JP3402243B2 - Organic electroluminescent device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an organic electroluminescent device.
More specifically, the use of certain aromatic methylidene compounds
High-luminance light emission with low voltage application and stability
Also relates to an excellent organic electroluminescent device. [0002] 2. Description of the Related Art Electroluminescence utilizing the electroluminescence phenomenon of a substance
The device is self-luminous compared to the liquid crystal device, so it is visible
High visibility, clear display when used for displays, etc.
Is possible, and is also completely solid
It has characteristics such as excellent impact resistance. As a result,
Type display, liquid crystal display backlight,
Or expected to be widely used for flat light sources, etc.
It is. [0003] The electroluminescent devices currently in practical use include:
There is a dispersion type electroluminescent device using an inorganic material such as zinc sulfide.
However, this dispersion type electroluminescent device is relatively expensive to drive.
Requires a high AC voltage, which complicates the drive circuit.
And the brightness is low.
The fact is that it has not been put to practical use. On the other hand, an organic electroluminescent device using an organic material
In 1987, C.W.Tang et al.
The light substance and the organic substance having the hole transporting property
Lamination to emit light by injecting both carriers into the phosphor layer
Where the elements of the configuration have come to the forefront since they were proposed
It became. (C.W.Tang and S.A.VAN Slyke, Appl.Phys.L
ett., vol. 51, pp. 913-915 (1987);Akira63-264692Issuer
Information). With this device, at a driving voltage of 10 V or less, 1000 cd / m^Two
It is said that the above light emission can be obtained.
Active research on the surrounding area began to be conducted
I have. At present, various materials and element configurations have been proposed,
R & D for commercialization is being actively conducted. [0005] On the other hand, until now
Organic electroluminescent devices using the materials proposed in
It is true that there are various problems and issues. Several
For example, whether it is in the driving state or the non-driving state
However, the function of the element is deteriorated just by storing
The brightness may decrease, or may be reduced during driving or non-driving.
A non-light-emitting area called a light spot
And eventually the element is short-circuited and destroyed
Can occur. like this
Phenomena are inherent problems of the materials used there.
It is thought that this depends greatly. [0006] Under such circumstances, the element using the current material is used.
It is difficult to say that the life of a child is sufficient,
Are limited to devices that can be used with a relatively short lifetime.
It is the fact that it will. Also consider element colorization
And there are enough methods and materials
It is hard to say that, in any case,
To achieve widespread practical use, solve these problems and issues
There is a need to. From this, the high performance used there
New materials such as light-emitting materials or charge transport materials
It can be said that departure is extremely important. [0007] SUMMARY OF THE INVENTION The present invention provides such an apparatus.
Considering the actual condition of electroluminescent devices,
Eager to obtain an organic electroluminescent device capable of emitting high-intensity light
As a result of repeated research, certain organic compounds were converted to organic electric fields.
It was found to be excellent as a constituent material for light-emitting devices,
The present invention has been completed. That is, the present invention is represented by the following general formula:
Characterized in that a specific aromatic methylidene compound is used.
Organic electroluminescent device. [0009] Embedded image (However, in the formula, Ar₁Is a divalent to hexavalent unsubstituted
OrAlkyl group, cycloalkyl group, alkoxy group,
Rogen group, cyano group, nitro group, acyl group, carboxy
And its esters and acyl groupsSubstituted aromatic hydrocarbons
LingeringBaseRepresents, Ar_TwoIs divalent unsubstituted orAlkyl group,
Cycloalkyl group, alkoxy group, halogen group, cyano
Group, nitro group, acyl group, carboxyl group and
Ter and acyl groupsSubstituted aromatic hydrocarbon residueBaseRepresent. Ma
Ar_ThreeIs unsubstituted orAlkyl group, cycloalkyl
Group, alkoxy group, halogen group, cyano group, nitro group,
Acyl group, carboxyl group and its ester and acyl
GroupSubstituted aromatic hydrocarbon residue, unsubstituted orAlkyl
Group, cycloalkyl group, alkoxy group, halogen group,
Ano group, nitro group, acyl group, carboxyl group and their
Ester and acyl groupsSubstituted aromatic heterocyclic hydrocarbon residue
Represents a group. R is unsubstituted orAlkyl group, cycloal
Kill group, alkoxy group, halogen group, cyano group, nitro
Groups, acyl groups, carboxyl groups and their esters and
Sil groupSubstituted aromatic hydrocarbon residue, unsubstituted orArchi
Group, cycloalkyl group, alkoxy group, halogen group,
Cyano, nitro, acyl, carboxyl and other
Esters and acyl groups ofSubstituted aromatic heterocyclic hydrocarbon
Residue, unsubstituted orAryl group, aryloxy group,
Lucoxy group and halogenSubstituted alkylBaseRepresent. Also
Ar_ThreeAnd R may jointly form a ring. n isTwoThrough 6
Represents a positive number. ) Next, Ar in the above general formula₁, Ar_Two, Ar
