JP2015106661A - Organic electroluminescent element and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element of a low drive voltage and a long life.SOLUTION: An organic electroluminescent element comprises a light-emitting layer. The light-emitting layer includes: a first material expressed by the general formula (10) or (11); a second material expressed by the general formula (20); and a phosphorescent third material. In the general formulas (10) and (11), Az represents a nitrogen-containing ring; Czand Czeach represent a carbazolyl group; Land Leach represent a single bond or coupling group; and HAr is expressed by the general formula (11a). In the general formula (20), Xto Xeach represent a nitrogen atom, CR, or a carbon atom which binds to a structure expressed by the general formula (20a).

Description

  The present invention relates to an organic electroluminescence element and an electronic apparatus.

  When a voltage is applied to an organic electroluminescence element (hereinafter sometimes referred to as an organic EL element), holes from the anode and electrons from the cathode are injected into the light emitting layer. Then, in the light emitting layer, the injected holes and electrons are recombined to form excitons. At this time, singlet excitons and triplet excitons are generated at a ratio of 25%: 75% according to the statistical rule of electron spin. When classified according to the light emission principle, the fluorescence type uses light emitted from singlet excitons, and therefore the internal quantum efficiency of the organic EL element is said to be limited to 25%. On the other hand, in the phosphorescent type, since light emission by triplet excitons is used, it is known that the internal quantum efficiency can be increased to 100% when intersystem crossing is efficiently performed from singlet excitons.

  The phosphorescent organic EL element is described in Patent Document 1, for example. Patent Document 1 describes a phosphorescent organic EL element containing a first material, a second material, and a phosphorescent material. In the organic EL element of Patent Document 1, a compound having an azine ring and a condensed carbazole ring is used as the first material, and a compound having a condensed carbazole ring and a non-condensed carbazole ring is used as the second material. Yes.

International Publication No. 2013/041176 International Publication No. 2013/056776 International Publication No. 2012/136295

  Incidentally, the organic EL element is required to have a reduced drive voltage and a longer life.

  The objective of this invention is providing the organic electroluminescent element which can reduce a drive voltage and can extend a lifetime. Another object of the present invention is to provide an electronic apparatus provided with the organic electroluminescence element.

  An organic electroluminescence device according to one embodiment of the present invention includes an anode, a light emitting layer, and a cathode, and the light emitting layer includes a first represented by the following general formula (10) or the following general formula (11). And a second material represented by the following general formula (20), and a phosphorescent third material.

(In the general formula (10),
Cz ₁ and Cz ₂ are each independently a substituted or unsubstituted carbazolyl group,
L ₁₀ and L ₁₁ are each independently a single bond or a linking group;
Az is a nitrogen-containing ring represented by the following general formula (12). )

(In the general formula (12), X _{13 to} X ₁₅ are each independently a nitrogen atom or CR ^V , provided that at least one of X _{13 to} X ₁₅ is a nitrogen atom, and R ₁ , R ₂ and R ^V are each independently a hydrogen atom or a substituent. In this case, the substituent is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, a substituted or unsubstituted carbon An alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, a substituted or unsubstituted An unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heterocyclic ring having 5 to 30 ring atoms A substituent selected from the group consisting of groups, wherein R ₁ and R ^V may be bonded to each other to form a ring structure, and R ₂ and R ^V are bonded to each other to form a ring structure. May be.)

(In the general formula (11), Az is a nitrogen-containing ring represented by the general formula (12),
L ₁₀ is a single bond or a linking group;
HAr is represented by the following general formula (11a). )

In (Formula _(11a), X 1 to X ₈ are each independently a nitrogen atom, CR ^X or carbon atom bonded to the structure represented by the following general formula (11b),, _{X 1} and X 1 or more and 4 or less of ₂ sets, X ₂ and X ₃ sets, X ₃ and X ₄ sets, X ₅ and X ₆ sets, X ₆ and X ₇ sets, and X ₇ and X ₈ sets Is a carbon atom bonded to a structure represented by the following general formula (11b), and when a plurality of structures represented by the following general formula (11b) are bonded, they may be the same or different. )

(In the general formula _{(11b), X} 9 ~X ₁₂ are each independently a nitrogen atom or CR ^Y,.
Y ₂ is a sulfur atom, an oxygen atom or NR ^Z,.
* ₁₁ and _{* 12,} respectively, _{X 1} and _{X 2} of the set of the general formula (11a), a set of _{X 2} and _{X 3, X 3} and _{X 4} set, a set of _{X 5} and _{X 6, X 6} And X ₇ , and a bonding site with a carbon atom in a group selected from the group consisting of X ₇ and X ₈ . )

(In the general formula (20),
Ar ₂₁ and Ar ₂₂ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group. A group selected from the group consisting of:
L ₂₁ and L ₂₂ are each independently a single bond or an arylene group having 6 to 18 ring carbon atoms,
m and n are 3,
R ₂₁ and R ₂₂ are each bonded to a carbon atom constituting a 6-membered ring;
X _{21 to} X ₂₄ are each independently a nitrogen atom, CR ^W , or a carbon atom bonded to a structure represented by the following general formula (20a), and a pair of X ₂₁ and X ₂₂ , X ₂₂ and X ₂₃ And one set of X ₂₃ and X ₂₄ is a carbon atom bonded to the structure represented by the following general formula (20a). )

In (Formula _{(20a), * 21} and _{* 22} are the set of _{X 21} and _{X 22} of each of the general formula _(20), selected set of _{X 22} and _{X 23,} and a set of _{X 23} and _{X 24} The bonding sites with carbon atoms in
In the general formula (20a), R _A and R _B are each independently a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted ring forming carbon number of 3 to 3 20 cycloalkyl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms Substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted Or an unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, and R _A and R _B may be bonded to each other to form a ring structure,
R ^X , R ^Y , R ^Z , R ^W , R _{21 to} R ₃₀ are each independently a hydrogen atom or a substituent. In this case, the substituent is a halogen atom, a cyano group, a substituted or unsubstituted group. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring carbon number 6 ~ 30 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and substituted or unsubstituted group It is a substituent selected from the group consisting of heterocyclic group ring atoms 5-30. )

  An electronic device according to one embodiment of the present invention includes the organic electroluminescence element according to one embodiment of the present invention described above.

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element which can reduce a drive voltage and can extend a lifetime can be provided.

It is a figure which shows schematic structure of an example of the organic electroluminescent element which concerns on embodiment of this invention.

  Hereinafter, an exemplary embodiment of the organic EL device of the present invention will be described.

(Element structure of organic EL element)
The configuration of the organic EL element according to the first embodiment will be described.
The organic EL element includes an organic layer between both an anode and a cathode. This organic layer has one or more layers composed of an organic compound. The organic layer may further contain an inorganic compound. The organic EL device of this embodiment includes at least a light emitting layer as an organic layer. Therefore, the organic layer may be composed only of a light emitting layer, or a layer employed in an organic EL element, for example, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole barrier. A layer, an electron barrier layer, or the like.
As a typical element configuration of the organic EL element,
(A) Anode / light emitting layer / cathode (b) Anode / hole injection / transport layer / light emitting layer / cathode (c) Anode / light emitting layer / electron injection / transport layer / cathode (d) Anode / hole injection / transport Layer / light emitting layer / electron injection / transport layer / cathode (e) anode / hole injection / transport layer / first light emitting layer / second light emitting layer / electron injection / transport layer / cathode (f) anode / hole injection Examples thereof include a transport layer / light emitting layer / barrier layer / electron injection / transport layer / cathode structure.

In FIG. 1, schematic structure of an example of the organic EL element in this embodiment is shown.
The organic EL element 1 includes a translucent substrate 2, an anode 3, a cathode 4, and an organic layer 10 disposed between the anode 3 and the cathode 4.
The organic layer 10 includes a light emitting layer 5, a hole injection / transport layer 6 provided between the anode 3 and the light emitting layer 5, and an electron injection / transport layer 7 provided between the light emitting layer 5 and the cathode 4. It consists of
The hole injection / transport layer 6 means at least one of a hole injection layer and a hole transport layer. The electron injection / transport layer 7 means at least one of an electron injection layer and an electron transport layer. Here, when it has a positive hole injection layer and a positive hole transport layer, it is preferable that the positive hole injection layer is provided in the anode 3 side. Moreover, when it has an electron injection layer and an electron carrying layer, it is preferable that the electron injection layer is provided in the cathode 4 side. Further, each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be composed of a single layer, or a plurality of layers may be laminated.

In the present embodiment, the light emitting layer 5 includes a first material, a second material, and a phosphorescent third material.
First, the first material will be described. The first material is represented by the following general formula (10) or the following general formula (11).

(In the general formula (10),
Cz ₁ and Cz ₂ are each independently a substituted or unsubstituted carbazolyl group,
L ₁₀ and L ₁₁ are each independently a single bond or a linking group;
Az is a nitrogen-containing ring represented by the following general formula (12). )

(In the general formula (12), X _{13 to} X ₁₅ are each independently a nitrogen atom or CR ^V , provided that at least one of X _{13 to} X ₁₅ is a nitrogen atom, and R ₁ , R ₂ and R ^V are each independently a hydrogen atom or a substituent. In this case, the substituent is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, a substituted or unsubstituted carbon An alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, a substituted or unsubstituted An unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heterocyclic ring having 5 to 30 ring atoms A substituent selected from the group consisting of groups, wherein R ₁ and R ^V may be bonded to each other to form a ring structure, and R ₂ and R ^V are bonded to each other to form a ring structure. May be.)

