01136897 A CN 01136897A CN 1418041 A CN1418041 A CN 1418041A
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Abstract
An organic electrofluorescent element for retaining emission characteristics for a long time includes: a laminate panel, in which organic electrofluorescent material layer is clamped between a pair of eletrodes relative to each other; a close container for accomodating the said laminate panel; and a drying member, which is placed in the said close container in order to prevent the said organic electrofluorescent material layer contaminated by water, wherein the drying member made of a metal orgnic compound. The metal orgnic compound can adsorb water in the form of chemistry, as adhesive agent of other physical and chamical desiccant, without side effect for organic electrofluorescent element, and preventing dark stain growing.
Description
Background
The present invention relates to an organic electroluminescent element capable of maintaining stable emission characteristics for a long period of time.
An organic electroluminescent element (hereinafter referred to as an organic EL (electroluminescent) element) includes an organic EL thin film layer containing a fluorescent organic compound and sandwiched between a pair of electrodes (a cathode and an anode). An organic EL element is a natural light emitting element in which a hole and an electron are injected into a thin film and recombined to generate an exciton. When the exciton is inactive, it is used to emit light (fluorescence or phosphorescence).
The main problem of the organic EL element described above is to improve its durability, particularly to suppress the generation of a non-light emitting portion called "dark spot" and its growth. When the diameter of the dark spot is as long as several tens of micrometers (μm), a non-light emitting portion thereof can be observed with the naked eye. The main cause of the occurrence of dark spots is the influence of water and oxygen, especially water, which even in trace amounts can have a severe effect on the element.
Because of this, water must be removed from the material constituting the EL element. It is particularly important to exclude water to purify the organic material used for the light-emitting part. The organic EL element is manufactured in a drying process, and film formation is carried out under vacuum conditions or in a similar sealing process in an effort to remove water from the container. However, at present, water cannot be completely removed, and thus generation of dark spots cannot be completely avoided.
As described above, the first problem of the organic EL element is to thoroughly remove water in the container to eliminate dark spots and prolong the service life. One of the known solutions is that water removal can be significantly improved by sealing the organic EL element container with a water absorbing agent as an additional drying means (for example, unexamined patent document (KOKAI) No. 9-148066).
Fig. 4 is a side view of a conventional organic EL element structure obtained by using a water absorbing agent as a drying means. The organic EL element 41 shown in fig. 4 includes a transparent insulating glass substrate 42 on which a transparent conductor film comprising Indium Tin Oxide (ITO) is formed and constitutes an anode 45.
Over the anode 45, an organic EL layer 44 composed of an organic compound material is formed. A cathode of a metal (e.g., Al — Li) thin film is formed on the organic EL layer 44, and a laminated light-emitting portion including an anode 45, the organic EL layer 44, and the cathode 46 is formed. The organic EL layer 44 is composed of one hole injection layer, one hole transport layer, one electron injection layer, etc., and includes at least one organic light emitting layer for EL emission.
The metal cap 43 is fixed with an adhesive 48 around the periphery of the glass substrate 42 in an inert gas (e.g., dry nitrogen gas) in which water is completely removed or in a dry atmosphere of dry air. Thereby protecting the anode 45, the organic EL layer 44, and the cathode 46 on the glass substrate.
A groove 49 is formed on the inner surface of the metal cap 43 by extrusion molding or the like. In the recess 49 a powdered desiccant 47, for example barium oxide or calcium oxide, is provided as a desiccant member. The recess 49 containing the powdered desiccant 47 has a sheet-like, water-permeable cover 50. The desiccant 47 in the grooves 49 absorbs the residual moisture in the container to form hydroxide, thereby removing the residual moisture in the container and moisture from the outside.
However, in the case of the conventional organic EL element 41 shown in fig. 4, the desiccant 47 loaded in the recess 49 of the metal cap 43 thereof is powder. There is a problem that when calcium oxide used as the drying agent 47 is attached to the cathode 46, aluminum and calcium oxide of the cathode chemically react with water, resulting in corrosion of the aluminum thin film cathode and the like of the cathode 46. In order to solve this problem, it is necessary to cover the groove 49 in which the desiccant 47 is loadedwith a cover 50 so as to isolate the desiccant 47 from the light-emitting portion, so that calcium oxide as a desiccant does not stick to the cathode.
Therefore, the metal cap 43 used should have a special shape, and the structure becomes complicated. Another problem is that a large space is required for accommodating the desiccant, thus making the entire element thick.
There is also a problem that when the drying agent 47 is confined in the groove 49 of the metal cap 43, it is difficult to handle such an organic EL element without contamination because the drying agent 47 is a powder, and its workability is particularly poor.
Still another problem is that even if dark spots are suppressed by the drying means of the metal cap, the generation and growth of dark spots cannot be effectively prevented in the peripheral region of the sealing portion of the organic EL element.
Summary of The Invention
Accordingly, an object of the present invention is to overcome the above-mentioned problems and to provide an organic EL element which can be made thinner by using a film-like drying agent as a drying member, which can effectively absorb moisture and has good workability, and which can effectively suppress the generation and growth of dark spots in the peripheral region of the organic EL element.
According to the present invention, there is provided an organic EL element comprising: a laminate having a structure in which an organic EL material layer is interposed between a pair of opposing electrodes; a sealed container containing said laminate; a drying member disposed in the sealed container for preventing the organic EL material layer from being contaminated with moisture, characterized in that the drying member is composed of a metal organic compound.
Preferably, the drying member is composed of a metal organic compound represented by structural formula (1):
wherein R is a group selected from the group consisting of alkyl, alkenyl, aryl, cycloalkyl, heterocyclic group and acyl group containing at least one carbon atom, M is a trivalent metal atom, and n is an integer of more than 1.
Preferably, the drying member is composed of a metal organic compound represented by structural formula (2):
in the formula, R1，R2，R3，R4And R5Each of which is selected from the group consisting of alkyl, alkenyl, aryl, cyclicA group selected from the group consisting of an alkyl group, a heterocyclic group and an acyl group containing at least one carbon atom, and M is a trivalent metal atom.
Preferably, the drying member is composed of a metal organic compound represented by structural formula (3):in the formula, R1，R2，R3And R4Each of which is a group selected from the group consisting of alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, heterocyclic groups and acyl groups containing at least one carbon atom, and M is a trivalent metal atom.
Preferably, the metal organic compound drying part is disposed on an inner surface of the sealed container.
Preferably, the drying member is so placed as to cover the organic EL layer as a protective member.
Alternatively, the metal organic compound drying means may be used in combination with an inorganic desiccant.
Alternatively, the organometallic compound drying component may be used in combination with an inorganic desiccant using physical adsorption.
Alternatively, the drying means of the organometallic compound may be used in combination with an inorganic desiccant which utilizes chemical action.
Alternatively, the drying means of the metal organic compound may be used in combination with an inorganic drying agent using chemical adsorption and an inorganic drying agent using physical adsorption.
