JP2002151256A - Organic electroluminescent element, its manufacturing method and display element using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element with excellent thermal stability by development of electrolytic polymerization in which homogenous films are generated without jeopardizing merits of electrolytic polymerization and by the use of polymer obtained by the method. SOLUTION: 1) The organic electroluminescent element has a polymer formed from electrolytic reaction between its pair of electrodes with a nitrogen- containing aromatic compound having not less than two nitrogen atoms in the molecule of which at least two have one hydrogen atom each combined, as a monomer. 2) The organic electroluminescent element has a polymer formed from electrolytic reaction between its pair of electrodes with a nitrogen- containing aromatic compound having not less than three nitrogen atoms in the molecule of which at least three have one or more hydrogen atoms each combined, and at least one has two hydrogen atoms combined, as a monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device, a method for manufacturing the same, and a display device using the same.

[0002]

2. Description of the Related Art In recent years, there has been remarkable progress in reducing the size, thickness, and weight of electronic devices.
In the field, from desktop type to laptop type,
The size has been reduced to a notebook type. In addition, new small electronic devices such as electronic organizers and translators have emerged,
Furthermore, in addition to the multifunctionality and miniaturization of the conventional stationary phone,
Mobile phones, PHSs, and PDAs, which are small communication devices, are also being developed. In the wave of the miniaturization, thinning, and weight reduction of such electronic devices, high-performance display devices that support man interfaces have been developed. Is being demanded. Therefore,
In order to meet such demands, a display device using an electroluminescent element, which is characterized by being thin, self-luminous, and capable of being colored, is a small and medium-sized electronic device that can replace CRTs and liquid crystals. It has been developed as a display device for equipment.

[0003] Thin-film electroluminescent devices include those utilizing inorganic compounds and those utilizing organic compounds.
Examples of the inorganic thin film electroluminescent element include a glass transparent electrode (eg, ITO), an insulating layer (eg, silicon nitride), a light emitting layer (eg, ZnS: Mn), an insulating layer (eg, silicon nitride), and a metal electrode (eg, Al). Generally, the layers are sequentially laminated. Such an inorganic thin-film electroluminescent device has a problem that a high-luminance luminance is high but a driving voltage is high (up to 200 V), so that a dedicated driving IC is required and a color of a light-emitting material cannot always be freely selected. ing. On the other hand, in recent years, the production of an electroluminescent device in which organic thin films are laminated has been actively attempted. As old as JP-A-57-51
No. 781 discloses that an organic thin film layer to be a luminous body is sandwiched between thin films of a material that selectively transports electrons and / or holes, and electrodes are provided on both sides thereof. The organic thin-film electroluminescent device has a lower driving voltage (up to 20 V) and a wider selection range of light-emitting materials than the inorganic thin-film electroluminescent device, and thus is essentially suitable for producing a full-color display device.

An organic thin film electroluminescent device has a structure in which several kinds of organic thin film laminates are sandwiched between electrodes, and several methods have been proposed as methods for producing an organic thin film. General methods include (a) a method by vapor deposition and (b) a method by coating. The method (a) is a method generally applied to low molecular weight organic substances, and is a thin film region (領域 3000).
In (ii), it is possible to obtain a reliable thin film because the film thickness can be precisely controlled, but the device becomes large-scale, and the overall element manufacturing time becomes long. In addition, since low-molecular-weight organic substances are not always stable at the deposition temperature, the materials are limited.
The method (b) is a method generally applied to high-molecular-weight organic substances (polymers and oligomers), and is a method with excellent productivity. Organic substances that cannot be vapor-deposited essentially (decompose at the vapor-deposition temperature) However, compared to the vapor deposition method, it is difficult to precisely control the film thickness, and the insulating property may be poor. We considered the method (b) as a preferred method because of its high productivity. However, this method cannot handle materials that are essentially insoluble and infusible, and has the trouble of preparing a coating solution for the electroluminescent element material. There is a problem that it takes.

