JP2001203081A - Thin film electroluminescent element and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high efficiency, low driving voltage and a long life element that is made of a laminated structure of a hole carrier layer using hole carrier material which has a bisymmetric structure such as triphenyldiamine generally in use, and electron carrier luminescent layer. SOLUTION: The element structure comprises at least an transparent hole injection electrode, a transparent conductive layer formed on the above transparent hole injection electrode by applying paint, an microfilm electron block layer, a luminescent layer, and a cathode on a transparent substrate and this structure gives an excellent element performance. In particular, the use of a specific microfilm electron block layer gives a superior element performance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin-film electroluminescence (EL) device, and more particularly to a self-luminous device which can be used as a light source for various purposes such as a flat type self-luminous display device, communication, lighting and the like. is there.

[0002]

2. Description of the Related Art In recent years, LCD panels have been widely used as flat-type display devices, but they still have drawbacks such as slow response speed and narrow viewing angle, and many new systems in which these have been improved have been improved. There are problems such as insufficient characteristics and an increase in cost as a panel. Under such circumstances, the thin-film EL as a new light-emitting element that is self-luminous, has excellent visibility, has a high response speed, and can be expected to be used in a wide range of applications
Expectations are gathering on the device. In particular, thin-film EL devices that use organic materials that can use simple film-forming processes such as evaporation and coating at room temperature for all or some of the layers of the device are also called organic EL devices. Many studies have been conducted due to the attractiveness of cost.

A thin-film EL element (organic EL element) is one in which electrons and holes are injected from electrodes to obtain light emission by recombination, and many studies have been made for a long time. It was far from being applied to a typical light emitting element.

Under such circumstances, a device proposed by Tang et al. In 1987 (CW Tang and
S. A. Vanslyke: Appl. Phys. Le
tt. 51 (1987) 913. ) Is a device having a transparent hole injecting electrode, a hole transporting layer, a light emitting layer and a cathode on a transparent substrate, wherein ITO is used as the transparent hole injecting electrode and a 75 nm-thick diamine derivative is used as the hole transporting layer. An aluminum quinoline complex layer having a thickness of 60 nm was used as the layer and the light emitting layer, and a MgAg alloy having both electron injection properties and stability was used as the cathode. In particular, by adopting a diamine derivative having excellent transparency, in addition to improving the cathode, 7
Even at a film thickness of 5 nm, sufficient transparency can be maintained, and at this film thickness, a uniform thin film free of pinholes or the like can be obtained. This makes it possible to obtain a light emission with a relatively low voltage and a high luminance. Specifically, at a low voltage of 10 V or less, 1000 c
High brightness of d / m ² or more and high efficiency of 1.5 lm / W or more are realized. The report of Tang et al. Triggered further improvement of the cathode, insertion of an electron injection layer,
Although active studies have been continued up to the present time, such as ingenuity in device configuration such as insertion of a hole injection layer, the thickness of the device is still generally 100 nm or more.

[0005] The thin film EL generally studied below is
The (organic EL) element will be outlined.

Each layer of the device is formed by laminating a hole injection electrode, a hole transport layer, a light emitting layer, and a cathode on a transparent substrate in this order.
Providing a hole injection layer between the hole injection electrode and the hole transport layer,
An electron transport layer may be provided between the light emitting layer and the cathode, and an electron injection layer may be provided at the interface with the cathode. In this way, by making each layer play a role by separating the function, an appropriate material can be selected for each layer, and the characteristics of the element are also improved.

As a transparent substrate, generally, Corning 173 is used.
Glass substrates such as 7 are widely used. Sheet thickness is 0.7
mm is easy to handle from the viewpoint of strength and weight.

As the hole injection electrode, a transparent electrode such as an ITO sputtered film, an electron beam evaporated film, or an ion plating film is used. The film thickness is determined from the required sheet resistance value and the visible light transmittance. However, since the driving current density of the organic EL element is relatively high, the organic EL element may be used at a thickness of 100 nm or more to reduce the sheet resistance. Many.

The hole transport layer is made of N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine (hereinafter referred to as T
PD), N, N'-bis (α-naphthyl)-
Diamine derivatives used by Tang et al., Such as N, N'-diphenylbenzidine (hereinafter referred to as NPD), especially Q1-G- disclosed in Japanese Patent No. 2037475.
Vacuum deposited films of a diamine derivative having a Q2 structure are widely used. These materials generally have excellent transparency,
Even when the film thickness is about m, it is almost transparent and has excellent film formability, so that a film without defects such as pinholes can be obtained. There is a feature that the problem of hardly occurs.

As in the case of the report by Tang et al., The light-emitting layer is generally formed by using an electron-transporting light-emitting material such as tris (8-quinolinolato) aluminum in a thickness of several tens nm by vacuum deposition. The light emitting layer is made relatively thin and the electron transporting layer is made of
A so-called double hetero structure in which m layers are stacked may be employed.

The cathode is made of an alloy of a metal having a low work function and a low electron injection barrier, such as an MgAg alloy or an AlLi alloy proposed by Tang et al., And a metal having a relatively large work function and being stable, or various electron injection layers such as LiF. A laminated cathode with aluminum or the like is often used.

[0012] Between the hole injection electrode (ITO) and the hole transport layer, a star is used for the purpose of smoothing the surface roughness of the ITO, lowering the driving voltage by improving the hole injection efficiency, and extending the life. Burst amine (for example, JP-A-3-308688) and oligoamine (for example, International Publication WO96 / 96)
/ 22273) is often provided as a hole injection layer or a buffer layer.

Also, in a polymer-coated organic EL device, polyaniline (for example, PANI-CS) is formed on ITO.
A, Nature 357, p. 477) or polythiophene (for example, PEDOT-PS manufactured by Bayer Corporation)
S, Physics World June 1999, 35
It is a common practice to provide a layer formed by applying a conductive polymer (eg, page) to lower the driving voltage and extend the life by smoothing the surface roughness of ITO and improving the hole injection efficiency. .

[0014] Recently, even in a low-molecular-weight evaporation type organic EL device, a polymer layer containing various dopants is formed by an I-layer.
There is a report aiming at lowering the driving voltage, extending the service life, and increasing the reliability of the element by providing the element on the TO and forming a hole transport layer, a light emitting layer, and the like thereon. The Physical Society Academic Lecture 1998 Fall 16a-YH-5, The Society of Polymer Science, Japan 9
May 2009 Annual Meeting Polymer Preprints48
Vol. 3, page 424).

[0015]

As described above, by using a stacked-type element configuration proposed by Tang et al. With separated functions, and particularly by using the above-described Q1-GQ2 type diamine derivative as a hole transport layer, An element capable of obtaining a sufficient luminance of about several hundred candela even at a low voltage of about several V can be realized.

However, symmetric compounds having a triphenylamine dimer skeleton, such as TPD, which has been generally and widely used so far, have relatively flat molecules and are relatively agglomerated because of their symmetry. It was difficult to obtain a stable and high hole transporting ability uniformly because of easy association or crystallization. In addition, many materials have been studied to improve the characteristics, such as NPD in which one of the phenyl groups of triphenylamine is replaced with a naphthyl group in order to improve the flatness. At present, there is no element that can obtain the characteristics.

In particular, when used as a passive matrix type line-sequential scanning display, since the peak luminance is large, the driving voltage increases, the power consumption increases, the reliability decreases, and the cost of the driving circuit increases. In addition, the life tends to be shorter than when used in a continuous light emitting state. For this reason, there has been a demand for a device which can obtain high luminance with a low driving voltage, has a long life and is excellent in reliability, as compared with the related art.

In many hole transporting materials synthesized for higher heat resistance as compared with widely used TPDs, the heat resistance as a device is improved, and the luminance half life is improved. Characteristics such as high voltage and insufficient efficiency are also observed.
It is considered that it is not easy to develop a device capable of sufficiently driving at a low voltage and achieving high efficiency, long life and high reliability simply by optimizing the device characteristics by improving the hole transport material.

By providing the above-mentioned starburst amine or oligoamine as a hole injection layer between the ITO and the hole transport layer, the life of the device can be prolonged.
In particular, an element having sufficient characteristics has not yet been obtained from the viewpoint of lower driving voltage.

[0020]

In view of such a situation,
The authors used materials with various physical properties, laminated functional thin films with various characteristics in various configurations, and evaluated them in particular from the viewpoint of drive voltage, luminous efficiency, reliability, and life. The use of the element configuration makes it difficult to develop a hole transport material, which has been a very large problem in the past (as described above,
Compared to TPD, many hole transporting materials synthesized for high heat resistance have problems such as an increase in driving voltage and inability to obtain sufficient efficiency, and a synthesis route. Is complicated and difficult to purify, which has forced development at a disadvantage in terms of cost), and using compounds that can be easily synthesized and purified,
The present inventors have found that high luminance can be stably obtained with high efficiency at a very low voltage and can be stably obtained over a long life, and that a highly reliable and extremely easy-to-manufacture element can be realized, thereby completing the present invention.

Specifically, the thin-film EL device according to the first aspect of the present invention provides a transparent hole injection electrode on a transparent substrate and a transparent conductive layer formed on the transparent hole injection electrode by coating. , An ultra-thin electron block layer, a light-emitting layer and a cathode.

The thin film EL device according to the second aspect of the present invention comprises:
2. The thin-film EL device according to claim 1, wherein the thickness of the ultra-thin electronic block layer is equal to or less than 1/3 of the thickness of the layer from the light-emitting layer to the cathode.

The thin-film EL device according to the third aspect of the present invention comprises:
3. The thin-film EL device according to claim 2, wherein the ultra-thin electronic block layer has a thickness equal to or greater than the average surface roughness of the transparent conductive layer formed by coating.

The thin film EL device according to the invention of claim 4 of the present application is
4. The thin film EL device according to claim 3, wherein the electron mobility of the ultra-thin electron blocking layer at an electric field of 1 × 10 ⁶ V / cm is 1 × 10 ⁻⁵ cm ² / V · s or less. is there.

The thin film EL device according to the invention of claim 5 of the present application is
The thin film EL device according to claim 3, wherein the electron affinity of the ultra-thin electron block layer is 2.7 eV or less.

The thin film EL device according to the invention of claim 6 of the present application is
4. The thin-film EL device according to claim 3, wherein the forbidden band width of the ultra-thin electron block layer is 2.5 eV or more.

The thin film EL device according to the invention of claim 7 of the present application is
4. The thin film EL device according to claim 3, wherein a thickness of the device sandwiched between the anode and the cathode is 60 nm or less.

The thin film EL device according to the invention of claim 8 of the present application is
4. The device according to claim 3, further comprising a layer having a resistivity of 10 ⁷ Ωcm or less between the light emitting layer and the cathode as an electron injecting and transporting layer, and having a film thickness of 10 nm or more. 5. Is a thin film EL element.

The thin film EL device according to the ninth aspect of the present invention is
Between the light emitting layer and the cathode, at least as an electron injecting and transporting layer, having a layer containing a low work function alkali metal or alkaline earth metal, and the film thickness is 10 nm or more, A thin-film EL device according to claim 3.

The thin-film EL device according to the tenth aspect of the present invention comprises a phenanthroline derivative and a low work function alkali metal or alkaline earth metal at least as an electron injecting and transporting layer between the light emitting layer and the cathode. 4. The thin-film EL device according to claim 3, comprising a layer and having a thickness of 10 nm or more.

In the thin film EL device according to the eleventh aspect of the present invention, the ultra-thin electron blocking layer has a thickness less than the thickness of the light emitting layer and more than the average surface roughness of the transparent conductive layer formed by coating. 2. The thin-film EL device according to claim 1, wherein, of the device sandwiched between the anode and the cathode, a region to which a voltage is substantially applied has a thickness of 50 nm or less.

A thin film EL device according to a twelfth aspect of the present invention is a thin film EL device comprising: a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 1) (wherein R1, R2, and R3 may be the same or different; (Representing a hydrogen atom, an alkyl group or an alkoxy group).

In the thin film EL device according to the thirteenth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) 13. The thin film E according to claim 12, which is [phenyl] phenylamine.
L element.

In the thin film EL device according to the fourteenth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- (2,2-diphenylvinyl) phenyl] (4-methoxyphenyl)}. 13. The thin-film EL device according to claim 12, wherein the device is 4-[(4-methoxyphenyl) phenylamino] phenyl} amine.

According to a fifteenth aspect of the present invention, there is provided a thin-film EL device comprising at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (wherein R1 and R2 may be the same or different; , An alkyl group or an alkoxy group).

In the thin film EL device according to the sixteenth aspect of the present invention, the compound mainly contained in the ultrathin electron blocking layer is bis [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino). 17) The thin-film EL device according to claim 15, which is [phenyl] amine.

In the thin film EL device according to the seventeenth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- (2,2-diphenylvinyl) phenyl] [4- {bis ( 16. The thin-film EL device according to claim 15, wherein the thin film EL device is methoxyphenyl) amino @ phenyl] amine.

The thin-film EL device according to the eighteenth aspect of the present invention provides a thin-film EL device comprising: a transparent substrate having at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 3) (wherein R1, R2, and R3 may be the same or different; (Representing a hydrogen atom, an alkyl group or an alkoxy group).

In the thin film EL device according to the nineteenth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [ 4. (4- (diphenylamino) phenyl] phenylamine.
9. A thin film EL device according to item 8.

In the thin film EL device according to the twentieth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [ The thin film E according to claim 18, which is 4- {bis (4-methoxyphenyl) amino} phenyl] (4-methoxyphenyl) amine.
L element.

The thin film EL device according to the twenty-first aspect of the present invention is a thin film EL device comprising: a transparent substrate; at least a transparent hole injection electrode; a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Chemical Formula 4) (wherein R1 and R2 may be the same or different, and a hydrogen atom , An alkyl group or an alkoxy group).

In the thin film EL device according to the invention of claim 22 of the present application, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- (4,4-diphenylbuta-1,3).
-Dienyl) phenyl] [4- (diphenylamino)
22. The thin-film EL device according to claim 21, which is [phenyl] amine.