These and other objects and advantages of the present invention will be well understood and appreciated by those skilled in the art from the specification and appended claims.
Brief description of the drawings
The invention may be carried into practice in a number of ways and a number of embodiments of the invention are described below by way of example with reference to the accompanying drawings. In the drawings:
FIG. 1 is a side view of a first embodiment of the present invention;
FIG. 2 is a side view of a second embodiment of the present invention;
FIG. 3 is a side view of a third embodiment of the present invention;
fig. 4 is a side view of a conventional organic EL element;
FIG. 5 is a graph showing the growth of dark spots according to the present invention;
FIG. 6 is a graph showing the growth of dark spots according to the present invention;
FIG. 7 is a graph showing the growth of dark spots according to the present invention.
Description of The Preferred Embodiment
Fig. 1, 2 and 3 are side views of specific embodiments of the organic EL element of the present invention.
As shown in fig. 1, an organic EL element 1 of the present invention includes a rectangular insulating transparent glass substrate base member 2 as a base. In fig. 1, the anode 5 of the ITO film is a transparent conductive material formed on the base member 2. An ITO film is formed on the substrate 2, for example, by a deposition method like PVD (physical vapor deposition), a sputtering method, or the like. Then, a given template is applied to the film, and the anode 5 is formed by etching with a photoresist. A portion of the anode 5 is pulled out to the end of the substrate 2 and connected to a driving circuit (not shown).
The organic EL layer 4 in FIG. 1 includes three layers, an organic layer 4a of copper phthalocyanine (CuPc) as a hole injection layer having a thickness of several tens of nanometers formed on the anode 5, a bis (N- (1-naphthyl-N-phenyl)) benzidine (α -NPD) organic layer 4b as a hole transport layer having a film thickness of several tens of nanometers formed on the upper surface of the organic layer 4a, and tris (8-quinoline) aluminum (Alq) having a film thickness of several tens of nanometers formed on the upper surface of the organic layer 4b3) The organic layer 4c serves as a light-emitting layer and an electron transport layer. The light-emitting portion is constituted by a laminate including the above-described anode 5 and organic EL layer 4 and the below-described cathode 6.
The cathode 6 is made of a metal thin film and is disposed on the organic EL layer 4 (Alq)3On the upper surface of the organic layer 4c), as shown in fig. 1. The material for the metal thin film includes a single metal material having a weak function, such as Al, Mg, etc., and an alloy having a weak function, such as Al-Li, Mg-Ag alloy, etc. The film thickness of the cathode 6 is, for example, 10 to 1000nm, preferably 50 to 200 nm. A portion of the cathode 6 is pulled to the end of the base element 2 and connected to a driving circuit (not shown).
A rectangular sealing cap 3 is fixed to the outer periphery of the substrate 2 with an adhesive 8 such as an ultraviolet curable resin as a sealing member under an atmosphere of an inert gas (e.g., dry nitrogen gas) from which moisture is completely removed or under a dry air atmosphere, thereby protecting the anode 5, the organic EL layer 4 and the cathode 6.
A drying film 7 is placed as a drying means on the substrate 2 and/or the sealing cap 3 in the container that has been sealed with the substrate 2, the sealing cap 3, and the adhesive 8. A metal organic compound is used as the dry film.
The reaction of the above chelate-type metal complex of an aluminum-containing metal organic compound with water is carried out according to the following reaction formula (4):
as shown in the reaction formula (4), three alkoxy groups are released from the aluminum complex, and aluminum reacts with three hydroxyl groups of water. It can therefore be concluded that the above-mentioned compounds can be used as desiccants to chemically remove moisture.
The reaction of a chelate type metal complex, which is different from the above-mentioned aluminum metal complex, with water is carried out according to the following reaction formula (5):
as shown in the reaction formula (5), an organic compound in an amount corresponding to the valence of the metal atom is released, and the metal reacts with n hydroxyl groups. Therefore, the compound represented by the structural formula (1) can also be used as a desiccant to chemically remove moisture.
In a similar manner to the above, the present inventors have found that the metal-organic compound represented by the structure (1) absorbs water molecules by hydrolysis, that is, moisture around the organic EL element reacts with the metal-organic compound to separate the M — O bond of the 2 n-membered ring, and H and OH groups in the water molecules react to generate a hydroxyl (OH) bond. The present inventors have also found that 1 mole of the metal-organic compound represented by the structural formula (1) can react with 3 moles of water molecules to produce a hydroxide, and thus the metal-organic compound represented by the structural formula (1) has an absorbing effect on moisture. Meanwhile, the present inventors have presumed the action and principle possessed by the metal-organic compound represented by the structural formula (1), whereby the metal-organic compound represented by the structural formula (1) can be used as a drying agent for an organic EL element, and found that the metal-organic compound represented by the structural formula (1) is an effective drying agent. R in the structural formula (1) is exemplified by the following, but not limited thereto:
r is a group selected from the group consisting of alkyl, alkenyl, aryl, cycloalkyl, heterocyclic group and acyl group containing at least one carbon atom. The alkyl group may be substituted or unsubstituted, such as methyl, ethyl, propyl, butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and the like, with those having more than eight carbon atoms being preferred. Examples of preferred substituted or unsubstituted alkylgroups are preferably those described below, and may be oligomers or polymers thereof. The alkenyl group may be a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, or the like, and examples of substituted or unsubstituted alkenyl groups having eight or more carbon atoms are preferably those described below, and may also be oligomers or polymers thereof.
Aryl groups may be substituted or unsubstituted, for example the groups listed below: phenyl, tolyl, 4-cyanophenyl, biphenyl, o, m, p-terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, 9-phenylanthryl, 9, 10-diphenylanthryl, pyrenyl and the like, with those having eight or more carbon atoms being preferred. And may be an oligomer or a polymer thereof.
Examples of the substituted or unsubstituted alkoxy group may be methoxy, n-butoxy, t-butoxy, trichloromethoxy, trifluoromethoxy and the like, and preferably those having eight or more carbon atoms. Oligomers or polymers thereof may also be used.
Examples of the substituted or unsubstituted cycloalkyl group may be a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a 4-methylcyclohexyl group, a 4-cyanocyclohexyl group and the like, and preferably those containing eight or more carbon atoms. And may be an oligomer or a polymer thereof.
Examples of the substituted or unsubstituted heterocyclic group may be pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, imidazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzopyrimidinyl, purinyl, quinolyl, isoquinolyl, cinolone (cinorin) yl, quinoxalyl, benzoquinolyl, fluorenylonyl, dicyanofluorenonyl, carbazolyl, oxazolyl, dioxazolyl, thiazolyl, dithiazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, dibenzooxazolyl, dibenzothiazolyl, dibenzoimidazolyl and the like. Oligomers or polymers thereof may also be used.
