JP5693532B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescent device (hereinafter, also referred to as “organic EL device”, “light emitting device” or “device”) that can emit light by converting electric energy into light, and in particular, emission characteristics and durability. The present invention relates to an organic electroluminescent device having excellent resistance.

  Today, research and development on various display elements (organic light-emitting elements) using organic light-emitting materials is active, and among them, organic EL elements can obtain high-luminance light emission at a low voltage and attract attention as promising display elements. ing. For example, an EL element that forms an organic thin film by vapor deposition of an organic compound is known (see, for example, Non-Patent Document 1). The organic EL device described in this document has a laminated structure of an electron transport material and a hole transport material, and its light emission characteristics are greatly improved as compared with a conventional single layer device.

  In recent years, the use of phosphorescent light emitting materials has led to higher device efficiency. Known phosphorescent materials include iridium complexes and platinum complexes (see, for example, Patent Documents 1, 2, and 3).

  In the light emitting layer of Patent Document 3, Ir (ppy) (iridium tris (phenylpyridine)) is used as a dopant, and CBP (4,4'-dicarbazole biphenyl) is combined as a host material.

  In Patent Documents 4, 5, and 6, MCP (meta-dicarbazo-9-lylbenzene) is used as a host material. However, the host material is required to be improved in terms of luminous efficiency and durability.

US Pat. No. 6,303,238 International Publication No. 00/57676 Pamphlet International Publication No. 00/70655 Pamphlet International Patent Publication No. WO04 / 016711 International Patent Publication WO03 / 059015 US Patent Publication US2003 / 0175553

Applied Physics Letters, 51, 913, 1987

  An object of the present invention is to provide a light emitting device having high luminous efficiency and excellent durability. Another object is to provide a compound suitable for the light-emitting element.

（一般式(Ｉ)中、Ｑ¹〜Ｑ^４はそれぞれ独立に炭素原子またはケイ素原子であり、Ｒ⁰は水素原子、置換もしくは無置換の、炭素数１〜１０のアルキル基を表し、Ｒ¹は水素原子を表す。Ｒ²〜Ｒ¹⁵はそれぞれ独立に水素原子もしくは置換基を表す。Ｚ¹〜Ｚ¹²はそれぞれ独立に、置換もしくは無置換の、アルキル基、アリール基、ヘテロアリール基を表す。Ｚ¹〜Ｚ^３、Ｚ^４〜Ｚ^６、Ｚ^７〜Ｚ^９、Ｚ^1０〜Ｚ¹²は、それぞれ結合して環を形成しても良い。）
＜２＞
前記一般式（Ｉ）におけるＲ⁰、及びＲ^２〜Ｒ¹⁵が水素原子を表すことを特徴とする＜１＞に記載の化合物。
本発明は＜１＞及び＜２＞に関するものであるが、参考のためその他の事項（例えば下記（１）〜（３）に記載した事項など）についても記載した。
（１）一対の電極間に発光層を含む少なくとも一層の有機層を有する有機電界発光素子であって、下記一般式（Ｉ）で表される化合物の少なくとも一種と、４座配位子を有する錯体系燐光発光材料の少なくとも一種とを発光層に含有することを特徴とする有機電界発光素子。 This object has been achieved by the following means.
<1>
Compound represented by the following general formula (I).

(In General Formula (I), Q ^{1 to} Q ⁴ are each independently a carbon atom or a silicon atom, R ⁰ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and R ¹ Represents a hydrogen atom, R ^{2 to} R ¹⁵ each independently represents a hydrogen atom or a substituent, and Z ^{1 to} Z ¹² each independently represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. ^{.Z 1 ~Z 3, Z 4 ~Z} 6, Z 7 ~Z 9, Z 10 ~Z 12 may be bonded to each other to form a ring.)
< 2>
<0> The compound according to <1>, wherein R ⁰ and R ^{2 to} R ¹⁵ in the general formula (I) represent a hydrogen atom .
The present invention relates to <1> and <2> , but other matters (for example, the matters described in (1) to (3) below) are also described for reference.
(1) An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, and having at least one compound represented by the following general formula (I) and a tetradentate ligand An organic electroluminescence device comprising a light emitting layer containing at least one kind of a complex phosphorescent material.

(In General Formula (I), Q ^{1 to} Q ⁴ are each independently a carbon atom or a silicon atom, and R ⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heteroaryl bonded with a carbon atom. R ¹ represents a hydrogen atom, R ^{2 to} R ¹⁵ each independently represents a hydrogen atom or a substituent, and Z ^{1 to} Z ¹² each independently represents a substituted or unsubstituted alkyl group or aryl group. Z ^{1 to} Z ³ , Z ^{4 to} Z ⁶ , Z ^{7 to} Z ⁹ , and Z ^{10 to} Z ¹² may be bonded to each other to form a ring.
(2) An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein the layer between the light emitting layer and the cathode contains a metal complex (1) The organic electroluminescent element of description.
(3) An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, and containing at least one compound containing at least two carbazole skeletons in at least one layer adjacent to the light emitting layer The organic electroluminescent element as described in (1) or (2) above, wherein

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element excellent in luminous efficiency and durability can be provided.