_ThreeAnd R will be described in more detail. Ar₁A divalent to hexavalent unsubstituted or substituted
Permuted aromatic hydrocarbon residuebaseSpecific examples are divalent to pentavalent
Unsubstituted or substituted benzene, hexavalent benzene, 2 to 6
Bivalent unsubstituted or substituted biphenyl, divalent to hexavalent unsubstituted
Or substituted terphenyl, di- or hexavalent unsubstituted or substituted qua
Terphenyl, di- to hexavalent unsubstituted or substituted kinkfe
Nil, di- to hexavalent unsubstituted or substituted naphthalene,
6-valent unsubstituted or substituted acenaphthene, 2- to 6-valent
Unsubstituted or substituted acenaphthylene, di- to hexavalent unsubstituted
Or substituted anthracene, di- to hexavalent unsubstituted or substituted
Substituted phenanthrene, di- to hexavalent unsubstituted or substituted
Len, di- to hexavalent unsubstituted or substituted fluorene,
6-valent unsubstituted or substituted fluorenone, 2Or hexavalent
Unsubstituted or substituted phenanthrenequinone, divalent to hexavalent
Unsubstituted or substituted binaphthyl, di- to hexavalent unsubstituted or
Is substituted triphenylbenzeEtc.Is mentioned. Ar₁To
Specific examples of the substituent in the C 1 -C 12
Linear or branched alkyl and cyclopentyl groups
Or cycloalkyl group such as cyclohexyl group, carbon number
1 to 12 linear or branched alkoxy groups, fluorine,
Halogen atoms such as chlorine or bromine, cyano groups,
Acyl such as toro, acetyl or benzoyl
Group, carboxyl group and its ester, trifluoromethyl
A substituted alkyl group such as a tyl group or a benzyl group;
Examples can be given. The number of substitutions is 1 or
There may be more than one, in which case they are the same.
Or a different one. Ar_TwoA divalent unsubstituted or substituted aroma
Group hydrocarbon residuebaseSpecific examples include bivalent unsubstituted
Or substituted benzene, divalent unsubstituted or substituted biphenyl
, Divalent unsubstituted or substituted terphenyl, divalent unsubstituted
Or substituted quaterphenyl, divalent unsubstituted or substituted
Kink phenyl, divalent unsubstituted or substituted naphthale
, Divalent unsubstituted or substituted acenaphthene, divalent unsubstituted
Substituted or substituted acenaphthylene, divalent unsubstituted or substituted
Substituted anthracene, divalent unsubstituted or substituted phenane
Tren, divalent unsubstituted or substituted pyrene, divalent unsubstituted
Or substituted fluorene, divalent unsubstituted or substituted
Luorenone, 2Unsubstituted or substituted phenanthrene
Quinone, divalent unsubstituted or substituted binaphthyl, divalent unsubstituted
Substituted or substituted triphenylbenzene,etcIs mentioned
You. Ar_TwoExamples of the substituents in the above include those having 1 to 12 carbon atoms.
Linear or branched alkyl and cyclopentyl groups
Or cycloalkyl group such as cyclohexyl group, carbon number
1 to 12 linear or branched alkoxy groups, fluorine,
Halogen atoms such as chlorine or bromine, cyano groups,
Acyl such as toro, acetyl or benzoyl
Group, carboxyl group and its ester, trifluoromethyl
A substituted alkyl group such as a tyl group or a benzyl group;
Examples can be given. The number of substitutions is 1 or
There may be more than one, in which case they are the same.
Or a different one. Ar_ThreeUnsubstituted or substituted aromatic carbon
Hydride residue and unsubstituted or substituted aromatic heterocyclic carbon
Specific examples of hydrogen residues include monovalent unsubstituted or substituted
Substituted benzene, monovalent unsubstituted or substituted biphenyl, monovalent
Unsubstituted or substituted terphenyl, monovalent unsubstituted or substituted
Substituted quaterphenyl, monovalent unsubstituted or substituted kink
Phenyl, monovalent unsubstituted or substituted naphthalene, monovalent unsubstituted
Substituted or substituted acenaphthene, monovalent unsubstituted or substituted
Substituted acenaphthylene, monovalent unsubstituted or substituted ant
Helix, monovalent unsubstituted or substituted phenanthrene, monovalent
Unsubstituted or substituted pyrene, monovalent unsubstituted or substituted
Fluorene, monovalent unsubstituted or substituted fluoreno
Monovalent unsubstituted or substituted anthraquinone, monovalent unsubstituted
Substituted or substituted phenanthrenequinone, monovalent unsubstituted
Or substituted binaphthyl, monovalent unsubstituted or substituted
Liphenylbenzene, monovalent unsubstituted or substituted thiof
, Monovalent unsubstituted or substituted pyrrole, monovalent unsubstituted
Or substituted furan, monovalent unsubstituted or substituted bithio
Phen, monovalent unsubstituted or substituted pyridine, monovalent unsubstituted
Substituted or substituted pyridazine, monovalent unsubstituted or substituted
Pyrimidine, monovalent unsubstituted or substituted pyrazine, monovalent
Unsubstituted or substituted triazine, monovalent unsubstituted or substituted
Substituted quinoline, monovalent unsubstituted or substituted isoquinolin
, Monovalent unsubstituted or substituted cinnoline, monovalent unsubstituted
Or substituted quinoxaline, monovalent unsubstituted or substituted
Phthalazine, monovalent unsubstituted or substituted dibenzothiophene
, Monovalent unsubstituted or substituted dibenzofurans, monovalent
Unsubstituted or substituted carbazole, monovalent unsubstituted or
Substituted diphenyloxadiazole, monovalent unsubstituted or
Is substituted diphenylthiophene, monovalent unsubstituted or substituted
And dithienylbenzene. Ar_ThreeAt
Examples of the substituent include a straight or branched chain having 1 to 12 carbon atoms.