The method used in the present invention overcomes this disadvantage, and is a thin film forming method generally called an electrolytic polymerization method. Since the electropolymerization method uses an electrolytic reaction, a thin film is basically formed only on the electrode, and there is no need for alignment with ITO, etc., or an essentially insoluble and infusible material that cannot be handled by coating However, there is an advantage that a film can be formed on an electrode by utilizing electrolytic synthesis. In addition, although the film quality for the electroluminescent element must be uniform and dense, the polymerization reaction on the conductor (the polymerization reaction in this case includes dimerization and trimerization. ,
This means that the product generated by the electrolysis is deposited on the electrode, and the electrolysis product is not always a polymer. The film quality of the film formed by the above is determined by conducting detailed examination of the electrolysis conditions [monomer type, solvent type, electrolyte type, electrolysis conditions (constant voltage electrolysis, constant current electrolysis, constant potential electrolysis, etc.), additives]. A film far superior to the coating method can be formed, and a film quality comparable to the vapor deposition method can be obtained. Further, the film produced under such conditions has an advantage that, due to the nature of the electrolytic reaction (polymerization proceeds almost simultaneously from numerous reaction points on the electrodes), a film having a strong amorphous property is easily obtained.

Attempts to utilize the electropolymerization method for producing an organic thin film electroluminescent device are described in JP-A-2-195681, JP-A-5-13171, and JP-A-8-45667. In the technique described in Japanese Unexamined Patent Publication No. Hei 2-195681, an organic monomer is vapor-deposited on an electrode and then subjected to an electrolytic reaction. Since the vapor deposition is used before the step of obtaining an electrolytic film, the process is complicated. Some of the advantages of electropolymerization have been lost. The technique described in Japanese Patent Application Laid-Open No. Hei 5-13171 is to produce an electron transport layer by an electrolytic polymerization method. However, a polymer obtained by the electrolytic polymerization is dissolved in a solvent, and the electron transport layer is formed by coating. Therefore, there are still many steps and the advantage of electrolytic polymerization is not fully utilized. In the technique described in JP-A-8-45667, electrolytic polymerization is performed using a polymer-coated electrode as an electrode, so that the number of steps for producing a coated electrode increases and the concentration of a polymer that functions actively decreases. As a result, the functional material grows in the coated polymer, and the electron or hole transporting ability and the light emitting ability of the material cannot be fully utilized.

[0007] In general, the amorphous property of a material is mentioned as a required characteristic for a material for a thin film electroluminescent element. This is because one of the causes of deterioration of the electroluminescent device is the generation of a non-light emitting portion due to crystallization of the material. Preventing crystallization of this material, that is, increasing the amorphousness, extends the life of the device. It is one of the means. Specifically, molecular design has been performed to enhance the thermal stability of amorphous materials, that is, to increase the glass transition point and the crystallization temperature, but at present, it has not yet reached a sufficient region.

[0008]

SUMMARY OF THE INVENTION The present invention has developed an electropolymerization method capable of forming a uniform film without deteriorating the advantages of the above-mentioned electropolymerization, and using the polymer obtained by the method, it has been proposed to use a polymer having a high thermal stability. An object is to provide an excellent electroluminescent element.

[0009]