(In the general formula (11), Az is a nitrogen-containing ring represented by the general formula (12),
L ₁₀ is a single bond or a linking group;
HAr is represented by the following general formula (11a). )

In (Formula _(11a), X 1 to X ₈ are each independently a nitrogen atom, CR ^X or carbon atom bonded to the structure represented by the following general formula (11b),, _{X 1} and X 1 or more and 4 or less of ₂ sets, X ₂ and X ₃ sets, X ₃ and X ₄ sets, X ₅ and X ₆ sets, X ₆ and X ₇ sets, and X ₇ and X ₈ sets Is a carbon atom bonded to a structure represented by the following general formula (11b), and when a plurality of structures represented by the following general formula (11b) are bonded, they may be the same or different. )

In the general formula _{(11b), X} 9 ~X ₁₂ are each independently a nitrogen atom or CR ^Y,.
Y ₂ is a sulfur atom, an oxygen atom or NR ^Z,. In the case where a plurality of structures represented by the general formula (11b) are bonded to the structure represented by the general formula (11a), the plurality of Y ₂ may be the same as or different from each other.
* ₁₁ and _{* 12,} respectively, _{X 1} and _{X 2} of the set of the general formula (11a), a set of _{X 2} and _{X 3, X 3} and _{X 4} set, a set of _{X 5} and _{X 6, X 6} And X ₇ , and a bonding site with a carbon atom in a group selected from the group consisting of X ₇ and X ₈ .

R ^X , R ^Y , and R ^Z are each independently a hydrogen atom or a substituent. In this case, the substituent is a halogen atom, a cyano group, a substituted or unsubstituted C 1-20. An alkyl group, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms Substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted An arylsilyl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring atom number It is a substituent selected from the group consisting of heterocyclic group 30.

In the general formula (12), when R ₁ and R ^V are bonded to each other to form a ring structure, or R ₂ and R ^V are bonded to each other to form a ring structure, Examples thereof include the following general formulas (12-1), (12-2), (12-3), (12-4), and (12-5).

In the general formulas (12-1) to (12-5), X _{13 to} X ₁₅ and X _{31 to} X ₃₈ are each independently a nitrogen atom or CR ^V , provided that among X _{13 to} X ₁₅ At least one of them is a nitrogen atom, and R ₁ , R ₂ , and R ^V are each independently synonymous with R ₁ , R ₂ , and R ^V in the general formula (12).

  In the present embodiment, the Az is preferably a nitrogen-containing 6-membered ring. In this case, the general formula (12) is represented by the following general formulas (12-6) to (12-10).

In the general formulas (12-6) to (12-10), R ₁ , R ₂ and R ^V are each independently synonymous with R ₁ , R ₂ and R ^V in the general formula (12).

Moreover, in this embodiment, it is preferable that said X <_13> , said X <_14>, and said X <_15> are nitrogen atoms. That is, it is preferable that Az is represented by the general formula (12-6).

  In the present embodiment, the substituted or unsubstituted carbazolyl group may include, for example, a group in which a ring is further condensed to a carbazole ring represented by the following formula. Such a group may also have a substituent. Also, the position of the joint can be changed as appropriate.

  In the present embodiment, the general formula (10) is preferably represented by the following general formula (13).

In the general formula (13), L ₁₀ and L ₁₁ are each independently synonymous with L ₁₀ and L ₁₁ in the general formula (10),
Ar ₁₁ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms,
X _{13 to} X ₁₅ are each independently a nitrogen atom or CR ^V , provided that at least one of X _{13 to} X ₁₅ is a nitrogen atom,
p and q are 3,
R _{1 to} R ₁₂ and R ^V are each independently a hydrogen atom or a substituent, and the substituent in this case is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, substituted or Unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted ring formation An arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring atom having 5 to 30 ring atoms; It is a substituent selected from the group consisting of heterocyclic group.
R ₇ and R ₈ shown in the general formula (13) are each bonded to a carbon atom constituting a 6-membered ring.
L ₁₁ shown in the general formula (13) bonds carbon atoms constituting a 6-membered ring.

In the present embodiment, the structure of Cz ₂ -L ₁₁ -Cz ₁ -in the general formula (10) is preferably represented by the following general formula (10a) or the following general formula (10b).

(In the general formula (10a) and the general formula _{(10b), L 11} has the same meaning as _{L 11} in the general formula (10).
Ar ₁₁ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms,
R _{31 to} R ₄₄ are each independently a hydrogen atom or a substituent. In this case, examples of the substituent include a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or Unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, substituted or unsubstituted An alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, and a substituted or unsubstituted ring carbon number. An arylsilyl group having 6 to 50, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring atom having 5 to 30 ring atoms; It is a substituent selected from the group consisting of heterocyclic group. )

  In the first material represented by the general formula (11), the HAr is represented by any of the following general formulas (11c), (11d), (11e), and (11f), for example, (11c) or the following general formula (11d) is preferable.

Formula (11c) and the general formula _(11e), X 1 ~X ₆ are each independently a nitrogen atom or CR ^X,,
Formula (11d) and the general formula _{(11f), X 1 ~X 4} , X 7 ~X 8 are each independently a nitrogen atom or CR ^X,,
Formula (11c), in (11d), (11e), (11f), X 9 ~X 12 are each independently a nitrogen atom or CR ^Y,, _{Y 2} is a sulfur atom, an oxygen atom, or NR ^Z. R ^X , R ^Y , and R ^Z are synonymous with a hydrogen atom or the aforementioned substituent.

In the present embodiment, the _{Y 2} is preferably an oxygen atom or NR ^Z,. When Y ₂ is NR ^Z , R ^Z is preferably selected from the group of substituents listed above.

In the present embodiment, Ar ₁₁ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted aromatic carbon group having 6 to 18 ring carbon atoms. A hydrogen group is more preferable, and a phenyl group is more preferable.

In this embodiment, the linking group in L ₁₀ and L ₁₁ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. ring _{group, -CR 81 R 82 -, -} NR 83 -, - O -, - S -, - SiR 84 R 85 -, - CR 86 R 87 -CR 88 R 89 -, - CR 90 = CR 91 -, —NR ₉₂ —, —N═CR ₉₃ —, a substituted or unsubstituted aliphatic hydrocarbon ring group, and a substituted or unsubstituted aliphatic heterocyclic group are preferable. R _{81 to} R ₉₃ are each independently a hydrogen atom or a substituent. In this case, examples of the substituent include a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or Unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, substituted or unsubstituted An alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, and a substituted or unsubstituted ring carbon number. An arylsilyl group having 6 to 50, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring atom having 5 to 30 ring atoms; It is a substituent selected from the group consisting of heterocyclic group.
L ₁₀ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and among the aromatic hydrocarbon groups, a phenylene group is preferable.
On the other hand, the L ₁₀ is preferably a single bond.

  Specific examples of the first material in the present embodiment are shown below. The present invention is not limited to these specific examples.

  Next, the second material will be described. The second material is represented by the following general formula (20).

(In the general formula (20),
Ar ₂₁ and Ar ₂₂ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group. A group selected from the group consisting of:
L ₂₁ and L ₂₂ are each independently a single bond or an arylene group having 6 to 18 ring carbon atoms,
m and n are 3,
R ₂₁ and R ₂₂ are each bonded to a carbon atom constituting a 6-membered ring;
In the general formula (20), X _{21 to} X ₂₄ are each independently a nitrogen atom, CR ^W , or a carbon atom bonded to a structure represented by the following general formula (20a), and X ₂₁ and X ₂₂ , X ₂₂ and X ₂₃ , and X ₂₃ and X ₂₄ are carbon atoms bonded to the structure represented by the following general formula (20a). )

In the general formula _{(20a), * 21} and _{* 22} are selected from each set of _{X 21} and _{X 22} in the general formula _(20), a set of _{X 22} and _{X 23,} and a set of _{X 23} and _{X 24} The bonding site with the carbon atom in the set is shown.

In the general formula (20a), R _A and R _B are each independently a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted ring forming carbon number of 3 to 3 20 cycloalkyl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms Substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted Or an unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, and R _A and R _B may be bonded to each other to form a ring structure,
R ^X , R ^Y , R ^Z , R ^W , R _{21 to} R ₃₀ are each independently a hydrogen atom or a substituent. In this case, the substituent is a halogen atom, a cyano group, a substituted or unsubstituted group. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring carbon number 6 ~ 30 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and substituted or unsubstituted group It is a substituent selected from the group consisting of heterocyclic group ring atoms 5-30. )

For example, in the general formula (20a), * ₂₁ and * ₂₂ represent the following general formula (20−) when the bonding site of the carbon atom in the group of X ₂₂ and X _{23 in} the general formula (20) is represented. 1) or represented by the following general formula (20-2).

