JP4715329B2 - Manufacturing method of substrate for electronic device - Google Patents

Description

The present invention relates to a method for manufacturing an electronic device substrate .

As an electronic device including an organic semiconductor layer and an electrode, and an electronic device substrate provided such that these are in contact with each other, for example, an organic electroluminescence element (hereinafter simply referred to as “organic EL element”). And organic thin film transistors.
Among these, the organic EL element is considered to be promising for use as an inexpensive large-area full-color display element (light emitting element) of a solid light emitting type, and many developments have been made.

In general, an organic EL device has a light emitting layer between a cathode and an anode. When an electric field is applied between the cathode and the anode, electrons are injected into the light emitting layer from the cathode side, and holes are formed from the anode side. Is injected.
At this time, when the molecular structure of the organic EL material (light-emitting layer material) and the molecular aggregation state are in a specific state, the injected electrons and holes are not immediately combined with each other as a special excited state. Hold for a certain time. Therefore, the total energy of the molecule is increased by the excitation energy compared to the ground state, which is a normal state. A pair of electrons and holes holding this special excited state is called an exciton.

Then, when the exciton decays and the electrons and holes are combined after a certain period of time, the increased excitation energy is released to the outside as heat or light.
This light emission is performed in the vicinity of the light emitting layer, and the ratio of the light emission within the excitation energy is greatly influenced by the molecular structure of the organic EL material and the molecular aggregation state.
Further, in such an organic EL device, in order to obtain high light emission, an organic semiconductor layer composed of organic semiconductor materials having different carrier transport properties of carriers (electrons or holes) is formed by combining a light emitting layer, a cathode, and / or It has also been found that an element structure laminated between the anode and the anode is effective.

  Therefore, in an organic EL element having a configuration in which a light emitting layer and an organic semiconductor layer are stacked between an anode and a cathode, in order to obtain high light emission efficiency, the molecular structure and the molecular state of the organic EL material and the organic semiconductor material Furthermore, the number and position of the light emitting layer and the organic semiconductor layer to be stacked are being studied.

However, even in the organic EL element having such a configuration, the actual situation is that the improvement in characteristics such as light emission efficiency is not expected (see, for example, Patent Document 1).
This is because the interaction between the organic semiconductor materials is larger than the interaction between the organic semiconductor material and the constituent material of the electrode (metal material), and the organic semiconductor material and the metal material repel each other. It has been found that sufficient adhesion between the electrode and the electrode cannot be obtained, and carriers are not smoothly transferred between these layers.

As a method for solving such problems, a hole injection layer mainly composed of a metal complex such as copper phthalocyanine is formed between the anode and the hole transport layer (organic semiconductor layer) by a vacuum deposition method or an ion beam. A method of improving carrier transport by forming using a vapor deposition method such as a vapor deposition method is disclosed.
However, even when such a method is used, the adhesion between the anode and the hole injection layer cannot be sufficiently improved, and the characteristics of the organic EL element are not sufficiently improved. .
There is a concern that such a problem also occurs in an organic thin film transistor or the like.

Japanese Patent Laid-Open No. 9-255774 JP 2002-151269 A

The objective of this invention is providing the manufacturing method of the board | substrate for electronic devices which can manufacture the board | substrate for electronic devices excellent in carrier transport ability.

［式中、３つのＲ ^１ は、それぞれ独立して、水素原子、または、下記一般式（５）または下記一般式（６）で表される置換基のうちのいずれかを表し、同一であっても、異なっていてもよい。ただし、３つのＲ ^１ のうちの少なくとも１つは、下記一般式（５）または下記一般式（６）で表される置換基のうちのいずれかを表す。］

［各式中、Ｒ ^２ は、単結合または炭素数１〜２０のアルキレン基を表す。Ｒ ^３ は、水素原子、アルカリ金属、アミノ基または炭素数１〜２０のアルキル基を表す。２つのＲ ^４ は、それぞれ独立して、水素原子または炭素数１〜２０のアルキル基を表し、同一であっても、異なっていてもよい。Ｘ ^１ は、単結合、

を表す。Ｙ ^１ は、単結合、

を表す。］

［式中、３つのＲ ^１ は、それぞれ独立して、水素原子、または、下記一般式（５）または下記一般式（６）で表される置換基のうちのいずれかを表し、同一であっても、異なっていてもよい。ただし、３つのＲ ^１ のうちの少なくとも１つは、下記一般式（５）または下記一般式（６）で表される置換基のうちのいずれかを表す。］

［各式中、Ｒ ^２ は、単結合または炭素数１〜２０のアルキレン基を表す。Ｒ ^３ は、水素原子、アルカリ金属、アミノ基または炭素数１〜２０のアルキル基を表す。２つのＲ ^４ は、それぞれ独立して、水素原子または炭素数１〜２０のアルキル基を表し、同一であっても、異なっていてもよい。Ｘ ^１ は、単結合、

を表す。Ｙ ^１ は、単結合、

を表す。］

［式中、２つのＲ ^１ は、それぞれ独立して、水素原子、または、下記一般式（５）または下記一般式（６）で表される置換基のうちのいずれかを表し、同一であっても、異なっていてもよい。ただし、２つのＲ ^１ のうちの少なくとも１つは、下記一般式（５）または下記一般式（６）で表される置換基のうちのいずれかを表す。］

［各式中、Ｒ ^２ は、単結合または炭素数１〜２０のアルキレン基を表す。Ｒ ^３ は、水素原子、アルカリ金属、アミノ基または炭素数１〜２０のアルキル基を表す。２つのＲ ^４ は、それぞれ独立して、水素原子または炭素数１〜２０のアルキル基を表し、同一であっても、異なっていてもよい。Ｘ ^１ は、単結合、

を表す。Ｙ ^１ は、単結合、

を表す。］
これにより、中間層を介した電極から有機半導体層へのキャリアの受け渡しが円滑に行われ、キャリア輸送能に優れた電子デバイス用基板を製造することができる。
また、前記有機物がキャリアを輸送する機能を有するキャリア輸送部位と、該キャリア輸送部位に結合する帯電可能な部位とを有する化合物であることにより、液体に電圧を印加した際に、有機物を確実に電極に集めることができる。
また、前記キャリア輸送部位が、正孔を輸送する機能を有するものであることにより、中間層に正孔を輸送する機能を付与することができる。
さらに、前記有機物が、前記一般式（２）または前記一般式（３）で表される化合物を主成分とすることにより、得られる中間層は、正孔輸送能に優れ、電極および有機半導体層に対して優れた密着性を発揮するものとなる。
また、前記キャリア輸送部位が、電子を輸送する機能を有するものであることにより、中間層に電子を輸送する機能を付与することができる。
さらに、前記有機物が、前記一般式（４）で表される化合物を主成分とすることにより、得られる中間層は、電子輸送能に優れ、電極および有機半導体層に対して優れた密着性を発揮するものとなる。 Such an object is achieved by the present invention described below.
The method for manufacturing a substrate for an electronic device according to the present invention includes an organic semiconductor layer, an electrode, a contact between both of the organic semiconductor layer and the electrode, and a carrier including a conjugated structure. An electronic device substrate applied to an organic electroluminescent element having a carrier transporting part having a transporting function and an intermediate layer composed mainly of an organic substance having a chargeable part bonded to the carrier transporting part. A manufacturing method comprising:
In a state where the electrode is in contact with a liquid containing the organic substance, the organic substance charged in the liquid is collected on the electrode by applying a voltage to the liquid using the electrode as one electrode. Forming the intermediate layer;
After the organic semiconductor layer material formed by dissolving the constituent material of the organic semiconductor layer in a solvent or dispersing in a dispersion medium is applied on the surface of the intermediate layer opposite to the electrode, the organic semiconductor by removing the solvent or dispersion medium contained in the layer material have a a step of providing the organic semiconductor layer,
As the organic substance, a compound represented by the following general formula (2) or a compound represented by the following general formula (3) having a function of transporting holes as the carrier transport site, or an electron as the carrier transport site. The main component is a compound represented by the following general formula (4), which has a function of transporting water .

[In the formula, three R ^{1 s} each independently represent a hydrogen atom or any one of substituents represented by the following general formula (5) or the following general formula (6). Or different. However, at least 1 of three R < ¹ > represents either of the substituents represented by the following general formula (5) or the following general formula (6). ]

[In each formula, R ² represents a single bond or an alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkali metal, an amino group, or an alkyl group having 1 to 20 carbon atoms. Two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may be the same or different. X ¹ is a single bond,

Represents. Y ¹ is a single bond,

Represents. ]

[In the formula, three R ^{1 s} each independently represent a hydrogen atom or any one of substituents represented by the following general formula (5) or the following general formula (6). Or different. However, at least 1 of three R < ¹ > represents either of the substituents represented by the following general formula (5) or the following general formula (6). ]

[In each formula, R ² represents a single bond or an alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkali metal, an amino group, or an alkyl group having 1 to 20 carbon atoms. Two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may be the same or different. X ¹ is a single bond,

Represents. Y ¹ is a single bond,

Represents. ]

[In the formula, two R ^{1 s} each independently represent a hydrogen atom or any one of substituents represented by the following general formula (5) or the following general formula (6). Or different. However, at least 1 of two R < ¹ > represents either of the substituents represented by the following general formula (5) or the following general formula (6). ]

[In each formula, R ² represents a single bond or an alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkali metal, an amino group, or an alkyl group having 1 to 20 carbon atoms. Two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may be the same or different. X ¹ is a single bond,

Represents. Y ¹ is a single bond,

Represents. ]
Thereby, delivery of the carrier from the electrode through the intermediate layer to the organic semiconductor layer is smoothly performed, and an electronic device substrate having excellent carrier transport capability can be manufactured.
In addition, since the organic substance is a compound having a carrier transport site having a function of transporting carriers and a chargeable site that binds to the carrier transport site, the organic substance can be reliably removed when a voltage is applied to the liquid. Can be collected on the electrode.
In addition, since the carrier transport site has a function of transporting holes, a function of transporting holes to the intermediate layer can be provided.
Furthermore, when the organic substance contains the compound represented by the general formula (2) or the general formula (3) as a main component, the obtained intermediate layer has an excellent hole transporting ability, and an electrode and an organic semiconductor layer It exhibits excellent adhesion to.
In addition, since the carrier transport site has a function of transporting electrons, a function of transporting electrons to the intermediate layer can be provided.
Furthermore, when the organic substance contains the compound represented by the general formula (4) as a main component, the obtained intermediate layer has excellent electron transport ability and excellent adhesion to the electrode and the organic semiconductor layer. It will be demonstrated.