In the thin film EL device according to the twenty-third aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- (4,4-diphenylbuta-1,3).
22. The thin-film EL device according to claim 21, which is -dienyl) phenyl] [4- {bis (4-methoxyphenyl) amino} phenyl] amine.

According to a twenty-fourth aspect of the present invention, there is provided a thin film EL device comprising at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 5) (wherein R1, R2, and R3 may be the same or different; (Representing a hydrogen atom, an alkyl group or an alkoxy group).

In the thin film EL device according to the twenty-fifth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- {2-aza-2- (diphenylamino)].
25. Vinyl diphenyl] [4- (diphenylamino) phenyl] phenylamine.
3. The thin-film EL device according to item 1.

In the thin film EL device according to the twenty-sixth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- {2-aza-2- (diphenylamino)].
25. The thin film EL according to claim 24, wherein the thin film EL is vinyl @ phenyl] [4- {bis (4-methoxyphenyl) amino} phenyl] (4-methoxyphenyl) amine.
Element.

The thin-film EL device according to the twenty-seventh aspect of the present invention provides a thin-film EL device comprising at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Chemical Formula 6) (wherein R1 and R2 may be the same or different, and a hydrogen atom , An alkyl group or an alkoxy group).

In the thin film EL device according to the twenty-eighth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [ 28. The thin-film EL device according to claim 27, which is 4- (diphenylamino) phenyl] amine.

In the thin film EL device according to the invention of claim 29, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [ 28. The thin-film EL device according to claim 27, which is 4- {bis (4-methoxyphenyl) amino} phenyl] amine.

The thin-film EL device according to the invention of claim 30 of the present application is characterized in that at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 7) (wherein R1, R2, and R3 may be the same or different; A hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group,
1 and R2 or R2 and R3 may each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group).
Element.

The thin film EL device according to claim 31 of the present invention is characterized in that the compound mainly contained in the ultra-thin electron blocking layer is [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] diphenylamine. 31. The thin-film EL device according to claim 30, wherein:

In the thin film EL device according to the invention of claim 32 of the present application, the compound mainly contained in the ultra-thin electron blocking layer is [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] bis ( 31. The thin film EL according to claim 30, which is 4-methoxyphenyl) amine.
Element.

The thin-film EL device according to the invention of claim 33 of the present application is characterized in that at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 8) (wherein R1, R2, and R3 may be the same or different; A hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group,
1 and R2 or R2 and R3 may each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group).
Element.

In the thin-film EL device according to the invention of claim 34, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] phenyl 34. The thin film EL device according to claim 33, wherein the device is an amine.

In the thin film EL device according to the invention of claim 35 of the present application, the compound mainly contained in the ultrathin electron blocking layer is bis [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] ( 34. The thin film E according to claim 33, which is 4-methoxyphenyl) amine.
L element.

The thin-film EL device according to claim 36 of the present invention provides a thin-film EL device comprising at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly described by the following general formula (Formula 9) (wherein R1 represents a hydrogen atom or an alkyl group). A thin-film EL device containing a compound.

In the thin film EL device according to the invention of claim 37, the compound mainly contained in the ultra-thin electron blocking layer is tris [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] amine The thin film EL device according to claim 36, wherein:

In the thin-film EL device according to claim 38 of the present application, the compound mainly contained in the ultra-thin electron blocking layer is tris [4- {4- (2,2-diphenylvinyl) -2-methylphenyl]. 37. The thin film E according to claim 36, which is [-3-methylphenyl] amine.
L element.

The thin-film EL device according to claim 39 of the present application is a thin-film EL device comprising: a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 10) (wherein R1, R2, and R3 may be the same or different; Hydrogen atom, alkyl group,
Represents an alkoxy group, a substituted or unsubstituted aryl group,
R1 and R2 or R2 and R3 may each form a ring. In the formula, R4 represents a hydrogen atom or an alkyl group.
A thin film E comprising a compound described in
L element.

In the thin-film EL device according to the forty-fourth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- {4- (4,4-diphenylbuta-1,1-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1
40. The thin film EL according to claim 39, which is 3-dienyl) phenyl @ phenyl] diphenylamine.
Element.

In the thin film EL device according to the invention of claim 41 of the present application, the compound mainly contained in the ultra-thin electron blocking layer is [4- {4- (4,4-diphenylbuta-1,1,2-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1,4-diphenylbuta-1
3. Di- (3-dienyl) phenyl @ phenyl] bis (4-methoxyphenyl) amine.
10. A thin film EL device according to item 9.

The thin-film EL device according to claim 42 of the present application is characterized in that at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 11) (wherein R1, R2, and R3 may be the same or different; Hydrogen atom, alkyl group,
Represents an alkoxy group, a substituted or unsubstituted aryl group,
R1 and R2 or R2 and R3 may each form a ring. In the formula, R4 represents a hydrogen atom or an alkyl group.
A thin film E comprising a compound described in
L element.

The thin-film EL device according to claim 43 of the present invention is characterized in that the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {4- (4,4-diphenylbuta-
43. The thin film E according to claim 42, which is (1,3-dienyl) phenyl @ phenyl] phenylamine.
L element.

In the thin film EL device according to the forty-fourth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {4- (4,4-diphenylbuta-
5. A 1,3-dienyl) phenyl @ phenyl] (4-methoxyphenyl) amine.
3. The thin film EL device according to item 2.

A thin-film EL device according to a forty-fifth aspect of the present invention is a thin-film EL device comprising: a transparent substrate; at least a transparent hole injection electrode; a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly described by the following general formula (Formula 12) (wherein R1 represents a hydrogen atom or an alkyl group). A thin-film EL device containing a compound.

In the thin film EL device according to the invention of claim 46, the compound mainly contained in the ultra-thin electron blocking layer is tris [4- {4- (4,4-diphenylbuta-1,3-dienyl). 46) The thin film EL device according to claim 45, wherein phenyl [phenyl] amine is used.

In the thin film EL device according to the invention of claim 47, the compound mainly contained in the ultrathin electron blocking layer is tris [4- {4- (4,4-diphenylbuta-1,3-dienyl). ) -2-Methylphenyl} -3-
46. The thin-film EL device according to claim 45, which is [methylphenyl] amine.

The thin-film EL device according to claim 48 of the present invention is a thin-film EL device comprising at least a transparent hole injecting electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injecting electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is mainly composed of the following general formula (Formula 13) (wherein R1, R2, and R3 may be the same or different; Hydrogen atom, alkyl group,
Represents an alkoxy group, a substituted or unsubstituted aryl group,
R1 and R2 or R2 and R3 may each form a ring. In the formula, R4 represents a hydrogen atom or an alkyl group.
A thin film E comprising a compound described in
L element.

In the thin film EL device according to the invention of claim 49, the compound mainly contained in the ultra-thin electron blocking layer is [4- {4-} 2-aza-2- (diphenylamino) vinyl} phenyl 49. The thin-film EL device according to claim 48, wherein [{phenyl] diphenylamine "is used.

In the thin film EL device according to the fiftyth aspect of the present invention, the compound mainly contained in the ultra-thin electron blocking layer is [4- {4-} 2-aza-2- (diphenylamino) vinyl} phenyl 49. It is [{phenyl] bis (4-methoxyphenyl) amine.
3. The thin-film EL device according to item 1.

The thin-film EL device according to the fifty-first aspect of the present invention is directed to a thin-film EL device comprising at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electronic block layer is mainly composed of the following general formula (Formula 14) (wherein R1, R2, and R3 may be the same or different; Hydrogen atom, alkyl group,
Represents an alkoxy group, a substituted or unsubstituted aryl group,
R1 and R2 or R2 and R3 may each form a ring. In the formula, R4 represents a hydrogen atom or an alkyl group.
A thin film E comprising a compound described in
L element.

The thin-film EL device according to the invention of claim 52 is characterized in that the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {4- {2-aza-2- (diphenylamino) vinyl}]. 52. The thin film EL according to claim 51, which is [phenyl @ phenyl] phenylamine.
Element.

In the thin film EL device according to the invention of claim 53, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {4- {2-aza-2- (diphenylamino) vinyl}. 52. Phenyl @ phenyl] (4-methoxyphenyl) amine.
3. The thin-film EL device according to item 1.

The thin-film EL device according to the fifty-fourth aspect of the present invention is directed to a thin-film EL device comprising: a transparent substrate; at least a transparent hole injection electrode; a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein an ultra-thin electron block layer is mainly described by the following general formula (Formula 15) (wherein R1 represents a hydrogen atom or an alkyl group). A thin-film EL device containing a compound.

In the thin film EL device according to the fifty-fifth aspect of the present invention, the compound mainly contained in the ultrathin electron blocking layer is tris [4- {4- {2-aza-2- (diphenylamino) vinyl}. 55. The thin-film EL device according to claim 54, wherein the device is phenyl [phenyl] amine.

In the thin-film EL device according to claim 56 of the present application, the compound mainly contained in the ultrathin electron blocking layer is tris [4- {4- {2-aza-2- (diphenylamino) vinyl}. -2-methylphenyl} -3-methylphenyl] amine.
5. A thin film EL device according to item 4.

The thin-film EL device according to the fifty-seventh aspect of the present invention provides a thin-film EL device comprising at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein an ultra-thin electron block layer is mainly composed of the following general formula (Formula 16) (where R1 is a hydrogen atom,
An alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group; and R2 represents a hydrogen atom, an alkyl group, or an alkoxy group).

The thin film EL device according to claim 58 of the present invention is characterized in that the compound mainly contained in the ultra-thin electron blocking layer is bis [4- {bis (3-methylphenyl) amino} phenyl] (4-phenyl 58. The thin-film EL device according to claim 57, wherein the device is phenyl) amine.

The thin-film EL device according to claim 59 of the present invention is characterized in that the compound mainly contained in the ultrathin electron blocking layer is bis [4- {bis (4-methoxyphenyl) amino} phenyl] (4-phenyl 58. The thin-film EL device according to claim 57, wherein the device is phenyl) amine.

The thin film EL device according to claim 60 of the present application is characterized in that the compound mainly contained in the ultra-thin electron blocking layer is bis [4- (diphenylamino) phenyl].
58. The thin film EL device according to claim 57, wherein the device is (4-methylphenyl) amine.

In the thin film EL device according to the invention of claim 61, the compound mainly contained in the ultra-thin electron blocking layer is bis [4- (diphenylamino) phenyl].
58. The thin-film EL device according to claim 57, wherein the device is {4- (4-methoxyphenyl) phenyl} amine.

In the thin film EL device according to the invention of claim 62, the compound mainly contained in the ultrathin electron blocking layer is bis [4- (diphenylamino) phenyl].
58. The thin film E according to claim 57, which is [4- {4- (4-phenyl) phenyl} phenyl] amine.
L element.

The thin-film EL device according to claim 63 of the present application comprises a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL element having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is an ultra-thin coated layer formed by coating at least.

The thin-film EL device according to claim 64 of the present invention, wherein the ultra-thin coating layer formed by the coating contains at least a polymer hole transport material. It is a thin film EL element.

The thin-film EL device according to claim 65 of the present application, wherein the ultra-thin coating layer formed by the coating contains at least a low-molecular-weight hole transport material. It is a thin film EL element.

The thin-film EL device according to claim 66 of the present application is characterized in that the low-molecular-weight hole transport material is mainly composed of 4,4 ′, 4 ″.
66. The thin-film EL device according to claim 65, which is -trismethyltriphenylamine.

The thin film EL device according to claim 67 of the present application, wherein said low molecular weight hole transport material is mainly 4-N, N-diphenylamino-α-phenylstilbene. Is a thin film EL element.

In the thin-film EL device according to claim 68 of the present application, the low-molecular-weight hole transport material is mainly composed of (1-aza-
66. The thin film EL device according to claim 65, which is 6,6-diphenylhexa-1,3,5-trienyl) naphthylphenylamine.

The thin-film EL device according to claim 69 of the present application is characterized in that at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin film EL device having a block layer, a light emitting layer, and a cathode, wherein the ultra-thin film electron block layer is an oxide film.

The thin-film EL device according to claim 70 of the present application.
Means that the oxide is Al_TwoO_Three, SiO _Two, TiO_Two, Ta
_TwoO_Five, ZnO, ZrO_Two, More than one type selected
70. The thin film according to claim 69, comprising a compound.
EL element.

The thin-film EL device according to the seventy-first aspect of the present invention is directed to a thin-film EL device, comprising: a transparent substrate; at least a transparent hole injection electrode; a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer has a relative dielectric constant of 30 or more.

The thin-film EL device according to claim 72 of the present application is the thin-film EL device according to claim 71, wherein said ultra-thin electron blocking layer is made of LiNbO ₃ or PbTiO ₃ .

The method of manufacturing a thin film EL device according to claim 73 of the present application is characterized in that at least a transparent hole injection electrode is formed on a transparent substrate, and a transparent conductive layer formed by coating on the transparent hole injection electrode. A method for manufacturing a thin-film EL device having an ultra-thin electronic block layer, a light-emitting layer, and a cathode, wherein a plasma treatment is performed after forming the ultra-thin electronic block layer and before forming the next layer. This is a method for manufacturing a thin film EL element.

The method of manufacturing a thin film EL device according to claim 73, wherein the plasma treatment is an oxygen plasma treatment.

The thin film EL device according to claim 75 of the present application is the thin film EL device according to claim 64, wherein the high molecular hole transport material is a fluorene-based polymer.

The thin film EL device according to claim 76 of the present application is the thin film EL device according to claim 75, wherein the fluorene-based polymer has a fluorene portion and a hole transporting portion.

The thin film EL device according to claim 77 of the present application, wherein said hole transporting portion contains at least triphenylamine.
Element.

[0098]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a thin film EL device according to an embodiment of the present invention will be described.

The thin-film EL device of the present invention is formed on a transparent substrate.
It comprises at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer and a cathode.

The transparent substrate in the present invention may be any as long as it can carry the thin film EL element of the present invention.
Normal glass substrates such as 737 glass are often used, but polyester and other resin films can also be used.

