JPH11242995A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve luminous efficiency and luminance by forming a structure by holding at least one layer containing one or more kinds of bisnaphtho[1',8':5,6,7]-s-indaceno[1,2,3-cd:1',2',3'-c',d']benzo[1,2-k :4,5-k']difluoranthene derivatives between a pair of electrodes. SOLUTION: This derivative has a framework expressed by a formula and is structured by substituting a predetermined halogen atom group, alkoxyl group, aryl group or the like for one or more out of 30 hydrogen atoms, and an organic electroluminescent element using it for its luminescent layer emits red-colored light that is high in luminance and excellent in durability. A layer containing the derivative contains a luminous organic metal complex including aluminum and the like or a triallylamine derivative and may have a hole injection/transfer layer and/or an electron injection/transfer layer between a pair of electrodes. If the luminescent layer is formed by combining it with another luminous ingredient, white-colored light that is high in luminance and excellent in durability can be also emitted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic electroluminescent device.

[0002]

2. Description of the Related Art Conventionally, an inorganic electroluminescent device has been used as a panel-type light source such as a backlight. However, driving the light emitting device requires a high AC voltage. Recently, an organic electroluminescent device (organic electroluminescent device: organic EL device) using an organic material as a light emitting material has been developed [Appl. Phys. Lett., 51 ,
913 (1987)]. The organic electroluminescent element has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode,
An exciton is generated by injecting electrons and holes into the thin film and recombining them, and emits light using light emitted when the exciton is deactivated. is there. The organic electroluminescent element can emit light at a low DC voltage of about several volts to several tens of volts, and various colors (for example, red, blue, and green) can be obtained by selecting the type of the fluorescent organic compound. ) Is possible. Organic electroluminescent devices having such features include various light emitting devices,
Application to display elements and the like is expected. However,
Generally, the light emission luminance is low and is not practically sufficient.

As a method for improving the light emission luminance, for example, an organic electroluminescent device using tris (8-quinolinolato) aluminum as a host compound, a coumarin derivative, and a pyran derivative as a guest compound (dopant) as a light emitting layer has been proposed. J. Appl. Phys., 65 , 361
0 (1989)]. Further, as a light emitting layer, for example, a screw (2
An organic electroluminescent device using -methyl-8-quinolinolate) (4-phenylphenolate) aluminum as a host compound and an acridone derivative (for example, N-methyl-2-methoxyacridone) as a guest compound has been proposed ( JP-A-8-67873). However, it is difficult to say that these light emitting elements also have sufficient light emission luminance. At present, an organic electroluminescent device that emits light with higher luminance is desired.

Bisnaphtho [1 ', 8': 5,6,7] -s-indaceno [1,2,3-cd: 1 ', 2', 3'-c 'according to the organic electroluminescent device of the present invention
The d '] benzo [1,2-k: 4,5-k'] difluoranthene derivative includes 4,7,9,12,19,22,24,27-octakis (4'-dodecylphenyl) bisnaphtho. [1 ',
8 ': 5,6,7] -s-indaceno [1,2,3-cd: 1', 2 ', 3'-c'd'] benzo [1,2-k: 4,5-k ' Difluoranthene is known [for example, Angew. Chem. Int. Ed. Engl., 36 , 1996 (1997)].
It is described in〕. However, Angew. Chem. Int. Ed.
Engl., 36 , 1996 (1997) describes the electrochemical properties of the compound, but does not describe an organic electroluminescent device.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescent device which is excellent in luminous efficiency and emits light with high luminance.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on the organic electroluminescent device and the compounds used in the device, and as a result, completed the present invention. That is,
The present invention provides bisnaphtho [1 ′, 8 ′: 5,6,7] -s-indaceno [1,2,3-cd: 1 ′, 2 ′, 3′-c′d ′ between a pair of electrodes. Bisnaphtho [1 ', 8': 5,6] An organic electroluminescent device comprising at least one layer containing at least one layer containing at least one benzo [1,2-k: 4,5-k '] difluoranthene derivative , 7] -s-indaceno [1,2,3-cd:
The organic electric field according to the above description, wherein the layer containing at least one 1 ', 2', 3'-c'd '] benzo [1,2-k: 4,5-k'] difluoranthene derivative is a light-emitting layer. Light-emitting element, bisnaphtho [1 ', 8': 5,6,7] -s-indaceno [1,2,3-cd:
The layer containing at least one 1 ', 2', 3'-c'd '] benzo [1,2-k: 4,5-k'] difluoranthene derivative further contains a luminescent organometallic complex Organic electroluminescent device described or described, bisnaphtho [1 ', 8': 5,6,7] -s-indaceno [1,2,3-cd:
The layer containing at least one 1 ', 2', 3'-c'd '] benzo [1,2-k: 4,5-k'] difluoranthene derivative further contains a triarylamine derivative Or the organic electroluminescent device according to any one of the above-mentioned, further comprising a hole injection transport layer between the pair of electrodes, further comprising an electron injection transport layer between the pair of electrodes. The organic electroluminescent device according to any of the above, wherein bisnaphtho [1 ′, 8 ′: 5,6,7] -s-indaceno [1,2,3-cd:
1 ′, 2 ′, 3′-c′d ′] benzo [1,2-k: 4,5-k ′] difluoranthene derivative represented by general formula (1-A) The organic electroluminescent device according to any one of the above to
It is about.

[0007]

Embedded image (Wherein X _{1 to} X ₃₀ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group or a substituted or unsubstituted aryl group; X ₇ and X ₂₄ , and X ₉ and X _{22 which} are mutually adjacent groups selected from _{1 to} X ₃₀ are bonded to each other to form a substituted or unsubstituted carbocyclic aliphatic ring together with a substituted carbon atom. (It may be formed.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The organic electroluminescent device of the present invention, between a pair of electrodes,
Bisnaphtho [1 ', 8': 5,6,7] -s-indaceno [1,2,3-cd: 1 ',
At least one layer containing at least one kind of 2 ′, 3′-c′d ′] benzo [1,2-k: 4,5-k ′] difluoranthene derivative is sandwiched.

The bisnaphtho [1 ', 8': 5,6,7] -s- according to the present invention
Indaceno [1,2,3-cd: 1 ', 2', 3'-c'd '] benzo [1,2-k: 4,5
The -k ′] difluoranthene derivative (hereinafter abbreviated as compound A according to the present invention) represents a compound having a skeleton represented by the general formula (1) (formula 3), and is represented by the general formula (1 ) May have various substituents,
Preferably, it is a compound represented by the general formula (1-A) (Formula 3).