In the method for manufacturing an electronic device substrate according to the present invention, it is preferable that the chargeable portion can be charged in the vicinity of the end opposite to the carrier transporting portion.
Thereby, when a voltage is applied to the liquid, a chemical bond is formed relatively easily between the chargeable portion and the electrode, and the adhesion between the electrode and the intermediate layer can be improved.
In the method for manufacturing an electronic device substrate of the present invention, it is preferable that the carrier transporting portion includes a structure having a high affinity with the constituent material of the organic semiconductor layer.
Thereby, the adhesiveness between an intermediate | middle layer and an organic-semiconductor layer improves, and the delivery of the carrier from an intermediate | middle layer to an organic-semiconductor layer can be performed smoothly.

Hereinafter, the manufacturing method of the board | substrate for electronic devices of this invention is demonstrated in detail based on suitable embodiment shown to an accompanying drawing.
Hereinafter, a case where the electronic device is applied to an organic electroluminescence element (hereinafter simply referred to as “organic EL element”) will be described as an example.
<Organic EL device>
<< First Embodiment >>
First, a first embodiment of an organic EL element will be described.

FIG. 1 is a longitudinal sectional view showing a first embodiment of an organic EL element. In the following description, for convenience of explanation, the upper side in FIG. 1 will be described as “upper” and the lower side as “lower”.
An organic EL element 1 shown in FIG. 1 includes a laminated body 9 including an anode 7, a cathode 3, an intermediate layer 4 that is sequentially laminated between the anode 7 and the cathode 3, and a light emitting layer 5. Is provided. The entire organic EL element 1 is provided on the substrate 2 and sealed with a sealing member 8.

In the present embodiment, in this organic EL element 1, an electronic device to which the method for manufacturing a substrate for an electronic device of the present invention is applied using the anode (electrode) 7, the intermediate layer 4, and the light emitting layer (organic semiconductor layer) 5. A substrate is configured.
The substrate 2 serves as a support for the organic EL element 1. When the organic EL element 1 is configured to extract light from the side opposite to the substrate 2 (top emission type), the substrate 2 and the anode 7 are not particularly required to have transparency. Further, when the organic EL element 1 is configured to extract light from the substrate 2 side (bottom emission type), each of the substrate 2 and the anode 7 is substantially transparent (colorless transparent, colored transparent, translucent). What you have is used.

Examples of the substrate 2 include resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, and polyarylate, and quartz glass and soda glass. Transparent substrate composed of glass material, substrate composed of ceramic material such as alumina, metal substrate such as stainless steel with oxide film (insulating film) formed on it, composed of opaque resin material An opaque substrate such as a patterned substrate can be used.
Although the average thickness of such a board | substrate 2 is not specifically limited, It is preferable that it is about 0.1-10 mm, and it is more preferable that it is about 0.1-5 mm.

The anode 7 is an electrode that injects holes into the intermediate layer 4 described later.
Moreover, as a constituent material (anode material) of the anode 7, it is preferable to use a material having a large work function and excellent conductivity from the viewpoint of injecting holes.
Examples of such an anode material include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , oxides such as Al-containing ZnO, Au, Pt, and Ag. Cu, Al, or an alloy containing these, and at least one of them can be used.

The average thickness of the anode 7 is not particularly limited, but is preferably about 10 to 200 nm, and more preferably about 50 to 150 nm. If the thickness of the anode 7 is too thin, the function as the anode 7 may not be sufficiently exhibited. On the other hand, if the anode 7 is too thick, the light emission efficiency of the organic EL element 1 may be reduced.
Further, the surface resistance of the anode 7 is preferably as low as possible. Specifically, it is preferably 100Ω / □ or less, more preferably 50Ω / □ or less. The lower limit value of the surface resistance is not particularly limited, but is usually preferably about 0.1Ω / □.

The cathode 3 is an electrode for injecting electrons into the light emitting layer 5 described later. As a constituent material of the cathode 3, a material having a small work function is preferably used.
Examples of the constituent material of the cathode 3 include Li, Na, K, Be, Mg, Ca, Sr, Ba, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb or Examples include alloys containing these, and one or more of these can be used in combination.

In particular, when an alloy is used as the constituent material of the cathode 3, it is preferable to use an alloy containing a stable metal element such as Ag, Al, or Cu, specifically an alloy such as MgAg, AlLi, or CuLi. By using such an alloy as the constituent material of the cathode 3, the electron injection efficiency and stability of the cathode 3 can be improved.
The cathode 3 can also have a multilayer structure. In this case, the layer closer to the light emitting layer 5 is preferably made of a cathode material having a lower work function. For example, when the cathode 3 has a laminated structure of two layers, a layer far from the light emitting layer 5 is made of Ca as a main material, and a layer near the light emitting layer 5 is made of Al, Ag, or an alloy containing these. Can be configured as the main material.

Although the average thickness of such a cathode 3 is not specifically limited, It is preferable that it is about 1-1000 nm, and it is more preferable that it is about 100-400 nm. If the thickness of the cathode 3 is too thin, the specific resistance becomes high and a voltage drop occurs, or the electrical conductivity characteristics become unstable due to an oxidation reaction, and the function as the cathode 3 may not be sufficiently exhibited. On the other hand, when the cathode 3 is too thick, when the cathode 3 is formed by using a vacuum deposition method, a sputtering method, or the like, the temperature in the film is remarkably increased or the residual stress is increased, which is provided as a lower layer described later. There is a possibility that the light emitting layer 5 is destroyed or the cathode 3 or the light emitting layer 5 is peeled off and the light emission efficiency of the organic EL element 1 is lowered.
The surface resistance of the cathode 3 is preferably as low as possible. Specifically, it is preferably 50Ω / □ or less, more preferably 20Ω / □ or less. The lower limit value of the surface resistance is not particularly limited, but is usually preferably about 0.1Ω / □.

A laminated body 9 in which an intermediate layer 4 and a light emitting layer (organic semiconductor layer) 5 are laminated in this order from the anode 7 side is in contact with the anode 7 and the cathode 3 between the anode 7 and the cathode 3. It is formed as follows.
The intermediate layer 4 has a function of transporting holes injected from the anode 7 to the light emitting layer 5. This electronic device ( an electronic device including the above-described electronic device substrate) is characterized by a step of forming an intermediate layer 4 composed mainly of an organic substance having a function of transporting carriers. The formation process, configuration, and constituent material of the intermediate layer 4 will be described in detail later.

Since the intermediate layer 4 is formed by a forming process described later, the intermediate layer 4 exhibits excellent adhesion to both the anode 7 and the light emitting layer 5 on the surface in contact with them. As a result, injection of holes from the anode 7 to the intermediate layer 4 and extraction of holes from the intermediate layer 4 to the light emitting layer 5 can be performed smoothly.
In addition, since the organic substance has a function of transporting carriers (holes in the present embodiment), the transport of holes in the intermediate layer 4 can also be performed smoothly.

Therefore, by providing the intermediate layer 4 between the anode 7 and the light emitting layer 5, it is possible to smoothly transfer holes from the anode 7 to the light emitting layer 5 through the intermediate layer 4. Become. As a result, the substrate for electronic devices exhibits excellent hole (carrier) transporting ability.
The thickness (average) of the intermediate layer 4 is not particularly limited, but is preferably about 1 to 50 nm, and more preferably about 2 to 20 nm. If the thickness of the intermediate layer 4 is too thin, pinholes are generated, and there is a risk that holes will not be transferred from the cathode 3 to the light emitting layer 5 via the intermediate layer 4. On the other hand, when the thickness of the intermediate layer 4 is too thick, the resistance value in the thickness direction of the intermediate layer 4 increases, and the power consumption of the organic EL element 1 increases.

  When energization (voltage is applied) between the anode 7 and the cathode 3, holes move in the intermediate layer 4 and electrons move in the light emitting layer 5, mainly the interface of the light emitting layer 5 on the intermediate layer 4 side. In the vicinity, excitons are generated by holes and electrons. This exciton recombines in a certain time, but at this time, the excitation energy accumulated by the exciton generation is mainly emitted as light such as fluorescence or phosphorescence. This is electroluminescence emission.

As a constituent material of the light emitting layer 5, holes can be injected from the anode 7 side when electrons are applied, and electrons can be injected from the cathode 3 side, and a field where holes and electrons recombine can be provided. Anything may be used.
Such luminescent materials include various low-molecular luminescent materials and various high-molecular luminescent materials as described below, and at least one of them can be used.

  In addition, since the precise | minute light emitting layer 5 is obtained by using a low molecular light emitting material, the light emission efficiency of the light emitting layer 5 improves. Moreover, since the polymer light-emitting material can be dissolved in a solvent relatively easily, the light-emitting layer 5 can be easily formed by various coating methods such as an ink jet printing method. Furthermore, by using a combination of a low-molecular light-emitting material and a high-molecular light-emitting material, the light-emitting layer has the effect of using a low-molecular light-emitting material and a high-molecular light-emitting material. 5 can be easily formed by various coating methods such as an ink jet printing method.

