JP2009081409A - Organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element with high durability and luminescence brightness. <P>SOLUTION: The organic electroluminescent element contains at least a silane derivative represented by a general formula (1) and a platinum complex having a quadridentate ligand between a pair of electrodes. R<SP>101</SP>to R<SP>104</SP>represent hydrogen atoms or substituents. Then R<SP>105</SP>to R<SP>108</SP>represent hydrogen atoms or substituents. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a light-emitting element that can emit light by converting electric energy into light, and particularly relates to an organic electroluminescent element (light-emitting element or EL element).

  An organic electroluminescence (EL) element has attracted attention as a promising display element because it can emit light with high luminance at a low voltage. An important characteristic value of the organic electroluminescent element is power consumption. The power consumption is represented by the product of voltage and current, and the lower the voltage value necessary to obtain the desired brightness and the smaller the current value, the lower the power consumption of the element.

As one attempt to lower the value of current flowing through the element, a light-emitting element using light emission from an orthometalated iridium complex (Ir (ppy) ₃ : tris-ortho-metalated complex of iridium (III) with 2-phenylpyridine) It has been reported (for example, see Patent Document 1). The phosphorescent light-emitting devices described in these documents have significantly improved external quantum efficiency and succeeded in reducing the current value as compared with conventional singlet light-emitting devices.
In contrast, Patent Document 2 reports that a light-emitting element using a platinum complex compound having a 5-membered ring azolyl group (such as an imidazolyl group) as a tetradentate ligand for light emission improves the light emission efficiency. .

  For the purpose of improving the luminous efficiency and durability of phosphorescent light emitting devices, devices containing silane derivatives (Patent Document 3 and Patent Document 4) have been reported, but further improvements are desired in terms of durability and efficiency. It was.

JP 2001-247859 A JP 2007-19462 A JP 2003-243178 A JP 2006-140219 A

  An object of the present invention is to provide an organic electroluminescent device having good durability and luminous efficiency.

This object has been achieved by the following means.
(1) An organic electroluminescent device comprising a platinum complex having at least a silane derivative represented by the general formula (1) and a tetradentate ligand between a pair of electrodes.

R ^{101 to} R ¹⁰⁴ represent a hydrogen atom or a substituent. R ^{105 to} R ¹⁰⁸ represent a hydrogen atom or a substituent.
(2) The organic electroluminescent element as described in (1) above, wherein the silane derivative represented by the general formula (1) is a compound represented by the general formula (2).

R ²⁰¹ to R ²⁰⁴ represents a hydrogen atom or a substituent. X ²⁰¹ to X ²⁰⁸ is a substituted or unsubstituted carbon atom or a nitrogen atom.
(3) The organic electroluminescent element as described in (1) above, wherein the silane derivative represented by the general formula (1) is a compound represented by the general formula (3).

R ^{301 to} R ³⁰⁴ represent a hydrogen atom or a substituent. R ³⁰⁵ and R ³⁰⁶ each represent a hydrogen atom or a substituent. X ^{301 to} X ³⁰⁴ represent a substituted or unsubstituted carbon atom or a nitrogen atom.
(4) The organic electroluminescent element as described in (3) above, wherein the silane derivative represented by the general formula (3) is a compound represented by the general formula (4).

R ^{401 to} R ⁴⁰⁸ represent a hydrogen atom or a substituent. R ^{409 to} R ⁴¹² each represents a hydrogen atom or a substituent. X ⁴⁰¹ and X ^{402 each} represents a substituted or unsubstituted carbon atom or a nitrogen atom.
(5) The organic electroluminescence according to any one of (1) to (4) above, wherein the light emitting layer contains a silane derivative represented by at least one of the general formulas (1) to (4). element.
(6) The organic electroluminescent element as described in any one of (1) to (5) above, wherein the silane derivative is contained in a layer adjacent to the light emitting layer.
(7) The silane derivative represented by at least one of the general formulas (1) to (4) is contained in a layer adjacent to the cathode, described in any one of (1) to (6) above Organic electroluminescent device.
(8) The glass transition temperature of the silane derivative represented by at least one of the general formulas (1) to (4) is 130 ° C. or higher and 450 ° C. or lower, (1) to (7) above The organic electroluminescent element in any one.
(9) The lowest excited triplet energy level of the silane derivative represented by at least one of the general formulas (1) to (4) is 65 kcal / mol (272.35 kJ / mol) or more and 80 kcal / mol or less (335. 2 kJ / mol or less), The organic electroluminescent element as described in any one of (1) to (8) above.

  The organic electroluminescent element of the present invention can emit light with high efficiency and is excellent in durability.

  The present invention is an organic electroluminescent device characterized by containing at least a silane derivative represented by the general formula (1) and a platinum complex having a tetradentate ligand between a pair of electrodes. The general formula (1) will be described.

In the general formula ^{(1), R} 101 ~R ¹⁰⁴ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as methyl, ethyl, iso-propyl, n-octyl, and each group such as n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 carbon atoms). For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.) and alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl group and 3-pentynyl group), aryl group (preferably 6 to 6 carbon atoms) 0, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, and anthranyl groups, and amino groups (preferably having carbon atoms). 0 to 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino. ), An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, each group such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc. An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms). Preferably it is C6-C12, for example, each group, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), heterocyclic oxy group (preferably C1-C30, more preferably carbon is mentioned). The number is 1 to 20, particularly preferably 1 to 12, and examples thereof include groups such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy).

An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl groups), alkoxy. A carbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group), an aryloxycarbonyl group (Preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonyl group), acyloxy groups (preferably 2 to 2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an acetoxy group, An azoyloxy group, etc.), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an acetylamino group and a benzoylamino group). An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group). An aryloxycarbonylamino group (preferably having a carbon number of 7 to 30, more preferably a carbon number of 7 to 20, particularly preferably a carbon number of 7 to 12, such as a phenyloxycarbonylamino group), a sulfonylamino group (Preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably carbon. 1 to 12, for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 carbon atoms). -12, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, and the like, and carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 1 carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, for example, each group such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably 1 to 30 carbon atoms, more preferably carbon atoms) 1 to 20, particularly preferably 1 to 12 carbon atoms, for example methylthio O group, ethylthio group and the like. ), An arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc. And sulfonyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as mesyl group and tosyl group). ), A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Group, and the like benzene sulfinyl group.)

Ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido and phenylureido groups), phosphorus. Acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide group and phenyl phosphoric acid amide group) , Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thieny. , Piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group and the like, and a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms). Particularly preferably, it has 3 to 24 carbon atoms, and examples thereof include trimethylsilyl group and triphenylsilyl group), silyloxy group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably C3-C24, for example, a trimethylsilyloxy group, a triphenylsilyloxy group, etc.) are mentioned. These substituents may be further substituted. R ¹⁰¹ and R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ may be linked to each other to form a ring structure. Examples of the ring formed include a silole ring, a disilole ring, an oxacilol ring, an azacilol ring, a thiasilole ring, Phosphacylol ring, silolane ring, dicilolane ring, oxasilolane ring, azasilolane ring, thiasilolane ring, phosphacirolane ring, syringe ring, dicilin ring, oxacillin ring, azacillin ring, thiacillin ring, phosphacillin ring, syrinan ring, disilinan ring, oxacillinan ring, Azacillinane ring, thiacillinane ring, phosphacillinane ring, silolane ring, disilolane ring, oxasilolan ring, azasilolan ring, thiacilolane ring, phosphacirolane ring, silepin ring, disilepin ring, oxasilepin ring, azasilepin ring, thiacilein ring, phospha Lepin ring, silepan ring, disilepane ring, oxasilepan ring, azashilepan ring, thiacilepane ring, phosphacilepan ring, silolane ring, disilolane ring, oxasilolan ring, azasilolan ring, thiacilolane ring, phosphacirolane ring, silepin ring, disilepin ring, oxasilepin ring, azasilepin ring, azalepine ring , Thiasilepin ring, phosphacilepin ring, silepan ring, disilepane ring, oxasilepan ring, azasilepan ring, thiacilepane ring, phosphacilepan ring, etc. These ring structures further form condensed rings (for example, benzo condensed ring, pyridine condensed ring, etc.) You may do it. Preferred examples in the case where R ¹⁰¹ and R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ are linked to each other to form a ring structure are a silole ring, a disilole ring, an oxacilol ring, an azacilol ring, a thiasilole ring, a phosphacilol ring, a syringe ring, and a dicillin A ring, an oxacillin ring, an azacillin ring, a thiacillin ring, and a phosphacillin ring, and more preferably a syrin ring, a dicilin ring, an oxacillin ring, an azacillin ring, a thiacillin ring, and a phosphacillin ring.