The substituted or unsubstituted acyl group may be formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, oxalyl, malonyl, succinyl, glutaryl, adipyl, pimeloyl, suberoyl, azepinoyl, sebacoyl, acryloyl, propioloyl, methacryloyl, crotonyl, methacryloyl, oleoyl, elaeoyl, maleoyl, fumaroyl, citraconyl, mesoconyl, kaempferoyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydrogenated 2-phenylpropenoyl, cinnamoyl, furoyl, thenoyl, nicotinoyl, naphthoyl, quinophthaloyl, phthaloyl, and the like, Isonicotinoyl, glycoloyl, propoxoyl, glyceroyl, propoxydioyl, hydroxysuccinyl, tartharoyl, tropinoyl, diphenoxyoyl, o-hydroxyphenylacyl, methoxybenzoyl, 4-hydroxy-3-methoxybenzoyl, 3, 4-dimethoxybenzoyl, piperonyl, orotocartoyl, 3, 4, 5-trihydroxybenzoyl, glyoxyl, pyruvoyl, acetoacetyl, m-oxalyl, butanone diacyl, oxaloaceto group, levulinoyl and the like. These acyl groups may be substituted with fluorine, chlorine, bromine, iodine, etc. The number of carbon atoms on the acyl group is preferably eight or more. Oligomers or polymers thereof may also be used.
R quiltExamples of the metal organic compound in which aluminum is a trivalent metal substituted by one of the above substituents are those metal organic complexes represented by structural formulae (6), (7) and (8):
in addition, the present inventors have found that the metal organic compound represented by the structural formula (2) absorbs water molecules by hydrolysis, that is, moisture around the organic EL element reacts with the metal organic compound to separate the M — O bond on the 2 n-membered ring, and H and OH in the water molecules react to form a hydroxyl (OH) bond. The present inventors have also found that 1 mole of the organometallic compound represented by the structural formula (2) can react with 3 moles of water molecules to produce a hydroxide, and therefore, the organometallic compound represented by the structural formula (2) has an absorbing effect on moisture. Further, the present inventors have already estimated the reaction and principle possessed by the metal organic compound represented by the structural formula (2), whereby the metal organic compound represented by the structural formula (2) can be used as a desiccant for an organic EL element, and found that the metal organic compound represented by the structural formula (2) is an effective desiccant. R in the formula (2)1、R2、R3、R4And R5Examples are listed below, but are not limited thereto:
r in the formula (2)1、R2、R3、R4And R5Each is a group selected from the group consisting of alkyl, alkenyl, aryl, cycloalkyl, heterocyclic and acyl groups. The alkyl group may be substituted or unsubstituted, such as methyl, ethyl, propyl, butyl, 2-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and the like, and preferably those having eight or more carbon atoms. Examples of the substituted or unsubstituted alkyl group are preferably as followsThe oligomer or polymer of those described below may also be used. The alkenyl radical may beAre ethenyl, propenyl, butenyl, pentenyl, ethenyl and the like, and examples of substituted or unsubstituted alkenyl groups having eight or more carbon atoms are preferably those described below. Oligomers or polymers thereof may also be used.
The aryl group may be substituted or unsubstituted, such as phenyl, tolyl, 4-cyanophenyl, biphenyl, o, m, p-terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, 9-phenylanthryl, 9, 10-diphenylanthryl, pyrenyl, and the like. Oligomers or polymers thereof may also be used.
Examples of substituted or unsubstituted alkoxy groups are methoxy, n-butoxy, t-butoxy, trichloromethoxy, trifluoromethoxy and the like. Oligomers or polymers thereof may also be used.
Examples of the substituted or unsubstituted cycloalkyl group include cyclopentyl, cyclohexyl, norbornyl, adamantyl, 4-methylcyclohexyl, 4-cyanocyclohexyl and the like. Oligomers or polymers thereof may also be used.
Examples of substituted or unsubstituted heterocyclic groups are pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, imidazole, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzimidazolyl, purinyl, quinolyl, isoquinolyl, coumarinyl, quinoxalyl, benzoquinolyl, fluorenone, dicyanofluorenoyl, carbazolyl, oxazolyl, dioxazolyl, thiazolyl, dithiazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, dibenzooxazolyl, dibenzothiazolyl, dibenzoimidazolyl and the like. Oligomers or polymers thereof may also be used.
Examples of substituted or unsubstituted acyl groups are formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, oxalyl, malonyl, succinyl, glutaryl, adipyl, pimeloyl, suberoyl, azepinoyl, sebacoyl, acryloyl, propioloyl, methacryloyl, crotonoyl, methacryloyl, oleoyl, elactoyl, maleoyl, fumaroyl, citraconyl, mesoconyl, kaempferoyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydrogenated 2-phenylpropenoyl, cinnamoyl, furoyl, thenoyl, nicotinoyl, naringenyl, phthaloyl, isophthaloyl, naphthoyl, oleoyl, 2-phenylpropenoyl, cinnamoyl, furoyl, nicotinoyl, Isonicotinoyl, glycoloyl, propoxoyl, glyceroyl, propoxydioyl, hydroxysuccinyl, tartharoyl, tropinoyl, diphenoxyoyl, o-hydroxyphenylacyl, methoxybenzoyl,4-hydroxy-3-methoxybenzoyl, 3, 4-dimethoxybenzoyl, piperonyl, orotocartoyl, 3, 4, 5-trihydroxybenzoyl, glyoxyl, pyruvoyl, acetoacetyl, m-oxalyl, butanone diacyl, oxaloaceto group, levulinoyl and the like. These acyl groups may be substituted with fluorine, chlorine, bromine, iodine, etc. Oligomers or polymers thereof may also be used.
R1、R2、R3、R4And R5Examples of the organometallic compounds in which each of the above-mentioned substituents is substituted with one of the substituents, and the trivalent metal is aluminum are organometallic complexes represented by structural formulae (9), (10), (11) and (12):
general structural formula of Chelope of structural formula (9)
Aluminum-bis-2-ethylhexyloxy-monoethylacetyl acetate Chelope-EH-2 of the formula (10)
Aluminum-bis-2-methylnonanyloxy-monoethylacetyl acetate Chelope C10-2 of formula (11)
Aluminium-di-n-dodecyloxy-monoethyl acetyl acetate Chelope C12-2 of formula (12)
Metal organic with lanthanum as trivalent metalExamples of the compounds are metal organic complexes represented by the structural formula (13).
Structural formula (13)
Lanthanum complex
An example of the organometallic compound in which the trivalent metal is yttrium is a organometallic complex represented by the structural formula (14).
Structural formula (14)
Yttrium complexes
An example of the organometallic compound in which the trivalent metal is gallium is a organometallic complex represented by the structural formula (15).