Examples of low-molecular light emitting materials include benzene compounds such as distyrylbenzene (DSB) and diaminodistyrylbenzene (DADSB), naphthalene compounds such as naphthalene and nile red, phenanthrene compounds such as phenanthrene, Chrysene, chrysene compounds such as 6-nitrochrysene, perylene, N, N′-bis (2,5-di-t-butylphenyl) -3,4,9,10-perylene-di-carboximide (BPPC) Perylene compounds such as coronene, anthracene compounds such as anthracene and bisstyrylanthracene, pyrene compounds such as pyrene, 4- (di-cyanomethylene) -2-methyl-6 Such as-(para-dimethylaminostyryl) -4H-pyran (DCM) Pyran compounds, acridine compounds such as acridine, stilbene compounds such as stilbene, thiophene compounds such as 2,5-dibenzoxazole thiophene, benzoxazole compounds such as benzoxazole, benzos such as benzimidazole Imidazole compounds, benzothiazole compounds such as 2,2 '-(para-phenylenedivinylene) -bisbenzothiazole, bistyryl (1,4-diphenyl-1,3-butadiene), butadienes such as tetraphenylbutadiene Compounds, naphthalimide compounds such as naphthalimide, coumarin compounds such as coumarin, perinone compounds such as perinone, oxadiazole compounds such as oxadiazole, aldazine compounds, 1, 2, 3 , 4, Cyclopentadiene compounds such as 5-pentaphenyl-1,3-cyclopentadiene (PPCP), quinacridone compounds such as quinacridone and quinacridone red, pyridine compounds such as pyrrolopyridine and thiadiazolopyridine, 2,2 Spiro compounds such as', 7,7'-tetraphenyl-9,9'-spirobifluorene, phthalocyanine (H ₂ Pc), metal or non-metal phthalocyanine compounds such as copper phthalocyanine, florene such as fluorene Compounds, (8-hydroxyquinoline) aluminum (Alq ₃ ), tris (4-methyl-8quinolinolate) aluminum (III) (Almq ₃ ), (8-hydroxyquinoline) zinc (Znq ₂ ), (1,10- Phenanthroline) -tris- (4,4,4-trif Oro-1- (2-thienyl) - butane-1,3-Jioneto) europium _{(III) (Eu (TTA)} 3 (phen)), factory scan (2-phenylpyridine) iridium (Ir _(ppy) 3), Various metal complexes such as (2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine) platinum (II) can be mentioned.

  Examples of the polymer light-emitting material include polyacetylene compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), poly (alkyl, phenylacetylene) (PAPA), and poly (para-para-). Fenvinylene) (PPV), poly (2,5-dialkoxy-para-phenylenevinylene) (RO-PPV), cyano-substituted-poly (para-phenvinylene) (CN-PPV), poly (2-dimethyloctyl) Polyparaphenylene vinylene compounds such as silyl-para-phenylene vinylene (DMOS-PPV), poly (2-methoxy, 5- (2′-ethylhexoxy) -para-phenylene vinylene) (MEH-PPV), poly ( 3-alkylthiophene) (PAT), poly (oxypropylene) Polythiophene compounds such as riol (POPT), poly (9,9-dialkylfluorene) (PDAF), α, ω-bis [N, N′-di (methylphenyl) aminophenyl] -poly [9,9- Bis (2-ethylhexyl) fluorene-2,7-diyl] (PF2 / 6am4), poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10-diyl) Polyfluorene compounds such as poly (para-phenylene) (PPP), polyparaphenylene compounds such as poly (1,5-dialkoxy-para-phenylene) (RO-PPP), poly (N-vinyl) Polycarbazole compounds such as carbazole (PVK), poly (methylphenylsilane) (PMPS), poly (naphthylphenylsilane) PnPs), polysilane-based compounds such as poly (biphenylyl phenyl silane) (pBPS), and the like.

The thickness (average) of the light emitting layer 5 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 50 to 100 nm. By setting the thickness of the light emitting layer 5 within the above range, recombination of holes and electrons is efficiently performed, and the light emission efficiency of the light emitting layer 5 can be further improved.
Note that the light emitting layer 5 is not limited to a single layer, and may be, for example, a multilayer having an electron transport layer having excellent electron transport capability on the side in contact with the cathode 3. By making the light emitting layer 5 have such a configuration, the electron transport ability in the light emitting layer 5 can be further improved.

The constituent material (electron transport material) of the electron transport layer is not particularly limited. For example, 1,3,5-tris [(3-phenyl-6-tri-fluoromethyl) quinoxalin-2-yl] benzene (TPQ1) ), 1,3,5-tris [{3- (4-t-butylphenyl) -6-trisfluoromethyl} quinoxalin-2-yl] benzene (TPQ2) (starburst compound) , Naphthalene compounds such as naphthalene, phenanthrene compounds such as phenanthrene, chrysene compounds such as chrysene, perylene compounds such as perylene, anthracene compounds such as anthracene, pyrene compounds such as pyrene, acridine Acridine compounds such as stilbene compounds such as stilbene, BBOT Thiophene compounds, butadiene compounds such as butadiene, coumarin compounds such as coumarin, quinoline compounds such as quinoline, bistyryl compounds such as bistyryl, pyrazine compounds such as pyrazine and distyrylpyrazine, Quinoxaline compounds such as quinoxaline, benzoquinone, benzoquinone compounds such as 2,5-diphenyl-para-benzoquinone, naphthoquinone compounds such as naphthoquinone, anthraquinone compounds such as anthraquinone, oxadiazole, 2- (4 -Biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), oxadiazole compounds such as BMD, BND, BDD, BAPD, triazole, 3,4, 5-triphenyl-1,2 Triazole compounds such as 4-triazole, oxazole compounds, anthrone compounds such as anthrone, fluorenone, fluorenone compounds such as 1,3,8-trinitro-fluorenone (TNF), diphenoquinone, diphenoquinone such as MBDQ Compounds, stilbene quinones, stilbene quinone compounds such as MBSQ, anthraquinodimethane compounds, thiopyran dioxide compounds, fluorenylidene methane compounds, diphenyldicyanoethylene compounds, fluorene compounds such as fluorene, phthalocyanine, copper phthalocyanine, metal or metal-free phthalocyanine compound such as iron phthalocyanine, (8-hydroxyquinoline) aluminum (Alq _3), benzoxazole or Benzochiazo Various metal complexes such as complexes having a ligand, and the like, can be used at least one of them.

The sealing member 8 is provided so as to cover the anode 7, the intermediate layer 4, the light emitting layer 5, and the cathode 3, and has a function of hermetically sealing them and blocking oxygen and moisture. By providing the sealing member 8, it is possible to suppress or prevent the oxidation of the cathode 3 in particular, and to obtain the effects of improving the reliability of the organic EL element 1 and preventing deterioration / deterioration (improvement of durability).
Examples of the constituent material of the sealing member 8 include Al, Au, Cr, Nb, Ta, Ti, alloys containing these, silicon oxide, various resin materials, and the like.

Further, the sealing member 8 may be formed in a flat plate shape so as to face the substrate 2 and be sealed with a sealing material such as a thermosetting resin.
Such an organic EL element 1 has such a characteristic that when a voltage of 0.5 V is applied so that the cathode 3 is negative and the anode 7 is positive, the resistance value is 100 Ω / cm ² or more. Is preferable, and it is more preferable to have a characteristic of 1 kΩ / cm ² or more. This characteristic indicates that in the organic EL element 1, a short circuit (leakage) between the cathode 3 and the anode 7 is preferably prevented or suppressed, and the organic EL element 1 having such characteristics is provided. Has a particularly high luminous efficiency.

In the present embodiment, the case where the intermediate layer 4 is provided between the anode 7 and the light emitting layer 5 so as to be in contact with both of them has been described. However, the present invention is not limited to such a case. A hole transport layer having a function of transporting holes injected from the intermediate layer 4 to the light emitting layer 5 may be provided between the light emitting layer 4 and the light emitting layer 5.
As the constituent material of the hole transport layer, the same constituent materials as those of the hole transport layer 6 described later in the second embodiment of the organic EL element can be used.
Further, an electron transporting intermediate layer having a function of transporting electrons injected from the cathode 3 to the light emitting layer 5 may be provided between the cathode 3 and the light emitting layer 5.
This electron transporting intermediate layer can be the same as the intermediate layer 14 described later in the second embodiment of the organic EL element.

Such an organic EL element 1 can be manufactured as follows, for example.
In the method of manufacturing the organic EL element 1, the step of providing the intermediate layer 4 (intermediate layer forming step) and the step of providing the light emitting layer (organic semiconductor layer) 5 (light emitting layer forming step) Manufacturing methods are applied.
FIG. 2 is a schematic diagram (longitudinal sectional view) for explaining a step of providing an intermediate layer.
In the following description, the upper side in FIG. 2 is referred to as “upper” and the lower side is referred to as “lower”.

[1A] Anode Formation Step First, the substrate 2 is prepared, and the anode 7 is formed on the substrate 2.
The anode 7 is, for example, a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, or laser CVD, a dry plating method such as vacuum deposition, sputtering, or ion plating, or a wet method such as electrolytic plating, immersion plating, or electroless plating. It can be formed by using a plating method, a thermal spraying method, a sol-gel method, a MOD method, a metal foil bonding, or the like.

[2A] Intermediate Layer Formation Step As described above, this electronic device (organic EL element) has a feature in the formation step of the intermediate layer 4.
That is, in a state where the anode 7 formed on the substrate 2 is in contact with a liquid containing an organic substance having a function of transporting holes (carriers), a voltage is applied to the liquid using the anode 7 as one electrode. Thus, the organic substance charged in the liquid is collected on the anode 7 to form the intermediate layer 4 on the anode 7.
By forming the intermediate layer 4 by this process, the intermediate layer 4 has excellent adhesion to both the anode 7 and the light-emitting layer 5 formed in the next step [3A] on the surface in contact with them. Will be demonstrated. As a result, injection of holes from the anode 7 to the intermediate layer 4 and extraction of holes from the intermediate layer 4 to the light emitting layer 5 can be performed smoothly.
Hereinafter, the formation process of such an intermediate | middle layer 4 is explained in full detail.