Branched alkyl, cyclopentyl or cyclohexyl
A cycloalkyl group such as a xyl group;
Chain or branched alkoxy, fluorine, chlorine, or
Are halogen atoms such as bromine, cyano groups, nitro groups,
Acyl groups such as tyl or benzoyl groups,
Sil group and its ester, trifluoromethyl group or
Represents a substituted alkyl group such as a benzyl group
Can be done. The number of substitutions is one or more.
In some cases, they are the same or different
Any of these may be used. Further, an unsubstituted or substituted aromatic group in R
Aromatic hydrocarbon residue, unsubstituted or substituted aromatic heterocyclic carbon
Specific examples of hydrogen residues and unsubstituted or substituted alkyl groups
Examples are monovalent unsubstituted or substituted benzene, monovalent
Unsubstituted or substituted biphenyl, monovalent unsubstituted or substituted
Terphenyl, monovalent unsubstituted or substituted quaterphenyl
, Monovalent unsubstituted or substituted kink phenyl, monovalent unsubstituted
Substituted or substituted naphthalene, monovalent unsubstituted or substituted
Acenaphthene, monovalent unsubstituted or substituted acenaphthyl
Monovalent, unsubstituted or substituted anthracene, monovalent unsubstituted
Substituted or substituted phenanthrene, monovalent unsubstituted or substituted
Substituted pyrene, monovalent unsubstituted or substituted fluorene, monovalent
Unsubstituted or substituted fluorenone, monovalent unsubstituted or
Are substituted anthraquinones, monovalent unsubstituted or substituted
Enanthrenequinone, monovalent unsubstituted or substituted binaph
Cyl, monovalent unsubstituted or substituted triphenylbenze
, Monovalent unsubstituted or substituted thiophene, monovalent unsubstituted
Or substituted pyrrole, monovalent unsubstituted or substituted
, Monovalent unsubstituted or substituted bithiophene, monovalent unsubstituted
Substituted or substituted pyridine, monovalent unsubstituted or substituted pyridine
Lidazine, monovalent unsubstituted or substituted pyrimidine, monovalent
Unsubstituted or substituted pyrazine, monovalent unsubstituted or substituted
Triazine, monovalent unsubstituted or substituted quinoline, monovalent
Unsubstituted or substituted isoquinoline, monovalent unsubstituted or
Is substituted cinnoline, monovalent unsubstituted or substituted quinoki
Sarin, monovalent unsubstituted or substituted phthalazine, monovalent unsubstituted
Substituted or substituted dibenzothiophene, monovalent unsubstituted
Or substituted dibenzofuran, monovalent unsubstituted or substituted
Carbazole, monovalent unsubstituted or substituted diphenyl
Xadiazole, monovalent unsubstituted or substituted diphenyl
Thiophene, monovalent unsubstituted or substituted dithienylben
Benzene, methyl, ethyl, n-propyl, iso-propyl
Group, n-butyl group, iso-butyl group, sec-butyl group, tert
-Butyl group, benzyl group, phenethyl group, etc.
You. R substituted aromatic hydrocarbon residue, substituted aromatic heterocyclic
Examples of the substituent in the hydrocarbon residue include those having 1 carbon atom
From 12 straight-chain or branched alkyl groups, cyclopentene
Or cycloalkyl such as cyclohexyl
Group, straight or branched alkoxy having 1 to 12 carbon atoms
Groups, halogen atoms such as fluorine, chlorine or bromine,
Cyano group, nitro group, acetyl group or benzoyl group
Such as acyl group, carboxyl group and its ester,
Substituted alkyl such as trifluoromethyl or benzyl
Examples include a kill group. Also, as the number of replacements
May be one or more.
They may be the same or different. Aromatic methylidene compound according to the present invention
Are, for example,
Substituted with an aromatic hydrocarbon group or an aromatic heterocyclic hydrocarbon group
Dialkyl methylphosphonate derivative under basic conditions
Reaction and other common stilbene derivatives
It can be synthesized by a method according to the synthesis method or the like. The aromatic methylidene compound according to the present invention
In some cases, so-called cis or trans
There are structural isomers, but the present invention limits them.
, And any structural isomer is preferably used
It is possible. Next, specific examples of the compound of the present invention are shown below.
This is merely an example, and the present invention is limited to these compounds.
It is not done. [0018] Embedded image[0019] Embedded image[0020] Embedded image[0021] Embedded image[0022] Embedded image[0023] Embedded image[0024] Embedded image[0025] Embedded image[0026] Embedded imageIn the organic electroluminescent device of the present invention,
Special restrictions on the mode of use of aromatic methylidene compounds of the general formula
There is no limitation, but at least the aromatic methylidene of the above general formula
Do not sandwich the thin film layer with the compound between a pair of electrodes.