[0010]

Embedded image (Wherein, X _{1 to} X ₃₀ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, adjacent groups selected from ₁ to X _30, X ₇ and X _24, and X ₉ and X ₂₂ are bonded to each other,
Together with the substituted carbon atom, it may form a substituted or unsubstituted carbocyclic aliphatic ring. )

In the compound represented by the general formula (1-A), X _{1 to} X ₃₀ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. Represents a group or a substituted or unsubstituted aryl group, and further, adjacent groups selected from X _{1 to} X ₃₀ , X ₇ and X ₂₄ , and X ₉ and X ₂₂ are mutually bonded and substituted. Represents a group which may form a substituted or unsubstituted carbocyclic aliphatic ring together with a carbon atom. In the present invention, the aryl group is, for example,
It represents a carbocyclic aromatic group such as a phenyl group and a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group and a pyridyl group.

In the compound represented by the general formula (1-A), X _{1 to} X ₃₀ are more preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, Represents a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms or a substituted or unsubstituted aryl group having 4 to 24 carbon atoms.

Specific examples of X _{1 to} X ₃₀ in the general formula (1-A) include, for example, a hydrogen atom, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, for example,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, te
rt-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-
Methylpentyl group, 4-methyl-2-pentyl group, 3,
3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propyl Pentyl group, n-nonyl group, 2,2-dimethylheptyl group,
2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-undecyl group,
1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n
-Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-
Tricosyl group, n-tetracosyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group,
4-tert-butylcyclohexyl group, cycloheptyl group, straight-chain, branched or cyclic alkyl group such as cyclooctyl group,

For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, n-pentyloxy, neopentyloxy, cyclopentyloxy,
n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2
-Ethylhexyloxy group, n-nonyloxy group, n-
Decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group Linear chains such as n-octadecyloxy group, n-eicosyloxy group, n-tricosyloxy group, n-tetracosyloxy group;
A branched or cyclic alkoxy group,

For example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3
-Ethylphenyl group, 4-ethylphenyl group, 4-n-
Propylphenyl group, 4-isopropylphenyl group, 4
-N-butylphenyl group, 4-isobutylphenyl group,
4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-heptyl Phenyl group,
4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexadecylphenyl group, 4-n-octadecylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-
Dimethylphenyl group, 2,6-dimethylphenyl group,
3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3
5,6-tetramethylphenyl group, 5-indanyl group,
1,2,3,4-tetrahydro-5-naphthyl group, 1,
2,3,4-tetrahydro-6-naphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group A 4-isopropoxyphenyl group, a 4-n-butoxyphenyl group,
4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-
Cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxyphenyl group,
4-n-nonyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-undecyloxyphenyl group,
4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl group,

2,3-dimethoxyphenyl group, 2,4-
Dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 2-methoxy-4-methylphenyl group, 2-methoxy -5-methylphenyl group, 3-methoxy-4-methylphenyl group, 2-methyl-4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-fluoro Phenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group,
4-bromophenyl group, 4-trifluoromethylphenyl group, 2,4-difluorophenyl group, 2,4-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-
Dichlorophenyl group, 2-methyl-4-chlorophenyl group, 2-chloro-4-methylphenyl group, 3-chloro-
4-methylphenyl group, 2-chloro-4-methoxyphenyl group, 3-methoxy-4-fluorophenyl group, 3-
Methoxy-4-chlorophenyl group, 3-fluoro-4-
A methoxyphenyl group, a 4-phenylphenyl group, a 3-phenylphenyl group, a 4- (4′-methylphenyl) phenyl group, a 4- (4′-methoxyphenyl) phenyl group,
1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-ethoxy-1-naphthyl group, 6-n-butyl-2-naphthyl group, 6-methoxy-2-naphthyl group, 7- Ethoxy-2-naphthyl group, 2-furyl group, 2
-Thienyl group, 3-thienyl group, 2-pyridyl group, 3-
Examples thereof include a substituted or unsubstituted aryl group such as a pyridyl group and a 4-pyridyl group, and more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a straight chain having 1 to 20 carbon atoms,
A branched or cyclic alkyl group, a straight chain having 1 to 20 carbon atoms,
A branched or cyclic alkoxy group, or 6 to 2 carbon atoms
0 aryl group, more preferably a hydrogen atom,
A linear, branched or cyclic alkyl group having 1 to 16 carbon atoms,
Alternatively, it is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

Further, X _{1 to} X ₃₀ , groups adjacent to each other, X ₇ and X ₂₄ , and X ₉ and X ₂₂ are bonded to each other,
A substituted or unsubstituted carbocyclic aliphatic ring may be formed together with the substituted carbon atom, and preferably forms a substituted or unsubstituted carbocyclic aliphatic ring having 4 to 20 carbon atoms in total. It may be.

In the general formula (1-A), X ₄ , X ₇ ,
X ₉ , X ₁₂ , X ₁₉ , X ₂₂ , X ₂₄ and X _{27 each} have 1 to 1 carbon atoms.
A linear, branched or cyclic alkyl group of 16 or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;
Further, other compounds in which X is a hydrogen atom are more preferred.

In the organic electroluminescent device of the present invention, bisnaphtho [1 ', 8': 5,6,7] -s-indaceno [1,2,3-cd: 1 ', 2',
3'-c'd '] benzo [1,2-k: 4,5-k'] difluoranthene derivative is characterized by using at least one derivative, for example,
Bisnaphtho [1 ', 8': 5,6,7] -s-indaceno [1,2,3-cd: 1 ',
When a 2 ', 3'-c'd'] benzo [1,2-k: 4,5-k '] difluoranthene derivative is used in the light-emitting layer as a light-emitting component, high brightness and durability are unprecedented. It is possible to provide an organic electroluminescent element that emits red light with excellent characteristics. In addition, when a light-emitting layer is formed in combination with another light-emitting component, an organic electroluminescent element that emits white light with high luminance and excellent durability can be provided.

Specific examples of the compound A according to the present invention include:
For example, the following compounds (Chemical Formulas 4 to 27) can be exemplified, but the present invention is not limited thereto.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The compound A according to the present invention, for example, the compound represented by the general formula (1-A) can be prepared by a method known per se [for example, Angew. Chem. Int. Ed. Engl., 36 , 1996].
(1997)]. That is, for example, a compound represented by the general formula (2) (Chemical formula 28), a compound represented by the general formula (3) (Chemical formula 28), and a compound represented by the general formula (4) (Chemical formula 28) Can be produced.