Means for Solving the Problems The present inventor has found that the above object can be achieved by using a monomer having a specific structure in electrolytic polymerization. That is, the above problems are solved by the following inventions 1) to 26) (hereinafter referred to as the present inventions 1 to 26). 1) As a monomer, a nitrogen-containing aromatic compound having two or more nitrogen atoms in a molecule and one hydrogen atom bonded to at least two nitrogen atoms among the nitrogen atoms,
An organic electroluminescent device comprising a polymer formed by performing an electrolytic reaction between a pair of electrodes. 2) A compound having three or more nitrogen atoms in a molecule, having one or less hydrogen atoms bonded to the nitrogen atom, and having three or more nitrogen atoms bonded to one hydrogen atom The organic electroluminescent device according to 1), wherein a polymer formed by performing an electrolytic reaction is used as a monomer between a pair of electrodes. 3) having three or more nitrogen atoms in the molecule, at least one hydrogen atom bonded to at least three nitrogen atoms of the nitrogen atoms, and at least one nitrogen atom An organic electroluminescent device comprising, as a monomer, a nitrogen-containing aromatic compound having two hydrogen atoms bonded, and a polymer formed by performing an electrolytic reaction between a pair of electrodes. . 4) The organic electroluminescent device according to 1), wherein the monomer is a compound represented by the following (1).

Embedded image A1-NH-A2-NH-A3 (1) (where A1 to A3 are substituted / unsubstituted aromatic groups.) 5) A1 to A3 are substituted / unsubstituted other than fused rings The organic electroluminescent device according to 4), wherein the organic electroluminescent device is an aromatic group. 6) The organic electroluminescent device according to 5), wherein A1 and A3 are both groups having a structure shown in the following (2), and A2 is a group having a structure shown in the following (3).

Embedded image

Embedded image 7) The organic electroluminescence described in 6), wherein when n of A1 and A3 is odd, m of A2 is odd, and when n is 0 or even, m is even. element. 8) The organic electroluminescent device according to 6) or 7), wherein A1 and A3 are both phenyl groups. 9) The organic electroluminescent device according to 2) or 3), wherein the monomer is a compound represented by the following (4).

A4-NH-A5-NH-A6-NH-A7 (4) (where A4 is a hydrogen atom or a substituted / unsubstituted aromatic group, and A5 and A6 are substituted / It is an unsubstituted aromatic group, and A7 is a substituted / unsubstituted aromatic group.) 10) A4, A7 is a substituted / unsubstituted aromatic group other than a condensed ring 9) The organic electroluminescent device according to claim 1. 11) An organic electroluminescent device according to 10), wherein A4 and A7 are both groups having the structure shown in the following (5), and A5 and A6 are both groups having the structure shown in the following (6). .

Embedded image

Embedded image 12) When n of A4 and A7 is odd, A5 and A6
M is an even number, and when n is 0 or an even number,
m) is an odd number, wherein the organic electroluminescent device according to the item 11) is provided. 13) The organic electroluminescent device according to 11) or 12), wherein both A4 and A7 are phenyl groups. 14) The organic electroluminescent device according to any one of 1) to 3), wherein the monomer is a compound represented by the following (7).

Embedded image (In the formula, A8 to A12 are substituted / unsubstituted aromatic groups, and A8 and A9 may be hydrogen atoms.) 15) When A8 to A12 are aromatic groups, substituted / unsubstituted groups other than fused rings The organic electroluminescent device according to 14), wherein the organic electroluminescent device is a substituted aromatic group. 16) The organic electroluminescent device according to 15), wherein A8 to A11 are substituted / unsubstituted phenyl groups, and A12 is a group having the structure shown in the following (8) and (9).

Embedded image

Embedded image 17) The organic electroluminescent device according to any one of 1) to 3), wherein the monomer is a compound represented by the following (10).

Embedded image (In the formula, A15 to A21 are substituted / unsubstituted aromatic groups, and A18 and A19 may be hydrogen atoms.) 18) The aromatic group is a substituted / unsubstituted aromatic group other than a condensed ring. 17. The organic electroluminescent device according to 17), wherein 19) A15 to A17 are paraphenylene groups,
20. The organic electroluminescent device according to 18), wherein A21 is a substituted / unsubstituted phenyl group. 20) The organic electroluminescent device according to any one of 1) to 19), wherein the polymer is produced by performing an electrolytic reaction in the presence of a hydrogen acceptor. 21) The organic electroluminescent device according to any one of 1) to 20), wherein the light-emitting layer contains the polymer. 22) The organic electroluminescent device according to any one of 1) to 20), wherein the hole injecting and transporting layer contains the polymer. 23) The organic electroluminescent device according to any one of 1) to 20), wherein the polymer is formed on a conductive transparent substrate. 24) The organic electroluminescent device according to 23), wherein the electrolytic reaction is an anodic oxidation reaction performed on a transparent electrode. 25) The method for manufacturing an organic electroluminescent device according to 23), wherein the electrolytic reaction of the polymer is performed by an anodic oxidation reaction on a transparent electrode. 26) A display device using the organic electroluminescent device according to any one of 1) to 24).