Organic electroluminescent device. [0028] BEST MODE FOR CARRYING OUT THE INVENTION Aromatic methylidene compound of the present invention
The configuration of an organic electroluminescent device using
But basically, between a pair of electrodes (anode and cathode)
This is a configuration in which a light emitting layer is sandwiched. This can be positive if necessary.
A hole transport layer or an electron transport layer can be interposed. Specifically, (1) the anode 1/1 shown in FIG.
(2) FIG. 2 shows an element having a structure including a light emitting layer 3 and a cathode 5.
From the indicated anode 1 / hole transport layer 2 / light emitting layer 3 / cathode 5,
(3) Anode / hole transport shown in FIG.
Element composed of layer 2 / light-emitting layer 3 / electron transport layer 4 / cathode 5
(4) anode 1 / light-emitting layer 3 / electron transport layer shown in FIG.
4 / cathode 5, and the like.
You. The hole transport layer and the electron transport layer are not necessarily essential
In general, but not necessarily, the layers
It often improves the characteristics, so depending on the need
Preferably, it is provided. Also, in any element configuration
Basically, it is preferable to be supported by the substrate
No. Hereinafter, a more detailed description will be given for each component. First, as for the substrate, there is no particular limitation.
For example, glass, transparent plastic, or quartz
These are appropriately determined according to the necessity of the device configuration.
The material is selected and its thickness and shape are determined.
You. As the anode, gold having a relatively large work function is used.
Metals, alloys, electrically conductive substances and their mixtures
Can be A specific example of such an electrode is gold such as Au.
Genus, CuI, ITO, SnO_Two, Including dielectric transparent materials such as ZnO
Can be The anode is used for evaporation, sputtering, etc.
According to the method, it is generally formed as a thin film. As an electrode
The sheet resistance is preferably several hundred Ω / □ or less. Furthermore, the film thickness
Usually about 10 nm to 500 nm, depending on the material.
More preferably, the range is usually 20 nm to 300 nm
Is selected in the range. The cathode is made of a metal having a relatively small work function,
Gold, electrically conductive compounds and their mixtures are used
You. Specific examples of such electrodes include sodium and sodium.
Thorium-potassium alloy, magnesium, lithium,
Gnesium / copper mixture, Al / AlO _Two, Indium, etc.
I can do it. The cathode can be deposited and sputtered in the same way as the anode.
It is formed as a thin film by a method such as a ring. Electrodes and
The sheet resistance is preferably several hundreds Ω / □ or less. The film thickness is
Usually 50 nm to 1000 nm, preferably 100 nm to 500 nm.
It is an enclosure. The hole transporting layer is made of a hole transporting compound.
Transports holes injected from the anode to the light-emitting layer
-Has a function to inject. About hole transport compounds
Is not particularly limited as long as it has the functions described above.
As a hole transport material in organic photoconductive materials
What is used and the hole transport layer of the organic electroluminescent device
Select any of the known ones used for
Can be used. As such a compound, for example, tria
Zole derivatives, oxadiazole derivatives, imidazole
Derivatives, polyarylalkane derivatives, pyrazoline derivatives
Body, pyrazolone derivative, phenylenediamine derivative,
Reelamine derivative, amino-substituted chalcone derivative, oki
Sazol derivative, styryl anthracene derivative, fluor
Lenone derivatives, hydrazone derivatives, stilber derivatives,
Porphyrin derivatives, aromatic tertiary amine derivatives and
Tyrylamine compounds and the like can be mentioned. these
Is a single or two or more
Or a different type from the above-mentioned layer.
It may be a stack of hole transport layers made of a compound
No. This hole transport layer is generally used frequently.
Methods such as evaporation or spin coating, which are film forming methods
The film thickness is usually 10 nm or less
It is 1 μm, preferably 20 nm to 500 nm. The electron transporting layer comprises an electron transporting compound.
Transports electrons injected from the cathode to the light-emitting layer
-Has a function to inject. Such electron transportability
As for the compound, any one of conventionally known compounds can be used.
Can be selected and used. Examples of electron transport compounds
Nitro-substituted fluorenone derivatives, thiopyran
Dioxide derivatives, diphenoquinone derivatives, anthraceki
Nodimethane derivatives, fluorenylidene methane derivatives,
And the like. These electron transporting compounds may be used alone or in combination.
It may be composed of one or more layers, or
An electron transport layer made of a compound different from the above layer was laminated.
It may be something. This electron transport layer
Deposition is a commonly used deposition method,
Or can be formed by a method such as spin coating.
Usually, the film pressure is 10 nm to 1 μm, preferably 20 nm.
It is 500nm. The hole transporting layer and the electron transporting layer are
This layer has functions such as injection, transport, and barrier properties.
Use inorganic materials such as Si, SiC, CdS, etc.
You can also be. Hole transport layer using inorganic material and electrode
The transport layer is formed by vacuum evaporation or sputtering.
Can be achieved. Next, the light emitting layer is formed by an electrode or hole transport.
Layer and the electron transport layer receive electrons and holes
This layer has a function of emitting light by recombination. Related to the present invention
Aromatic methylidene compounds are used especially in this light emitting layer.