The transparent hole injection electrode of the present invention can function as an anode to inject holes into the device.
Any material may be used as long as it is transparent and can emit light emitted in the device to the outside. In general, an ITO (indium tin oxide) film is often used. ITO films are formed by sputtering, electron beam evaporation, ion plating, etc., with the aim of improving the transparency or reducing the resistivity, and various post-treatments for the purpose of controlling the resistivity and shape. Is often performed. The film thickness is determined from the required sheet resistance value and visible light transmittance. However, since the driving current density is relatively high in the organic EL element,
It is often used with a thickness of 100 nm or more to reduce sheet resistance. These normal ITO films can be used for the hole injection electrode of the present invention.
Various improved transparent conductive layers, including IXO, can also be used widely. Further, a coating film of a transparent conductive paint in which a conductive powder is dispersed and other electrodes can be used.

It is important that the transparent conductive layer formed by coating in the present invention is formed by coating, whereby the surface of the coating film is viewed microscopically by the action of the surface tension of the coating used for coating. The smoothing effect can be obtained. As a material, a material prepared by coating a material such as polypyrrole, polyacetylene, polythiophene, or polyaniline, which is generally widely used as a conductive polymer, with an appropriate dopant can be used. Although a general conductive polymer having an extremely low specific resistance of 1 Ωcm or less has been obtained, it is generally 10 ⁴ to 1 for use in the present invention.
0 ⁵ [Omega] cm can be used as long as the following resistivity. In applications such as passive matrix displays, in order to prevent crosstalk, it may be necessary to maintain the resistivity at 10 ³ Ωcm or more, depending on the film thickness. This is the range where the resistance value can be controlled. Further, the ionization potential is preferably in a range of plus 0.4 eV to minus 0.2 eV as compared with the ionization potential of the ultra-thin electron blocking layer from the viewpoint of hole injection, but is not always a necessary condition.

The ultra-thin electron blocking layer according to the present invention comprises:
Any material that can suppress the passage of electrons without hindering the injection of holes as much as possible may be used, and various specific hole transport layers, insulating layers, and the like can be used. When the light-emitting layer is provided directly on the coating type conductive layer without providing this layer, electrons injected from the cathode do not recombine with holes, and holes are injected through the coating type conductive layer. Reaches the electrode,
Only low emission quantum efficiency can be obtained. That is, in the present invention, this ultra-thin electronic block layer is an essential component.

In the ultra-thin electron blocking layer, it is preferable that the film thickness is small from the viewpoint of not impeding the first condition of hole injection, and from the viewpoint of blocking electrons under the second condition. An extremely thin ultrathin film is sufficient. Unlike the hole transport layer in a normal organic EL device, the ultra-thin electron blocking layer of the present invention has a high surface smoothness of the underlying coating type conductive layer, and it is easy to obtain a uniform film without pinholes even in an extremely thin film. In some cases, the film thickness is used as a minimum necessary ultra-thin film. Here, the ultra-thin film is used to mean an extremely thin film as compared with a conventional hole transport layer or the like, and does not mean a specific film thickness. The optimum film thickness in an actual device configuration depends on the material used, but is extremely thin as compared with the film thickness generally used in the conventional hole transport layer.

Therefore, even when a hole transporting material is used for the ultra-thin electron blocking layer, it is completely free from the difficulty of developing the conventional hole transporting material as described in the problem to be solved. Excellent characteristics can be realized by using completely different materials or using completely different film thicknesses and element configurations even with conventional materials.

As the light emitting layer in the present invention, a material generally known as a light emitting layer of an organic EL device can be widely used, and the most common example is tris (8-quinolinolato).
This is a layer in which aluminum is provided with a thickness of several tens of nm. It is known that tris (8-quinolinolato) aluminum is a green fluorescent substance and an electron-transporting material. For example, when this is formed to a thickness of 40 nm, its cathode side is about 1/2. Functions as an electron transport layer,
It is considered that about も の of the ultra-thin electron block layer side actually functions as a part where carriers recombine and emit light.

In general, when the portion where carriers actually emit light due to recombination is in contact with the vicinity of the cathode, there is a problem that it is difficult to obtain a high luminous efficiency due to a so-called cathode quenching effect. A layer may be provided between the light emitting layer and the cathode to form a double hetero structure. Providing the light-emitting layer and the electron transport layer separately in this manner is advantageous in that elements of various colors can be obtained by selecting a light-emitting material of each color with a high degree of freedom.

Although not an essential component of the device of the present invention, an electron transport layer is often provided between the light emitting layer and the cathode as described above.

The cathode according to the present invention is made of MgAg alloy or A
In addition to an alloy of a metal having a low work function and a low electron injection barrier and a metal having a relatively large work function and a stable metal such as an lLi alloy, a laminated cathode of Li and Al, LiF and A
Various generally reported cathodes can be used, such as the laminated cathode 1 described above.

The essential part of the invention according to claim 1 of the present application is that the essential part has a configuration in which a transparent conductive layer formed by coating, an ultra-thin electronic block layer, and a light emitting layer are formed on a transparent hole injection electrode. More specifically, it has a configuration having an ultra-thin electron blocking layer. That is, unlike a conventional hole transport layer having a thickness of about 80 nm, an ultra-thin layer (at least 40 nm or less, preferably 20 nm or less, more preferably 10 nm or less) is provided on the coating type conductive layer as an electron block layer. Therefore, even in the case of pulse driving requiring high instantaneous luminance, there is no fear of deterioration such as current leakage or short circuit, and a highly efficient, low driving voltage and highly reliable device can be obtained stably for a long life. Things.

In the conventional device, even if the thickness of the hole transport layer is reduced, the driving voltage is only slightly reduced, the emission quantum efficiency is reduced, the life is shortened, and short-circuit is easily caused. Many disadvantages are remarkable, for example, a current leak (a current flowing in the reverse direction without obtaining rectification) and an element having such a thin hole transport layer can withstand practical use. I could not imagine. However, by using in combination with the coating type conductive layer as described above, it is possible to reduce the film thickness, and this configuration is made practical. Here, the conductive paint used for application may be any one that can obtain a microscopically smooth surface by the surface tension of the paint, and various conductive polymers as described above can be used. As the conductive paint, not only a type in which a conductive polymer is dissolved in a solvent together with a dopant, but also a type in which fine particles are dispersed can be used.

In the invention of claim 2 of the present application, the essential part is that, in addition to the requirement of claim 1, the thickness of the ultra-thin electronic block layer is one of the thickness of the layer from the light emitting layer to the cathode.
/ 3 or less. As a result, substantially the majority of the driving voltage is applied to the layers from the light-emitting layer to the cathode, that is, the part responsible for light emission, the part responsible for electron transport, and the part responsible for electron injection. Thus, the efficiency of injection and transport of electrons is improved, and high luminous efficiency, which cannot be obtained by the conventional devices, can be realized.

In the invention of claim 3 of the present application, the essential part is that, in addition to the requirement of claim 2, the thickness of the ultra-thin electronic block layer is further adjusted by the average surface roughness of the transparent conductive layer formed by coating. That is all. This allows
There is no leakage of pinholes in the function of the ultra-thin electron block layer, and high-efficiency recombination of electron-holes is realized, and high luminous efficiency, which was not obtained by conventional devices, can be realized for a long life. . In this application, the average surface roughness means the center line average roughness.

In the invention of claim 4 of the present application, the essential part is that, in addition to the requirement of claim 3, the ultrathin electron blocking layer has an electron mobility of 1 × 10 ⁶ V / cm at an electric field of 1 × 10 ⁶ V / cm.
× 10 ^- in ⁵ cm ² / V · s be less. This makes it possible to effectively confine electrons in the light-emitting layer even in an ultra-thin electron block layer, especially in pulse driving. Can be realized with a long service life.

In the invention of claim 5 of the present application, the essential part is that, in addition to the requirement of claim 3, the electron affinity of the ultra-thin electron blocking layer is 2.7 eV or less. This effectively suppresses the injection of electrons from the light-emitting layer into the ultra-thin electron blocking layer, and in particular, remarkably during pulse driving, high luminous efficiency that could not be obtained with the conventional device can be realized for a long life. Things.

In the invention of claim 6 of the present application, the essential part is that, in addition to the requirement of claim 3, the forbidden band width of the ultra-thin electronic block layer is 2.5 eV or more. This effectively suppresses the injection of electrons from the light-emitting layer into the ultra-thin electron blocking layer, and in particular, remarkably during pulse driving, high luminous efficiency that could not be obtained with the conventional device can be realized for a long life. Things.

In the invention of claim 7 of the present application, the essential part is that, in addition to the requirement of claim 3, the thickness of the element sandwiched between the anode and the cathode is 60 nm or less. Due to this, even at a low driving voltage, the layers from the light emitting layer to the cathode, that is, the part responsible for light emission, the part responsible for electron transport, and the part responsible for electron injection,
A high electric field is generated, the efficiency of injection and transport of electrons is improved, and a high luminous efficiency which cannot be obtained by the conventional device can be realized.

In the invention of claim 8 of the present application, in addition to the requirement of claim 3, the essential part is that between the light-emitting layer and the cathode, at least as an electron injection / transport layer, the resistivity is 1%.
0 ⁷ [Omega] cm has the following layers, and the film thickness thereof thickness 10n
m or more. As a result, the efficiency of injection and transport of electrons is directly improved. Compared with the conventional device configuration, the above-described configuration according to claim 3 does not have a hole transport layer having a thickness of 80 nm and uses an ultra-thin electron blocking layer. The efficiency is extremely high. This works at the same time as the above-mentioned improvement of the electron injection efficiency, thereby achieving extremely high emission quantum efficiency and low driving voltage, which could not be expected in the past, in other words, high emission efficiency (low power consumption). .

According to the ninth aspect of the present invention, in addition to the requirement of the third aspect, the essential part is that a low work function alkali metal or alkaline earth is provided at least as an electron injection / transport layer between the light emitting layer and the cathode. It has a layer containing a kind of metal and has a thickness of 10 nm or more. As a result, the electron injection efficiency is improved in the same manner as described above, and works with the high hole injection efficiency of the device of the present invention, so that high luminous efficiency (low power consumption) is obtained.

According to the tenth aspect of the present invention, in addition to the features of the third aspect, the essential part is that a phenanthroline derivative and an alkali having a low work function are provided between the light emitting layer and the cathode, at least as an electron injection / transport layer. A layer containing a metal or an alkaline earth metal and having a thickness of 10
nm or more. As a result, the electron injection efficiency is improved in the same manner as described above, and works with the high hole injection efficiency of the device of the present invention, so that high luminous efficiency (low power consumption) is obtained.

In the eleventh aspect of the present invention, in addition to the requirements of the first aspect, the essential part is that the thickness of the ultra-thin electronic block layer is equal to or less than the thickness of the light emitting layer and that the transparent conductive layer formed by coating is formed. The thickness is not less than the average surface roughness of the layer, and the thickness of a substantially voltage-applied region of the element sandwiched between the anode and the cathode is not more than 50 nm. The substantially voltage-applied region refers to a portion excluding a portion having a low resistivity, such as a conductive layer, to which a voltage is not practically applied, and specifically, for example, is formed in Example 1 described in detail below. In the case of a device, it refers to an ultrathin electron blocking layer and an electron transporting light emitting layer. As a result, a high electric field is applied to the light emitting layer even at a low driving voltage, and the efficiency of injection of electrons and holes into the light emitting layer is improved, and high light emitting efficiency is obtained.

Claims 12, 15, 18, 21, 2 of the present application
4, 27, 30, 33, 36, 39, 42, 45, 4
In the inventions of 8, 51, 54 and 57, the essential part is that the ultra-thin electron blocking layer mainly contains the compound represented by the general formula shown in each claim. By using these compounds in the ultra-thin electron blocking layer, it is possible to effectively block electrons and enhance recombination efficiency despite being an ultra-thin film, and to effectively inject holes at a low voltage. With high emission quantum efficiency,
An element having a low driving voltage, high luminous efficiency (low power consumption), no current leakage and short circuit, and extremely high reliability and long life can be stably obtained. Any of these compounds can be used as a single ultra-thin film to form a good ultra-thin electron blocking layer, or can be used in combination of two or more, or can be co-evaporated with another compound.

Claims 13, 14, 16, 17, 1 of the present application
9, 20, 22, 23, 25, 26, 28, 29, 3,
1, 32, 34, 35, 37, 38, 40, 41, 4
3, 44, 46, 47, 49, 50, 52, 53, 5
In the inventions of 5, 56, 58, 59, 60, 61 and 62, the essential part is that the ultra-thin electron blocking layer mainly contains the compound described in each claim.
By using these compounds in the ultra-thin electron blocking layer, it is possible to effectively block electrons and enhance recombination efficiency despite being an ultra-thin film, and to effectively inject holes at a low voltage. It is possible to stably obtain an extremely reliable and long-life element having high emission quantum efficiency, low driving voltage, high emission efficiency (low power consumption), no current leakage and short circuit. All of these compounds are relatively easy to synthesize and purify, and stable supply of materials at relatively low cost can be expected. Any of these compounds can be used as a single deposited film to form a good ultra-thin electron block layer, or in combination of two or more,
It can be used by co-evaporation with another compound.

In the invention of claim 63 of the present application, the essential parts are that at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL element having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electronic block layer is an ultra-thin coated layer formed by coating at least. By properly selecting the solvent used when forming the ultra-thin electronic block layer by coating, it is possible to improve the affinity between the coating type conductive layer and the ultra-thin electronic block coating layer and eliminate pinholes and the like. A good ultra-thin film can be easily formed. As a result, there is no leakage in the electron blocking action of the ultra-thin electron blocking layer, and high-efficiency electron-hole recombination is realized, and high luminous efficiency, which cannot be obtained by the conventional devices, can be realized for a long life. It is.

In the invention of claim 64 of the present application, the essential part is that, in addition to the requirement of claim 63, the ultra-thin coating layer formed by the coating contains at least a polymer hole transport material. is there. This makes it possible to realize a highly reliable and highly efficient device having excellent heat resistance and, in particular, significantly improved life.