R ^{101 to} R ¹⁰⁴ are preferably an alkyl group, an aryl group, or a heteroaryl group, or R ¹⁰¹ and R ¹⁰² and / or R ¹⁰³ and R ¹⁰⁴ are preferably linked to each other to form a ring structure. It is more preferable that it is an aryl group or an aryl group.

R ^{105 to} R ¹⁰⁸ represent a hydrogen atom or a substituent. R ¹⁰⁵ and R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ may be linked to each other to form a ring structure. Examples of the ring formed include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, and a pyridazine ring. , Pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole ring, thiazole ring, thiadiazole ring, furan ring, thiophene ring, selenophene ring, silole ring, silanthrene ring, germol ring, phosphorol ring, etc. It is done. The condensed rings formed by condensing R ¹⁰⁵ and R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ to form a ring structure include benzo condensed ring, pyridine condensed ring, pyrrol condensed ring, pyrazole condensed ring and imidazole condensed ring. , A triazole condensed ring and a silane toren ring are preferable, and a benzo condensed ring, a pyridine condensed ring and a silane toren condensed ring are more preferable.

  Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, n-octyl). , N-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon number). 2-10, for example, each group such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably Has 2 to 10 carbon atoms, and examples thereof include propargyl group and 3-pentynyl group), aryl group (preferably 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples include groups such as phenyl, p-methylphenyl, naphthyl, anthranyl, and the like, amino groups (preferably carbon numbers) 0 to 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino. ), An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, each group such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc. An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, Preferably have 6 to 12 carbon atoms, and examples thereof include phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like, and heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably C1-C20, Most preferably, it is C1-C12, for example, each cyclic group, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), an acyl group (preferably C1-C30, more preferably). Has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl groups, and alkoxycarbonyl groups (preferably having 2 to 30 carbon atoms, more preferably Has 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl group, ethoxy Bonyl group etc. are mentioned. ), An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonyl group), an acyloxy group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group.

An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (Preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably carbon 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group), a sulfonylamino group (preferably 1 to 30 carbon atoms, More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms. Amino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methyl And groups such as famoyl, dimethylsulfamoyl, and phenylsulfamoyl), carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). And examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, and the like.

An alkylthio group (preferably each group having 1 to 30 carbon atoms, more preferably each group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylthio group, and a heterocyclic thio group (preferably 1 to 30 carbon atoms). More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like. ), A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. And sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl group and benzenesulfinyl group). A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, each of ureido, methylureido, phenylureido, etc. Group), phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide group, phenylphosphoric acid Amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine) A cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, and a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms). A heteroatom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically a group containing these, such as imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, A heterocyclic group such as a carbazolyl group and an azepinyl group), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, such as a trimethylsilyl group). , Triphenylsilyl group, etc.), silyloxy group (preferably carbon The number is from 3 to 40, more preferably from 3 to 30 carbons, particularly preferably from 3 to 24 carbons, and examples thereof include a trimethylsilyloxy group and a triphenylsilyloxy group. ) And the like. These substituents may be further substituted.

R ^{105 to} R ¹⁰⁸ are preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group in which R ¹⁰⁵ and R ¹⁰⁶ and / or R ¹⁰⁷ and R ¹⁰⁸ are linked to each other to form a ring structure. , An aryl group, a heteroaryl group, or a group in which R ¹⁰⁵ and R ¹⁰⁶ and / or R ¹⁰⁷ and R ¹⁰⁸ are linked to each other to form a ring structure, and is preferably an aryl group or R ^{A group in which 105} and R ¹⁰⁶ and / or R ¹⁰⁷ and R ¹⁰⁸ are connected to each other to form a ring structure is more preferable, and R ¹⁰⁵ and R ¹⁰⁶ and / or R ¹⁰⁷ and R ¹⁰⁸ are connected to each other to form a ring structure. The group is particularly preferred. By having a rigid condensed ring structure, it is expected that durability against carrier charges injected into the device is increased and device durability is improved.

  One of the preferred forms as the compound represented by the general formula (1) is a compound represented by the following general formula (2). The general formula (2) will be described.

R ²⁰¹ to R ²⁰⁴ represents a hydrogen atom or a substituent. X ²⁰¹ to X ²⁰⁸ is a substituted or unsubstituted carbon atoms, or, represent a nitrogen atom.
R ^{201 to} R ²⁰⁴ have the same meanings as R ^{101 to} R ¹⁰⁴ , respectively, and the preferred ranges are also the same.

X ²⁰¹ to X ²⁰⁸ is a substituted or unsubstituted carbon atoms, or, represent a nitrogen atom. Examples of the substituent on the carbon atom include the groups mentioned in the above R ¹⁰⁵ (preferably an alkyl group, aryl group, heteroaryl group, silyl group, more preferably an aryl group, heteroaryl group silyl group. And more preferably an aryl group).

X ^{201 to} X ²⁰⁸ are preferably an unsubstituted carbon atom or a nitrogen atom, and at least one is preferably a nitrogen atom.

Another preferred form of the compound represented by the general formula (1) is a compound represented by the following general formula (3). The general formula (3) will be described.

R ^{301 to} R ³⁰⁴ represent a hydrogen atom or a substituent. R ³⁰⁵ and R ³⁰⁶ each represent a hydrogen atom or a substituent. X ^{301 to} X ³⁰⁴ represent a substituted or unsubstituted carbon atom or a nitrogen atom.

R ^{301 to} R ³⁰⁴ , R ³⁰⁵ and R ³⁰⁶ have the same meanings as R ^{101 to} R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ , respectively, and preferred ranges are also the same. ^Further, X 301 ^{to X 304} is synonymous with the ^X 201 ^{to X 204,} and the preferred range is also the same.

  The compound represented by the general formula (3) is more preferably a compound represented by the following general formula (4). By substituting with tetrasilyl and delocalizing the charge also on the silicon atom, the resistance to the carrier charge injected into the device is improved. Hereinafter, the general formula (4) will be described.

R ^{401 to} R ⁴⁰⁸ represent a hydrogen atom or a substituent. R ^{409 to} R ⁴¹² each represents a hydrogen atom or a substituent. X ⁴⁰¹ and X ^{402 each} represents a substituted or unsubstituted carbon atom or a nitrogen atom.
R ^{401 to} R ³⁰⁸ , R ^{409 to} R ⁴¹² , and X ^{401 to} X ⁴⁰² are synonymous with R ^{301 to} R ³⁰⁴ , R ^{305 to} R ^306, and X ^{301 to} X ³⁰⁴ , respectively, and the preferred ranges are also the same.

  Next, although the compound example represented by either of General formula (1)-(4) used for the organic electroluminescent element of this invention is shown, this invention is not limited to this.