Particularly suitable are the aromatic methylidene compounds
Is mainly used in this layer. The light emitting layer according to the present invention may be one kind or two or more kinds.
It may be composed of a layer consisting of the above, or
A layer in which a light-emitting layer made of a different kind of compound is laminated
There may be. Of course, the aromatic methylidene related to the present invention
Compounds can be used in combination with known luminescent materials, depending on their needs.
Can be done. In this light emitting layer, the structure of the light emitting layer
A relatively small amount of the guest compound to the host compound
So-called “guest-host” configuration
It is possible. In the light emitting layer of the guest / host configuration, the main
The light emission is composed of a guest compound. In the light emitting layer having the guest / host configuration,
Therefore, the guest compound has an energy gap of the host compound.
It is preferable that it is smaller than the object and has strong fluorescence.
New Examples of this type of guest compound include various types of fireflies.
Optical dyes and laser dyes, among which coumarin
Derivatives, condensed ring compounds and the like are preferred. With this configuration, it is possible to improve the luminous efficiency of the element and
It can contribute to improvement of dynamic durability. In the present invention
The aromatic methylidene compound involved is
Combination with a guest compound as listed above
As a host compound for the light emitting layer,
Also available as a guest compound in combination with
The present invention encompasses this concept. Incidentally, the guest compound with respect to the host compound
The concentration may be within a concentration range that does not cause concentration quenching,
Preferably, it is used in the range of about 0.01 to 40 mol%. Change
The main component is a mixture of a host compound and a guest compound.
Layer with another light-emitting material layer,
A mixture of host and guest compounds
It is also possible to form a light emitting layer in which the separated layers are stacked. Also for this light emitting layer, the film is generally formed.
Evaporation, which is often used for film formation, or spin coating
The film pressure can be
Usually 10 nm to 500 nm, preferably 20 nm to 200 nm.
You. Now, the present invention will be described in further detail with reference to Examples.
explain. Example 1 A transparent electrode was used as the anode.
Glass preformed with a thin film of indium tin oxide
The electrode on the substrate (hereinafter abbreviated as ITO glass substrate)
Hole transport layer, light emitting layer, electron transport layer, cathode
In order of the aluminum / lithium electrodes (hereinafter abbreviated as Al / Li electrodes).
To form the organic electroluminescent device of the present invention.
Made. Specifically, first, an ITO glass substrate, holes
N, N'-diphenyl-N, N'-bis (3-methyl
Phenyl) benzidine (hereinafter abbreviated as TPD), luminescent material
Aromatic methylidene compound of compound No. 1
Tris (8-hydroxyquinolino) aluminum as transport material
Ni (hereinafter abbreviated as Alq) is set in a vacuum evaporation system
Then 10^-Four It was evacuated to Pa. Next, TPD was applied on the electrode of the ITO glass substrate by 0.1%.
Deposited at a deposition rate of ~ 0.5 nm / sec to form a hole transport layer of 50 nm
Done. Next, Compound No. 1 was deposited at a deposition rate of 0.1 to 0.5 nm / sec.
The light emitting layer was formed at a thickness of 50 nm. Then Alq is 0.1nm
/ Sec to form an electron transport layer with a thickness of 10 nm.
Was. Further, the deposition of the Al / Li electrode is performed at a rate of 0.5 nm / sec.
And the thickness was set to 150 nm. No need for these depositions
These are continuous without breaking the vacuum, and the film thickness is a quartz crystal
Controlled by monitoring by Device fabrication
After that, immediately take out the electrode in dry nitrogen and
Field emission devices were created. A voltage is applied to the device fabricated in this manner.
As a result, uniform blue light emission was obtained. The light emission
The peak wavelength of the spectrum is 480nm, 100mA / cm^TwoCurrent
The drive voltage and the emission luminance were measured when
However, the driving voltage is 7.5 V and the emission luminance is 2400 cd / m^TwoSo
Was. Also, as a guide to the life of this element, half of the emission luminance is used.
20 mA / cm^TwoTo drive continuously by applying constant current of
Investigation of the half-life of
Was. Next, for comparison with a conventional luminescent material,
4,4'-bis (2,2-diphenyl) described in JP-A-3-231970
Vinyl) biphenyl was used in place of the luminescent material of Example 1.
A device was prepared in exactly the same manner as in Example 1 except for the above.
When a voltage was applied to the obtained device, a uniform blue emission
Light is obtained and the peak wavelength of the emission spectrum is 450 nm.
Was. 100mA / cm for this element^TwoDrive voltage when is applied
Is 6V, emission luminance is 1200cd / m^TwoMet. As a measure of the life of the device, the emission luminance
Half life time, 20mA / cm^TwoTo drive continuously by applying constant current of
When the half-time of the degree was checked, three hours passed
Agglomeration occurs in part of the organic film, causing an electrical short between the electrodes
And light emission stopped. Example 2 Compound No. 1 used in Example 1
Is the same as Example 1 except that compound number 2 was used instead of
An organic electroluminescent device was prepared. Apply voltage to the resulting device
Upon application, uniform blue light emission was observed. Its departure
The peak wavelength of the light spectrum is 480 nm, 100 mA / cm^Twoof
Measures drive voltage and emission brightness when current is applied
As a result, the driving voltage was 7 V and the emission luminance was 2300 cd / m^TwoIn
Was. As a measure of the life of the device, light emission
20mA / cm brightness half-time^TwoContinuous driving by applying a constant current of
The half-life time of the brightness was examined, and the brightness decreased in 200 hours.