Structural formula (15)
Gallium complexes
Further, the present inventors have found that the metal-organic compound of the structural formula (3) absorbs water molecules by hydrolysis, that is, moisture around the organic EL element reacts with the metal-organic compound, so that the M — O bond on the 2 n-membered ring is broken, and H and OH in the water molecule form a hydroxyl (OH) bond by reaction. The present inventors have also found that 1 mole of the metal organic compound represented by the structural formula (3) can react with 3 moles of water molecules to produce a hydroxide, and that the metal organic compound represented by the structural formula (3) has an absorbing effect on moisture. Further, the present inventors have already speculated that the metal-organic compound represented by the structural formula (3) has a reaction and a principle, and accordingly, the metal-organic compound represented by the structural formula (3) can be used as a drying agent for an organic EL element, and found that the metal-organic compound represented by the structural formula (3) is effective as a drying agent. R in the formula (3)1、R2、R3And R4Examples of (a) are described below, but not limited thereto:
structural formula (3)) R in (1)1、R2、R3And R4Each of which is one group selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a heterocyclic group, and an acyl group having eight or more carbon atoms. Alkyl groups may be substituted or unsubstituted, for example methyl, ethyl, propyl, butyl, 2-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecylAlkyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and the like, and those having eight or more carbon atoms are preferable. Examples of substituted or unsubstituted alkyl groups are preferably those described below, and oligomers or polymers thereof may also be used. The alkenyl group may be vinyl, propenyl, butenyl, pentenyl, hexenyl, etc., and examples of substituted or unsubstituted alkenyl groups having eight or more carbon atoms are preferably those described below, and oligomers or polymers thereof may also be used.
The aryl group may be substituted or unsubstituted, and is, for example, phenyl, tolyl, 4-cyanophenyl, biphenyl, o, m, p-terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, 9-benzanthryl, 9, 10-dibenzanthryl, pyrenyl, and the like. Oligomers or polymers thereof may also be used.
Examples of substituted or unsubstituted alkoxy groups may be methoxy, n-butoxy, t-butoxy, trichloromethoxy, trifluoromethoxy and the like. Oligomers or polymers thereof may also be used.
Examples of the substituted or unsubstituted cycloalkyl group may be a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a 4-methylcyclohexyl group, a 4-cyanocyclohexyl group and the like. Oligomers or polymers thereof may also be used.
Examples of the substituted or unsubstituted heterocyclic group may be pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, imidazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzimidazolyl, purinyl, quinolyl, isoquinolyl, warfaryl, quinoxalyl, benzoquinolyl, fluorenone, dicyanofluorenoyl, carbazolyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, dibenzooxazolyl, dibenzothiazolyl, dibenzoimidazolyl and the like. Oligomers or polymers thereof may also be used.
Examples of the substituted or unsubstituted acyl group may be a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a dodecanoyl group, a tetradecanoyl group, a hexadecanoyl group, an octadecanoyl group, an oxalyl group, a malonyl group, a succinyl group, a glutaryl group, an adipoyl group, a pimeloyl group, an suberoyl group, an azepinoyl group, a sebacoyl group, an acryloyl group, a propioyl group, a methacryloyl group, a crotonyl group, an methacryloyl group, an oleoyl group, a elaidic group, a maleoyl group, a fumaroyl group, a citraconoyl group, a mesoconyl group, a kaempferoyl group, a benzoyl group, a phthaloyl group, an isophthaloyl group, a terephthaloyl group, a naphthoyl group, a toluoyl group, a hydrogenated 2, Nicotinyl, isonicotinyl, glycolyl, propanoyl, glyceryl, propanoyl diacyl, hydroxysuccinyl, tartharoyl, tropinoyl, diphenoxyacyl, orthohydroxybenzoyl, methoxybenzoyl, 4-hydroxy-3-methoxybenzoyl, 3, 4 dimethoxybenzoyl, piperonyl, orotocaryl group, 3, 4, 5-trihydroxybenzoyl, glyoxyl, pyruvoyl, acetoacetyl, m-oxalyl, butanone diacyl, oxaloaceto group, levulinyl group and the like. These acyl groups may be substituted with fluorine, chlorine, bromine, iodine, etc. Oligomers or polymers thereof may also be used.
R1、R2、R3And R4An example of the organometallic compound in which the trivalent metal is gallium, each of which is substituted with one substituent described above, is a organometallic complex represented by the structural formula (16):
structural formula (16)
Germanium complexes
An example of the organometallic compound in which R is substituted with the substituent described above and the tetravalent metal is silicon is a organometallic complex represented by the structural formula (17):
structural formula (17)
Silicon complex
It is inferred that the compounds represented by the structural formulae (1), (2) and (3) have the action and principle, and it is based on the action and principle that conventionally used desiccants such as physical desiccants, chemical organic solvents and the like can be dispersed and adhered to the compounds represented by the structural formulae (1), (2) and (3) because they are soluble in aromatic organic solvents such as toluene, xylene and the like or aliphatic organic solvents. A desiccant film 7 is formed as a desiccant on the inner surface of the sealing cap 2. The type of construction of the desiccant membrane 7 that may be considered is described below. First, the desiccant film 7 can be constituted only by one metal organic compound represented by the structural formula (1), (2) or (3) and the other metal organic compound. Since the desiccant film 7 made of the metal organic compound represented by the structural formula (1), (2) or (3) and other metal organic compounds can be obtained in a solution in which the metal organic compound containing an n-valent metal is soluble in an organic solvent such as aromatic hydrocarbon, xylene or the like or an aliphatic organic solvent, the above solution can be applied to the inner surface of the substrate 3 by, for example, a printing method, a spin coating method, a coating method or the like and dried to form a film.
The desiccant film 7 may be formed by adding an inorganic desiccant to a desiccant film made of a metal organic compound represented by the structural formula (1), (2), or (3) and another metal organic compound. The desiccant added to the desiccant membrane may be a desiccant that chemically adsorbs water molecules (chemisorption) or a desiccant that physically adsorbs water molecules (physisorption) or any other desiccant.
For a desiccant that chemically adsorbs water molecules (chemisorption), its drying efficiency can be further improved in the following way: a compound selected from a metal oxide, a sulfate, a metal halide, a perchlorate and a metal is dispersed in a solution in which a solvent is an organic solvent such as aromatic hydrocarbon, toluene, xylene or the like or an aliphatic organic solvent in which a metal organic compound represented by the structural formula (1), (2) or (3) and other metal organic compounds have been dissolved.
An example of an alkali metal oxide may be sodium oxide (Na)2O) and potassium oxide (K)2O). Examples of the alkaline earth metal oxide may be calcium oxide (CaO), barium oxide (BaO), and magnesium oxide (MgO). The sulfate salt mentioned above may be lithium sulfate (Li)2SO4) Sodium sulfate (Na)2SO4) Calcium sulfate (CaSO)4) Magnesium sulfate (MgSO)4) Cobalt sulfate (CoSO)4) Gallium sulfate (Ga)2SO4) Titanium sulfate (Ti (SO)4)2) Nickel sulfate (NiSO)4) And the like. For these salts, anhydride compounds thereof are preferably used.