  Compounds represented by any one of the general formulas (1) to (4) are described in J.P. Am. Chem. Soc. 1960, 82, 3605, (1-1); Organomet. Chem. 1984, 271, 319, (1-2); Chem. Soc. Chem. Commun. 1993, 9, 744, (1-3); (1-7), Chem. Lett. 2005, 34, 1698, (1-4); Am. Chem. Soc. 1964, 86, 5854. (1-5), J.M. Organomet. Chem. 1968, No. 11, p. 55, (1-6); and the like, and the method can be synthesized with reference to the method.

  The glass transition temperature of the silane derivative represented by any one of the general formulas (1) to (4) is preferably 80 ° C. or higher and 500 ° C. or lower, more preferably 90 ° C. or higher and 480 ° C. or lower, 110 ° C. or higher and 450 ° C. or lower is more preferable, and 130 ° C. or higher and 450 ° C. or lower is particularly preferable.

The lowest excited triplet energy level of the silane derivative represented by any one of the general formulas (1) to (4) is 60 kcal / mol or more (251.4 kJ / mol or more), 90 kcal / mol or less (377.1 kJ / mol). Or less), preferably 62 kcal / mol or more (259.78 kJ / mol or more), 85 kcal / mol or less (356.15 kKJ / mol or less), more preferably 65 kcal / mol or more (272.35 kJ / mol or more), 80 kcal / mol. The following (335.2 kJ / mol or less) is more preferable.
Here, the T ₁ energy can be obtained from the short wavelength end of a phosphorescence emission spectrum of a thin film of material. For example, a material is deposited on a cleaned quartz glass substrate to a film thickness of about 50 nm by vacuum deposition. The phosphorescence emission spectrum of the thin film is measured using an F-7000 Hitachi spectrofluorometer (Hitachi High-Technologies) under liquid nitrogen temperature. It can be determined by converting the rising wavelength on the short wavelength side of the obtained emission spectrum into energy units.

<Platinum complex with tetradentate ligand>
The organic electroluminescence device of the present invention is characterized in that it contains at least one kind of platinum compound having a compound represented by the general formula (1) and a tetradentate ligand in an organic compound layer.
By using a platinum complex having a tetradentate ligand, the light emission efficiency of the device is improved and the driving durability is improved.
In addition, it is considered that injection of electrons into the light emitting layer is further promoted by the combined use of the compound represented by the general formula (1) and the platinum complex having a tetradentate ligand, and the charge recombination position and the light emission center emit light. By being in the center of the layer, the durability of the element is improved and the variation in chromaticity of each element is reduced.

  Examples of the platinum complex having a tetradentate ligand include the compounds described in International Publication No. 00-57676.

  More specifically, examples of platinum complex (phosphorescent) materials having a tetradentate ligand include US Pat. No. 6,653,654, International Publication No. 2004-099339, International Publication No. 04-108857, JP, 2005-310733, JP 2005-317516, JP 2006-261623, JP 2006-93542, JP 2006-256999, WO 06-098505, JP 2007-19462, JP 2007-96255, JP The compounds described in 2007-96259, International Publication No. 05-042444, Japanese Patent Application Laid-Open No. 2006-232784, US Patent No. 0134461, International Publication No. 05-042550 are preferred.

  A platinum complex (phosphorescent) material having a tetradentate ligand preferably includes a 2-arylpyridine derivative, a 2- (1-pyrazolyl) pyridine derivative, and a 1-arylpyrazole derivative as a partial structure of the ligand. More preferred are those containing 2-arylpyridine derivatives and 2- (1-pyrazolyl) pyridine derivatives as partial structures of ligands, and particularly those containing 2- (1-pyrazolyl) pyridine derivatives as partial structures of ligands. preferable.

  In addition, partial structures of the above ligands (for example, 2-arylpyridine derivatives, 2- (1-pyrazolyl) pyridine derivatives, 1-arylpyrazole derivatives, etc.) are linked at an appropriate site to form a tetradentate arrangement. Constructs a scale.

When a 2-arylpyridine derivative is included as a partial structure of the ligand, it is preferable to connect the 6-position of the pyridine ring or the meta-position to the pyridine ring of the aryl group, Alternatively, it is more preferable to connect the meta positions to the pyridine ring of the aryl group, and it is particularly preferable to connect the 6 positions of the pyridine ring.
When a 2- (1-pyrazolyl) pyridine derivative is included as a partial structure of the ligand, it is preferable to link at the 6-position of the pyridine ring or the 4-position of the 1-pyrazolyl group, Alternatively, it is more preferable to connect the 4-positions of the 1-pyrazolyl group, and it is particularly preferable to connect the 6-positions of the pyridine ring.
When a 1-arylpyrazole derivative is included as a partial structure of the ligand, it is preferable to connect the 3-position of the pyrazole ring or the meta-position with respect to the pyrazole ring of the aryl group, Or it is more preferable to connect with meta positions with respect to the pyrazole ring of an aryl group, and it is especially preferable to connect with 3 positions of a pyrazole ring.

The structure connecting the partial structures of the ligand may be a single bond or a divalent linking group, but is preferably a divalent linking group. As, for example, methylene linkage, ethylene linkage, phenylene linkage, nitrogen atom linkage, oxygen atom linkage, sulfur atom linkage, silicon atom linkage is preferred, methylene linkage, nitrogen atom linkage, silicon atom linkage is more preferred, and methylene linkage is particularly preferred preferable. Specific examples of the methylene linking group include a methylene group (—CH ₂ —), a methylmethylene group (—CHMe—), a fluoromethylmethylene group (—CFMe—), a dimethylmethylene group (—CMe ₂ —), and methylphenylmethylene. Group (—CMePh—), diphenylmethylene group (—CPh ₂ —), 9,9-fluorenediyl group, 1,1-cyclopentanediyl group, 1,1-cyclohexanediyl group, dimethylmethylene group, A diphenylmethylene group, a 9,9-fluorenyl group, a 1,1-cyclopentanediyl group, and a 1,1-cyclohexanediyl group are preferable, and a dimethylmethylene group, a diphenylmethylene group, and a 1,1-cyclohexanediyl group are more preferable. A methylene group is particularly preferred.

  Further, as a platinum complex (phosphorescent) material having a tetradentate ligand, one more preferable is a Pt complex represented by the general formula (A).

In general formula (A), R ^A3 and R ^A4 each independently represent a hydrogen atom or a substituent, and R ^A1 and R ^A2 each independently represent a substituent. If having a plurality of R ^{A1, R A2,} respectively, the plurality of ^{R A1, R A2} may be the same or different, may form a ring. n ^A1 and n ^A2 each independently represent an integer of 0 to 4. Y ^A1 represents a linking group.

The substituent represented by R ^A1 , R ^A2 , R ^A3 , and R ^A4 can be arbitrarily selected from the substituent groups A listed below.
Substituent group A:
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as a methyl group, ethyl group, iso-propyl group, tert-butyl group, n- Octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, especially Preferably it is C2-C10, for example, a vinyl group, an allyl group, 2-butenyl group, 3-pentenyl group etc.), an alkynyl group (preferably C2-C30, more preferably C2-C2). To 20, particularly preferably 2 to 10 carbon atoms, such as a propargyl group and a 3-pentynyl group), an aryl group (preferably The number of carbon atoms is 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12, and examples thereof include a phenyl group, a p-methylphenyl group, a naphthyl group, and an anthranyl group.), An amino group (Preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms. For example, amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, diphenyl Amino group, ditolylamino group, etc.), alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy group, ethoxy group, Butoxy group, 2-ethylhexyloxy group, etc.), aryloxy group (preferably having 6 to 30 carbon atoms, more preferred) Or having 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, etc.), heterocyclic oxy group (preferably carbon The number is 1 to 30, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Examples thereof include a pyridyloxy group, a pyrazyloxy group, a pyrimidyloxy group, a quinolyloxy group, and the like, and an acyl group (preferably. C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group etc. are mentioned), an alkoxycarbonyl group (preferably). Has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms. Examples thereof include a rubonyl group and an ethoxycarbonyl group. ), An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonyl group), an acyloxy group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group.