In the invention of claim 65 of the present application, the essential part is that, in addition to the requirement of claim 63, the ultra-thin coating layer formed by the coating contains at least a low-molecular hole transport material. is there. This makes it possible to easily obtain an ultra-thin electron block layer without pinholes by selecting an appropriate solvent and forming a film, even if the compound is difficult to form a thin film using the conventional vapor deposition method. A high luminous efficiency, which could not be obtained with the device of the above, can be realized with a long life.

In the invention of claim 66 of the present application, the essential part is that, in addition to the requirement of claim 65, the low-molecular-weight hole transport material is mainly 4,4 ', 4 "-trismethyltriphenylamine. Conventionally, it has been difficult to form a thin film by a vapor deposition method using this hole transport material, but by selecting an appropriate solvent, it can be easily formed as an ultra-thin electron block layer having no pinholes or the like on a coating type conductive layer. It can be formed, and high luminous efficiency, which cannot be obtained by a conventional device, can be realized for a long life.

In the invention of claim 67 of the present application, the essential part is that, in addition to the requirement of claim 65, the low-molecular-weight hole transport material is mainly 4-N, N-diphenylamino-α-phenylstilbene. It is in. In the case of the hole transport material, a device having a sufficient life was not obtained when a thin film was formed by a conventional vapor deposition method, but by selecting an appropriate solvent having good affinity for the coating type conductive layer, the coating type conductive layer was selected. By coating on the top, it can be easily formed as an ultra-thin electronic block layer without pinholes and the like, and high luminous efficiency, which cannot be obtained by the conventional device, can be realized with a long life.

In the sixty-eighth aspect of the present invention, the essential part is that, in addition to the requirement of the sixty-fifth aspect, the low molecular weight hole transport material is mainly composed of (1-aza-6,6-diphenylhexa-
(1,3,5-trienyl) naphthylphenylamine. This hole transport material is easily formed as an ultra-thin electron block layer without pinholes by selecting an appropriate solvent having a good affinity for the coating type conductive layer and coating and forming it on the coating type conductive layer. Thus, high luminous efficiency, which cannot be obtained by the conventional device, can be realized for a long life.

In the invention of claim 69 of the present application, the essential parts are that at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode, A thin-film EL element having a block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electron block layer is an oxide film. As a result, even in the case of an extremely thin ultra-thin film, the function of the ultra-thin electron block layer is free from pinholes and the like and can be used in an extremely ultra-thin film, so that the hole injection efficiency is high and the efficiency is high. Thus, recombination of electron holes can be realized, and high luminous efficiency, which cannot be obtained by the conventional devices, can be realized for a long life.

In the invention of claim 70, the essential part is that the oxide is composed of Al ₂ O ₃ , SiO ₂ , TiO ₂ , Ta
_It consists of one or more compounds selected from the group consisting of ₂ O ₅ , ZnO, and ZrO ₂ . All of these compounds can form a dense and ultra-thin ultra-thin film at a relatively low temperature on the coating type conductive layer. Since it can be used as a thin film, it has a high hole injection efficiency, realizes highly efficient electron-hole recombination, and can achieve high luminous efficiency, which could not be obtained by conventional devices, for a long life. .

[0132] In the invention of claim 71 of the present application, the essential parts are: at least a transparent hole injection electrode on a transparent substrate; a transparent conductive layer formed by coating on the transparent hole injection electrode; A thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein the relative permittivity of the ultra-thin electron block layer is 30 or more. Due to this, particularly in the case of pulse driving, almost immediately after the pulse voltage is applied, most of the driving voltage is not applied to the ultrathin electronic block layer, and almost all the voltage is applied to the light emitting layer, The efficiency of injecting holes and electrons into the light emitting layer is improved, and high light emitting efficiency can be realized for a long life.

The essential part of the present invention is that the ultra-thin electron blocking layer is made of LiNbO ₃ or PbTiO ₃ . All of these compounds can form a dense and ultra-thin ultra-thin film at a relatively low temperature on the coating type conductive layer. Since it can be used as a thin film, the hole injection efficiency is high, and highly efficient electron-hole recombination is realized. Also, since its relative permittivity is extremely high, in the case of pulse driving,
Immediately after the pulse voltage is applied, most of the drive voltage is not applied to the ultra-thin electron blocking layer, and almost all voltage is applied to the light-emitting layer, so injection of holes and electrons into the light-emitting layer Efficiency is improved, and high luminous efficiency can be realized for a long life.

In the invention of claim 73, the essential parts are that at least a transparent hole injection electrode on a transparent substrate, a transparent conductive layer formed by coating on the transparent hole injection electrode, A method for manufacturing a thin-film EL device having a block layer, a light-emitting layer, and a cathode, wherein a plasma treatment is performed after forming an ultra-thin electron block layer and before forming a layer. As a result, the microscopic adhesion between the coating type conductive layer and the ultra-thin electronic block layer can be improved, the hole injection efficiency can be improved, and high efficiency can be obtained for a long life.

The essential part of the invention of claim 74 is that the plasma processing is oxygen plasma processing, and by performing this processing, the coating type conductive layer and the ultra-thin electronic block layer are particularly remarkably formed. The micro-adhesion can be improved, the hole injection efficiency can be improved, and high efficiency can be obtained for a long life.

In the invention of claim 75 of the present application, the essential part is that, in addition to the requirement of claim 64, the high molecular hole transporting material is a fluorene-based polymer. Therefore, a stable and long-life element can be realized even when the element is thinned, and both excellent light emission characteristics and element life can be achieved. Although the reason is considered to reflect the properties of the rigid fluorene skeleton, even when compared with the life characteristics and the like when used as a normal fluorene-based light-emitting polymer element, especially when used in a specific combination according to the invention Only a remarkable improvement in the life is recognized, so that it is considered that it is particularly suitable for use in a device having the configuration of the present invention. As the fluorene-based polymer in the present invention, those having a fluorene moiety in the polymer chain and those which are soluble in a solvent and can be formed by coating may be used, such as homopolymers of various alkylfluorenes and various other segments. Many materials which are generally reported as a light emitting polymer, such as a copolymer with a polymer, a block polymer, or a homopolymer containing a fluorene moiety as a part of a repeating unit, can be used.
The formation by solvent-soluble coating means that the monomer is soluble,
It may be a type of film formed by polymerization after film formation.

In the invention of claim 76, the essential part is that, in addition to the requirement of claim 75, the fluorene-based polymer has a fluorene portion and a hole-transporting portion. Element performance can be obtained.

In the invention of claim 77 of the present application, the essential part is that, in addition to the requirement of claim 76, the hole transporting portion contains at least triphenylamine. Is obtained.

Next, the present invention will be described in more detail with reference to specific examples, but the embodiments of the present invention are not limited to the specific examples shown here.

Example 1 As a substrate having a hole injection electrode formed on a transparent substrate, a commercially available glass substrate with ITO (manufactured by Sanyo Vacuum Corporation, size 100 × 100 mm × t =
0.7 mm, sheet resistance of about 14 Ω / □), and the emission area is 1.4 × 1.4 mm due to overlap with the electron injection electrode.
It was patterned by photolithography so that Substrate processing after photolithography is performed by immersing in a commercially available resist stripping solution (a mixed solution of dimethyl sulfoxide and N-methyl-2-pyrrolidone) to perform stripping, rinsing with acetone, and further immersing in fuming nitric acid for 1 minute. Then, the resist was completely removed. The surface of the ITO was sufficiently cleaned on both sides of the back surface of the substrate, and mechanically rubbed and cleaned with a nylon brush while sufficiently supplying a 0.238% aqueous solution of tetramethylammonium hydroxide. Then, it was sufficiently rinsed with pure water and spin-dried. Then, in a commercially available plasma reactor (PR41, manufactured by Yamato Scientific Co., Ltd.), an oxygen flow rate of 20 sccm,
Oxygen plasma treatment was performed for 1 minute under the conditions of a pressure of 0.2 Torr and a high frequency output of 300 W.

A commercially available polypyrrole-based conductive polymer paint was spin-coated on the transparent hole injection electrode thus prepared, and dried by heating at 150 ° C. for 10 minutes.
A coating type conductive layer of 0 nm was obtained. The resistivity of the coating type conductive layer obtained in this manner is about 10 ⁴ Ωcm, which has a suitable resistivity in the range described above, and an ultraviolet photoelectron spectrometer (AC-1 manufactured by Riken Keiki Co., Ltd.) Was about 5.2 eV. The 10-point average roughness measured by a stylus type surface roughness meter (Surfcom manufactured by Tokyo Seimitsu Co., Ltd.) is about 5% of the ITO surface after the plasma treatment.
It was confirmed that the surface was greatly smoothed to about 20 nm with respect to 0 nm.

The substrate thus formed up to the coating type conductive layer was placed in a vacuum chamber. The vacuum evaporation apparatus is a commercially available high vacuum evaporation apparatus (EBV-6DA, manufactured by Japan Vacuum Engineering Co., Ltd.).
(Model) was modified. The main evacuation device is a turbo molecular pump (TC 1500, manufactured by Osaka Vacuum Co., Ltd.) with an evacuation speed of 1500 liter / min. The ultimate degree of vacuum is about 1 × 10 ⁻⁶ Torr or less.
The test was performed within a range of × 10 ^-6 Torr. All evaporations were performed by connecting a direct current power supply (PAK10-70A, manufactured by Kikusui Electronics Co., Ltd.) to a tungsten resistance heating evaporation boat.

On the coating type conductive layer disposed in the vacuum layer in this way, [4-
(2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was converted to 0.3n
The film was formed to a thickness of about 10 nm at a deposition rate of m / s.

Here, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Phenylamine was obtained by synthesis as follows.

In a 300 ml four-necked flask, 41.4 g of N, N'-diphenyl-p-phenylenediamine, 66 g of iodobenzene, 100 ml of nitrobenzene, K ₂ CO ₃
45 g, 10.8 g of copper powder and I ₂ (trace)
Reflux gently for 24 hours with stirring while distilling off the water formed. After that, steam distillation was performed, and when no distillate was generated, the residue was cooled, filtered, washed with water, and extracted with toluene. After distilling off the toluene, ethanol was added to the residue and the mixture was filtered off. Recrystallization was performed from toluene: ethanol = 4: 1, and 36.5 g of N,
N, N ', N'-tetraphenyl-p-phenylenediamine was obtained. mp = 200-2 [deg.] C.

Next, 24 g of N-methylformanilide and 20 g of o-dichlorobenzene were placed in a 200 ml four-necked flask.
24 g of POCl ₃ at 25 ° C. (14 m
1) is added dropwise over 1 hour. N obtained above,
36 g of N, N ', N'-tetraphenyl-p-phenylenediamine was added, and the mixture was further stirred at 90-95 ° C for 2 hours (solidified in the course of o-dichlorobenzene 30).
ml). After the reaction was cooled, 10% -H ₂ SO ₄ 7
Pour into 0 ml and extract with toluene. The toluene solution is water, 5
% -Na ₂ CO _3, washed with water, dried over Na ₂ SO _4. After toluene was distilled off, the residue was dissolved in a small amount of toluene and subjected to silica column chromatography. 25.8 g of yellow crystals, p-
(N-phenyl-Np'-N ', N'-diphenylaminophenyl) aminobenzaldehyde was obtained. mp =
136-8 ° C.

Then, in a 200 ml three-necked flask, 8 g of diethyl-1,1-diphenylmethylphosphonate, p- (N-phenyl-N-p'-N ', N'-
Diphenylaminophenyl) aminobenzaldehyde 1
Dissolve 3.3 g in dry DMF (80 ml) and add t-BuOK
3.5 g are added at 21-33 ° C over 30 minutes. Thereafter, stirring is continued at 20 to 25 ° C. for 3.5 hours. Then, pour into 300 ml of ice water while stirring. After extracting with toluene, washing with water, and distilling off toluene, alumina column chromatography was performed with a toluene solvent to obtain 0.9 g of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine. mp = 218-9 [deg.] C.

Next, Tris (8
-Quinolinolato) aluminum (manufactured by Dojin Chemical Co., Ltd.)
Was formed to a film thickness of about 40 nm at a deposition rate of 0.3 nm / s.

Next, as the cathode, only Li was deposited from an AlLi alloy (manufactured by Kojundo Chemical Co., Ltd., Al / Li weight ratio: 99/1) at a low temperature and a film thickness of about 1 nm at a deposition rate of about 0.1 nm / s.
After that, the AlLi alloy was further heated to a state in which Li was exhausted, and only Al was reduced to about 1.5 n
The film was formed to a film thickness of about 100 nm at a vapor deposition rate of m / s to obtain a laminated cathode.

The thin-film EL device thus prepared is
After the inside of the vapor deposition tank was leaked with dry nitrogen, a lid made of Corning 7059 glass was attached with an adhesive (manufactured by Anelva Co., trade name: Super Back Seal 953-7) under a dry nitrogen atmosphere.
000) to make a sample.

The thus obtained thin film EL element samples were evaluated as follows.

The initial evaluation was performed in a normal laboratory environment at room temperature and normal humidity 12 hours after the glass lid was adhered after the deposition of the device, and the luminous efficiency (cd / A) and the driving voltage at the time of light emission of 1000 cd / m ² were obtained. Was evaluated. Also, the initial luminance is 1000 cd /
At a current value of m ² , a continuous light emission test was performed with a DC constant current drive in a normal laboratory environment at normal temperature and normal humidity. From this test,
The time when the luminance reached half (500 cd / m ² ) was evaluated as the life.

As the DC drive power source, a DC constant current power source (manufactured by Advantest Co., Ltd., product name: Multi-channel current voltage controller TR6163) was used to measure the voltage-current characteristics, and the luminance was measured using a luminance meter (manufactured by Tokyo Optical Machine Co., Ltd.) Name Topcon Luminescence Meter B
M-8). Luminance image quality such as uneven brightness and black spots (non-light-emitting portions) was observed with a 50-fold optical microscope.

The pulse drive uses a self-made constant current pulse drive circuit, the pulse cycle is 100 Hz (10 ms), the duty is 1/240 (pulse width 42 μs), the pulse waveform is a square wave, and the pulse current value is set to various values. Was evaluated. The luminance was measured by a luminance meter (trade name: Topcon Luminescence Meter BM-8, manufactured by Tokyo Optical Machine Co., Ltd.), and the pulse drive voltage when the average luminance was 270 cd / m ² was evaluated. The initial luminance is 270 cd / m
^At a pulse voltage value of ² , continuous pulse driving was performed in a normal laboratory environment at normal temperature and normal humidity to perform a continuous light emission test. From this test, the time when the luminance reached half (135 cd / m ² ) was evaluated.