The halide may be calcium chloride (CaCl)2) Magnesium chloride (MgCl)2) Strontium chloride (SrCl)2) Yttrium chloride (YCl)2) Copper chloride (CuCl)2) Cesium fluoride (CsF), fluorineTantalum (TaF)5) Niobium fluoride (NbF)5) Calcium bromide (CaBr)2) Cerium bromide (CeBr)2) Selenium bromide (SeBr)4) Vanadium bromide (VBr)2) Magnesium bromide (MgBr)2) Barium iodide (BaI)2) Magnesium iodide (MgI)2) And so on. For these halides, anhydride compounds thereof are preferably used.
The perchlorate salt mentioned above may be barium perchlorate (Ba (ClO)4)2) And magnesium perchlorate (Mg (ClO)4)2). For these perchlorates, acid anhydride compounds thereof are preferably used. The drying efficiency for a desiccant that physically absorbs water molecules (physisorption) can be further improved in the following way: from zeolite, silica gel, activated aluminium, oxygenOne selected from the group consisting of titanium oxide, carbon nanotubes and fullerene is dispersed in a solution in which the solvent is an organic solvent such as aromatic hydrocarbon, toluene, xylene or the like, or an aliphatic organic solvent in which a metal organic compound represented by the structural formula (1), (2) or (3) and other metal organic compounds have been dissolved.
After an anode film, an organic EL layer and a cathode are formed on a substrate 2 by a physical deposition method, CuPc as a buffer layer and GeO as a protective layer are physically deposited, and a desiccant layer containing a metal organic compound represented by the structural formula (1), (2) or (3) and other metal organic compounds is provided thereon to constitute a moisture impermeable layer. The drying efficiency can be further improved by dispersing a drying agent such as the above-mentioned chemical drying agent or physical drying agent into the above-mentioned drying agent layer of the present invention.
Similar effects can be obtained by using a high polymer type organic EL element containing Polyvinylcarbazole (PVK) or the like in place of theabove-described organic layers (4a, 4b, 4 c).
Similar effects can be obtained by using a functional organic compound such as a solar cell in the organic functional element instead of the above-described organic layers (4a, 4b, 4 c).
The present invention is described in more detail below with reference to examples, which are provided for illustration only and are not intended to be limiting. Example 1
As shown in fig. 1, an organic EL element 1 includes a base element 2 of a rectangular transparent rim glass substrate as a base. In FIG. 1, an anode 5 having an ITO film thickness of 200nm was formed as a transparent conductive material on a substrate 2 by a sputtering method. Thereafter, the anode is formed by etching and patterning in the template by a photoresist method. A part of the anode 5 is drawn out as an electrode to the substrate 2 and connected to a driving circuit (not shown in the figure).
A phthalein bronze organic layer 4a having a film thickness of 70nm was formed as a hole injection layer on the upper surface of the anode 5 by a resistance heating method, a bis (N- (1-naphthyl-N-phenyl)) benzidine (α -NPD) organic layer 4b having a film thickness of 30nm was formed as a hole transport layer on the upper surface of the organic layer 4a, and a thick layer was formed on the upper surface of the organic layer 4bTris (8-hydroxyquinoline) aluminium (Alq) with a degree of 50nm3) The organic layer 4c serves as a light-emitting layer and an electron transport layer. Then, an Al-Li film having a thickness of 200nm was formed as the cathode 6 by a co-deposition method. A portion of the cathode 6 is pulled out to the end of the substrate 2 and connected to a driving circuit (not shown in the figure).
The above-described process for producing an organic EL element was used in the following examples.
In a dry environment in which moisture is removed maximally with dry air, the outer periphery of the element substrate 2 is coated with a solution containing only 48% by weight of octyl aluminum oxide represented by structural formula (6) (manufactured by HOPE pharmaceuticals, Inc., under the trade name "OLIVE"), and dried.
Subsequently, in a dry environment in which moisture was completely removed with dry air, the seal cap 3 was coated with only a solution containing 48% by weight of octyl aluminum oxide (manufactured by HOPE pharmaceuticals Co., Ltd., trade name: OLIVE) (structural formula 6, which is a metal organic compound represented by structural formula (1)). In this manner, a transparent film of a metal organic compound having a thickness of 100 μm was formed as a desiccant. When the metal organic compound is applied as a drying agent to the entire area of the flat member 3 of the sealing cap shown in fig. 1, it may be applied to the flat member 3 except for the area of the ultraviolet-curable epoxy resin in the sealing member.
The metal organic EL element base member and the sealing cap are placed opposite to each other in a dry atmosphere of dry air from which moisture is completely removed, coated with an ultraviolet-curable epoxy resin, and dried to be sealed. Then, the mixture was heated at 100 ℃ for 1 hour, and after sealing, the reaction with moisture was started.
After an accelerated lifetime test of the light-emitting portion of the metal organic EL element was carried out in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, the growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and it was only as long as 10 μm in the central region after 500 hours. While dark spots smaller than 10 μm cannot be observed with the naked eye and have no influence on practical use. Also, the generation and growth of dark spots in the peripheral area are effectively prevented. It can be considered that 500 hours in the rapid life test corresponds to several hundred hours in the usual life test (fig. 5). Example 2
The method for producing the organic EL element was the same as in example 1. FIG. 2 shows an embodiment of forming a groove having a depth of 0.2-0.25mm in the sealing cap of FIG. 1. The organic EL element 21 in embodiment 2 is described below.
The sealing cap 23 having a groove with a depth of 0.2 to 0.25mm was coated with a solution containing 48% by weight of octyl aluminum oxide (manufactured by HOPE pharmaceuticals, Inc., trade name "OLIVE") (formula 4, which is a metal organic compound represented by formula (1)), and the evaporated solvent was dried on a heating plate at 100-120 ℃ in a dry environment, thereby fixing the metal organic compound on the sealing cap 23. Except for this step, the rest of the procedure was the same as in example 1. After sealing, the mixture was heated at 100 ℃ for 1 hour to effect a reaction with moisture.
After a rapid life test of a light-emitting portion of the metal organic EL element was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and only 10 μm was grown in the central region after 500 hours. The generation and growth of dark spots in the peripheral area is not different from that in the central area (fig. 5). Example 3
Example 3 the desiccant of example 2 was used to mix with a chemical desiccant (figure 2) (in this example, a recess 0.2-0.25mm deep was formed in the sealing cap of figure 1).
The procedure of example 1 was repeated except that the grooves 29 were coated with the fluid dispersion. The fluid dispersion was obtained by dispersing a chemical desiccant calcium oxide (CaO) in a solution containing 48% by weight of octyl aluminum oxide (manufactured by HOPE pharmaceuticals, Inc., trade name: OLIVE) (formula 6, which is a metal organic compound represented by formula (2)) in a dry environment at a weight ratio of 1: 1.