Formula _(20-1), the _{* 21} becomes _a binding site to the carbon atom in _{X 22, * 22 is} a structure when a binding site to the carbon atom in _{X 23.}
Formula _(20-2), the _{* 21} becomes _a binding site to the carbon atom in _{X 23, * 22 is} a structure when a binding site to the carbon atom in _{X 22.}

  In the present embodiment, the general formula (20) is preferably represented by the following general formula (21), the following general formula (22), or the following general formula (23).

(In the general formulas (21) to (23), Ar ₂₁ , Ar ₂₂ , L ₂₁ , L ₂₂ , and X _{21 to} X ₂₄ are respectively Ar ₂₁ , Ar ₂₂ , L ₂₁ in the general formula (20). , L ₂₂ , and X _{21 to} X ₂₄ ,
R _{23 to} R ₂₆ , R _{211 to} R ₂₁₃ , and R _{221 to} R ₂₂₃ are each independently a hydrogen atom or a substituent. In this case, the substituent includes a halogen atom, a cyano group, a substituted or unsubstituted group. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring carbon number 6 ~ 30 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms And a substituent selected from the group consisting of substituted or unsubstituted heterocyclic group ring atoms 5-30. )

In the present embodiment, the _{X 22} and the _{X 23} is preferably a carbon atom bonded to the _{* 21} and _{* 22} in the general formula (20a).

In the present embodiment, X ₂₂ is preferably a carbon atom bonded to * ₂₁ , and X ₂₃ is preferably a carbon atom bonded to * ₂₂ .

  In the present embodiment, the general formula (20) is preferably represented by the following general formula (21a).

(In the general formula (21a), Ar ₂₁ , Ar ₂₂ , L ₂₁ , L ₂₂ , X ₂₁ , and X ₂₄ are respectively Ar ₂₁ , Ar ₂₂ , L ₂₁ , L ₂₂ , Synonymous with X ₂₁ and X ₂₄ ;
R _A and _{R B} are the same as _{R A} and _{R B} in the general formula (20a),
R _{23 to} R ₃₀ , R _{211 to} R ₂₁₃ , and R _{221 to} R ₂₂₃ are each independently a hydrogen atom or a substituent. In this case, the substituent includes a halogen atom, a cyano group, a substituted or unsubstituted group. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring carbon number 6 ~ 30 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms And a substituent selected from the group consisting of substituted or unsubstituted heterocyclic group ring atoms 5-30. )

In the present embodiment, the L ₂₁ and the L ₂₂ are preferably single bonds.

In the present embodiment, Ar ₂₁ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms. Ar ₂₁ is preferably a group selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a terphenyl group, and a fluorenyl group.
Ar ₂₂ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms.

In this embodiment, R _A and R _B are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 ring carbon atoms. It is preferably a group.

  Specific examples of the second material in the present embodiment are shown below. The present invention is not limited to these specific examples.

In this embodiment, the compound represented by the general formula (20) is used as the second material. The second material has a structure in which a ring structure in which the structure represented by the general formula (20a) is bonded to a carbazole ring.
Here, a biscarbazole compound in which two carbazole rings are bonded has a strong hole transporting property. Therefore, when this biscarbazole compound is used for the light emitting layer, the light emitting region tends to concentrate on the cathode side interface of the light emitting layer. As a result, the lifetime of the organic EL element tends to be shortened.
On the other hand, the second material has the specific ladder structure as described above, and the durability is improved as compared with the biscarbazole compound. Furthermore, since the structure represented by the general formula (20a) is condensed in the second material, conjugation is widened and the energy gap is narrower than that of the biscarbazole compound described above. As a result, the driving voltage of the organic EL element can be lowered by using the second material.
Further, the second material has a hole transport property suppressed more than that of the biscarbazole compound. In the present embodiment, not only the second material but also the compound represented by the general formula (10) or the general formula (11) is used as the first material. The first material has a nitrogen-containing heterocycle that enhances electron transport properties. Therefore, in this embodiment, the carrier balance in the light emitting layer is improved by allowing the first material and the second material to coexist in the same light emitting layer. As a result, the light emitting region is distributed over the entire light emitting layer, and the organic EL element can have a low voltage and a long life.

Wherein the first material is a compound represented by the general formula (11), wherein _{Y 2} in the general formula (11b) is a _CR C _{R D} compound _{(R C} and _{R D} is an alkyl group) than the Y ₂ compounds where an oxygen atom, is reduced it is an electron-transporting property of the compound Y ₂ is NR ^Z, or a compound represented by the general formula (13), a longer and more life be able to.
Further, by increasing the electron injecting property of the first material, it is possible to further lower the voltage and extend the life of the organic EL element. The compound represented by the general formula (11), wherein the compound represented by the general formula (13) has a larger affinity (electron affinity) than the compound in which the Y ₂ is an oxygen atom, Y ₂ is greater than found the following compound is NR ^Z.

Next, the third material will be described. The third material is a phosphorescent material.
As a blue phosphorescent material that can be used for the light emitting layer, a metal complex such as an iridium complex, an osmium complex, or a platinum complex is used. Specifically, bis [2- (4 ′, 6′-difluorophenyl) pyridinato-N, C2 ′] iridium (III) tetrakis (1-pyrazolyl) borate (abbreviation: FIr6), bis [2- (4 ′ , 6′-difluorophenyl) pyridinato-N, C2 ′] iridium (III) picolinate (abbreviation: FIrpic), bis [2- (3 ′, 5′bistrifluoromethylphenyl) pyridinato-N, C2 ′] iridium (III ) Picolinate (abbreviation: Ir (CF3ppy) ₂ (pic)), bis [2- (4 ′, 6′-difluorophenyl) pyridinato-N, C2 ′] iridium (III) acetylacetonate (abbreviation: FIracac), etc. Can be mentioned.
An iridium complex or the like is used as a green phosphorescent material that can be used for the light emitting layer. Tris (2-phenylpyridinato-N, C2 ′) iridium (III) (abbreviation: Ir (ppy) ₃ ), bis (2-phenylpyridinato-N, C2 ′) iridium (III) acetylacetonate ( Abbreviations: Ir (ppy) ₂ (acac)), bis (1,2-diphenyl-1H-benzimidazolato) iridium (III) acetylacetonate (abbreviation: Ir (pbi) ₂ (acac)), bis (benzo [ h] quinolinato) iridium (III) acetylacetonate (abbreviation: Ir (bzq) ₂ (acac)) and the like.
As a red phosphorescent material that can be used for the light emitting layer, a metal complex such as an iridium complex, a platinum complex, a terbium complex, or a europium complex is used. Specifically, bis [2- (2′-benzo [4,5-α] thienyl) pyridinato-N, C3 ′] iridium (III) acetylacetonate (abbreviation: Ir (btp) ₂ (acac)), Bis (1-phenylisoquinolinato-N, C2 ′) iridium (III) acetylacetonate (abbreviation: Ir (piq) ₂ (acac)), (acetylacetonato) bis [2,3-bis (4-fluoro Phenyl) quinoxalinato] iridium (III) (abbreviation: Ir (Fdpq) ₂ (acac)), 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum (II) (abbreviation) : PtOEP) and the like.
In addition, tris (acetylacetonato) (monophenanthroline) terbium (III) (abbreviation: Tb (acac) ₃ (Phen)), tris (1,3-diphenyl-1,3-propanedionate) (monophenanthroline) europium (III) (abbreviation: Eu (DBM) ₃ (Phen)), tris [1- (2-thenoyl) -3,3,3-trifluoroacetonato] (monophenanthroline) europium (III) (abbreviation: Eu ( Since rare earth metal complexes such as TTA) ₃ (Phen)) emit light from rare earth metal ions (electron transition between different multiplicity), they can be used as phosphorescent compounds.

In the present embodiment, the ratio of the first material to the second material is preferably 99: 1 to 1:99, more preferably 90:10 to 10:90 in terms of mass ratio. 80:20 to 20:80 is more preferable.
In the present embodiment, the ratio between the total amount of the first material and the second material and the third material is preferably 99: 1 to 50:50 in terms of mass ratio.

(substrate)
The substrate is used as a support for the organic EL element. For example, glass, quartz, plastic, or the like can be used as the substrate. Further, a flexible substrate may be used. The flexible substrate is a substrate that can be bent (flexible), and examples thereof include plastic substrates made of polycarbonate, polyarylate, polyethersulfone, polypropylene, polyester, polyvinyl fluoride, and polyvinyl chloride. . Moreover, an inorganic vapor deposition film can also be used.