[0046]

Embedded image [In the above formula, X _{1 to} X ₃₀ represent the same meaning as in the general formula (1-A). ]

The compound represented by the general formula (2) can be prepared by a method known per se [for example, Angew. Chem. Int. Ed. Eng.
l, 36 , 1996 (1997) and Synlett, 75 (1994)]. That is, the compound represented by the general formula (5) (Formula 29) and the general formula (6)
It can be produced by reacting a compound represented by the following formula (Chemical formula 29) and a 1,4-benzadiyne derivative represented by the general formula (7) (Chemical formula 29).

[0048]

Embedded image [In the above formula, X _{5 to} X ₁₁ and X _{20 to} X ₂₆ represent the general formula (1
It has the same meaning as -A). ]

The cyclopenta [a] acenaphthylene-8-one derivatives represented by the general formulas (3) and (4) can be prepared by a known method [for example, Chem. Rev., 65 , 26].
1 (1965)].

The compound A according to the present invention, for example, the compound represented by the general formula (1-A) may be a solvent (for example, an aromatic hydrocarbon solvent such as toluene) used in some cases.
May be produced in a form that forms a solvate with
The organic electroluminescent device of the present invention includes the compound A according to the present invention.
Such a solvate can be used as well as a non-solvate. When the compound A according to the present invention, for example, the compound represented by the general formula (1-A) is used for an organic electroluminescent device, a recrystallization method, a column chromatography method,
It is preferable to use a purification method such as a sublimation purification method, or a compound having an increased purity by using these methods in combination.

The organic electroluminescent element usually has at least one light-emitting layer containing at least one light-emitting component sandwiched between a pair of electrodes. In consideration of the functional levels of hole injection and hole transport, electron injection and electron transport of the compound used in the light emitting layer, a hole injection transport layer containing a hole injection transport component and / or An electron injection / transport layer containing an injection / transport component can also be provided. For example, when the compound used for the light emitting layer has a good hole injection function, a hole transport function and / or an electron injection function, and an electron transport function, the light emitting layer is formed of the hole injection transport layer and / or the electron injection transport layer. The element can also be configured to serve as Needless to say, depending on the case, a structure of a device (single-layer device) in which both the hole injection transport layer and the electron injection transport layer are not provided may be employed. Also,
Each of the hole injecting and transporting layer, the electron injecting and transporting layer, and the light emitting layer may have a single-layer structure or a multilayer structure, and the hole injecting and transporting layer and the electron injecting and transporting layer are each A layer having an injection function and a layer having a transport function may be separately provided.

In the organic electroluminescent device of the present invention, the compound A according to the present invention is preferably used for a hole injecting and transporting component, a light emitting component or an electron injecting and transporting component. Is more preferable,
It is particularly preferable to use it for a light emitting component. In the organic electroluminescent device of the present invention, the compound A according to the present invention may be used alone or in combination.

The structure of the organic electroluminescent device of the present invention is not particularly limited.
Hole injection / transport layer / emission layer / electron injection / transport layer / cathode device (FIG. 1), (B) anode / hole injection / transport layer / emission layer / cathode device (FIG. 2), (C) anode / emission Layer / electron injection / transport layer / cathode type device (FIG. 3), (D) anode / light emitting layer / cathode type device (FIG. 4) and the like. Further, the device is of a type in which a light emitting layer is sandwiched between electron injection and transport layers (E).
Anode / hole injection / transport layer / electron injection / transport layer / emission layer / electron injection / transport layer / cathode type device (FIG. 5).
The element configuration of the (D) type is, of course, an element of a type in which a light emitting component is sandwiched between a pair of electrodes in a single layer form, and further, for example, (F) a hole injection / transport component, a light emitting component, An element of a type in which an electron injection / transport component is mixed and sandwiched between a pair of electrodes (FIG. 6), and (G) a layer in which a hole injection / transport component and a light emitting component are mixed, between a pair of electrodes. There is an element of the sandwiched type (FIG. 7) and an element of the type (H) sandwiched between a pair of electrodes in the form of a single layer in which a light emitting component and an electron injection / transport component are mixed (FIG. 8).

The organic electroluminescent device of the present invention is not limited to these device configurations, but may be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers in each type of device. Can be. Further, in each type of device, between the hole injection transport layer and the light emitting layer,
A mixed layer of a light emitting component and an electron injection / transport component may be provided between the hole injection / transport component and the light emitting component and / or between the light emitting layer and the electron injection / transport layer. More preferred configurations of the organic electroluminescent element include (A) type element, (B) type element, (C) type element, (E) type element, (F) type element,
It is a (G) type element or an (H) type element, and more preferably an (A) type element, a (B) type element, a (C) type element or a (F) type element.

As the organic electroluminescent device of the present invention, for example, (A) anode / hole injection / transport layer / emission layer / electron injection / transport layer / cathode device shown in FIG. 1 will be described.
In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection / transport layer, 4 is a light emitting layer, 5 is an electron injection / transport layer, 6 is a cathode,
Reference numeral 7 denotes a power supply.

The organic electroluminescent device of the present invention is preferably supported on a substrate 1. The substrate is not particularly limited, but is preferably transparent or translucent. Transparent plastic sheet (for example, polyester, polycarbonate, polysulfone, polymethyl methacrylate, polypropylene,
A sheet made of polyethylene or the like), a translucent plastic sheet, quartz, a transparent ceramic, or a composite sheet combining these. Further, the luminescent color can be controlled by combining, for example, a color filter film, a color conversion film, and a dielectric reflection film on the substrate.

As the anode 2, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively large work function as an electrode material. As the electrode material used for the anode, for example, gold, platinum, silver, copper, cobalt, nickel,
Palladium, vanadium, tungsten, tin oxide, zinc oxide, ITO (indium tin oxide), polythiophene, polypyrrole, and the like can be given. These electrode substances may be used alone or in combination of two or more. The anode can be formed on the substrate by using such an electrode material by a method such as a vapor deposition method and a sputtering method. Further, the anode may have a single-layer structure or a multilayer structure. The sheet electric resistance of the anode is preferably several hundred Ω / □.
Hereinafter, more preferably, it is set to about 5 to 50 Ω / □. The thickness of the anode depends on the material of the electrode substance to be used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm.

The hole injection / transport layer 3 is a layer containing a compound having a function of facilitating the injection of holes (holes) from the anode and a function of transporting the injected holes. The hole injecting and transporting layer is formed of the compound A according to the present invention and / or another compound having a hole injecting and transporting function (for example, a phthalocyanine derivative, a triarylmethane derivative, a triarylamine derivative, an oxazole derivative, a hydrazone derivative, a stilbene derivative). , Pyrazoline derivatives, polysilane derivatives, polyphenylenevinylene and its derivatives,
Polythiophene and a derivative thereof, a poly-N-vinylcarbazole derivative, and the like). The compounds having a hole injection / transport function may be used alone or in combination.

