JP2005093427A - Composition for organic electroluminescent element, and manufacturing method of organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for organic light emitting element which is suitable for forming a hole injecting/transporting layer by a wet film-forming method without denaturing a hole injecting/transporting material and/or an electron-accepting compound. <P>SOLUTION: The solution composition is composed of a hole injecting/transporting material such as an aromatic diamine compound, an electron accepting compound such as tri(pentafluorophenyl) boron, and an aromatic ester group solvent such as benzoic ester for dissolving the above compounds. The concentration of moisture, alcohol group solvent or halogen group solvent which deactivates these hole injecting/transporting material and electron-accepting compound is reduced to ≤1 wt.%, further, the solution composition is used within 20 hours after preparation at the formation of the hole injection layer or the like by the wet film-forming method. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a composition for an organic electroluminescent element, and more particularly to a composition for an organic electroluminescent element used when forming a hole injection / transport layer by a wet film forming method.

  In recent years, an electroluminescent element (organic electroluminescent element) using an organic material instead of an inorganic material such as ZnS has been developed. In particular, the luminous efficiency of the organic electroluminescence device provided with the hole transport layer made of aromatic diamine and the light emitting layer made of aluminum complex of 8-hydroxyquinoline was greatly improved.

  In addition, the reason why the driving voltage of the organic electroluminescence device is increased is that the contact between the anode and the hole transport layer is considered to be insufficient. Therefore, a hole injection layer is provided between the anode and the hole transport layer. Thus, means for improving the contact between the anode and the hole transport layer and reducing the driving voltage has been studied.

  On the other hand, a method for forming a hole injection layer or a hole transport layer of such an organic electroluminescence device by a wet film forming method has been reported. For example, spin coating is performed using a solution in which an aromatic diamine-containing polyether as a hole transporting material and tris (4-bromophenyl) ammonium hexachloroantimonate (TBPAH) as an electron-accepting compound are dissolved in dichloromethane. A method for forming a hole injection / transport layer by a method (see Patent Document 1), a method for forming a hole injection layer by a spin coating method using a 1,2-dichloroethane solution containing an aromatic diamine-containing polyether (Refer to Patent Document 2), a 1,2-dichloroethane solution of a mixture of 4,4′-bis [(N- (m-tolyl) -N-phenylamino] biphenyl and an electron-accepting compound, antimony pentachloride. And a method of forming a hole transport layer by spin coating (see Patent Document 3).

JP-A-11-283750 JP 2000-36390 A JP 2002-56985 A

  By the way, a hole injection layer and a hole transport layer are provided in the upper layer of the anode of an organic electroluminescent element, and play the role which conveys the hole inject | poured from the anode to a light emitting layer. As a hole injecting / transporting material for forming a hole injecting layer and a hole transporting layer, the efficiency of injecting holes injected from the anode is high, and the injected holes are efficiently transported to the light emitting layer. It must be a material that can be used.

  As described above, the material for forming such a hole injection layer or a hole transport layer of the organic electroluminescence device is 4,4′-bis [(N- (m-tolyl) -N-phenylamino] biphenyl. And those having a triarylamine partial structure or a carbazole partial structure as a hole injection / transport site, such as polyether containing aromatic diamine, and the like. Since the injection barrier is required to be small, an electron-accepting compound such as antimony pentachloride and TBPAH is often added together with the hole injecting / transporting material.

  However, these hole injection / transport materials and electron-accepting compounds may be altered by charge transfer with other compounds contained in the same layer formed in the organic electroluminescence device. When the hole injecting / transporting material or the electron-accepting compound is altered, there is a problem that the hole injecting / transporting property of a layer formed of these materials or the like is lowered.

  The organic electroluminescent element uses a material that easily deteriorates, such as aluminum used as a cathode. There exists a problem that the performance as a light emitting element tends to deteriorate.

  Further, as described above, the hole injecting / transporting material and the electron accepting compound may be altered by charge transfer with other compounds. For this reason, there exists a tendency for an impurity to produce | generate easily in the coating liquid prepared for wet film forming methods, and there exists a problem that the storage stability of a coating liquid is low.

As described above, the present invention relates to a decrease in hole injection / transport properties that are highlighted when forming a hole injection / transport layer of an organic electroluminescence device by a wet film formation method, and a coating used for the wet film formation method. It was made to solve the problem of low storage stability of the liquid.
That is, an object of the present invention is to provide an organic electroluminescent device suitable for forming a hole injection / transport layer by a wet film forming method without altering the hole injection / transport material and / or electron accepting compound. It is to provide a composition for use.
Another object of the present invention is to provide a method for producing an organic electroluminescent element which does not impair the storage stability of a coating solution prepared for a wet film-forming method.

  In order to solve such problems, in the present invention, the amount of impurities and the like contained in the coating solution used in the wet film-forming method is reduced to stabilize the hole injecting / transporting material. That is, the composition for an organic electroluminescent device to which the present invention is applied includes a hole injection / transport material that forms at least one of the hole injection layer and the hole injection / transport layer of the organic electroluminescence device, and In a composition containing an electron-accepting compound and such a hole-injecting / transporting material and / or a solvent that dissolves the electron-accepting compound, The concentration of the deactivating substance for deactivating the transporting material and / or the electron-accepting compound or the compound for generating the deactivating substance is 1% by weight or less.

  In the composition for organic electroluminescent elements to which the present invention is applied, the concentration of the alcohol-based solvent, the aldehyde-based solvent, or the ketone-based solvent that is a compound that generates a deactivated substance or a deactivated substance in the composition is 1% by weight or less. Reducing the deactivation of cation radicals in the hole injecting / transporting material resulting from the mixing of the hole injecting / transporting material and / or the electron accepting compound contained in the composition. Can do.

  Moreover, in the composition for organic electroluminescent elements to which the present invention is applied, the concentration of the protonic acid or halogen-based solvent that is a deactivating substance or a compound that generates the deactivating substance in the composition is 1% by weight or less. The hole injection / transport portion of the hole injection / transport material contained in the composition is prevented from being altered, and the hole injection / transport of the layer obtained by the wet film formation method is prevented. The fall of property can be reduced.

  As described above, alcohol solvent, aldehyde solvent and ketone solvent, and proton acid and halogen solvent are not preferred even if only one is present, but if both are present, it is not preferred. Or less, and more preferably 1% by weight or less in total.

  In the composition for organic electroluminescence device to which the present invention is applied, it is preferable to use an aromatic amine compound as the hole injecting / transporting material and an aromatic boron compound as the electron accepting compound.

  Further, in the composition for organic electroluminescence device to which the present invention is applied, the water content in the composition containing the hole injecting / transporting material and / or the electron accepting compound and the solvent for dissolving them is 1% by weight. If it is characterized by the following, it is possible to prevent the deterioration of the cathode constituting the organic electroluminescent element.

  Furthermore, an organic electroluminescent device composition to which the present invention is applied is an organic electroluminescent device in which at least an anode, a hole injection / transport layer, a light emitting layer, and a cathode are laminated on a substrate by a wet film forming method. It can be used as a coating solution for forming a hole injection / transport layer.

  The present invention also provides an anode forming step for forming an anode on a substrate, and a positive injection layer for forming a hole injection layer containing a hole injection / transport material and an electron accepting compound on the formed anode. A hole injection layer forming step, a light emitting layer forming step of forming a light emitting layer directly or via another layer on the formed hole injection layer, and a layer directly on top of the formed light emitting layer. A cathode forming step of forming a cathode through the layer, and the hole injection layer forming step comprises preparing a composition containing a hole injecting / transporting material and an electron accepting compound, According to a method of manufacturing an organic electroluminescent device, wherein a hole injection layer is formed by a wet film-forming method using the composition within 24 hours, the hole injection / transport contained in the composition is characterized. Organic field generation in a stable state without deterioration of the conductive material and / or electron-accepting compound It is possible to manufacture an element.

  Further, in such a method for producing an organic electroluminescent element, by using the composition for organic electroluminescent element to which the present invention is applied as a coating liquid, by forming a hole injection / transport layer by a wet film forming method, An organic electroluminescence device that does not show a decrease in hole injection / transport properties can be produced.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for organic electroluminescent elements suitable for forming a positive hole injection / transport layer by the wet film forming method with improved solubility of the positive hole injection / transport material is provided. .

Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as an embodiment) will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.
The organic electroluminescent element composition to which the present embodiment is applied is an organic electroluminescent element having a light emitting layer sandwiched between an anode and a cathode, and a hole injection layer provided between the anode and the light emitting layer, and / Or used as a coating liquid when the hole transport layer is formed by a wet film forming method.

  Here, when there is one layer between the anode and the light emitting layer in the organic electroluminescent element, this is referred to as a “hole injection layer”, and when there are two or more layers, the layer in contact with the anode is The “hole injection layer” and the other layers are collectively referred to as “hole transport layer”. In addition, layers provided between the anode and the light emitting layer may be collectively referred to as a “hole injection / transport layer”.

