JP5799820B2 - Organic electroluminescence element, display device and lighting device - Google Patents

Description

  The present invention relates to an organic electroluminescence element, a display device, and a lighting device.

  An organic electroluminescence element (hereinafter also referred to as an organic EL element) has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode. Then, by injecting electrons and holes into the light emitting layer and recombining them, excitons (excitons) are generated, and light emission (fluorescence / phosphorescence) is emitted when the excitons are deactivated. It is an element to do. Since organic EL elements can emit light at a voltage of several volts to several tens of volts, they attract attention as next-generation flat displays and illumination.

Since an organic EL device using phosphorescence emission from an excited triplet with an upper limit of internal quantum efficiency of 100% has been reported by Princeton University (for example, see Non-Patent Document 1), Research has become active (see, for example, Non-Patent Document 2 and Patent Document 1).
Further, iridium complex-based heavy metal complexes have been studied as materials exhibiting phosphorescence at room temperature (see, for example, Non-Patent Document 3). For example, a tris (2-phenylpyridine) iridium complex is widely known (see, for example, Non-Patent Document 2). Further, for the purpose of improving the durability and luminous efficiency of the dopant, an iridium complex having a ligand in which a silyl group is introduced into a tris (2-phenylpyridine) skeleton is disclosed (for example, see Patent Document 2).

In addition to tris (2-phenylpyridine) iridium complexes, iridium complexes having a phenylimidazole ligand or a carbene ligand are disclosed (for example, see Patent Documents 3 and 4).
On the other hand, a complex in which a ligand of an iridium complex is bound (see Patent Documents 5 to 7) and a complex using a deuterium-substituted ligand are disclosed (see Patent Document 8 and Non-Patent Document 4).

US Pat. No. 6,097,147 JP 2005-327526 A International Publication No. 2006/046980 International Publication No. 2005/019373 International Publication No. 2005/76380 International Publication No. 2004/81017 EP1603923B JP 2008-270737 A

M.M. A. Baldo et al. , Nature, 395, 151-154 (1998) M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) C. Adachi et al. , Appl. Phys. Lett. 79, 2082-2084 (2001) Yuji Kawanishi, Satoshi Miyazawa, Taichi Abe, Wako Organic Square, No. 36, 2, (2011).

However, in the iridium complexes described in Patent Document 2 and Non-Patent Documents 2 and 3, even in an organic EL device using these dopants, sufficient device performance including a light emission lifetime is not obtained.
In addition, in the iridium complexes described in Patent Documents 3 and 4, these materials have a shallower HOMO, a larger hole-injection barrier, and a shorter wavelength compared to complexes composed of phenylpyridine ligands. When a bulky substituent or the like is introduced for this purpose, the reorientation energy increases as a molecule. Therefore, there has been a problem that the charge transport capability is lowered, and as a result, the drive voltage is increased.
Furthermore, in the complexes described in Patent Documents 5 to 8 and Non-Patent Document 4, the thermal stability of the material itself is improved and the lifetime of the element is also improved, but there is room for improvement in practical use.
As described above, the conventional organic EL elements have not sufficiently satisfied these performances with respect to the light emission efficiency, the light emission lifetime, the low drive voltage, and the like.

  An object of the present invention is to provide an organic electroluminescence element that exhibits high light emission efficiency, has a long light emission lifetime, and has a low driving voltage, an illumination device including the element, and a display device.

The above object of the present invention has been achieved by the following constitution.
1. In the organic electroluminescence device having at least one light emitting layer between the anode and the cathode, the organic electroluminescence device contains a hexadentate ortho metal iridium complex represented by the following general formula (1): An organic electroluminescence device wherein at least one hydrogen atom in the complex molecule is substituted with deuterium.