Other compounds having a hole injection / transport function used in the present invention include triarylamine derivatives (for example, 4,4'-bis [N-phenyl-N- (4 ")
-Methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N-
(3 "-methoxyphenyl) amino] biphenyl, 4,
4'-bis [N-phenyl-N- (1 "-naphthyl) amino] biphenyl, 3,3'-dimethyl-4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino] Biphenyl, 1,1-bis [4 ′-[N, N-di (4 ″ -methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4′-methylphenyl) -N- (4 "-N-butylphenyl) amino] phenanthrene, 3,8-bis (N, N-diphenylamino) -6-phenylphenanthridine, 4-methyl-
N, N-bis [4 ″, 4 ″ ′-bis [N ′, N′-di (4-methylphenyl) amino] biphenyl-4-yl] aniline, N, N′-bis [4- (diphenylamino) ) Phenyl) -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4- (diphenylamino) phenyl] -N, N'-diphenyl-1,4-diaminobenzene, 5, 5 ″ -bis [4- (bis [4-methylphenyl] amino) phenyl] -2,2 ′: 5 ′,
2 "-terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ', 4" -tris (N-carbazoyl) triphenylamine, 4,4', 4 "-tris [N- ( 3 "'-methylphenyl) -N-phenylamino) triphenylamine, 4,4', 4" -tris [N, N-bis (4 ""-tert-butylbiphenyl-
4 ""-yl) amino] triphenylamine, 1,3
5-tris [N- (4'-diphenylaminophenyl)
-N-phenylaminobenzene), polythiophene and derivatives thereof, and poly-N-vinylcarbazole derivatives are more preferred. When the compound A according to the present invention is used in combination with another compound having a hole injecting and transporting function, the proportion of the compound A according to the present invention in the hole injecting and transporting layer is preferably 0.1 to 40% by weight. Prepare to about.

The light emitting layer 4 has a hole and electron injection function,
This is a layer containing a compound having a transport function thereof and a function of generating excitons by recombination of holes and electrons. The light-emitting layer is formed of the compound A according to the present invention and / or a compound having a light-emitting function (eg, an acridone derivative, a quinacridone derivative, a diketopyrrolopyrrole derivative, a polycyclic aromatic compound [eg, rubrene, anthracene, tetracene, pyrene). , Perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9'-ethynylanthracenyl) ) Benzene, 4,4′-bis (9 ″ -ethynylanthracenyl) biphenyl], a triarylamine derivative (for example, the compounds described above as compounds having a hole injecting and transporting function), and organometallic complexes [For example, Tris (8- Rinorato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, 2
Zinc salt of-(2'-hydroxyphenyl) benzoxazole, zinc salt of 2- (2'-hydroxyphenyl) benzothiazole, zinc salt of 4-hydroxyacridine,
Zinc salt of 3-hydroxyflavone, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], stilbene derivative [for example, 1,1,4,
4-tetraphenyl-1,3-butadiene, 4,4′-
Bis (2,2-diphenylvinyl) biphenyl, 4,
4'-bis [(1,1,2-triphenyl) ethenyl]
Biphenyl], coumarin derivatives [for example, coumarin 1,
Coumarin 6, Coumarin 7, Coumarin 30, Coumarin 10
6, Coumarin 138, Coumarin 151, Coumarin 15
2, Coumarin 153, Coumarin 307, Coumarin 31
1. Coumarin 314, Coumarin 334, Coumarin 33
8, coumarin 343, coumarin 500], pyran derivatives [for example, DCM1, DCM2], oxazone derivatives [for example, Nile Red], benzothiazole derivatives,
Benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, poly-
N-vinyl carbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and its derivatives, polyphenylene vinylene and its derivatives, polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and And at least one of its derivatives, polythienylenevinylene and derivatives thereof). In the organic electroluminescent device of the present invention, the light emitting layer preferably contains the compound A according to the present invention. When the compound A according to the present invention and a compound having another light-emitting function are used in combination,
The ratio of the compound A according to the present invention in the light emitting layer is preferably about 0.001 to 99.999% by weight, more preferably about 0.01 to 99.99% by weight, and further preferably about 0.1 to 99.99% by weight. It is adjusted to about 1 to 99.9% by weight.

As the other compound having a light-emitting function used in the present invention, a light-emitting organometallic complex is more preferable. For example, as described in J. Appl. Phys., 65 , 3610 (1989) and JP-A-5-214332, the light-emitting layer can be composed of a host compound and a guest compound (dopant). The compound A according to the present invention can be used as a host compound to form a light emitting layer, and further can be used as a guest compound to form a light emitting layer. When the light emitting layer is formed using the compound A according to the present invention as a guest compound, the host compound includes
For example, the above-mentioned compounds having another light-emitting function can be mentioned. For example, a light-emitting organic metal complex or a triarylamine derivative is more preferable. In this case, for the luminescent organometallic complex or the triarylamine derivative,
The compound represented by the general formula (1) is preferably used in an amount of 0.0
About 01 to 40% by weight, more preferably 0.01 to 3% by weight.
About 0% by weight, particularly preferably about 0.1 to 20% by weight is used.

The light-emitting organometallic complex used in combination with the compound A according to the present invention is not particularly limited, but a light-emitting organic aluminum complex is preferable, and a light-emitting having a substituted or unsubstituted 8-quinolinolate ligand. Organic aluminum complexes are more preferred. Preferred luminescent organic metal complexes include, for example, luminescent organic aluminum complexes represented by general formulas (a) to (c). (Q) ₃ -Al (a) (wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand) (Q) ₂ -Al-OL (b) (where Q represents substituted 8 -Represents a quinolinolate ligand, O
-L is a phenolate ligand, and L represents a hydrocarbon group having 6 to 24 carbon atoms including a phenyl moiety.) (Q) ₂ -Al-O-Al- (Q) ₂ (c) Q represents a substituted 8-quinolinolate ligand)

Specific examples of the luminescent organometallic complex include, for example, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, tris ( 3,4-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) (Phenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-
Methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(4-methylphenolate) aluminum, bis (2-
Methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum,
Bis (2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (2,3-dimethylphenolate)
Aluminum, bis (2-methyl-8-quinolinolate) (2,6-dimethylphenolate) aluminum,
Bis (2-methyl-8-quinolinolate) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8- Quinolinolate) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-
Triphenylphenolate) aluminum, bis (2-
Methyl-8-quinolinolate) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2-naphtholate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate)
(3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenolate) ) Aluminum, bis (2,4-dimethyl-8-)
Quinolinolate) (3,5-di-tert-butylphenolato) aluminum, bis (2-methyl-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-8-quinolinolate) aluminum, bis (2,4 −
Dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate)
Aluminum, bis (2-methyl-4-ethyl-8-quinolinolate) aluminum-μ-oxo-bis (2-
Methyl-4-ethyl-8-quinolinolate) aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-
4-methoxy-8-quinolinolate) aluminum, bis (2-methyl-5-cyano-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolate) aluminum, bis (2- Methyl-5-trifluoromethyl-8-quinolinolate)
Aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum and the like can be mentioned. Of course, the luminescent organometallic complex may be used alone or in combination.