  The composition for an organic electroluminescence device to which this exemplary embodiment is applied is a hole injection / transport material that forms at least one of the hole injection layer and the hole transport layer of the organic electroluminescence device, and / or An electron-accepting compound, and a hole-injecting / transporting material and / or a solvent that dissolves the electron-accepting compound, and further included in the composition; Alternatively, the concentration of the deactivating substance that deactivates the electron-accepting compound or the compound that generates the deactivating substance is 1% by weight or less. Here, the solvent that dissolves the hole injecting / transporting material and / or the electron accepting compound is usually 0.05% by weight or more of the hole injecting / transporting material and / or the electron accepting compound, preferably 0.5% by weight or more, more preferably 1% by weight or more. The hole injecting / transporting material and / or the electron accepting compound will be described later.

  Such a solvent is not particularly limited as long as it can dissolve a hole injecting / transporting material and / or an electron accepting compound, and for example, an ether solvent and an ester solvent are preferable. Specifically, examples of the ether solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1, 3 -Aromatic ethers such as dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and the like. Examples of the ester solvent include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, ethyl benzoate, benzoic acid And aromatic esters such as propyl, n-butyl benzoate, and 2-phenoxyethyl acetate. The concentration of these solvents in the composition is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more. In addition to the solvents described above, various other solvents may be included as necessary as the solvent. Examples of such other solvents include aromatic hydrocarbons such as benzene, toluene and xylene, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethyl sulfoxide. Moreover, various additives, such as a leveling agent and an antifoamer, may be included.

  A deactivating substance that deactivates a hole injecting / transporting material and / or an electron accepting compound, or a compound that generates such deactivating substance, contained in the organic electroluminescent composition to which the present embodiment is applied Examples thereof include alcohol solvents such as ethyl alcohol; aldehyde solvents such as benzaldehyde; ketone solvents such as methyl ethyl ketone, cyclohexanone and acetophenone. Such alcohol-based solvents, aldehyde-based solvents, and ketone-based solvents are particularly easy to react with electron-accepting compounds. Specifically, the alcohol is oxidized to an aldehyde or carboxylic acid, the aldehyde is oxidized to a receiving carboxylic acid, and the ketone undergoes a condensation reaction between solvent molecules, or a hole injection / transport property. For example, it adheres to the cation radical of the material and generates impurities.

  Therefore, when a layer containing a hole injecting / transporting material and / or an electron-accepting compound is formed by a wet film-forming method, the inclusion of these in the solution makes it easy to oxidize the solvent and the electron-accepting layer. Reactive compounds react. Solvents that are susceptible to oxidation are cation radicals of the hole-injecting / transporting material generated from the mixture of the hole-injecting / transporting material and the electron-accepting compound. May also react. From the reaction of these oxidizable solvents, the electron-accepting compounds or cation radicals in the coating solution are consumed and impurities are generated, so that the solution is gradually deactivated and the storage stability of the solution is reduced. Industrially unfavorable.

  Examples of the deactivating substance that deactivates the hole injecting / transporting material and / or the electron accepting compound or the compound that generates such deactivating substance include protonic acids and halogen-based solvents. Specifically, examples of the protonic acid include inorganic acids such as hydrochloric acid and hydrobromic acid; and organic acids such as formic acid, acetic acid, and lactic acid. Examples of the halogen-based solvent include a chlorine solvent, a bromine-containing solvent, and an iodine-containing solvent.

  When a layer is formed by a wet film-forming method using a solution containing a hole injecting / transporting material and / or an electron-accepting compound, when an organic acid or a halogen-based solvent is contained in the solution, For example, an organic acid reacts with a hole injecting / transporting site and transforms into an ammonium salt, so that the hole injecting / transporting property of the obtained layer is lowered. In addition, when a halogen-based solvent is contained, these halogen-based solvents often contain a corresponding acid, and this acid, like the above-mentioned organic acid, is used for hole injection / transport. Since the property site is altered, the hole injection / transport property of the obtained layer also deteriorates. In addition, it is not preferable that halides are mixed even in terms of a large environmental load.

  In addition, since an organic electroluminescent element is formed by laminating a plurality of layers made of organic compounds, each layer is required to be a uniform layer. When a layer is formed by a wet film forming method, moisture is mixed into the coating solution (composition) for forming the layer, so that moisture is mixed into the coating film and the uniformity of the film is impaired. Is preferably as small as possible. Specifically, the amount of water contained in the composition for organic electroluminescent elements is 1% by weight or less, preferably 0.1% by weight or less, and more preferably 0.05% by weight or less.

  In general, since organic electroluminescent elements use many materials such as cathodes that deteriorate significantly due to moisture, the presence of moisture is not preferable from the viewpoint of element degradation. Examples of the method for reducing the amount of water in the solution include nitrogen gas sealing, use of a desiccant, dehydration of the solvent in advance, use of a solvent with low water solubility, and the like. In particular, it is preferable to use a solvent having low water solubility because the solution coating film can prevent whitening by absorbing moisture in the air during the coating process. From such a point of view, the composition for organic electroluminescence device to which the present embodiment is applied is, for example, a solvent having a water solubility at 25 ° C. of 1% by weight or less, preferably 0.1% by weight or less. It is preferable to contain 10% by weight or more in the composition. The solvent satisfying the solubility condition is more preferably 30% by weight or more, and particularly preferably 50% by weight or more.

  Next, a hole injecting / transporting material and an electron accepting compound, which are components of the composition for organic electroluminescent elements to which the exemplary embodiment is applied, will be described. Examples of the hole injection / transport material include aromatic amine compounds, phthalocyanine derivatives or porphyrin derivatives, metal complexes of 8-hydroxyquinoline derivatives having a diarylamino group, oligothiophene derivatives, and the like. Furthermore, a polymer compound having a hole transporting site in the molecule can also be used. Examples of the electron-accepting compound capable of oxidizing the hole injecting / transporting material include triaryl boron compounds, metal halides, Lewis acids, organic acids, salts of arylamines and metal halides, arylamines, and the like. And one or two or more compounds selected from the group consisting of salts of bismuth and Lewis acids.

  Examples of the aromatic amine compound as the hole injection / transport material include compounds having a triarylamine structure, and compounds that have been conventionally used as a layer forming material for hole injection / transport in organic electroluminescence devices. You may select from among these. As an aromatic amine compound, the binaphthyl type compound represented by following General formula (1) is mentioned, for example.

(In the general formula (1), Ar ^{4 to} Ar ⁷ are each independently a monocyclic group or condensed ring group of a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent. Yes, Ar ⁴ and Ar ⁵ , Ar ⁶ and Ar ⁷ may be bonded to each other to form a ring, m and n each represents an integer of 0 to 4, and m + n ≧ 1, X ¹ and X ² each independently represents a direct bond or a divalent linking group, and the naphthalene ring in the general formula (1) is represented by — (X ¹ NAr ⁴ Ar ⁵ ) and — (X ² NAr ⁶ Ar ⁷ ). In addition to the above, it may have an optional substituent.)

In the general formula (1), Ar ^{4 to} Ar ⁷ are each independently a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or condensed ring group which may have a substituent, for example, A 5- or 6-membered monocyclic ring or a 2-3 condensed ring, specifically, an aromatic hydrocarbon ring such as a phenyl group, a naphthyl group or an anthryl group; an aromatic heterocyclic ring such as a pyridyl group or a thienyl group Can be mentioned. Any of these may have a substituent. Examples of the substituent that Ar ^{4 to} Ar ⁷ may have include those described later as the substituent that Ar ^{8 to} Ar ¹⁵ may have, and an arylamino group (that is,-(NAr ⁸ Ar ⁹ ) described later, - corresponds to ^(NAr 10 ^{Ar 11))} and the like.

Ar ⁴ and Ar ⁵ and / or Ar ⁶ and Ar ⁷ may be bonded to each other to form a ring. In this case, specific examples of the ring to be formed include a carbazole ring, a phenoxazine ring, an iminostilbene ring, a phenothiazine ring, an acridone ring, an acridine ring, an iminodibenzyl ring and the like that may have a substituent. Of these, a carbazole ring is preferred.

  In the general formula (1), m and n each represent an integer from 0 to 4, and m + n ≧ 1. Particularly preferred are m = 1 and n = 1. The arylamino groups when m and / or n is 2 or more may be the same or different.

X ¹ and X ² each independently represent a direct bond or a divalent linking group. Although there is no restriction | limiting in particular as a bivalent coupling group, For example, what is shown below etc. are mentioned. A direct bond is particularly preferable as X ¹ and X ² .

In addition to — (X ¹ NAr ⁴ Ar ⁵ ) and — (X ² NAr ⁶ Ar ⁷ ), the naphthalene ring in the general formula (1) has one or more arbitrary substituents at an arbitrary position. There is. Preferred examples of such a substituent include a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. Are one or more substituents selected from the group consisting of an alkoxycarbonyl group. Of these, an alkyl group is particularly preferred.

The binaphthyl compound represented by the general formula (1) is preferably a binaphthyl compound in which Ar ⁴ and Ar ⁶ are each further substituted with an arylamino group as represented by the following general formula (2).

(In the general formula (2), Ar ^{8 to} Ar ¹⁵ each independently represents a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or condensed ring group which may have a substituent. represents, .X ¹ and ^{X 2} may .m and n be Ar ⁸ and ^Ar 9, ^{Ar 10} and ^{Ar 11} are each bonded to form a ring is the same as in the general formula (1) is generally (It has the same meaning as in formula (1).)