[2A-1] First, a liquid containing an organic substance having a function of transporting holes is prepared.
In the present embodiment, the intermediate layer 4 is formed for the purpose of transporting holes injected from the anode 7 to the light emitting layer 5, and therefore, an organic material that transports holes as carriers is selected.
The organic substance having a function of transporting holes (hereinafter sometimes simply referred to as “organic substance”) is not particularly limited as long as it can maintain a charged state when a voltage is applied to the liquid. For example, it is preferable to use one having a carrier transporting site having a function of transporting holes and a chargeable site bonded to the carrier transporting site. As a result, the organic substance has a structure in which a chargeable part protrudes outside the carrier transporting part. Therefore, when a voltage is applied to the liquid in the post-process [2A-3], the structure of the organic substance is obtained. It is possible to prevent the chargeable portion from being surrounded by the inside. As a result, the organic substance is reliably affected by the electric field due to the application of the voltage. Thereby, organic substances can be reliably collected on the anode 7.

Note that the organic substance having a carrier transporting part and a chargeable part may have a structure in which the carrier transporting part is charged in addition to the chargeable part when a voltage is applied to the liquid. Thereby, the charge amount as the whole organic substance becomes large, and the organic substance can be more reliably collected on the anode 7.
The carrier transporting portion preferably has a structure having a high affinity with the constituent material of the light emitting layer 5, that is, the organic constituent material. Thereby, when the light emitting layer 5 is formed on the intermediate | middle layer 4, the adhesiveness between these layers can be improved. As a result, holes can be smoothly transferred from the intermediate layer 4 to the light emitting layer 5.

Further, as described above, in the present embodiment, as the organic substance, one that transports holes as carriers is selected. That is, in an organic substance having a carrier transporting part and a chargeable part, one having a function of transporting holes is selected as the carrier transporting part.
From the above, as the carrier transport site, one having an excellent hole transport capability and an organic structure is preferably selected.

Specifically, examples of the carrier transport site include those having a copper phthalocyanine skeleton, a hexaazatriphenylene skeleton, and a hexaazatrinaphthylene skeleton. These skeletons are preferable because they contain many conjugated bonds such as a benzene ring and are particularly excellent in hole transporting ability, like the constituent material of the light emitting layer 5.
The chargeable part may be, for example, a part that can be charged in the vicinity of the part that binds to the carrier transporting part or the center of the part that can be charged, but in particular, near the end opposite to the carrier transporting part. It is preferable that the material can be charged in the above. Thereby, in the post-process [2A-3], when the voltage is applied to the liquid, the vicinity of the charged end can be brought into contact with the anode 7. As a result, a chemical bond is formed relatively easily between the chargeable portion and the anode 7. Thereby, the adhesiveness between the intermediate layer 4 and the anode 7 can be improved, and holes can be transferred through this chemical bond.

  Considering this, as the chargeable site, for example, a substituent represented by the following general formula (5) or the following general formula (6) is a preferable structure. Since these substituents can stably maintain a charged state even when a relatively low voltage is applied, organic substances can be reliably collected on the anode 7. Furthermore, since it has excellent reactivity with the constituent material of the anode 7, a chemical bond can be reliably formed with the anode 7.

［各式中、Ｒ^２は、単結合（結合手）または炭素数１〜２０のアルキレン基を表す。Ｒ^３は、水素原子、アルカリ金属、アミノ基または炭素数１〜２０のアルキル基を表す。Ｘ^１は、単結合（bonding dash）、

[In each formula, R ² represents a single bond (bond) or an alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkali metal, an amino group, or an alkyl group having 1 to 20 carbon atoms. X ¹ is a single bond (bonding dash),

を表す。Ｙ^１は、単結合、

Represents. Y ¹ is a single bond,

を表す。２つのＲ^４は、それぞれ独立して、水素原子または炭素数１〜２０のアルキル基を表し、同一であっても、異なっていてもよい。］

Represents. Two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may be the same or different. ]

In addition, when using the substituent represented by the said General formula (6) as a site | part which can be charged, it is preferable to set the carbon number of two R < ⁴ > respectively as small as possible. As a result, charging can be performed in the vicinity of the end of the chargeable portion opposite to the carrier transporting portion, and the effects as described above can be reliably obtained.
When a voltage is applied to the liquid, the substituents represented by the general formula (5) and the general formula (6) are charged. The structure of the substituent at this time is, for example, The thing like this is mentioned.

That is, in the substituent represented by the general formula (5), when R ³ is a hydrogen atom or an alkali metal such as sodium, potassium, or lithium, R ³ is released from the substituent, thereby releasing R ^3. The substituted group becomes negatively charged.
Further, in the substituent represented by the general formula (5), when R ³ is an alkyl group having 1 to 20 carbon atoms, the hydrogen atom contained in the alkyl group is removed from the substituent, whereby the hydrogen atom is removed. The substituted group becomes negatively charged. When the alkyl group has 2 or more carbon atoms, the hydrogen atom bonded to the terminal carbon atom tends to be more easily separated.

Furthermore, in the substituent represented by the general formula (5), when R ³ is an amino group or the substituent represented by the general formula (6), a hydrogen atom is bonded to the nitrogen atom. Thus, the substituent to which a hydrogen atom is bonded becomes positively charged.
Taking these into consideration, for example, compounds represented by the following general formula (1) to the following general formula (3) are preferably used as the organic substance having a carrier transporting portion and a chargeable portion. By using an organic substance having such a configuration, the above-described effects can be reliably obtained.
In these compounds, R ¹ constitutes a chargeable site, and the main skeleton other than R ¹ constitutes a carrier transport site.

［式中、４つのＲ^１は、それぞれ独立して、水素原子、または、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表し、同一であっても、異なっていてもよい。ただし、４つのＲ^１のうちの少なくとも１つは、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表す。］

[In the formula, four R ^{1 s} each independently represent a hydrogen atom or any one of the substituents represented by the general formula (5) or the general formula (6). Or different. However, at least 1 of four R < ¹ > represents either of the substituents represented by the said General formula (5) or the said General formula (6). ]

［式中、３つのＲ^１は、それぞれ独立して、水素原子、または、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表し、同一であっても、異なっていてもよい。ただし、３つのＲ^１のうちの少なくとも１つは、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表す。］

[In the formula, three R ^{1 s} each independently represent a hydrogen atom or any one of the substituents represented by the general formula (5) or the general formula (6). Or different. However, at least 1 of three R < ¹ > represents either of the substituents represented by the said General formula (5) or the said General formula (6). ]

［式中、３つのＲ^１は、それぞれ独立して、水素原子、または、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表し、同一であっても、異なっていてもよい。ただし、３つのＲ^１のうちの少なくとも１つは、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表す。］

[In the formula, three R ^{1 s} each independently represent a hydrogen atom or any one of the substituents represented by the general formula (5) or the general formula (6). Or different. However, at least 1 of three R < ¹ > represents either of the substituents represented by the said General formula (5) or the said General formula (6). ]

Although the density | concentration of the organic substance in a liquid changes a little also with the kind of organic substance, it is preferable that it is about 0.01-0.5 mol / L, and it is more preferable that it is about 0.1-0.3 mol / L. By satisfying such a relationship, in the next step [2A-3], the organic substance can be reliably collected on the anode 7 to form the intermediate layer 4.
The liquid may be a solution in which an organic substance is dissolved in a solvent, or may be a dispersion liquid in which an organic substance is dispersed in a dispersion medium.

Examples of the solvent or dispersion medium used in preparing the organic substance-containing liquid include various water, methanol, ethanol, isopropyl alcohol, acetonitrile, ethyl acetate, ether, methylene chloride, NMP (N-methyl-2-pyrrolidone), and the like. These can be used, and one or more of these can be used in combination.
In the following steps, the case where the compounds represented by the general formula (1) to the general formula (3) are used as organic substances will be described as an example.

[2A-2] Next, the anode 7 provided on the substrate 2 was set as a cathode or an anode, and an electrode made of a conductive material was set as a counter electrode, and these were prepared in the step [2A-1]. Contact with liquid.
As a method of bringing the anode 7 and the counter electrode into contact with the liquid, for example, a surface on the side on which the intermediate layer 4 of the anode 7 is formed in the liquid in the container having the counter electrode on the inner wall in addition to an immersion method in which these are immersed in the liquid. And the like.

Here, whether the anode 7 is placed on the cathode or the anode depends on whether the chargeable portion is charged, in other words, whether the chargeable portion is positive or negative when a voltage is applied to the liquid. It may be selected depending on whether it is charged. That is, when a chargeable site is negatively charged like the substituent represented by the general formula (5), the anode can be charged like the substituent represented by the general formula (6). When such a part is positively charged, the anode 7 may be installed on the cathode.
For convenience of explanation, FIG. 2 shows a case where the chargeable portion (substituent R ¹ ) is negatively charged and the anode 7 is installed on the anode.

[2A-3] Next, a voltage is applied between the anode and the cathode installed in the step [2A-2].
Thus, in accordance with the charged state of the substituents R ^1, organics, as shown in FIG. 2 (a), so that the move to the anode 7 side.
When the negatively charged substituent R ¹ comes into contact with the surface of the anode 7 as shown in FIG. 2B, the substituent R ¹ and the constituent material of the anode 7 form a chemical bond. Become.

Such chemical bonds are sequentially formed by the substituent R ¹ that has reached the surface of the anode 7, and thus are formed until the substituent R ¹ cannot contact the surface of the anode 7 due to steric hindrance due to the carrier transport site. Is done. Thus, as shown in FIG. 2 (c), in a state in which the substituent R ¹ is bonded to the anode 7, the structure of the membrane anode carrier transporting moiety are arrayed in a row so as to be parallel to the surface direction of the anode 7 7 will be formed on the surface. Thereby, since the anode 7 and the organic substance are chemically bonded, the anode 7 and the intermediate layer 4 to be formed have excellent adhesion.

  When a voltage is further applied after such a film is formed, the carrier transport site approaching the anode 7 has an affinity for the carrier transport sites arranged in a line on the anode 7. Thus, a strong interaction can be obtained. As a result, the organic material is laminated with the carrier transporting portions in contact with each other, and the intermediate layer 4 as shown in FIG. 2D is formed.