Halved. Example 3 Compound No. 1 used in Example 1
Is the same as Example 1 except that Compound No. 3 was used instead of
An organic electroluminescent device was prepared. Apply voltage to the resulting device
Upon application, uniform green light emission was observed. Its departure
The peak wavelength of the light spectrum was 545 nm. Example 4 Compound No. 1 used in Example 1
Is the same as Example 1 except that compound number 4 was used instead of
An organic electroluminescent device was prepared. Apply voltage to the resulting device
Upon application, uniform blue light emission was observed. Example 5 Compound No. 1 used in Example 1
Is the same as Example 1 except that compound number 5 was used instead of
An organic electroluminescent device was prepared. Apply voltage to the resulting device
Upon application, uniform blue-green light emission was observed. Example 6 Compound No. 1 used in Example 1
Is the same as Example 1 except that compound number 7 was used instead of
An organic electroluminescent device was prepared. Apply voltage to the resulting device
Upon application, uniform blue-green light emission was observed. Example 7: Compound No. 1 used in Example 1
Is the same as Example 1 except that compound number 9 was used instead of
An organic electroluminescent device was prepared. Apply voltage to the resulting device
Upon application, uniform blue light emission was observed. Example 8 Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 10 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 9 Compound No. 1 used in Example 1
In place of Example 1 except that Compound No. 11 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue-green light emission was observed. Example 10 Compound No. 1 used in Example 1
In place of Example 1 except that Compound No. 12 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 11 Compound No. 1 used in Example 1
In place of Example 1, except that Compound No. 14 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 12 Compound No. 1 used in Example 1
In place of Example 1 except that Compound No. 15 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 13 Compound No. 1 used in Example 1
In place of Example 1 except that Compound No. 16 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. (Example 14) Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 17 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 15 Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 18 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 16 Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 19 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. (Example 17) Compound No. 1 used in Example 1
In place of Example 1 except that Compound No. 20 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 18 Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 21 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 19: Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 23 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform green light emission was observed. Example 20 Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 27 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 21 Compound No. 1 used in Example 1
In place of Example 1 except that Compound No. 30 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. Example 22 Compound No. 1 used in Example 1
In place of Example 1, except that Compound No. 31 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue-green light emission was observed. (Example 23) Compound number 1 used in Example 1
In place of Example 1 except that Compound No. 32 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue-green light emission was observed. (Example 24) Compound No. 1 used in Example 1
In place of Example 1 except that Compound No. 34 was used.
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
Was applied, uniform yellow-green light emission was observed. (Example 25) Compound No. 1 used in Example 1
Was the same as Example 1 except that Compound No. 35 was used instead of
Thus, an organic electroluminescent device was prepared. Voltage is applied to the obtained device.
, Uniform blue light emission was observed. (Example 26) On an electrode of an ITO glass substrate,
Form a hole transport layer, a light emitting layer, a cathode, and
An electroluminescent device was manufactured. Specifically, ITO glass base
Plate, TPD as hole transport material, compound number as luminescent material
No. 1 was set on the vacuum evaporation system, and 10^-FourIt was evacuated to Pa. Next, hole transport was performed on the electrode of the ITO glass substrate.
The layer was formed to a thickness of 50 nm. Next, Compound No. 1 was deposited to a thickness of 50 nm and emitted.
An optical layer was formed. Further, an Al / Li electrode was formed to a thickness of 150 nm. this
All of these depositions are performed continuously without breaking vacuum,
Is controlled by monitoring with a crystal oscillator
Was. Immediately after device fabrication, take out the electrode in dry nitrogen.
Then, an organic electroluminescent device was manufactured. Work in this way
When a voltage is applied to the manufactured device, uniform blue light emission
was gotten. Driving voltage is 8V, emission luminance is 1800cd / m^TwoIn
Was. (Example 27) On an electrode of an ITO glass substrate,
An organic electroluminescent device according to the present invention comprising a light emitting layer and a cathode
Was prepared. Specifically, ITO glass substrates, luminescent materials and
And set Compound No. 1 in a vacuum evaporation apparatus.^-FourPa
Exhausted. Next, the compound number is placed on the electrode of the ITO glass substrate.
No. 1 was formed to 100 nm. Furthermore, an Al / Li electrode was formed to a thickness of 150 nm.
Was. All of these depositions are performed continuously without breaking vacuum.
The film thickness is monitored by a quartz oscillator.
Controlled. Immediately after device fabrication, remove electrodes in dry nitrogen.
Then, an organic electroluminescent device was manufactured. in this way
When a voltage was applied to the device manufactured by
Was obtained. Driving voltage is 9.7V, emission luminance is 950cd /
m^TwoMet. Example 28 On an electrode of an ITO glass substrate,
Forming a light emitting layer, an electron transport layer, a cathode, and forming an organic layer according to the present invention.