Naphthalene ring in the general formula (2), the substituents include respective linked arylamino group to the naphthalene ring ^{- (X 1 NAr 12 Ar 13} NAr 9 Ar 8) and ^{- (X 2 NAr 14 Ar 15} NAr 10 Ar 11 ) And may have an optional substituent. Further, these substituents — (X ¹ NAr ¹² Ar ¹³ NAr ⁹ Ar ⁸ ) and — (X ² NAr ¹⁴ Ar ¹⁵ NAr ¹⁰ Ar ¹¹ ) may be substituted at any substitution position of the naphthalene ring. Especially, the binaphthyl type compound each substituted to 4-position and 4'-position of the naphthalene ring in General formula (2) is more preferable.

  Similarly to the compound represented by the general formula (1), the binaphthylene structure in the compound represented by the general formula (2) preferably has a substituent at the 2,2′-position. Examples of the substituent bonded to the 2,2′-position include a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. And an alkoxycarbonyl group which may have a group. In the compounds represented by the general formulas (1) and (2), the binaphthylene structure may have an optional substituent other than the 2,2′-position. Examples of the substituent include 2 , 2'-position, the above-mentioned groups and the like can be mentioned. The molecular weight of the binaphthyl compound represented by the general formula (1) is usually less than 2,000, preferably less than 1,200, but usually 500 or more, preferably 700 or more.

  As an aromatic amine compound, the compound represented by the following general formula (3) or general formula (4) is also preferable. The molecular weight of the compound represented by the general formula (3) or the general formula (4) is approximately the same as that of the general formula (1), and the preferable molecular weight is also the same.

(In the formula (3), R ²¹ and R ²² are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aromatic that may have a substituent. An aromatic hydrocarbon group that may have a substituent, an acenaphthyl group that may have a substituent, a fluorenyl group that may have a substituent, and R ²¹ and R ²² are bonded to each other. A non-aromatic ring which may have a substituent may be formed.)

(R ^{23 to} R ²⁶ are each independently an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, an acenaphthyl group that may have a substituent, or a substituent. R ²³ and R ²⁴ , R ²³ and carbon atom constituting ring a, R ²⁴ and carbon atom constituting ring a, R ²⁵ and R ²⁶ , R ²⁵ and ring The carbon atom constituting b, or the carbon atom constituting R ²⁶ and the ring b may be bonded to each other to form a ring which may have a substituent, wherein ring a and ring b are substituted. Represents a benzene ring which may have a group.)

In the general formula (3), R ^{23 to} R ²⁶ are specifically aromatic groups that are 6-membered monocyclic or 2 to 4 condensed rings such as phenyl, naphthyl, anthryl, pyrenyl, and phenanthyl. A hydrocarbon group; an aromatic heterocyclic group which is a 5- or 6-membered monocyclic ring or a 2-4 condensed ring, such as a pyridyl group, a thienyl group, a pyrazyl group, a thiazolyl group, a phenanthridyl group, a quinolyl group or a carbazolyl group; Examples include a fluorenyl group and an acenaphthyl group.

R ²³ and R ²⁴ , R ²³ and carbon atom constituting ring a, R ²⁴ and carbon atom constituting ring a, R ²⁵ and R ²⁶ , R ²⁵ and carbon atom constituting ring b, or R ²⁶ And the carbon atoms constituting ring b may be bonded to each other to form a ring that may have a substituent.

As R ²¹ and R ²² , in addition to the groups described above as R ^{23 to} R ²⁶ , a hydrogen atom, a hydroxyl group, a linear / branched / cyclic alkyl group having 1 to 10 carbon atoms, or a straight chain having 2 to 11 carbon atoms It may be a chain, branched or cyclic alkenyl group. R ²¹ and R ²² may be bonded to form a non-aromatic ring that may have a substituent. Examples of the non-aromatic ring include a cyclohexane ring, a cyclopentane ring, a cyclohexene ring, and a cyclopentene ring. The 5- or 6-membered ring is preferred.

An alkyl group of R ^{21 to} R ²⁶ , an alkenyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, an acenaphthyl group, a fluorenyl group, a non-aromatic ring formed by combining R ²¹ and R ²² , and R ²³ The substituent that may be possessed by R ²⁶ , a ring formed by combining two or more selected from the carbon atoms constituting ring a and ring b, is not particularly limited, and examples thereof include a halogen atom and an alkyl group. Alkenyl group, aromatic hydrocarbon group, aralkyl group, dialkylamino group, diarylamino group, and the like.

Furthermore, when at least one of R ^{21 to} R ²⁶ is a condensed ring group formed by condensation of three or more aromatic rings (aromatic hydrocarbon ring or aromatic heterocyclic ring), the glass transition temperature ( Tg) is preferred because it increases. In particular, it is preferable that at least one of R ^{21 to} R ²⁶ is a phenanthryl group which may have a substituent, because the driving life of an element produced using the same tends to be extended.

  Next, the compound represented by the general formula (4) is as follows.

(In the general formula (4), Ar ^{31 to} Ar ³⁴ each independently represents an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may have a substituent, and L is It is a bivalent coupling group represented by either of the following.

^{-Ar 35 -, - Ar 36 -Ar} 37 -, - Ar 38 -Ar 39 -Ar 40 -, - Ar 41 -Ar 42 -Ar 43 -Ar 44 -

(In the formula, Ar ^{35 to} Ar ⁴⁴ are each independently a divalent aromatic hydrocarbon ring having 5 to 6 members that may be substituted, a monocyclic aromatic heterocyclic ring, or a divalent condensed ring having 2 to 4 condensed rings. Represents a group of

In the general formula (4), Ar ^{31 to} Ar ³⁴ each independently represents an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent. Examples of the hydrogen group and the aromatic heterocyclic group include the same groups as those exemplified as R ^{23 to} R ²⁶ in the general formula (3). L represents a divalent linking group represented by any of the following.

^{-Ar 35 -, - Ar 36 -Ar} 37 -, - Ar 38 -Ar 39 -Ar 40 -, - Ar 41 -Ar 42 -Ar 43 -Ar 44 -

Ar ^{35 to} Ar ⁴⁴ are each independently a divalent group consisting of a monocyclic or 2 to 4 condensed ring having 5 to 6 members of an aromatic hydrocarbon ring or aromatic heterocyclic ring, which may be substituted. Specific examples of such a group include a divalent group obtained by removing one hydrogen atom from the groups exemplified as R ^{23 to} R ²⁶ in the general formula (3).

Examples of the substituent that Ar ^{31 to} Ar ⁴⁴ may have include, for example, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, a dialkylamino group, a diarylamino group, an arylalkylamino group, an acyl group, and an alkoxycarbonyl group. Group, carboxyl group, alkoxy group, aryloxy group, alkylsulfonyl group, hydroxyl group, amide group, aromatic hydrocarbon ring group, aromatic heterocyclic group and the like. Among these, a halogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group are preferable.

Since the aromatic amine compound contained in the organic electroluminescent element to which this embodiment is applied is used for layer formation by a wet film-forming method, it is preferable that the compound be easily soluble in various solvents. For example, in the case of the compound represented by the general formula (1), it is considered that by having substituents at the 2-position and the 2′-position, the two naphthalene rings are twisted so that the solubility is improved. In addition, in the case of the compound represented by the general formula (3), the molecular structure can take a non-conjugated structure in the methylene group part that may have a substituent that connects the ring a and the ring b. It is considered that solubility in For the compound represented by the general formula (4), as a linking group ^{L, -Ar 36 -Ar 37 -,} - Ar 38 -Ar 39 -Ar 40 -, - Ar 41 -Ar 42 -Ar 43 -Ar 44 - It is considered that the solubility is improved by selecting one of the groups and having a substituent at a specific position, resulting in a twisted molecular arrangement. That is, for example, each ^{Ar 36} and ^{Ar 37 is,} by having a substituent at the α- position to the bond between Ar 36 ^{-Ar 37,} and the ^{Ar 36} and ^{Ar 37} do not exist in the same plane, twisted Therefore, the solubility is improved. The same applies to Ar ³⁸ and Ar ³⁹ , Ar ³⁹ and Ar ⁴⁰ , Ar ⁴¹ and Ar ⁴² , Ar ⁴² and Ar ⁴³ , and Ar ⁴³ and Ar ⁴⁴ .