The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating the injection of electrons from the cathode and a function of transporting the injected electrons. The electron injecting and transporting layer is formed of the compound A according to the present invention and / or another compound having an electron injecting and transporting function (for example, an organometallic complex [for example, tris (8-quinolinolate) aluminum, bis (10-benzo [h] quinolinolate) ) Beryllium, 5
-Hydroxyflavone beryllium salt, 5-hydroxyflavone aluminum salt], oxadiazole derivatives [eg, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4-oxadiazole] -2'-yl] benzene], a triazole derivative [eg, 3-
(4′-tert-butylphenyl) -4-phenyl-5
-(4 "-biphenyl) -1,2,4-triazole], a triazine derivative, a perylene derivative, a quinoline derivative, a quinoxaline derivative, a diphenylquinone derivative,
A nitro-substituted fluorenone derivative, a thiopyrandioxide derivative, etc.). When the compound A according to the present invention is used in combination with another compound having an electron injecting and transporting function, the ratio of the compound A according to the present invention in the electron injecting and transporting layer is preferably 0.1%.
It is adjusted to about 1 to 40% by weight. In the present invention, the compound A according to the present invention and an organometallic complex [for example, the compounds represented by the general formulas (a) to (c)] are used together to form an electron injecting and transporting layer. preferable.

As the cathode 6, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium,
Manganese, yttrium, aluminum, an aluminum-lithium alloy, an aluminum-calcium alloy, an aluminum-magnesium alloy, a graphite thin film, and the like can be given. These electrode substances may be used alone or in combination of two or more. The cathode, these electrode substances, for example, a vapor deposition method, a sputtering method,
It can be formed on the electron injection transport layer by a method such as an ionization vapor deposition method, an ion plating method, and a cluster ion beam method. Further, the cathode may have a single-layer structure or a multilayer structure. The sheet electric resistance of the cathode is preferably set to several hundreds Ω / □ or less. The thickness of the cathode depends on the material of the electrode substance used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm. In order to efficiently extract the light emitted from the organic electroluminescent device, it is preferable that at least one of the anode and the cathode is transparent or translucent, and the transmittance of the emitted light is generally 70% or more. It is more preferable to set the material and thickness of the anode.

The organic electroluminescent device of the present invention may contain a singlet oxygen quencher in at least one layer. The singlet oxygen quencher is not particularly limited and includes, for example, rubrene,
Nickel complexes, diphenylisobenzofuran and the like can be mentioned, and rubrene is particularly preferred. The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer.
For example, when a singlet oxygen quencher is contained in the hole injecting and transporting layer, the singlet oxygen quencher may be contained uniformly in the hole injecting and transporting layer. (An electron injection / transport layer having a light emitting function). The content of the singlet oxygen quencher is from 0.01 to 50% by weight, preferably from 0.0 to 50% by weight of the total amount constituting the contained layer (for example, the hole injection / transport layer).
5 to 30% by weight, more preferably 0.1 to 20% by weight
It is.

The method for forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited, and may be, for example, a vacuum evaporation method, an ionization evaporation method, a solution coating method (for example, a spin coating method, a casting method, or the like). Method, dip coating method,
It can be manufactured by forming a thin film by a bar coating method, a roll coating method, a Langmuir-Brosette method, an inkjet method, or the like. By vacuum evaporation method,
When each layer is formed, the conditions of the vacuum deposition is not particularly limited, the following under vacuum of about 10 ^-5 Torr, 50
~ 600 ° C boat temperature (deposition source temperature), -50 ~
At a substrate temperature of about 300 ° C., 0.005 to 50 nm / se
It is preferable to carry out at a deposition rate of about c. In this case, by forming each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer continuously under a vacuum, an organic electroluminescent element having more excellent characteristics can be manufactured.
When each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer is formed using a plurality of compounds by a vacuum deposition method, each boat containing the compounds is individually temperature-controlled and co-deposited. Is preferred.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin or the like are dissolved or dispersed in a solvent to form a coating liquid. Examples of the binder resin that can be used for each of the hole injection transport layer, the light emitting layer, and the electron injection transport layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, and the like.
Polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamide imide,
Polyparaxylene, polyethylene, polyethylene ether, polypropylene ether, polyphenylene oxide, polyether sulfone, polyaniline and its derivatives, polythiophene and its derivatives, polyphenylene vinylene and its derivatives, polyfluorene and its derivatives, polythienylene vinylene and its derivatives, etc. High molecular compounds are exemplified. The binder resin may be used alone or in combination.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin are combined with a suitable organic solvent (for example, hexane, octane,
Decane, toluene, xylene, ethylbenzene, hydrocarbon solvents such as 1-methylnaphthalene, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, for example, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, Halogenated hydrocarbon solvents such as tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, for example, ethyl acetate, butyl acetate, ester solvents such as amyl acetate, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, Alcohol solvents such as cyclohexanol, methyl cellosolve, ethyl cellosolve and ethylene glycol, for example, dibutyl ether, tetrahydrofuran, dioxane Down, ether solvents anisole, for example, N, N-dimethylformamide, N, N-
Dimethylacetamide, 1-methyl-2-pyrrolidone,
A polar solvent such as 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide) and / or dissolved or dispersed in water to form a coating solution, and a thin film can be formed by various coating methods. .

The method of dispersion is not particularly limited. For example, the particles can be dispersed into fine particles using a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like. The concentration of the coating solution is not particularly limited, and can be set to a concentration range suitable for producing a desired thickness by a coating method to be performed. Preferably, the solution concentration is about 1 to 30% by weight. When a binder resin is used, the amount of the binder resin used is not particularly limited. 5) to 99.9% by weight
Level, preferably about 10 to 99% by weight, more preferably about 15 to 90% by weight.