After a rapid life test of the light-emitting portion of the metal organic EL element was carried out in a test chamber maintained at 85 ℃ and 85% humidity, the growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and after 500 hours, it was only as long as 7 μm in the central region. The generation and growth of dark spots in the peripheral area was not different from that in the central area (fig. 5). Example 4
Example 4 the desiccant used in example 2 was used in combination with a physical desiccant.
The procedure of example 1 was repeated except that the grooves 29 were coated with the fluid dispersion. The fluid dispersion was obtained by dispersing a physical desiccant zeolite in a solution containing 48 wt% of octyl aluminum oxide (manufactured by HOPE pharmaceuticals, Inc., trade name "OLIVE") (formula 6, which is a metal organic compound represented by formula (1)) in a dry environment, the weight ratio of zeolite to octyl aluminum oxide being 1: 1.
After a rapid life test of a light-emitting portion of the metal organic EL element was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and it was only as long as 9 μm in the central region after 500 hours. The generation and growth of dark spots in the peripheral area was not different from that in the central area (fig. 5). Example 5
Example 5 the desiccant used in example 2 was used in combination with a chemical desiccant and a physical desiccant.
The procedure of example 1 was repeated except that the grooves 29 were coated with the fluid dispersion. The fluid dispersion was obtained by dispersing a chemical desiccant, calcium oxide (CaO) (abbreviated as "X") and a physical desiccant, zeolite (abbreviated as "Y"), in a solution containing 48 wt% of octyl aluminum oxide (manufactured by HOPE pharmaceutical company, ltd., trade name "oli") (formula 6, which is a metal-organic compound represented by formula (1) (abbreviated as "Z") in a dry environment. The weight ratio of X to Y to Z is 1: 2.
After a rapid life test of the light-emitting portion of the metal organic EL element was carried out in a test chamber maintained at 85 ℃ and 85% humidity, the growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage and it was only as long as 7 μm at the center after 500 hours. The generation and growth of dark spots in the peripheral area was not different from that in the central area (fig. 5). Example 6
An organic EL element in which electrodes and an organic EL layer are protected by a protective film (FIG. 3).
ITO having a thickness of 150nm as an anode 35, CuPc having a thickness of 20nm as a hole injection layer 34a, and Alq having a thickness of 50nm were formed on a substrate 32 by physical deposition3As the electron transporting light emitting layer 34c, lithium fluoride having a thickness of 0.5nm was used as the electron injecting layer 34d, alumina having a thickness of 200nm was used as the cathode 36, CuPc having a thickness of 500nm was used as the buffer layer 38, and GeO having a thickness of 1000nm was used as the protective layer 39, thereby obtaining a single layer plate.
The laminate thus obtained was immersed in a solution containing only 48% by weight of octyl aluminum oxide (trade name "OLIVE", manufactured by HOPE pharmaceuticals Co., Ltd.) (structural formula 6) in a dry atmosphere, and then dried to obtain a dried part 37 having a coating film thickness of 10 μm, and then an impermeable layer 33 (e.g., epoxy resin) having a thickness of 20 μm was coated by printing.
After a rapid life test of a light-emitting portion of the metal organic EL element was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and it was only as long as 10 μm in the central region after 500 hours. The generation and growth of dark spots in the peripheral area was not different from that in the central area (fig. 5). Example 7
Example 7 utilizes the desiccant of example 6 in combination with a chemical desiccant.
Example 6 was repeated except that calcium oxide (CaO), a chemical desiccant, was dispersed in a solution containing 48 wt% of octyl aluminum oxide (manufactured by HOPE pharmaceutical co., ltd., trade name "oli") (structural formula 6, which is a metal organic compound represented by structural formula (1)) under dry conditions. The weight ratio of calcium oxide (CaO) to octyl aluminum oxide is 1: 1.
After a rapid life test of a light-emitting portion of the metal organic EL element was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and it was only as long as 7 μm in the central region after 500 hours. The generation and growth of dark spots in the peripheral area was not different from that in the central area (fig. 5). Example 8
Example 8 utilizes the desiccant of example 6 in combination with a physical desiccant.
The procedure of example 6 was repeated except that a physical desiccant zeolite was dispersed in a solution containing 48 wt% of octyl aluminum oxide (manufactured by HOPE pharmaceuticals, Ltd., trade name: OLIVE) (structural formula 6, which is a metal organic compound represented by structural formula (1)) under a dry environment. The weight ratio of zeolite to octyl aluminum oxide was 1: 1.
After a rapid life test of a light-emitting portion of the metal organic EL element was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and it was only as long as 9 μm in the central region after 500 hours. The generation and growth of dark spots in the peripheral area was not different from that in the central area (fig. 5). Example 9
Example 9 utilizes the desiccant used in example 6 mixed with a physical desiccant and a chemical desiccant.
The procedure of example 6 was repeated except that a physical desiccant zeolite (abbreviated as "X") and a chemical desiccant calcium oxide (CaO) (abbreviated as "Y") were dispersed in a solution containing 48 wt% of aluminum oxide octyl ester (manufactured by HOPE pharmaceutical company, ltd., trade name "oli") (formula 4, whichis a metal organic compound represented by formula (1) (abbreviated as "Z") under dry conditions. The weight ratio of X to Y to Z is 1: 2.
After a rapid life test of a light-emitting portion of the metal organic EL element was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and it was only as long as 7 μm in the central region after 500 hours. The generation and growth of dark spots in the peripheral area was not different from that in the central area (fig. 5). Comparative example 1
ITO as an anode having a thickness of 150nm, CuPc as a hole injection layer having a thickness of 20nm, α -NPD as a hole transport layer having a thickness of 30nm, and Alq as a hole transport layer having a thickness of 50nm were formed on a substrate by physical deposition3As an electron transport layer, lithium fluoride having a thickness of 0.5nm was used as an electron injection layer, and alumina having a thickness of 200nm was used as a cathode, thereby obtaining an organic EL laminate.
The thus-obtained organic EL laminate and a sealing cap of a groove containing CaO were placed as drying members opposite to each other and sealed with an ultraviolet-curable epoxy resin.
After a rapid life test of a light-emitting portion of the metal organic EL element was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed under a microscope. As a result, it was confirmed that the diameter of the dark spot was 1 μm at the initial stage, and it was only as long as 11 μm in the central region after 500 hours. The number of dark spots generated in the peripheral region of the organic EL element is much larger than that in the central region (fig. 5). Example 10
The inner surface of the sealing glass was coated with a toluene solution containing 50% by weight of di-2-ethylhexyloxy-mono-ethylacetoacetaluminum acetate (manufactured by HOPE drugs Co., Ltd., trade name: Chelope-EH-2 ") (structural formula 10), and dried to obtain a substrate. The substrate thus obtained is sealed together with the organic EL element with an adhesive.
