JP2005174921A - Manufacturing method of organic electroluminescent element and organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an organic electroluminescent element for enhancing light emitting luminance and light emitting efficiency. <P>SOLUTION: The organic electroluminescent element comprises a pair of electrodes composed of a cathode and an anode at least one of which is transparent or semi-transparent, and an organic compound layer held between the pair of electrodes composed of two or more layers. The manufacturing method of the organic electroluminescent element comprises at least an organic thin film lamination process laminating the organic thin film, and an organic solvent contact process making an organic solvent contact with an exposed surface of the organic thin film formed by laminating at least two organic thin films. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention opens to a method for producing an organic electroluminescent element and an organic electroluminescent element produced using the method.

  An electroluminescent element (hereinafter referred to as an “EL element”) is a self-luminous all-solid-state element, and is highly visible and resistant to impacts. However, as the conventional EL elements, those using inorganic phosphors are the mainstream. For example, Zn, CaS, SrS, etc., which are inorganic material II-VI group compound semiconductors, are generally doped with rare earth elements such as Mn, Eu, Ce, Tb, Sn, which are luminescent centers, An EL element manufactured using an inorganic material has problems such as high manufacturing cost because it requires an AC voltage of 200 V or more for driving, difficulty in full color, and insufficient luminance. .

However, in recent years, Tang et al. Have devised an EL device in which two extremely thin layers (a charge transport layer and a light-emitting layer) are laminated between an anode and a cathode by vacuum deposition, and achieve high brightness with a low driving voltage. Realized (see Non-Patent Document 1). This type of stacked organic EL device has been actively studied since then.
Furthermore, an EL element having a three-layer structure in which charge transport and light emission functions are separated has been reported. In such an EL element, the restriction of charge transport performance is eased even when selecting the dye of the light emitting layer that determines the light emission color, so that the degree of freedom in selecting the dye increases, and further, holes and electrons ( It is also suggested that light emission may be improved by effectively confining excitons).

Through the progress of such research and development, the organic EL element can emit light at a direct current low voltage of several volts to several tens of volts, and various colors (by selecting the type of the fluorescent organic compound) For example, it has become possible to emit red, blue, green).
In addition, in order to solve the problem regarding the thermal stability of the EL element, a starburst amine that can obtain a stable amorphous glass state is used as a hole transport material (for example, see Non-Patent Document 2), polyphosphazene The use of a polymer in which triphenylamine is introduced into the side chain has been reported (for example, see Non-Patent Document 3).
The organic EL element having the above characteristics is expected to be applied to various light emitting elements, display elements and the like.
App1. Phys. Lett. 51,913 (1987) Proceedings of the 40th Joint Conference on Applied Physics 30a-SZK-14 (1993) 42nd Polymer Symposium Proceedings 20J21 (1993)

However, conventional organic EL elements are still insufficient in terms of light emission luminance and light emission efficiency, and further improvements have been demanded.
The present invention has been made in view of the above problems, and its object is to provide a method for producing an organic EL element capable of further increasing the light emission luminance and light emission efficiency, and an organic material produced using the method. It is an object to provide an electroluminescent element.

In order to achieve the above-mentioned problems, the present inventors have focused on the configuration of the organic EL element and have made studies as described below.
That is, a general organic EL element has a hole transport layer, a light emitting layer, and an organic compound layer in which an electron transport layer is laminated on these layers. On the other hand, when driving the organic EL element, the movement of electric charges between the respective layers constituting the organic compound layer becomes important.

Here, the inventors of the present invention have found that the movement of charges between the layers constituting the organic compound layer is not the contact between the physical layer and the layer other than the energy level of the material constituting each layer. The state, that is, the affinity between layers provided in contact with each other, was considered important. Furthermore, if the affinity between the layers provided in contact with each other is poor, charge accumulation, etc. may occur, which will have a very large effect on the electrical characteristics of the organic EL element and may ultimately have a negative effect on the light emission characteristics. I thought there was.
The present inventors have found the following present invention based on the above-described assumption. That is, the present invention

<1> a pair of electrodes composed of an anode and a cathode, at least one of which is transparent or translucent, and an organic compound layer composed of two or more layers sandwiched between the pair of electrodes,
In the method of manufacturing an organic electroluminescent element, the organic compound layer is formed through at least an organic thin film stacking step of stacking an organic thin film.
An organic electroluminescent element manufacturing method comprising an organic solvent contact step of bringing an organic solvent into contact with an exposed surface of an organic thin film laminate formed by laminating at least two organic thin films.

    <2> The method for producing an organic electroluminescent element according to <1>, wherein the organic solvent contact step is performed by exposing an exposed surface of the organic thin film laminate to the vapor of the organic solvent. is there.

    <3> The organic electroluminescent element production according to <1>, wherein the organic solvent contact step is performed by applying the liquid organic solvent to the exposed surface of the organic thin film laminate. Is the method.

    <4> The method for producing an organic electroluminescent element as described in <1>, wherein at least one organic thin film constituting the organic thin film laminate is formed by a dry film forming method.

    <5> The method for producing an organic electroluminescent element according to <4>, wherein the dry film-forming method is a vapor deposition method.

<6> a pair of electrodes composed of an anode and a cathode, at least one of which is transparent or translucent, and an organic compound layer composed of two or more layers sandwiched between the pair of electrodes,
In the organic electroluminescence device in which the organic compound layer is formed through at least an organic thin film stacking step of stacking an organic thin film,
An organic electroluminescence device comprising an organic solvent contact step of bringing an organic solvent into contact with an exposed surface of an organic thin film laminate formed by laminating at least two organic thin films.