(anode)
For the anode formed on the substrate, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more). Specifically, for example, indium oxide-tin oxide (ITO): indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, tungsten oxide, and indium oxide containing zinc oxide And graphene. In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium ( Pd), titanium (Ti), or a metal material nitride (for example, titanium nitride).
These materials are usually formed by sputtering. For example, indium oxide-zinc oxide can be formed by a sputtering method by using a target in which 1% by mass to 10% by mass of zinc oxide is added to indium oxide. For example, indium oxide containing tungsten oxide and zinc oxide contains 0.5% by mass to 5% by mass of tungsten oxide and 0.1% by mass to 1% by mass of zinc oxide with respect to indium oxide. By using a target, it can be formed by a sputtering method. In addition, you may produce by the vacuum evaporation method, the apply | coating method, the inkjet method, a spin coat method, etc.
Of the EL layers formed on the anode, the hole injection layer formed in contact with the anode is formed using a composite material that facilitates hole injection regardless of the work function of the anode. Any material that can be used as an electrode material (for example, a metal, an alloy, an electrically conductive compound, and a mixture thereof, and other elements belonging to Group 1 or Group 2 of the periodic table) can be used.
An element belonging to Group 1 or Group 2 of the periodic table, which is a material having a low work function, that is, an alkali metal such as lithium (Li) or cesium (Cs), and magnesium (Mg), calcium (Ca), or strontium Alkaline earth metals such as (Sr), and alloys containing these (eg, MgAg, AlLi), rare earth metals such as europium (Eu), ytterbium (Yb), and alloys containing these can also be used. Note that when an anode is formed using an alkali metal, an alkaline earth metal, and an alloy containing these, a vacuum evaporation method or a sputtering method can be used. Furthermore, when using a silver paste etc., the apply | coating method, the inkjet method, etc. can be used.

(cathode)
It is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a low work function (specifically, 3.8 eV or less) for the cathode. Specific examples of such cathode materials include elements belonging to Group 1 or Group 2 of the periodic table of elements, that is, alkali metals such as lithium (Li) and cesium (Cs), and magnesium (Mg) and calcium (Ca ), Alkaline earth metals such as strontium (Sr), and alloys containing these (for example, rare earth metals such as MgAg, AlLi), europium (Eu), ytterbium (Yb), and alloys containing these.
Note that in the case where the cathode is formed using an alkali metal, an alkaline earth metal, or an alloy containing these, a vacuum evaporation method or a sputtering method can be used. Moreover, when using a silver paste etc., the apply | coating method, the inkjet method, etc. can be used.
By providing an electron injection layer, a cathode is formed using various conductive materials such as indium oxide-tin oxide containing Al, Ag, ITO, graphene, silicon, or silicon oxide regardless of the work function. can do. These conductive materials can be formed by a sputtering method, an inkjet method, a spin coating method, or the like.

(Hole injection layer)
The hole injection layer is a layer containing a substance having a high hole injection property. Substances with high hole injection properties include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, Tungsten oxide, manganese oxide, or the like can be used.
As a substance having a high hole injection property, 4,4 ′, 4 ″ -tris (N, N-diphenylamino) triphenylamine (abbreviation: TDATA), 4,4 ′, which is a low molecular organic compound, is used. , 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (abbreviation: MTDATA), 4,4′-bis [N- (4-diphenylaminophenyl) -N-phenyl Amino] biphenyl (abbreviation: DPAB), 4,4′-bis (N- {4- [N ′-(3-methylphenyl) -N′-phenylamino] phenyl} -N-phenylamino) biphenyl (abbreviation: DNTPD), 1,3,5-tris [N- (4-diphenylaminophenyl) -N-phenylamino] benzene (abbreviation: DPA3B), 3- [N- (9-phenylcarbazol-3-yl) -N -F Enylamino] -9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis [N- (9-phenylcarbazol-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviation: PCzPCA2), 3- An aromatic amine compound such as [N- (1-naphthyl) -N- (9-phenylcarbazol-3-yl) amino] -9-phenylcarbazole (abbreviation: PCzPCN1) can also be used.
As the substance having a high hole injecting property, a high molecular compound (an oligomer, a dendrimer, a polymer, or the like) can also be used. For example, poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyltriphenylamine) (abbreviation: PVTPA), poly [N- (4- {N ′-[4- (4-diphenylamino)] Phenyl] phenyl-N′-phenylamino} phenyl) methacrylamide] (abbreviation: PTPDMA), poly [N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine] (abbreviation: Polymer compounds such as Poly-TPD). In addition, a polymer compound to which an acid such as poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonic acid) (PEDOT / PSS), polyaniline / poly (styrenesulfonic acid) (PAni / PSS) is added is used. You can also.

(Hole transport layer)
The hole transport layer is a layer containing a substance having a high hole transport property. An aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used for the hole transport layer. Specifically, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB) or N, N′-bis (3-methylphenyl) -N, N′— Diphenyl- [1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 4-phenyl-4 ′-(9-phenylfluoren-9-yl) triphenylamine (abbreviation: BAFLP), 4 , 4′-bis [N- (9,9-dimethylfluoren-2-yl) -N-phenylamino] biphenyl (abbreviation: DFLDPBi), 4,4 ′, 4 ″ -tris (N, N-diphenylamino) ) Triphenylamine (abbreviation: TDATA), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (abbreviation: MTDATA), 4,4′-bis [N- (Spiro-9,9'-Biff Oren-2-yl) -N- phenylamino] biphenyl (abbreviation: BSPB) can be used aromatic amine compounds such as. The substances described here are mainly substances having a hole mobility of 10 −6 cm 2 / Vs or higher.
For the hole transport layer, a carbazole derivative such as CBP, CzPA, or PCzPA, or an anthracene derivative such as t-BuDNA, DNA, or DPAnth may be used. A high molecular compound such as poly (N-vinylcarbazole) (abbreviation: PVK) or poly (4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used.
Note that other than these substances, any substance that has a property of transporting more holes than electrons may be used. Note that the layer containing a substance having a high hole-transport property is not limited to a single layer, and two or more layers containing the above substances may be stacked.

(Electron transport layer)
The electron transport layer is a layer containing a substance having a high electron transport property. For the electron transport layer, 1) metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes, 2) heteroaromatic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, and phenanthroline derivatives, and 3) polymer compounds Can be used. Specifically, as a low-molecular organic compound, Alq, tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq ₃ ), bis (10-hydroxybenzo [h] quinolinato) beryllium (abbreviation: BeBq ₂ ), A metal complex such as BAlq, Znq, ZnPBO, ZnBTZ, or the like can be used. In addition to metal complexes, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- (Pert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4-phenyl-5- (4- Biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) -1,2,4- Triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproin (abbreviation: BCP), 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene (abbreviation: B) Heteroaromatic compounds such as zOs) can also be used. The substances mentioned here are mainly substances having an electron mobility of 10 ⁻⁶ cm ² / Vs or higher. Note that any substance other than the above substances may be used for the electron-transport layer as long as the substance has a higher electron-transport property than the hole-transport property. Further, the electron-transport layer is not limited to a single layer, and two or more layers including the above substances may be stacked.
Moreover, a high molecular compound can also be used for an electron carrying layer. For example, poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5-diyl)] (abbreviation: PF-Py), poly [(9,9-dioctylfluorene-2) , 7-diyl) -co- (2,2′-bipyridine-6,6′-diyl)] (abbreviation: PF-BPy) and the like can be used.

(Electron injection layer)
The electron injection layer is a layer containing a substance having a high electron injection property. For the electron injection layer, lithium (Li), cesium (Cs), calcium (Ca), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF ₂ ), lithium oxide (LiOx), etc. An alkali metal, an alkaline earth metal, or a compound thereof can be used. In addition, a substance in which an alkali metal, an alkaline earth metal, or a compound thereof is contained in a substance having an electron transporting property, specifically, a substance in which magnesium (Mg) is contained in Alq may be used. In this case, electron injection from the cathode can be performed more efficiently.
Alternatively, a composite material obtained by mixing an organic compound and an electron donor (donor) may be used for the electron injection layer. Such a composite material is excellent in electron injecting property and electron transporting property because electrons are generated in the organic compound by the electron donor. In this case, the organic compound is preferably a material excellent in transporting the generated electrons. Specifically, for example, a substance (metal complex, heteroaromatic compound, or the like) constituting the electron transport layer described above is used. be able to. The electron donor may be any substance that exhibits an electron donating property to the organic compound. Specifically, alkali metals, alkaline earth metals, and rare earth metals are preferable, and lithium, cesium, magnesium, calcium, erbium, ytterbium, and the like can be given. Alkali metal oxides and alkaline earth metal oxides are preferable, and lithium oxide, calcium oxide, barium oxide, and the like can be given. A Lewis base such as magnesium oxide can also be used. Alternatively, an organic compound such as tetrathiafulvalene (abbreviation: TTF) can be used.

(Layer formation method)
The method for forming each layer of the organic EL element of the present embodiment is not limited except as specifically mentioned above, but a dry film forming method such as a vacuum evaporation method, a sputtering method, a plasma method, an ion plating method, a spin method, Known methods such as a coating method, a dipping method, a flow coating method, and a wet film forming method such as an ink jet method can be employed.

(Film thickness)
The film thickness of each organic layer of the organic EL element of the present embodiment is not limited except as specifically mentioned above. Generally, if the film thickness is too thin, defects such as pinholes are likely to occur, and conversely, if it is too thick, it is high. Since an applied voltage is required and the efficiency is deteriorated, the range of several nm to 1 μm is usually preferable.