  In addition to the compounds represented by the general formulas (1), (3) and (4), conventionally known compounds can be used as the hole injecting / transporting material. As such a conventionally known compound, for example, an aromatic diamine compound in which a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane is linked (Japanese Patent Laid-Open No. Sho 59-59). No. 194393); 2,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl represented by two or more tertiary amines and two or more condensed aromatic rings are nitrogen atoms Aromatic amine substituted with (A) (Japanese Patent Laid-Open No. 5-234681); A derivative of triphenylbenzene and an aromatic triamine having a starburst structure (US Pat. No. 4,923,774); N, N′-diphenyl-N , N′-bis (3-methylphenyl) biphenyl-4,4′-diamine and other aromatic diamines (US Pat. No. 4,764,625); α, α, α ′, α′-teto Methyl-α, α′-bis (4-di-p-tolylaminophenyl) -p-xylene (Japanese Patent Laid-Open No. 3-269084); A compound in which a plurality of aromatic diamino groups are substituted on a pyrenyl group (JP-A-4-175395); an aromatic diamine in which a tertiary aromatic amine unit is linked by an ethylene group (JP-A-4-264189). An aromatic diamine having a styryl structure (Japanese Patent Laid-Open No. 4-290851); an aromatic tertiary amine unit linked by a thiophene group (Japanese Patent Laid-Open No. 4-304466); a starburst aromatic triamine ( JP-A-4-308688); benzylphenyl compound (JP-A-4-364153); tertiary with fluorene group Minine-linked (JP-A-5-25473); Triamine compound (JP-A-5-239455); Bisdipyridylaminobiphenyl (JP-A-5-320634); N, N, N-triphenylamine Derivatives (JP-A-6-1972); Aromatic diamines having a phenoxazine structure (JP-A-7-138562); Diaminophenylphenanthridine derivatives (JP-A-7-252474); 2-311591); silazane compounds (US Pat. No. 4,950,950); silanamine derivatives (JP-A-6-49079); phosphamine derivatives (JP-A-6-25659); quinacridone compounds, etc. Can be mentioned. These compounds may be used alone or in combination of two or more as required.

  Next, preferred specific examples of the phthalocyanine derivative or porphyrin derivative used as the hole injecting / transporting material include the following compounds. For example, porphyrin, 5,10,15,20-tetraphenyl-21H, 23H-porphyrin, 5,10,15,20-tetraphenyl-21H, 23H-porphyrin cobalt (II), 5,10,15,20- Tetraphenyl-21H, 23H-porphyrin copper (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin zinc (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin Vanadium (IV) oxide, 5,10,15,20-tetra (4-pyridyl) -21H, 23H-porphyrin 29H, 31H-phthalocyanine copper (II) phthalocyanine zinc (II) phthalocyanine titanium phthalocyanine oxide magnesium phthalocyanine lead phthalocyanine copper ( II), 4, ', 4' ', 4' '' - tetraaza-29H, 31H-phthalocyanine, and the like.

  Furthermore, examples of the metal complex of an 8-hydroxyquinoline derivative having a diarylamino group used as a hole injecting / transporting material include those represented by the following general formula (5).

(In General Formula (5), Ar ²¹ and Ar ²² each independently represent an aromatic group or an aromatic heterocyclic group that may have a substituent. R ^{11 to} R ¹⁵ are each independently Hydrogen atom, halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, cyano group, amino group, amide group, nitro group, acyl group, alkoxycarbonyl group, carboxyl group, alkoxy group, alkylsulfonyl group, hydroxyl group, aromatic Represents an aromatic hydrocarbon group or an aromatic heterocyclic group.

R ¹¹ and R ¹² , R ¹² and R ¹³ , or R ¹⁴ and R ¹⁵ may form a ring, and any one of R ^{11 to} R ¹⁵ is an alkyl group, an aralkyl group, or an alkenyl group. , An alkynyl group, a secondary or tertiary amino group, an amide group, an acyl group, an alkoxycarbonyl group, an alkoxy group, an alkylsulfonyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group, The hydrocarbon portion may have a substituent.

  M is an alkali metal, alkaline earth metal, Sc, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Sm, Eu. Or it represents Tb, and l represents an integer of 2 to 4. )

  Specific examples of the compound represented by the general formula (5) include the following.

  Other examples of the oligothiophene derivative used as the hole injecting / transporting material include α-sexithiophene. The molecular weight of these hole injecting / transporting materials is usually less than 2,000, preferably less than 1,800, more preferably less than 1,200, but usually 500 or more, preferably 700 or more. is there.

  Moreover, as a high molecular compound which has a positive hole transport site | part in a molecule | numerator used as a hole injection / transport material, the high molecular compound which contains an aromatic tertiary amino group as a structural unit in a main skeleton is mentioned, for example. Specific examples include hole injecting / transporting materials having a structure represented by the following general formulas (II) and (III) as a repeating unit.

(In formula (II), Ar ^{45 to} Ar ⁴⁸ each independently represent a divalent aromatic ring group that may have a substituent, and R ^{31 to} R ³² may be monovalent that may have a substituent. And X is selected from a direct bond or the following linking group, wherein “aromatic ring group” means “group derived from aromatic hydrocarbon ring” and “derived from aromatic heterocycle” Including both ").)

(In the formula (III), Ar ⁴⁹ represents a divalent aromatic ring group which may have a substituent, and Ar ⁵⁰ represents a monovalent aromatic ring group which may have a substituent.)
In the general formula (II), Ar ^{45 to} Ar ⁴⁸ are each preferably a divalent benzene ring, naphthalene ring, anthracene ring, or biphenyl group each independently having a substituent, preferably a benzene ring. It is. As a substituent, a halogen atom; a C1-C6 linear or branched alkyl group such as a methyl group or an ethyl group; an alkenyl group such as a vinyl group; a C2-C7 such as a methoxycarbonyl group or an ethoxycarbonyl group Linear or branched alkoxycarbonyl group; linear or branched alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; aryloxy group having 6 to 12 carbon atoms such as phenoxy group and benzyloxy group; diethylamino group And a dialkylamino group having an alkyl chain having 1 to 6 carbon atoms, such as a diisopropylamino group. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable. The case where Ar ^{45 to} Ar ⁴⁸ are all unsubstituted aromatic ring groups is most preferable.

R ³¹ and R ³² are preferably each independently a phenyl group, naphthyl group, anthryl group, pyridyl group, triazyl group, pyrazyl group, quinoxalyl group, thienyl group, or biphenyl group, which may have a substituent. Preferably a phenyl group, a naphthyl group or a biphenyl group, more preferably a phenyl group. As a substituent, the group similar to the group mentioned above is mentioned as a group which the aromatic ring in Ar < ⁴⁵ > -Ar < ⁴⁸ > may have.
The compound having the structure represented by the general formula (II) as a repeating unit is disclosed in, for example, the method of Kido et al. (Polymers for Advanced Technologies, 7, 31 pages, 1996; JP-A-9-188756). Is synthesized by the route.

In the general formula (III), Ar ⁴⁹ is a divalent aromatic ring group which may have a substituent, preferably an aromatic hydrocarbon ring group from the viewpoint of hole transportability. And a divalent benzene ring, naphthalene ring, anthracene ring, biphenyl group, and terphenyl group that may have a group. As the substituent, a group in which an aromatic ring may have at Ar ⁴⁵ to Ar ^48, include the same groups as previously described. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable.

Ar ⁵⁰ is an aromatic ring group that may have a substituent, preferably an aromatic hydrocarbon ring group from the viewpoint of hole transportability, specifically, a phenyl group that may have a substituent, Examples include naphthyl group, anthryl group, pyridyl group, triazyl group, pyrazyl group, quinoxalyl group, thienyl group, and biphenyl group. As a substituent, the group similar to the group mentioned above is mentioned as a group which the aromatic ring in Ar < ⁴⁵ > -Ar < ⁴⁸ > of general formula (II) may have.
In the compound represented by the general formula (III), it is most preferable that Ar ⁴⁹ and Ar ⁵⁰ are both unsubstituted aromatic ring groups. The compound having the structure represented by the general formula (III) as a repeating unit is allowed to react at 110 ° C. for 16 hours in the presence of a palladium catalyst in an organic solvent such as xylene according to the following raw materials and reaction formula, for example. Can be synthesized.

  Examples of the hole injecting / transporting material containing an aromatic tertiary amino group as a side chain include compounds having a repeating unit having a structure represented by the following general formulas (IV) and (V).

(In the formula, Ar ⁵¹ represents a divalent aromatic ring group which may have a substituent, Ar ^{52 to} Ar ⁵³ represent a monovalent aromatic ring group which may have a substituent, and R ³³ to R ³⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a monovalent aromatic ring group that may have a substituent.

(In the formula, Ar ^{54 to} Ar ⁵⁸ each independently represent a divalent aromatic ring group that may have a substituent, and R ³⁶ and R ³⁷ represent an aromatic ring group that may have a substituent. Y is selected from a direct bond or the following linking group.)

In the general formula (IV), Ar ⁵¹ is preferably a divalent benzene ring, naphthalene ring, anthracene ring, or biphenyl, each of which may have a substituent. Examples of the group that the aromatic ring in Ar ^{45 to} Ar ⁴⁸ of formula (II) may have include the same groups as those described above, and preferred groups are also the same.
Ar ⁵² and Ar ⁵³ are preferably each independently a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a triazyl group, a pyrazyl group, a quinoxalyl group, a thienyl group, and a biphenyl group. May have. Examples of the substituent include the same groups as those described above as the groups that the aromatic ring in Ar ^{45 to} Ar ⁴⁸ of the general formula (II) may have, and preferred groups are also the same.