  The organic electroluminescent element of the present invention (hereinafter sometimes referred to as “the element of the present invention”) is at least one organic layer including a light emitting layer (a layer composed of only an organic compound) between a pair of electrodes. Or an organic layer containing an inorganic compound), wherein the compound represented by the following general formula (I) and a tetradentate ligand are included in the light emitting layer: And a complex-type phosphorescent light-emitting material.

  Hereinafter, the compound represented by formula (I) will be described.

(In General Formula (I), Q ^{1 to} Q ⁴ are each independently a carbon atom or a silicon atom, and R ⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heteroaryl bonded with a carbon atom. R ¹ represents a hydrogen atom, R ^{2 to} R ¹⁵ each independently represents a hydrogen atom or a substituent, and Z ^{1 to} Z ¹² each independently represents a substituted or unsubstituted alkyl group or aryl group. Z ^{1 to} Z ³ , Z ^{4 to} Z ⁶ , Z ^{7 to} Z ⁹ , and Z ^{10 to} Z ¹² may be bonded to each other to form a ring.

R ⁰ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group (that is, a group bonded to a benzene ring at a carbon atom in the heteroaryl group), preferably a hydrogen atom or an alkyl group, Particularly preferred is an atom.

The preferred range of the alkyl group, aryl group, and heteroaryl group for R ⁰ is the same as the substituents for R ^{4 to} R ¹⁵ described later. These substituents may be further substituted with other substituents, and these substituents may be bonded to R ² and R ³ to form a ring.

Q ¹ to Q ⁴ are each independently a carbon atom or a silicon atom, it is preferred that all all Q ¹ to Q ⁴ is a carbon atom or Q ¹ to Q ⁴ is a silicon atom, the Q ¹ to Q ⁴ It is particularly preferred that all are carbon atoms.

Z ^{1 to} Z ¹² each independently represents an alkyl group, an aryl group, or a heteroaryl group, preferably an alkyl group or an aryl group, and particularly preferably an alkyl group. Z ^{1 to} Z ³ , Z ^{4 to} Z ⁶ , Z ^{7 to} Z ⁹ , and Z ^{10 to} Z ¹² may be bonded to each other to form a ring.

The preferred ranges of the alkyl group, aryl group and heteroaryl group of Z ^{1 to} Z ¹² are the same as the substituents of R ^{4 to} R ¹⁵ described later. These substituents may be further substituted with other substituents.

R ^{2 to} R ¹⁵ each independently represents a hydrogen atom or a substituent. Although it does not specifically limit as a substituent, For example, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryl Oxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group , Phosphoric acid amide group, hydroxy group, mercapto group, halogen group, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group, silyl group, silyloxy And the like.

The substituent for R ² and R ³ is preferably an alkyl group, an aryl group, a heteroaryl group, an acyl group, an amino group, or a halogen group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably t-Butyl group and phenyl group. These substituents may be further substituted with other substituents.

R ^{4 to} R ¹⁵ are preferably an alkyl group, an aryl group, a heteroaryl group, an acyl group, an amino group, or a halogen group, more preferably an alkyl group, an aryl group, or a heteroaryl group, particularly preferably. t-Butyl group and phenyl group. These substituents may be further substituted with other substituents, and these substituents may be bonded to each other to form a ring.

  Here, as an alkyl group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C10, for example, methyl, ethyl, n-propyl, iso-propyl, n -Butyl, tert-butyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-octadecyl, n-hexadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, etc. It is done.

  Moreover, as an alkenyl group, Preferably it is C2-C30, More preferably, it is C2-C20, Most preferably, it is C2-C10, for example, vinyl, allyl, 1-propenyl, 1-isopropenyl, -Butenyl, 2-butenyl, 3-pentenyl and the like can be mentioned.

  The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Examples thereof include ethynyl, propargyl, 1-propynyl, and 3-pentynyl. It is done.

  Moreover, as an aryl group, Preferably it is C6-C30, More preferably, it is C6-C20, Most preferably, it is C6-C12, for example, phenyl, o-methylphenyl, m-methylphenyl, p- Examples include methylphenyl, 2,4-xylyl, p-cumenyl, mesityl, naphthyl, anthranyl and the like.

  Further, the heteroaryl group preferably has 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, specifically, for example, imidazolyl and pyrazolyl. , Pyridyl, pyrazyl, pyrimidyl, triazinyl, quinolyl, isoquinolinyl, pyrrolyl, indolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl and the like.

  The amino group preferably has 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms. For example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, Examples include diphenylamino and ditolylamino.

  Moreover, as an alkoxy group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C10, for example, methoxy, an ethoxy, butoxy, 2-ethylhexyloxy etc. are mentioned. It is done.

  Moreover, as an aryloxy group, Preferably it is C6-C30, More preferably, it is C6-C20, Most preferably, it is C6-C12, for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc. Is mentioned.