The thicknesses of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer are not particularly limited, but are generally preferably set to about 5 nm to 5 μm.
A protective layer (sealing layer) may be provided on the fabricated device for the purpose of preventing contact with oxygen, moisture, or the like, or the device may be formed of, for example, paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite, It can be protected by being enclosed in an inert substance such as a contained fluorocarbon oil. Examples of the material used for the protective layer include organic polymer materials (for example, fluorinated resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene) , Polyphenylene oxide), inorganic materials (for example, diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide,
Metal sulfide), furthermore, a photocurable resin, and the like. The material used for the protective layer may be used alone or in combination of two or more. The protective layer may have a single-layer structure or a multilayer structure.

Further, a metal oxide film (for example, an aluminum oxide film) or a metal fluoride film may be provided as a protective film on the electrode. Also, for example, on the surface of the anode,
For example, an interface layer (intermediate layer) made of an organic phosphorus compound, polysilane, an aromatic amine derivative, a phthalocyanine derivative (for example, copper phthalocyanine), or carbon can be provided. In addition, an electrode, for example, an anode,
For example, it can be used after being treated with an acid, ammonia / hydrogen peroxide, or plasma.

The organic electroluminescent device of the present invention is generally used as a DC-driven device, but can also be used as a pulse-driven or AC-driven device.
Incidentally, the applied voltage is generally about 2 to 30 V. The organic electroluminescent device of the present invention can be used for, for example, a panel light source, various light emitting devices, various display devices, various labels, various sensors, and the like.

[0074]

The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the scope of the present invention. Example 1 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, bis (2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum and the compound of Exemplified Compound No. A-1 were deposited thereon from different evaporation sources at a deposition rate of 0. .2 nm / sec
Co-deposition to a thickness of 50 nm (weight ratio 100: 0.5)
Thus, a light emitting layer was obtained. Next, tris (8-quinolinolato) aluminum is deposited at a deposition rate of 0.2 nm / sec.
It was deposited to a thickness of nm to form an electron injection transport layer. Further thereon, magnesium and silver were deposited at a deposition rate of 0.2 nm / se.
A co-evaporation (weight ratio 10: 1) was carried out to a thickness of 200 nm at c to obtain a cathode, thereby producing an organic electroluminescent device. In addition, evaporation is
The test was performed while maintaining the reduced pressure of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 55 mA / cm ² flowed. Red light emission with a luminance of 2470 cd / m ² was confirmed.

Examples 2 to 16 In Example 1, instead of using the compound of Exemplified Compound No. A-1 in forming the light emitting layer, the compound of Exemplified Compound No. A-3 (Example 2) and the Exemplified Compound No. A-5
(Example 3), the compound of Exemplified Compound No. A-8 (Example 4), the compound of Exemplified Compound No. A-10 (Example 5), the compound of Exemplified Compound No. A-16 (Example 6), Compound of Exemplified Compound No. A-20 (Example 7),
Compound of Exemplified Compound No. A-24 (Example 8), Compound of Exemplified Compound No. A-25 (Example 9), Compound of Exemplified Compound No. A-27 (Example 10), Exemplified Compound No. A
-32 (Example 11), Exemplified Compound No. B-1
(Example 12), compound of Exemplified Compound No. B-4 (Example 13), compound of Exemplified Compound No. C-1 (Example 14), compound of Exemplified Compound No. C-7 (Example 1)
5), Compound of Exemplified Compound No. C-10 (Example 16)
An organic electroluminescent device was produced by the method described in Example 1 except that was used. When a DC voltage of 12 V was applied to each device under a dry atmosphere, red light emission was confirmed. The characteristics were further examined, and the results are shown in Table 1 (Table 1).

Comparative Example 1 In Example 1, when forming the light emitting layer, the compound of Exemplified Compound No. A-1 was not used and bis (2-methyl-
An organic electroluminescent device was prepared by the method described in Example 1, except that only 8-quinolinolate) (4-phenylphenolate) aluminum was used to form a light emitting layer by vapor deposition to a thickness of 50 nm. 1
When a DC voltage of 2 V was applied, blue light emission was confirmed. The characteristics were further examined, and the results are shown in Table 1 (Table 1).

Comparative Example 2 In Example 1, when forming the light emitting layer, instead of using the compound of Exemplified Compound No. A-1, N-methyl-
An organic electroluminescent device was produced by the method described in Example 1 except that 2-methoxyacridone was used. When a DC voltage of 12 V was applied to this device under a dry atmosphere, blue light emission was confirmed. Further investigate its properties,
The results are shown in Table 1 (Table 1).

[0078]

[Table 1]

Example 17 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, bis (2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum and the compound of Exemplified Compound No. A-2 were deposited thereon from different evaporation sources at a deposition rate of 0. .2 nm / sec
Co-deposition to a thickness of 50 nm (weight ratio 100: 1.0)
Thus, a light emitting layer was obtained. Next, tris (8-quinolinolato) aluminum is deposited at a deposition rate of 0.2 nm / sec.
It was deposited to a thickness of nm to form an electron injection transport layer. Further thereon, magnesium and silver were deposited at a deposition rate of 0.2 nm / se.
A co-evaporation (weight ratio 10: 1) was carried out to a thickness of 200 nm at c to obtain a cathode, thereby producing an organic electroluminescent device. In addition, evaporation is
The test was performed while maintaining the reduced pressure of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 58 mA / cm ² flowed. Red light emission with a luminance of 2470 cd / m ² was confirmed.

Example 18 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, tris (8-quinolinolato) aluminum and the compound of Exemplified Compound No. A-4 were deposited thereon from different evaporation sources at an evaporation rate of 0.2.
Co-deposition to a thickness of 50 nm at nm / sec (weight ratio 100:
2.0) to form a light emitting layer. Next, tris (8-quinolinolate) aluminum was deposited at a deposition rate of 0.2 nm / sec.
Was deposited to a thickness of 50 nm to form an electron injection transport layer. Further, magnesium and silver were further deposited thereon at a deposition rate of 0.2 n.
Co-deposition at 200 m / sec to a thickness of 200 nm (weight ratio 10:
1) The resultant was used as a cathode to produce an organic electroluminescent device. still,
The vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 57 mA / cm ² flowed. Red light emission with a luminance of 2480 cd / m ² was confirmed.

Example 19 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, bis (2,4-dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate) aluminum and Exemplified Compound No. A- Compound 7 was co-deposited from different deposition sources at a deposition rate of 0.2 nm / sec to a thickness of 50 nm (weight ratio 100: 4.0),
It was a light emitting layer. Next, tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injection transport layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 60 mA / cm ² flowed. Brightness 25
Red light emission of ²⁰ cd / m ² was confirmed.