R ^{33 to} R ³⁵ are preferably each independently a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; a carbon such as a methoxy group or an ethoxy group. A linear or branched alkoxy group of 1 to 6; a phenyl group; or a tolyl group. A compound having a structure represented by the general formula (IV) as a repeating unit is synthesized, for example, by the route disclosed in JP-A-1-105954.
In the general formula (V), Ar ^{54 to} Ar ⁵⁸ are preferably a divalent benzene ring, naphthalene ring, anthracene ring, or biphenyl, each of which may independently have a substituent, and preferably a benzene ring. . As a substituent, the group similar to the group mentioned above is mentioned as a group which the aromatic ring in Ar < ⁴⁵ > -Ar < ⁴⁸ > of general formula (II) may have, A preferable group is also the same.

R ³⁶ and R ³⁷ are each preferably a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a triazyl group, a pyrazyl group, a quinoxalyl group, a thienyl group, or a biphenyl group, each of which may have a substituent. . As a substituent, the group similar to the group mentioned above is mentioned as a group which the aromatic ring in Ar < ⁴⁵ > -Ar < ⁴⁸ > of general formula (II) may have, A preferable group is also the same. The compound represented by the general formula (V) is synthesized, for example, by the route disclosed in the method of Kido et al. (Polymers for Advanced Technologies, Vol. 7, page 31, 1996; JP-A-9-188756). The

  Of the structures represented by the general formulas (II) to (V), preferred examples are shown below, but are not limited thereto.

  The hole injecting / transporting material, which is a polymer compound having a hole transporting site in the molecule, is most preferably a homopolymer having a structure represented by any one of the general formulas (II) to (V). Further, it may be a copolymer (copolymer) with any other monomer. When it is a copolymer, it is preferable to contain 50 mol% or more, especially 70 mol% or more of the structural units represented by the general formulas (II) to (V). The hole injecting / transporting material which is a polymer compound may contain a plurality of structures represented by the general formulas (II) to (V) in one compound. Moreover, you may use the compound containing the structure represented by general formula (II)-(V) in combination of multiple types. Of the general formulas (II) to (V), a homopolymer comprising a repeating unit represented by the general formula (II) is particularly preferable. Examples of the hole injecting / transporting material made of a polymer compound further include conjugated polymers. For this purpose, polyfluorene, polypyrrole, polyaniline, polythiophene, polyparaphenylene vinylene are preferred.

  Further, examples of the polymer compound having a hole transporting site in the molecule used as the hole injecting / transporting material include, for example, an aromatic diamine-containing polyether (Japanese Patent Laid-Open No. 2000-36390); polyvinylcarbazole, polysilane, Polyphosphazene (JP-A-5-310949); Polyamide (JP-A-5-310949); Polyvinyltriphenylamine (JP-A-7-53953); Polymer having a triphenylamine skeleton (JP-A-4-4) No. 1333065); polymethacrylates containing aromatic amines and the like.

  Next, the electron accepting compound will be described. Examples of the electron-accepting compound contained in the composition for an organic electric field element to which the present embodiment is applied include, for example, a triaryl boron compound, a metal halide, a Lewis acid, an organic acid, an arylamine, and a metal halide. Examples thereof include one or two or more compounds selected from the group consisting of a salt, a salt of an arylamine and a Lewis acid. These electron-accepting compounds are used in combination with a hole injecting / transporting material, and the conductivity of the hole injecting layer can be improved by oxidizing the hole injecting / transporting material.

  Examples of the triarylboron compound as the electron-accepting compound include boron compounds represented by the following general formula (6). The boron compound represented by the general formula (6) is preferably a Lewis acid. Further, the electron affinity of the boron compound is usually 4 eV or more, preferably 5 eV or more.

In the general formula (6), preferably, Ar ^{1 to} Ar ³ are each independently a 5- or 6-membered monocycle such as a phenyl group, a naphthyl group, an anthryl group, or a biphenyl group that may have a substituent, Or an aromatic hydrocarbon ring group formed by condensing and / or directly bonding 2 to 3 thereof; or 5 or 6 such as a thienyl group, pyridyl group, triazyl group, pyrazyl group, quinoxalyl group, etc., which may have a substituent. It represents a monocyclic member or an aromatic heterocyclic group formed by condensing 2 or 3 thereof and / or directly bonding them.

  Examples of such a substituent include a halogen atom such as a fluorine atom; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkenyl group such as a vinyl group; a methoxycarbonyl group and an ethoxy group. C1-C6 linear or branched alkoxycarbonyl group such as carbonyl group; C1-C6 linear or branched alkoxy group such as methoxy group and ethoxy group; Aryloxy such as phenoxy group and benzyloxy group Groups; dialkylamino groups such as dimethylamino group and diethylamino group; acyl groups such as acetyl group; haloalkyl groups such as trifluoromethyl group; and cyano groups.

As such substituents, at least one of Ar ¹ to Ar ^3, is preferably Hammett constants (sigma _m and / or sigma _p) is a compound having a substituent having a positive value, Ar ¹ to Ar ³ Are particularly preferably compounds having a substituent with a positive Hammett constant (σ _m and / or σ _p ). By having such an electron-withdrawing substituent, the electron acceptability of these compounds is improved. Further, it is more preferable that Ar ^{1 to} Ar ³ are all compounds representing an aromatic hydrocarbon group or an aromatic heterocyclic group substituted with a halogen atom.

  Although the preferable specific examples (1-30) of the boron compound represented by General formula (6) are shown below, it is not limited to these.

(30) The ionic compound of number A-1 described in the table in the paragraph (0059) column of the specification of Japanese Patent Application No. 2004-68958.

  Of these, the following compounds are particularly preferred.

(30) The ionic compound of number A-1 described in the table in the paragraph (0059) column of the specification of Japanese Patent Application No. 2004-68958.

  Further, as the electron-accepting compound, one or more compounds selected from the group consisting of metal halides, Lewis acids, organic acids, salts of arylamines and metal halides, and salts of arylamines and Lewis acids Specific examples of these include the compounds shown below.

  In addition, the content of the electron-accepting compound with respect to the hole injecting / transporting material is usually 0.1 mol% or more, preferably 1 mol% or more. However, it is usually 100 mol% or less, preferably 40 mol% or less.

  Next, the organic electroluminescent element produced using the organic electroluminescent element composition to which this embodiment is applied will be described. FIG. 1A to FIG. 1C illustrate an organic electroluminescent element having a thin layer formed by a wet film forming method using the organic electroluminescent element composition to which the present embodiment is applied. FIG. An organic electroluminescent element 100a shown in FIG. 1A includes a substrate 101, an anode 102, a hole injection layer 103, a light emitting layer 105, and a cathode 107, which are sequentially stacked on the substrate 101.

  The substrate 101 is a support for the organic electroluminescent element 100a. Examples of the material for forming the substrate 101 include a quartz plate, a glass plate, a metal plate, a metal foil, a plastic film, and a plastic sheet. Among these, a transparent plastic sheet such as a glass plate, polyester, polymethacrylate, polycarbonate, polysulfone is preferable. Note that in the case where plastic is used for the substrate 101, it is preferable to provide a dense silicon oxide film or the like on one or both surfaces of the substrate 101 to enhance gas barrier properties.

  The anode 102 is provided on the substrate 101 and plays a role of hole injection into the hole injection layer 103. Materials for the anode 102 include metals such as aluminum, gold, silver, nickel, palladium, and platinum; conductive metal oxides such as oxides of indium and / or tin; metal halides such as copper iodide; carbon black A conductive polymer such as poly (3-methylthiophene), polypyrrole, and polyaniline; The anode 102 is usually formed by sputtering on the substrate 101, vacuum deposition, etc .; fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, or conductive polymer fine particles. A method in which powder or the like is dispersed in an appropriate binder resin solution and applied onto the substrate 101; a method in which a conductive polymer thin film is formed directly on the substrate 101 by electrolytic polymerization; a conductive polymer solution is applied onto the substrate 101 Methods and the like. The anode 102 usually has a visible light transmittance of 60% or more, particularly preferably 80% or more. The thickness of the anode 102 is usually 1000 nm or less, preferably 500 nm or less, and usually 5 nm or more, preferably 10 nm or more.

  The hole injection layer 103 is provided on the anode 102, and is preferably formed by a wet film forming method using the organic electroluminescent element composition to which the present embodiment is applied. The hole injection layer 103 is preferably formed using a hole injection / transport material and an electron-accepting compound capable of oxidizing the hole injection / transport material. The film thickness of the hole injection layer 103 formed in this way is usually 5 nm or more, preferably 10 nm or more. However, it is usually 1,000 nm or less, preferably 500 nm or less.

  The light emitting layer 105 is provided on the hole injection layer 103, and efficiently recombines electrons injected from the cathode 107 and holes transported from the hole injection layer 103 between electrodes to which an electric field is applied, and It is formed from a material that emits light efficiently by recombination. As a material for forming the light-emitting layer 105, a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, (2-hydroxyphenyl) Low molecular light emitting materials such as metal complexes of benzothiazole and silole derivatives; poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3- Examples thereof include a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as alkylthiophene) or polyvinylcarbazole.