The results of these evaluations are shown in (Table 1).

[0156]

[Table 1]

According to this embodiment, high luminous efficiency is obtained,
Light emission with excellent visibility is obtained by self-emission at low drive voltage,
Even in the continuous light emission test, a thin-film EL element which has a small decrease in luminance, has no problems such as black spots and luminance unevenness, and can be used stably for an extremely long period of time was realized.

In particular, even during the pulse driving corresponding to the driving of an actual panel, the driving voltage is high and the driving voltage is low, the luminance is small even in the continuous light emission test, and there are no problems such as black spots and luminance unevenness. A thin-film EL element that can be used stably was realized.

Example 2 In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Instead of phenylamine, [4- (2,2-diphenylvinyl) phenyl] (4-methoxyphenyl) {4-
Thin film E was prepared in the same manner as in Example 1 except that [(4-methoxyphenyl) phenylamino] phenyl diamine was used.
An L element sample was prepared.

Here, [4- (2,2-diphenylvinyl) phenyl] (4-methoxyphenyl) {4-[(4
[-Methoxyphenyl) phenylamino] phenyl diamine was synthesized and obtained as follows.

In a 300 ml four-necked flask, 27.6 g of N, N'-diphenyl-p-phenylenediamine, 50 g of p-iodoanisole, 75 ml of nitrobenzene, K ₂
30 g of CO ₃ , 7.2 g of copper powder and I ₂ (trace) were added, and the mixture was gently refluxed for 24 hours with stirring while distilling off the generated water. After that, steam distillation was performed. When no distillate was generated, the residue was cooled and the residue was extracted with toluene. After the toluene is distilled off, alumina column chromatography is performed using a toluene solvent. After distilling off toluene, recrystallization was performed with a toluene: ethanol (1: 3) solvent, and 35.3 g of N, N′-diphenyl-N,
N′-bis (p-methoxyphenyl) -p-phenylenediamine was obtained. mp = 132-4 [deg.] C.

Then, in a 200 ml four-necked flask, 20.4 g of POCl ₃ was placed at 25 ° C. in a mixture of 20.4 g of N-methylformanilide and 17 ml of o-dichlorobenzene.
(12 ml) is added dropwise over 1 hour. Thereafter, 35 g of N, N′-diphenyl-N, N′-bis (p-methoxyphenyl) -p-phenylenediamine obtained above was added,
Stirring is further continued at 90-95 ° C for 2 hours. Cooled after the reaction, poured into 10% -H ₂ SO ₄ 70ml, toluene extraction. The toluene solution was washed successively with water, 5% -Na ₂ CO ₃ and water, and dried over Na ₂ SO ₄ . After toluene is distilled off, silica column chromatography is performed using a toluene solvent. After distilling off the toluene,
Recrystallized with ethanol. 16.9 g of orange crystals, p-
[N- (p-methoxyphenyl) -N- {p-N'-phenyl-N '-(p-methoxyphenyl) aminophenyl}]-aminobenzaldehyde was obtained. mp = 160
-1 ° C.

Next, 9.9 was added to a 200 ml three-necked flask with diethyl-1,1-diphenylmethylphosphonate.
g, p- [N- (p-methoxyphenyl)-obtained above.
N- {p-N'-phenyl-N '-(p-methoxyphenyl) aminophenyl}]-aminobenzaldehyde 1
Dissolve 6.4 g in dry DMF (65 ml) and add t-BuOK
4.4 g are added at 21-33 ° C over 30 minutes. Thereafter, stirring is continued at 20 to 25 ° C. for 3.5 hours. Then, pour into 300 ml of ice water while stirring. After extracting with toluene, washing with water and distilling off toluene, alumina column chromatography was performed using a toluene solvent to obtain 0.7 g of [4- (2,2-diphenylvinyl) phenyl] (4-methoxyphenyl) ｛4.
-[(4-Methoxyphenyl) phenylamino] phenyl diamine was obtained. mp = 271-2 [deg.] C.

The sample prepared as described above using the material synthesized in this manner was evaluated as described in Example 1.

Table 1 shows the results.

Example 3 In forming the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] was used.
A thin film EL device sample was prepared in the same manner as in Example 1 except that [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] diphenylamine was used instead of phenylamine.

Here, {4- [4- (2,2-diphenylvinyl) phenyl] phenyl} diphenylamine was obtained by synthesizing as follows.

In a 1000 ml four-necked flask, 92.4 g of biphenyl and 420 ml of AcOH are added, and water is added at 80 ° C. until the solution becomes turbid (about 90 ml). Then _{conc-H 2 SO 4 18ml,} 2 61.2g, iodate 24 g, the CCl ₄ 48 ml was added, stirred vigorously until the color of iodine disappeared (about 3 hours). After that the liquid temperature is 60 ℃
After lowering to a degree, pour into 1800 ml of water while stirring. The crystals are separated by filtration, washed with water and dried. Distillation under reduced pressure (bp5: 160-180 ° C) in an oil bath, 113.2 g
Of p-iodobiphenyl was obtained.

Next, 27 g of diphenylamine and p-iodobiphenyl 4 obtained above were placed in a 300 ml four-necked flask.
5 g, 100 ml of nitrobenzene, 45 g of K ₂ CO ₃ , 10.8 g of copper powder, and I ₂ (trace) were added, and the mixture was refluxed gently for 24 hours with stirring while distilling off the generated water. After that, steam distillation was carried out. When no distillate was generated, the residue was cooled and washed with water until the residue (harz) was neutralized (harz solidified).
After extracting with toluene and distilling off toluene, alumina column chromatography is performed with a small amount of a toluene solvent. After distilling off toluene, the residue was recrystallized with ethanol containing toluene to obtain 48.3 g of diphenylbiphenylamine. mp = 105-6
° C.

Then, N-neck was placed in a 200 ml four-necked flask.
36 g of methylformanilide, o-dichlorobenzene 3
21 ml of POCl ₃ at 25 ° C. in 1 ml of 0 ml mixture
Drops take time. Thereafter, 42 g of the diphenylbiphenylamine obtained above is added, and stirring is further continued at 90 to 95 ° C. for 2 hours. After the reaction was cooled, 10% -H ₂ SO ₄ 70
Then, the mixture was poured into the resulting mixture and extracted with toluene. The toluene solution is water,
5% -Na ₂ CO _3, successively washed with water, and dried over Na ₂ SO _4. After distilling off toluene, silica column chromatography was performed with a toluene solvent. After the toluene was distilled off, the residue was recrystallized from ethanol to obtain 24.6 g of 4- (4) as pale yellow crystals.
-N, N-diphenylaminophenyl) benzaldehyde was obtained. mp = 124.5-5.5 [deg.] C.

Then, in a 200 ml three-necked flask, diethyl-1,1-diphenylmethylphosphonate 21.4 was added.
g, 24.5 g of 4- (4-N, N-diphenylaminophenyl) benzaldehyde obtained above in dry DMF13
0 ml and dissolve 9.4 g of t-BuOK at 21-33 ° C.
It takes 1 hour to add. Thereafter, stirring is continued at 20 to 25 ° C. for 4 hours. Then, pour into 300 ml of ice water while stirring. After extracting with toluene, washing with water and distilling off toluene, alumina column chromatography is performed using a toluene solvent. After distilling off the solvent, the residue was dissolved in AcOEt, and then ethanol was added for crystallization, followed by suction filtration, and 15 g of {4- [4- (2,2-
[Diphenylvinyl) phenyl] phenyl} diphenylamine was obtained. mp = 142.5-3.5 [deg.] C.

The samples prepared as described above using the materials synthesized as described above were evaluated as described in Example 1.

The results are shown in (Table 1).

Example 4 In forming the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Instead of phenylamine, bis [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino)
A thin film EL device sample was prepared in the same manner as in Example 1 except that [phenyl] amine was used, and evaluated as described in Example 1.

Table 1 shows the results.

(Example 5) In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Thin film EL device sample in the same manner as in Example 1 except that bis [4- (2,2-diphenylvinyl) phenyl] [4- {bis (methoxyphenyl) amino} phenyl] amine was used instead of phenylamine. Was prepared and evaluated as described in Example 1.

Table 1 shows the results.

Example 6 In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Thin film EL was prepared in the same manner as in Example 1 except that [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of phenylamine. An element sample was prepared and evaluated as described in Example 1.

Table 1 shows the results.

(Example 7) In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
[4- (4,4-Diphenylbuta-1,3-dienyl) phenyl] [4- {bis (4-methoxyphenyl) amino} phenyl] (4-methoxyphenyl) amine was used instead of phenylamine. A thin film EL device sample was prepared in the same manner as in Example 1 except for the above, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

Example 8 In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Instead of phenylamine, bis [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that (diphenylamino) phenyl] amine was used.
The evaluation was performed as described in Example 1.

The results are shown in (Table 1).

(Example 9) In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Instead of phenylamine, bis [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4-
Thin film EL device samples were prepared in the same manner as in Example 1 except that {bis (4-methoxyphenyl) amino} phenyl] amine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

Example 10 In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was replaced by [ 4- ｛2-aza-2
A thin film EL device sample was prepared in the same manner as in Example 1 except that-(diphenylamino) vinyl @ phenyl] [4- (diphenylamino) phenyl] phenylamine was used, and evaluation was performed as described in Example 1. went.

The results are shown in (Table 1).

(Example 11) In forming the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was replaced by [ 4- ｛2-aza-2
-(Diphenylamino) vinyl} phenyl] [4- {bis (4-methoxyphenyl) amino} phenyl] (4-
A thin-film EL device sample was prepared in the same manner as in Example 1 except that (methoxyphenyl) amine was used, and evaluated as described in Example 1.

The results are shown in (Table 1).

Example 12 In forming the ultrathin electron blocking layer of Example 1, bis- [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that (diphenylamino) phenyl] amine was used.
The evaluation was performed as described in Example 1.

The results are shown in (Table 1).

(Example 13) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine, [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [4-
Thin film EL device samples were prepared in the same manner as in Example 1 except that {bis (4-methoxyphenyl) amino} phenyl] amine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

Example 14 In the formation of the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was replaced with [ 4- ｛4- (2,2
-Diphenylvinyl) phenyl @ phenyl] bis (4-
A thin-film EL device sample was prepared in the same manner as in Example 1 except that (methoxyphenyl) amine was used, and evaluated as described in Example 1.

The results are shown in (Table 1).

(Example 15) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine, [4- @ 4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that (2,2-diphenylvinyl) phenyl @ phenyl] phenylamine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

(Example 16) In forming the ultrathin electron blocking layer of Example 1, bis- [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. [4- @ 4-
(2,2-diphenylvinyl) phenyl @ phenyl]
A thin film EL device sample was prepared in the same manner as in Example 1 except that (4-methoxyphenyl) amine was used, and was evaluated as described in Example 1.

The results are shown in (Table 1).

Example 17 In the formation of the ultra-thin electron blocking layer of Example 1, tris was used instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine. [4- @ 4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that (2,2-diphenylvinyl) phenyl @ phenyl] amine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

Example 18 In the formation of the ultra-thin electron blocking layer of Example 1, tris was used instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine. [4- @ 4-
(2,2-diphenylvinyl) -2-methylphenyl}
Example 1 except that [-3-methylphenyl] amine was used.
In the same manner as in Example 1, a thin film EL element sample was prepared.
The evaluation was performed as described in the above section.

The results are shown in (Table 1).

Example 19 In forming the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was replaced by [ 4- ｛4- (4,4
A thin-film EL device sample was prepared in the same manner as in Example 1 except that -diphenylbuta-1,3-dienyl) phenyl {phenyl] diphenylamine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

Example 20 In the formation of the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was replaced by [ 4- ｛4- (4,4
A thin-film EL device sample was prepared in the same manner as in Example 1 except that -diphenylbuta-1,3-dienyl) phenyl {phenyl] bis (4-methoxyphenyl) amine was used. An evaluation was performed.

The results are shown in (Table 1).

(Example 21) In forming the ultra-thin electron blocking layer of Example 1, bis- [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. [4- @ 4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that (4,4-diphenylbuta-1,3-dienyl) phenyl {phenyl] phenylamine was used, and evaluation was performed as described in Example 1. went.

The results are shown in (Table 1).

(Example 22) In forming the ultra-thin electron blocking layer of Example 1, bis- [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. [4- @ 4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that (4,4-diphenylbuta-1,3-dienyl) phenyl @ phenyl] (4-methoxyphenyl) amine was used, and described in Example 1. The evaluation was performed as follows.

The results are shown in (Table 1).

(Example 23) In forming the ultra-thin electron blocking layer of Example 1, tris-tris was used instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine. [4- @ 4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that (4,4-diphenylbuta-1,3-dienyl) phenyl {phenyl] amine was used, and evaluation was performed as described in Example 1. Was.

The results are shown in (Table 1).

(Example 24) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine, tris [4- @ 4-
(4,4-diphenylbuta-1,3-dienyl) -2
A thin film EL device sample was prepared in the same manner as in Example 1 except that [-methylphenyl {-3-methylphenyl] amine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

(Example 25) In forming the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was replaced by [ A thin film EL device sample was prepared in the same manner as in Example 1 except that 4- {4- {2-aza-2- (diphenylamino) vinyl} phenyl} phenyl] diphenylamine was used. Was evaluated.

The results are shown in (Table 1).

(Example 26) In forming the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was replaced by [ A thin film EL device sample was prepared in the same manner as in Example 1 except that 4- {4- {2-aza-2- (diphenylamino) vinyl} phenyl} phenyl] bis (4-methoxyphenyl) amine was used. The evaluation was performed as described in Example 1.

The results are shown in (Table 1).