An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (Preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably carbon 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group), a sulfonylamino group (preferably 1 to 30 carbon atoms, More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms. Amino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl group, methyl A sulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to carbon atoms). For example, carbamoyl, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably carbon number). 1 to 12, and examples thereof include a methylthio group and an ethylthio group. An arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably carbon atoms). 1-30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, such as pyridylthio group, 2-benzimidazolylthio group, 2-benzoxazolylthio group, 2-benzthiazolyl group. A luthio group, etc.),

A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl group, tosyl group, etc.), sulfinyl group (preferably carbon 1-30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms such as methanesulfinyl group and benzenesulfinyl group), ureido group (preferably 1-30 carbon atoms). , More preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido group, methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably 1 to 1 carbon atom). 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a diethylphosphoric acid amide group, a phenylphosphoric acid group Hydroxy group, mercapto group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group , Hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, Is an imidazolyl group, pyridyl group, quinolyl group, furyl group, thienyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, carbazolyl group, azepinyl group, etc.), silyl group ( Preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 2 carbon atoms. For example, a trimethylsilyl group, a triphenylsilyl group, etc.), a silyloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, A trimethylsilyloxy group, a triphenylsilyloxy group, etc.), a phosphoryl group (for example, a diphenylphosphoryl group, a dimethylphosphoryl group, etc.).

The linking group represented by Y ^A1 can be arbitrarily selected from those listed as the linking group group A below.
Linking group A:
Alkylene groups (methylene, ethylene, propylene, etc.), arylene groups (phenylene, naphthalenediyl), heteroarylene groups (pyridinediyl, thiophenediyl, etc.), imino groups (-NR-) (phenylimino groups, etc.), oxy groups (- O-), thio group (-S-), phosphinidene group (-PR-) (phenylphosphinidene group etc.), silylene group (-SiRR'-) (dimethylsilylene group, diphenylsilylene group etc.), or these A combination. These linking groups may further have a substituent.

As a substituent which R ^{< A1>} , R ^<A2> , R ^<A3> and R ^<A4> represent, an alkyl group, an aryl group, and a heterocyclic group are preferable, an aryl group and a heterocyclic group are more preferable, and an aryl group is especially preferable.

The linking group represented by Y ^A1 is preferably a vinyl group substituted at the 1,2-position, a phenylene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring or an alkylene group having 1 to 8 carbon atoms, and a vinyl substituted at the 1,2-position. Group, a phenylene ring, and an alkylene group having 1 to 6 carbon atoms are more preferable, and a phenylene ring is particularly preferable.

The substituent represented by R ^A3 and R ^A4 may be linked to the linking group represented by Y ^A1 to form a ring. For example, when Y ^A1 is a phenylene ring linked at the 1,2-position, R ^A3 and R ^A4 may be linked to each other at the 3 and 6 positions to form a 1,10-phenanthroline ring and may further have a substituent.

  As a platinum complex (phosphorescence) material having a tetradentate ligand, one more preferable is a Pt complex represented by the general formula (B).

(In the general formula (B), A ^{B1 to} A ^B6 each independently represent C—R or N. R represents a hydrogen atom or a substituent. L ^B1 represents a single bond or a divalent linking group. X Represents C or N. Z represents a 5- or 6-membered aromatic ring or aromatic heterocycle formed together with X—C in the formula, and Q ^B1 represents an anionic group bonded to Pt.)

The general formula (B) will be described.
A ^{B1 to} A ^B6 each independently represent C—R or N. R represents a hydrogen atom or a substituent. The substituent represented by R is synonymous with those exemplified as the substituent group A, and preferred ones are also the same.
A ^{B1 to} A ^B6 are preferably C—R, and Rs may be connected to each other to form a ring. When A ^{B1 to} A ^B6 are C—R, R of A ^B2 and A ^B5 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group. More preferably a hydrogen atom, an amino group, an alkoxy group, an aryloxy group, or a fluorine group, particularly preferably a hydrogen atom or a fluorine group, and preferably a hydrogen atom as R in A ^B1 , A ^B3 , A ^B4 , and A ^B6. , Alkyl group, aryl group, amino group, alkoxy group, aryloxy group, fluorine group, cyano group, more preferably hydrogen atom, amino group, alkoxy group, aryloxy group, fluorine group, particularly preferably hydrogen atom. It is.

L ^B1 represents a single bond or a divalent linking group.
^Examples of the divalent linking group represented by L ^B1 include alkylene groups (methylene, ethylene, propylene, etc.), arylene groups (phenylene, naphthalenediyl), heteroarylene groups (pyridinediyl, thiophenediyl, etc.), imino groups (- NR-) (such as phenylimino group), oxy group (-O-), thio group (-S-), phosphinidene group (-PR-) (such as phenylphosphinidene group), silylene group (-SiRR'-) (Dimethylsilylene group, diphenylsilylene group, etc.), or a combination thereof. These linking groups may further have a substituent.
L ^B1 is preferably a single bond, an alkylene group, an arylene group, a heteroarylene group, an imino group, an oxy group, a thio group or a silylene group, more preferably a single bond, an alkylene group, an arylene group or an imino group, An alkylene group is preferred, a methylene group is more preferred, a disubstituted methylene group is more preferred, and a dimethylmethylene group, diethylmethylene group, diisobutylmethylene group, dibenzylmethylene group, ethylmethylmethylene group is more preferred. Methylpropylmethylene group, isobutylmethylmethylene group, diphenylmethylene group, methylphenylmethylene group, cyclohexanediyl group, cyclopentanediyl group, fluorenediyl group, fluoromethylmethylene group, particularly preferably dimethylmethylene group, A phenylmethylene group and a cyclohexanediyl group.

X represents C or N. Z represents a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocycle formed together with X—C in the formula. Examples of the aromatic hydrocarbon ring or aromatic heterocycle represented by Z include a benzene ring, naphthalene ring, anthracene ring, pyrene ring, phenanthrene ring, perylene ring, pyridine ring, quinoline ring, isoquinoline ring, phenanthridine ring, Pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, cinnoline ring, acridine ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, pteridine ring, pyrrole ring, pyrazole ring, triazole ring, indole ring, carbazole ring, indazole ring , Benzimidazole ring, oxazole ring, thiazole ring, oxadiazole ring, thiadiazole ring, benzoxazole ring, benzothiazole ring, imidazopyridine ring, thiophene ring, benzothiophene ring, furan ring, benzofuran ring, phosphole , Phosphinine ring, and a silol ring. Z may have a substituent, and as the substituent, those exemplified as the substituent group A can be applied. Z may form a condensed ring with other rings.
Z is preferably a benzene ring, naphthalene ring, pyrazole ring, imidazole ring, triazole ring, pyridine ring, indole ring or thiophene ring, more preferably a benzene ring, pyrazole ring or pyridine ring.

Q ^B1 represents an anionic group bonded to Pt. Examples of the anionic group represented by Q ^B1 include a vinyl ligand, an aromatic hydrocarbon ring ligand (for example, a benzene ligand, a naphthalene ligand, an anthracene ligand, a phenanthracene ligand, etc. ), Heterocyclic ligands (eg furan ligands, thiophene ligands, pyridine ligands, pyrazine ligands, pyrimidine ligands, pyridazine ligands, triazine ligands, thiazole ligands, oxazoles) And a ligand, a pyrrole ligand, an imidazole ligand, a pyrazole ligand, a triazole ligand, and a condensed ring containing them (for example, a quinoline ligand, a benzothiazole ligand, etc.). At this time, the bond of Q ^B1 and Pt is a covalent bond, ionic bond, may be any such coordination bond. The atoms bound to Pt in Q ^B1, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, are preferred phosphorus atom, atom bound to Pt in Q ^B1 is a carbon atom, an oxygen atom, a nitrogen atom Is preferable, and a carbon atom is more preferable.
The group represented by Q ^B1 is preferably an aromatic hydrocarbon ring ligand bonded to Pt by a carbon atom, an aromatic heterocyclic ligand bonded to Pt by a carbon atom, or a nitrogen-containing bond bonded to Pt by a nitrogen atom An aromatic heterocyclic ligand and an acyloxy ligand, more preferably an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, and an aromatic heterocyclic ligand bonded to Pt with a carbon atom . The group represented by Q ^B1 is particularly preferably the same group as the Z ring formed together with C—X in the general formula (B).

  The Pt complex represented by the general formula (B) is more preferably a Pt complex represented by the general formula (C).

(In the general formula (C), A ^{C1 to} A ^C14 each independently represent C—R or N. R represents a hydrogen atom or a substituent. L ^C1 represents a single bond or a divalent linking group.)

The general formula (C) will be described.
A ^{C1 to} A ^C14 each independently represent C—R or N. R represents a hydrogen atom or a substituent. A ^{C1 to} A ^C6 have the same ^meanings as A ^{B1 to} A ^B6 in the general formula (B), and preferred ranges thereof are also the same.

As A ^{C7 to} A ^C14 , 0 to 2 is preferable and 0 to 1 is more preferable as the number of N (nitrogen atoms) in each of A ^{C7 to} A ^C10 and A ^{C11 to} A ^C14 . N is preferably selected from A ^{C8 to} A ^C10 and A ^{C12 to} A ^C14 , more preferably selected from A ^C8 , A ^C9 , A ^C12 and A ^C13, and selected from A ^C8 and A ^C12. It is particularly preferred that
When A ^{C7 to} A ^C14 represent C—R, R of A ^C8 and A ^C12 is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, or a fluorine group. And a cyano group, more preferably a hydrogen atom, a polyfluoroalkyl group, an alkyl group, an aryl group, a fluorine group and a cyano group, and particularly preferably a hydrogen atom, a polyfluoroalkyl group and a cyano group. R represented by A ^C7 , A ^C9 , A ^C11 and A ^C13 is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group or a cyano group, and more A hydrogen atom, a polyfluoroalkyl group, a fluorine group, and a cyano group are preferable, and a hydrogen atom and a fluorine group are particularly preferable. R represented by A ^C10 and A ^C14 is preferably a hydrogen atom or a fluorine group, and more preferably a hydrogen atom. When any of A ^{C7 to} A ^C9 and A ^{C11 to} A ^C13 represents C—R, Rs may be connected to each other to form a ring.

The linking group represented by L ^C1 has the same meaning as the linking group represented by L ^B1 in the general formula (B), and the preferred range is also the same.

  The Pt complex represented by the general formula (B) is more preferably a Pt complex represented by the general formula (D).

(In General Formula (D), A ^{D1 to} A ^D12 each independently represent C—R or N. R represents a hydrogen atom or a substituent. L ^D1 represents a single bond or a divalent linking group.)

General formula (D) is demonstrated.
A ^{D1 to} A ^D12 each independently represent C—R or N. R represents a hydrogen atom or a substituent.
A ^{D1 to} A ^D6 are synonymous with the substituents represented by A ^{B1 to} A ^B6 in the general formula (B), and the preferred ranges are also the same.

As A ^{D7 to} A ^D12 , in each of A ^{D7 to} A ^D9 and A ^{D10 to} AC ¹² , the number of N (nitrogen atoms) is preferably 0 to 2, more preferably 1 to 2, and particularly preferably 1. preferable. It represents the N ^is preferably selected from A D7 ^{to A D9} and ^A D10 ^{~A C12, A D7} is more preferably selected from, A ^{D9, A D10} and ^{A D12,} selected from ^{A D7} and ^{A D10} It is particularly preferred that
When A ^{D7 to} A ^D12 are C—R, R of A ^D8 and A ^D11 is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, or a fluorine group. A cyano group, more preferably a hydrogen atom, a polyfluoroalkyl group, an alkyl group, an aryl group, a fluorine group or a cyano group, and particularly preferably a polyfluoroalkyl group (for example, a trifluoromethyl group or a perfluoroethyl group). , A cyano group. R in A ^D7 , A ^D9 , A ^D10 , and A ^D12 is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group, and more preferably Is a hydrogen atom or a fluorine group, particularly preferably a hydrogen atom. When any of A ^{D7 to} A ^D12 represents D—R, Rs may be connected to each other to form a ring.

The linking group represented by L ^D1 has the same meaning as the linking group represented by L ^B1 in the general formula (B), and the preferred range is also the same.

  As a platinum complex (phosphorescent light emitting) material having a tetradentate ligand, one more preferable is a Pt complex represented by the general formula (E).

(In General Formula (E), A ^{E1 to} A ^E14 each independently represent C—R or N. R represents a hydrogen atom or a substituent. L ^E1 represents a single bond or a divalent linking group.)

The general formula (E) will be described. A ^{E1 to} A ^E12 each independently represent C—R or N. R represents a hydrogen atom or a substituent. A ^{E1 to} A ^E6 have the same ^meanings as A ^{B1 to} A ^B6 in the general formula (B), and preferred ranges thereof are also the same. A ^{E7 to} A ^E14 have the same ^meanings as A ^{C7 to} A ^C14 in the general formula (C), and preferred ranges thereof are also the same.

The linking group represented by L ^E1 has the same meaning as the linking group represented by L ^B1 in the general formula (B).
L ^E1 is preferably a single bond, an alkylene group, an arylene group, a heteroarylene group, an imino group, an oxy group, a thio group or a silylene group, more preferably an alkylene group, an imino group, an oxy group, a thio group or a silylene group. More preferably an alkylene group, more preferably a methylene group, still more preferably a disubstituted methylene group, still more preferably a dimethylmethylene group, diethylmethylene group, diisobutylmethylene group, dibenzylmethylene group, ethyl A methylmethylene group, a methylpropylmethylene group, an isobutylmethylmethylene group, a diphenylmethylene group, a methylphenylmethylene group, a cyclohexanediyl group, a cyclopentanediyl group, a fluorenediyl group, and a fluoromethylmethylene group, particularly preferably dimethylmethylene. Group, diphenylmethylene group, cyclohexanediyl group.

  As a platinum complex (phosphorescence) material having a tetradentate ligand, one of more preferable ones is a Pt complex represented by the general formula (F).

(In Formula (F), A ^{F1 to} A ^F14 each independently represent C—R or N. R represents a hydrogen atom or a substituent. L ^F1 represents a single bond or a divalent linking group.)

The general formula (F) will be described.
A ^{F1 to} A ^F14 each independently represent C—R or N. R represents a hydrogen atom or a substituent. A ^{F1 to} A ^F5 have the same ^meanings as A ^{B1 to} A ^B5 in the general formula (B). A ^{F1 to} A ^F5 are preferably C—R, and Rs may be connected to each other to form a ring. When A ^{F1 to} A ^F5 are C—R, R of A ^{F1 to} A ^F5 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group. More preferably a hydrogen atom, an aryl group, a fluorine group or a cyano group, and particularly preferably a hydrogen atom.

A ^{F7 to} A ^F14 have the same ^meanings as A ^{C7 to} A ^C14 in the general formula (C), and preferred ranges thereof are also the same. In particular, when any of A ^{C7 to} A ^C9 and A ^{C11 to} A ^C13 is C—R, the ring structure formed by connecting Rs to each other includes a furan ring, a benzofuran ring, a pyrrole ring, and a benzopyrrole. A ring, a thiophene ring, a benzothiophene ring, and a fluorene ring are preferable, and these rings may further have a substituent.

The linking group represented by L ^F1 has the same meaning as the linking group represented by L ^B1 in the general formula (B), and the preferred range is also the same.

  Examples of the platinum complex phosphorescent material having a tetradentate ligand include, but are not limited to, the following.

  The compounds exemplified as the complex compound can be produced, for example, by the steps shown below.

The above-mentioned metal complex compound is described in Journal of Organic Chemistry 53, 786, (1988), GR Newkome et al.), Page 789, left line 53 to right line 7, line 790, left line 18 line. -Method described in line 38, page 790, right column, line 19-30, and combinations thereof, Chemische Berichte 113, 2749 (1980), H. Lexy et al.), Page 2752, line 26-35. It can be synthesized by various methods such as the method described in 1.
For example, a ligand or a dissociated product thereof and a metal compound are mixed with a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent, In the presence of a sulfoxide solvent, water, etc., or in the absence of a solvent, in the presence of a base (inorganic and organic bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.) Or in the absence of a base, at room temperature or below, or by heating (in addition to normal heating, a method of heating with a microwave is also effective).

  In the present invention, a platinum complex having a tetradentate ligand is preferably used as a light emitting material.

  The platinum complex having a tetradentate ligand is contained in an amount of 0.1% by mass to 50% by mass with respect to the total compound mass generally forming the light emitting layer in the light emitting layer. In view of the above, the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.

[Organic electroluminescence device]
Hereinafter, the organic electroluminescent element of the present invention (hereinafter sometimes referred to as “organic EL element” as appropriate) will be described in detail.
The light-emitting element of the present invention has a cathode and an anode on a substrate, and an organic compound layer including an organic light-emitting layer (hereinafter sometimes simply referred to as “light-emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  The organic electroluminescent element of the present invention may be a white light emitting element.

  As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.

  The light-emitting element of the present invention is preferably an element having at least three layers of a hole transport layer, a light-emitting layer, and an electron transport layer. More preferably, a layer that promotes hole injection into the light emitting layer, a layer that blocks electrons, and a layer that blocks excitons are added between the hole transport layer and the light emitting layer.

  Next, the elements constituting the light emitting material of the present invention will be described in detail.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic compound layer. Specific examples include yttria stabilized zirconia, inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin, norbornene resin. And organic materials such as poly (chlorotrifluoroethylene).
For example, when glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

  There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. In general, the shape of the substrate is preferably a plate shape. The substrate structure may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.

  The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the organic light emitting layer.

The substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.
As a material for the moisture permeation preventive layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method.
When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.

<Anode>
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the organic electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element. Is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is detailed in Yutaka Sawada's “New Development of Transparent Conductive Film” published by CMC (1999), and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say.

  The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

<Organic compound layer>
The organic compound layer in the present invention will be described.
The organic electroluminescent element of the present invention has at least one organic compound layer including a light emitting layer, and the organic compound layer other than the organic light emitting layer includes a hole transport layer, an electron transport layer as described above. , Charge blocking layer, hole injection layer, electron injection layer and the like.

-Formation of organic compound layer-
In the organic electroluminescent element of the present invention, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

-Organic light emitting layer-
The organic light emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer having a function of providing a field to emit light.
The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material.

  The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed.

  Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

The compound represented by the general formula (1) may be contained in any one of the organic compound layers, and may be contained in a plurality of layers. The light emitting layer, the hole blocking layer, the electron It is preferably contained in the transport layer and the electron injection layer, more preferably contained in the light emitting layer and the electron transport layer, and when contained in the light emitting layer, it is most preferably contained as a host material. preferable.
When the light emitting layer contains a compound represented by any one of the general formulas (1) to (4) as a host material, the compound represented by any one of the general formulas (1) to (4) in the light emitting layer The content is preferably 5 to 99.9% by mass, and more preferably 60 to 99% by mass. When contained in the hole blocking layer, the electron transport layer, and the electron injection layer, the content of the compound of the present invention in each layer is preferably 70 to 100%, more preferably 85 to 100%, Most preferably, it is 100%.

In the organic electroluminescent element of the present invention, the compound represented by any of the general formulas (1) to (4) is preferably contained in a layer adjacent to the light emitting layer. Thereby, accumulation of electric charges (holes and electrons) in the light emitting layer can be suppressed.
Moreover, when the compound represented by any one of the general formulas (1) to (4) is contained in a layer adjacent to the light emitting layer, it may be contained in an amount of 70 to 100% by mass in the layer adjacent to the light emitting layer. Preferably, 90 to 100% by mass is contained.
Furthermore, when the compound represented by any one of the general formulas (1) to (4) is contained in a layer adjacent to the light emitting layer, the compound represented by any one of the general formulas (1) to (4) is used. A single layer is preferred in terms of film uniformity.

In the organic electroluminescence device of the present invention, it is preferable that the compound represented by any one of the general formulas (1) to (4) is contained in a layer adjacent to the cathode. This enables efficient electron injection from the cathode.
When the compound represented by any one of the general formulas (1) to (4) is contained in a layer adjacent to the cathode, it is preferably contained in an amount of 70 to 100% by mass in the layer adjacent to the cathode. More preferably, the content is 100% by mass.

  When the silane derivative represented by any one of the general formulas (1) to (4) is included in the layer adjacent to the cathode, the film thickness is preferably 1 nm to 50 nm, and preferably 1 nm to 30 nm. Is more preferably 1 nm or more and 10 nm or less, and particularly preferably 1 nm or more and 5 nm or less.

  The silane derivatives represented by the general formulas (1) to (4) are more preferably contained in a layer adjacent to the light emitting layer and the cathode.

The charge mobility of the host material contained in the light emitting layer is preferably 1 × 10 ⁻⁶ cm ² / Vs or more and preferably 1 × 10 ⁻¹ cm ² / Vs or less, and 5 × 10 ⁻⁶ cm ² / Vs or more. It is more preferably 1 × 10 ⁻² cm ² / Vs or less, further preferably 1 × 10 ⁻⁵ cm ² / Vs or more and 1 × 10 ⁻² cm ² / Vs or less, and more preferably 5 × 10 ⁻⁵ cm. ² / Vs or more and 1 × 10 ⁻² cm ² / Vs or less is particularly preferable.

The T ₁ level (the energy level of the lowest triplet excited state) of the host material included in the light-emitting element of the present invention is 60 kcal / mol or more (251.4 kJ / mol or more), 90 kcal / mol or less (377.1 kJ / mol or less). ), Preferably 62 kcal / mol or more (259.78 kJ / mol or more), 85 Kcal / mol or less (356.15 kJ / mol or less), more preferably 65 kcal / mol or more (272.35 kJ / mol or more), More preferably, it is 80 kcal / mol or less (335.2 kJ / mol or less).

The T ₁ level (energy level in the lowest triplet excited state) of the layer adjacent to the light emitting layer of the light emitting element of the present invention is 60 kcal / mol or more (251.4 kJ / mol or more), 90 kcal / mol or less (377.1 kJ / mol or less), preferably 62 kcal / mol or more (259.78 kJ / mol or more), 85 kcal / mol or less (356.15 kJ / mol or less), more preferably 65 kcal / mol or more (272.35 kJ / mol). mol) or more and 80 kcal / mol or less (335.2 kJ / mol or less).

  The glass transition point of the host material, the electron transport layer, and the hole transport material included in the organic electroluminescent device of the present invention is preferably 90 ° C. or higher and 400 ° C. or lower, and more preferably 100 ° C. or higher and 380 ° C. or lower. 120 ° C. or higher and 370 ° C. or lower is more preferable, and 140 ° C. or higher and 360 ° C. or lower is particularly preferable.

The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of fluorescent materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and pyromethene derivatives And various metal complexes typified by metal complex, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the phosphorescent material that can be used in the present invention include complexes containing transition metal atoms or lanthanoid atoms.
Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.
Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include, for example, G. Wilkinson et al., Comprehensive Coordination Chemistry, PergamonPress 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag 1987, Akio Yamamoto Examples of the ligand include those described in “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982.
Specific ligands are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketones Ligand (for example, acetylacetone), carboxylic acid ligand (for example, acetic acid ligand), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing Heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  The phosphorescent material is preferably an iridium complex or a platinum complex. In particular, a platinum complex of a tetradentate ligand or an iridium complex having a fluorine-substituted phenylpyridine as a ligand is preferable, and a platinum complex of a tetradentate ligand is most preferable.

  Specific examples of the phosphorescent material include, but are not limited to, the following compounds in addition to the aforementioned tetradentate platinum complex.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass.

  The emission maximum wavelength of the phosphorescent material is preferably 500 nm or less, more preferably 480 nm or less, further preferably 470 nm or less, and particularly preferably 460 nm or less.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon In addition, a layer containing various metal complexes represented by an Ir complex having phenylazole or phenylazine as a ligand is preferable.
The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and still more preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side.
Examples of organic compounds constituting the hole blocking layer include aluminum complexes such as BAlq [bis- (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum], triazole derivatives, BCP (2,9 And phenanthroline derivatives such as -dimethyl-4,7-diphenyl-1,10-phenanthroline).
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<Protective layer>
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerization of a copolymer having a cyclic structure in the copolymer main chain. Copolymer, 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like.

  The method for forming the protective layer is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

<Sealing>
Furthermore, the organic electroluminescent element of this invention may seal the whole element using a sealing container.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Obtainable.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving method described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6023308, and the like can be applied.

The external quantum efficiency of the light emitting device of the present invention is preferably 5% or more, more preferably 10% or more, and further preferably 13% or more. The value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency near 100 to 300 cd / m ² when the device is driven at 20 ° C. Can do.

  The internal quantum efficiency of the light emitting device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. The internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%. However, the shape of the substrate, the shape of the electrode, the thickness of the organic layer, the thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.

[Comparative Example 1-1]

The cleaned ITO substrate is put in a vapor deposition apparatus, and copper phthalocyanine is vapor-deposited to a thickness of 10 nm. Vapor deposited to thickness. On top of this, compound B-1 and compound A were vapor-deposited at a ratio of 12:88 (mass ratio) to a thickness of 30 nm (light emitting layer), and on this, BAlq [bis- (2-methyl-8-quinolinolate) -4- (Phenylphenolate) aluminum] was vapor-deposited to a thickness of 6 nm, and Alq (tris (8-hydroxyquinoline) aluminum complex) was vapor-deposited thereon to a thickness of 20 nm. On top of this, lithium fluoride was vapor-deposited to a thickness of 3 nm, and then 60 nm of aluminum was vapor-deposited to produce a device. The OLED test system ST-D type manufactured by Tokyo System Development Co., Ltd. was set and driven at a current density of 10 mA / cm ² . Phosphorescence emission of λmax = 470 nm derived from compound B-1 was obtained.
[Comparative Example 1-2]
A device D was similarly evaluated by using Compound D-1 instead of Compound A of Comparative Example 1-1. Phosphorescence emission derived from compound B-1 was obtained.
[Comparative Example 1-3]
A device D was similarly evaluated using Compound D-2 instead of Compound A of Comparative Example 1-1. Phosphorescence emission derived from compound B-1 was obtained.
[Comparative Example 1-4]
A device D was similarly evaluated using Compound D-3 instead of Compound A of Comparative Example 1-1. Phosphorescence emission derived from compound B-1 was obtained.
[Comparative Example 1-5]
A device was evaluated in the same manner using Compound B-2 instead of Compound B-1 of Comparative Example 1-1. No phosphorescence emission derived from compound B-2 was observed.
[Comparative Example 1-6]
A device D was similarly evaluated by using Compound D-1 instead of Compound A of Comparative Example 1-5. No phosphorescence emission derived from compound B-2 was observed.
[Comparative Example 1-7]
A device D was similarly evaluated using Compound D-2 instead of Compound A of Comparative Example 1-5. No phosphorescence emission derived from compound B-2 was observed.
[Comparative Example 1-8]
A device D was similarly evaluated using Compound D-3 instead of Compound A of Comparative Example 1-5. No phosphorescence emission derived from compound B-2 was observed.
[Comparative Example 1-9]
A device was evaluated in the same manner using Compound B-3 instead of Compound B-1 of Comparative Example 1-1. Phosphorescence emission of λmax = 479 nm derived from compound B-3 was obtained.
[Comparative Example 1-10]
A device B was similarly evaluated by using Compound B-4 instead of Compound B-1 of Comparative Example 1. Phosphorescence emission of λmax = 470 nm derived from compound B-4 was obtained.
[Comparative Example 1-11]
A device was evaluated in the same manner using Compound B-5 instead of Compound B-1 of Comparative Example 1. Phosphorescence emission of λmax = 499 nm derived from compound B-5 was obtained.
[Comparative Example 1-12]
A device was evaluated in the same manner using Compound B-6 instead of Compound B-1 of Comparative Example 1. A phosphorescence emission of λmax = 483 nm derived from the compound B-6 was obtained.
[Comparative Example 1-13]
A device was evaluated in the same manner using Compound B instead of Compound A of Comparative Example 1-1. Phosphorescence emission derived from compound B-1 was obtained.

[Example 1-1]
The device was evaluated in the same manner as in Comparative Example 1-1 using the compound (D-1) of the general formula (2) instead of the compound A in Comparative Example 1-3. Blue phosphorescence emission derived from the compound B-3 was obtained.
[Example 1-2]
The device was evaluated in the same manner as in Comparative Example 1-1 using the compound (D-2) of the general formula (2) instead of the compound (D-1) of Example 1-1. Blue phosphorescence emission derived from the compound B-3 was obtained.
[Example 1-3]
The device was evaluated in the same manner as Comparative Example 1-1 using the compound (D-3) of the general formula (2) instead of the compound (D-1) of Example 1-1. Phosphorescence emission derived from the compound B-3 was obtained.
[Example 1-4]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-4 instead of Compound B-3 in Example 1-1. Blue phosphorescence emission derived from the compound B-4 was obtained.
[Example 1-5]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-4 instead of Compound B-3 in Example 1-2. Blue phosphorescence emission derived from the compound B-4 was obtained.
[Example 1-6]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-4 instead of Compound B-3 in Example 1-3. Phosphorescence emission derived from the compound B-4 was obtained.
[Example 1-7]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-5 instead of Compound B-3 in Example 1-1. Blue phosphorescence emission derived from compound B-5 was obtained.
[Example 1-8]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-5 instead of Compound B-3 in Example 1-2. Blue phosphorescence emission derived from compound B-5 was obtained.
[Example 1-9]
The device was evaluated in the same manner as in Comparative Example 1-1 by using Compound B-5 instead of Compound B-3 in Example 1-3. Phosphorescence emission derived from compound B-5 was obtained.
[Example 1-10]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-6 instead of Compound B-3 in Example 1-1. Blue phosphorescence emission derived from compound B-6 was obtained.
[Example 1-11]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-6 instead of Compound B-3 in Example 1-2. Blue phosphorescence emission derived from compound B-6 was obtained.
[Example 1-12]
The device was evaluated in the same manner as in Comparative Example 1-1 using Compound B-6 instead of Compound B-3 in Example 1-3. Phosphorescence emission derived from compound B-6 was obtained.

  Table 1 shows that the light-emitting element of the present invention is excellent in both efficiency and durability.

[Comparative Example 2-1]
The cleaned ITO substrate was put into a vapor deposition apparatus, and NPD (N, N′-di-α-naphthyl-N, N′-diphenyl) -benzidine) was vapor-deposited to a thickness of 100 nm. On top of this, compound B-3 and compound C were vapor-deposited at a ratio of 13:87 (mass ratio) to a thickness of 15 nm (light emitting layer), and on this, BAlq [bis- (2-methyl-8-quinolinolate) -4- (Phenylphenolate) aluminum] was deposited to a thickness of 40 nm (electron transport layer). On top of this, lithium fluoride was vapor-deposited to a thickness of 3 nm, and then 60 nm of aluminum was vapor-deposited to produce a device. As a result of applying a constant DC voltage to the EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, phosphorescence emission derived from the compound B-3 was obtained.
[Comparative Example 2-2]
A device B was similarly evaluated by using Compound B-4 instead of Compound B-3 of Comparative Example 2-1. Phosphorescence emission derived from B-4 was obtained.
[Comparative Example 2-3]
A device was evaluated in the same manner using Compound B-5 instead of B-3 in Comparative Example 2-1. Phosphorescence emission derived from compound B-5 was obtained.
[Comparative Example 2-4]
A device was evaluated in the same manner using Compound B-6 instead of B-3 of Comparative Example 2-1. Phosphorescence emission derived from compound B-6 was obtained.

[Comparative Example 2-5]
The film pressure of BAlq, which is the electron transport layer of Comparative Example 2-1, was changed from 40 nm to 39 nm, and further Alq was deposited thereon to a thickness of 1 nm. On top of this, lithium fluoride was vapor-deposited to a thickness of 3 nm, and then 60 nm of aluminum was vapor-deposited to produce a device. The device was evaluated in the same manner as in Comparative Example 2-1, and blue phosphorescence emission derived from the compound B-3 was obtained.
[Comparative Example 2-6]
A device was evaluated in the same manner using Compound B-4 instead of Compound B-3 of Comparative Example 2-4. Phosphorescence emission derived from B-4 was obtained.
[Comparative Example 2-7]
A device was evaluated in the same manner using Compound B-5 instead of B-3 in Comparative Example 2-4. Phosphorescence emission derived from B-5 was obtained.
[Comparative Example 2-8]
A device was evaluated in the same manner using Compound B-6 instead of B-3 in Comparative Example 2-4. Phosphorescence emission derived from B-6 was obtained.

[Example 2-1]
A device was evaluated in the same manner using Compound D-4 of the general formula (4) instead of Alq of Comparative Example 2-5. Phosphorescence emission derived from B-3 was obtained.
[Example 2-2]
A device was evaluated in the same manner using Compound D-5 of the general formula (2) instead of Alq of Comparative Example 2-5. Phosphorescence emission derived from B-3 was obtained.
[Example 2-3]
The device fabrication was evaluated in the same manner using Compound D-6 of the general formula (3) instead of Alq of Comparative Example 2-5. Phosphorescence emission derived from B-3 was obtained.
[Example 2-4]
The device fabrication was evaluated in the same manner using Compound D-4 of the general formula (4) instead of Alq of Comparative Example 2-6. Phosphorescence emission derived from B-4 was obtained.
[Example 2-5]
A device was evaluated in the same manner by using Compound D-5 of the general formula (2) instead of Alq of Comparative Example 2-6. Phosphorescence emission derived from B-4 was obtained.
[Example 2-6]
The device fabrication was evaluated in the same manner using Compound D-6 of the general formula (3) instead of Alq of Comparative Example 2-6. Phosphorescence emission derived from B-4 was obtained.
[Example 2-7]
The device fabrication was evaluated in the same manner using Compound D-4 of the general formula (4) instead of Alq of Comparative Example 2-7. Phosphorescence emission derived from B-5 was obtained.
[Example 2-8]
A device was evaluated in the same manner by using Compound D-5 of the general formula (2) instead of Alq of Comparative Example 2-7. Phosphorescence emission derived from B-5 was obtained.
[Example 2-9]
The device fabrication was evaluated in the same manner using Compound D-6 of the general formula (3) instead of Alq of Comparative Example 2-7. Phosphorescence emission derived from B-5 was obtained.
[Example 2-10]
A device was evaluated in the same manner using Compound D-4 of the general formula (4) instead of Alq of Comparative Example 2-8. Phosphorescence emission derived from B-6 was obtained.
[Example 2-11]
A device was evaluated in the same manner by using Compound D-5 of the general formula (2) instead of Alq of Comparative Example 2-8. Phosphorescence emission derived from B-6 was obtained.
[Example 2-12]
A device was evaluated in the same manner using Compound D-6 of the general formula (3) instead of Alq of Comparative Example 2-8. Phosphorescence emission derived from B-6 was obtained.

  Known compounds represented by compounds D-1 to D-4 are described in J. Org. Org. Chem. 1962, 27, 1836, (D-1); Organomet. Chem. 1984, 271, 319, (D-2); Chem. Lett. 2005, 34, 1698, (D-3); Chem. Soc. Chem. Commun. It can be synthesized by the method described in 1993, No. 9, page 744, (D-4). In addition, novel compounds D-5 and D-6 can also be synthesized with reference to the method described in the above document.

Table 2 shows that the silane derivative compound represented by any one of the general formulas (1) to (4) according to the present invention exhibits the effect of the present invention even when included in a layer adjacent to the light emitting layer. .
The same effect could be obtained even in a light emitting device using a combination of any of the other silane derivative compounds of general formulas (1) to (4) and a platinum complex compound according to the present invention.

Claims (9)

An organic electroluminescent element comprising a platinum complex having at least a silane derivative represented by the general formula (1) and a tetradentate ligand between a pair of electrodes.

R ^{101 to} R ¹⁰⁴ represent a hydrogen atom or a substituent. R ^{105 to} R ¹⁰⁸ each represents a hydrogen atom or a substituent. The organic electroluminescent element according to claim 1, wherein the silane derivative represented by the general formula (1) is a compound represented by the general formula (2).

R ²⁰¹ to R ²⁰⁴ represents a hydrogen atom or a substituent. X ²⁰¹ to X ²⁰⁸ is a substituted or unsubstituted carbon atoms, or, represent a nitrogen atom. The organic electroluminescent element according to claim 1, wherein the silane derivative represented by the general formula (1) is a compound represented by the general formula (3).

R ^{301 to} R ³⁰⁴ represent a hydrogen atom or a substituent. R ³⁰⁵ and R ³⁰⁶ each represent a hydrogen atom or a substituent. X ^{301 to} X ³⁰⁴ represent a substituted or unsubstituted carbon atom or a nitrogen atom. The organic electroluminescent element according to claim 3, wherein the silane derivative represented by the general formula (3) is a compound represented by the general formula (4).

R ^{401 to} R ⁴⁰⁸ represent a hydrogen atom or a substituent. R ^{409 to} R ⁴¹² each represents a hydrogen atom or a substituent. X ⁴⁰¹ and X ^{402 each} represents a substituted or unsubstituted carbon atom or a nitrogen atom.   The organic electroluminescent element according to claim 1, wherein the light emitting layer contains a silane derivative represented by at least one of the general formulas (1) to (4).   6. The organic electroluminescent element according to claim 1, wherein the silane derivative represented by at least one of the general formulas (1) to (4) is contained in a layer adjacent to the light emitting layer.   The organic electroluminescent element according to any one of claims 1 to 6, wherein a silane derivative represented by at least one of the general formulas (1) to (4) is contained in a layer adjacent to the cathode.   The organic material according to any one of claims 1 to 7, wherein a glass transition temperature of the silane derivative represented by at least one of the general formulas (1) to (4) is 130 ° C or higher and 450 ° C or lower. Electroluminescent device.   The lowest excited triplet energy level of the silane derivative represented by at least one of the general formulas (1) to (4) is 65 kcal / mol (272.35 kJ / mol) or more and 80 kcal / mol or less (335.2 kJ / The organic electroluminescent element according to claim 1, wherein the organic electroluminescent element is 1 mol or less.