    <7> The organic electroluminescent element according to <6>, wherein the organic compound layer includes at least a hole transport layer and a light emitting layer, and the hole transport layer includes a polymer hole transport material. It is.

    <8> The organic compound layer includes an electron transport layer, and has a layer configuration in which the hole transport layer, the light emitting layer, and the electron transport layer are stacked in this order. This is an organic electroluminescent element.

    <9> The organic electroluminescent element according to <7>, wherein the light emitting layer contains an organic low molecular weight material.

［但し、一般式（Ｉ−１）及び（Ｉ−２）中、Ａｒは置換もしくは未置換の芳香環数１〜１０の１価の多核芳香環、または、置換もしくは未置換の芳香環数２〜１０の１価の縮合芳香環を表し、Ｘは置換または未置換の２価の芳香族基を示し、ｋ、ｌはそれぞれ０又は１を示し、Ｔは炭素数１〜１０の直鎖状の２価の炭化水素基または炭素数１〜１０の分枝状の２価の炭化水素基を示す。］ <10> The polymer hole transport material includes at least one selected from structures represented by the following general formulas (I-1) and (I-2) in a repeating unit structure. The organic electroluminescence device according to <7>.

[In the general formulas (I-1) and (I-2), Ar represents a substituted or unsubstituted monovalent polynuclear aromatic ring having 1 to 10 aromatic rings, or a substituted or unsubstituted aromatic ring number 2. Represents a monovalent condensed aromatic ring of 10 to 10, X represents a substituted or unsubstituted divalent aromatic group, k and l each represents 0 or 1, and T represents a straight chain having 1 to 10 carbon atoms. Or a branched divalent hydrocarbon group having 1 to 10 carbon atoms. ]

［但し、一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）及び（Ｖ）中、Ａは、前記一般式（Ｉ−１）又は（Ｉ−２）を表し、Ｂは、−Ｏ−（Ｙ’−Ｏ）ｍ’−、又は、Ｚ’を示し、Ｙ、Ｙ’、Ｚ、Ｚ’は２価の炭化水素基を表し、ｍ、ｍ’は１〜５の整数を表し、ｎは０又は１を表し、ｐは５〜５００の整数を表し、ｑは１〜５０００の整数を表し、ｒは１〜３５００の整数を表す。］ <11> The polymer hole transport material includes any one selected from repeating structures represented by the following general formulas (II), (III), (IV) and (V) <10>.

[In the general formulas (II), (III), (IV) and (V), A represents the general formula (I-1) or (I-2), and B represents —O— (Y '-O) m'- or Z', Y, Y ', Z, Z' represents a divalent hydrocarbon group, m, m 'represents an integer of 1-5, and n is 0. Or 1 is represented, p represents the integer of 5-500, q represents the integer of 1-5000, r represents the integer of 1-3500. ]

  As described above, according to the present invention, it is possible to provide a method for manufacturing an organic EL element that can further increase the light emission luminance and the light emission efficiency, and an organic electroluminescent element manufactured using the method. .

  The method for producing an organic electroluminescent element of the present invention comprises a pair of electrodes composed of an anode and a cathode, at least one of which is transparent or translucent, and an organic compound layer composed of two or more layers sandwiched between the pair of electrodes; And the organic compound layer is formed by laminating at least two organic thin films in a method for producing an organic electroluminescent element, wherein the organic compound layer is formed through at least an organic thin film laminating step of laminating organic thin films. It includes an organic solvent contact step of bringing an organic solvent into contact with the exposed surface of the laminate.

Therefore, the organic EL device produced by using the method for manufacturing an organic electroluminescent device of the present invention has better emission luminance and luminous efficiency than an organic electroluminescent device having the same organic compound layer structure. Can be obtained.
The method for producing an organic electroluminescent element of the present invention has an organic compound layer sandwiched between a pair of electrodes as described above, and the organic compound layer has two or more layers (that is, a single layer). If it is an organic electroluminescent element which has a layer structure of two or more layers instead of the above layer, it can be applied without particular limitation.

In addition, the organic compound layer is formed through at least an organic thin film laminating step of laminating an organic thin film, but the method for forming individual layers (organic thin film) constituting the organic compound layer is not particularly limited, and a known film formation It can be formed using the law. Further, the method for laminating the organic thin film is not particularly limited. For example, the organic thin film may be sequentially laminated on the electrode layer formed on the substrate by using a vapor phase film forming method or a liquid phase film forming method. Often, an organic thin film (including a laminate of two or more layers) formed in advance on a substrate is transferred onto an electrode layer or an organic thin film already formed on the electrode layer. It can also be laminated by.

On the other hand, an organic solvent contact process is performed by making an organic solvent contact the exposed surface of the organic thin film laminated body formed by laminating | stacking an organic thin film of at least 2 layers.
However, “organic thin film laminate” means a layer in which at least two organic thin films are laminated among each layer (organic thin film) constituting the organic compound layer, and is not necessarily the number of layers constituting the organic compound layer. Need not be the same. In other words, the organic solvent contacting step can be performed in the middle of the organic thin film stacking step.
For example, when the organic compound layer has a three-layer structure, the organic solvent contact step is performed at the time when the second layer is stacked (that is, on the organic thin film stack in which two organic thin films are stacked). Thereafter, an organic compound layer can be formed by forming a third layer. Of course, it is also possible to further carry out the organic solvent contact step after forming the third layer. In terms of work efficiency, an organic solvent contact step is performed after all the layers constituting the organic compound layer are stacked (that is, for an organic thin film stack having the same layer configuration as the organic compound layer). It is preferable to do.