(Example 27) In the formation of the ultrathin electron blocking layer of Example 1, bis-bis [2- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. [4- ｛4- ｛2
-Aza-2- (diphenylamino) vinyl {phenyl}
A thin film EL device sample was prepared in the same manner as in Example 1 except that [phenyl] phenylamine was used, and evaluated as described in Example 1.

The results are shown in (Table 1).

(Example 28) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine, [4- ｛4- ｛2
-Aza-2- (diphenylamino) vinyl {phenyl}
A thin film EL device sample was prepared in the same manner as in Example 1 except that [phenyl] (4-methoxyphenyl) amine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

Example 29 In the formation of the ultra-thin electron blocking layer of Example 1, tris was added instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine. [4- @ 4-
A thin film EL device sample was prepared in the same manner as in Example 1 except that {2-aza-2- (diphenylamino) vinyl} phenyl} phenyl] amine was used, and evaluation was performed as described in Example 1. .

The results are shown in (Table 1).

(Example 30) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine, tris [4- @ 4-
{2-aza-2- (diphenylamino) vinyl} -2-
A thin film EL device sample was prepared in the same manner as in Example 1 except that methylphenyl {-3-methylphenyl] amine was used, and evaluation was performed as described in Example 1.

The results are shown in (Table 1).

(Example 31) In forming the ultra-thin electron blocking layer of Example 1, bis- [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. [4- ｛bis (3
A thin film EL device sample was prepared in the same manner as in Example 1 except that -methylphenyl) amino {phenyl] (4-phenylphenyl) amine was used, and evaluation was performed as described in Example 1. Here, the synthesis of bis [4- {bis (3-methylphenyl) amino} phenyl] (4-phenylphenyl) amine is described in International Publication WO96 / 2227.
No. 3 and other known synthesis methods.

The results are shown in (Table 1).

(Example 32) In forming the ultrathin electron blocking layer of Example 1, bis- (4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- ｛bis (4
A thin film EL device sample was prepared in the same manner as in Example 1 except that -methoxyphenyl) aminodiphenyl] (4-phenylphenyl) amine was used, and evaluation was performed as described in Example 1. Here, the synthesis of bis [4- {bis (4-methoxyphenyl) amino} phenyl] (4-phenylphenyl) amine is described in International Publication WO96 / 222.
No. 73 and other known synthesis methods.

The results are shown in (Table 1).

Example 33 In forming the ultra-thin electron blocking layer of Example 1, bis-bis [2- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of bis-phenylamine. A thin film EL device sample was prepared in the same manner as in Example 1 except that [4- (diphenylamino) phenyl] (4-methylphenyl) amine was used, and evaluation was performed as described in Example 1. Here, bis [4- (diphenylamino) phenyl] (4-
The synthesis of methylphenyl) amine is described in WO 9
The synthesis was performed by a known synthesis method such as No. 6/22273.

The results are shown in (Table 1).

Example 34 In forming the ultra-thin electron blocking layer of Example 1, bis- [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. [4- (diphenylamino) phenyl] @ 4- (4-methoxyphenyl)
A thin film EL device sample was prepared in the same manner as in Example 1 except that phenyl diamine was used, and evaluated as described in Example 1. Here, the synthesis of bis [4- (diphenylamino) phenyl] {4- (4-methoxyphenyl) phenyl} amine is described in International Publication WO96 / 2227.
No. 3 and other known synthesis methods.

The results are shown in (Table 1).

(Example 35) In forming the ultrathin electron blocking layer of Example 1, bis- [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine was used instead of [4- (2,2-diphenylvinyl) phenyl] phenylamine. A thin film EL device sample was prepared in the same manner as in Example 1 except that [4- (diphenylamino) phenyl] [4- {4- (4-phenyl) phenyl} phenyl] amine was used, and described in Example 1. The evaluation was performed as follows. Here, the synthesis of bis [4- (diphenylamino) phenyl] [4- {4- (4-phenyl) phenyl} phenyl] amine is described in International Patent Publication WO
The synthesis was performed by a known synthesis method such as No. 96/22273.

The results are shown in (Table 2).

[0238]

[Table 2]

(Example 36) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, The procedure of Example 1 was repeated, except that a toluene solution of polyvinyl carbazole (manufactured by Anan Co., Ltd., molecular weight: 28,000) was spin-coated, and heated and dried at 150 ° C. for 10 minutes to form an ultrathin polyvinylcarbazole thin film having a thickness of 3 nm. Thin film EL
An element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 2).

(Example 37) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, Polyvinylcarbazole (manufactured by Annan Co., Ltd., molecular weight 28,000)
And 4,4 ', 4 "of the same weight as polyvinyl carbazole
-Except that a coating solution of trismethyltriphenylamine and toluene dissolved in toluene was spin-coated and dried by heating at 150 ° C. for 10 minutes to form a 3 nm-thick low-molecular-weight hole transport agent-dispersed ultrathin electron block layer. In the same manner as in Example 1, a thin film EL element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 2).

(Example 38) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, Polyvinylcarbazole (manufactured by Annan Co., Ltd., molecular weight 28,000)
And a coating solution obtained by dissolving polyvinyl carbazole and 4-N, N-diphenylamino-α-phenylstilbene in an equal weight in toluene is spin-coated, and heated and dried at 150 ° C. for 10 minutes to obtain a low-molecular-weight 3 nm thick film. A thin film EL device sample was prepared in the same manner as in Example 1 except that the hole transporting agent-dispersed ultrathin electron blocking layer was formed, and evaluation was performed as described in Example 1.

The results are shown in (Table 2).

(Example 39) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, Polyvinylcarbazole (manufactured by Annan Co., Ltd., molecular weight 28,000)
And polyvinylcarbazole and (1-aza-
6,6-diphenylhexa-1,3,5-trienyl) naphthylphenylamine and a coating solution prepared by dissolving in toluene are spin-coated, and dried by heating at 150 ° C. for 10 minutes to transport a low-molecular-weight hole having a thickness of 3 nm. A thin-film EL device sample was prepared in the same manner as in Example 1 except that an agent-dispersed ultrathin electron block layer was formed, and evaluation was performed as described in Example 1.

Table 2 shows the results.

(Example 40) In the formation of the ultra-thin electron blocking layer of Example 1, a vapor deposition film of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine having a thickness of 10 nm was formed. Instead, [4
-(2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine in toluene is spin-coated with a coating solution, and heated and dried at 150 ° C. for 10 minutes to form a 5 nm-thick coating type. A thin-film EL device sample was prepared in the same manner as in Example 1 except that the low-molecular-weight hole transporting agent layer was formed as an ultra-thin electron blocking layer, and evaluation was performed as described in Example 1.

Table 2 shows the results.

(Example 41) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, Spin-coat a toluene solution of polyparaphenylene vinylene and apply
Example 1 except that a heat-drying process was performed at 0 ° C. for 10 minutes to form an ultra-thin polyparaphenylenevinylene thin film having a thickness of 3 nm.
In the same manner as in Example 1, a thin film EL element sample was prepared.
The evaluation was performed as described in the above section.

The results are shown in (Table 2).

Example 42 In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A toluene solution of methylphenylpolysilane (molecular weight 30,000) was spin-coated, and dried by heating at 150 ° C. for 10 minutes.
A thin-film EL element sample was prepared in the same manner as in Example 1 except that an ultrathin methylphenylpolysilane thin film having a thickness of 3 nm was formed, and evaluation was performed as described in Example 1.

Table 2 shows the results.

Example 43 In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, Polyvinyl butyral (Sekisui Chemical Co., Ltd., trade name SREC BL
-1) and polyvinyl butyral and 4,4 ′,
A coating in which 4 "-trismethyltriphenylamine is dissolved in THF is spin-coated, and heated and dried at 150 ° C. for 10 minutes to form a 3 nm-thick low molecular weight hole transporting agent dispersed ultrathin electron block layer. A thin-film EL device sample was prepared in the same manner as in Example 1 except that the evaluation was performed, and evaluation was performed as described in Example 1.

Table 2 shows the results.

Example 44 In the formation of the light emitting layer of Example 1, the tris (8-
Instead of 40 nm of a (quinolinolato) aluminum vapor-deposited film, tris (8-quinolinolato) aluminum (manufactured by Dojindo Co., Ltd.) was formed as a light emitting layer at a deposition rate of 0.3 nm / s to a film thickness of about 20 nm, and then a 2,9- Dimethyl-
4,7-diphenyl-1,10-phenanthroline (A
ldrich, bathocuproine) at 0.1 nm /
s and lithium are co-deposited at 0.1 nm / s, and the film thickness is 20 n.
m of electron injection transport layers. The cathode was formed of aluminum at a deposition rate of about 1.5 nm / s to a thickness of about 100 nm. In all other respects, a thin film EL device sample was prepared in the same manner as in Example 1, and the evaluation was performed as described in Example 1.

Table 2 shows the results.

The resistivity of the electron injecting and transporting layer used in this device was about 10 ⁶ Ωcm when the layer alone was formed and the resistivity was measured.

(Example 45) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL device sample was prepared in the same manner as in Example 1 except that an ultrathin SiO ₂ film having a thickness of 1 nm was formed by the EB vapor deposition method, and evaluation was performed as described in Example 1.

Table 2 shows the results.

(Example 46) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL device sample was prepared in the same manner as in Example 1 except that an Al ₂ O ₃ ultrathin film having a thickness of 1 nm was formed by a sputtering method, and evaluation was performed as described in Example 1.

The results are shown in (Table 2).

(Example 47) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL device sample was prepared in the same manner as in Example 1 except that an ultra-thin TiO ₂ film having a thickness of 1 nm was formed by a sputtering method, and evaluation was performed as described in Example 1.

The results are shown in (Table 2).

(Example 48) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL device sample was prepared in the same manner as in Example 1 except that a 1 nm-thick LiNbO ₃ ultrathin film was formed by a sputtering method.
The evaluation was performed as described in Example 1.

Table 2 shows the results.

(Example 49) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin-film EL device sample was prepared in the same manner as in Example 1 except that an ultra-thin PbTiO ₃ film having a thickness of 1 nm was formed by sputtering.
The evaluation was performed as described in Example 1.

The results are shown in (Table 2).

(Example 50) In forming the coating type conductive layer of Example 1, a polyaniline-based conductive polymer paint was used instead of a commercially available polypyrrole-based conductive polymer paint, and spin coating was performed in the same manner. A thin film EL device sample was prepared in the same manner as in Example 1 except that the coating type conductive layer was formed, and evaluation was performed as described in Example 1.

Table 2 shows the results.

(Example 51) In forming the coating type conductive layer of Example 1, a polythiophene-based conductive polymer paint was used instead of a commercially available polypyrrole-based conductive polymer paint, and spin coating was performed in the same manner. A thin film EL device sample was prepared in the same manner as in Example 1 except that the coating type conductive layer was formed, and evaluation was performed as described in Example 1.

The results are shown in (Table 2).

(Example 52) In forming the ultrathin electron blocking layer of Example 1, before forming [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine at 10 nm. Then, a thin-film EL device sample was prepared in the same manner as in Example 1 except that oxygen plasma treatment (pressure 0.2 Torr, high-frequency input power 50 W) was performed for 1 minute in a vacuum chamber. Was evaluated.

The results are shown in (Table 2).

(Example 53) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL was prepared in the same manner as in Example 1 except that a polymer represented by the following chemical formula was spin-coated and heated and dried at 150 ° C. for 10 minutes to form an ultra-thin fluorene polymer thin film having a thickness of 3 nm.
An element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 2).

(Example 54) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL was prepared in the same manner as in Example 1 except that a polymer represented by the following chemical formula was spin-coated and heated and dried at 150 ° C. for 10 minutes to form an ultra-thin fluorene polymer thin film having a thickness of 3 nm.
An element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 2).

(Example 55) In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL was prepared in the same manner as in Example 1 except that a polymer represented by the following chemical formula was spin-coated and heated and dried at 150 ° C. for 10 minutes to form an ultra-thin fluorene polymer thin film having a thickness of 3 nm.
An element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 2).

(Example 56) In forming the ultra-thin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL was prepared in the same manner as in Example 1 except that a polymer represented by the following chemical formula was spin-coated and heated and dried at 150 ° C. for 10 minutes to form an ultra-thin fluorene polymer thin film having a thickness of 3 nm.
An element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 2).

Example 57 In forming the ultrathin electron blocking layer of Example 1, instead of [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, A thin film EL was prepared in the same manner as in Example 1 except that a polymer represented by the following chemical formula was spin-coated and heated and dried at 150 ° C. for 10 minutes to form an ultra-thin fluorene polymer thin film having a thickness of 3 nm.
An element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 2).

(Comparative Example 1) In forming the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Instead of phenylamine, N, N'-diphenyl-
Example 1 except that N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine was used.
In the same manner as in Example 1, a thin film EL element sample was prepared.
The evaluation was performed as described in the above section.

Table 3 shows the results.

[0286]

[Table 3]

(Comparative Example 2) In the formation of the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
A thin film EL device sample was prepared in the same manner as in Example 1 except that N, N′-bis (α-naphthyl) -N, N′-diphenylbenzidine was used instead of phenylamine, and described in Example 1. The evaluation was performed as follows.

Table 3 shows the results.

Comparative Example 3 In forming the ultrathin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Except for forming 80 nm of N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine as a hole transport layer instead of phenylamine 10 nm. Is a thin film E in the same manner as in Example 1.
An L element sample was prepared and evaluated as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 4) In forming the ultra-thin electron blocking layer of Example 1, [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl]
Thin film EL device samples were prepared in the same manner as in Example 1 except that 80 nm of N, N′-bis (α-naphthyl) -N, N′-diphenylbenzidine was formed as a hole transport layer instead of 10 nm of phenylamine. It was prepared and evaluated as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 5) In Example 1, the coating type conductive layer was not formed on the ITO, but was placed in a vacuum chamber immediately after the oxygen plasma treatment. Instead of 4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, N, N ′ was used as a hole transport layer.
-Diphenyl-N, N'-bis (3-methylphenyl)
80 n of 1,1′-biphenyl-4,4′-diamine
A thin-film EL device sample was prepared in the same manner as in Example 1 except that m was formed, and evaluation was performed as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 6) In Example 1, the coating type conductive layer was not formed on the ITO, but was placed in a vacuum chamber immediately after the oxygen plasma treatment. Instead of 4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, N, N ′ was used as a hole transport layer.
A thin-film EL device sample was prepared in the same manner as in Example 1 except that -bis (α-naphthyl) -N, N′-diphenylbenzidine was formed to a thickness of 80 nm, and evaluated as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 7) In Example 1, the coating type conductive layer was not formed on the ITO, but was placed in a vacuum chamber immediately after the oxygen plasma treatment. Instead of 4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, N, N ′ was used as a hole transport layer.
-Diphenyl-N, N'-bis (3-methylphenyl)
40n of -1,1'-biphenyl-4,4'-diamine
A thin-film EL device sample was prepared in the same manner as in Example 1 except that m was formed, and evaluation was performed as described in Example 1.