Hereinafter, the present invention will be described in detail.
You. The electrolytic polymerization method used in the present invention is, for example, "Chemical industry"
June 1986, p. 43, "Polymer" Vol. 35, February
(1986), page 124, etc.
A solution obtained by dissolving the electrolyte and the solvent in a predetermined electrolytic cell,
Immerse a pair of electrodes and pass an electric current to anodize or shade
Initiates a polymerization reaction due to polar reduction, leaving a cathode or anode
This is a method of forming a thin film of a device. Examples of electrolytes
For example, as an anion, BF₄ ⁻, AsF₆ ⁻, SbF
₆ ⁻, PF₆ ⁻, ClO₄ ⁻, HSO₄ ⁻, S
O₄ ^2-, Aromatic sulfonate ion, Cl⁻, Br⁻,
I⁻And the like, as a cation,
H⁺Quaternary ammonium cation, lithium, sodium
And alkali metal cations such as potassium
Is not limited to these, but
It can be appropriately selected depending on the desired film quality. Also, dark
The degree can also be set as appropriate,
Is preferred.

Examples of the solvent include acetonitrile,
Examples thereof include benzonitrile, propylene carbonate, γ-butyrolactone, dichloromethane, dioxane, dimethylformamide, nitromethane, nitropropane, and nitrobenzene. These may be used in combination of two or more. However, the compounds are not particularly limited to these exemplified compounds, and can be appropriately selected depending on the monomers and desired film quality. As the electrolytic polymerization, any of constant-voltage electrolysis, constant-current electrolysis, constant-potential electrolysis, electrolysis depending on the amplitude of potential or voltage, and the like may be used.

The monomer used in the present invention has two or more nitrogen atoms in the molecule, and at least two nitrogen atoms
A nitrogen-containing aromatic compound in which one hydrogen atom is bonded to one nitrogen atom is used. By performing electrolytic polymerization using such a monomer, an insoluble, infusible and highly heat-stable amorphous organic substance can be formed on the electrode in one step without alignment. Further, in terms of thermal stability, it preferably has three or more nitrogen atoms in the molecule,
Nitrogen-containing aromatic compounds having one hydrogen atom on each of at least three of the nitrogen atoms are used. Representative monomers are represented by the following formulas (1) and (4)
(7) The compound represented by (10).

[0013]

A1-NH-A2-NH-A3 (1) In the formula (1), A1 to A3 are substituted / unsubstituted aromatic groups, and preferably A1 = A3. Also, A1,
A3 is more preferably a substituted / unsubstituted aromatic group other than a condensed ring. In particular, both A1 and A3 have the following (2)
And the most preferred among them is a phenyl group (that is, n = 0).

Embedded image A2 is more preferably a substituted / unsubstituted aromatic group other than a condensed ring, and particularly preferably a group having the structure shown in the following (3).

Embedded image Further, when n of A1 and A3 is an odd number, m of A2 is
Is preferably an odd number, and when n is 0 or an even number, m is preferably an even number.

[0014]

Embedded image A4-NH-A5-NH-A6-NH-A7 (4) In the formula (4), A4 is a hydrogen atom or a substituted / unsubstituted aromatic group, and A7 is a substituted / unsubstituted aromatic group. Group, preferably A4 = A7. More preferably, A4 and A7 are substituted / unsubstituted aromatic groups other than a condensed ring, and particularly preferably, A4 and A7 are both groups having the structure shown in the following (5). Preferred is a phenyl group (ie, n = 0).