  Moreover, as a heterocyclic oxy group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy etc. are mentioned. .

  The acyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl.

  Moreover, as an alkoxycarbonyl group, Preferably it is C2-C30, More preferably, it is C2-C20, Most preferably, it is C2-C12, for example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned.

  The aryloxycarbonyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl.

  Moreover, as an acyloxy group, Preferably it is C2-C30, More preferably, it is C2-C20, Most preferably, it is C2-C10, for example, acetoxy, benzoyloxy, etc. are mentioned.

  The acylamino group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino.

  Moreover, as an alkoxycarbonylamino group, Preferably it is C2-C30, More preferably, it is C2-C20, Most preferably, it is C2-C12, for example, methoxycarbonylamino etc. are mentioned.

  The aryloxycarbonylamino group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino.

  Moreover, as a sulfonylamino group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, methanesulfonylamino, benzenesulfonylamino, etc. are mentioned.

  The sulfamoyl group preferably has 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 12 carbon atoms. For example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamo Famoyl etc. are mentioned.

  The carbamoyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. .

  Moreover, as an alkylthio group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, methylthio, ethylthio, etc. are mentioned.

  Moreover, as an arylthio group, Preferably it is C6-C30, More preferably, it is C6-C20, Most preferably, it is C6-C12, for example, phenylthio etc. are mentioned.

  The heterocyclic thio group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, pyridylthio, 2-benzimidazolylthio, 2-benz Examples include oxazolylthio and 2-benzthiazolylthio.

  Moreover, as a sulfonyl group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, mesyl, tosyl, trifluoromethanesulfonyl etc. are mentioned.

  Moreover, as a sulfinyl group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, methanesulfinyl, benzenesulfinyl, etc. are mentioned.

  Moreover, as a ureido group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, ureido, methylureido, phenylureido etc. are mentioned.

  Moreover, as a phosphoric acid amide group, Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, diethyl phosphoric acid amide, phenylphosphoric acid amide etc. are mentioned. It is done.

  Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

  Moreover, as a heterocyclic group, Preferably it is C1-C30, More preferably, it is C1-C12, As a hetero atom, it is a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, piperidyl, Examples thereof include morpholino and pyrrolidyl.

  Moreover, as a silyl group, Preferably it is C3-C40, More preferably, it is C3-C30, Most preferably, it is C3-C24, for example, trimethylsilyl, triphenylsilyl, etc. are mentioned.

  Moreover, as a silyloxy group, Preferably it is C3-C40, More preferably, it is C3-C30, Most preferably, it is C3-C24, for example, trimethylsilyloxy, triphenylsilyloxy, etc. are mentioned.

The compound represented by the general formula (I) of the present invention may be a low molecular compound, or an oligomer compound or a polymer compound having a structure represented by the general formula (I) in the main chain or side chain (weight) The average molecular weight (in terms of polystyrene) may preferably be 1,000 to 5,000,000, more preferably 2,000 to 1,000,000, and still more preferably 3,000 to 100,000. The compound represented by the general formula (I) of the present invention is preferably a low molecular compound.
In the case where the compound represented by the general formula (I) of the present invention is an oligomer compound or a polymer compound having a structure represented by the general formula (I) in the main chain or side chain, R ⁰ as the main chain or side chain. Any one or a plurality of R ¹⁵ are included, more preferably any of R ^{0 to} R ³ is included, and R ⁰ is particularly preferably included.

In the present invention, the compound represented by the general formula (I) of the present invention is included in the light emitting layer, but its use is not limited, and it may be contained in any layer other than the light emitting layer in the organic layer. Good. The introduction layer other than the light emitting layer is preferably contained in one or more of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer. More preferably, it is contained in the hole transport layer and the electron transport layer.
In the light emitting layer, the compound represented by the general formula (I) of the present invention is preferably contained in an amount of 1 to 100% by mass, more preferably 50 to 100% by mass, and more preferably 80 to 100% by mass. Is more preferable.
In addition, when the compound represented by the general formula (I) of the present invention is contained in a layer other than the light emitting layer, it is preferably contained in an amount of 1 to 100% by mass, more preferably 50 to 100% by mass, More preferably, it is contained in an amount of 80 to 100% by mass.

  Specific examples of the compound represented by formula (I) are listed below, but the present invention is not limited to these compounds.

  Specific examples of the polymer compound and oligomer compound containing the compound represented by the general formula (I) are given below, but the present invention is not limited to these compounds. In the case of a polymer compound, it may be a homopolymer compound or a copolymer, and the copolymer may be a random copolymer, an alternating copolymer, or a block copolymer. In the figure, m: n represents the molar ratio of each monomer contained in the polymer, m represents 1 to 100, n represents a numerical value of 0 to 99, and the sum of m and n is 100.

Hereinafter, the light emitting material contained in the light emitting layer together with the compound represented by the general formula (I) will be described.
In the present invention, a complex phosphorescent material having a tetradentate ligand is used as the light emitting material. The complex phosphorescent material is preferably a metal complex containing iridium or platinum, and specific examples thereof include compounds described in WO 04-108857.
By using a complex phosphorescent material having a tetradentate ligand, there is an effect of improving luminous efficiency and durability.