  Further, for example, using a metal complex such as an aluminum complex of 8-hydroxyquinoline as a host material, a condensed polycyclic aromatic ring such as a naphthacene derivative such as rubrene, a quinacridone derivative, and perylene is 0.1 to 0.1% relative to the host material. By doping 10% by weight, the light emission characteristics of the device, particularly the driving stability, can be greatly improved. These materials are coated on the hole injection layer 103 by a vacuum deposition method or a wet film formation method to form a thin film on the hole injection layer 103. The thickness of the light emitting layer 105 formed in this manner is usually 10 nm or more, preferably 30 nm or more. However, it is usually 200 nm or less, preferably 100 nm or less.

  The cathode 107 serves to inject electrons into the light emitting layer 105. The material used for the cathode 107 is preferably a metal having a low work function. For example, a suitable metal such as tin, magnesium, indium, calcium, aluminum, silver, or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy. The film thickness of the cathode 107 is usually the same as that of the anode 102. In order to protect the cathode 107 made of a low work function metal, it is effective to increase the stability of the device by further laminating a metal layer having a high work function and stable to the atmosphere. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used. Furthermore, the efficiency of the device can be improved by inserting an extremely thin insulating film (film thickness of 0.1 to 5 nm) such as LiF, MgF 2, or Li 2 O at the interface between the cathode 107 and the light emitting layer 105.

  FIG. 1B is a diagram for explaining a function-separated light-emitting element. In the organic electroluminescent device 100b shown in FIG. 1B, a hole transport layer 104 is provided between the hole injection layer 103 and the light emitting layer 105 in order to improve the light emitting characteristics of the device. The layer has a configuration similar to that of the organic electroluminescent element 100a shown in FIG. The material of the hole transport layer 104 needs to be a material that has high hole injection efficiency from the hole injection layer 103 and can efficiently transport the injected holes. For this purpose, it is required that the ionization potential is low, the hole mobility is high, the stability is high, and impurities that become traps are not easily generated during production or use. In addition, since the layer is in direct contact with the light-emitting layer 105, it is preferable that a substance that quenches light emission is not included.

  Examples of the hole injecting / transporting material for forming the hole transporting layer 104 include the same compounds as those exemplified as the hole injecting / transporting material in the composition for organic electroluminescent elements to which the exemplary embodiment is applied. Can be mentioned. In addition, polymer materials such as polyarylene ether sulfone containing polyvinyl carbazole, polyvinyl triphenylamine, and tetraphenylbenzidine can be given. The hole transport layer 104 is formed by laminating these hole injection / transport materials on the hole injection layer 103 by a wet film forming method or a vacuum deposition method. The thickness of the hole transport layer 104 formed in this way is usually 10 nm or more, preferably 30 nm. However, it is usually 300 nm or less, preferably 100 nm or less.

  FIG.1 (c) is a figure for demonstrating other embodiment of a function separation type light emitting element. In the organic electroluminescent device 100c shown in FIG. 1C, an electron transport layer 106 is provided between the light emitting layer 105 and the cathode 107, and the other layers are organic electroluminescent devices shown in FIG. The structure is similar to that of the element 100b. The compound used for the electron transport layer 106 is required to easily inject electrons from the cathode 107 and to have a larger electron transport capability. Examples of such electron transporting materials include 8-hydroxyquinoline aluminum complexes, oxadiazole derivatives, or systems in which they are dispersed in a resin such as polymethyl methacrylate (PMMA), phenanthroline derivatives, 2-t-butyl. Examples include -9,10-N, N'-dicyanoanthraquinone diimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, and n-type zinc selenide. The film thickness of the electron transport layer 106 is usually 5 nm or more, preferably 10 nm or more. However, it is usually 200 nm or less, preferably 100 nm or less.

  Note that the organic electroluminescent elements 100a to 100c shown in FIGS. 1A to 1C are not limited to the illustrated ones. For example, a structure reverse to that shown in FIGS. 1A to 1C, that is, a cathode 107, a light emitting layer 105, a hole injection layer 103, and an anode 102 may be stacked on the substrate 101 in this order. Is possible. It is also possible to provide an organic electroluminescent element between two substrates, at least one of which is highly transparent. Further, the layer containing the hole injecting / transporting material and the electron accepting compound need not be the hole injecting layer 103 in contact with the anode 102, and may be provided between the anode 102 and the light emitting layer 105. In particular, the hole injection layer 103 is preferable. Moreover, you may have arbitrary layers between each layer shown to Fig.1 (a)-FIG.1 (c).

  Next, a method for producing organic electroluminescent elements 100a to 100c having a thin layer formed by a wet film-forming method using the composition for organic electroluminescent elements to which the exemplary embodiment is applied will be described. . The organic electroluminescent element 100a to the organic electroluminescent element 100c are formed by forming the anode 102 by sputtering, vacuum deposition, or the like on the substrate 101, and the hole injection layer 103 and the hole transport layer 104 are formed on the formed anode 102. Is formed by a wet film forming method using an organic electric field element composition containing a hole injecting / transporting material and / or an electron accepting compound to which the present embodiment is applied. A light emitting layer 105 is formed on the hole injection layer 103 and / or the hole transport layer 104 by a vacuum deposition method or a wet film forming method, and vacuum deposition is performed on the formed light emitting layer 105 as necessary. The electron transport layer 106 is formed by a method or a wet film forming method, and the cathode 107 is formed on the formed electron transport layer 106.

  When at least one of the hole injection layer 103 and the hole transport layer 104 is formed by a wet film forming method, it is usually necessary to add a predetermined amount of the hole injection / transport material and / or the electron-accepting compound as necessary. Add additives such as binder resin or coating property improver that does not trap holes, dissolve to prepare a coating solution, that is, a composition for an organic electroluminescent device, and usually within 24 hours after preparation, Preferably, within 12 hours, particularly preferably within 6 hours, the film is applied onto the anode 102 by a wet film formation method such as spin coating or dip coating, and dried to form the hole injection layer 103 and the hole transport layer. At least one layer 104 is formed.

  In a solution containing a hole injecting / transporting material and / or an electron accepting compound, if there is a compound susceptible to oxidation, such as alcohol, aldehyde or ketone, these compounds susceptible to oxidation and the electron accepting compound May react. In addition, these compounds, which are susceptible to oxidation, are cation radicals of the hole injection / transport material generated by the combined use of a hole injection / transport material and an electron accepting compound (this radical generation is based on hole injection characteristics, May also react). When the electron accepting compound or cation radical in the coating solution is consumed due to the reaction of these compounds that are susceptible to oxidation, it is considered that impurities are generated. For this reason, the solution is gradually deactivated and the solution is stored. Stability is reduced. At least one of the hole injection layer 103 and the hole transport layer 104 is formed by a wet film forming method using a solution within 20 hours after preparing a solution containing a hole injection / transport material and an electron accepting compound. By doing so, the organic electroluminescent elements 100a to 100c can be manufactured in a state where the hole injecting / transporting material or the electron accepting compound in the solution is stable.

  The binder resin content is usually preferably 50% by weight or less in these layers, more preferably 30% by weight or less, and most preferably no binder resin from the viewpoint of hole mobility. .

  In addition, the layer containing the hole injecting / transporting material and / or the electron transporting compound activates the migration of molecules contained in the obtained film through a heating process after the wet film formation and drying process. Therefore, it is possible to reach a thermally stable thin film structure, which is preferable because the surface flatness of the film is improved and the light emission efficiency of the device is improved.

  Specifically, after a layer containing a hole injecting / transporting material and / or an electron-accepting compound is formed by a wet film forming method, the temperature is equal to or lower than the glass transition point Tg of the used hole injecting / transporting material. Heat with. The heating temperature is preferably 10 ° C. or more lower than the glass transition point Tg of the hole injecting / transporting material. Moreover, in order to fully acquire the effect by heat processing, it is preferable to process at 60 degreeC or more. The heating time is usually about 1 minute to 8 hours. Since the layer containing the hole injecting / transporting material and / or the electron accepting compound formed by the wet film forming method in this way has a smooth surface, it is caused by the surface roughness of the anode 102 such as ITO. It is possible to solve the problem of a short circuit at the time of manufacturing the device.

Hereinafter, the present embodiment will be described more specifically based on examples, comparative examples, and reference examples. In addition, this Embodiment is not limited to description of the following Examples.
(Reference Example 1)
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 120 nm (manufactured by Geomat Corp .; electron beam film-formed product; sheet resistance 15Ω) is ultrasonically cleaned with acetone, washed with pure water, and with isopropyl alcohol After ultrasonic cleaning, drying with dry nitrogen, and UV / ozone cleaning, a hole transporting polymer represented by the following structural formula (P1) (homopolymer. Mw = 27,000, Mn = 13,000) And a composition film containing PPB (tris (pentafluorophenyl) borane) represented by the following structural formula (A1) as an electron-accepting compound by spin coating on the substrate under the following conditions to form a uniform thin film having a thickness of 30 nm Formed. Spin coating was performed in air. The environmental conditions at this time were a temperature of 23 ° C. and a relative humidity of 60%.

Solvent Ethyl benzoate coating solution concentration 2% by weight of hole transporting polymer / 0.2% by weight of electron accepting compound
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying condition After drying at 80 ° C for 1 minute on a hot plate,
Heat drying at 0 ° C. for 60 minutes.