In this specification, the number of ring-forming carbon atoms refers to a compound having a structure in which atoms or molecules are bonded in a ring (for example, a monocyclic compound, a condensed ring compound, a bridged compound, a spiro ring compound, a carbocyclic compound, or a heterocyclic compound). This represents the number of carbon atoms among atoms constituting the ring itself. When the ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of ring-forming carbons. The “ring-forming carbon number” described below is the same unless otherwise specified.
The number of ring-forming atoms refers to the ring itself of a compound having a structure in which atoms or molecules are bonded in a ring (for example, a monocyclic compound, a condensed ring compound, a bridging compound, a spiro ring compound, a carbocyclic compound, or a heterocyclic compound). This represents the number of atoms to be played. An atom that does not constitute a ring (for example, a hydrogen atom that terminates the dangling bond of an atom that constitutes a ring) or an atom contained in a substituent when the ring is substituted by a substituent is included in the number of ring-forming atoms Absent. The “number of ring-forming atoms” described below is the same unless otherwise specified.
Next, each substituent described in the general formula will be described.

Examples of the aromatic hydrocarbon group having 6 to 30 ring carbon atoms in the present embodiment include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group, a chrysenyl group, Fluoranthenyl group, benzo [a] anthryl group, benzo [c] phenanthryl group, triphenylenyl group, benzo [k] fluoranthenyl group, benzo [g] chrycenyl group, benzo [b] triphenylenyl group, picenyl group, perylenyl group Etc.
As an aromatic hydrocarbon group in this embodiment, it is preferable that ring forming carbon number is 6-20, More preferably, it is still more preferable that it is 6-12. Of the aromatic hydrocarbon groups, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a terphenyl group, and a fluorenyl group are particularly preferable. For the 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group and 4-fluorenyl group, the 9-position carbon atom is substituted with a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms in the present embodiment described later. It is preferable that

Examples of the heterocyclic group having 5 to 30 ring atoms in the present embodiment include a pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinolyl group, isoquinolinyl group, naphthyridinyl group, phthalazinyl group, quinoxalinyl group, Quinazolinyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, indolyl group, benzimidazolyl group, indazolyl group, imidazolpyridinyl group, benz Triazolyl, carbazolyl, furyl, thienyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, benzofuranyl, benzothiophenyl, benzoxazolyl Group, benzothiazolyl group, benzisoxazolyl group, benzoisothiazolyl group, benzoxiadiazolyl group, benzothiadiazolyl group, dibenzofuranyl group, dibenzothiophenyl group, piperidinyl group, pyrrolidinyl group, piperazinyl group, morpholyl Group, phenazinyl group, phenothiazinyl group, phenoxazinyl group and the like.
The number of ring-forming atoms of the heterocyclic group in this embodiment is preferably 5-20, and more preferably 5-14. Among the above heterocyclic groups, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3- A dibenzothiophenyl group, 4-dibenzothiophenyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, and 9-carbazolyl group are particularly preferable. As for the 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group and 4-carbazolyl group, the substituted or unsubstituted aromatic hydrocarbon having 6 to 30 ring carbon atoms in the present embodiment is attached to the 9th-position nitrogen atom. The group or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms is preferably substituted.

In the present embodiment, the alkyl group having 1 to 30 carbon atoms may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, amyl group, isoamyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1- A heptyloctyl group and a 3-methylpentyl group.
The linear or branched alkyl group in the present embodiment preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Among the linear or branched alkyl groups, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group , An amyl group, an isoamyl group, and a neopentyl group are particularly preferable.
Examples of the cycloalkyl group in this embodiment include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, an adamantyl group, and a norbornyl group. The ring-forming carbon number of the cycloalkyl group is preferably 3 to 10, and more preferably 5 to 8. Among the cycloalkyl groups, a cyclopentyl group and a cyclohexyl group are particularly preferable.
Examples of the halogenated alkyl group in which the alkyl group is substituted with a halogen atom include those in which the alkyl group having 1 to 30 carbon atoms is substituted with one or more halogen groups. Specific examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a trifluoromethylmethyl group, a trifluoroethyl group, and a pentafluoroethyl group.

  Examples of the alkylsilyl group having 3 to 30 carbon atoms in the present embodiment include a trialkylsilyl group having an alkyl group exemplified as the alkyl group having 1 to 30 carbon atoms, specifically, a trimethylsilyl group and a triethylsilyl group. , Tri-n-butylsilyl group, tri-n-octylsilyl group, triisobutylsilyl group, dimethylethylsilyl group, dimethylisopropylsilyl group, dimethyl-n-propylsilyl group, dimethyl-n-butylsilyl group, dimethyl-t- Examples thereof include a butylsilyl group, a diethylisopropylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, and a triisopropylsilyl group. The three alkyl groups in the trialkylsilyl group may be the same or different.

Examples of the arylsilyl group having 6 to 30 ring carbon atoms in the present embodiment include a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group.
The dialkylarylsilyl group has, for example, two alkyl groups exemplified as the alkyl group having 1 to 30 carbon atoms, and one dialkylarylsilyl group having one aromatic hydrocarbon group having 6 to 30 ring carbon atoms. Is mentioned. The carbon number of the dialkylarylsilyl group is preferably 8-30.
The alkyldiarylsilyl group has, for example, one alkyl group exemplified for the alkyl group having 1 to 30 carbon atoms, and two alkyldiarylsilyl groups having the two aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. Is mentioned. The alkyldiarylsilyl group preferably has 13 to 30 carbon atoms.
Examples of the triarylsilyl group include a triarylsilyl group having three aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. The carbon number of the triarylsilyl group is preferably 18-30.

Alkoxy group having 1 to 30 carbon atoms in the present embodiment is represented as -OZ _1. Examples of _{Z 1,} include alkyl groups of 1 to 30 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Examples of the halogenated alkoxy group in which the alkoxy group is substituted with a halogen atom include those in which the C 1-30 alkoxy group is substituted with one or more halogen groups.

Aryloxy group ring forming C6-30 in this embodiment is expressed as -OZ _2. Examples of this Z ₂ include the aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. Examples of the aryloxy group include a phenoxy group.

Alkylamino group having 2 to 30 carbon atoms is represented as -NHR _V or -N _{(R V) 2,.} Examples of _{R V,} include alkyl groups of 1 to 30 carbon atoms.

The arylamino group having 6 to 60 ring carbon atoms is represented as —NHR _W or —N (R _W ) ₂ . Examples of R _W, and an aromatic hydrocarbon group of the ring-forming C6-30.

Alkylthio group having 1 to 30 carbon atoms is represented as -SR _V. Examples of _{R V,} include alkyl groups of 1 to 30 carbon atoms.
Ring formation arylthio group having 6 to 30 carbon atoms is expressed as -SR _W. Examples of R _W, and an aromatic hydrocarbon group of the ring-forming C6-30.

In the present invention, “ring-forming carbon” means a carbon atom constituting a saturated ring, an unsaturated ring, or an aromatic ring. “Ring-forming atom” means a carbon atom and a hetero atom constituting a hetero ring (including a saturated ring, an unsaturated ring, and an aromatic ring).
In the present invention, the hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (Protium), deuterium (Deuterium), and tritium (Tritium).

In the case of “substituted or unsubstituted”, examples of the substituent include the aromatic hydrocarbon group, the heterocyclic group, and the alkyl group (straight chain or branched chain alkyl group, cycloalkyl group, haloalkyl group) as described above. , Alkylsilyl group, arylsilyl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylthio group, arylthio group, alkenyl group, alkynyl group, aralkyl group, halogen atom, cyano group, hydroxyl group , A nitro group, and a carboxy group.
Among the substituents mentioned here, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group, a halogen atom, an alkylsilyl group, an arylsilyl group, and a cyano group are preferable, and more preferable in the description of each substituent. The specific substituents are preferred.

  The alkenyl group is preferably an alkenyl group having 2 to 30 carbon atoms, which may be linear, branched or cyclic, for example, vinyl group, propenyl group, butenyl group, oleyl group, eicosapentaenyl group. , Docosahexaenyl group, styryl group, 2,2-diphenylvinyl group, 1,2,2-triphenylvinyl group, 2-phenyl-2-propenyl group, cyclopentadienyl group, cyclopentenyl group, cyclohexenyl group And cyclohexadienyl group.

  The alkynyl group is preferably an alkynyl group having 2 to 30 carbon atoms, and may be linear, branched or cyclic, and examples thereof include ethynyl, propynyl, 2-phenylethynyl and the like.

As the aralkyl group, an aralkyl group having 6 to 30 ring carbon atoms is preferable and represented by -Z ₃ -Z ₄ . Examples of Z ₃ include alkylene groups corresponding to the alkyl groups having 1 to 30 carbon atoms. Examples of this Z ₄ include the above aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. This aralkyl group is an aralkyl group having 7 to 30 carbon atoms (the aryl moiety is 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms), and the alkyl moiety is 1 to 30 carbon atoms (preferably 1 to 1 carbon atoms). 20, more preferably 1-10, still more preferably 1-6). Examples of the aralkyl group include benzyl group, 2-phenylpropan-2-yl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, and phenyl-t-butyl. Group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β- Examples include naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, and 2-β-naphthylisopropyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The term “unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted with the substituent.
In the present specification, “carbon number ab” in the expression “XX group having a substituted or unsubstituted carbon number ab” represents the number of carbon atoms when the XX group is unsubstituted. The number of carbon atoms of the substituent when the XX group is substituted is not included.
In the compound described below or a partial structure thereof, the case of “substituted or unsubstituted” is the same as described above.
“These substituents may be further substituted with the above-mentioned substituents. Also, a plurality of these substituents may be bonded to each other to form a ring.”