Example 20 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4 ′, 4 ″ -tris [N
-(3 "'-methylphenyl) -N-phenylamino]
Triphenylamine was deposited at a deposition rate of 0.1 nm / sec.
Evaporation was performed to a thickness of 0 nm to form a first hole injection transport layer. Then, 4,4'-bis [N-phenyl-N-
(3 "-Methylphenyl) amino] biphenyl was deposited at a deposition rate of 0.2 nm / sec to a thickness of 45 nm to form a second hole injecting and transporting layer.
-Quinolinolate) aluminum and exemplary compound number B-
Compound No. 2 was obtained from different deposition sources by a deposition rate of 0.2 nm.
/ Sec and co-evaporation to a thickness of 50 nm (weight ratio 100: 1.
0) to form a light emitting layer. Furthermore, Tris (8-
Quinolinolate) aluminum at a deposition rate of 0.2 nm
/ Sec at a thickness of 50 nm to form an electron injecting and transporting layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. The prepared organic electroluminescent device was dried under an atmosphere of 12
When a DC voltage of V was applied, a current of 58 mA / cm ² flowed. Red light emission with a luminance of 2,720 cd / m ² was confirmed.

Example 21 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, tris (8-quinolinolato) aluminum and the compound of Exemplified Compound No. C-4 were deposited thereon from different evaporation sources at a deposition rate of 0.2.
Co-deposition to a thickness of 50 nm at nm / sec (weight ratio 100:
4.0) to form a light-emitting layer also serving as an electron injection / transport layer. Further, magnesium and silver were further deposited thereon at a deposition rate of 0.2 n.
Co-deposition at 200 m / sec to a thickness of 200 nm (weight ratio 10:
1) The resultant was used as a cathode to produce an organic electroluminescent device. still,
The vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 14 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 52 mA / cm ² flowed. Red light emission with a luminance of 1860 cd / m ² was confirmed.

Example 22 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, tris (8-quinolinolate) aluminum and the compound of Exemplified Compound No. C-12 were deposited thereon from different evaporation sources at a deposition rate of 0.1 mm.
Co-deposition to a thickness of 50 nm at 2 nm / sec (weight ratio 10
0: 1.0) to obtain a light emitting layer. Then, on top of that,
1,3-bis [5 ′-(p-tert-butylphenyl)-
[1,3,4-oxadiazol-2'-yl] benzene was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injecting and transporting layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. In the manufactured organic electroluminescent element,
When a DC voltage of 14 V was applied in a dry atmosphere,
A current of 8 mA / cm ² flowed. Brightness 1920 cd / m
Red light emission of ² was confirmed.

Example 23 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, the compound of Exemplified Compound No. A-3 was further deposited thereon with a vapor deposition rate of 0.2 nm / sec.
Was deposited to a thickness of 50 nm to form a light emitting layer. Then, thereover, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4-oxadiazol-2′-yl]
Benzene was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injection transport layer. Further on that,
Magnesium and silver are deposited at a deposition rate of 0.2 nm / sec.
A cathode was formed by co-evaporation (weight ratio: 10: 1) to a thickness of 0 nm to produce an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 14 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 48 mA / cm ² flowed. Brightness 178
Red light emission of 0 cd / m ² was confirmed.

Example 24 A glass substrate having a 200 nm thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, the compound of Exemplified Compound No. A-25 was deposited on the ITO transparent electrode to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form a light emitting layer. Then, on top of that, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4
[Oxadiazol-2'-yl] benzene was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injecting and transporting layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 17 V was applied to the produced organic electroluminescent device in a dry atmosphere, the voltage was 50 mA /
cm ² of current flowed. Red light emission with a luminance of 1260 cd / m ² was confirmed.

Example 25 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4 ′, 4 ″ -tris [N
-(3 "'-methylphenyl) -N-phenylamino] triphenylamine at 50 nm at a deposition rate of 0.1 nm / sec.
m to form a first hole injection / transport layer. Then, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl and the compound of Exemplified Compound No. A-1 were deposited from different evaporation sources at an evaporation rate of 0.2 nm / sec.
And co-evaporated to a thickness of 20 nm (weight ratio 100: 5),
The light emitting layer also served as the second hole injection / transport layer. Next, tris (8-quinolinolate) aluminum was co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 50 nm (weight ratio: 100: 1.0) to form an electron injection transport layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. The prepared organic electroluminescent device was dried under a dry atmosphere for 15 minutes.
When a DC voltage of V was applied, a current of 65 mA / cm ² flowed. Red light emission with a luminance of 2960 cd / m ² was confirmed.

Examples 26 to 32 In Example 25, instead of using the compound of Exemplified Compound No. A-1, the compound of Exemplified Compound No. A-2 (Example 26) and the compound of Exemplified Compound No. A-7 (Example 26) Example 2
7), Compound of Exemplified Compound No. A-10 (Example 2)
8), Compound of Exemplified Compound No. A-19 (Example 2)
9), Compound of Exemplified Compound No. A-22 (Example 3)
0), compound of Exemplified Compound No. C-7 (Example 31),
An organic electroluminescent device was produced by the method described in Example 25 except that the compound of Exemplified Compound No. C-10 (Example 32) was used. For each element, under dry atmosphere,
When a DC voltage of 12 V was applied, red light emission was confirmed. The characteristics were further examined, and the results are shown in Table 2 (Table 2).
It was shown to.

[0089]

[Table 2]

Example 33 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, poly-N-vinylcarbazole (weight average molecular weight 1
50,000), 1,1,4,4-tetraphenyl-1,
3-butadiene (blue light-emitting component), coumarin 6 ["3
-(2'-benzothiazolyl) -7-diethylaminocoumarin "(green light-emitting component)] and the compound of Exemplified Compound No. A-13 at a weight ratio of 100: 5: 3:
A light emitting layer having a thickness of 400 nm was formed by dip coating using a 3% by weight dichloroethane solution containing 2 parts by weight. Next, after fixing the glass substrate having the light-emitting layer to the substrate holder of the vapor deposition apparatus, the vapor deposition tank is
The pressure was reduced to × 10 ⁻⁶ Torr. Further, on the light emitting layer,
(4′-tert-butylphenyl) -4-phenyl-5
After depositing-(4 "-biphenyl) -1,2,4-triazole at a deposition rate of 0.2 nm / sec to a thickness of 20 nm, tris (8-quinolinolate) aluminum is further deposited thereon. 30 at 0.2 nm / sec
An electron injecting and transporting layer was formed by vapor deposition to a thickness of nm. Further, magnesium and silver are further deposited thereon at a deposition rate of 0.2 nm / sec.
Then, co-evaporation (weight ratio: 10: 1) was performed to a thickness of 200 nm to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 74 mA / cm ² flowed. Brightness 1
White light emission of 370 cd / m ² was confirmed.