  As the complex phosphorescent material having a tetradentate ligand, a metal complex represented by the following general formula (II) is preferable, and a metal complex represented by the following general formula (III) is more preferable.

(In the general formula (II), M ¹¹ represents a metal ion or an atomic group containing a metal ion. Q ¹¹ , Q ¹² , Q ¹³ , and Q ¹⁴ each represents an atomic group coordinated to M ^11. L ¹¹ , L ¹² , L ¹³ and L ¹⁴ each represent a single bond or a linking group, n ¹¹ represents 0 or 1. When n ¹¹ is 0, a bond via L ¹⁴ between Q ¹³ and Q ¹⁴ The bond between M ^{11 and} Q ^11, the bond between M ^{11 and} Q ¹² , the bond between M ^{11 and} Q ^13, and the bond between M ^{11 and} Q ¹⁴ may be a covalent bond, (It may be a coordinate bond or an ionic bond.)

(In General Formula (III), M ²¹ represents a metal ion or an atomic group containing a metal ion. Q ²³ and Q ²⁴ each represent an atomic group coordinated to M ^21. L ²² represents a single bond or a linking group. the representative ^{.R 21, R 22} is a bond between ^.M 21 -N represents an integer of each ^{.m 21, m 22} indicating a substituent 0-3 (dotted line) is, ^{.M 21} showing a coordinate bond binding between binding and M ²¹ -Q ²⁴ between -Q ²³ may be a covalent bond may be a coordinate bond may be ionic bonds.)

The general formula (II) will be described. M ¹¹ represents a metal ion or a group of atoms including a metal ion, and is preferably a transition metal ion, ruthenium ion, rhodium ion, palladium ion, silver ion, tungsten ion, rhenium ion, osmium ion, iridium ion, platinum Ions and gold ions are preferable, rhodium ions, palladium ions, rhenium ions, iridium ions, and platinum ions are more preferable, platinum ions, iridium ions, and palladium ions are further preferable, and platinum ions are particularly preferable.

The valence of M ¹¹ is preferably 0 to 4 valence, more preferably divalent or trivalent, divalent particularly preferred.

Q ¹¹ , Q ¹² , Q ¹³ , and Q ¹⁴ each represent an atomic group that coordinates to M ¹¹ (the bond formed by coordination includes, for example, a coordinate bond, a covalent bond, and an ionic bond). Q ¹¹ , Q ¹² , Q ¹³ , and Q ¹⁴ are not particularly limited as long as they are an atomic group that coordinates to M ¹¹ , but an atomic group that coordinates with a carbon atom, an atomic group that coordinates with a nitrogen atom, and an oxygen atom Preferred are an atomic group coordinated, an atomic group coordinated with a sulfur atom, and an atomic group coordinated with a phosphorus atom.

Examples of an atomic group coordinated by a carbon atom include an imino group, an aromatic hydrocarbon ring group (benzene, naphthalene, etc.), a heterocyclic group (thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, Imidazole, pyrazole, triazole, etc.) and condensed rings containing them, and tautomers thereof. These groups may further have a substituent. Examples of the substituent include groups described for R ²¹ described later.

Examples of the atomic group coordinated by the nitrogen atom include nitrogen-containing heterocyclic groups (pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, etc.), amino groups (preferably alkylamino groups (preferably , Having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as methylamino), arylamino groups (for example, phenylamino) and the like), acylamino groups ( 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 acetylamino, benzoylamino and the like, and an alkoxycarbonylamino group (preferably having a carbon number). 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms). Such as phenyloxycarbonylamino), sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, methanesulfonyl Amino, benzenesulfonylamino, etc.), and imino groups. These groups may be further substituted. Examples of the substituent include groups described for R ²¹ described later.

As an atomic group coordinated by an oxygen atom, an 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, ethoxy, butoxy, 2 -Ethylhexyloxy and the like), an aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyl). Oxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, Pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyloxy group (preferably having 2 to 30 carbon atoms, more preferred) Has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), silyloxy group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, Particularly preferred are those having 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), carbonyl groups (for example, ketone groups, ester groups, amide groups, etc.), ether groups (for example, dialkyl ether groups, diaryls). Ether group, furyl group, etc.). These groups may be further substituted. Examples of the substituent include groups described for R ²¹ described later.

As an atomic group coordinated by a sulfur atom, an alkylthio 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 methylthio and ethylthio. ), 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 phenylthio), 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. ), A thiocarbonyl group (for example, a thioketone group, a thioester group, etc.), a thioether group (for example, a dialkylthioe group). Ether groups, diaryl thioether, etc. thiofuryl group). These groups may be further substituted. Examples of the substituent include groups described for R ²¹ described later.

Examples of the atomic group coordinated by the phosphorus atom include a dialkylphosphino group, a diarylphosphino group, a trialkylphosphine, a triarylphosphine, and a phosphinin group. These groups may be further substituted. Examples of the substituent include groups described for R ²¹ described later.