In such an intermediate layer 4, since the carrier transport sites are in contact with each other, the holes injected from the anode 7 are directed toward the light emitting layer 5 formed in the next step [3]. Can be transported smoothly.
Furthermore, as described above, the carrier transport site contained in the compounds represented by the general formula (1) to the general formula (3) contains a lot of conjugated structures. It also exhibits excellent affinity for materials. As a result, the intermediate layer 4 has excellent adhesion to the light emitting layer 5.

The voltage difference (applied voltage) between the cathode and the anode is slightly different depending on the kind of the chargeable part, but is preferably about 1 to 50V, more preferably about 5 to 20V.
Moreover, it is preferable that the temperature of a liquid is about 20-90 degreeC, and it is more preferable that it is about 50-80 degreeC.
The pH of the liquid is preferably about 2 to 10, more preferably about 4 to 8.5.
By setting the applied voltage and the temperature and pH of the liquid within such ranges, the intermediate layer 4 can be reliably formed on the anode 7 and the film formation rate can be made relatively slow. Can be controlled more easily and reliably.

[3A] Light-Emitting Layer Formation Step Next, the light-emitting layer 5 is formed on the intermediate layer 4, that is, on the surface of the intermediate layer 4 opposite to the anode 7.
The light emitting layer 5 is formed by, for example, applying (supplying) a light emitting layer material obtained by dissolving the light emitting material as described above in a solvent or dispersing in a dispersion medium onto the intermediate layer 4, and then adding the solvent or It can be obtained by removing the dispersion medium.

  Various methods can be used as a method for supplying the light emitting layer material onto the intermediate layer 4. For example, an inkjet method, a spin coating method, a liquid mist chemical volume method (LSMCD method), a casting method, a microgravure coating Coating methods such as coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, and micro contact printing. 1 type or 2 types or more of these can be used in combination.

  Examples of the solvent or dispersion medium include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate, methyl ethyl ketone (MEK), acetone, diethyl ketone, and methyl isobutyl ketone. (MIBK), ketone solvents such as methyl isopropyl ketone (MIPK), cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxy Ethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ether Ether solvents such as ruether (carbitol), cellosolve solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, toluene, xylene, benzene, trimethylbenzene, Aromatic hydrocarbon solvents such as tetramethylbenzene, aromatic heterocyclic solvents such as pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide Amide solvents such as (DMA), halogen compound solvents such as dichloromethane, chloroform and 1,2-dichloroethane, ester solvents such as ethyl acetate, methyl acetate and ethyl formate, sulfur such as dimethyl sulfoxide (DMSO) and sulfolane Compound solvents, various organic solvents such as nitrile solvents such as acetonitrile, propionitrile, acrylonitrile, organic acid solvents such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, or mixed solvents containing these. Can be mentioned.

[4A] Cathode Formation Step Next, the cathode 3 is formed on the light emitting layer 5.
The cathode 3 can be formed using, for example, a vacuum evaporation method, a sputtering method, a metal foil bonding, or the like.
[5A] Sealing Member Forming Step Next, the sealing member 8 is formed so as to cover the anode 7, the intermediate layer 4, the light emitting layer 5, and the cathode 3.

The sealing member 8 can be formed (provided), for example, by bonding a box-shaped protective cover made of the above-described material with various curable resins (adhesives).
As the curable resin, any of a thermosetting resin, a photocurable resin, a reactive curable resin, and an anaerobic curable resin can be used.
The organic EL element 1 is manufactured through the above processes.

  In the present embodiment, the case where the organic EL element 1 is manufactured by sequentially stacking the intermediate layer 4, the light emitting layer 5, the hole transport layer 6, and the anode 7 on the cathode 3 has been described. However, the present invention is not limited to such cases. That is, for example, a laminate in which the intermediate layer 4 is formed on the anode 7 and a laminate in which the light emitting layer 5 is laminated on the cathode 3 are prepared, and the intermediate layer 4 and the light emitting layer 5 are opposed to each other. In this state, they may be manufactured by bringing them into contact with each other and bonding them together.

The organic EL element 1 can be used, for example, for a display device, but can also be used as a light source or the like, and can be used for various optical applications.
When the organic EL element 1 is used for a display device, a plurality of organic EL elements 1 are provided in the display device. Examples of such a display device include the following.

FIG. 3 is a longitudinal sectional view showing a display device including a plurality of organic EL elements.
A display device 100 shown in FIG. 3 includes a base body 20 and a plurality of organic EL elements 1 provided on the base body 20.
The base body 20 includes a substrate 21 and a circuit unit 22 formed on the substrate 21.
The circuit unit 22 includes a protective layer 23 made of, for example, a silicon oxide layer formed on the substrate 21, a driving TFT (switching element) 24 formed on the protective layer 23, a first interlayer insulating layer 25, And a second interlayer insulating layer 26.

The driving TFT 24 includes a semiconductor layer 241 made of silicon, a gate insulating layer 242 formed on the semiconductor layer 241, a gate electrode 243 formed on the gate insulating layer 242, a source electrode 244, and a drain electrode 245. have.
On the circuit part 22, the organic EL elements 1 are provided corresponding to the respective driving TFTs 24. Adjacent organic EL elements 1 are partitioned by a first partition wall 31 and a second partition wall 32.

In the present embodiment, the anode 7 of each organic EL element 1 constitutes a pixel electrode and is electrically connected to the drain electrode 245 of each driving TFT 24 by the wiring 27. The cathode 3 of each organic EL element 1 is a common electrode.
And the sealing member (not shown) is joined to the base | substrate 20 so that each organic EL element 1 may be covered, and each organic EL element 1 is sealed.
The display device 100 may be monochromatic display, and color display is also possible by selecting a light emitting material used for each organic EL element 1.

<< Second Embodiment >>
Next, a second embodiment of the organic EL element will be described.
FIG. 4 is a longitudinal sectional view showing a second embodiment of the organic EL element. In the following description, for convenience of explanation, the upper side in FIG. 3 will be described as “upper” and the lower side as “lower”.
Hereinafter, the second embodiment will be described with a focus on differences from the first embodiment, and description of similar matters will be omitted.

The organic EL element 10 shown in FIG. 3 includes a cathode 3, an anode 7, an intermediate layer 14 sequentially stacked from the cathode 3 side between the cathode 3 and the anode 7, a light emitting layer 5, and a hole transport layer. 6 is provided. The entire organic EL element 10 is provided on the substrate 2 and sealed with a sealing member 8.
In the present embodiment, in the organic EL element 10, the cathode (electrode) 3, the intermediate layer 14, and the light emitting layer (organic semiconductor layer) 5 constitute an electronic device substrate .
The substrate 2 is composed of the same as described in the first embodiment.

  Further, as described in the first embodiment, a material having a small work function is usually selected as the constituent material of the cathode 3 from the viewpoint of injecting electrons. However, in the organic EL element 10 of the present embodiment, an intermediate layer 14 having a configuration as described later is provided between the cathode 3 and the light emitting layer 5 to improve the adhesion between these layers. Can do. As a result, even when a material having a high work function is used as the constituent material of the cathode 3, electrons can be smoothly transferred between the cathode 3 and the intermediate layer 14.

As such a material having a high work function, the same material as that of the anode 7 described in the first embodiment can be used.
The constituent materials of the cathode 3 are conductive metal oxides such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , and Al-containing ZnO. Is preferably used. Since these materials are particularly excellent in stability and conductivity with respect to oxygen, moisture, etc., electrons can be more reliably injected from the cathode 3 to the intermediate layer 14.

As described above, when the organic EL element 1 is a bottom emission type, the cathode 3 is substantially transparent. That is, as the conductive metal oxide, one having substantially transparency is selected. Thereby, the light emitted from the light emitting layer 5 can be reliably extracted from the substrate 2 side.
Incidentally, the organic EL element 10 is provided with a sealing member 8 as shown in FIG. The sealing member 8 is provided for the purpose of suppressing or preventing deterioration and deterioration of the cathode 3 because a material having a small work function is generally easily oxidized. Therefore, when the cathode 3 is made of a material that is relatively stable with respect to oxygen and moisture, such as a conductive metal oxide, the formation of the sealing member 8 may be omitted. Thereby, size reduction of the organic EL element 10, reduction of manufacturing cost, etc. can be aimed at. Further, when the substrate 2 is made of a flexible material, the organic EL element 10 can be given flexibility.

Further, the anode 7 is composed of the same as described in the first embodiment. Thereby, the delivery of holes from the anode 7 to the hole transport layer 6 described later can be performed more smoothly.
Now, between the cathode 3 and the anode 7, the laminate 9 in which the intermediate layer 14, the light emitting layer 5 and the hole transport layer 6 are laminated in this order from the cathode 3 side is in contact with the cathode 3 and the anode 7. It is formed to do.

  The intermediate layer 14 has a function of transporting electrons injected from the cathode 3 to the light emitting layer 5. The intermediate layer 14 has the same configuration as that of the intermediate layer 4 described in the first embodiment, except that an organic substance that is a constituent material of the layer is selected from those having a function of transporting electrons. As a result, the intermediate layer 14 exhibits excellent adhesion to both the cathode 3 and the light emitting layer 5 on the surface in contact with the cathode 3 and the light emitting layer 5. Electrons can be smoothly injected into the light emitting layer 5.

The hole transport layer 6 has a function of transporting holes injected from the anode 7 to the light emitting layer 5.
The constituent material of the hole transport layer 6 may be any material as long as it has a hole transport capability, but various low molecular hole transport materials and various polymer positive materials as shown below. It is preferable that the pore transport material has a basic structure and is a conjugated compound. A conjugated compound is particularly excellent in hole transport capability because it can transport holes very smoothly due to the property of its unique electron cloud spread.