  In the present embodiment, the linking group includes a multiple linking group. A multiple linking group formed by bonding 2 to 4 groups selected from the aromatic hydrocarbon group, a multiple linking group formed by bonding 2 to 4 groups selected from the heterocyclic group, or Examples of the multiple linking group in which 2 to 4 groups selected from the aromatic hydrocarbon group and the heterocyclic group are bonded to each other include two selected from the aromatic hydrocarbon group and the heterocyclic group Examples thereof include a divalent group formed by bonding four groups. Examples of the multiple linking group formed by bonding 2 to 4 groups selected from the aromatic hydrocarbon group and the heterocyclic group include heterocyclic group-aromatic hydrocarbon group, aromatic hydrocarbon group-heterocycle Group, aromatic hydrocarbon group-heterocyclic group-aromatic hydrocarbon group, heterocyclic group-aromatic hydrocarbon group-heterocyclic group, aromatic hydrocarbon group-heterocyclic group-aromatic hydrocarbon group-heterocycle Group, heterocyclic group-aromatic hydrocarbon group-heterocyclic group-aromatic hydrocarbon group, and the like. Preferably, a divalent group formed by bonding the aromatic hydrocarbon group and the heterocyclic group one by one, that is, a heterocyclic group-aromatic hydrocarbon group, and an aromatic hydrocarbon group-heterocyclic group. . Specific examples of the aromatic hydrocarbon group and the heterocyclic group in these multiple linking groups include the groups described above for the aromatic hydrocarbon group and the heterocyclic group.

[Modification of Embodiment]
In addition, this invention is not limited to the above-mentioned embodiment, The change in the range which can achieve the objective of this invention, improvement, etc. are included in this invention.

The light emitting layer is not limited to one layer, and a plurality of light emitting layers may be stacked. When the organic EL device has a plurality of light emitting layers, at least one light emitting layer is a compound represented by the general formula (10) or the general formula (11), a compound represented by the general formula (20), The other light emitting layer may be a fluorescent light emitting layer or a phosphorescent light emitting layer as long as it contains a phosphorescent compound.
In addition, when the organic EL element has a plurality of light emitting layers, these light emitting layers may be provided adjacent to each other, or a so-called tandem organic material in which a plurality of light emitting units are stacked via an intermediate layer. It may be an EL element.

  Further, for example, an electron barrier layer may be provided adjacent to the anode side of the light emitting layer, and a hole barrier layer may be provided adjacent to the cathode side of the light emitting layer. Thereby, electrons and holes can be confined in the light emitting layer, and the exciton generation probability in the light emitting layer can be increased.

  An organic EL element according to an embodiment of the present invention is a display component such as an organic EL panel module, a display device such as a television, a mobile phone, a tablet or a personal computer, and an electronic device such as a light emitting device for lighting or a vehicle lamp. Can be used for

  In addition, the specific structure and shape in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

  EXAMPLES Next, although an Example is given and this invention is demonstrated, this invention is not restrict | limited at all to the description content of these Examples.

  The compounds used in this example are as follows.

<Evaluation of compound>
Next, the physical properties of the compounds used in this example were measured. The measurement method and calculation method are shown below, and the measurement results and calculation results are shown in Table 1.
Measurement of electron mobility μ (e) and hole mobility μ (h) The mobility was evaluated using impedance spectroscopy. The following single carrier device is manufactured, and a complex modulus is measured by applying a DC voltage on which an alternating voltage of 0.25 mV is applied for the hole mobility μ (h) and 1 mV for the electron mobility μ (e). did. When the frequency at which the imaginary part of the modulus is the maximum is f _max (Hz), the response time T (seconds) is calculated as T = 1/2 / π / f _{max and} the electric field strength of the mobility is calculated using this value. Dependency was determined. The single carrier devices used for the measurement of hole mobility μ (h) and electron mobility μ (e) are described below. The electric field strength was 500 (v / cm) ^ 0.5.
Single carrier device used for measurement of hole mobility μ (h): Al / measurement target compound (150) / ET (5) / LiF (1) / Al
Single carrier device used for measurement of electron mobility μ (e): ITO / HT (5) / measurement target compound (100) / Al
(Numerical values in parentheses in the device configuration shown here represent film thickness. Unit: nm).

Measurement was performed using a photoelectron spectrometer (Riken Keiki Co., Ltd .: AC-3) under an ionization potential atmosphere. Specifically, the measurement was performed by irradiating the compound to be measured with light and measuring the amount of electrons generated by charge separation.

・ Singlet energy EgS
A 10 μmol / L toluene solution of the compound to be measured was prepared and placed in a quartz cell, and the emission spectrum (vertical axis: emission intensity, horizontal axis: wavelength) of this sample was measured at room temperature (300 K). A single line energy was calculated by drawing a tangent line from the short wavelength side rise of the emission spectrum and substituting the wavelength value λ _edge [nm] at the intersection of the tangent line and the horizontal axis into the following conversion formula 2.
Conversion formula 2: EgS [eV] = 1239.85 / λ _edge
In this example, the emission spectrum was measured with a spectrophotometer manufactured by Hitachi (device name: U3310).

A tangent to the rising edge of the emission spectrum on the short wavelength side was drawn as follows. When moving on the spectrum curve from the short wavelength side of the emission spectrum to the maximum value on the shortest wavelength side of the maximum value of the spectrum, tangents at each point on the curve are considered toward the long wavelength side. The slope of this tangent line increases as the curve rises (that is, as the vertical axis increases). The tangent drawn at the point where the value of the slope takes the maximum value (that is, the tangent at the inflection point) was taken as the tangent to the rise on the short wavelength side of the emission spectrum.
Note that the maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the above-mentioned maximum value on the shortest wavelength side, and has the maximum slope value closest to the maximum value on the shortest wavelength side. The tangent drawn at the point where the value was taken was taken as the tangent to the rising edge of the emission spectrum on the short wavelength side.

・ Triplet energy EgT
First, a measurement sample was prepared as follows. The compound to be measured is dissolved in EPA (diethyl ether: isopentane: ethanol = 5: 5: 5 (volume ratio)) as a solvent so that the concentration becomes 10 μmol / L, and this solution is placed in a quartz cell. It was put into a measurement sample.
With respect to this measurement sample, a phosphorescence spectrum (vertical axis: phosphorescence emission intensity, horizontal axis: wavelength) is measured at a low temperature (77 [K]), and a tangent line is drawn with respect to the rising edge of the phosphorescence spectrum on the short wavelength side. Based on the wavelength value λ _edge [nm] at the intersection of the tangent and the horizontal axis, the amount of energy calculated from the following conversion formula 1 was defined as triplet energy EgT.
Conversion formula 1: EgT [eV] = 1239.85 / λ _edge
For measurement of phosphorescence, an F-4500 spectrofluorometer main body manufactured by Hitachi High-Technology Co., Ltd. was used.
The tangent to the rising edge on the short wavelength side of the phosphorescence spectrum is drawn as follows. When moving on the spectrum curve from the short wavelength side of the phosphorescence spectrum to the maximum value on the shortest wavelength side among the maximum values of the spectrum, tangents at each point on the curve are considered toward the long wavelength side. The slope of this tangent line increases as the curve rises (that is, as the vertical axis increases). A tangent drawn at a point where the value of the slope takes a maximum value (that is, a tangent at the inflection point) is a tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.
Note that the maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the above-mentioned maximum value on the shortest wavelength side, and has the maximum slope value closest to the maximum value on the shortest wavelength side. The tangent drawn at the point where the value is taken is taken as the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.

・ Affinity (electron affinity)
Using the measured values of the ionization potential Ip and singlet energy EgS of the compound measured by the method described above, the calculation was performed from the following formula.
Af = Ip-EgS

<Production and Evaluation of Organic EL Element>
An organic EL element was produced and evaluated as follows.

Example 1
A glass substrate (manufactured by Geomatic Co., Ltd.) with an ITO transparent electrode (anode) having a thickness of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol, and then UV ozone cleaning was performed for 30 minutes. The film thickness of ITO was 130 nm.
The glass substrate with the transparent electrode line after the cleaning is mounted on the substrate holder of the vacuum deposition apparatus, and first, the compound HI is vapor deposited so as to cover the transparent electrode on the surface where the transparent electrode line is formed, and the film thickness is 10 nm. The hole injection layer was formed.
Next, Compound HT-1 was vapor-deposited on this hole injection layer, and a 40-nm-thick first hole transport layer was formed on the HI film.
Next, Compound HT-2 was vapor-deposited on the first hole transport layer to form a second hole transport layer having a thickness of 10 nm.
Furthermore, on this second hole transport layer, a compound PH-11 as a first material, a compound PH-21 as a second material, a compound Ir (ppy) ₃ as a third material, Were co-evaporated to form a light emitting layer having a thickness of 30 nm. The concentration of the compound PH-11 in the light emitting layer was 47.5% by mass, the concentration of the compound PH-21 was 47.5% by mass, and the concentration of the compound Ir (ppy) ₃ was 5% by mass.
Next, compound ET was vapor-deposited on this light emitting layer, and the 35-nm-thick electron carrying layer was formed.
Next, lithium fluoride (LiF) was vapor-deposited on the electron transport layer to form an electron injecting electrode (cathode) having a thickness of 1 nm.
And metal aluminum (Al) was vapor-deposited on this electron injecting electrode, and the metal Al cathode with a film thickness of 80 nm was formed.
A device arrangement of the organic EL device of Example 1 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-11: PH-21: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)
The numbers in parentheses indicate the film thickness (unit: nm). Similarly, in the parentheses, the number displayed as a percentage indicates the ratio (mass%) of each component in the light emitting layer. This also applies to the case where the element configuration of the organic EL element is schematically shown below.