Q ¹¹ and Q ¹² are preferably an atom group coordinated by a nitrogen atom, an atom group coordinated by an oxygen atom, or an atom group coordinated by a phosphorus atom, more preferably an atom group coordinated by a nitrogen atom, A nitrogen-containing heterocyclic group that coordinates is more preferable, and a monocyclic nitrogen-containing heterocyclic group that coordinates with a nitrogen atom is particularly preferable.

Q ¹³ and Q ¹⁴ are preferably an atom group coordinated by a carbon atom, an atom group coordinated by a nitrogen atom, or an atom group coordinated by an oxygen atom, and coordinated by an aryl group coordinated by a carbon atom or a carbon atom. More preferred are a heteroaryl group, a heteroaryl group coordinated with a nitrogen atom, a carboxyl group coordinated with an oxygen atom, an aryloxy group coordinated with an oxygen atom, and a heteroaryloxy group coordinated with an oxygen atom. More preferred are an aryl group to be coordinated, a heteroaryl group to be coordinated with a carbon atom, a heteroaryl group to be coordinated with a nitrogen atom, and a carboxyl group to be coordinated with an oxygen atom, an aryl group coordinated with a carbon atom, and a carbon atom A coordinating heteroaryl group is particularly preferred.

L ¹¹ , L ¹² , L ¹³ and L ¹⁴ each represent a single bond or a linking group. The linking group is not particularly limited, but an alkylene group (eg, methylene group, dimethylmethylene group, diisopropylmethylene group, diphenylmethylene group, ethylene group, tetramethylethylene group, etc.), alkenylene group (vinylene group, dimethylvinylene group, etc.) , Alkynylene groups (such as ethynylene groups), arylene groups (such as phenylene groups and naphthylene groups), heteroarylene groups (such as pyridylene groups, pyrazylene groups, and quinolylene groups), oxygen linking groups, sulfur linking groups, nitrogen linking groups (methylamino linking) Group, a phenylamino linking group, a tbutylamino linking group, etc.), a silicon linking group, and a linking group combining these (for example, an oxylenmethylene group).

L ¹¹ and L ¹³ are preferably a single bond, an alkylene group or an oxygen linking group, more preferably a single bond or an alkylene group, and even more preferably a single bond.

L ¹² and L ¹⁴ are preferably a single bond, an alkylene group, an oxygen linking group or a nitrogen linking group, more preferably an alkylene group or a nitrogen linking group, and particularly preferably an alkylene linking group.

n ¹¹ represents 0 or 1. When n ¹¹ is 0, there is no bond through L ¹⁴ between Q ¹³ and Q ¹⁴ .

The bond between M ^{11 and} Q ^11, the bond between M ^{11 and} Q ¹² , the bond between M ^{11 and} Q ^13, and the bond between M ^{11 and} Q ¹⁴ may be covalent bonds or coordinate bonds. There may be an ionic bond.

The bond between M ^{11 and} Q ¹¹ and the bond between M ^{11 and} Q ¹² are preferably coordination bonds (bonds represented by dotted lines), a bond between M ^{11 and} Q ¹³ , and M ^{11 to} Q ^14. The bond between them is preferably a covalent bond (a bond represented by a solid line) or an ionic bond (a bond represented by a solid line), and more preferably a covalent bond.

  Hereinafter, the general formula (III) will be described.

M ²¹ has the same meaning as M ¹¹ , and the preferred range is also the same. Q ²³ and Q ²⁴ each represent an atomic group coordinated to M ²¹ .

Q ²³ and Q ²⁴ are preferably an atom group coordinated by a carbon atom, an atom group coordinated by a nitrogen atom, or an atom group coordinated by an oxygen atom, and is coordinated by an aryl group coordinated by a carbon atom or a carbon atom. More preferred are a heteroaryl group, a heteroaryl group coordinated with a nitrogen atom, a carboxyl group coordinated with an oxygen atom, an aryloxy group coordinated with an oxygen atom, and a heteroaryloxy group coordinated with an oxygen atom. More preferred are an aryl group to be coordinated, a heteroaryl group to be coordinated with a carbon atom, a heteroaryl group to be coordinated with a nitrogen atom, and a carboxyl group to be coordinated with an oxygen atom, an aryl group coordinated with a carbon atom, and a carbon atom A coordinating heteroaryl group is particularly preferred. Among these, a 5-membered heteroaryl group coordinated with a carbon atom is particularly preferable.

In particular, among the 5-membered heteroaryl groups coordinated by carbon atoms, Q ²³ and Q ²⁴ are preferably 5-membered heteroaryl groups (pyrrole, pyrazole, triazole) linked to a pyridine ring by a nitrogen atom.