  In addition, since the precise | minute hole transport layer 6 is obtained by using a low molecular hole transport material, the hole transport efficiency of the hole transport layer 6 improves. Further, when a high-molecular hole transport material is used for the hole transport layer 6, it can be dissolved in a solvent relatively easily. Therefore, the hole transport layer 6 can be formed by various coating methods such as an ink jet printing method and a spin coat printing method. Can be easily formed. Further, by using a combination of a low-molecular hole transport material and a high-molecular hole transport material, that is, a fine hole transport layer 6 having excellent hole transport efficiency can be applied to various coating methods such as an ink jet printing method. As a result, the effect of being easily formed can be obtained.

As a low molecular weight hole transport material, 1,1-bis (4-di-para-triaminophenyl) cyclohexane, 1,1′-bis (4-di-para-tolylaminophenyl) -4- Arylcycloalkane compounds such as phenyl-cyclohexane, 4,4 ′, 4 ″ -trimethyltriphenylamine, N, N, N ′, N′-tetraphenyl-1,1′-biphenyl-4,4 ′ -Diamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD1), N, N'-diphenyl-N, N '-Bis (4-methoxyphenyl) -1,1'-biphenyl-4,4'-diamine (TPD2), N, N, N', N'-tetrakis (4-methoxyphenyl) -1,1'- Biphenyl-4,4′-diamine (TPD3), N, N′-di 1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine (α-NPD), arylamine compounds such as TPTE, N, N, N ′, N′— Tetraphenyl-para-phenylenediamine, N, N, N ′, N′-tetra (para-tolyl) -para-phenylenediamine, N, N, N ′, N′-tetra (meta-tolyl) -meta-phenylene Phenylenediamine compounds such as diamine (PDA), carbazole, N-isopropylcarbazole, carbazole compounds such as N-phenylcarbazole, stilbene, stilbene compounds such as 4-di-para-tolylaminostilbene, O _x Oxazole compounds such as Z, triphenylmethane compounds such as triphenylmethane m-MTDATA, 1-phenyl-3 (Para-dimethylaminophenyl) pyrazoline compounds such as pyrazoline, benzine (cyclohexadiene) compounds, triazole compounds such as triazole, imidazole compounds such as imidazole, 1,3,4-oxadiazole, 2 Oxadiazole compounds such as 1,5-di (4-dimethylaminophenyl) -1,3,4, -oxadiazole, anthracene, anthracene compounds such as 9- (4-diethylaminostyryl) anthracene, fluorenone , 2,4,7-trinitro-9-fluorenone, 2,7-bis (2-hydroxy-3- (2-chlorophenylcarbamoyl) -1-naphthylazo) fluorenone compounds such as fluorenone, anilines such as polyaniline Compounds, silane compounds, Like thiophene, thiophene compounds such as poly (thiophene vinylene), poly (2,2′-thienylpyrrole), 1,4-dithioketo-3,6-diphenyl-pyrrolo- (3,4-c) pyrrolopyrrole Pyrrole compounds, fluorene compounds such as fluorene, porphyrins, porphyrin compounds such as metal tetraphenylporphyrin, quinacridone compounds such as quinacridone, phthalocyanine, copper phthalocyanine, tetra (t-butyl) copper phthalocyanine, iron phthalocyanine Metal or metal-free phthalocyanine compounds such as copper naphthalocyanine, vanadyl naphthalocyanine, metal or metal-free naphthalocyanine compounds such as monochlorogallium naphthalocyanine, N, N′-di (naphthalen-1-yl) -N N'- diphenyl - benzidine, N, N, N ', benzidine-based compounds such as N'- tetraphenyl benzidine and the like may be used singly or in combination of two or more of them. All of these have a high hole transport ability.

  As a polymer hole transport material, it can be used as a prepolymer or polymer (polymer hole transport material) having the monomer or oligomer (low molecular hole transport material) compound in the main chain or side chain. .

Examples of other hole transport materials include positive polymers such as poly (thiophene / styrene sulfonic acid) compounds such as poly (3,4-ethylenedioxythiophene / styrene sulfonic acid) (PEDOT / PSS). A hole transport material can also be used. This has a high hole transport ability.
The average thickness of the hole transport layer 6 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 50 to 100 nm. If the thickness of the hole transport layer 6 is too thin, pinholes may be generated. On the other hand, if the hole transport layer 6 is too thick, the transmittance of the hole transport layer 6 may be deteriorated, resulting in an organic EL element. There is a possibility that the chromaticity (hue) of the ten emission colors may change.

The light emitting layer 5 and the sealing member 8 are comprised by the thing similar to what was demonstrated in the said 1st Embodiment.
As described above, when the cathode 3 is made of a material that is relatively stable to oxygen and moisture, such as a conductive metal oxide, the formation of the sealing member 8 is omitted. Also good.

In the present embodiment, the case where the light emitting layer 5 is provided on the cathode 3 has been described. However, the present invention is not limited to such a case. For example, the cathode 3 is interposed between the cathode 3 and the light emitting layer 5. A hole transporting intermediate layer having a function of transporting the injected holes to the light emitting layer 5 may be provided.
The hole transporting intermediate layer may be the same as the intermediate layer 4 described above in the first embodiment of the organic EL element.
Such an organic EL element 10 can be manufactured, for example, as follows. In the method for manufacturing the organic EL element 1, a step of providing the intermediate layer 14 (intermediate layer forming step) and a light emitting layer (organic semiconductor layer) ) 5 is applied to the step of forming the light emitting layer (light emitting layer forming step).

[1B] Cathode Formation Step First, the substrate 2 is prepared, and the cathode 3 is formed on the substrate 2.
The formation of the cathode 3 can be performed in the same manner as in the step [1A] described in the first embodiment except that an organic substance having a carrier transporting part having a function of transporting electrons is used.

[2B] Intermediate Layer Forming Step Next, the intermediate layer 14 is formed on the cathode 3.
For the formation of the intermediate layer 14, in step [2A] described in the first embodiment, instead of using an organic substance having a function of transporting holes, a substance having a function of transporting electrons is used. This can be carried out in the same manner as in the above step [2A].
Hereinafter, the organic substance having a function of transporting electrons will be described.

The organic material having a function of transporting electrons is the same as the organic material having a function of transporting holes, except that the structure of the carrier transport site contained in the organic material is different.
As such a carrier transport site, one having an electron transport ability and an organic structure is preferably selected, and specifically, one having a tetrathiofulvalene skeleton can be mentioned.
Therefore, as an organic substance having a function of transporting electrons, for example, a compound represented by the following general formula (4) is preferably used.

［式中、２つのＲ^１は、それぞれ独立して、水素原子、または、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表し、同一であっても、異なっていてもよい。ただし、２つのＲ^１のうちの少なくとも１つは、前記一般式（５）または前記一般式（６）で表される置換基のうちのいずれかを表す。］

[In the formula, two R ^{1 s} each independently represent a hydrogen atom or any one of the substituents represented by the general formula (5) or the general formula (6), and are the same. Or different. However, at least 1 of two R < ¹ > represents either of the substituents represented by the said General formula (5) or the said General formula (6). ]

[3B] Light-Emitting Layer Formation Step Next, the light-emitting layer 5 is formed on the intermediate layer 14.
The formation of the intermediate layer 14 can be performed in the same manner as the step [3A] described in the first embodiment.
[4B] Hole Transport Layer Formation Step Next, the hole transport layer 6 is formed on the light emitting layer 5.
The hole transport layer 6 can be formed in the same manner as the light emitting layer 5. That is, the hole transport layer 6 can be formed by using the hole transport material as described above by the method such as the process [3A] described in the first embodiment.

[5B] Anode Formation Step Next, the anode 7 is formed on the hole transport layer 6.
The formation of the anode 7 can be performed in the same manner as the step [1A] described in the first embodiment.
[6B] Sealing Member Formation Step Next, the sealing member 8 is formed so as to cover the cathode 3, the intermediate layer 14, the light emitting layer 5, the hole transport layer 6, and the anode 7.
The sealing member 8 can be formed in the same manner as the process [5A] described in the first embodiment.

The organic EL element 10 is manufactured through the above processes.
Similar to the organic EL element 1, the organic EL element 10 can be used as a display device or a light source, and can be used for various optical applications.
Further, when the organic EL element 10 is used for a display device, it can be applied to the display device in the same manner as in the first embodiment.

<< Third Embodiment >>
Next, a third embodiment of the organic EL element will be described.
FIG. 5 is a longitudinal sectional view showing a third embodiment of the organic EL element. In the following description, the upper side in FIG. 5 is referred to as “upper” and the lower side is referred to as “lower”.
Hereinafter, the third embodiment will be described with a focus on differences from the second embodiment, and description of similar matters will be omitted.

In the organic EL element 11 of the third embodiment, a laminate 19 including the intermediate layer 14, the light emitting layer 5, and the hole transport layer 6 as in the second embodiment is provided between the cathode 3 and the anode 7. Instead of this, it is the same as the second embodiment except that a laminated body 19 ″ as shown in FIG. 3 is provided.
This laminated body 19 ″ is further formed on a transparent body 3 ′, an intermediate layer 14 ′, a light emitting layer 5 ′, and a hole transport layer 6 ′ on the laminated body 19 included in the organic EL element 10 as shown in FIG. In other words, the laminate 19 and the laminate 19 ′ are connected in series.
In the present embodiment, in the organic EL element 11, an electronic device substrate is formed by the cathode 3, the intermediate layer 14, and the light emitting layer 5, and further by the transparent electrode 3 ′, the intermediate layer 14 ′, and the light emitting layer 5. Composed.

Hereinafter, the configuration of the laminate 19 '' will be mainly described.
A transparent electrode 3 ′ is provided on the laminate 19, that is, on the hole transport layer 6.
The transparent electrode 3 ′ is an electrode having both a function of injecting holes into the hole transport layer 6 and a function of injecting electrons into the intermediate layer 14 ′.
Further, when the organic EL element 11 is a top emission type, light emission of the light emitting layer 5 is transmitted to the anode 7 side, and when the organic EL element 11 is a bottom emission type, light emission of the light emitting layer 5 ′ is transmitted to the cathode 3 side. Since it is necessary, as the constituent material of the transparent electrode 3 ′, a material having substantially transparency (colorless transparent, colored transparent, translucent) among the constituent materials described for the cathode 3 is used.