Table 3 shows the results.

(Comparative Example 8) In Example 1, the coating type conductive layer was not formed on the ITO, but was placed in a vacuum chamber immediately after the oxygen plasma treatment. Instead of 4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, N, N ′ was used as a hole transport layer.
A thin film EL device sample was prepared in the same manner as in Example 1 except that -bis (α-naphthyl) -N, N′-diphenylbenzidine was formed to a thickness of 40 nm, and evaluated as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 9) In Example 1, the coating type conductive layer was not formed on the ITO, but was placed in a vacuum chamber immediately after the oxygen plasma treatment. Instead of 4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine 10 nm, N, N ′ was used as a hole transport layer.
-Diphenyl-N, N'-bis (3-methylphenyl)
−1,1′-biphenyl-4,4′-diamine at 20 n
A thin-film EL device sample was prepared in the same manner as in Example 1 except that m was formed, and evaluation was performed as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 10) In Example 1, ITO
Without forming a coating type conductive layer thereon, immediately after the oxygen plasma treatment, it was placed in a vacuum chamber, and [4- (2,2-diphenylvinyl) phenyl] [4 -(Diphenylamino) phenyl] phenylamine Instead of 10 nm, N,
A thin-film EL device sample was prepared in the same manner as in Example 1 except that N'-bis (α-naphthyl) -N, N'-diphenylbenzidine was formed to a thickness of 20 nm, and evaluated as described in Example 1. .

[0304] The results are shown in Table 3.

(Comparative Example 11) In Example 1, ITO was used.
Without forming a coating type conductive layer thereon, immediately after the oxygen plasma treatment, it was placed in a vacuum chamber, and [4- (2,2-diphenylvinyl) phenyl] [4 -(Diphenylamino) phenyl] phenylamine Instead of 10 nm, N,
N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine
A thin film EL device sample was prepared in the same manner as in Example 1 except that the film was formed to a thickness of 0 nm, and evaluated as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 12) In Example 1, ITO was used.
Without forming a coating type conductive layer thereon, immediately after the oxygen plasma treatment, it was placed in a vacuum chamber, and [4- (2,2-diphenylvinyl) phenyl] [4 -(Diphenylamino) phenyl] phenylamine Instead of 10 nm, N,
A thin film EL device sample was prepared in the same manner as in Example 1 except that N′-bis (α-naphthyl) -N, N′-diphenylbenzidine was formed to a thickness of 10 nm, and evaluation was performed as described in Example 1. .

The results are shown in (Table 3).

(Comparative Example 13) In Example 1, ITO was used.
Without forming a coating type conductive layer thereon, after oxygen plasma treatment, as a hole transport layer, a toluene solution of polyvinyl carbazole (manufactured by Anan Co., Ltd., molecular weight: 28,000) was spin-coated, and heated and dried at 150 ° C. for 10 minutes. After forming a thin film of polyvinylcarbazole with a thickness of 80 nm, the thin film was immediately placed in a vacuum chamber. A light emitting layer was formed on the hole transport layer in the same manner as in Example 1 without forming an ultra-thin electron blocking layer. In all other respects, a thin film EL device sample was prepared in the same manner as in Example 1, and the evaluation was performed as described in Example 1.

[0310] The results are shown in Table 3.

(Comparative Example 14) In Example 1, ITO was used.
After oxygen plasma treatment without forming a coating type conductive layer on the top, polyvinyl carbazole (Molecular weight: 28,000, manufactured by Anan Co., Ltd.) and 4-N, N-diphenylamino having the same weight as polyvinyl carbazole were used as a hole transport layer. -Α-
A coating solution in which phenylstilbene was dissolved in toluene was spin-coated, and dried by heating at 150 ° C. for 10 minutes to form a low-molecular-weight hole transporting agent-dispersed hole transporting layer having a thickness of 80 nm. Placed within. A light emitting layer was formed on the hole transport layer in the same manner as in Example 1 without forming an ultra-thin electron blocking layer. In all other respects, a thin film EL device sample was prepared in the same manner as in Example 1, and the evaluation was performed as described in Example 1.

The results are shown in (Table 3).

(Comparative Example 15) In Example 1, ITO was used.
After oxygen plasma treatment without forming a coating type conductive layer thereon, polyvinyl carbazole (manufactured by Anan Co., Ltd., molecular weight: 28,000) and 4-N, N-diphenylamino having the same weight as polyvinyl carbazole were used as a hole transport layer. -Α-
A coating solution in which phenylstilbene was dissolved in toluene was spin-coated, and dried by heating at 150 ° C. for 10 minutes to form a 20 nm-thick low-molecular-weight hole transporting agent-dispersed hole transporting layer. Placed within. A light emitting layer was formed on the hole transport layer in the same manner as in Example 1 without forming an ultra-thin electron blocking layer. In all other respects, a thin film EL device sample was prepared in the same manner as in Example 1, and the evaluation was performed as described in Example 1.

The results are shown in (Table 3).

In Tables 1, 2 and 3, the device configurations of the examples and comparative examples are abbreviated by abbreviations. Alq3 is tris (8-quinolinolato) aluminum, PPDA-PS is , [4- (2,2
-Diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] phenylamine, M2PPDA-PS
Is [4- (2,2-diphenylvinyl) phenyl]
(4-methoxyphenyl) {4-[(4-methoxyphenyl) phenylamino] phenyl} amine, PPDA-
2PS is bis [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] amine, and M2PPDA-2PS is bis [4- (2,2-diphenylvinyl) phenyl] [4- {Bis (methoxyphenyl) amino} phenyl] amine, PPDA-PB
Is [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4- (diphenylamino) phenyl] phenylamine, M2PPDA-PB is [4-
(4,4-diphenylbuta-1,3-dienyl) phenyl] [4- {bis (4-methoxyphenyl) amino}
Phenyl] (4-methoxyphenyl) amine, PPDA
-2PB is bis [4- (4,4-diphenylbuta-
1,3-Dienyl) phenyl] [4- (diphenylamino) phenyl] amine, M2PPDA-2PB is bis [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4- {bis ( 4-methoxyphenyl)
Amino diphenyl] amine and PPDA-PH are [4-
{2-aza-2- (diphenylamino) vinyl} phenyl] [4- (diphenylamino) phenyl] phenylamine, M2PPDA-PH is [4- {2-aza-2-
(Diphenylamino) vinyl {phenyl] [4- {bis (4-methoxyphenyl) amino} phenyl] (4-methoxyphenyl) amine and PPDA-2PH are bis [4- {2-aza-2- (diphenylamino) )vinyl}
Phenyl] [4- (diphenylamino) phenyl] amine, M2PPDA-2PH is bis [4- {2-aza-
2- (diphenylamino) vinyl @ phenyl] [4-
{Bis (4-methoxyphenyl) amino} phenyl] amine and TPA-PS are [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] diphenylamine,
M2TPA-PS is [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] bis (4-methoxyphenyl) amine, and TPA-2PS is bis [4- {4-
(2,2-diphenylvinyl) phenyl} phenyl] phenylamine and MTPA-2PS are bis [4- {4-
(2,2-diphenylvinyl) phenyl @ phenyl]
(4-methoxyphenyl) amine, TPA-3PS,
Tris [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] amine and TPA-M3PS are tris [4- {4- (2,2-diphenylvinyl) -2-methylphenyl} -3- Methylphenyl] amine, TPA-
PB is [4- {4- (4,4-diphenylbuta-1,
3-Dienyl) phenyl} phenyl] diphenylamine, M2TPA-PB is [4- {4- (4,4-diphenylbuta-1,3-dienyl) phenyl} phenyl] bis (4-methoxyphenyl) amine, TPA- 2
PB is bis [4- {4- (4,4-diphenylbuta-
1,3-dienyl) phenyl @ phenyl] phenylamine and MTPA-2PB are bis [4- {4- (4,4
-Diphenylbuta-1,3-dienyl) phenyl {phenyl] (4-methoxyphenyl) amine, TPA-3
PB is tris [4- {4- (4,4-diphenylbuta-1,3-dienyl) phenyl} phenyl] amine,
TPA-M3PB is tris [4- {4- (4,4-diphenylbuta-1,3-dienyl) -2-methylphenyl} -3-methylphenyl] amine, TPA-PH
Is [4- {4- {2-aza-2- (diphenylamino) vinyl} phenyl} phenyl] diphenylamine,
M2TPA-PH is [4- {4-} 2-aza-2-
(Diphenylamino) vinyl {phenyl} phenyl] bis (4-methoxyphenyl) amine, TPA-2PH
Is bis [4- {4- {2-aza-2- (diphenylamino) vinyl} phenyl} phenyl] phenylamine,
MTPA-2PH is bis [4- {4-} 2-aza-2
− (Diphenylamino) vinyl {phenyl} phenyl]
(4-methoxyphenyl) amine, TPA-3PH,
Tris [4- {4- {2-aza-2- (diphenylamino) vinyl} phenyl} phenyl] amine, TPA-M
3PH is tris [4- {4- {2-aza-2- (diphenylamino) vinyl} -2-methylphenyl} -3-
Methylphenyl] amine, MTA-P, is bis [4-
{Bis (3-methylphenyl) amino} phenyl] (4
-Phenylphenyl) amine, MOTA-P is bis [4- {bis (4-methoxyphenyl) amino} phenyl] (4-phenylphenyl) amine, TA-MP is
Bis [4- (diphenylamino) phenyl] (4-methylphenyl) amine and TA-MOP are bis [4- (diphenylamino) phenyl] {4- (4-methoxyphenyl) phenyl} amine and TA-PP are , Screw [4-
(Diphenylamino) phenyl] [4- {4- (4-phenyl) phenyl} phenyl] amine, TTA is 4,
4 ', 4 "-trismethyltriphenylamine, PS
Is 4-N, N-diphenylamino-α-phenylstilbene, DPB-PH is (1-aza-6,6-diphenylhexa-1,3,5-trienyl), naphthylphenylamine, PVK is polyvinylcarbazole , PP
V is polyparaphenylenevinylene, PMPS is methylphenylpolysilane (molecular weight 30,000), PVB
Is polyvinyl butyral, BCP is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocuproin), and F8 is a polymer represented by the following chemical formula.

[0316]

Embedded image

F8BT is a polymer represented by the following chemical formula.

[0318]

Embedded image

F8TPA is a polymer represented by the following chemical formula.

[0320]

Embedded image

F8ANT is a polymer represented by the following chemical formula.

[0322]

Embedded image

F8TPD is a polymer represented by the following chemical formula.

[0324]

Embedded image

TPD is N, N'-diphenyl-N,
N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, NPD is N, N′-bis (α-naphthyl) -N, N′-diphenylbenzidine,
Al represents aluminum, and Li represents lithium, and is described in order from the ITO electrode side, separated from each other by / as a symbol indicating a laminated configuration from the left. Numbers in parentheses indicate film thickness in nm, and + indicates a coexisting film of both components such as doping mixture.

[0326]

As described above, the thin-film EL device according to the present invention and the method of manufacturing the same have been described. The present invention is directed to a method of coating a transparent substrate with at least a transparent hole injection electrode and coating the transparent hole injection electrode with the transparent hole injection electrode. By a formed thin film EL element having a transparent conductive layer, an ultra-thin electron blocking layer, a light emitting layer and a cathode, or on a transparent substrate, at least a transparent hole injecting electrode and on the transparent hole injecting electrode A thin-film EL device having a transparent conductive layer formed by coating, an ultra-thin electronic block layer, a light-emitting layer, and a cathode, wherein the ultra-thin electronic block layer has a thickness from the light-emitting layer to the cathode. Or less than 1/3 of the film thickness of the layer, or the film thickness of the ultra-thin electronic block layer is not less than the average surface roughness of the transparent conductive layer formed by coating, or As the ultra-thin film block layer, by using a specific configuration disclosed in the claims of the present application, or as the ultra-thin film block layer, by using a specific material disclosed in the claims of the present application, or By using a combination of the specific ultra-thin electron blocking layer and the electron injection layer disclosed in the claims, it has high luminous efficiency, no defects such as unevenness and black spots, and self-luminous at low driving voltage to improve visibility. An excellent light emission can be obtained, and a thin film EL element which can be used stably for an extremely long time with small power consumption and small power consumption even in a continuous light emission test can be realized.