Embedded image A5 and A6 each represent a substituted / unsubstituted aromatic group other than a condensed ring, preferably A5 = A6, and particularly preferably A
5 and A6 are both groups having the structure shown in the following (6).

Embedded image Further, when n of A4 and A7 is an odd number, A5 and A7
M of 6 is preferably an even number, and when n is 0 or an even number,
m is preferably an odd number.

[0015]

Embedded image In the formula (7), A8 to A12 are substituted / unsubstituted aromatic groups, and A8 and A9 may be hydrogen atoms. Also, A
When 8-A12 is an aromatic group, a substituted / unsubstituted aromatic group other than a condensed ring is preferred, and the most preferred of A8-A11 is a substituted / unsubstituted phenyl group,
Most preferred as A12 are groups having the following structures (8) and (9).

Embedded image

Embedded image

[0016]

Embedded image In the formula (10), A15 to A21 are substituted / unsubstituted aromatic groups, and A18 and A19 may be hydrogen atoms.
A15 to A17 are preferably a substituted / unsubstituted aromatic group other than a condensed ring, and more preferably A15 = A
16 = A17, and among them, the most preferred is a paraphenylene group. Further, when A18 to A21 are aromatic groups, a substituted / unsubstituted aromatic group other than a condensed ring is preferred, and among them, a most preferred is a substituted / unsubstituted phenyl group.

The electrolytic reaction using these as a monomer is preferably carried out in the presence of a hydrogen acceptor. The reactant prepared in the presence of the hydrogen acceptor is subjected to the reaction by extracting the hydrogen atom on the nitrogen atom and / or the aromatic carbon atom, and the reaction proceeds. On nitrogen atom /
A reaction product containing no hydrogen atom on the aromatic carbon atom (less hydrogen atom) can be obtained. The vibration energy level of the NH bond and the aromatic CH bond is 3000 cm.
It is generally at least ^-1 and belongs to a high class as the vibration energy level of the organic bond. When an organic material having many such bonds is used as a material for an electroluminescent element,
Probability that the energy of an organic substance in an excited state (a state in which energy was obtained) is not effectively used for emission energy, or is not effectively transferred to another molecule, and is partially used as vibrational energy within the molecule. And the energy efficiency is reduced (a part of the excitation energy is used as vibration energy due to a high vibration energy level; energy deactivation).

The hydrogen acceptor used in the present invention includes:
Examples include Bronsted bases and Lewis bases. Whether the substance used acts as an acid or a base is determined by the acid-base equilibrium of the reaction solution (polymerization solution), and thus cannot be unconditionally determined to be this substance (which should be appropriately selected depending on the reaction system). , The equivalent of the Lewis base concept,
That is, a substance that functions as an electron pair donor is preferable. More specifically, those which are stable under electrolytic polymerization conditions and have an unpaired electron pair in a molecule (for example, a substance having an oxygen, nitrogen, sulfur, or phosphorus atom) can be used, and pyrrole,
Diazole, thiazole, oxazole, pyrazolidine, piperidine, oxazine, thiazine, triazole, pyridine, pyrimidine, triazine and the like can be used.

As the conductive substrate used in the present invention, known substrates can be used, for example, In ₂ O ₃ , SnO ₂ , ZnO,
_{CdO, TiO 2, In 2 O} 3 -Sn, SnO 2 -Sb
Such as an oxide thin film, a metal thin film such as Au, Ag, and Pt;
An electrode in which a conductive nitride thin film such as TiN or ZrN is patterned on a substrate such as glass or plastic can be used, but it is necessary to select a material that is stable under an applied electric field. Preferably, a light-emitting element from which light is emitted to the outside, that is, a transparent electrode is used, and most preferably, a thin film having high conductivity and being transparent to visible light is used.
It is a TO electrode.