(Reference Example 2)
In the same manner as in Reference Example 1, a composition solution containing a hole transporting polymer (P1) and PPB as an electron-accepting compound was spin-coated on a substrate under the following conditions, and a uniform film thickness of 30 nm was obtained. A thin film was formed. Spin coating was performed in air. The environmental conditions at this time were an air temperature of 23 ° C. and a relative humidity of 60%.
Solvent Cyclohexanone coating concentration 1% by weight of hole transporting polymer / 0.1% by weight of electron accepting compound
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying conditions Heat drying at 100 ° C. for 60 minutes in an oven.

(Reference Example 3)
In the same manner as in Reference Example 1, a hole transporting polymer (homopolymer. Mw = 17,000, Mn = 8,300) represented by the following structural formula (P2) and an electron accepting compound are represented by the following structural formula (A2). The composition solution containing TBPAH (tris (4-bromophenyl) amine tetrachloroantimonate) shown in FIG. 3 was spin-coated on the substrate under the following conditions to form a uniform thin film having a thickness of 15 nm. Spin coating was performed in air. The environmental conditions at this time were an air temperature of 23 ° C. and a relative humidity of 60%.

Solvent Cyclohexanone coating solution concentration Hole transporting polymer 0.5 wt% / electron accepting compound 0.05 wt%
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying conditions Heat drying at 100 ° C. for 60 minutes in an oven.

(Reference Example 4)
In the same manner as in Reference Example 3, a composition solution containing a hole-transporting polymer (P2) and TBPAH as an electron-accepting compound was spin-coated on the substrate under the following conditions, and a uniform film thickness of 15 nm was obtained. A thin film was formed. Spin coating was performed in air. The environmental conditions at this time were an air temperature of 23 ° C. and a relative humidity of 60%.
Solvent chloroform coating solution concentration hole transporting polymer 0.5% by weight / electron accepting compound 0.05% by weight
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying conditions Heat drying at 100 ° C. for 60 minutes in an oven.

(Example 1)
An organic electroluminescent device having the same structure as the organic electroluminescent device 100b shown in FIG. 1B was produced by the following method.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 120 nm (manufactured by Geomat Corp .; electron beam film-formed product; sheet resistance 15 Ω) is 2 mm wide using ordinary photolithography and hydrochloric acid etching. An anode was formed by patterning the stripes. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

First, a composition solution containing a hole transporting polymer (P1) and PPB as an electron-accepting compound was prepared in the same manner as in Reference Example 1, and spin-coated on the ITO glass substrate under the same conditions as in Reference Example 1. did. In addition, the composition solution at this time used the thing which 30 minutes passed after melt | dissolving the hole transportable polymer (P1) and PPB in the ethyl benzoate which is a solvent. By this spin coating, a hole injection layer having a uniform thin film shape with a thickness of 30 nm was formed.
Next, the substrate on which the hole injection layer was applied and formed was placed in a vacuum evaporation apparatus. An oil diffusion pump equipped with a liquid nitrogen trap until the degree of vacuum in the apparatus becomes 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less after rough exhaust of the above apparatus by an oil rotary pump Was evacuated. An aromatic amine compound represented by the following structural formula (H1), 4,4′-bis [N- (9-phenanthyl) -N-phenylamino] biphenyl, heated in a ceramic crucible placed in the apparatus was heated. The vapor deposition was performed. The degree of vacuum during deposition is 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition rate is 0.3 nm / second, and a 40 nm-thick film is stacked on the hole injection layer. Thus, a hole transport layer was completed.

Subsequently, vapor deposition was performed by heating an aluminum 8-hydroxyquinoline complex represented by the following structural formula (E1), Al (C ₉ H ₆ NO) ₃ using a crucible as a material of the light emitting layer. At this time, the temperature of the crucible was controlled in a range of 282 to 294 ° C. The degree of vacuum during the deposition was 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition rate was 0.1 to 0.3 nm / second, and the deposition time was 2 minutes and 40 seconds. . As a result, a light emitting layer having a thickness of 60 nm was obtained.

The substrate temperature during vacuum deposition of the hole transport layer and the light emitting layer was kept at room temperature. Here, a striped shadow mask having a width of 2 mm is used as a mask for cathode vapor deposition with the element deposited up to the light-emitting layer in close contact with the element so as to be orthogonal to the ITO stripe of the anode, and in another vacuum vapor deposition apparatus. It was evacuated until the degree of vacuum in the apparatus was 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less. As the cathode, first, lithium fluoride (LiF) was used at a deposition rate of 0.1 nm / second, a degree of vacuum of 7.0 × 10 ⁻⁶ Torr (about 9.3 × 10 ⁻⁴ Pa) using a molybdenum boat, and 0 A film having a thickness of 0.5 nm was formed on the light emitting layer. Next, aluminum is similarly heated by a molybdenum boat to form an aluminum layer having a thickness of 80 nm at a deposition rate of 0.5 nm / second and a degree of vacuum of 1 × 10 ⁻⁵ Torr (about 1.3 × 10 ⁻³ Pa). Thus, a cathode was formed. The substrate temperature at the time of vapor deposition of the above two-layer cathode was kept at room temperature. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. The light emission characteristics of this device are shown in Table 1.

Table 1 shows light emission luminance (unit: cd / m ² ) at an electric current of 250 mA / cm ² , light emission efficiency (unit: lm / W) at light emission luminance of 100 cd / m ² , luminance / current (unit: cd / A), and The numerical values of drive voltage (unit: V) are shown respectively.

(Example 2)
Except that the hole-injecting layer was formed using a composition solution that was stored for 4 weeks in the dark at 23 ° C. after dissolving the hole-transporting polymer (P1) and PPB in ethyl benzoate as a solvent. In the same manner as in Example 1, an organic electroluminescent element having the same structure as that of the organic electroluminescent element 100b shown in FIG. The light emission characteristics of this device are shown in Table 1.
From Table 1, the driving voltage is almost equal to the device described in Example 1, and the coating composition prepared by the method described in Reference Example 1 has an organic electric field having the same characteristics even when stored at 23 ° C. for 2 weeks. It can be seen that a light emitting element was obtained.

(Example 3)
After mixing 30 minutes after mixing the hole transporting polymer (P1) as the coating liquid and PPB as the electron accepting compound in cyclohexanone as the solvent with the composition described in Reference Example 2, the same as in Reference Example 2 An organic electroluminescent device having the same structure as that of the organic electroluminescent device 100b shown in FIG. 1B was prepared in the same manner as in Example 1 except that the hole injection layer was formed by forming the film under the above conditions. The light emission characteristics of this device are shown in Table 1.

(Comparative Example 1)
In the composition described in Reference Example 2, after dissolving the hole transporting polymer (P1) and PPB in cyclohexanone as a solvent, the composition solution was stored at 23 ° C., protected from light for 4 weeks. An organic electroluminescent device having the same structure as the organic electroluminescent device 100b shown in FIG. 1b was prepared in the same manner as in Example 1 except that the hole injection layer was formed by forming the film under the same conditions as in FIG. . The light emission characteristics of this device are shown in Table 1. The drive voltage of this element was higher than that of the element described in Example 3.

Example 4
An organic electroluminescent element having the same structure as that of the organic electroluminescent element 100c shown in FIG. 1C was produced by the following method.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 120 nm (manufactured by Geomat Corp .; electron beam film-formed product; sheet resistance 15 Ω) is 2 mm wide using ordinary photolithography technology and hydrochloric acid etching. The anode was formed by patterning into stripes. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

First, a composition solution containing a hole transporting polymer (P1) and PPB which is an electron accepting compound was prepared in the same manner as in Reference Example 2, and spinned on the ITO glass substrate under the same conditions as in Example 2. Coated. In addition, the coating liquid at this time used what melt | dissolved the hole transportable polymer (P1) and PPB in cyclohexanone which is a solvent, and stored at 23 degreeC for 1 hour. By this spin coating, a hole injection layer having a uniform thin film shape with a thickness of 30 nm was formed.
Next, the substrate on which the hole injection layer was applied and formed was placed in a vacuum evaporation apparatus. An oil diffusion pump equipped with a liquid nitrogen trap until the degree of vacuum in the apparatus becomes 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less after rough exhaust of the above apparatus by an oil rotary pump Was evacuated. The compound (H1) placed in a ceramic crucible placed in the above apparatus was heated for vapor deposition. The degree of vacuum during deposition is 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition rate is 0.3 nm / second, and a 40 nm-thick film is stacked on the hole injection layer. Thus, a hole transport layer was formed.

Subsequently, as a material for the light emitting layer, vapor deposition was performed by simultaneously heating the compound (E1) and rubrene represented by the following structural formula (D1) using separate crucibles. The temperature of each crucible at this time was controlled in the range of 282 to 294 ° C. for the compound (E1) and in the range of 180 to 190 ° C. for the compound (D1). The degree of vacuum during the deposition was 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition rate was 0.1 to 0.3 nm / second, and the deposition time was 2 minutes and 45 seconds. . As a result, a light emitting layer in which the film thickness was 30.7 nm and the compound (D1) was doped 2.5% by film thickness with respect to the complex (E1) was obtained.