〔式中、Ｖは２価又は３価の連結基を表し、Ｌ_１、Ｌ_２と共有結合で連結している。ＶとＬ_３を結ぶ点線は共有結合、又は非結合を表わす。一般式（１）中の少なくとも一つの水素原子は、重水素で置換されているものとする。Ｌ_１〜Ｌ_３は、下記一般式（１-Ａ）で表され、Ｘ₆とＩｒが配位結合し、Ｘ₈とＩｒが共有結合を形成している。〕

[Wherein, V represents a divalent or trivalent linking group and is linked to L ₁ and L _{2 through a} covalent bond. A dotted line connecting V and L ₃ represents a covalent bond or a non-bond. It is assumed that at least one hydrogen atom in the general formula (1) is substituted with deuterium. L _{1 to} L ₃ are represented by the following general formula (1-A), wherein X ₆ and Ir are coordinated and X ₈ and Ir form a covalent bond. ]

〔式中、Ｘ_１〜Ｘ₆は含窒素５員又は含窒素六員の複素環を形成する元素群であり、炭素原子又は窒素原子から選ばれ、Ｘ₅とＸ₆のうち少なくとも一つは窒素原子を表す。Ｘ₃、Ｘ₁₁はそれぞれ炭素原子を表わし、n1、n2は０または１の整数を表わす。Ｘ_７〜Ｘ_１２は５員環又は６員環を形成する元素群であり、炭素原子又は窒素原子から選ばれる。Ｘ_２〜Ｘ_５、Ｘ_９〜Ｘ_１２の少なくとも一つは重水素で置換されているものとする。〕

[Wherein, X _{1 to} X ₆ are an element group forming a nitrogen-containing 5-membered or _6- membered nitrogen-containing heterocyclic ring, selected from a carbon atom or a nitrogen atom, and at least one of X ₅ and X ₆ is Represents a nitrogen atom. X ₃ and X ₁₁ each represent a carbon atom, and n 1 and n 2 each represents an integer of 0 or 1. X < ₇ > -X < ₁₂ > is an element group which forms a 5-membered ring or a 6-membered ring, and is selected from a carbon atom or a nitrogen atom. It is assumed that at least one of X _{2 to} X ₅ and X _{9 to} X ₁₂ is substituted with deuterium. ]

2. _2. The organic electroluminescence device according to 1 above, wherein in the general formula (1), a site where a hydrogen atom in the complex molecule is substituted with deuterium is L ₁ , L ₂ , or L ₃ .

3. 3. The organic electroluminescence device as described in 1 or 2 above, wherein in the general formula (1), a site where a hydrogen atom in the complex molecule is substituted with deuterium is V.

4). 2. The organic electroluminescence device according to 1 above, wherein in the general formula (1), all hydrogen atoms in the complex molecule are substituted with deuterium.

5. In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is an aromatic hetero 6-membered ring, and the aromatic 6. The organic electroluminescence device according to any one of 1 to 4, wherein the group 6-membered ring is a pyridine ring.

6). In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is a hetero 5-membered ring, and the complex 5-membered 5. The organic electroluminescence device according to any one of 1 to 4, wherein the ring is an imidazole ring.

7). In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is a hetero 5-membered ring, and the complex 5-membered 5. The organic electroluminescence device according to any one of 1 to 4, wherein the ring is a pyrazole ring.

8). In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is a hetero 5-membered ring, and the complex 5-membered 5. The organic electroluminescence device according to any one of 1 to 4, wherein the ring is a triazole ring.

9. 5. The organic electroluminescent element according to any one of 1 to 4, wherein the general formula (1-A) is represented by the following general formula (1-B).

〔式中、Ｘ_７〜Ｘ_１２で表される元素群、n2は、前記一般式（１−Ａ）と同義である。Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は各々水素原子、重水素原子又は置換基を表す。〕

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, a deuterium atom or a substituent. ]

10. 5. The organic electroluminescence device according to any one of 1 to 4, wherein the general formula (1-A) is represented by the following general formula (1-C).