Also, even in the case of pulse driving corresponding to actual driving with a passive matrix panel, it has a low driving voltage, high efficiency and high reliability, can be used stably for a very long time with little power consumption, and consumes little power. This can realize a thin film EL element.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H05B 33/28 H05B 33/28 (72) Inventor Hisanori Sugiura 1006 Kazuma Kazuma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. In-company (72) Inventor Hitoshi Hisada 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor Shinichi Mizuguchi 1006 Odaka Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Ryuichi Shingae 1006, Kazuma, Kazuma, Kazuma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. CB01 DA00 DB03 EA02 EB00 EC02 EC03 EC04 FA01 FA03 GA02

Claims (77)

[Claims] 1. A transparent substrate having at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Thin film EL element. 2. The thin-film EL device according to claim 1, wherein the thickness of the ultra-thin electron blocking layer is equal to or less than 膜厚 of the thickness of the layer from the light-emitting layer to the cathode. 3. The thin-film EL device according to claim 2, wherein the ultra-thin electronic block layer has a thickness equal to or greater than the average surface roughness of the transparent conductive layer formed by coating. 4. An electric field of 1 × 1 of the ultra-thin electron blocking layer.
0 ⁶ electron mobility in V / cm is ^{1 × 10 -5 cm 2 / V} · s
4. The thin film EL according to claim 3, wherein
element. 5. The thin-film EL device according to claim 3, wherein the electron affinity of the ultra-thin electron blocking layer is 2.7 eV or less. 6. The thin-film EL device according to claim 3, wherein the forbidden band width of the ultra-thin electron block layer is 2.5 eV or more. 7. The thin film EL device according to claim 3, wherein the thickness of the device sandwiched between the anode and the cathode is 60 nm or less. 8. A layer having a resistivity of at most 10 ⁷ Ωcm between the light emitting layer and the cathode as an electron injecting and transporting layer, and having a thickness of at least 10 nm. The thin film EL device according to claim 3. 9. A layer containing a low work function alkali metal or alkaline earth metal containing at least an electron injecting and transporting layer between the light emitting layer and the cathode and having a film thickness of 10 nm or more. 4. The thin-film EL device according to claim 3, wherein: 10. A layer containing a phenanthroline derivative and a low work function alkali metal or alkaline earth metal as at least an electron injecting and transporting layer between the light emitting layer and the cathode, and having a film thickness. The thin film EL device according to claim 3, wherein the thickness is 10 nm or more. 11. The film thickness of the ultra-thin electronic block layer is equal to or less than the thickness of the light-emitting layer, is equal to or greater than the average surface roughness of the transparent conductive layer formed by coating, and is sandwiched between the anode and the cathode. 2. The thin-film EL device according to claim 1, wherein a thickness of a substantially voltage-applied region of the device is 50 nm or less. 12. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer mainly comprises the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, or an alkoxy group). 13. The compound mainly contained in the ultrathin electron blocking layer is [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl].
13. The thin-film EL device according to claim 12, which is phenylamine. 14. The compound mainly contained in the ultrathin electron blocking layer is [4- (2,2-diphenylvinyl) phenyl] (4-methoxyphenyl) {4-[(4
The thin film EL according to claim 12, which is -methoxyphenyl) phenylamino] phenyl} amine.
element. 15. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1 and R2 may be the same or different and each represent a hydrogen atom, an alkyl group, or an alkoxy group). 16. The compound mainly contained in the ultra-thin electron blocking layer is bis [4- (2,2-diphenylvinyl) phenyl] [4- (diphenylamino) phenyl] amine. A thin film EL device according to claim 15. 17. The compound mainly contained in the ultrathin electron blocking layer is bis [4- (2,2-diphenylvinyl) phenyl] [4- {bis (methoxyphenyl)
16. The thin-film EL device according to claim 15, which is [amino [phenyl] amine]. 18. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, or an alkoxy group). 19. The compound mainly contained in the ultrathin electron blocking layer is [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4- (diphenylamino) phenyl] phenylamine. 19. The thin-film EL device according to claim 18, wherein: 20. A compound mainly contained in the ultrathin electron blocking layer is [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4- {bis (4-
19. The thin-film EL device according to claim 18, which is [methoxyphenyl) amino} phenyl] (4-methoxyphenyl) amine. 21. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultrathin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1 and R2 may be the same or different and each represent a hydrogen atom, an alkyl group, or an alkoxy group). 22. The compound mainly contained in the ultrathin electron blocking layer is bis [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4- (diphenylamino) phenyl] amine. 22. The thin-film EL device according to claim 21, wherein: 23. A compound mainly contained in the ultrathin electron blocking layer is bis [4- (4,4-diphenylbuta-1,3-dienyl) phenyl] [4- {bis (4-methoxyphenyl)]. 22. The thin-film EL device according to claim 21, which is [amino [phenyl] amine]. 24. A transparent substrate comprising at least a transparent hole injecting electrode, a transparent conductive layer formed by coating on the transparent hole injecting electrode, an ultra-thin electron blocking layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, or an alkoxy group). 25. A compound mainly contained in the ultrathin electron blocking layer is [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [4- (diphenylamino) phenyl] phenylamine. The thin-film EL device according to claim 24, wherein: 26. A compound mainly contained in the ultra-thin electron blocking layer is [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [4- {bis (4-methoxyphenyl) amino}. 25. The thin-film EL device according to claim 24, which is [phenyl] (4-methoxyphenyl) amine. 27. A transparent substrate comprising at least a transparent hole injecting electrode, a transparent conductive layer formed by coating on the transparent hole injecting electrode, an ultrathin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1 and R2 may be the same or different and each represent a hydrogen atom, an alkyl group, or an alkoxy group). 28. A compound mainly contained in the ultrathin electron blocking layer is bis [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [4- (diphenylamino) phenyl] amine. The thin film EL device according to claim 27, wherein: 29. A compound mainly contained in the ultrathin electron blocking layer is bis [4- {2-aza-2- (diphenylamino) vinyl} phenyl] [4-} bis (4
28. The thin-film EL device according to claim 27, which is -methoxyphenyl) amino {phenyl] amine. 30. A transparent substrate comprising at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electron blocking layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, and R1 and R2 or R2 and R3 each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group). 31. The compound according to claim 30, wherein the compound mainly contained in the ultrathin electron blocking layer is [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] diphenylamine. Thin film EL device. 32. The compound mainly contained in the ultrathin electron blocking layer is [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] bis (4-methoxyphenyl) amine. 31. The thin film EL device according to claim 30, wherein 33. A transparent substrate comprising at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electron blocking layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer mainly comprises the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, and R1 and R2 or R2 and R3 each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group). 34. The compound mainly contained in the ultrathin electron blocking layer is bis [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] phenylamine. 3. The thin film EL device according to 1. 35. A compound mainly contained in the ultrathin electron blocking layer is bis [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] (4-methoxyphenyl) amine. The thin-film EL device according to claim 33, wherein: 36. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electron blocking layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer mainly comprises the following general formula: (Wherein R1 represents a hydrogen atom or an alkyl group). 37. The compound according to claim 36, wherein the compound mainly contained in the ultrathin electron blocking layer is tris [4- {4- (2,2-diphenylvinyl) phenyl} phenyl] amine. The thin film EL device according to the above. 38. The compound mainly contained in the ultrathin electron blocking layer is tris [4- {4- (2,2-diphenylvinyl) -2-methylphenyl} -3-methylphenyl] amine. The thin film EL device according to claim 36, wherein: 39. A transparent substrate comprising at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electron blocking layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron blocking layer is mainly composed of the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, and R1 and R2 or R2 and R3 each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group). 40. The compound mainly contained in the ultrathin electron blocking layer is [4- {4- (4,4-diphenylbuta-1,3-dienyl) phenyl} phenyl] diphenylamine. 40. The thin-film EL device according to claim 39. 41. The compound mainly contained in the ultra-thin electron blocking layer is [4- {4- (4,4-diphenylbuta-1,3-dienyl) phenyl} phenyl] bis (4-methoxyphenyl) 40. The thin film EL device according to claim 39, which is an amine. 42. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, and R1 and R2 or R2 and R3 each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group). 43. A compound mainly contained in the ultra-thin electron blocking layer is bis [4- {4- (4,4-diphenylbuta-1,3-dienyl) phenyl} phenyl] phenylamine. Claim 42. The method of claim 42.
3. The thin film EL device according to 1. 44. The compound mainly contained in the ultra-thin electron blocking layer is bis [4- {4- (4,4-diphenylbuta-1,3-dienyl) phenyl} phenyl] (4-methoxyphenyl). 43. The thin film EL device according to claim 42, which is an amine. 45. A transparent substrate comprising at least a transparent hole injecting electrode, a transparent conductive layer formed by coating on the transparent hole injecting electrode, an ultrathin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1 represents a hydrogen atom or an alkyl group). 46. A compound mainly contained in the ultra-thin electron blocking layer is tris [4- {4- (4,4-diphenylbuta-1,3-dienyl) phenyl} phenyl] amine. The thin film EL device according to claim 45, wherein: 47. A compound mainly contained in the ultrathin electron blocking layer is tris [4- {4- (4,4-diphenylbuta-1,3-dienyl) -2-methylphenyl} -3-methyl 46. The thin-film EL device according to claim 45, which is [phenyl] amine. 48. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer is mainly composed of the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, and R1 and R2 or R2 and R3 each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group). 49. The compound mainly contained in the ultrathin electron blocking layer is [4- {4-} 2-aza-2-
49. The thin-film EL device according to claim 48, which is (diphenylamino) vinyl {phenyl} phenyl] diphenylamine. 50. The compound mainly contained in the ultra-thin electron blocking layer is [4- {4-} 2-aza-2-
49. The thin-film EL device according to claim 48, which is (diphenylamino) vinyl {phenyl} phenyl] bis (4-methoxyphenyl) amine. 51. A transparent substrate comprising at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron blocking layer is mainly composed of the following general formula: (Wherein R1, R2, and R3 may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, and R1 and R2 or R2 and R3 each form a ring. Wherein R4 represents a hydrogen atom or an alkyl group). 52. The compound mainly contained in the ultrathin electron blocking layer is bis [4- {4-} 2-aza-2
− (Diphenylamino) vinyl {phenyl} phenyl]
The thin-film EL device according to claim 51, wherein the device is phenylamine. 53. A compound mainly contained in the ultrathin electron blocking layer is bis [4- {4-} 2-aza-2.
− (Diphenylamino) vinyl {phenyl} phenyl]
52. The thin-film EL device according to claim 51, which is (4-methoxyphenyl) amine. 54. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer mainly comprises the following general formula: (Wherein R1 represents a hydrogen atom or an alkyl group). 55. The compound mainly contained in the ultrathin electron blocking layer is tris [4- {4-} 2-aza-
55. The thin-film EL device according to claim 54, wherein the device is 2- (diphenylamino) vinyl {phenyl} phenyl] amine. 56. The compound mainly contained in the ultrathin electron blocking layer is tris [4- {4-} 2-aza-
55. The thin-film EL device according to claim 54, which is 2- (diphenylamino) vinyl {-2-methylphenyl} -3-methylphenyl] amine. 57. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. Wherein the ultra-thin electron block layer mainly comprises the following general formula: (Wherein R1 is a hydrogen atom, an alkyl group, an alkoxy group,
A substituted or unsubstituted aryl group, and R2 represents a hydrogen atom, an alkyl group, or an alkoxy group). 58. A compound mainly contained in the ultrathin electron blocking layer is bis [4- {bis (3-methylphenyl) amino} phenyl] (4-phenylphenyl)
58. The thin film EL device according to claim 57, which is an amine. 59. The compound mainly contained in the ultrathin electron blocking layer is bis [4- {bis (4-methoxyphenyl) amino} phenyl] (4-phenylphenyl) amine. Item 58. The thin film EL device according to Item 57. 60. A compound mainly contained in the ultrathin electron blocking layer is bis [4- (diphenylamino)
58. The thin-film EL device according to claim 57, which is [phenyl] (4-methylphenyl) amine. 61. The compound mainly contained in the ultrathin electron blocking layer is bis [4- (diphenylamino)
Phenyl] {4- (4-methoxyphenyl) phenyl}
58. The thin film EL device according to claim 57, which is an amine. 62. A compound mainly contained in the ultrathin electron blocking layer is bis [4- (diphenylamino)
58. The thin-film EL device according to claim 57, which is [phenyl] [4- {4- (4-phenyl) phenyl} phenyl] amine. 63. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. A thin-film EL device comprising: an ultra-thin electron blocking layer formed by coating at least an ultra-thin electron blocking layer. 64. The thin-film EL device according to claim 63, wherein the ultra-thin coating layer formed by the coating contains at least a polymer hole transport material. 65. The thin-film EL device according to claim 63, wherein the ultra-thin coating layer formed by the coating contains at least a low-molecular-weight hole transport material. 66. The thin-film EL device according to claim 65, wherein the low-molecular-weight hole transport material is mainly 4,4 ′, 4 ″ -trismethyltriphenylamine. 67. The low-molecular-weight hole transport material is mainly composed of 4
The thin-film EL device according to claim 65, wherein the device is -N, N-diphenylamino-α-phenylstilbene. 68. The low-molecular-weight hole transport material is mainly composed of (1-aza-6,6-diphenylhexa-1,3,5-
66. The thin-film EL device according to claim 65, wherein the device is trienyl) naphthylphenylamine. 69. A transparent substrate comprising at least a transparent hole injecting electrode, a transparent conductive layer formed by coating on the transparent hole injecting electrode, an ultra-thin electron blocking layer, a light emitting layer, and a cathode. A thin-film EL device having an ultra-thin electron blocking layer made of an oxide film.
element. 70. The method according to claim 70, wherein the oxide is Al ₂ O ₃ , SiO ₂ ,
1 selected from TiO ₂ , Ta ₂ O ₅ , ZnO, ZrO ₂
70. A compound comprising at least one compound.
3. The thin film EL device according to 1. 71. A transparent substrate comprising at least a transparent hole injecting electrode, a transparent conductive layer formed by coating on the transparent hole injecting electrode, an ultrathin electronic block layer, a light emitting layer, and a cathode. A thin film EL device comprising: an ultra-thin electron blocking layer having a relative dielectric constant of 30 or more. 72. The ultra-thin electron blocking layer is made of LiN
thin-film EL element according to claim 71, characterized by comprising from bO ₃ or PbTiO _3. 73. On a transparent substrate, at least a transparent hole injection electrode, a transparent conductive layer formed by coating on the transparent hole injection electrode, an ultra-thin electronic block layer, a light emitting layer, and a cathode. A method for manufacturing a thin film EL element having
A method for manufacturing a thin film EL device, comprising: performing a plasma treatment after forming an ultra-thin film electron block layer and before forming a next layer. 74. The method according to claim 73, wherein the plasma processing is an oxygen plasma processing. 75. The thin film EL device according to claim 64, wherein the high molecular hole transport material is a fluorene-based polymer. 76. The thin film EL device according to claim 75, wherein the fluorene-based polymer has a fluorene portion and a hole transporting portion. 77. The thin film EL device according to claim 76, wherein the hole transporting portion contains at least triphenylamine.