Thereafter, the organic EL element was heated to 100 ℃ in an oven to absorb moisture in the element. The emission state of this organic EL element was observed under a microscope. Then, in a test chamber maintained at 85 ℃ and 85% humidity, a rapid lifetime test was performed on the light-emitting portion of the metal organic EL element, and the growth of dark spots was observed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of this organic EL element was observed under a microscope. As a result, it was found that almost no non-light emitting portion (dark spot) was observed in the central region, and the generation and growth of the dark spot were different from nothing in the central region in the peripheral portion (fig. 6). Example 11
The same procedure as in example 10 was used to prepare an organic EL device, except that bis-2-ethylnonyloxy-monoethyl aluminum acetoacetate represented by the structural formula (11) (manufactured by HOPE pharmaceuticals, ltd., trade name: Chelope C10-2) was used. The other steps are the same as in example 1. The emission state of the thus obtained organic EL element was observed under a microscope. Then, in a test chamber maintained at 85G and 85% humidity, a rapid life test was performed, and growth of dark spots was observed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under amicroscope. As a result, it was found that almost no non-light emitting portion (dark spot) was observed in the central region, and the generation and growth of the dark spot were not different from those in the central region in the peripheral portion (fig. 6). Example 12
The same procedure as in example 10 was used to prepare an organic EL device, except that di-n-dodecyloxy-monoethyl-aluminum acetoacetate represented by structural formula (12) (manufactured by HOPE pharmaceuticals, ltd., trade name: Chelope C11-2) was used, and the other procedures were the same as those in example 1. The emission state of the organic EL element thus obtained was observed under a microscope. After a rapid life test was performed in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, the growth of dark spots was observed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of this organic EL element was observed under a microscope. As a result, it was found that almost no non-light emitting portion (dark spot) was observed in the central region, and the generation and growth of the dark spot were different from nothing in the central region in the peripheral portion (fig. 6). Comparative example 2
An organic EL element was produced by the same method as that used in example 10 except that the water-absorbing agent was not used at the time of sealing. The other steps were the same as those used in example 1. The emission state of the organic EL element thus obtained was observed under a microscope. After a rapid life test in a test chamber maintained at a temperature of 85 ℃ and a humidity of 85%, growth of dark spots was observed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under a microscope. As a result, a non-light emitting portion (dark spot) was observed, and the emission region area was reduced to 60%. After the lapse of 200 hours, no light-emitting portion was observed at all.
Then, a series of experiments were conducted on a metal-organic complex having a trade name of "Chelope" manufactured by HOPE pharmaceutical limited, which was obtained by changing the central metal of the metal-organic complex. Example 13
The inner surface of the sealing glass as a substrate was coated with a lanthanum (La) complex solution as a drying agent represented by structural formula (13) and dried. The substrate and the organic EL element are sealed with an adhesive. The other steps were the same as those used in example 1. The organic EL element was heated to 100 ℃ to absorb moisture in the element. The emission state of the organic EL element thus obtained was observed under a microscope. In a test chamber maintained at 85 ℃ and 85% humidity, a rapid life test was carried out to confirm the generation of dark spots. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under a microscope. As a result, a non-light emitting portion (dark spot) is hardly observed in the central region, while the generation and growth of the dark spot are not different in the peripheral region from those in the central region. The area of the non-light emitting region is small compared to the element without the water absorbing agent (fig. 6).
The results obtained for examples 14 to 17 and comparative example 3 are shown in FIG. 6. Example 14
A metal-organic complex having silicon as a central metal, which is one of the "Chelope" series manufactured by HOPE drugs Co., Ltd, represented by the structural formula (17) was synthesized as a water absorbent for a drying member. The procedure of example 1 was repeated except that the metal-organic complex represented by the structural formula (17) was previously dissolved in toluene. The silicon complex solvent coats the inner surface of the sealing glass as a substrate and dries. The organic EL element was sealed together with the substrate with an adhesive, and then placed in an oven heated to 100 ℃ to absorb moisture in the element. The emission state of the EL element thus obtained was observed under a microscope. After a rapid life test in a test chamber maintained at 85 ℃ and 85% temperature and humidity, the growth of dark spots was confirmed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under a microscope. As a result, a non-light emitting portion (dark spot) was hardly observed (fig. 7). As the water-absorbing agent, the silicon complex does not perform as much as the lanthanum complex, and the area of the non-light-emitting portion is smaller than that of the element without the water-absorbing agent. The generation and growth of dark spots in the peripheral area is not different from that in the central area. Example 15
A metal-organic complex having yttrium as a central metal, which is one of the "Chelope" series manufactured by HOPE drugs Co., Ltd, represented by the structural formula (14) was synthesized as a water absorbent for a drying member. The other steps were the same as those of example 1. The test chamber was then evacuated and the sealing operation was completed under a dry nitrogen atmosphere. The inner surface of the sealing glass as a substrate was coated with an yttrium complex solution and dried. The organic EL element was sealed together with the substrate with an adhesive, and then placed in an oven heated to 100 ℃ to absorb moisture in the element. The emission state of the EL element thus obtained was observed under a microscope. After a rapid life test in a test chamber maintained at 85 ℃ and 85% temperature and humidity, theformation of dark spots was confirmed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under a microscope. As a result, a non-light emitting portion (dark spot) was hardly observed in the central region. As the water-absorbing agent, the yttrium complex does not perform as well as the lanthanum complex, and the area of the non-light-emitting portion is smaller than that of the element without the water-absorbing agent. The generation and growth of dark spots in the peripheral area is not different from that in the central area (fig. 7). Example 16
A metal-organic complex having germanium as a central metal, which is one of "Chelope" series manufactured by HOPE drugs Co., Ltd, represented by the structural formula (16) was synthesized as a water absorbent for a drying member. The other steps were the same as in example 1. The test chamber was then evacuated and the sealing operation was completed under a dry nitrogen atmosphere. The inner surface of the sealing glass for a substrate is coated with a germanium complex solution and dried. The organic EL element was sealed together with the substrate with an adhesive, and then placed in an oven heated to 100 ℃ to absorb moisture in the element. The emission state of the EL element thus obtained was observed under a microscope. After a rapid life test in a test chamber maintained at 85 ℃ and 85% temperature and humidity, the formation of dark spots was confirmed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under a microscope. As a result, almost no growth of the non-light emitting portion (dark spot) was observed in the central region. The dark spots are not different in the peripheral area from the central area. As a water-absorbing agent, the germanium complex does not perform as well as the lanthanum complex, and thearea of the non-light-emitting portion is smaller than that of the element without the water-absorbing agent (fig. 7). Example 17
A metal-organic complex having gallium as a central metal, which is one of "Chelope" series manufactured by HOPE drugs Co., Ltd, represented by the structural formula (15) was synthesized as a water absorbent for a drying member. The inner surface of the sealing glass as a substrate was coated with a germanium complex solution and dried. The organic EL element is sealed together with the substrate with an adhesive. The other steps were the same as those of example 1. The organic EL element was then placed in an oven and heated to 100 ℃ to absorb moisture in the element. The emission state of the EL element thus obtained was observed under a microscope. After a rapid life test in a test chamber maintained at 85 ℃ and 85% temperature and humidity, the formation of dark spots was confirmed. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under a microscope. As a result, a non-light emitting portion (dark spot) was hardly observed in the central region. The generation and growth of dark spots in the peripheral area is not different from that in the central area. As a water absorbent, gallium complex did not perform as well as lanthanum complex, and the area of the non-light emitting part was smaller than that of the element without water absorbent (fig. 7). Comparative example 3
As comparative example, no water absorbing agent was used in sealing. The other steps used were the same as those of example 1 except for sealing. The emission state of the organic EL element prepared in comparative example 3 was observed under a microscope. The water absorption was tested in a test chamber maintained at 85 ℃ and 85% humidity. After the lapse of 100 hours, the element was taken out from the test chamber, and the emission state of the organic EL element was observed under a microscope. As a result, a non-light emitting portion (dark spot) was observed, and the proportion of the light emitting area was reduced to 60%. After 200 hours had elapsed, no light-emitting state was observed at all.