R ²¹ and R ²² each represent 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, tert-butyl. , 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 atoms). 2 to 10 such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon). 2-10, for example, propargyl, 3-pentynyl, etc.), aryl group (preferably carbon number) To 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl, and the like, and amino groups (preferably having 0 to 0 carbon atoms). 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, ditolylamino, and the like. (Preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like), aryloxy Group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably carbon 6-12, for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1-30 carbons, more preferably having 1-20 carbons, especially Preferably it is C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy etc.), an acyl group (preferably C1-C30, more preferably C1-C20, especially preferably carbon) 1 to 12, for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 2 carbon atoms). 12 and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like. Xoxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino 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 methanesulfonylamino and benzenesulfonylamino). ), A 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, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having a carbon number). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). Rufinyl 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 methanesulfinyl and benzenesulfinyl. ), 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, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An 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 and phenylphosphoric acid amide), a 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 it is C1-C30, More preferably, it is C1-C12, As a hetero atom, for example, a nitrogen atom, oxygen Children, sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably). Has 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl, triphenylsilyl, and the like, and a silyloxy group (preferably 3 to 40 carbon atoms). More preferably, it has 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy, triphenylsilyloxy, and the like. These substituents may be further substituted.

R ²¹ and R ²² are preferably an alkyl group, an alkoxy group, or a substituted amino group, more preferably an alkyl group or a substituted amino group, and even more preferably an alkyl group.

L ²² has the same meaning as L ¹² described above, and the preferred range is also the same.

m ²¹ and m ²² each represent an integer of 0 to 3, preferably 0 or 1, and more preferably 0. When there are a plurality of m ²¹ and m ²² , the plurality of R ²¹ and R ²² may be the same or different.

The metal complex contained in the layer between the light emitting layer and the cathode will be described. Although it does not specifically limit as a metal ion which comprises a metal complex, A bivalent or trivalent metal ion is preferable, A trivalent aluminum ion, a bivalent zinc ion, a trivalent gallium ion, a bivalent beryllium ion, 2 A trivalent magnesium ion is more preferable, a trivalent aluminum ion, a trivalent gallium ion, a divalent zinc ion is more preferable, and a trivalent aluminum ion is particularly preferable.
By including a metal complex in the layer between the light emitting layer and the cathode, preferably in the electron injection layer or the electron transport layer, an effect of improving efficiency and durability can be obtained. The metal complex is preferably contained in the layer to be added in an amount of 1 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 80 to 100% by mass.

Further, in the present invention, it is preferable that at least one of the layers adjacent to the light emitting layer, preferably a material including a carbazole skeleton is included in the layer adjacent to the light emitting layer on the anode side. The material containing the carbazole skeleton is preferably a material containing two or more carbazole skeletons, more preferably 2 to 8 carbazole skeletons, and particularly preferably 2 to 3 carbazole skeletons. As the material containing a carbazole skeleton, the compound represented by the general formula (I) of the present invention can also be used.
By including a material containing a carbazole skeleton in at least one of the layers adjacent to the light emitting layer, light emission efficiency and durability can be improved. The material containing a carbazole skeleton is preferably contained in the added layer in an amount of 1 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 80 to 100% by mass.

  Each element constituting the element of the present invention will be described in detail.

[Organic electroluminescence device]
Hereinafter, the element of the present invention 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 layer (a layer made of only an organic compound) including an organic light-emitting layer (hereinafter sometimes simply referred to as “light-emitting layer”) between both electrodes. Or an organic layer containing an inorganic compound). In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  As an aspect of lamination of the organic 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.

  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 layer. Specific examples include zirconia-stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Organic materials such as norbornene resin and 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 structure of the substrate 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 only needs to have a function as an electrode for supplying holes to the organic 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. 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 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 described in detail in the book “New Development of Transparent Electrode Films” published by CMC (1999), supervised by Yutaka Sawada, 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 layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light-emitting element. The electrode material can be selected as appropriate.

  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 forming position is not particularly limited, and may be formed on the entire organic 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 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 layer>
The organic layer in the present invention will be described.
The element of the present invention has at least one organic layer including a light emitting layer, and as the organic layer other than the organic light emitting layer, as described above, a hole transport layer, an electron transport layer, a charge blocking layer, Examples thereof include a hole injection layer and an electron injection layer.

-Formation of organic layer-
In the element of the present invention, each layer constituting the organic 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 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. 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. 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 light-emitting 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 G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.
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 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.

  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.

  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 layer adjacent to the light emitting layer on the cathode side.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. 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% or more 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, and 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 element of the present invention may be sealed 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 element of the present invention can obtain light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. it can.
Regarding the driving method of the element of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-214447, The driving methods described in Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6023308, etc. can be applied.

  The element of the present invention can be suitably used for display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Synthesis Example: Synthesis of Exemplary Compound>
The synthesis of the compound represented by the general formula (I) is described below with reference to J. Org. Chem. 43, 1413, 1978, and Adv. Mater. 18, 1216, 2006. It can be manufactured by the process shown. For example, Exemplified Compound 1 can be obtained by treating MCP (meta-dicarbazo-9-rylbenzene) and BHT (2,6-di-tert-butyl-4-methylphenol) with aluminum chloride in nitromethane. The exemplified compound 27 can be obtained by treating a precursor in which the position of the silicon substituent is substituted with bromine with a trimethylchlorosilane after a metal halogen exchange reaction with an organometallic reagent.