Specific examples include transparent conductive metal oxides such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , and Al-containing ZnO. Of these, one or two or more of these can be used in combination.
Further, the intermediate layer 14 ′, the light emitting layer 5 ′, and the hole transport layer 6 ′ included in the stacked body 19 ′ have the same configurations as the intermediate layer 14, the light emitting layer 5, and the hole transport layer 6 included in the stacked body 19, respectively. belongs to.

The constituent materials of the intermediate layer 14 ′, the light emitting layer 5 ′, and the hole transport layer 6 ′ may be the same as the constituent materials of the intermediate layer 14, the light emitting layer 5, and the hole transport layer 6, respectively. As long as they are included in those described in the first embodiment or the second embodiment, they may be different.
By making the organic EL element 11 having such a configuration, electroluminescence emission can be obtained from the two light emitting layers 5 and 5 ′, so that this emission can be performed more stably and the emission efficiency can be improved. Improvements can be made.

Such an organic EL 11, for example, after performing the steps [1B] to [4B] described in the second embodiment and performing the steps [1B] to [4B] again, It can manufacture by performing process [6B].
Similar to the organic EL elements 1 and 10, the organic EL element 11 can be used as a display device or a light source, and can be used for various optical applications.
Further, when the organic EL element 11 is used for a display device, it can be applied to the display device in the same manner as in the first embodiment.

<Electronic equipment>
The organic EL elements 1, 10, and 11 ( electronic devices ) as described above can be incorporated into various electronic devices.
FIG. 6 is a perspective view illustrating a configuration of a mobile (or notebook) personal computer to which an electronic device is applied.

In this figure, a personal computer 1100 includes a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatable with respect to the main body 1104 via a hinge structure. It is supported by.
In the personal computer 1100, the display unit included in the display unit 1106 includes the organic EL elements 1, 10, and 11 described above.

FIG. 7 is a perspective view illustrating a configuration of a mobile phone (including PHS) to which an electronic device is applied.
In this figure, a cellular phone 1200 includes a plurality of operation buttons 1202, an earpiece 1204 and a mouthpiece 1206, and a display unit.
In the mobile phone 1200, the display unit includes the organic EL elements 1, 10, and 11 described above.

FIG. 8 is a perspective view illustrating a configuration of a digital still camera to which an electronic device is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver salt photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an image sensor such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

  A display unit is provided on the back of a case (body) 1302 in the digital still camera 1300, and is configured to display based on an imaging signal from the CCD, and functions as a finder that displays an object as an electronic image.

In the digital still camera 1300, the display unit includes the organic EL elements 1, 10, and 11 described above.
A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).

When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.
In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the data communication input / output terminal 1314 as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

In addition to the personal computer (mobile personal computer) shown in FIG. 6, the mobile phone shown in FIG. 7, and the digital still camera shown in FIG. 8, the electronic apparatus may be, for example, a television, a video camera, a viewfinder type, or a monitor direct view type. Video tape recorders, laptop personal computers, car navigation devices, pagers, electronic notebooks (including those with communication functions), electronic dictionaries, calculators, electronic game machines, word processors, workstations, videophones, security TV monitors, electronic Devices equipped with binoculars, POS terminals, touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographs, ultrasonic diagnostic devices, endoscopes) Display device), fish finder, various measuring instruments, instruments ( In example, gages for vehicles, aircraft, ships), a flight simulator, various monitors, and a projection display such as a projector.

Although the method of manufacturing a substrate for an electronic device of the present invention has been described with reference to the illustrated embodiments, the present invention is not such limited thereto.

Next, specific examples of the present invention will be described.
1. Manufacture of an organic EL element In each of the following Examples and Comparative Examples, 5 organic EL elements were manufactured.
Example 1A
-1A- First, two transparent glass substrates having an average thickness of 1.1 mm were prepared, and ITO electrodes having an average thickness of 150 nm were formed on these substrates by sputtering.
-2A- Next, a 1.0 wt% aqueous solution of copper phthalocyanine sulfonate ester dye (Direct Blue 199), which is a composition of the compound shown in Chemical Formula 24, was prepared.

［式中、４つのＲ^１は、それぞれ独立して、水素原子、または、下記一般式（７）〜下記一般式（９）で表される置換基のうちのいずれかである。ただし、４つのＲ^１のうちの少なくとも１つは、下記一般式（７）〜下記一般式（９）で表される置換基のうちのいずれかである。］

[Wherein, four R ^{1 s} are each independently a hydrogen atom or a substituent represented by the following general formula (7) to the following general formula (9). However, at least one of the four R ¹ is any one of substituents represented by the following general formula (7) to the following general formula (9). ]

［各式中、ｎは、１〜１５の整数である。］

[In each formula, n is an integer of 1-15. ]

-3A- Next, after setting one of the ITO electrodes provided on the quartz substrate as a cathode and the other as an anode, the cathode electrode and the anode were immersed in the aqueous solution prepared in the step-2A- A voltage was applied between them.
Various conditions at the time of voltage application are as follows.
・ Applied voltage: 20V
-Current flowing between electrodes: 2-4 [mu] A / cm < ² >
-Liquid temperature: 60 ° C
-PH of liquid: 5.5
Treatment time: 10 minutes Thereby, a sulfonic acid ester dye derivative of copper phthalocyanine was deposited on the ITO electrode (anode) placed on the anode side, and an intermediate with an average thickness of 8 nm mainly composed of this derivative. A layer was obtained.

-4A- Next, this intermediate layer was taken out of the aqueous solution, washed with pure water, and then dried under a nitrogen atmosphere at 100 ° C. for 60 minutes.
-5A- Next, 1. poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10-diyl) (weight average molecular weight 200000) on the intermediate layer. A 7 wt% xylene solution is applied by spin coating, and then dried under a nitrogen atmosphere at 100 ° C. for 10 minutes and under reduced pressure at 100 ° C. for 60 minutes to form a light emitting layer with an average thickness of 50 nm. did.

-6A- Next, a multi-layer electrode (cathode) composed of Ca having an average thickness of 1 nm and Al having an average thickness of 300 nm is formed by continuously depositing Ca and Al on the light emitting layer by a vacuum evaporation method. Formed.
-7A- Next, a protective cover made of polycarbonate was covered so as to cover each formed layer, and fixed and sealed with an ultraviolet curable resin, thereby completing an organic EL element.

(Example 2A)
An organic EL device was produced in the same manner as in Example 1A, except that a 1.0 wt% aqueous solution of the compound represented by Chemical Formula 26 was prepared in Step-2A-.
As a result, a derivative of the compound represented by Chemical Formula 26 was precipitated on the ITO electrode (anode) placed on the anode side to obtain an intermediate layer having an average thickness of 10 nm mainly composed of this derivative.

(Example 3A)
In the step-2A-, a 1.0 wt% water / methanol solution of the compound shown in Chemical Formula 27 was prepared, and the various conditions at the time of voltage application in the step-3A- were as follows. In the same manner, an organic EL device was produced.
・ Applied voltage: 20V
-Electric current between electrodes: 1 to 4 μA / cm ²
-Liquid temperature: 60 ° C
-PH of the liquid: 5.5-7.0
・ Processing time: 10 minutes

  As a result, a derivative of the compound represented by Chemical Formula 27 was deposited on the ITO electrode (anode) placed on the anode side, and an intermediate layer having an average thickness of 5 nm mainly composed of this derivative was obtained.

(Example 4A)
In the step-2A-, a 2.0 wt% water / methanol solution of the compound shown in Chemical formula 28 was prepared, and the conditions of the voltage application in the step-3A- were as follows. In the same manner, an organic EL device was produced.
・ Applied voltage: 20V
-Current flowing between electrodes: 1 to 4 [mu] A / cm < ² >
-Liquid temperature: 60 ° C
-PH of the liquid: 5.5-7.0
・ Processing time: 10 minutes

  As a result, a derivative of the compound shown in Chemical formula 28 was deposited on the ITO electrode (anode) placed on the cathode side, and an intermediate layer having an average thickness of 5 nm mainly composed of this derivative was obtained.

(Example 5A)
In the step-2A-, a 3.0 wt% water / methanol solution of the compound shown in Chemical formula 29 was prepared, and various conditions at the time of voltage application in the step-3A- were as follows. In the same manner, an organic EL device was produced.
・ Applied voltage: 20V
-Current flowing between electrodes: 1 to 4 [mu] A / cm < ² >
-Liquid temperature: 60 ° C
-PH of the liquid: 5.5-6.0
・ Processing time: 10 minutes

  As a result, a derivative of the compound shown in Chemical formula 29 was deposited on the ITO electrode (anode) placed on the anode side, and an intermediate layer having an average thickness of 5 nm mainly composed of this derivative was obtained.

(Comparative Example 1A)
Instead of forming the intermediate layer as in Step-2A- to Step-4A-, except that copper phthalocyanine was vapor-deposited by a vacuum evaporation method to form an intermediate layer having an average thickness of 15 nm, An organic EL element was produced in the same manner as Example 1A.
(Comparative Example 2A)
An organic EL device was produced in the same manner as in Example 1A, except that Step-2A- to Step-4A- (intermediate layer forming step) were omitted.

(Example 1B)
-1B- First, two transparent glass substrates having an average thickness of 1.1 mm were prepared, and ITO electrodes having an average thickness of 150 nm were formed on these substrates by sputtering.
-2B- Next, a 3.0 wt% aqueous solution of tetrathiofulvalene carboxylic acid sodium salt was prepared.
-3B- Next, after setting one of the ITO electrodes provided on the quartz substrate as a cathode and the other as an anode, the cathode electrode and the anode were immersed in the aqueous solution prepared in the step-2B- A voltage was applied between them.