The results obtained for examples 14 to 17 and comparative example 3 are shown in the following figure (FIG. 7).
In summary, the present invention achieves the following effects:
(1) a novel material has been found which can suppress the generation of dark spots on an organic EL element
Grow and grow.
(2) Since the desiccant of the present invention is liquid, it can be easily formed into a film upon assembly,
therefore, the method is easy to process in industry and has great benefit.
(3) Because the desiccant of the present invention can be used in combination with other chemical desiccants to enhance
The effect has great benefit in industry.
(4) Because the desiccant of the invention can be mixed with other physical desiccants for enhancement
The effect has great benefit in industry.
(5) The drying member of the present invention can suppress dark spots of an organic EL element in a peripheral region
And can be easily placed on the periphery of the organic EL element
Meanwhile, the method has great benefits in industry.
Claims (11)
1. An organic EL element comprising: a laminate having a structure in which an organic EL material layer is sandwiched between a pair of opposed electrodes; a sealed container for placing said laminate; a drying member disposed in the sealed container to prevent the organic EL material layer from being contaminated with moisture; characterized in that the drying means consist of a metal organic compound.
2. An organic EL element as claimed in claim 1, wherein the drying member is composed of a metal organic compound represented by structural formula (1):wherein R is a group selected from the group consisting of alkyl, alkenyl, aryl, cycloalkyl, heterocyclic and acyl containing at least one carbon atom, M is a trivalent metal atom, and n is an integer greater than 1.
3. The organic EL element as claimed in claim 1 or 2, wherein the drying member is composed of a metal organic compound represented by structural formula (2):in the formula, R1、R2、R3、R4And R5Each of which is a group selected from the group consisting of alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, heterocyclic groups and acyl groups containing at least one carbon atom, and M is a trivalent metal atom.
4. An organic EL element as claimed in any one of the preceding claims, wherein the drying member is composed of a metal-organic compound represented by structural formula (3):in the formula, R1、R2、R3And R4Each of which is a group selected from the group consisting of alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, heterocyclic groups and acyl groups containing at least one carbon atom, and M is a trivalent metal atom.
5. An organic EL element as claimed in any one of the preceding claims, wherein the metal-organic compound drying member is disposed on an inner surface of the sealed container.
6. An organic EL element as claimed in any one of the preceding claims, wherein said drying means covers said organic EL layer for protecting the element.
7. An organic EL element as claimed in any one of the preceding claims, characterized in that the means for drying the metal-organic compound and an inorganic drying are provided
7. An organic EL element as claimed in any one of the preceding claims, characterized in that the drying means of the metal-organic compound are used in combination with an inorganic desiccant.
8. The organic EL element as claimed in claim 7, wherein the inorganic desiccant is a desiccant having physical adsorption advantage.
9. The organic EL element as claimed in claim 7, wherein the inorganic desiccant is a chemical reaction-promoting desiccant.
10. An organic EL element as claimed in any one of the preceding claims, wherein the drying means of the metal organic compound is used in combination with an inorganic desiccant having an advantage of physical adsorption and an inorganic desiccant having an advantage of chemical reaction.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438122C (en) * | 2004-05-27 | 2008-11-26 | 株式会社日立显示器 | Organic electroluminescence display device and manufacturing method thereof |
| CN102374400A (en) * | 2010-08-17 | 2012-03-14 | 华信精密股份有限公司 | light emitting device |
| CN102397779A (en) * | 2010-08-10 | 2012-04-04 | 双叶电子工业株式会社 | Water-trapping agent and organoelectronic device comprising the same |
| CN103059620A (en) * | 2011-10-24 | 2013-04-24 | Jsr株式会社 | Thermosetting composition for forming water capture body, water capture body and electronic equipment |
| CN103223289A (en) * | 2012-01-31 | 2013-07-31 | 双叶电子工业株式会社 | Desiccant and the same desiccant-employing organic el element |
| CN104098598A (en) * | 2013-04-09 | 2014-10-15 | 双叶电子工业株式会社 | Complex compound, drying agent, sealing structure and organic EL element |
-
2001
- 2001-11-07 CN CNB011368977A patent/CN100471351C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438122C (en) * | 2004-05-27 | 2008-11-26 | 株式会社日立显示器 | Organic electroluminescence display device and manufacturing method thereof |
| CN102397779A (en) * | 2010-08-10 | 2012-04-04 | 双叶电子工业株式会社 | Water-trapping agent and organoelectronic device comprising the same |
| CN102397779B (en) * | 2010-08-10 | 2015-10-14 | 双叶电子工业株式会社 | Water-capturing agent and use the organic electronic device of this water-capturing agent |
| CN102374400A (en) * | 2010-08-17 | 2012-03-14 | 华信精密股份有限公司 | light emitting device |
| CN103059620A (en) * | 2011-10-24 | 2013-04-24 | Jsr株式会社 | Thermosetting composition for forming water capture body, water capture body and electronic equipment |
| CN103223289A (en) * | 2012-01-31 | 2013-07-31 | 双叶电子工业株式会社 | Desiccant and the same desiccant-employing organic el element |
| CN103223289B (en) * | 2012-01-31 | 2016-04-13 | 双叶电子工业株式会社 | Drier and use the organic electroluminescence assembly of this drier |
| US9662633B2 (en) | 2012-01-31 | 2017-05-30 | Futaba Corporation | Desiccant and the same desiccant-employing organic EL element |
| CN104098598A (en) * | 2013-04-09 | 2014-10-15 | 双叶电子工业株式会社 | Complex compound, drying agent, sealing structure and organic EL element |
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| Publication number | Publication date |
|---|---|
| CN100471351C (en) | 2009-03-18 |
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