〔式中、Ｘ_７〜Ｘ_１２で表される元素群、n2は、前記一般式（１−Ａ）と同義である。Ｒ_５、Ｒ_６、Ｒ_７は各々水素原子、重水素原子又は置換基を表す。〕

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₅ , R ₆ and R ₇ each represent a hydrogen atom, a deuterium atom or a substituent. ]

11. 5. The organic electroluminescence device according to any one of 1 to 4, wherein the general formula (1-A) is represented by the following general formula (1-D).

〔式中、Ｘ_７〜Ｘ_１２で表される元素群、n2は、前記一般式（１−Ａ）と同義である。Ｒ_８、Ｒ_９、Ｒ_１０は各々水素原子、重水素原子又は置換基を表す。〕

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom, a deuterium atom or a substituent. ]

12 5. The organic electroluminescent element according to any one of 1 to 4, wherein the general formula (1-A) is represented by the following general formula (1-E).

〔式中、Ｘ_７〜Ｘ_１２で表される元素群、n2は、前記一般式（１−Ａ）と同義である。Ｒ_１１、Ｒ_１２、Ｒ_１３は各々水素原子、重水素原子又は置換基を表す。〕

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, a deuterium atom or a substituent. ]

13. 5. The organic electroluminescent element according to any one of 1 to 4, wherein the general formula (1-A) is represented by the following general formula (1-F).

〔式中、Ｘ_７〜Ｘ_１２で表される元素群、n2は、前記一般式（１−Ａ）と同義である。Ｒ_１４、Ｒ_１５は各々水素原子、重水素原子又は置換基を表す。〕

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁₄ and R ₁₅ each represent a hydrogen atom, a deuterium atom or a substituent. ]

14 5. The organic electroluminescence element according to any one of 1 to 4, wherein the general formula (1-A) is represented by the following general formula (1-G).

〔式中、Ｘ_７〜Ｘ_１２で表される元素群、n2は、前記一般式（１−Ａ）と同義である。Ｒ_１６、Ｒ_１７は各々水素原子、重水素原子又は置換基を表す。〕

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁₆ and R ₁₇ each represent a hydrogen atom, a deuterium atom or a substituent. ]

15. 15. The organic electroluminescence device according to 1 to 14, wherein the element group represented by X _{7 to} X ₁₂ is a benzene ring.

16. 16. The organic electroluminescence device as described in any one of 1 to 15 above, wherein the general formula (1) is a hexadentate ortho metal iridium complex represented by the following general formula (2): .

〔式中、Ｖは３価の連結基を表し、Ｌ_１〜Ｌ_３と共有結合で連結している。Ｌ_１〜Ｌ_３は、各々前記１における一般式（１-Ａ）で表され、Ｘ₆とＩｒが配位結合し、Ｘ₈とＩｒが共有結合を形成している。〕

[Wherein, V represents a trivalent linking group and is linked to L _{1 to} L _{3 through a} covalent bond. L _{1 to} L ₃ are each represented by the general formula (1-A) in 1 above, wherein X ₆ and Ir are coordinated and X ₈ and Ir form a covalent bond. ]

１８．前記一般式（１）において、６座配位型オルトメタルイリジウム錯体の重水素置換純度が８０％以上であることを特徴とする前記１から前記１７のいずれか１項に記載の有機エレクトロルミネッセンス素子。 17. 17. The organic electroluminescence device according to any one of 1 to 16, wherein V is any one of compounds having the structures shown below.
[In the compounds of the following structure, * represents the union of _L 1 ~L _3, n represents 1-2. ]

18 . 18. The organic electroluminescence device as described in any one of 1 to 17 above, wherein in the general formula (1), the deuterium substitution purity of the hexadentate ortho metal iridium complex is 80% or more. .

19 . 18. The organic electroluminescence device as described in any one of 1 to 17 above, wherein in the general formula (1), the deuterium substitution purity of the hexadentate ortho metal iridium complex is 90% or more. .

20 . 18. The organic electroluminescence device as described in any one of 1 to 17 above, wherein, in the general formula (1), the deuterium substitution purity of the hexadentate ortho metal iridium complex is 99% or more. .