An electroluminescent device was manufactured. Specifically, ITO glass base
Board, compound No. 1 as light emitting material, electron transport material
And 2- (biphenyl-4-yl) -5- (4-tert-butylphen
Nyl) -1,3,4-oxadiazole in a vacuum evaporation system.
10^-FourIt was evacuated to Pa. Next, a light emitting layer was formed on the electrode of the ITO glass substrate.
Thus, Compound No. 1 was formed to a thickness of 50 nm. Next, the electron transport layer
Was formed to a thickness of 50 nm. Further, an Al / Li electrode was formed to a thickness of 150 nm.
All of these depositions are performed continuously without breaking vacuum,
Film thickness is controlled by monitoring with a crystal oscillator
did. Immediately after device fabrication, take out the electrode in dry nitrogen
Was performed to produce an organic electroluminescent device. Like this
When a voltage was applied to the fabricated device, a uniform blue emission
Light was obtained. Drive voltage is 8.9V, emission luminance is 600cd / m^Twoso
there were. (Example 29) On an electrode of an ITO glass substrate,
Form a hole transport layer, a light emitting layer, a cathode, and
An electroluminescent device was manufactured. Specifically, ITO glass base
Plate, TPD as hole transport material, compound as host compound
The product number 1 is represented by the following (Chemical formula 12) as a guest compound.
Compound (hereinafter abbreviated as EM-1) in a vacuum evaporation system.
10^-FourIt was evacuated to Pa. [0087] Embedded image Next, hole transport was performed on the electrode of the ITO glass substrate.
The layer was formed to a thickness of 50 nm. Next, Compound No. 1 and EM
1 was formed into a 50 nm film by co-evaporation. EM1 for Compound No. 1
The concentration was 3 mol%. Further, an Al / Li electrode is formed to a thickness of 150 nm.
Was. All of these depositions are performed continuously without breaking vacuum.
The film thickness is monitored by a quartz oscillator.
Controlled. Immediately after the fabrication of the device, the electrodes were taken out in dry nitrogen.
Then, an organic electroluminescent device was manufactured. like this
When a voltage was applied to the device fabricated in
Green light emission was obtained. Driving voltage is 8.5V, emission luminance is 31
00cd / m^TwoMet. This device was initially placed in dry nitrogen.
Brightness 1000cd / m^Two, The brightness is half of the initial
500cd / m which is a minute^TwoIt takes 750 hours to become
Was. (Example 30) An ITO glass substrate was placed in a vacuum apparatus.
Set to 10^-FourAfter pumping down to Pa, as a hole transport layer
TPD was formed into a 50 nm film. Then, with the host compound of the light emitting layer
And rubrene as a guest compound
The light emitting layer was formed to a thickness of 25 nm. The concentration of rubrene relative to compound No. 1 was
The degree was 5 mol%. Next, as an electron transport layer, Alq
Al / Li electrode is formed as a pole with a thickness of 150 nm to create a device
did. These films are continuous without breaking the vacuum
I went. The film thickness was monitored by a quartz oscillator.
did. Immediately after device fabrication, take out the electrode in dry nitrogen
Was performed, and the characteristics were measured subsequently. The obtained device is
When pressure is applied, a uniform
A yellow luminescence was obtained. 100 mA / cm^TwoDrive current when applying
When the voltage and emission luminance were measured, the
Light brightness is 4000cd / m^TwoMet. Put this device in dry nitrogen
In the initial brightness 1000cd / m^TwoWhen driven continuously with
500cd / m with half the initial degree ^TwoTime to become
(Brightness half life) was 1230 hours. (Examples 31 to 36) In the light emitting layer of Example 30
In place of rubrene, a guest compound,
Perylene, and in Example 32, 3- (2-benzoquinone).
Thiazoly) -7 (N, N-diethylamino) coumarin (hereafter bear
Phosphorus 6), and in Example 33, 3- (2-Benzoi
Midazolyl) -7 (N, N-diethylamino) coumarin (hereinafter
(Abbreviated as Marine 7), EM1 in Example 34, and Example 35
Is a compound represented by the following chemical formula (hereinafter referred to as EM-2)
In Example 36, 4-dicyanomethylene
2-methyl-6- (4-dimethylaminostyryl) -4H-pyran
(Hereinafter abbreviated as DCM).
An electroluminescent device was prepared. [0095] Embedded image The light emission peaks of the devices fabricated in these examples were
Wavelength, 100mA / cm^TwoDrive voltage and light emission brightness at the time of application, initial
Brightness 1000cd / m^TwoThe half-life of brightness when continuously driven by
The results are shown in Table 1 together with the results of Example 30. [0097] [Table 1](Examples 37 to 43) Hosting for Light Emitting Layer
Examples 30 to 36 except that the compound was changed to Compound No. 2.
In the same manner as in the above, an organic electroluminescent device was produced. These fruits
Emission peak wavelength of the device manufactured in the example, 100 mA / cm^TwoApplication
Drive voltage and emission brightness, initial brightness 1000cd / m^TwoContinuous driving
(Table 2) shows the half-life of luminance when the device is moved. [0099] [Table 2] (Example 44) An ITO substrate was set in a vacuum apparatus.