In the electropolymerization of the present invention, either an anodic oxidation reaction or a cathodic reduction reaction can be used, but it should be judged based on the stability of the electrode and the performance of the synthesized polymer as a material for an electroluminescent device. It is. When a transparent electrode (such as ITO) is used as a reaction electrode, it is preferable to perform an electrolytic reaction using an anodic oxidation reaction because these electrodes are weak to a reduction reaction (because they are dissolved). In addition, since the monomer used in the present invention does not always give a polymer which is stable against electrolytic reduction, an electrolytic oxidation reaction is preferably used also from this point.

[0021]

The present invention will be described below in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 N, N'-diphenylbenzidine 5 mM as a monomer
(Mmol), 0.1 M (mol) of tetra-n-butylammonium tetrafluoroborate as an electrolyte and 50 mM of 2,6-lutidine as a hydrogen acceptor were dissolved in propylene carbonate to prepare an electrolytic polymerization solution. Polymerization was performed at a potential of 2.0 V or less using an ITO glass electrode as a working electrode, platinum as a counter electrode, and SCE as a reference electrode. ITO
After taking out the electrode and washing, it was transferred to a propylene carbonate solution containing 50 mM of tetra-n-butylammonium p-toluenesulfonate, and after applying a voltage of -0.7 V to SCE, the electrode was taken out of the solution while applying the voltage and washed. After drying, a composite electrode with ITO was obtained.
An 8-quinolinol aluminum complex (Alq
₃ ) was evaporated, followed by co-evaporation of magnesium and silver.
When an electric field of 10 mA / cm ² was applied to the obtained electroluminescent device, light emission was observed. Subsequently, when the device was maintained at 70 ° C. and an electric field was applied, light emission was observed unchanged. Subsequently, when the device was maintained at 150 ° C. and an electric field was applied, light emission was observed unchanged.

Comparative Example 1 The procedure of Example 1 was repeated except that m, m'-dimethyltetraphenylbenzidine (TPD) was formed by vapor deposition on an ITO electrode in place of the N, N'-diphenylbenzidine polymer in Example 1. An electroluminescent device was produced in the same manner as in Example 1. When an electric field of 10 mA / cm ² was applied to this device, light emission was observed. Subsequently, when the electroluminescent device thus manufactured was maintained at 70 ° C. and an electric field was applied, it did not emit light. This is probably because the device characteristics were lost because the set temperature was higher than the glass transition point and crystallization temperature of TPD.

Comparative Example 2 An electroluminescent device was manufactured in the same manner as in Comparative Example 1 except that the following compound was used instead of TPD.

Embedded image When an electric field of 10 mA / cm ² was applied to this device, light emission was observed. Subsequently, when the device was maintained at 70 ° C. and an electric field was applied, light emission was observed unchanged. Subsequently, when the device was maintained at 150 ° C. and an electric field was applied, no light was emitted. This is probably because the device characteristics were lost because the set temperature was higher than the glass transition point or the crystallization temperature of the electroluminescent material.

Example 2 An electroluminescent device was produced in the same manner as in Example 1 except that the following compound was used as a monomer and no hydrogen acceptor was used.

Embedded image When an electric field of 10 mA / cm ² was applied to this device, light emission was observed. Subsequently, when the device was maintained at 70 ° C. and an electric field was applied, light emission was observed unchanged.

Example 3 An electroluminescent device was manufactured in the same manner as in Example 1 except that the following compounds were used as monomers.

Embedded image When an electric field of 10 mA / cm ² was applied to this device, light emission was observed. Subsequently, when the electroluminescent element was maintained at 70 ° C. and an electric field was applied, light emission was observed without change.