Examples 34 to 38 In Example 33, instead of using the compound of Exemplified Compound No. A-13, the compound of Exemplified Compound No. A-15 (Example 34), the compound of Exemplified Compound No. A-26 ( Example 35), Compound of Exemplified Compound No. A-28 (Example 36), Compound of Exemplified Compound No. A-30 (Example 37), and Compound of Exemplified Compound No. C-16 (Example 38) Used An organic electroluminescent device was manufactured by the method described in Example 33 except that the method was performed. When a DC voltage of 12 V was applied to each element under a dry atmosphere, white light emission was confirmed. The characteristics were further examined and the results
The results are shown in Table (Table 3).

[0092]

[Table 3]

Example 39 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, poly-N-vinylcarbazole (weight average molecular weight 1
50000), 1,3-bis [5 '-(p-tert-butylphenyl) -1,3,4-oxadiazole-2'-
Il] benzene and a compound of Exemplified Compound No. A-29 in a 3 wt% dichloroethane solution containing 100: 30: 1 by weight, respectively, to form a light emitting layer having a thickness of 300 nm by dip coating. did. Next, after fixing the glass substrate having the light emitting layer to a substrate holder of a vapor deposition device, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Further, on the light emitting layer, magnesium and silver were co-deposited (weight ratio: 10: 1) to a thickness of 200 nm at a deposition rate of 0.2 nm / sec to form an organic electroluminescent device. When a DC voltage of 15 V was applied to the produced organic electroluminescent device under a dry atmosphere, the voltage was 76 mA / c.
m ² of current flowed. Red light emission with a luminance of 1360 cd / m ² was confirmed.

Comparative Example 3 In Example 39, when forming the light emitting layer, instead of using the compound of Exemplified Compound No. A-29, 1,1,1,
Except for using 4,4-tetraphenylbutadiene,
An organic electroluminescent device was manufactured by the method described in Example 39. In a dry atmosphere, add 1
When a DC voltage of 5 V was applied, a current of 86 mA / cm ² flowed. Blue light emission with a luminance of 680 cd / m ² was confirmed.

Example 40 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, polycarbonate (weight average molecular weight: 50,000),
4,4′-Bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl, tris (8-quinolinolate) aluminum and the compound of Exemplified Compound No. A-30 were each in a weight ratio of 100: 40: 60. A light emitting layer having a thickness of 300 nm was formed by a dip coating method using a 3% by weight dichloroethane solution containing at a ratio of 1: 1. Then, the glass substrate having the light emitting layer was placed on a substrate holder of a vapor deposition apparatus. After fixing, set the vapor deposition tank to 3 × 10 ^-6 To
The pressure was reduced to rr. Further, on the light emitting layer, magnesium and silver were co-deposited (weight ratio: 10: 1) to a thickness of 200 nm at a deposition rate of 0.2 nm / sec to form an organic electroluminescent device. When a DC voltage of 15 V was applied to the produced organic electroluminescent device under a dry atmosphere, 66 mA was obtained.
/ Cm ² flowed. Red light emission with a luminance of 770 cd / m ² was confirmed.

[0096]

According to the present invention, it has become possible to provide an organic electroluminescent device having excellent light emission luminance.

[Brief description of the drawings]

FIG. 1 is a schematic structural view of an example (A) of an organic electroluminescent element.

FIG. 2 is a schematic structural diagram of an example (B) of an organic electroluminescent element.

FIG. 3 is a schematic structural view of an example (C) of an organic electroluminescent element.

FIG. 4 is a schematic structural diagram of an example (D) of an organic electroluminescent element.

FIG. 5 is a schematic structural diagram of an example (E) of an organic electroluminescent element.

FIG. 6 is a schematic structural diagram of an example (F) of an organic electroluminescent element.

FIG. 7 is a schematic structural diagram of an example (G) of an organic electroluminescent element.

FIG. 8 is a schematic structural view of an example (H) of an organic electroluminescent element.

[Explanation of symbols]

 Reference Signs List 1 substrate 2 anode 3 hole injection / transport layer 3a hole injection / transport component 4 light emitting layer 4a light emitting component 5 electron injection / transport layer 5 ″ electron injection / transport layer 5a electron injection / transport component 6 cathode 7 power supply

Claims (7)

[Claims] A bisnaphtho [1 ', 8': 5,5,5]
6,7] -s-indaceno [1,2,3-cd: 1 ', 2', 3'-c'd '] benzo [1,
An organic electroluminescent element comprising at least one layer containing at least one kind of [2-k: 4,5-k '] difluoranthene derivative. 2. Bisnaphtho [1 ', 8': 5,6,7] -s-indaceno
A layer containing at least one [1,2,3-cd: 1 ', 2', 3'-c'd '] benzo [1,2-k: 4,5-k'] difluoranthene derivative The organic electroluminescent device according to claim 1, which is a light emitting layer. 3. Bisnaphtho [1 ', 8': 5,6,7] -s-indaceno
A layer containing at least one [1,2,3-cd: 1 ', 2', 3'-c'd '] benzo [1,2-k: 4,5-k'] difluoranthene derivative The organic electroluminescent device according to claim 1, further comprising a luminescent organic metal complex. 4. Bisnaphtho [1 ', 8': 5,6,7] -s-indaceno
A layer containing at least one [1,2,3-cd: 1 ', 2', 3'-c'd '] benzo [1,2-k: 4,5-k'] difluoranthene derivative The organic electroluminescent device according to claim 1, further comprising a triarylamine derivative. 5. The organic electroluminescent device according to claim 1, further comprising a hole injection transport layer between the pair of electrodes. 6. The organic electroluminescent device according to claim 1, further comprising an electron injection / transport layer between the pair of electrodes. 7. Bisnaphtho [1 ′, 8 ′: 5,6,7] -s-indaceno
[1,2,3-cd: 1 ′, 2 ′, 3′-c′d ′] benzo [1,2-k: 4,5-k ′] difluoranthene derivative is represented by the general formula (1-A) The organic electroluminescent device according to any one of claims 1 to 6, which is a compound represented by the following formula (1). Embedded image (Wherein X _{1 to} X ₃₀ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group or a substituted or unsubstituted aryl group; X ₇ and X ₂₄ , and X ₉ and X _{22 which} are mutually adjacent groups selected from _{1 to} X ₃₀ are bonded to each other to form a substituted or unsubstituted carbocyclic aliphatic ring together with a substituted carbon atom. (It may be formed.)