10^-FourAfter evacuation to Pa, N, N'-
Bis [4 '-(N, N-diphenylamino) -4-biphenylyl] -N,
N'-diphenylbenzidine was formed into a 50 nm film. Then departure
Compound No. 1, guest compound as host compound in optical layer
Compound No. 3 was co-evaporated to form a light emitting layer of 25 nm.
Was. The concentration of Compound No. 3 relative to Compound No. 1 was 1 m
ol %%. Next, 25 nm of Alq was used as an electron transport layer,
Al / Li electrode is formed into a film with a thickness of 150 nm as
Was. These films are continuously formed without breaking the vacuum
went. When voltage was applied to the obtained device, it was 490 nm.
, A uniform blue-green emission having a peak was obtained. 100 mA / cm^TwoDrive current when applying
When the pressure and emission luminance were measured, the driving voltage was 6.9V,
Luminance brightness is 3200cd / m^TwoMet. Put this device in dry nitrogen
At an initial luminance of 1000 cd / m^TwoAfter continuous driving with
The luminance half life was 1150 hours. (Examples 45 to 46) Conversion to guest used for light emitting layer
The organic electric field was the same as in Example 44 except that the compound was changed.
A light-emitting element was manufactured. In Example 45 as the guest compound
A compound represented by the following chemical formula (hereinafter abbreviated as EM-3)
In Example 46, the compound represented by the following (Formula 15)
(Hereinafter abbreviated as EM-4). [0104] Embedded image [0105] Embedded image The light emission peaks of the devices fabricated in these examples were
Wavelength, 100mA / cm^TwoDrive voltage and light emission brightness at the time of application, initial
Brightness 1000cd / m^TwoThe half-life of brightness when continuously driven by
The results are shown in Table 3 together with the results of Example 44. [0107] [Table 3] (Examples 47 to 49) Hosting for Light Emitting Layer
The compound is converted to a compound represented by the following chemical formula (hereinafter abbreviated as EM-5).
Described in the same manner as in Examples 44 to 46, except that
An organic electroluminescent device was manufactured. [0109] Embedded image The light emission peaks of the devices fabricated in these examples were
Wavelength, 100mA / cm^TwoDrive voltage and light emission brightness at the time of application, initial
Brightness 1000cd / m^TwoThe half-life of brightness when continuously driven with
See 4). [0111] [Table 4] [0112] As described above, the aromatic film according to the present invention is used.
The organic electroluminescent device of the present invention using a tylidene compound,
Compared to devices using conventional compounds, it has excellent light-emitting properties,
Moreover, it is a long-life element excellent in stability. Therefore,
The organic electroluminescent device of the present invention can be used in various industrial fields.
It can be used effectively.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an embodiment of the present invention, an anode, a light-emitting layer,
FIG. 2 is a schematic cross-sectional view of an element including a cathode. FIG. 2 is a schematic cross-sectional view of an element including an anode, a hole transport layer, a light emitting layer, and a cathode according to one embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a device including an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.
Schematic cross-sectional view of an element comprising an electron transport layer and a cathode [Description of References] 1 anode 2 hole transport layer 3 light emitting layer 4 electron transport layer 5 cathode

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-179240 (JP, A) JP-A-6-271844 (JP, A) JP-A-8-22891 (JP, A) International Publication 92/005131 (WO, A1) (58) Fields surveyed (Int. Cl. ⁷ , DB name) C09K 11/06 H05B 33/14 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claim 1] An organic electroluminescent device using a specific aromatic methylidene compound represented by the following general formula. Embedded image (Where Ar ₁ is a divalent to hexavalent unsubstituted or alkyl
Group, cycloalkyl group, alkoxy group, halogen group,
Ano group, nitro group, acyl group, carboxyl group and their
Esters and acyl substituted aromatic hydrocarbon residues and Table <br/>, Ar ₂ is a divalent unsubstituted or alkyl group, a cycloalkyl
Kill group, alkoxy group, halogen group, cyano group, nitro
Groups, acyl groups, carboxyl groups and their esters and
It represents a sill-substituted aromatic hydrocarbon residues. Ar ₃ is
Unsubstituted or alkyl group, cycloalkyl group, alkoxy
Groups, halogen groups, cyano groups, nitro groups, acyl groups,
Ruboxyl group and its ester and acyl group- substituted aromatic hydrocarbon residue, unsubstituted or alkyl group, cycloalkyl
Kill group, alkoxy group, halogen group, cyano group, nitro
Groups, acyl groups, carboxyl groups and their esters and
Represents a sil- substituted aromatic heterocyclic hydrocarbon residue. R
Represents an unsubstituted or alkyl group, a cycloalkyl group,
Coxy group, halogen group, cyano group, nitro group, acyl
Group, carboxyl group and its ester and acyl group- substituted aromatic hydrocarbon residue, unsubstituted or alkyl group,
Loalkyl group, alkoxy group, halogen group, cyano group,
Nitro group, acyl group, carboxyl group and its ester
And acyl- substituted aromatic heterocyclic hydrocarbon residue, unsubstituted or aryl group, aryloxy group, alkoxy group
And a halogen- substituted alkyl group . Ar ₃ and R may form a ring together. n represents a positive number of 2 to 6. )