Furthermore, the heating of the compound (D1) was stopped, and the temperature of the aluminum 8-hydroxyquinoline complex alone was controlled in the range of 282 to 294 ° C., and the electron transport layer 106 having a film thickness of 45 nm was deposited. The degree of vacuum at this time was 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition rate was 0.1 to 0.4 nm / second, and the deposition time was 2 minutes 52 seconds. . The substrate temperature when vacuum-depositing the hole transport layer, the light emitting layer, and the electron transport layer was maintained at room temperature.
Here, another vacuum deposition apparatus in which a striped shadow mask having a width of 2 mm is closely attached to the element so as to be orthogonal to the ITO stripe of the anode, using the element deposited up to the electron transport layer as a mask for cathode deposition. The inside of the apparatus was evacuated until the degree of vacuum in the apparatus was 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less. As the cathode, first, lithium fluoride (LiF) was used at a deposition rate of 0.1 nm / second, a degree of vacuum of 7.0 × 10 ⁻⁶ Torr (about 9.3 × 10 ⁻⁴ Pa) using a molybdenum boat, and 0 A film having a thickness of 0.5 nm was formed on the light emitting layer. Next, aluminum was heated in the same molybdenum boat, deposition rate 0.5 nm / sec, the degree of vacuum 1 × ¹⁰ -5 Torr (about 1.3 × ¹⁰ - 3Pa) an aluminum layer having a thickness of 80nm was formed by The cathode was completed. The substrate temperature at the time of vapor deposition of the above two-layer cathode was kept at room temperature. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. The light emission characteristics of this element are shown in Table 2.

(Example 5)
With the composition described in Reference Example 2, the hole transporting polymer (P1) and PPB were dissolved in cyclohexanone as a solvent, and then stored at 23 ° C. for 5 hours. An organic electroluminescent device having the same structure as that of the organic electroluminescent device 100c shown in FIG. 1C is manufactured in the same manner as in Example 4 except that the hole injection layer is formed by forming a film under the same conditions. did. The light emission characteristics of this element are shown in Table 2.
From Table 2, the driving voltage is almost equal to the device described in Example 4, and the coating composition prepared by the method described in Reference Example 2 has an organic electric field having the same characteristics even when stored at 23 ° C. for 5 hours. It can be seen that a light emitting element was obtained.

(Comparative Example 2)
In the composition described in Reference Example 2, after dissolving the hole transporting polymer (P1) and PPB in cyclohexanone as a solvent, the composition solution stored in the dark for 24 hours at 23 ° C. was used as a reference example. Organic electroluminescence having the same structure as that of the organic electroluminescent device 100c shown in FIG. 1 (c) except that the hole injection layer was formed by forming the film under the same conditions as in FIG. An element was produced. The light emission characteristics of this element are shown in Table 2.
It can be seen that the drive voltage of this element was higher than that of the element described in Example 4.

(Example 6)
An organic electroluminescent device having the same structure as the organic electroluminescent device 100b shown in FIG. 1B was produced by the following method.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 120 nm (manufactured by Geomat Corp .; electron beam film-formed product; sheet resistance 15 Ω) is 2 mm wide using ordinary photolithography technology and hydrochloric acid etching. The anode was formed by patterning into stripes. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

First, in the method described in Reference Example 3, a hole transporting polymer (P2) and TBPAH as an electron-accepting compound were dissolved as a coating solution in cyclohexanone as a solvent, and a hole injection layer was formed after 30 minutes. This was applied to form a 15 nm-thick hole injection layer. Next, the substrate on which the hole injection layer was applied and formed was placed in a vacuum evaporation apparatus. An oil diffusion pump equipped with a liquid nitrogen trap until the degree of vacuum in the apparatus becomes 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less after rough exhaust of the above apparatus by an oil rotary pump Was evacuated. An aromatic amine compound represented by the following structural formula (H2), 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, heated in a ceramic crucible placed in the apparatus was heated. The vapor deposition was performed. The degree of vacuum during deposition is 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition rate is 0.3 nm / second, and a 40 nm-thick film is stacked on the hole injection layer. Thus, a hole transport layer was completed.

Subsequently, a compound (E1) was deposited as a material for the light emitting layer. At this time, the temperature of the crucible was controlled in the range of 282 to 294 ° C. The degree of vacuum during the deposition was 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition rate was 0.1 to 0.3 nm / second, and the deposition time was 5 minutes and 5 seconds. . As a result, a light emitting layer having a thickness of 60 nm was formed. The substrate temperature during vacuum deposition of the hole transport layer and the light emitting layer was kept at room temperature.

Here, a striped shadow mask having a width of 2 mm is used as a cathode vapor deposition mask with the element deposited up to the light-emitting layer in close contact with the element so as to be orthogonal to the ITO stripe of the anode, and in another vacuum deposition apparatus. It was evacuated until the degree of vacuum in the apparatus was 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less. As the cathode, first, lithium fluoride (LiF) was used at a deposition rate of 0.1 nm / second, a degree of vacuum of 7.0 × 10 ⁻⁶ Torr (about 9.3 × 10 ⁻⁴ Pa) using a molybdenum boat, and 0 A film having a thickness of 0.5 nm was formed on the light emitting layer. Next, aluminum is similarly heated by a molybdenum boat to form an aluminum layer having a thickness of 80 nm at a deposition rate of 0.5 nm / second and a degree of vacuum of 1 × 10 ⁻⁵ Torr (about 1.3 × 10 ⁻³ Pa). Thus, the cathode was completed. The substrate temperature at the time of vapor deposition of the above two-layer cathode was kept at room temperature.
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. Table 3 shows the light emission characteristics of the device.

(Comparative Example 3)
With the composition described in Reference Example 4, the hole-transporting polymer (P2) and TBPAH were dissolved in chloroform as a solvent, and after 30 minutes, a film was formed under the same conditions as in Reference Example 4 to inject holes. An organic electroluminescent element having the same structure as the organic electroluminescent element 100b shown in FIG. 1B was produced in the same manner as in Example 6 except that the layer was formed. Table 3 shows the light emission characteristics of the device. From the results shown in Table 3, it can be seen that the drive voltage of this element was higher than that of the element described in Example 6.

  A composition for an organic electroluminescent element and an organic electroluminescent element to which the present invention is applied include a light source (for example, a copier) utilizing characteristics of a flat panel display (for example, for an OA computer or a wall-mounted television) or a surface light emitter. Application to light sources for LCDs, backlight sources for liquid crystal displays and instruments), display panels, and sign lamps.

1 (a) to 1 (c) illustrate an organic electroluminescent device having a thin layer formed by a wet film forming method using the composition for organic electroluminescent device to which the present embodiment is applied. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100a, 100b, 100c ... Organic electroluminescent element, 101 ... Substrate, 102 ... Anode, 103 ... Hole injection layer, 104 ... Hole transport layer, 105 ... Light emitting layer, 106 ... Electron transport layer, 107 ... Cathode

Claims (8)

A hole injection / transport material and / or an electron-accepting compound forming at least one of the hole injection layer and the hole transport layer of the organic electroluminescence device;
In the composition containing the hole injecting / transporting material and / or the solvent for dissolving the electron accepting compound,
The concentration of the deactivating substance for deactivating the hole injecting / transporting material and / or the electron accepting compound or the compound for generating the deactivating substance contained in the composition is 1% by weight or less. The composition for organic electroluminescent elements characterized by these.   2. The composition for an organic electroluminescence device according to claim 1, wherein at least one of the deactivating substance or the compound generating the deactivating substance is an alcohol solvent, an aldehyde solvent or a ketone solvent. Stuff.   3. The composition for an organic electroluminescent element according to claim 1, wherein at least one of the deactivating substance or the compound that generates the deactivating substance is a protonic acid or a halogen-based solvent.   4. The organic electroluminescent element according to claim 1, wherein the hole injecting / transporting material is an aromatic amine compound, and the electron accepting compound is an aromatic boron compound. 5. Composition.   5. The composition for an organic electroluminescent element according to claim 1, wherein a water concentration in the composition is 1% by weight or less. In an organic electroluminescent device in which at least an anode, a hole injection layer, a hole transport layer, a light emitting layer and a cathode are laminated on a substrate,
6. At least one of the hole injection layer and the hole transport layer is formed by a wet film forming method using the composition for organic electroluminescent elements according to any one of claims 1 to 5. An organic electroluminescent element characterized by the above. An anode forming step of forming an anode on the substrate;
A hole injection layer forming step of forming a hole injection layer containing a hole injection / transport material and an electron accepting compound on the upper layer of the formed anode;
A light emitting layer forming step of forming a light emitting layer directly or through another layer on the hole injection layer formed;
A cathode forming step for forming a cathode directly or via another layer on the formed light emitting layer; and
In the hole injection layer forming step, after preparing a composition containing the hole injecting / transporting material and the electron accepting compound, the wet injection film forming method using the composition is performed within 20 hours. A method for producing an organic electroluminescent device, comprising forming a hole injection layer.   The said composition is the composition for organic electroluminescent elements of any one of Claims 1 thru | or 5, The manufacturing method of the organic electroluminescent element of Claim 7 characterized by the above-mentioned.

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