(Example 2)
The organic EL device according to Example 2 was produced in the same manner as in Example 1 except that Compound PH-12 was used instead of Compound PH-11 in the light emitting layer of the organic EL device according to Example 1.
A device arrangement of the organic EL device of Example 2 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-12: PH-21: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)

(Example 3)
The organic EL device according to Example 3 was manufactured in the same manner as in Example 1 except that Compound PH-13 was used instead of Compound PH-11 in the light emitting layer of the organic EL device according to Example 1.
A device arrangement of the organic EL device of Example 3 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-13: PH-21: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)

(Comparative Example 1)
The organic EL device according to Comparative Example 1 was produced in the same manner as in Example 1 except that Compound PH-14 was used instead of Compound PH-11 in the light emitting layer of the organic EL device according to Example 1.
A device arrangement of the organic EL device of Comparative Example 1 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-14: PH-21: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)

(Comparative Example 2)
The organic EL device according to Comparative Example 2 was prepared in the same manner as in Example 1 except that Compound PH-22 was used instead of Compound PH-21 in the light emitting layer of the organic EL device according to Example 1.
A device arrangement of the organic EL device of Comparative Example 2 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-11: PH-22: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)

(Comparative Example 3)
The organic EL device according to Comparative Example 3 was produced in the same manner as in Example 2 except that Compound PH-22 was used instead of Compound PH-21 in the light emitting layer of the organic EL device according to Example 2.
A device arrangement of the organic EL device of Comparative Example 3 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-12: PH-22: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)

(Comparative Example 4)
The organic EL device according to Comparative Example 4 was produced in the same manner as in Example 3 except that Compound PH-22 was used instead of Compound PH-21 in the light emitting layer of the organic EL device according to Example 3.
A device arrangement of the organic EL device of Comparative Example 4 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-13: PH-22: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)

(Comparative Example 5)
The organic EL device according to Comparative Example 5 was produced in the same manner as Comparative Example 1 except that Compound PH-22 was used instead of Compound PH-21 in the light emitting layer of the organic EL device according to Comparative Example 1.
A device arrangement of the organic EL device of Comparative Example 5 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-14: PH-22: Ir (ppy) ₃ (30, 47.5%: 47.5%: 5%) / ET (35) / LiF (1) / Al (80)

(Reference Example 1)
In the organic EL device according to Reference Example 1, the light emitting layer of the organic EL device according to Example 1 is formed by co-evaporation of Compound PH-21 and Compound Ir (ppy) _3, and the concentration of Compound PH-21 Was made in the same manner as in Example 1 except that the concentration of Compound Ir (ppy) ₃ was changed to 5% by mass.
The device configuration of the organic EL device of Reference Example 1 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-21: Ir (ppy) ₃ (30, 95%: 5%) / ET (35) / LiF ( 1) / Al (80)

(Reference Example 2)
The organic EL device according to Reference Example 2 was produced in the same manner as Reference Example 1 except that Compound PH-21 in the light emitting layer of the organic EL device according to Reference Example 1 was changed to Compound PH-22.
The element configuration of the organic EL element of Reference Example 2 is schematically shown as follows.
ITO (130) / HI (10) / HT-1 (40) / HT-2 (10) / PH-22: Ir (ppy) ₃ (30, 95%: 5%) / ET (35) / LiF ( 1) / Al (80)

[Evaluation of organic EL elements]
The following evaluation was performed about the organic EL element produced in Examples 1-3, Comparative Examples 1-5, and Reference Examples 1-2. The evaluation results are shown in Table 2.

-Driving voltage The voltage (unit: V) when electricity was passed between the ITO transparent electrode and the metal Al cathode so that the current density was 10.0 mA / cm ² was measured.

・ Lifetime LT80
The time (unit: hrs) until the initial luminance decreased from 10000 cd / m ² to 8000 cd / m ² was measured.

As shown in Table 2, the organic EL devices according to Examples 1 to 3 are the first materials (compounds PH-11, PH) represented by the general formula (10) or the general formula (11). -12, PH-13), a second material (compound PH-21) represented by the general formula (20), and a phosphorescent third material (Ir (ppy) ₃ ). A light emitting layer is provided. As a result, it was found that the organic EL elements according to Examples 1 to 3 were driven with a low driving voltage and had a long lifetime. The affinity of compound PH-11 is greater than that of compound PH-13, and the affinity of compound PH-12 is even greater. In this example, the driving voltage was lowered and the life was extended in the order of increasing affinity.
The compound PH-14 used in Comparative Example 1 does not correspond to the first material represented by the general formula (10) or the general formula (11). As in Comparative Example 1, even when Compound PH-14 and Compound PH-21 were combined, the lifetime was shorter than that of Examples 1-3. The compound PH-14, the formula _{Y 2} in (11b) is a _CR C _{R D} compound _{(R C} and _{R D,} methyl group), Compound PH-11, PH-12, PH- The electron mobility is larger than 13, and the electron transport property is strong. As a result, the organic EL element of Comparative Example 1 is considered to have a short lifetime.
The compound PH-22 used in Comparative Examples 2 to 4 does not correspond to the second material represented by the general formula (20). Like Comparative Examples 2-4, even if it combined compound PH-11, PH-12, or PH-13, and compound PH-22, the lifetime was notably shorter than Examples 1-3.
Further, as in Comparative Example 5, even when Compound PH-14 and Compound PH-22 were combined, the driving voltage was higher than those of Examples 1 to 3, and the lifetime was significantly shorter.
In addition, when only the compound PH-21 or compound PH-22 and Ir (ppy) ₃ were combined, the driving voltage was higher than that of Examples 1 to 3 by 1 V or more, and the lifetime was remarkably short.

DESCRIPTION OF SYMBOLS 1 ... Organic EL element 2 ... Substrate 3 ... Anode 4 ... Cathode 5 ... Light emitting layer 6 ... Hole injection / transport layer 7 ... Electron injection / transport layer 10 ... Organic layer

Claims (22)