Example 4 As monomers, A8 in the formula (7) is hydrogen and A9 to
An electroluminescent device was produced in the same manner as in Example 1, except that a compound having A11 was a phenyl group and A12 was a group represented by (8). When an electric field of 10 mA / cm ² was applied to this device, light emission was observed. Subsequently, when the device was maintained at 70 ° C. and an electric field was applied, light emission was observed unchanged. Subsequently, when the device was maintained at 100 ° C. and an electric field was applied, light emission was observed unchanged.

Comparative Example 3 An electroluminescent device was produced in the same manner as in Comparative Example 1, except that the following compound was used instead of TPD.

Embedded image When an electric field of 10 mA / cm ² was applied to this device, light emission was observed. Subsequently, when the device was maintained at 70 ° C. and an electric field was applied, light emission was observed unchanged. Subsequently, when the device was maintained at 100 ° C. and an electric field was applied, light emission was lost.
This is probably because the device characteristics were lost because the set temperature was higher than the glass transition point or the crystallization temperature of the electroluminescent material.

Example 5 As monomers, A15, A16,
A17 is a paraphenylene group, A18 is hydrogen, A19 to A
An electroluminescent device was fabricated in the same manner as in Example 1, except that a compound having a phenyl group was used. 1 for this element
When an electric field of 0 mA / cm ² was applied, light emission was observed. Subsequently, when the device was maintained at 70 ° C. and an electric field was applied, light emission was observed unchanged. Subsequently, when the device was maintained at 160 ° C. and an electric field was applied, light emission was observed unchanged.

Comparative Example 3 An electroluminescent device was produced in the same manner as in Comparative Example 1, except that the following compound was used instead of TPD.

Embedded image When an electric field of 10 mA / cm ² was applied to this device, light emission was observed. Subsequently, when the device was maintained at 70 ° C. and an electric field was applied, light emission was observed unchanged. Subsequently, when the device was maintained at 160 ° C. and an electric field was applied, light emission was lost.
This is probably because the device characteristics were lost because the set temperature was higher than the glass transition point or the crystallization temperature of the electroluminescent material.

[0031]

According to the inventions 1 to 19 and 21 to 22, a thin film having excellent thermal stability can be produced on an electrode in one step without alignment, and the use of the thin film provides excellent thermal stability. An organic electroluminescent device can be provided. According to the present invention 20, by using a hydrogen acceptor in a polymerization system, an organic electroluminescent device having more excellent thermal stability can be provided. According to the twenty-third aspect of the present invention, it is possible to provide an organic electroluminescent element that can extract light in a planar manner by using an electrode that is transparent to visible light. According to the present inventions 24 to 25, a thin film having good thermal stability can be produced without impairing the characteristics of the transparent electrode by using the anodic oxidation reaction, the heat stability using the thin film is excellent, and light is emitted on the surface. An organic electroluminescent device that can be taken out can be provided. According to the twenty-sixth aspect, a display element having excellent thermal stability can be provided by using an organic electroluminescent element capable of emitting light on a surface.

Claims (26)