Various conditions at the time of voltage application are as follows.
-Applied voltage: 5-20V
-Electric current between electrodes: 1 to 4 μA / cm ²
-Liquid temperature: 60 ° C
-PH of liquid: 5.5
-Treatment time: 20 minutes Thereby, a carboxylic acid sodium salt derivative of tetrathiofulvalene was deposited on the ITO electrode (cathode) placed on the anode side, and the average thickness of this derivative was 8 nm. An intermediate layer was obtained.

-4B- Next, this intermediate layer was taken out from the aqueous solution, washed with pure water, and then dried under a nitrogen atmosphere at 60 ° C. for 60 minutes.
-5B- Next, 1. poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10-diyl) (weight average molecular weight 200000) on the intermediate layer. A 7 wt% xylene solution is applied by spin coating, and then dried under a nitrogen atmosphere at 100 ° C. for 10 minutes and under reduced pressure at 100 ° C. for 60 minutes to form a light emitting layer with an average thickness of 50 nm. did.

-6B- Next, copper phthalocyanine was vacuum-deposited on the light-emitting layer to form a hole transport layer having an average thickness of 10 nm.
-7B- Next, an Al electrode (anode) having an average thickness of 300 nm was formed on the hole transport layer by vacuum deposition.
-8B- Next, a protective cover made of polycarbonate was placed so as to cover each formed layer, and fixed and sealed with an ultraviolet curable resin to complete an organic EL element.

(Example 2B)
-1C- First, a cathode, an intermediate layer, a light-emitting layer, and a hole transport layer were sequentially formed on a glass substrate in the same manner as in Step-1B- to Step-6B-.
-2C- Next, a transparent electrode, an intermediate layer, a light emitting layer, and a hole transport layer were sequentially formed on the hole transport layer in the same manner as in Step-1C-.
-3C- Next, an anode was formed on the hole transport layer in the same manner as in Step-7B-.
-4C- Next, in the same manner as in Step-8B-, each layer was sealed with a protective cover to produce an organic EL element.

(Comparative Example 1B)
Instead of forming the intermediate layer as in Step-2B- to Step-4B-, except that tetrathiofulvalene was vapor-deposited by a vacuum evaporation method to form an intermediate layer having an average thickness of 10 nm. The organic EL device was manufactured in the same manner as in Example 1B.
(Comparative Example 2B)
An organic EL device was produced in the same manner as in Example 1B except that Step-2B- to Step-4B- (intermediate layer forming step) were omitted.

2. Evaluation For each of the organic EL elements of the examples and comparative examples, the energization current (A), the light emission luminance (cd / m ² ), and the maximum light emission efficiency (lm / W) were measured, and the light emission luminance was an initial value. The time to halve (half life) was measured.
These measurements were performed by applying a voltage of 9 V between the cathode and the anode.

And each measured value measured by Example 1A-Example 5A and Comparative Example 2A is set by using each measured value (energization current, luminous brightness, maximum luminous efficiency, half-life) measured in Comparative Example 1A as a reference value. Each was evaluated according to the following four-stage criteria.
A: The measurement value of Comparative Example 1A is 1.50 times or more. O: The measurement value of Comparative Example 1A is 1.25 times or more and less than 1.50 times. Δ: The measurement value of Comparative Example 1A. In contrast, 1.00 times or more and less than 1.25 times x: 0.75 times or more and less than 1.00 times the measured value of Comparative Example 1A. Table 1 shows.
As an example, FIG. 9 shows a graph showing the relationship between the change in the value of the applied voltage measured in the organic EL elements of Example 1A and Comparative Example 1A and the change in the value of the energization current.

As shown in Table 1, each of the organic EL elements in each example had excellent results in terms of current flow, emission luminance, maximum luminous efficiency, and half-life as compared with the organic EL elements in each comparative example. It was.
As a result, in the organic EL element , the adhesion at the interface between the anode and the intermediate layer and the interface between the intermediate layer and the light emitting layer has been improved, so that it is preferable to transfer holes from the anode to the light emitting layer via the intermediate layer. It has become clear that this is happening.
Next, each measurement value measured in Example 1B, Example 2B, and Comparative Example 2B using each measurement value (energization current, light emission luminance, maximum light emission efficiency, half-life) measured in Comparative Example 1B as a reference value. Were evaluated according to the following four-stage criteria.

A: The measurement value of Comparative Example 1B is 1.50 times or more. O: The measurement value of Comparative Example 1B is 1.25 times or more and less than 1.50 times. Δ: The measurement value of Comparative Example 1B. In contrast, 1.00 times or more and less than 1.25 times ×: 0.75 times or more and less than 1.00 times with respect to the measurement value of Comparative Example 1B. It shows in Table 2.

As shown in Table 2, each of the organic EL elements of each example had superior results in terms of current, luminance, maximum luminous efficiency, and half-life compared to the organic EL elements of the comparative examples. It was.
As a result, in the organic EL element , the adhesion at the interface between the cathode and the intermediate layer and the interface between the intermediate layer and the light emitting layer is improved, so that the electrons are suitably transferred from the cathode to the light emitting layer via the intermediate layer. It became clear that

It is the longitudinal cross-sectional view which showed 1st Embodiment of the organic EL element. It is a schematic diagram (longitudinal sectional view) for explaining a process of providing an intermediate layer. It is a longitudinal cross-sectional view which shows embodiment of a display apparatus provided with the organic EL element of 1st Embodiment. It is the longitudinal cross-sectional view which showed 2nd Embodiment of the organic EL element. It is the longitudinal cross-sectional view which showed 3rd Embodiment of the organic EL element. FIG. 11 is a perspective view illustrating a configuration of a mobile (or notebook) personal computer to which an electronic device is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device is applied. It is a perspective view which shows the structure of the digital still camera to which an electronic device is applied. It is a graph which shows the relationship between the change of the value of the applied voltage measured in the organic EL element of Example 1A and Comparative Example 1A, and the change of the value of an energization current.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 10, 11 ... Organic EL element 2 ... Board | substrate 3 ... Cathode 3 '... Transparent electrode 4, 14, 14' ... Intermediate | middle layer 5, 5 '... Light emitting layer 6, 6' ... Positive Hole transport layer 7 …… Anode 8 …… Sealing member 9, 19, 19 ′, 19 ″ …… Laminated body 100 …… Display device 20 …… Substrate 21 …… Substrate 22 …… Circuit part 23 …… Protective layer 24 …… Drive TFT 241 …… Semiconductor layer 242 …… Gate insulating layer 243 …… Gate electrode 244 …… Source electrode 245 …… Drain electrode 25 …… First interlayer insulating layer 26 …… Second interlayer insulating layer 27 ... …… Wiring 31 …… First partition portion 32 …… Second partition portion 1100 …… Personal computer 1102 …… Keyboard 1104 …… Main body 1106 …… Display unit 1200 …… Cellular phone 1202 …… Operation buttons 1204 …… Earpiece 1206 ··· Mouthpiece 1300 · · · Digital still camera 1302 · · · Case (body) 1304 · · · Light receiving unit 1306 · · · Shutter button 1308 · · · Circuit board 1312 · · · Video signal output terminal 1314 · · · I / O terminal for data communication 1430 TV monitor 1440 Personal computer

Claims (3)

An organic semiconductor layer, an electrode, a carrier transporting portion provided between the organic semiconductor layer and the electrode so as to be in contact with both of them and having a conjugated structure and a function of transporting carriers; and the carrier A method for producing a substrate for an electronic device applied to an organic electroluminescent element having an intermediate layer composed mainly of an organic substance having a chargeable portion bonded to a transport portion,
In a state where the electrode is in contact with a liquid containing the organic substance, the organic substance charged in the liquid is collected on the electrode by applying a voltage to the liquid using the electrode as one electrode. Forming the intermediate layer;
After the organic semiconductor layer material formed by dissolving the constituent material of the organic semiconductor layer in a solvent or dispersing in a dispersion medium is applied on the surface of the intermediate layer opposite to the electrode, the organic semiconductor by removing the solvent or dispersion medium contained in the layer material have a a step of providing the organic semiconductor layer,
As the organic substance, a compound represented by the following general formula (2) or a compound represented by the following general formula (3) having a function of transporting holes as the carrier transport site, or an electron as the carrier transport site. The manufacturing method of the board | substrate for electronic devices characterized by using the thing which has as a main component the compound represented by the following general formula (4) which has the function to convey a metal .

[In the formula, three R ^{1 s} each independently represent a hydrogen atom or any one of substituents represented by the following general formula (5) or the following general formula (6). Or different. However, at least 1 of three R < ¹ > represents either of the substituents represented by the following general formula (5) or the following general formula (6). ]

[In each formula, R ² represents a single bond or an alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkali metal, an amino group, or an alkyl group having 1 to 20 carbon atoms. Two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may be the same or different. X ¹ is a single bond,

Represents. Y ¹ is a single bond,

Represents. ]

[In the formula, three R ^{1 s} each independently represent a hydrogen atom or any one of substituents represented by the following general formula (5) or the following general formula (6). Or different. However, at least 1 of three R < ¹ > represents either of the substituents represented by the following general formula (5) or the following general formula (6). ]

[In each formula, R ² represents a single bond or an alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkali metal, an amino group, or an alkyl group having 1 to 20 carbon atoms. Two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may be the same or different. X ¹ is a single bond,

Represents. Y ¹ is a single bond,

Represents. ]

[In the formula, two R ^{1 s} each independently represent a hydrogen atom or any one of substituents represented by the following general formula (5) or the following general formula (6). Or different. However, at least 1 of two R < ¹ > represents either of the substituents represented by the following general formula (5) or the following general formula (6). ]

[In each formula, R ² represents a single bond or an alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkali metal, an amino group, or an alkyl group having 1 to 20 carbon atoms. Two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may be the same or different. X ¹ is a single bond,

Represents. Y ¹ is a single bond,

Represents. ]   2. The method of manufacturing an electronic device substrate according to claim 1, wherein the chargeable portion can be charged in the vicinity of an end opposite to the carrier transporting portion.   The method for manufacturing a substrate for an electronic device according to claim 1, wherein the carrier transporting portion includes a structure having a high affinity with a constituent material of the organic semiconductor layer.

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