An anode, a light emitting layer, and a cathode;
The light-emitting layer includes a first material represented by the following general formula (10) or the following general formula (11), a second material represented by the following general formula (20), and a phosphorescent light-emitting layer. An organic electroluminescence device characterized by comprising three materials.
(In the general formula (10),
Cz ₁ and Cz ₂ are each independently a substituted or unsubstituted carbazolyl group,
L ₁₀ and L ₁₁ are each independently a single bond or a linking group;
Az is a nitrogen-containing ring represented by the following general formula (12). )
(In the general formula (12), X _{13 to} X ₁₅ are each independently a nitrogen atom or CR ^V , provided that at least one of X _{13 to} X ₁₅ is a nitrogen atom, and R ₁ , R ₂ and R ^V are each independently a hydrogen atom or a substituent. In this case, the substituent is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, a substituted or unsubstituted carbon An alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, a substituted or unsubstituted An unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heterocyclic ring having 5 to 30 ring atoms A substituent selected from the group consisting of groups, wherein R ₁ and R ^V may be bonded to each other to form a ring structure, and R ₂ and R ^V are bonded to each other to form a ring structure. May be.)
(In the general formula (11), Az is a nitrogen-containing ring represented by the general formula (12),
L ₁₀ is a single bond or a linking group;
HAr is represented by the following general formula (11a). )
In (Formula _(11a), X 1 to X ₈ are each independently a nitrogen atom, CR ^X or carbon atom bonded to the structure represented by the following general formula (11b),, _{X 1} and X 1 or more and 4 or less of ₂ sets, X ₂ and X ₃ sets, X ₃ and X ₄ sets, X ₅ and X ₆ sets, X ₆ and X ₇ sets, and X ₇ and X ₈ sets Is a carbon atom bonded to a structure represented by the following general formula (11b), and when a plurality of structures represented by the following general formula (11b) are bonded, they may be the same or different. )
(In the general formula _{(11b), X} 9 ~X ₁₂ are each independently a nitrogen atom or CR ^Y,.
Y ₂ is a sulfur atom, an oxygen atom or NR ^Z,.
* ₁₁ and _{* 12,} respectively, _{X 1} and _{X 2} of the set of the general formula (11a), a set of _{X 2} and _{X 3, X 3} and _{X 4} set, a set of _{X 5} and _{X 6, X 6} And X ₇ , and a bonding site with a carbon atom in a group selected from the group consisting of X ₇ and X ₈ . )
(In the general formula (20),
Ar ₂₁ and Ar ₂₂ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group. A group selected from the group consisting of:
L ₂₁ and L ₂₂ are each independently a single bond or an arylene group having 6 to 18 ring carbon atoms,
m and n are 3,
R ₂₁ and R ₂₂ are each bonded to a carbon atom constituting a 6-membered ring;
X _{21 to} X ₂₄ are each independently a nitrogen atom, CR ^W , or a carbon atom bonded to a structure represented by the following general formula (20a), and a pair of X ₂₁ and X ₂₂ , X ₂₂ and X ₂₃ And one set of X ₂₃ and X ₂₄ is a carbon atom bonded to the structure represented by the following general formula (20a). )
In (Formula _{(20a), * 21} and _{* 22} are the set of _{X 21} and _{X 22} of each of the general formula _(20), selected set of _{X 22} and _{X 23,} and a set of _{X 23} and _{X 24} The bonding sites with carbon atoms in
In the general formula (20a), R _A and R _B are each independently a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted ring forming carbon number of 3 to 3 20 cycloalkyl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms Substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted Or an unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, and R _A and R _B may be bonded to each other to form a ring structure,
R ^X , R ^Y , R ^Z , R ^W , R _{21 to} R ₃₀ are each independently a hydrogen atom or a substituent. In this case, the substituent is a halogen atom, a cyano group, a substituted or unsubstituted group. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring carbon number 6 ~ 30 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and substituted or unsubstituted group It is a substituent selected from the group consisting of heterocyclic group ring atoms 5-30. ) The organic electroluminescent device according to claim 1,
The organic electroluminescence device, wherein X ₁₃ , X _14, and X ₁₅ are nitrogen atoms. In the organic electroluminescent element according to claim 1 or 2,
Said general formula (10) is represented by the following general formula (13), The organic electroluminescent element characterized by the above-mentioned.
(In the general formula (13), L ₁₀ and L ₁₁ are each independently synonymous with L ₁₀ and L ₁₁ in the general formula (10),
Ar ₁₁ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms,
X _{13 to} X ₁₅ are each independently a nitrogen atom or CR ^V , provided that at least one of X _{13 to} X ₁₅ is a nitrogen atom,
p and q are 3,
R _{1 to} R ₁₂ and R ^V are each independently a hydrogen atom or a substituent, and the substituent in this case is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, substituted or Unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, substituted or unsubstituted ring formation An arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring atom having 5 to 30 ring atoms; Is a substituent selected from the group consisting of heterocyclic group, R ₇ and R ₈ are, respectively, bonded to the carbon atoms to construct a 6-membered ring. ) In the organic electroluminescent element according to any one of claims 1 to 3,
The structure of Cz ₂ -L ₁₁ -Cz ₁ -in the general formula (10) is represented by the following general formula (10a) or the following general formula (10b).
(In the general formula (10a) and the general formula _{(10b), L 11} has the same meaning as _{L 11} in the general formula (10).
Ar ₁₁ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms,
R _{31 to} R ₄₄ are each independently a hydrogen atom or a substituent. In this case, examples of the substituent include a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or Unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, substituted or unsubstituted An alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, and a substituted or unsubstituted ring carbon number. An arylsilyl group having 6 to 50, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring atom having 5 to 30 ring atoms; It is a substituent selected from the group consisting of heterocyclic group. ) In the organic electroluminescent element according to any one of claims 1 to 4,
Said HAr is represented by the following general formula (11c) or the following general formula (11d), The organic electroluminescent element characterized by the above-mentioned.
(In the general formula _(11c), X 1 ~X ₆ are each independently a nitrogen atom or CR ^X,,
X ₉ to X ₁₂ are each independently a nitrogen atom or CR ^Y,,
Y ₂ is a sulfur atom, an oxygen atom or NR ^Z,.
In the general formula _{(11d), X 1 ~X 4} , X 7 ~X 8 are each independently a nitrogen atom or CR ^X,,
X ₉ to X ₁₂ are each independently a nitrogen atom or CR ^Y,,
Y ₂ is a sulfur atom, an oxygen atom or NR ^Z,. ) In the organic electroluminescent element according to any one of claims 1 to 5,
Y ₂ is an oxygen atom or NR ^Z , wherein the organic electroluminescence device. In the organic electroluminescent element according to any one of claims 1 to 6,
The linking group in L ₁₀ and L ₁₁ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, -CR _{81 R 82 -, - NR 83} -, - O -, - S -, - SiR 84 R 85 -, - CR 86 R 87 -CR 88 R 89 -, - CR 90 = CR 91 -, - NR 92 -, -N = CR 93 _-, substituted or unsubstituted aliphatic hydrocarbon ring group, a substituted or unsubstituted aliphatic heterocyclic group,
R _{81 to} R ₉₃ are each independently a hydrogen atom or a substituent. In this case, examples of the substituent include a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or Unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, substituted or unsubstituted An alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms, and a substituted or unsubstituted ring carbon number. An arylsilyl group having 6 to 50, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring atom having 5 to 30 ring atoms; The organic electroluminescent device characterized by Arles with substituents selected from the group consisting of heterocyclic group. In the organic electroluminescent element according to any one of claims 1 to 7,
Wherein L ₁₀ is an organic electroluminescent device which is a substituted or unsubstituted aromatic ring formed C6-30 hydrocarbon group. In the organic electroluminescent element according to any one of claims 1 to 8,
Wherein L ₁₀ is an organic electroluminescent device which is a phenylene group. In the organic electroluminescent element according to any one of claims 1 to 6,
Wherein L ₁₀ is an organic electroluminescence element which is a single bond. In the organic electroluminescent element according to any one of claims 1 to 10,
Said general formula (20) is represented by the following general formula (21), the following general formula (22), or the following general formula (23), The organic electroluminescent element characterized by the above-mentioned.
(In the general formulas (21) to (23), Ar ₂₁ , Ar ₂₂ , L ₂₁ , L ₂₂ , and X _{21 to} X ₂₄ are respectively Ar ₂₁ , Ar ₂₂ , L ₂₁ in the general formula (20). , L ₂₂ , and X _{21 to} X ₂₄ ,
R _{23 to} R ₂₆ , R _{211 to} R ₂₁₃ , and R _{221 to} R ₂₂₃ are each independently a hydrogen atom or a substituent. In this case, the substituent includes a halogen atom, a cyano group, a substituted or unsubstituted group. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring carbon number 6 ~ 30 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms And a substituent selected from the group consisting of substituted or unsubstituted heterocyclic group ring atoms 5-30. ) In the organic electroluminescent element according to any one of claims 1 to 11,
The organic electroluminescent device, wherein X ₂₂ and X ₂₃ are carbon atoms bonded to * ₂₁ and * ₂₂ in the general formula (20a). In the organic electroluminescent element according to any one of claims 1 to 12,
The organic electroluminescence device, wherein the X ₂₂ is a carbon atom bonded to the * ₂₁ , and the X ₂₃ is a carbon atom bonded to the * ₂₂ . In the organic electroluminescent element according to any one of claims 1 to 11,
Said general formula (20) is represented by the following general formula (21a), The organic electroluminescent element characterized by the above-mentioned.
(In the general formula (21a), Ar ₂₁ , Ar ₂₂ , L ₂₁ , L ₂₂ , X ₂₁ , and X ₂₄ are respectively Ar ₂₁ , Ar ₂₂ , L ₂₁ , L ₂₂ , Synonymous with X ₂₁ and X ₂₄ ;
R _A and _{R B} are the same as _{R A} and _{R B} in the general formula (20a),
R _{23 to} R ₃₀ , R _{211 to} R ₂₁₃ , and R _{221 to} R ₂₂₃ are each independently a hydrogen atom or a substituent. In this case, the substituent includes a halogen atom, a cyano group, a substituted or unsubstituted group. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted ring carbon number 6 ~ 30 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 50 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 50 ring carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms And a substituent selected from the group consisting of substituted or unsubstituted heterocyclic group ring atoms 5-30. ) In the organic electroluminescent element according to any one of claims 1 to 14,
Wherein L ₂₁ and the L ₂₂ is an organic electroluminescence element which is a single bond. In the organic electroluminescent element according to any one of claims 1 to 15,
Ar ₂₁ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, and the organic electroluminescence element. In the organic electroluminescent element according to any one of claims 1 to 16,
The Ar ₂₁ is a group selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a terphenyl group, and a fluorenyl group. In the organic electroluminescent element according to any one of claims 1 to 17,
Ar ₂₂ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and the organic electroluminescence element. In the organic electroluminescent element according to any one of claims 1 to 18,
R _A and R _B are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms. An organic electroluminescence device characterized. In the organic electroluminescent element according to any one of claims 1 to 19,
An organic electroluminescence device, wherein a hole transport layer is provided between the anode and the light emitting layer. In the organic electroluminescent element according to any one of claims 1 to 20,
An organic electroluminescence element, wherein an electron transport layer is provided between the light emitting layer and the cathode. The electronic device provided with the organic electroluminescent element as described in any one of Claim 1- Claim 21.