[Claims] 1. A nitrogen-containing aromatic compound having two or more nitrogen atoms in a molecule, wherein one hydrogen atom is bonded to at least two nitrogen atoms among the nitrogen atoms, An organic electroluminescent device comprising, as a body, a polymer formed by performing an electrolytic reaction between a pair of electrodes. 2. A molecule having three or more nitrogen atoms in a molecule, and one or less hydrogen atom bonded to the nitrogen atom, and
2. A polymer formed by performing an electrolytic reaction using a compound having three or more nitrogen atoms bonded to two hydrogen atoms as a monomer and having a polymer between a pair of electrodes. The organic electroluminescent device according to claim 1. 3. A compound having three or more nitrogen atoms in a molecule, one or more hydrogen atoms bonded to at least three nitrogen atoms of the nitrogen atoms, and at least one nitrogen atom. An organic compound comprising a polymer formed by performing an electrolytic reaction between a pair of electrodes using a nitrogen-containing aromatic compound having two hydrogen atoms bonded on a nitrogen atom as a monomer. Electroluminescent device. 4. The organic electroluminescent device according to claim 1, wherein the monomer is a compound represented by the following (1). Embedded image A1-NH-A2-NH-A3 (1) (wherein, A1 to A3 are substituted / unsubstituted aromatic groups.) 5. The organic electroluminescent device according to claim 4, wherein A1 to A3 are substituted / unsubstituted aromatic groups other than a condensed ring. 6. The organic electroluminescence according to claim 5, wherein A1 and A3 are both groups having a structure shown in the following (2), and A2 is a group having a structure shown in the following (3). element. Embedded image Embedded image 7. When n of A1 and A3 is an odd number, A2
M is odd, and when n is 0 or even,
7. The organic electroluminescent device according to claim 6, wherein m is an even number. 8. The organic electroluminescent device according to claim 6, wherein both A1 and A3 are phenyl groups. 9. The organic electroluminescent device according to claim 2, wherein the monomer is a compound represented by the following (4). A4-NH-A5-NH-A6-NH-A7 (4) (where A4 is a hydrogen atom or a substituted / unsubstituted aromatic group, and A5 and A6 are substituted / unsubstituted It is an unsubstituted aromatic group, and A7 is a substituted / unsubstituted aromatic group.) 10. The organic electroluminescent device according to claim 9, wherein A4 and A7 are substituted / unsubstituted aromatic groups other than a condensed ring. 11. The method according to claim 10, wherein A4 and A7 are both groups having the structure shown in the following (5), and A5 and A6 are both groups having the structure shown in the following (6). Organic electroluminescent device. Embedded image Embedded image 12. When n of A4 and A7 is an odd number, A
12. The organic electroluminescent device according to claim 11, wherein m in A6 and A6 is an even number, and when n is 0 or an even number, m is an odd number. 13. The organic electroluminescent device according to claim 11, wherein both A4 and A7 are phenyl groups. 14. The organic electroluminescent device according to claim 1, wherein the monomer is a compound represented by the following (7). Embedded image (In the formula, A8 to A12 are substituted / unsubstituted aromatic groups, and A8 and A9 may be hydrogen atoms.) 15. The organic electroluminescent device according to claim 14, wherein when A8 to A12 are aromatic groups, they are substituted / unsubstituted aromatic groups other than fused rings. 16. The organic electroluminescent device according to claim 15, wherein A8 to A11 are substituted / unsubstituted phenyl groups, and A12 is a group having a structure shown in the following (8) and (9). . Embedded image Embedded image 17. The organic electroluminescent device according to claim 1, wherein the monomer is a compound represented by the following (10). Embedded image (In the formula, A15 to A21 are substituted / unsubstituted aromatic groups, and A18 and A19 may be hydrogen atoms.) 18. The organic electroluminescent device according to claim 17, wherein the aromatic group is a substituted / unsubstituted aromatic group other than a condensed ring. 19. The organic electroluminescent device according to claim 18, wherein A15 to A17 are paraphenylene groups, and A20 and A21 are substituted / unsubstituted phenyl groups. 20. The organic electroluminescent device according to claim 1, wherein the polymer is produced by performing an electrolytic reaction in the presence of a hydrogen acceptor. 21. The organic electroluminescent device according to claim 1, wherein the light emitting layer contains the polymer. 22. The organic electroluminescent device according to claim 1, wherein the polymer is contained in a hole injecting and transporting layer. 23. The organic electroluminescent device according to claim 1, wherein the polymer is formed on a conductive transparent substrate. 24. The organic electroluminescent device according to claim 23, wherein the electrolytic reaction is an anodic oxidation reaction performed on a transparent electrode. 25. The method according to claim 23, wherein the electrolytic reaction of the polymer is performed by an anodic oxidation reaction on a transparent electrode.
A method for producing the organic electroluminescent device according to the above. 26. A display device using the organic electroluminescent device according to claim 1. Description: