JP2918150B2 - Organic electroluminescent device using silacyclopentadiene derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electroluminescence (EL).
More particularly, the present invention relates to an EL device using a silacyclopentadiene derivative.

[0002]

2. Description of the Related Art In recent years, an organic EL element has been attracting attention as a candidate for a flat display with high luminance, and research and development thereof have been actively conducted. The organic EL element has a structure in which an organic light emitting layer is sandwiched between two electrodes, and holes injected from an anode and electrons injected from a cathode are recombined in the light emitting layer to emit light. The organic materials used include a low molecular weight material and a high molecular weight material, and both indicate that a high-luminance EL element can be formed. There are two types of such organic EL elements. One is tan (CW Tan).
g) in which a fluorescent dye disclosed in J. Appl. Phys. (J. Appl. Phys.), 65, 3610 (19)
89)), and the other uses a fluorescent dye alone (for example, Japanese Journal of Diapride Physics (Jpn. J. Appl. Phys.)).
s. ), 27, L269 (1988)). In the latter device, the luminous efficiency is improved when the fluorescent dye is laminated with a hole transport layer that transports only holes, which are one of the charges, and / or an electron transport layer that transports only electrons. It is shown. As the hole transporting material used in the organic EL device, although a variety of materials centering on triphenylamine derivatives are known, there are few electron transporting materials. In addition, existing electron transporting materials include existing hole transporting materials, for example, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-.
The charge transporting ability was lower than that of diaminobiphenyl (TPD), and when used in an organic EL device, the performance was limited by the electron transporting material used, and sufficient device characteristics could not be obtained. As a specific example of such an electron transport material, a metal complex of an oxine derivative (JP-A-59-1943)
93), 2- (4-biphenylyl)
-5- (4-tert-butylphenyl) -1,3,4
-Oxadiazole (PBD) and the like are known. The former can drive the organic EL element at a relatively low voltage, but is not yet sufficient, and it is difficult to obtain blue light emission because its own light emission is green. As an example in which the latter is used as an electron transporting layer, the above-mentioned organic EL device (Jpn. J. Appl. Phys., 27, L269) is used.
(1988)). However, it has been pointed out that the stability of the thin film is poor, for example, crystallization is likely to occur, and a compound having a plurality of oxadiazole rings has been developed (Journal of the Chemical Society of Japan, 11, 1540 (1991), JP-A-6-1456).
58, JP-A-6-92947, JP-A-5-15207
2, JP-A-5-202011, JP-A-6-136359
Etc.). However, these also did not have practically sufficient properties such as a high driving voltage. As another compound system, a quinoxaline derivative has been reported (JP-A-6-207169). Although the dimerization increases the molecular weight and improves the stability of the thin film, the driving voltage is too high in these cases and is not sufficient for practical use. The characteristics of the electron transporting material used in the organic EL device must be, first and foremost, excellent in the electron transporting ability, and it is expected that the efficiency of the organic EL device will be improved by using a material having an excellent electron transporting ability. Is done. On the other hand, a recent report of a silacyclopentadiene derivative is disclosed in Japanese Patent Application Laid-Open (JP-A) No. 7-179777. The present invention relates to a reactive intermediate intended for application to a π-electron conjugated organic polymer. And different. Examples of copolymers with thiophene are also disclosed in JP-A-6-166746, but these compounds have long absorption and emission wavelengths and are unsuitable as electron transport materials for organic EL devices. Examples of using a silane derivative in an organic EL device are disclosed in JP-A-5-343184 and JP-A-6-124.
784, JP-A-6-234968, JP-A-6-2937
78, JP-A-6-325871, JP-A-7-11244
However, the organic silane compound shown here does not contain a silacyclopentadiene ring, has no description of the electron transporting property, and the examples actually used are the same as the hole transporting material or the light emitting layer. This is used as an interface layer for improving the adhesion to the cathode, and is not described at all as an electron transport material.

[0003]

Accordingly, as a result of diligent studies to solve this problem and to find an organic EL device having a low voltage and a high luminous efficiency, when the silacyclopentadiene derivative is used for the organic EL device, the above problem is solved. The inventors have found that the points are solved and completed the present invention.

[0004]

The present invention provides the following (1):
It has each configuration of (2), (3), (4) and (5).

(1) An electroluminescent device using a silacyclopentadiene derivative represented by the general formula [4].

Embedded image (Wherein, X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group,
An alkenyloxy group, an alkynyloxy group, a hydroxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle, or a structure in which X and Y are combined to form a saturated ring, and R _{1 to} R ₄ are Each independently represents hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group , An alkoxycarbonyl group, an aryloxycarbonyl group,
Azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group, heterocyclic group, alkenyl group, nitro Group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group or cyano group. )

(2) An electroluminescent device comprising at least one of the silacyclopentadiene derivatives described in (1) above as a component of a charge transport layer.

(3) An electroluminescent device comprising at least one of the silacyclopentadiene derivatives described in (1) above as a component of a light emitting layer.

(4) An electroluminescent device characterized in that at least one of the silacyclopentadiene derivatives represented by the general formula [Chemical Formula 5] is used as a component of a hole blocking layer.

[0009]

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(Wherein X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, a substituted or unsubstituted Aryl group,
A substituted or unsubstituted heterocyclic ring or a structure in which X and Y are combined to form a saturated or unsaturated ring, and R _{1 to} R
₄ is each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, aryl Carbonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group, heterocyclic group An alkenyl group, an alkynyl group, a nitro group, a formyl group, a nitroso group, a formyloxy group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group or a cyano group or, if adjacent, a substituted or unsubstituted ring. It has a ring-fused structure. )

(5) An electroluminescent device characterized by using a silacyclopentadiene derivative represented by the general formula [6] as a component of a hole blocking layer.

[0012]

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(Wherein X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a substituted or unsubstituted aryl group, A substituted or unsubstituted heterocyclic ring, wherein R _{1 to} R ₈ each independently represent hydrogen, halogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, an amino group, Nitro group, alkylcarbonyl group, alkoxycarbonyl group, formyl group, nitroso group, azo group, alkylcarbonyloxy group, alkoxycarbonyloxy group, formyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, isocyano group, carbamoyl Group, cyanate group, isocyanate group, thiocyane DOO group, isothiocyanate group, an aryl group, an alkenyl group, ring substituted or unsubstituted in the case of an alkynyl group or a cyano group, or adjacent may be condensed.)

The present invention will be described in detail below. Examples of the silacyclopentadiene derivative used in the present invention include the following. 1,1-dimethyl-2,3,4,5-tetraphenylsilacyclopentadiene 1,1-diethyl-2,3,4,5-tetrakis (2-
Methylphenyl) silacyclopentadiene 1,1-diisopropyl-2,3,4,5-tetrakis (3-methylphenyl) silacyclopentadiene 1-ethyl-1-methyl-2,3,4,5-tetrakis (4- Methylphenyl) silacyclopentadiene 1,1-ditert-butyl-2,3,4,5-tetrakis (2-ethylphenyl) silacyclopentadiene 1,1-diphenyl-2,3,4,5-tetrakis (3
-Ethylphenyl) silacyclopentadiene 1-methyl-1-phenyl-2,3,4,5-tetrakis (4-ethylphenyl) silacyclopentadiene 1-phenyl-1-tert-butyl-2,3,4
5-tetrakis (3-tert-butylphenyl) silacyclopentadiene 1,1-dimethyl-2,5-bis (3-methylphenyl) -3,4-diphenylsilacyclopentadiene 1,1-di (4-toluyl) -2,5-bis (4-methylphenyl) -3,4-diphenylsilacyclopentadiene 1-silacyclohexane-1-spiro-2 ', 5'-di (2-biphenyl) -3', 4'-diphenyl -1'-
Silacyclopentadiene 1-silacyclopentane-1-spiro-2 ', 5'-di (3-biphenyl) -3', 4'-diphenyl-1'-
Silacyclopentadiene 9-silafluorene-9-spiro-2 ′, 5′-di (4
-Biphenyl) -3 ', 4'-diphenyl-1'-silacyclopentadiene 1,1-dimethyl-2,5-bis (2-trifluoromethylphenyl) -3,4-diphenylsilacyclopentadiene 1,1- Dimethyl-2,5-bis (3-fluorophenyl) -3,4-diphenylsilacyclopentadiene 1,2-bis (1-methyl-2,5-bis (3-methoxyphenyl) -3,4-diphenylsila Cyclopentadienyl) ethane 1,1-dimethyl-2,5-bis (4-cyanophenyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis {2- (2-benzo Oxazolyl) phenyl {-3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis {3- (2-benzothienyl) phenyl} -3, -Diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis {4- (2-benzofuryl) phenyl} -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis {2- ( 2-benzothiazolyl) phenyl {-3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis {3- (2-benzimidazolyl) phenyl} -3,4-diphenylsilacyclopentadiene 1,1-dimethyl -2,5-bis {4- (2-indolyl) phenyl} -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis {3- (5-methoxy-2-benzothiazolyl) phenyl} -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-di (1-naphthyl) -3,
4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-di (2-methyl-1-naphthyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethoxy-2,5-di (2-naphthyl )-
3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-di (2-benzothienyl)
-3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis (3-methyl-2-benzothienyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis (3-phenyl-2-
Benzothienyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis (2-methyl-3-benzothienyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2, 5-di (2-benzothiazolyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-di (2-benzoxazolyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl -2,5-bis (5-methyl-2-benzooxazolyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis (5-phenyl-2-
Benzothiadiazolyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-di (3-benzofuranyl)
-3,4-Diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis (3,4-difluorophenyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis (3 , 4,5-trifluorophenyl) -3,4-diphenylsilacyclopentadiene 1,1-dimethyl-2,5-bis (2,3,4,5,6
-Pentafluorophenyl) -3,4-diphenylsilacyclopentadiene 5,5'-dibromo-1,1,1 ', 1'-tetraethyl-3,3', 4,4'-tetraphenyl-2,2 ' −
Bisilol 5,5'-dimethyl-1,1,1 ', 1'-tetraethyl-3,3', 4,4'-tetraphenyl-2,2'-
Bicirol 5,5 '''-dibromo-1,1,1', 1 ',
1 '', 1 '', 1 ''',1'''-octaethyl-
3,3 ', 3'',3''', 4,4 ', 4'',
4 ″ ′-octaphenyl-2,2 ′: 5 ′, 2 ″:
5 ″, 2 ′ ″-quartersilole 9,9′-silaspiro-bifluorene 9,9-diphenyl-9-silafluorene 9,9-dinaphthyl-9-silafluorene

Compound represented by the following formula (TTSTT)

[0016]

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Compound represented by the following formula:

[0018]

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The silacyclopentadiene derivative used in the present invention can be obtained, for example, by the following production method. That is, the general formula [Formula 9]

[0020]

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(Wherein X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a substituted or unsubstituted aryl group, Represents a substituted or unsubstituted hetero ring, or X and Y are combined to form a saturated or unsaturated ring, and R ₁ and R ₂ are
Each independently hydrogen, halogen, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group, Alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group , Heterocyclic group, alkenyl group, alkynyl group, nitro group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group Or a cyano group, a substituted or unsubstituted ring may be condensed. ) Is reacted with an alkali metal complex, followed by the general formula [Chemical Formula 10].

[0022]

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(Wherein, X, Y and Z each independently represent a tertiary-butyl group or an aryl group). By reacting, the compound represented by the general formula [Formula 11]

[0024]

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Wherein A represents a zinc halide or a zinc halide complex, and X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group. A group, an alkynyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle, or X and Y are combined to form a saturated or unsaturated ring, and R ₁ and R ₂ are Each independently represents hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group , Alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbo Ruoxy, alkoxydicarbonyloxy, aryloxycarbonyloxy, sulfinyl, sulfonyl, sulfanyl, silyl, carbamoyl, aryl, heterocyclic, alkenyl, alkynyl, nitro, formyl, nitroso Group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group or cyano group, or a substituted or unsubstituted ring may be condensed.) A pentadiene derivative is obtained.

As the substituent attached to the acetylene derivative used herein, a substituent which does not easily inhibit the reaction between the alkali metal complex and acetylene is preferable, and particularly preferably a substituent which is inactive with respect to the alkali metal complex. As the alkali metal complex used, for example, lithium naphthalenide, sodium naphthalenide, potassium naphthalenide, lithium 4,4′-ditert-butyl-2,
2'-biphenylide or lithium (N, N-dimethylamino) naphthalenide. The solvent to be used is not particularly limited as long as it is inert to an alkali metal or an alkali metal complex, and usually an ether-based solvent such as ether or tetrahydrofuran is used. As the substituent of the silane derivative to be subsequently used, a bulky one is preferable, and specific examples thereof include tertiary-butyldiphenylchlorosilane and ditertiary-butylphenylchlorosilane. Examples of the zinc chloride or zinc chloride complex to be used subsequently include a solid zinc chloride directly used, a zinc chloride ether solution, and a zinc chloride tetramethylethylenediamine complex. It is preferable that these zinc chlorides are sufficiently dried, and if the amount of water is large, it is difficult to obtain a target product. This series of reactions is preferably performed in an inert gas stream, and argon gas is used. The reactive silacyclopentadiene derivative thus obtained is added to the general formula [Formula 12] in the presence of a catalyst.

[0027]

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(Wherein, X represents chlorine, bromine or iodine, and R is a halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group, an alkylcarbonyl group, an arylcarbonyl group. An alkoxycarbonyl group, an aryloxycarbonyl group, a sulfinyl group, a sulfonyl group, a sulfanyl group, a silyl group,
Represents an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group. By reacting the halide represented by the formula (1), the silacyclopentadiene derivative used in the present invention can be obtained.

The catalyst used here includes a palladium catalyst such as tetrakistriphenylphosphinepalladium or dichlorobistriphenylphosphinepalladium. In each stage of the first-speed reaction, the reaction temperature is not particularly limited, but an alkali metal complex,
When the silane derivative, zinc chloride and the like are added and stirred, the temperature is preferably room temperature or lower, and is usually performed at 0 ° C. or lower. The reaction temperature after the addition of the halide is preferably room temperature or higher. In general, when tetrahydrofuran is used as a solvent, the reaction is carried out under reflux. The reaction time is not particularly limited. When adding the alkali metal complex, the silane derivative, zinc chloride and the like and stirring the mixture, it is desirable that the reaction time is between a few minutes and several hours. The reaction after the addition of the halide may be followed by a general analytical means such as NMR or chromatography to determine the end point of the reaction.

When a benzene ring is condensed with a silacyclopentadiene ring in the compound used in the present invention, a method different from the above-mentioned production method is used. There is no particular limitation as long as it is a known method known so far, and for example, the following method is available. That is, the general formula [Formula 1]
3]

[0031]

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Wherein X represents chlorine, bromine or iodine, and R ₁ to R ₈ each independently represent a saturated or unsaturated hydrocarbon group, alkoxy group, or alkenyloxy group having 1 to 6 carbon atoms. Alkynyloxy group, fluorine, hydrogen, substituted or unsubstituted aryl group, substituted or unsubstituted heterocycle, cyano group, and when adjacent, a saturated or unsaturated ring is formed.) An alkali metal, an alkaline earth metal or an alkali metal complex is allowed to act on the 2,2′-dihalogenobiphenyl derivative represented by the general formula [Chemical Formula 14].

[0033]

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(Wherein X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a substituted or unsubstituted aryl group, Which represents a substituted or unsubstituted heterocyclic ring, or X and Y are combined to form a saturated or unsaturated ring.) A cyclopentadiene derivative can be obtained.

The metal used here includes lithium, sodium, magnesium or potassium, and the metal complex includes normal butyl lithium,
Tertiary butyl lithium, phenyl lithium and the like. The substituent of the 2,2'-dihalogenobiphenyl derivative to be used is not particularly limited as long as it is inert to the alkali metal, alkaline earth metal or alkali metal complex under the reaction conditions. There is no particular limitation on the reaction temperature when the alkali metal, alkaline earth metal or alkali metal complex is allowed to act, and the reaction is usually performed at 0 ° C. or lower. However, when a substituent such as a cyano group having high reactivity is present, a low temperature is preferable, and the reaction is usually performed at -70 ° C or lower. The reaction solvent used is not particularly limited as long as it is inert to an alkali metal, an alkaline earth metal or an alkali metal complex.
An ether solvent such as ether or tetrahydrofuran is used.

Substituents on silicon of the silacyclopentadiene derivative used in the present invention thus obtained include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a cyclopentyl group and a tertiary-butyl group. An alkenyl group such as an alkyl group, a vinyl group, an allyl group, a butenyl group or a styryl group, an alkynyl group such as an ethynyl group, a propargyl group or a phenylacetylinyl group, a methoxy group, an ethoxy group, an isopropoxy group or a tertiary group; An alkoxy group such as butoxy group, an alkenyloxy group such as vinyloxy group or allyloxy group, an alkynyloxy group such as ethynyloxy group or phenylacetyloxy group, a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, Ruyl, pyrenyl, perylenyl, anisyl, aryl such as terphenyl or phenanthrenyl, hydrofuryl, hydropyrenyl, dioxanyl, thienyl, furyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, Examples include heterocycles such as an acridinyl group, a quinolyl group, a quinoxaloyl group, a phenanthrolyl group, a benzothienyl group, a benzothiazolyl group, an indolyl group, a silacyclopentadienyl group, and a pyridyl group. Further, these substituents may be bonded to each other at an arbitrary position to form a spiro ring.

Examples of the substituent on the carbon of the silacyclopentadiene ring include halogen such as hydrogen, fluorine and chlorine, methyl, ethyl, normal propyl, isopropyl, cyclopentyl and tert-butyl. Alkenyl group such as alkyl group, vinyl group, allyl group, butenyl group or styryl group, alkynyl group such as ethynyl group, propargyl group or phenylacetylinyl group, methoxy group, ethoxy group, isopropoxy group or tert-butoxy group An alkenyloxy group such as an alkoxy group, a vinyloxy group or an allyloxy group, an alkynyloxy group such as an ethynyloxy group or a phenylacetyloxy group, a phenoxy group, a naphthoxy group, a biphenyloxy group or a pyrenyloxy group. Aryloxy groups such as shea group,
Perfluoro groups such as trifluoromethyl, trifluoromethoxy or pentafluoroethoxy groups,
Amino group such as dimethylamino group, diethylamino group or diphenylamino group, ketone such as acetyl group or benzoyl group, ester group such as acetoxy group or benzoyloxy group, methoxycarbonyl group, ethoxycarbonyl group or phenoxycarbonyl group. Ester group, sulfinyl group such as methylsulfinyl group or phenylsulfinyl group, silyl group such as trimethylsilyl group, dimethyltert-butylsilyl group, trimethoxysilyl group or triphenylsilyl group, phenyl group, biphenyl group, Phenyl, naphthyl, anthracenyl, pyrenyl, toluyl, anisyl, fluorophenyl, diphenylaminophenyl, dimethylaminophenyl, diethylamino Aryl group such as phenyl or phenanthrenyl, thienyl, furyl, silacyclopentadienyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, acridinyl, quinolyl, quinoxaloyl, phenanthrolyl, benzothienyl Group, benzothiazolyl group, indolyl group, carbazolyl group, pyridyl group, pyrrolyl group,
A benzoxazolyl group, a heterocycle such as a pyrimidyl group or an imidazolyl group, a nitro group, a formyl group, a nitroso group, a formyloxy group, an isocyano group, a cyanate group,
Examples include an isocyanate group, a thiocyanate group, an isothiocyanate group, and a cyano group. Further, these substituents may be bonded to each other at any position to form a ring.

These substituents may be introduced before the formation of the silacyclopentadiene ring or after the formation of the silacyclopentadiene ring. The silacyclopentadiene derivative used in the organic EL device of the present invention was found to be effective as an electron transporting material. Avignio calculations revealed that the silacyclopentadiene ring has a structure in which the lowest unoccupied molecular orbital is low and electrons are easily received as compared with the corresponding cyclopentadiene ring, thiophene ring, pyrrole ring or furan ring. This was found to be due to the interaction between the π ^* orbital of the diene portion and the σ ^* orbital of silicon. However, for this reason alone, it cannot be determined whether or not it is excellent as an electron transporting material for an organic EL device. It is considered that the structure of the silacyclopentadiene ring also has an effect on the electron transport property. Further, it was found that the compound of the present invention was superior to the organic silane compound disclosed in JP-A-6-325871 as an electron transporting material for an organic EL device. This is considered to be largely affected by the introduction of the silacyclopentadiene ring. Further, these silacyclopentadiene derivatives themselves exhibit strong fluorescence and are therefore useful as a light emitting material of an EL device. For example, 1,
1-dimethyl-2,5-bis (3-fluorophenyl)
-3,4-diphenylsilacyclopentadiene emits blue light, 1,1-dimethyl-2,5-bis (3-methylphenyl) -3,4-diphenylsilacyclopentadiene emits green light, and TTSTT emits red light. Emit light.

The EL device of the present invention has various configurations. Basically, the configuration is such that the silacyclopentadiene derivative is sandwiched between a pair of electrodes (anode and cathode).
If necessary, a hole transporting material, a light emitting material, and an electron transporting material may be added or stacked as another layer.
Specific examples include anode / silacyclopentadiene derivative layer / cathode, anode / hole transport layer / silacyclopentadiene derivative layer / cathode, anode / hole transport layer / emission layer / silacyclopentadiene derivative layer / cathode, anode / Hole transport material +
Light-emitting material + silacyclopentadiene derivative layer / cathode.

As another special use of the silacyclopentadiene derivative, there is an application to a hole blocking material. The hole blocking material is a material that transports only electrons among two charges of electrons and holes, and does not transmit or hardly transmits holes. Since the silacyclopentadiene derivative used in the present invention transports electrons preferentially or selectively, another specific example of the organic EL device of the present invention is an anode / electrode.
Hole transport layer / silacyclopentadiene derivative layer / electron transport layer / cathode. In this case, the light is emitted
It becomes a hole transport layer or a silacyclopentadiene derivative layer. In particular, as the silacyclopentadiene derivative exhibiting such a hole blocking effect, one having a short emission wavelength can be mentioned. For example, 9,9′-silaspirobifluorene and the like can be mentioned. In a device using 9,9′-silaspirospirobifluorene as a hole blocking layer, TPD as a hole transporting layer, and 8-hydroxyquinoline aluminum (Alq) as an electron transporting layer, the light emission of TPD is Only a purple color derived from light emission is observed, and it has very excellent hole blocking ability. As a device that emits light from the TPD as described above, there is a device using a triazole derivative by Kido et al., However, it is not perfect (Science, 267,
1332 (1995)). As a more specific example, the silacyclopentadiene derivative layer used in the present invention can be used as a light emitting layer or an electron transporting light emitting layer. In this case, the structure of the device includes an anode / hole transport layer / (silacyclopentadiene derivative + electron transport material) layer / cathode.

The device of the present invention is preferably supported on a substrate. The substrate is not particularly limited, and those conventionally used in EL devices, for example, glass, transparent plastic, and conductive materials A material made of a polymer, quartz, or the like can be used. Each layer used in the present invention can be formed by thinning by a known method such as a vapor deposition method and a coating method. The thickness of the thin film of each layer formed in this manner is not particularly limited and can be appropriately selected according to the situation, but is usually selected in the range of 2 nm to 5000 nm.

As the anode in the EL device of the present invention,
A metal, an alloy, an electrically conductive compound, or a mixture thereof having a large work function (4 eV or more) as an electrode material is preferably used. Specific examples of such an electrode material include metals such as Au, CuI, ITO, SnO ₂ , and ZnO.
And other transparent dielectric materials. The anode is a method of depositing or sputtering these electrode materials.
It can be manufactured by forming a thin film. When light is extracted from this electrode, the transmittance is desirably greater than 10%, and the sheet resistance of the electrode is preferably several hundreds Ω / square or less. Further, the film thickness depends on the material, but is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

On the other hand, as the cathode, a metal, an alloy, an electrically conductive compound or a mixture thereof having a low work function (4.3 eV or less) and an electrode material thereof is used. Specific examples of such electrode materials include calcium, magnesium, lithium, aluminum, magnesium alloy, lithium alloy, aluminum alloy, aluminum /
Lithium mixtures, magnesium / silver mixtures, indium and the like. The cathode can be manufactured by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. Further, the sheet resistance as an electrode is preferably several hundred Ω / square or less,
The film thickness is usually 10 nm to 1 μm, preferably 50 to 2 μm.
It is selected in the range of 00 nm.

The structure of the EL device of the present invention has various modes as described above, but the provision of the hole transport layer improves the luminous efficiency. As a hole transporting material used for the hole transporting layer, when a hole is injected from an anode placed between two electrodes to which an electric field is applied, the hole can be appropriately transmitted to the light emitting layer. A compound, for example, 10 ⁴ to 10 ⁶ V /
When an electric field of 10 cm is applied, at least 10 ⁻⁶ cm ² / V ·
Those having a hole mobility of seconds or more are preferred. There is no particular limitation on such a hole transporting material as long as it has the above-mentioned preferable properties. Conventionally, a photoconductive material commonly used as a hole charge transporting material or EL is used.
Any known materials used in the hole transport layer of the device can be selected and used.

Examples of the hole transport material include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.) and triarylamine derivatives (TP
D, a polymer having an aromatic tertiary amine in the main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N ′
-Dinaphthyl-4,4'-diaminobiphenyl),
Examples include phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), polysilanes, and the like. When a plurality of electron transporting materials are used in the layer for transporting electrons in the EL element of the present invention, not only the silacyclopentadiene derivative but also other electron transporting materials may be used. There is no particular limitation on such an electron transporting material, and any one of conventionally known compounds can be selected and used. Preferred examples of the electron transport material include:

[0046]

Embedded image

Diphenylquinone derivatives such as those described in Journal of the Electrographic Society of Japan, 30, 3 (1991), etc., or

[0048]

Embedded image

Embedded image

Compounds such as (J. Apply.
s. , 27, 269 (1988), etc.)
And oxadiazole derivatives (Jpn.
Appl. Phys. , 27, L713 (1988),
Applied Physics Letter (Appl. Phys.
Lett. ), 55, 1489 (1989)), thiophene derivatives (JP-A-4-212286).
And triazole derivatives (Jp
n. J. Appl. Phys. , 32, L917 (19
93)), thiadiazole derivatives (the 43rd Proceedings of the Society of Polymer Science, III P1a007, etc.), and metal complexes of oxine derivatives (IEICE Technical Report, 92 (311), 43). (199
2)) and polymers of quinoxaline derivatives (Jpn. J. Appl. Phys., 33, L25).
0 (1994)) and phenanthroline derivatives (described in the 43rd Polymer Symposium Proceedings, 14J07).

The light-emitting material used in the present invention includes a daylight fluorescent material and a fluorescent brightening agent as described in “Polyfunctional Material”, edited by the Society of Polymer Science, “Optical Functional Material”, Kyoritsu Shuppan (1991), page 236. Known light-emitting materials such as laser dyes, organic scintillators, and various fluorescent analysis reagents can be used. Specifically, polycyclic condensation such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene, and quinacridone can be used. Compounds, oligophenylene compounds such as quarterphenyl, 1,4-bis (2-methylstyryl) benzene, 1,4-bis (4
-Methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1,
4-bis (5-phenyl-2-oxazolyl) benzene, 2,5-bis (5-tert-butyl-2-benzoxazolyl) thiophene, 1,4-diphenyl-
1,3-butadiene, 1,6-diphenyl-1,3,5
-Hexatriene, 1,1,4,4-tetraphenyl-
Scintillators for liquid scintillation such as 1,3-butadiene, metal complexes of oxine derivatives described in JP-A-63-264892, coumarin dyes, dicyanomethylenepyran dyes, dicyanomethylenethiopyran dyes, polymethine dyes, oxobenzanthracene dyes, Xanthene dyes, carbostyril dyes and perylene dyes, oxazine-based compounds described in DE 2534713,
Proceedings of the 40th Lecture Meeting on Applied Physics, 114
6 (1993) and oxadiazole-based compounds described in JP-A-4-363891. Further, the silacyclopentadiene derivative described in the present invention may be used.

An example of a preferred method for producing the EL device of the present invention will be described for a device having the following structure. A method of manufacturing an EL device comprising an anode / the silacyclopentadiene derivative layer / a cathode will be described. First, a thin film made of a desired electrode material, for example, a material for an anode is formed on an appropriate substrate at a thickness of 1 μm or less, preferably 10 to 200 nm. Is formed by a method such as vapor deposition or sputtering so as to have a film thickness in the range described above, an anode is formed, and a thin film of a silacyclopentadiene derivative is formed thereon. Examples of the method for thinning include, for example, dip coating, spin coating, casting, and vapor deposition.However, from the viewpoint that a uniform film is easily obtained, impurities are hardly mixed, and pinholes are hardly generated. Evaporation is preferred. Next, after forming the silacyclopentadiene derivative layer, a thin film made of a cathode material is formed thereon by a method of 1 μm or less, for example, by vapor deposition or sputtering, and a cathode is provided to obtain a desired EL element. Can be In the production of this EL device, the production order can be reversed, and the cathode, the silacyclopentadiene derivative layer, and the anode can be produced in this order. When a DC voltage is applied to the EL device obtained in this manner, when a voltage of about 3 to 40 V is applied, light emission can be observed from the transparent or translucent electrode side. Furthermore, light is emitted by applying an AC voltage. The waveform of the applied alternating current may be arbitrary.

[0052]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 An IT was placed on a glass substrate of 25 mm × 75 mm × 1.1 mm.
A film obtained by forming O to a thickness of 50 nm by a vapor deposition method (manufactured by Tokyo Sanyo Vacuum Co., Ltd.) was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Vacuum Kiko Co., Ltd.), TPD was placed in a quartz crucible, and 1-allyl-1,2,3,4,5 was placed in another crucible. -Pentaphenylsilacyclopentadiene (APS) was charged, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. The crucible containing TPD was heated, and TPD was deposited to a thickness of 50 nm.
On top of this, a crucible containing APS is heated to a thickness of 50 n.
m was deposited on the APS. Deposition rate is 0.1 ~
0.2 nm / sec. Thereafter, the vacuum chamber is set at 2 × 10 ^−4.
After reducing the pressure to Pa, from a graphite crucible,
Magnesium at a deposition rate of 1.2-2.4 nm / sec,
At the same time, silver was added from the other crucible to 0.1 to 0.2 nm /
The deposition was performed at a deposition rate of seconds. Under the above conditions, a mixed metal electrode of magnesium and silver was stacked on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element. When a direct current voltage of 17 V is applied to the obtained device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, about 100 mA / cm ²
And a green light emission of 600 cd / m ² was obtained.
The emission wavelength was 503 nm.

Example 2 The APS used in Example 1 was replaced with 1-hydroxy-1,2,2,
A device was prepared in the same manner except that 3,4,5-pentaphenylsilacyclopentadiene was used. When a DC voltage of 17 V is applied to the obtained device, about 300 mA / cm
² and a green light emission of 500 cd / m ² was obtained. The emission wavelength was 516 nm.

Example 3 The APS used in Example 1 was 1,1-dimethyl-2,5-
A device was prepared in the same manner except that bis (3-methylphenyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 13 V is applied to the obtained device, a current of about 800 mA / cm ² flows and 1000 cd /
to give a blue-green light emission of m ^2. The emission wavelength was 488 nm.

Example 4 The APS used in Example 1 was 1,1-dimethyl-2,5-
A device was prepared in the same manner except that bis (3-trifluoromethylphenyl) -3,4-diphenylsilacyclopentadiene was used. A DC voltage of 4 V was applied to the obtained device.
When an electric current was applied, a current flowed and green light emission was obtained.

Example 5 The APS used in Example 1 was 1,1-dimethyl-2,5-
A device was prepared in the same manner except that bis (3-pyridyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 4 V was applied to the obtained device, a current flowed and green light was emitted.

Example 6 The APS used in Example 1 was 1,1-dimethyl-2,5-
A device was prepared in the same manner except that bis (2-pyridyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 9 V is applied to the obtained device, about 10
A current of 0 mA / cm ² flowed, and green light emission of about 500 cd / m ² was obtained.

Example 7 The APS used in Example 1 was 1-methyl-1-phenyl-
A device was prepared in the same manner except that 2,5-bis (3-pyridyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 10 V is applied to the obtained device, a current of about 300 mA / cm ² flows and about 900 cd
/ M ² of green light was obtained.

Example 8 The APS used in Example 1 was 1,1-diisopropyl-
A device was prepared in the same manner except that 2,5-bis (3-pyridyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 11 V is applied to the obtained element, a current of about 100 mA / cm ² flows, and about 200 cd
/ M ² of green light was obtained.

Example 9 The APS used in Example 1 was 1,1-dimethyl-2,5-
A device was prepared in the same manner except that bis (2-thienyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 3.5 V was applied to the obtained device, a current of about 30 mA / cm ² flowed, and green light emission of about 30 cd / m ² was obtained.

Example 10 The APS used in Example 1 was 1,1-diisoprole-2,
A device was prepared in the same manner except that 5-bis (2-thienyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 3.5 V was applied to the obtained device, a current flowed and yellow-green light emission was obtained.

Example 11 The APS used in Example 1 was 1,1-dimethyl-2,5-
Bis (5-tert-butyldiphenylsilyl-2-
A device was prepared in the same manner except that the device was replaced with (thienyl) -3,4-diphenylsilacyclopentadiene. When a DC voltage of 12.5 V is applied to the obtained device, about 600 m
A current of A / cm ² flowed, and yellow-green light emission of about 2000 cd / m ² was obtained. The emission wavelength was 551 nm.

Example 12 A device was prepared in the same manner as in Example 1, except that the APS used in Example 1 was changed to TTSTT. When a DC voltage of 4 V was applied to the obtained device, a current of about 10 mA / cm ² flowed, and orange light emission of about 1 cd / m ² was obtained.

Example 13 A device was prepared in the same manner as in Example 1, except that APS used in Example 1 was changed to 9,9'-silaspirobifluorene. When a DC voltage of 13 V is applied to the obtained device, about 300 m
A current of A / cm ² flowed, and purple light emission of about 50 cd / m ² was obtained. The emission spectrum completely coincided with the fluorescence spectrum of the TPD deposited film, and the emission wavelength was 405 nm.

Example 14 The transparent support substrate used in Example 1 was fixed to a substrate holder of a vapor deposition apparatus, and TPD was placed on a quartz crucible and A was placed on another crucible.
PS, 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi) was put in another crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. The crucible containing TPD was heated, and TPD was deposited to a thickness of 50 nm. On this, the crucible containing DPVBi was heated to deposit DPVBi to a thickness of 20 nm, and further,
A crucible containing APS was heated thereon to deposit APS to a thickness of 50 nm. The deposition rate is 0.1 to 0.1.
2 nm / sec. Thereafter, the vacuum chamber is set to 2 × 10 ⁻⁴ Pa
Then, from a graphite crucible, magnesium was deposited at a deposition rate of 1.2 to 2.4 nm / sec, and silver was deposited at the same time from another crucible at a deposition rate of 0.1 to 0.2 nm / sec. did. Under the above conditions, a mixed metal electrode of magnesium and silver was stacked on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element. Using the ITO electrode as the anode and the mixed electrode of magnesium and silver as the cathode,
When a DC voltage was applied, current flowed and blue light was emitted. The emission spectrum coincided with the fluorescence spectrum of the deposited film of DPVBi.

Example 15 An element was prepared in the same manner as in Example 14 except that the APS used in Example 14 was changed to TTSTT. When a DC voltage of 9.5 V was applied to the obtained device, a current of about 100 mA / cm ² flowed and blue light was emitted.

Example 16 The APS used in Example 14 was 1,1-dimethyl-2,5
A device was prepared in the same manner except that -bis (3-fluorophenyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 9 V was applied to the obtained device, a current of about 100 mA / cm ² flowed and blue light was emitted.

Example 17 The APS used in Example 14 was 1,1-dimethyl-2,5
A device was prepared in the same manner except that -bis (3-pyridyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 7 V is applied to the obtained device, about 1
A current of 00 mA / cm ² flowed and blue light was emitted.

Example 18 A device was prepared in the same manner as in Example 14, except that APS used in Example 14 was changed to 1,2-bis (9-methyl-dibenzosilacyclopentadienyl) ethane. In the obtained device,
When a DC voltage was applied, current flowed and blue light was emitted.

Example 19 The transparent support substrate used in Example 1 was fixed to a substrate holder of a vapor deposition apparatus, and TPD was placed on a quartz crucible, and TPD was placed on another crucible.
In TSTS, Alq was placed in another crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. The crucible containing TPD was heated, and TPD was deposited to a thickness of 50 nm.
On this, a crucible of TTSTT and Alq was heated together and vapor-deposited to a thickness of 50 nm. The deposition rate of Alq was 0.1-0.2 nm / sec, and that of TTSTT was 1/100 that of Alq. After that, the vacuum chamber is 2 × 1
After reducing the pressure to 0 ⁻⁴ Pa, magnesium was added from a graphite crucible at a deposition rate of 1.2 to 2.4 nm / sec.
The deposition was performed at a deposition rate of nm / sec. Under the above conditions, a mixed metal electrode of magnesium and silver was stacked on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element. When a direct current voltage of 11 V is applied to the obtained device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, about 900 mA /
A current of cm ² flowed and yellow-orange light emission of about 20,000 cd / m ² was obtained.

Example 20 An element was fabricated in the same manner as in Example 18, except that the deposition rate of TTSTT was changed to 3/100 of Alq. When a DC voltage of 12 V is applied to the obtained device, about 900 mA
/ Cm ² and a red-orange light emission of about 12000 cd / m ² was obtained. In this device, the same red-orange light emission was observed after driving for 300 hours.

Example 21 An element was fabricated in the same manner as in Example 18 except that TTSTT used in Example 18 was replaced with 1,1-diisoprole-2,5-bis (2-thienyl) -3,4-diphenylsilacyclopentadiene. Created. When a DC voltage of 10 V is applied to the obtained device, a current of about 500 mA / cm ² flows and about 8000 c
A yellow emission of d / m ² was obtained.

Example 22 The transparent support substrate used in Example 1 was fixed to a substrate holder of a vapor deposition device, TTSTT was placed in a crucible made of quartz, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. The crucible containing TTSTT is heated so that the thickness of TTTST becomes 100 nm.
T was deposited. The deposition rate was 0.1-0.2 nm / sec. Thereafter, the pressure in the vacuum chamber was reduced to 2 × 10 ⁻⁴ Pa, and then magnesium was added to the graphite crucible in an amount of 1.
Silver was deposited from the other crucible at a deposition rate of 0.1 to 0.2 nm / sec at a deposition rate of 2 to 2.4 nm / sec. Under the above conditions, a mixed metal electrode of magnesium and silver was stacked on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element. When a direct current voltage was applied to the obtained device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, current flowed and red-orange light emission was obtained.

Example 23 The transparent support substrate used in Example 1 was fixed to a substrate holder of a vapor deposition apparatus, and TPD was placed in a quartz crucible and TPD was placed in another crucible.
In TSTS, Alq was placed in another crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. The crucible containing TPD was heated and vapor-deposited to a thickness of 50 nm. On top of this, a crucible containing TTSTT was heated and vapor-deposited so as to have a film thickness of 10 nm, and an Alq crucible was further heated and vapor-deposited so as to have a film thickness of 20 nm. Deposition rate is 0.1 ~
0.2 nm / sec. Thereafter, the vacuum chamber is set at 2 × 10 ^−4.
After reducing the pressure to Pa, from a graphite crucible,
Magnesium at a deposition rate of 1.2-2.4 nm / sec,
At the same time, silver was added from the other crucible to 0.1 to 0.2 nm /
The deposition was performed at a deposition rate of seconds. Under the above conditions, a mixed metal electrode of magnesium and silver was stacked on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element. When a direct current voltage was applied to the obtained device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, current flowed and red-orange light emission was obtained.

Example 24 The transparent support substrate used in Example 1 was fixed on a commercially available spinner (manufactured by Kyoei Semiconductor Co., Ltd.), and 50 parts by weight of polyvinyl carbazole and 50 parts by weight of 9,9′-silaspiro-bifluorene were used. Was dissolved in 1,2-dichloroethane and applied at 5000 rpm. Then, this substrate is
After drying at 50 ° C. under a reduced pressure of 0 ⁻¹ Pa, it was fixed to a substrate holder of a vapor deposition device. Thereafter, the vacuum chamber is set to 2 × 10 ⁻⁴ Pa
Then, from a graphite crucible, magnesium was deposited at a deposition rate of 1.2 to 2.4 nm / sec, and silver was deposited at the same time from another crucible at a deposition rate of 0.1 to 0.2 nm / sec. did. Under the above conditions, a mixed metal electrode of magnesium and silver was stacked on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element. Using the ITO electrode as the anode and the mixed electrode of magnesium and silver as the cathode,
When a DC voltage of 14 V was applied, a current of about 300 mA / cm ² flowed, and purple light emission of ²⁰ cd / m ² was obtained.

Example 25 In place of the 1,2-dichloroethane solution of 50 parts by weight of polyvinyl carbazole and 50 parts by weight of 9,9'-spirobisilafluorene used in Example 24, 50 parts by weight of polyvinyl carbazole, 9, 9 Example 2 except that a 1,2-dichloroethane solution of 50 parts by weight of '-silaspiro-bifluorene and 1 part by weight of coumarin 6 (manufactured by KODAK) was used.
An element was prepared in the same manner as in No. 3. When a DC voltage was applied to the obtained device, a current flowed and green light was emitted.

Example 26 A device was fabricated in the same manner as in Example 25 except that coumarin 6 was replaced with perylene. When a DC voltage was applied to the obtained device, a current flowed and blue light was emitted.

Example 27 A device was prepared in the same manner as in Example 25, except that coumarin 6 was changed to Nile Red. In the obtained device,
When a DC voltage was applied, current flowed and orange light emission was obtained.

Example 28 An element was prepared in the same manner as in Example 14, except that DPVBi was changed to 9,9'-silaspirospirobifluorene and APS was changed to Alq. A DC voltage of 12 was applied to the obtained device.
When V was applied, a current of about 300 mA / cm ² flowed, and purple light emission of about 1200 cd / m ² was obtained. The emission spectrum completely matches the fluorescence spectrum of the TPD deposited film,
The emission wavelength was 405 nm.

Example 29 The transparent support substrate used in Example 1 was fixed to a substrate holder of a vapor deposition apparatus, and 40 parts by weight of TPD and AP were placed in a crucible made of quartz.
S60 parts by weight and 1 part by weight of coumarin 6 were charged, and the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Heat this crucible,
Evaporation was performed to a film thickness of 100 nm. The deposition rate is 1 to
1.2 nm / sec. Thereafter, the vacuum chamber is set at 2 × 10 ^−4.
After reducing the pressure to Pa, from a graphite crucible,
Magnesium at a deposition rate of 1.2-2.4 nm / sec,
At the same time, silver was added from the other crucible to 0.1 to 0.2 nm /
The deposition was performed at a deposition rate of seconds. Under the above conditions, a mixed metal electrode of magnesium and silver was stacked on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element. When a direct current voltage was applied to the obtained device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, current flowed and green light was emitted.

Example 30 The APS used in Example 14 was 1,1-dimethyl-2,5
A device was prepared in the same manner except that -bis (2-pyridyl) -3,4-diphenylsilacyclopentadiene was used. When a DC voltage of 4.5 V was applied to the obtained device, a current of about 7 mA / cm ² flowed, and blue light emission of about 130 cd / m ² was obtained. The maximum emission luminance of this element is 600
It exceeded 0 cd / m ² .

Example 31 An element was produced in the same manner as in Example 30, except that DPVBi was changed to Alq. When a DC voltage of 3 V was applied to the obtained device, a current of about 1 mA / cm ² flowed, and green light emission of about 20 cd / m ² was obtained. The maximum emission luminance of this device exceeded 13000 cd / m ² .

[0084]

Since the organic electroluminescent device of the present invention uses a silacyclopentadiene derivative having excellent electron transporting properties, it emits light with high luminance at a low voltage and has high practical value. By using these, a full-color flat panel display or the like can be produced.

────────────────────────────────────────────────── (5) References JP-A-9-194487 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09K 11/06 CA (STN) REGISTRY (STN) ) WPI (DIALOG)

Claims (5)

(57) [Claims] 1. An electroluminescent device using a silacyclopentadiene derivative represented by the general formula [1]. Embedded image (Wherein, X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group,
An alkenyloxy group, an alkynyloxy group, a hydroxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle, or a structure in which X and Y are combined to form a saturated ring, and R _{1 to} R ₄ are Each independently represents hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group , An alkoxycarbonyl group, an aryloxycarbonyl group,
Azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group, heterocyclic group, alkenyl group, nitro Group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group or cyano group. ) 2. An electroluminescent device using at least one of the silacyclopentadiene derivatives according to claim 1 as a component of a charge transport layer. 3. An electroluminescent device, wherein at least one of the silacyclopentadiene derivatives according to claim 1 is used as a component of a light emitting layer. 4. An electroluminescent device using at least one of the silacyclopentadiene derivatives represented by the general formula [Chemical Formula 2] as a component of a hole blocking layer. Embedded image (Wherein, X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group,
Alkenyloxy group, alkynyloxy group, hydroxy group, a substituted or unsubstituted aryl group, to form a saturated or unsaturated ring substituted or unsubstituted hetero ring, or X and Y are bonded to the structure, R ₁ ~ R ₄ is each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group, an aryloxy group, a perfluoroalkyl group, a perfluoroalkoxy group, an amino group, an alkylcarbonyl group, Arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl Group, ant Group, a heterocyclic group, an alkenyl group,
Alkynyl group, nitro group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group or cyano group or substituted or unsubstituted ring fused when adjacent Structure. ) 5. An electroluminescent device using a silacyclopentadiene derivative represented by the general formula [3] as a component of a hole blocking layer. Embedded image (Wherein, X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group,
An alkenyloxy group, an alkynyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic ring, and R _{1 to} R ₈ each independently represent hydrogen, halogen, an alkyl group having 1 to 6 carbon atoms, An alkoxy group,
Perfluoroalkyl group, perfluoroalkoxy group,
Amino group, nitro group, alkylcarbonyl group, alkoxycarbonyl group, formyl group, nitroso group, azo group, alkylcarbonyloxy group, alkoxycarbonyloxy group, formyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, isocyano A group, a carbamoyl group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, an aryl group, an alkenyl group, an alkynyl group or a cyano group, or a substituted or unsubstituted ring may be condensed when adjacent. )