  In the production methods shown above, when the defined substituents change under the conditions of a certain synthesis method or are inappropriate for carrying out the method, the functional groups are protected and deprotected (for example, , Protective Groups in Organic Synthesis, TW Greene, John Wiley & Sons Inc. (1981), etc.) It can be easily manufactured by such means. Moreover, it is also possible to change the order of reaction steps such as introduction of substituents as necessary.

Synthesis of Exemplary Compound 1 Under a nitrogen stream, a solution of MCl (2.0 g), BHT (2.9 g), and nitromethane (20 mL) was added dropwise with a solution of aluminum chloride (2.7 g) in nitromethane (10 mL) at room temperature. After stirring for 30 minutes, water was added and the mixture was extracted with ethyl acetate. The ethyl acetate solution was washed with 1 mol / L sodium hydroxide aqueous solution, water and saturated brine, dried over magnesium sulfate, and then ethyl acetate was distilled off to obtain 0.99 g (yield 30%) of Exemplary Compound 1. It was. The chemical shift of ¹ H NMR in deuterated chloroform is δ8.14 (s, 4H), 7.82-7.76 (m, 2H), 7.64 (dd, 2H), 7.50-7. 44 (m, 8H), 1.46 (s, 36H).

Synthesis of Exemplary Compound 27 Under a nitrogen stream, a mixture of 3,6-dibromocarbazole (6.5 g), chlorotrimethylsilane (10 mL), and tetrahydrofuran (100 mL) was cooled in an ice bath, and n-butyllithium (1.6 M hexane) Solution, 50 mL) was added dropwise over 30 minutes. The reaction mixture was warmed to room temperature, added with water, stirred and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. After filtering the drying agent, the solid obtained by concentrating the obtained organic phase was recrystallized using hexane to obtain 1.6 g of 3,6-bis (trimethylsilyl) carbazole (yield 27%). Obtained.
The obtained 3,6-bis (trimethylsilyl) carbazole (1.6 g) was added to 1,3-dibromobenzene (0.3 mL), palladium acetate (28 mg), tri (tert-butyl) phosphine (0.1 mL). The mixture was heated to reflux in xylene (40 mL) with rubidium carbonate (3.5 g) for 3 hours. After cooling to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered through silica gel. The solid obtained by concentrating the organic phase was washed with superheated methanol and recrystallized using tetrahydrofuran and methanol to obtain 1,5 g of Exemplified Compound 27 (yield 88%). The chemical shift of ¹ H NMR in deuterated chloroform is δ8.33 (s, 4H), 7.84 (t, 1H), 7.77 (s, 1H), 7.67 (d, 2H), 7 .58 (d, 4H), 7.52 (d, 4H), 0.38 (s, 36H).

<Production and evaluation of organic electroluminescence device>
(1) Preparation of organic electroluminescent element (TC-1) of comparative example A glass substrate having a 0.5 mm thickness and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10Ω / □) is placed in a cleaning container, After ultrasonic cleaning in 2-propanol, UV-ozone treatment was performed for 30 minutes. The following organic layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
The vapor deposition rate in the examples of the present invention is 0.2 nm / second unless otherwise specified. The deposition rate was measured using a crystal resonator film formation controller CRTM-9000 manufactured by ULVAC. The film thickness described below is also calculated from a calibration curve created based on the value of CRTM-9000 and the film thickness measured with a Dektak-type stylus-type film thickness meter.

<1> Co-deposition of compound A + compound B (0.3 wt%): film thickness 160 nm
<2> Compound C: Film thickness 10 nm
<3> Co-evaporation of MCP + luminescent material A (15 wt%): film thickness 60 nm
<4> Compound E: Film thickness 40 nm

  Finally, 0.1 nm of lithium fluoride and 100 nm of metal aluminum were deposited in this order to form a cathode. Without exposing it to the atmosphere, put it in a glove box substituted with argon gas, and seal it with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba). The organic electroluminescent element (TC-1) of the comparative example was obtained.

(2) Production of Organic Electroluminescent Device (TC-2) of Comparative Example Organic Electroluminescent Device (TC-2) of Comparative Example was produced in the same manner as TC-1, except that MCP was changed to Exemplary Compound 1 having the following structure. ) Was produced.

(3) Production of organic electroluminescent device (TC-3) of comparative example Organic electroluminescent device (TC) of comparative example was produced in the same manner as TC-1, except that luminescent material A was changed to luminescent material B having the following structure. -3) was produced.

(4) Preparation of organic electroluminescent device (TC-4) of Example of the present invention The organic electroluminescent device of the present invention (TC-3) was prepared in the same manner as TC-3 except that MCP was changed to the exemplified compound 1 having the following structure. TC-4) was produced.

(5) Preparation of organic electroluminescence device (TC-5) of Example of the present invention The organic electroluminescence of the present invention was performed in the same manner as TC-4 except that the luminescent material B was changed to the luminescent material C having the following structure. An element (TC-5) was produced.