  In carrying out the organic solvent contact step, the organic thin film laminate is in a state where at least one of the principal surfaces intersects perpendicularly to the film thickness direction can be in contact with the atmosphere (that is, exposed). Surface). The “state capable of being contacted with the atmosphere” is used not only in a state where the main surface is not completely covered with any solid matter but also in a porous body such as a sponge or an organic solvent contact step. A state in which the organic solvent molecules are covered with a gas-permeable film that can at least permeate the organic solvent molecules is also included. In addition, in addition to the main surface, a surface (side surface) parallel to the film thickness direction can be used as an exposed surface in the organic solvent contact step as long as it is in contact with the atmosphere.

Here, “the organic solvent is brought into contact immediately after the organic thin film stack is exposed” means that the organic solvent molecules are in contact with the exposed surface of the organic thin film stack, and from this exposed surface to the inside of the organic thin film stack. It means that it can penetrate and reach the interface between organic thin films.
Such an organic solvent contacting step includes, for example, [1] exposing the exposed surface of the organic thin film stack to vapor of the organic solvent, and [2] applying a liquid organic solvent to the exposed surface of the organic thin film stack. [3] Spraying the mist of the organic solvent on the exposed surface of the organic thin film laminate, [4] Contacting the exposed surface of the organic thin film laminate with a carrier such as a sponge impregnated with the organic solvent, etc. However, the present invention is not limited to this, and any method can be used as long as the organic solvent molecules can reach the interface between the organic thin films through the exposed surface of the organic thin film stack. Can also be implemented.
Since the organic compound layer is thin enough, the organic solvent molecules can easily reach the interface between the organic thin films unless the organic solvent is brought into contact with the exposed surface of the organic thin film stack, especially under extreme conditions. can do.

Moreover, as an organic solvent used for an organic-solvent contact process, all can be used if it is a well-known organic solvent. However, when selecting the organic solvent to be used, it is preferable to use a solvent capable of dissolving the main material constituting each layer (organic thin film) constituting the organic thin film laminate.
In consideration of the above-described viewpoint and various materials constituting the organic compound layer, the organic solvent used in the organic solvent contact step includes monochlorobenzene, cyclohexanone, tetrahydrofuran, toluene, cyclohexane, It is preferable to use p-xylene, o-xylene, m-xylene, 1,4-dioxane, methylene chloride, chloroform, 2-butanone, 2-methyl-4-pentanone, and the like.
Two kinds of organic solvents can be used as required. In this case, for example, in one organic solvent contact step, a solvent obtained by mixing two or more types of organic solvents may be used, or the organic solvent contact step may be repeated using different types of organic solvents.

The organic EL device produced by using the method for producing an organic electroluminescent device of the present invention can obtain more excellent light emission luminance and light emission efficiency. It is estimated that this is because the affinity between the layers constituting the layers (two adjacent layers provided) is improved.
The improvement of the affinity between the layers and the improvement of the light emission luminance and the light emission efficiency due to the improvement of the affinity are not sufficiently grasped at present, but the present inventors speculate as follows. Yes.

  That is, the improvement of the affinity between layers is facilitated by the movement of the material molecules constituting each layer by the permeation of organic solvent molecules from the exposed surface of the organic thin film stack, and the familiarity at the interface between the layers. This is considered to be because the condition (for example, interdiffusion of material molecules constituting each layer, loss or reduction of some interface defects due to movement of material molecules constituting each layer) is promoted. In addition, it is presumed that the light emission efficiency is improved as a result of facilitating such familiarity, since electric charges are easily transferred between the layers.

In addition, based on such a hypothesis, it is thought that the manufacturing method of the organic electroluminescent element of this invention can exhibit an effect more in the case which is demonstrated below.
That is, [1] In the case where at least one organic thin film constituting the organic thin film laminate is formed by a dry film forming method, or, further, a two-layer organic thin film forming either interface When both are formed by the dry protection method, [2] When all the organic thin films constituting the organic thin film stack are formed by the wet protection method, the two layers forming either interface are formed. The case where compatibility or affinity between organic thin films is bad is mentioned.
In such a case, it is considered that the affinity between adjacent layers is originally low. Therefore, by applying the organic electroluminescent device manufacturing method of the present invention, This is because there is a large room for improving the affinity between the two.

  In the present invention, the wet film forming method means a method of forming an organic thin film using a solution in which a material constituting the organic thin film is dissolved in a solvent. For example, a dipping method, a spin coating method, or a spray coating method is used. Method, roll coating method and the like. Further, the dry film forming method means a method of forming an organic thin film without using any solvent that dissolves the material constituting the organic thin film, and examples thereof include vapor phase film forming methods such as vapor deposition. Moreover, the method etc. which apply | coat in the state which heat-melted and liquefied the material which forms an organic thin film are also mentioned.

Next, the organic electroluminescent element of the present invention will be described. The organic electroluminescent element of the present invention includes a pair of electrodes composed of an anode and a cathode, at least one of which is transparent or translucent, and an organic compound layer composed of two or more layers sandwiched between the pair of electrodes. The organic compound layer is formed through at least an organic thin film stacking step of stacking organic thin films. Here, the organic electroluminescent element of the present invention is manufactured using the above-described method for manufacturing the organic electroluminescent element of the present invention.
Therefore, since the organic electroluminescent element of the present invention is produced using the above-described method for producing the organic electroluminescent element of the present invention, higher luminous efficiency and luminous efficiency can be obtained. Details of the layer configuration of the organic electroluminescent element of the present invention, materials constituting each layer, and the like will be described in detail below.

  First, the layer structure of the organic EL element of the present invention will be described in detail. The organic EL device of the present invention comprises a pair of electrodes, at least one of which is transparent or translucent, and an organic compound layer composed of two or more layers sandwiched between the electrodes. Here, at least one layer of the organic compound layer is a light emitting layer, and the other layer is formed of a charge transport layer such as a hole transport layer and / or an electron transport layer.

Next, the configuration of the organic EL element of the present invention will be specifically described with reference to the drawings.
1 and 2 are dual cross-sectional views showing an example of the configuration of the organic EL device of the present invention. In FIGS. 1 and 2, 1 is a transparent insulator substrate, 2 is a transparent electrode, and 3 is a hole transport layer. Reference numeral 4 denotes a light emitting layer, 5 denotes an electron transport layer, and 6 denotes a back electrode.
Here, the organic EL element shown in FIG. 1 has a structure in which a transparent electrode 2, a hole transport layer 3, a light emitting layer 4, and a back electrode 6 are sequentially laminated on a transparent insulator substrate 1. FIG. The organic EL element shown has a configuration in which a transparent electrode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a back electrode 6 are sequentially laminated on a transparent insulator substrate 1.

Hereinafter, details of materials of each layer used in the organic EL element having the configuration shown in FIGS. 1 and 2, a method of forming each layer, and the like will be described in detail.
First, charge transport materials (hole transport material, electron transport material) used for charge transport of each layer constituting the organic compound layer will be described. A polymer charge transport material can be used as the charge transport material used in the present invention.
As such a polymer charge transport material, a material containing at least one selected from the structures represented by the following general formulas (I-1) and (I-2) in the repeating unit structure is preferable. However, the present invention is not limited to this. The polymer charge transporting material containing at least one selected from the structures represented by the following general formulas (I-1) and (I-2) in the repeating unit structure is a hole transporting property (polymer More preferably, it is a hole transport material.

However, in the general formulas (I-1) and (I-2), Ar is a substituted or unsubstituted monovalent polynuclear aromatic ring having 1 to 10 aromatic rings, or a substituted or unsubstituted aromatic ring having 2 to 2 aromatic rings. 10 represents a monovalent condensed aromatic ring, X represents a substituted or unsubstituted divalent aromatic group, k and l each represents 0 or 1, and T represents a linear chain having 1 to 10 carbon atoms. A divalent hydrocarbon group or a branched divalent hydrocarbon group having 1 to 10 carbon atoms is shown.

In the present invention, the polynuclear aromatic ring and the condensed aromatic ring specifically mean an aromatic hydrocarbon as defined below.
That is, the “polynuclear aromatic ring” represents a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present, and the aromatic rings are bonded by a carbon-carbon bond. Specific examples include biphenyl and terphenyl. The “condensed aromatic ring” represents a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present and the aromatic rings share a pair of carbon atoms. Specific examples include naphthalene, anthracene, phenanthrene and fluorene.

Examples of the substituent on the polynuclear aromatic ring or condensed aromatic ring include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a substituted amino group, a halogen atom and the like.
As an alkyl group, a C1-C10 thing is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned. As an alkoxyl group, a C1-C10 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned.

As the aryl group, those having 6 to 20 carbon atoms are preferable, and examples thereof include a phenyl group and toluyl group. As the aralkyl group, those having 7 to 20 carbon atoms are preferable, and examples thereof include benzyl group and phenethyl group. Is mentioned.
Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, an aralkyl group, and the like, and specific examples are as described above.
Examples of the substituent for the substituted aryl group and the substituted aralkyl group include a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, and a halogen atom.

  In general formulas (I-1) and (I-2), X represents a substituted or unsubstituted divalent aromatic group, specifically, a group selected from the following formulas (1) to (7) Is mentioned.

In the formula (1) ~ (7), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted aralkyl group,, R ₂ ~ R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom, 0 or 1 is meant, and V represents a group selected from the following formulas (8) to (17).

  However, in formula (8)-(17), b means the integer of 1-10, c means the integer of 1-3.

  In general formulas (I-1) and (I-2), T is a linear divalent hydrocarbon group having 1 to 10 carbon atoms or a branched divalent hydrocarbon group having 1 to 10 carbon atoms. A hydrocarbon group is shown. In addition, when T is linear, carbon number is preferably in the range of 1-6, more preferably in the range of 2-6, and when it is branched, the carbon number is in the range of 2-10. Is preferable, and the range of 3-7 is more preferable. Examples of the specific structure of the group represented by T (hydrocarbon group T-1 to hydrocarbon group T-32) are shown below.

Specific examples of the partial structure represented by the general formula (I-1) are shown in Tables 1 to 9 (partial structure 1-1 to partial structure 1-56), and also represented by the general formula (I-2). Specific examples of the partial structure are shown in Tables 10 to 15 (partial structure 2-1 to partial structure 2-42).
In addition, the symbol shown in the column of “T” in Tables 1 to 15 means the numbers (T-1 to T-32) given to the structural formulas of the hydrocarbon groups specifically shown above.

  The polymer charge transport material containing at least one or more selected from the structures represented by the general formulas (I-1) and (I-2) as described above in the repeating unit structure is as follows. The charge transporting polyester or charge transporting polycarbonate having a repeating structure represented by any one of formulas (II), (III), (IV) and (V) is more preferable.

  However, in general formula (II), (III), (IV) and (V), A represents the said general formula (I-1) or (I-2), B represents -O- (Y ' -O) m'- or Z ', Y, Y', Z, Z 'represents a divalent hydrocarbon group, m, m' represents an integer of 1-5, and n is 0 or 1 is represented, p represents the integer of 5-500, q represents the integer of 1-5000, r represents the integer of 1-3500.

  Y, Y ′, Z, and Z ′ each represent a divalent hydrocarbon group, and specific examples include hydrocarbon groups represented by the following formulas (18) to (24).

In the formulas (18) to (24), R ₁₃ and R ₁₄ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, substituted Or an unsubstituted alkyl group or a halogen atom is represented, d and e show the integer of 1-10, f and g show 0, 1 or 2, h and i show 0 or 1.

Specific examples of the polymer charge transport material represented by the general formula (II) are shown in Table 16 (Compound CPT-1 to Compound CPT22), and specific examples of the polymer charge transport material represented by the general formula (III) are shown below. Table 17 (compound CPT-23 to compound CPT-28) shows specific examples of the polymer charge transport material represented by the general formula (IV) in Table 18 (compound CPT-29 to compound CPT-35). Specific examples of the polymer charge transporting material represented by V) are shown in Tables 19 to 22 (Compound CPT-36 to Compound CPT-107).
In addition, the column of “partial structure” in Tables 16 to 22 shows the structure A shown in the general formulas (II) to (V), and the numbers described in these columns are the numbers in Tables 1 to 15 Means the number shown in the “partial structure” column.

  When the polymer charge transporting material used in the present invention is an electron transporting property (polymeric electron transporting material), one or more of partial structures represented by the following general formula (X) are repeatedly included as a unit structure. Polymers can be preferably mentioned.

However, in the general formula (X), Ar ₁ , Ar ₂ and Ar ₃ each independently represent a substituted or unsubstituted arylene group, a divalent heterocyclic group, or a group consisting of a combination thereof, T ₁ , T ₂ represents a linear divalent hydrocarbon group having 1 to 10 carbon atoms or a branched divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 5.

The arylene group constituting Ar ₁ , Ar ₂ , and Ar ₃ is preferably a monocyclic or condensed arylene group having 6 to 60 carbon atoms, more preferably 6 to 40 carbon atoms, still more preferably 6 to 30 carbon atoms. Of the arylene group.

Specific examples of the arylene group constituting Ar ₁ , Ar ₂ and Ar ₃ include phenylene, biphenylene, triphenylene, tetraphenylene, naphthalenediyl, anthracenediyl, phenanthrolinediyl, pyrenediyl, triphenylenediyl, benzophenanthrolinediyl, perylenediyl, pentaphenylene Examples thereof include diyl and pentacenediyl, and phenylene, biphenylene, naphthalenediyl, anthracenediyl, pyrenediyl, and perylenediyl are preferable, and phenylene, biphenylene, and triphenylene are particularly preferable.

The divalent heterocyclic group constituting Ar ₁ , Ar ₂ , Ar ₃ is preferably a monocyclic or condensed heterocyclic group having 4 to 60 carbon atoms, more preferably a nitrogen atom, an oxygen atom or sulfur. It is a monocyclic or condensed heterocyclic group having 4 to 60 carbon atoms containing at least one atom, and more preferably a 5- or 6-membered heterocyclic group having 4 to 30 carbon atoms.

Specific examples of the divalent heterocyclic group constituting Ar ₁ , Ar ₂ , Ar ₃ include pyrrole diyl, frangyl, thienylene, pyridinediyl, pyridazinediyl, pyrimidinediyl, pyrazinediyl, quinolinediyl, isoquinolinediyl, cinnolinediyl, quinazolinediyl, Quinoxaline diyl, phthalazine diyl, pteridine diyl, acridine diyl, phenazine diyl, phenanthroline diyl and the like can be mentioned. Is theenylene or pyridinediyl.

The arylene group or heterocyclic group constituting Ar ₁ , Ar ₂ , and Ar ₃ may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom). -12, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. And an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl and p-methylphenyl). ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino). , Dibenzylamino, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms)
More preferably, it has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy), acyl. A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl), an alkoxycarbonyl group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, and the like, and an aryloxycarbonyl group (preferably 7 carbon atoms). To 20 and more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms. And an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy). ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms For example, phenyloxycarbonylamino, etc.), sulfonylamino groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino, benzene Sulfonylamino, etc.), a sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfuryl). And carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, carbamoyl, methylcarbamoyl, Examples include diethylcarbamoyl and phenylcarbamoyl. It is done. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably carbon 6 to 20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably carbon atoms). 1 to 16, particularly preferably 1 to 12 carbon atoms such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon atoms). 1 to 12, for example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably having 1 to 1 carbon atoms) 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably It has 1 to 12 carbon atoms, and the hetero atom is a nitrogen atom, an oxygen atom, or a sulfur atom, specifically an imidazoli , Pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benztheazolyl, etc.), a silyl group (preferably 3 to 40, more preferably 3 to 30 carbon atoms, particularly preferably carbon number). 3 to 24, and examples thereof include trimethylsilyl and triphenylsilyl).

These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.
As the substituent for further substituting the substituent of the heterocyclic group described above, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a cyano group, a hetero group is preferable. A cyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group and a heterocyclic group, and still more preferably an aryl group and an aromatic heterocyclic group.

The heterocyclic group represented by Ar ₂ is preferably a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O or S atoms, and these are monocyclic. Alternatively, a condensed ring may be formed with another ring.

  Specific examples of such heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, triazole, triazine, indole, indazole, purine, thiazoline, Thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazain Den and the like.

More preferable heterocyclic group represented by Ar ₂ is a 5- to 6-membered aromatic heterocyclic group, more preferably thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrimidine, thiazole, thiadiazole, oxazole, Oxadiazole, quinoline, benzimidazole, benzoxazole, and benzthiazole are preferable, and thiophene, furan, pyridine, pyrimidine, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, and quinoline are more preferable.

T ₁ and T _{2 each} represents a linear divalent hydrocarbon group having 1 to 10 carbon atoms or a branched divalent hydrocarbon group having 1 to 10 carbon atoms, and having 1 to 4 carbon atoms. More preferably within the range. Specific examples include methylene group, ethylene group, propylene group, butylene group and the like.

Specific examples of the polymer electron transport material represented by the general formula (X) are shown in Tables 23 to 39 (Compound No. (1) to Compound No. (119)).

Next, each component of the organic EL element shown in FIG. 1 and FIG.
The transparent insulator substrate 1 is preferably transparent in order to extract emitted light, and glass, plastic film or the like is used. The transparent electrode 2 is preferably transparent so as to extract emitted light in the same manner as the transparent insulator substrate, and preferably has a high work function for injecting holes. Indium tin oxide (ITO), tin oxide (NESA), An oxide film such as indium oxide or zinc oxide, and gold, platinum, palladium, or the like deposited or sputtered is used.

  In the organic EL element as shown in FIG. 1, a compound that exhibits a high fluorescence quantum yield in the solid state is used as the light emitting material for the light emitting layer 4. When the light-emitting material is an organic low-molecular material, it is a condition that a favorable thin film can be formed by applying and drying a solution or dispersion containing a low-molecular material and a binder resin. In addition, when the luminescent material is a polymer, it is a condition that a good thin film can be formed by applying and drying a solution or dispersion containing itself.

  When the light-emitting material is a low-molecular-weight organic material, preferably a chelate-type organometallic complex, a polynuclear or condensed aromatic ring compound, a perylene derivative, a coumarin derivative, a styrylarylene derivative, a silole derivative, an oxazole derivative, an oxathiazole derivative, an oxadiazole derivative In the case where the light emitting material is a low-molecular organic material, a polyparaphenylene derivative, a polyparaphenylene vinylene derivative, a polythiophene derivative, a polyacetylene derivative, or the like is preferably used. As preferred specific examples, the following compounds (VI-1) to (VI-15) are used, but are not limited thereto.

  In addition, for the purpose of improving the durability of the organic EL element or improving the light emission efficiency, the light emitting material may be doped with a dye compound different from the light emitting material as a guest material. When the light emitting layer 4 is formed by vacuum deposition, doping is performed by co-evaporation, and when the light emitting layer 4 is formed by applying and drying a solution or dispersion, doping is performed by mixing in the solution or dispersion. .

  The doping ratio of the dye compound in the light emitting layer 4 is about 0.001 to 40% by weight, preferably about 0.001 to 10% by weight. As the dye compound used for such doping, an organic compound that is compatible with the light emitting material and does not hinder the formation of a good thin film of the light emitting layer 4 is used, and preferably a DCM derivative, a quinacridone derivative, rubrene. Derivatives, porphyrins and the like are used. Preferable specific examples of such a compound include, but are not limited to, the following compounds (VII-1) to (VII-4).

  In addition, as a light emitting material, an organic EL element can be used in the case where a material that does not become a good thin film or that does not show a clear electron transport property can be applied by vacuum deposition, solution or dispersion, or drying. For the purpose of improving the durability or the luminous efficiency, an electron transport layer 5 may be inserted between the light emitting layer 4 and the back electrode 6 as in the organic EL element shown in FIG.

  As an electron transport material used for such an electron transport layer, an organic compound capable of forming a good thin film by a vacuum deposition method is used, and preferably an oxadiazole derivative, a nitro-substituted fluorenone derivative, a diphenoquinone derivative, a thiopyran. Dioxide derivatives, fluorenylidenemethane derivatives and the like are used. Preferred specific examples include, but are not limited to, the following compounds (VIII-1) to (VIII-3) and (IX).

  For the back electrode 6, a metal that can be vacuum-deposited and has a small work function is used for electron injection, but magnesium, aluminum, silver, indium, and alloys thereof are particularly preferable.

Hereinafter, the present invention will be described by way of examples. In addition, this invention is not limited only by these Examples.
(Example 1)
A 5 wt% dichloroethane solution of the following exemplary compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ] was prepared, and polytetrafluoroethylene (PTFE) having an opening of 0.1 μm. Filtered with a filter. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.

After sufficiently drying, the compound (VI-1) purified by sublimation as a luminescent material was put in a tungsten boat and evaporated by a vacuum evaporation method to form a luminescent layer having a thickness of 0.05 μm on the hole transport layer. . The degree of vacuum at this time was 10 ⁻⁵ Torr, and the boat temperature was 300 ° C. P-Xylene was applied to the produced laminated film by a spin coating method and sufficiently dried. Subsequently, a Mg—Ag alloy was vapor-deposited by co-evaporation by a vacuum vapor deposition method to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 2)
An organic EL device was produced in the same manner as in Example 1 except that the following exemplary compound (2) (weight average molecular weight Mw = 6.5 × 10 ⁴ ) shown below was used as the hole transporting polymer.

(Example 3)
An organic EL device was produced in the same manner as in Example 1 except that the following exemplified compound (3) (weight average molecular weight Mw = 5.5 × 10 ⁴ ) was used as the hole transporting polymer.

Example 4
A 5% by weight dichloroethane solution of Exemplified Compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ] is prepared and filtered through a polytetrafluoroethylene (PTFE) filter having an opening of 0.1 μm. did. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.
After sufficiently drying, the compound (VI-1) purified by sublimation as a luminescent material was put in a tungsten boat and deposited by a vacuum deposition method to form a luminescent layer having a thickness of 0.05 μm on the hole transport slaughter. . The degree of vacuum at this time was 10 ⁻⁵ Torr, and the boat temperature was 300 ° C. The laminated film thus produced was left in a THF atmosphere (vapor) chamber for 30 minutes and then sufficiently dried. Subsequently, a Mg—Ag alloy was vapor-deposited by co-evaporation by a vacuum vapor deposition method to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 5)
An organic EL device was produced in the same manner as in Example 4 except that the exemplified compound (2) (weight average molecular weight Mw = 6.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Example 6)
An organic EL device was produced in the same manner as in Example 4 except that the exemplified compound (3) (weight average molecular weight Mw = 5.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Example 7)
A 5% by weight dichloroethane solution of Exemplified Compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ] is prepared and filtered through a polytetrafluoroethylene (PTFE) filter having an opening of 0.1 μm. did. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.
After sufficiently drying, the exemplified compound (4) shown below as a light emitting material was dissolved in xylene, and a light emitting layer having a thickness of 0.05 μm was formed on the hole transport layer by spin coating. The produced laminated film was left in a chamber in a THF atmosphere (vapor) for 30 minutes and then sufficiently dried. Subsequently, a Mg—Ag alloy was vapor-deposited by co-evaporation by a vacuum vapor deposition method to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 8)
An organic EL device was produced in the same manner as in Example 4 except that the exemplified compound (2) (weight average molecular weight Mw = 6.5 × 10 ⁴ ) was used as the hole transporting polymer.

Example 9
An organic EL device was produced in the same manner as in Example 4 except that the exemplified compound (3) (weight average molecular weight Mw = 5.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Example 10)
A 5% by weight dichloroethane solution of Exemplified Compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ] is prepared and filtered through a polytetrafluoroethylene (PTFE) filter having an opening of 0.1 μm. did. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.
After sufficiently drying, the compound (VI-1) purified by sublimation as a luminescent material was put in a tungsten boat and evaporated by a vacuum evaporation method to form a luminescent layer having a thickness of 0.05 μm on the hole transport layer. . The manufactured laminated film was left in a chamber in a toluene atmosphere (steam) for 30 minutes and then sufficiently dried. Subsequently, a Mg—Ag alloy was vapor-deposited by co-evaporation by a vacuum vapor deposition method to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 11)
An organic EL device was produced in the same manner as in Example 10 except that the exemplified compound (2) (weight average molecular weight Mw = 6.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Example 12)
An organic EL device was produced in the same manner as in Example 10 except that the exemplified compound (3) (weight average molecular weight Mw = 5.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Example 13)
A 5% by weight dichloroethane solution of Exemplified Compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ] is prepared and filtered through a polytetrafluoroethylene (PTFE) filter having an opening of 0.1 μm. did. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.
After sufficiently drying, the compound (VI-1) purified by sublimation was placed in a tungsten boat and evaporated by a vacuum evaporation method to form a light emitting layer having a thickness of 0.05 μm on the hole transport layer. The laminated film thus produced was left in a chamber in a p-xylene atmosphere (vapor) for 30 minutes and then sufficiently dried. Subsequently, using the compound (VIII-1) as an electron transport material by a vacuum deposition method, an electron transport layer having a film thickness of about 0.05 μm is formed, and further, an Mg—Ag alloy is deposited by co-evaporation to obtain a width of 2 mm. A back electrode having a thickness of 0.15 μm was formed so as to cross the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 14)
An organic EL device was produced in the same manner as in Example 10 except that the exemplified compound (2) (weight average molecular weight Mw = 6.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Example 15)
An organic EL device was produced in the same manner as in Example 10 except that the exemplified compound (3) (weight average molecular weight Mw = 5.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Comparative Example 1)
A 5% by weight dichloroethane solution of Exemplified Compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ] is prepared and filtered through a polytetrafluoroethylene (PTFE) filter having an opening of 0.1 μm. did. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.

After sufficiently drying, the compound (VI-I) purified by sublimation as a luminescent material was put in a tungsten boat and deposited by a vacuum deposition method to form a luminescent layer having a thickness of 0.05 μm on the hole transport layer. . The degree of vacuum at this time was 10 ⁻⁵ Torr, and the boat temperature was 300 ° C. Subsequently, a Mg—Ag alloy was vapor-deposited by co-evaporation by a vacuum vapor deposition method to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Comparative Example 2)
An organic EL device was produced in the same manner as in Comparative Example 1 except that the exemplified compound (2) (weight average molecular weight Mw = 6.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Comparative Example 3)
An organic EL device was produced in the same manner as in Comparative Example 1 except that the exemplified compound (3) (weight average molecular weight Mw = 5.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Comparative Example 4)
5 of exemplary compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ]
A weight% dichloroethane solution was prepared and filtered through a polytetrafluoroethylene (PTFE) filter having an opening of 0.1 μm. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.

After sufficiently drying, Exemplified Compound (4) was dissolved in xylene as a light emitting material, and a 0.05 μm thick light emitting layer was formed on the hole transport layer by spin coating. Subsequently, a Mg—Ag alloy was vapor-deposited by co-evaporation by a vacuum vapor deposition method to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect the ITO electrode. The effective area of the formed organic EL element is 0.04 cm.
² .