(6) Preparation of Organic Electroluminescent Device (TC-6) of Example of the Present Invention A layer of compound D having a thickness of 3 nm is formed between the layer of compound C and the co-deposited layer of exemplary compound 1 and luminescent material C. An organic electroluminescent element (TC-6) of the present invention was produced in the same manner as TC-5 except that it was inserted.

(7) Preparation of organic electroluminescence device (TC-7) of Example of the present invention The organic electroluminescence of the present invention was performed in the same manner as TC-6 except that Exemplified Compound 1 was changed to Exemplified Compound 27 having the following structure. An element (TC-7) was produced.

  The chemical structures of Compound A to Compound E are as follows.

The chemical structures of the light emitting material A to the light emitting material C are as follows.

  The chemical structures of Example Compound 1, Example Compound 27 and MCP are as follows.

  The organic electroluminescent elements (TC-1 to 7) obtained above were evaluated by the following methods.

(1) Evaluation of EL external quantum yield The obtained organic electroluminescent elements (TC-1 to TC-7) were made to emit light by applying a DC constant voltage to the EL elements using a source measure unit 2400 type manufactured by Toyo Technica. It was. The EL external quantum yield was calculated from the front luminance at 100 cd / m ² .

(2) Evaluation of driving durability The obtained organic electroluminescent elements (TC-1 to TC-7) were set in the OLED test system ST-D type manufactured by Tokyo System Development Co., Ltd. Driving was performed under the condition of a constant current of 0.4 mA, and the luminance half time (time until the luminance decreased to 50% of the initial luminance) was obtained.

  The organic electroluminescent element TC-2 of the comparative example had a light emission efficiency of 1.1 times and a luminance half time of 1.1 times that of the TC-1 of the comparative example.

  The organic electroluminescent element TC-3 of the comparative example had a luminous efficiency of 1.5 times and a luminance half time of 1.1 times that of the comparative example TC-1.

  The organic electroluminescent device TC-4 had a luminous efficiency 2.0 times and a luminance half time 1.5 times that of the comparative example TC-1.

  The organic electroluminescent element TC-5 had a luminous efficiency of 1.7 times and a luminance half time of 1.4 times that of TC-1 of Comparative Example.

  The organic electroluminescent element TC-6 had a light emission efficiency of 2.1 times and a luminance half time 1.5 times that of TC-1 of Comparative Example.

  The organic electroluminescence device TC-7 had a luminous efficiency 2.3 times and a luminance half time 1.2 times that of TC-1 of the comparative example.

Claims (3)

The compound represented by the following general formula (I).

(In the general formula (I), Q ^{1 to} Q ⁴ are each independently a carbon atom or a silicon atom, and R ^{0 to} R ¹⁵ each represent a hydrogen atom. Z ^{1 to} Z ¹² are each independently substituted or unsubstituted. Z ^{1 to} Z ³ , Z ^{4 to} Z ⁶ , Z ^{7 to} Z ⁹ , and Z ^{10 to} Z ¹² may be bonded to each other to form a ring. A group represented by Q ¹ (Z ¹ ) (Z ² ) (Z ³ ), a group represented by Q ² (Z ⁴ ) (Z ⁵ ) (Z ⁶ ), Q ³ (Z ⁷ ) (Z ⁸ ) At least one of the group represented by (Z ⁹ ) and the group represented by Q ⁴ (Z ¹⁰ ) (Z ¹¹ ) (Z ¹² ) is an adamantyl group. Q ¹ (Z ¹ ) (Z ² ) (Z ³ ), Q ² (Z ⁴ ) (Z ⁵ ) (Z ⁶ ), Q ³ (Z ⁷ ) (Z ⁸ ) (Z ⁹ ) and Q representing an adamantyl group ^{4 (Z 10) (Z 11} ) Z 1 ~Z 12 Z 1 ~Z 12 except that constitute the (Z ¹²⁾ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms The compound according to claim 1, which is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms. Q ¹ (Z ¹ ) (Z ² ) (Z ³ ), Q ² (Z ⁴ ) (Z ⁵ ) (Z ⁶ ), Q ³ (Z ⁷ ) (Z ⁸ ) (Z ⁹ ) and Q representing an adamantyl group ^{4 (Z 10) (Z 11} ) Z 1 ~Z 12 Z 1 ~Z 12 except that constitute the (Z ¹²⁾ are each independently methyl, ethyl, n- propyl, iso- propyl, n- butyl, tert-butyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-octadecyl, n-hexadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, phenyl, o-methylphenyl , M-methylphenyl, p-methylphenyl, 2,4-xylyl, p-cumenyl, mesityl, naphthyl, anthranyl, imidazolyl, pyrazolyl, pyridyl, pyrazyl, pyrimidyl, triazini , Quinolyl, isoquinolinyl, pyrrolyl, indolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, A compound according to claim 1, characterized in that a radical selected from the group consisting of carbazolyl and azepinyl.