(Comparative Example 5)
An organic EL device was produced in the same manner as in Comparative Example 4 except that the exemplified compound (2) (weight average molecular weight Mw = 6.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Comparative Example 6)
An organic EL device was produced in the same manner as in Comparative Example 4 except that the exemplified compound (3) (weight average molecular weight Mw = 5.5 × 10 ⁴ ) was used as the hole transporting polymer.

(Comparative Example 7)
A 5% by weight dichloroethane solution of Exemplified Compound (1) [hole transporting polymer, weight average molecular weight Mw = 5.0 × 10 ⁴ ] is prepared and filtered through a polytetrafluoroethylene (PTFE) filter having an opening of 0.1 μm. did. Using this solution, a 2 mm wide strip ITO electrode was applied by spin coating on a glass substrate formed by etching to form a hole transport layer having a thickness of about 0.1 μm.
After sufficiently drying, the compound (VI-1) purified by sublimation as a luminescent material was put in a tungsten boat and evaporated by a vacuum evaporation method to form a luminescent layer having a thickness of 0.05 μm on the hole transport layer. . Subsequently, using the compound (VIII-1) as an electron transport material, an electron transport layer having a film thickness of about 0.05 μm is formed, and further, an Mg—Ag alloy is vapor-deposited by co-evaporation to have a width of 2 mm and a thickness of 0.15 μm. The back electrode was formed so as to cross the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

The results of Examples 1 to 15 and Comparative Examples 1 to 7 are shown in Table 40. As can be seen from Table 40, each of the organic electroluminescent elements of the Examples has the luminous efficiency and the organic thin-film laminate in contact with the organic solvent, compared with the case where the treatment is not performed. The light emission brightness was greatly improved and good light emission characteristics were exhibited.

It is a dual section showing an example of composition of an organic EL element of the present invention. It is a dual cross-sectional view showing another example of the configuration of the organic EL element of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent insulator board | substrate 2 Transparent electrode 3 Hole transport layer 4 Light emitting layer 5 Electron transport layer 6 Back electrode

Claims (11)

A pair of electrodes composed of an anode and a cathode, at least one of which is transparent or translucent, and an organic compound layer composed of two or more layers sandwiched between the pair of electrodes,
In the method of manufacturing an organic electroluminescent element, the organic compound layer is formed through at least an organic thin film stacking step of stacking an organic thin film.
An organic electroluminescent element manufacturing method comprising an organic solvent contacting step of bringing an organic solvent into contact with an exposed surface of an organic thin film laminate formed by laminating at least two organic thin films.   2. The method of manufacturing an organic electroluminescent element according to claim 1, wherein the organic solvent contact step is performed by exposing an exposed surface of the organic thin film laminate to a vapor of the organic solvent. 2. The method of manufacturing an organic electroluminescent element according to claim 1, wherein the organic solvent contact step is performed by applying the liquid organic solvent to an exposed surface of the organic thin film laminate.   2. The method of manufacturing an organic electroluminescent element according to claim 1, wherein at least one organic thin film constituting the organic thin film laminate is formed by a dry film forming method.   The method for producing an organic electroluminescent element according to claim 4, wherein the dry film forming method is a vapor deposition method. A pair of electrodes composed of an anode and a cathode, at least one of which is transparent or translucent, and an organic compound layer composed of two or more layers sandwiched between the pair of electrodes,
In the organic electroluminescence device in which the organic compound layer is formed through at least an organic thin film stacking step of stacking an organic thin film,
An organic electroluminescence device comprising an organic solvent contact step of bringing an organic solvent into contact with an exposed surface of an organic thin film laminate formed by laminating at least two organic thin films.   The organic electroluminescent device according to claim 6, wherein the organic compound layer includes at least a hole transport layer and a light emitting layer, and the hole transport layer includes a polymer hole transport material.   8. The organic electric field according to claim 7, wherein the organic compound layer includes an electron transport layer and has a layer structure in which the hole transport layer, the light emitting layer, and the electron transport layer are stacked in this order. Light emitting element.   The organic electroluminescent device according to claim 7, wherein the light emitting layer contains an organic low molecular weight material. The polymer hole transport material contains at least one selected from the structures represented by the following general formulas (I-1) and (I-2) in a repeating unit structure. 8. The organic electroluminescent device according to 7.

[In the general formulas (I-1) and (I-2), Ar represents a substituted or unsubstituted monovalent polynuclear aromatic ring having 1 to 10 aromatic moieties, or a substituted or unsubstituted aromatic ring number of 2; Represents a monovalent condensed aromatic ring of 10 to 10, X represents a substituted or unsubstituted divalent aromatic group, k and l each represents 0 or 1, and T represents a straight chain having 1 to 10 carbon atoms. A divalent hydrocarbon group or a branched divalent hydrocarbon group having 1 to 10 carbon atoms] The polymer hole transport material includes any one selected from repeating structures represented by the following general formulas (II), (III), (IV), and (V): The organic electroluminescent element as described.

[In the general formulas (II), (III), (IV) and (V), A represents the general formula (I-1) or (I-2), and B represents —O— (Y '-O) m'- or Z', Y, Y ', Z, Z' represents a divalent hydrocarbon group, m, m 'represents an integer of 1-5, and n is 0. Or 1 is represented, p represents the integer of 5-500, q represents the integer of 1-5000, r represents the integer of 1-3500. ]

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