21 . 21. The organic electroluminescence device according to any one of 1 to 20 , wherein the hexadentate ortho metal iridium complex is contained in at least one layer of the light emitting layer.

22 . 22. The organic electroluminescence device according to any one of 1 to 21 , wherein a host compound is contained in at least one layer of the light emitting layer.

23 . 23. The organic electroluminescence device as described in 22 above, wherein at least one hydrogen atom of the host compound is substituted with a deuterium atom.

24 . 23. The organic electroluminescence device as described in 22 above, wherein all hydrogen atoms of the host compound are substituted with deuterium atoms.

25 . 25. The organic electroluminescence device according to any one of 1 to 24 , which emits white light.

26 . 26. A display device comprising the organic electroluminescence element according to any one of 1 to 25 above.

27 . 26. An illumination device comprising the organic electroluminescence element according to any one of 1 to 25 above.

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element which shows high luminous efficiency, has a long light emission lifetime, and is a low drive voltage, the illuminating device provided with this element, and a display apparatus can be provided.

It is a schematic diagram which shows an example of the display apparatus comprised from an organic EL element. It is a schematic diagram which shows the display part of the display apparatus in FIG. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is a schematic diagram of an illuminating device.

Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not limited to these.
≪Organic EL element (Organic electroluminescence element) ≫
Hereinafter, the detail of each component of the organic electroluminescent element of this invention is demonstrated sequentially.
The organic EL device of the present invention is an organic electroluminescence device having at least one light emitting layer between an anode and a cathode. And this organic electroluminescent element contains the hexadentate ortho metal iridium complex represented by the following general formula (1), and at least one hydrogen atom in the complex molecule is substituted with deuterium. Is.

[Wherein, V represents a divalent or trivalent linking group and is linked to L ₁ and L _{2 through a} covalent bond. A dotted line connecting V and L ₃ represents a covalent bond or a non-bond. It is assumed that at least one hydrogen atom in the general formula (1) is substituted with deuterium. L _{1 to} L ₃ are represented by the following general formula (1-A), wherein X ₆ and Ir are coordinated and X ₈ and Ir form a covalent bond. ]

[Wherein, X _{1 to} X ₆ are an element group forming a nitrogen-containing 5-membered or _6- membered nitrogen-containing heterocyclic ring, selected from a carbon atom or a nitrogen atom, and at least one of X ₅ and X ₆ is Represents a nitrogen atom. X ₃ and X ₁₁ each represent a carbon atom, and n 1 and n 2 each represents an integer of 0 or 1. X < ₇ > -X < ₁₂ > is an element group which forms a 5-membered ring or a 6-membered ring, and is selected from a carbon atom or a nitrogen atom. It is assumed that at least one of X _{2 to} X ₅ and X _{9 to} X ₁₂ is substituted with deuterium. ]

  First, the background and characteristics of inventing the organic EL element will be described, and then the organic EL element of the present invention will be described in detail.

  An ortho metal iridium complex having a 5-membered ring as a component of the ligand is interesting because it can emit light at a shorter wavelength than a phenylpyridine-based ortho metal iridium complex composed of only a 6-membered ring. However, the device life and high light emission efficiency that can still be put into practical use have not been obtained. The present inventors have found that the ortho metal iridium complex of a ligand having a 5-membered ring has a shallow HOMO as compared with a phenyl pyridine type ortho metal iridium complex, poor hole injection, and increased driving voltage. Focused on being. In addition, it is presumed that conventionally known ortho metal iridium complexes are prone to aggregation of metal complexes in the constituent layers of the organic EL device, and that the device life and high luminous efficiency that can be put to practical use are not obtained. did. And we studied earnestly about the problems.

As a result, in the ortho metal iridium complex having a 5-membered ring as a component of the ligand, the device lifetime is improved by using the compound represented by the general formula (1) or the general formula (2) described later. In addition, the present inventors have found that the drive voltage can be lowered. In the general formula (1), the ligands L ₁ and L ₂ are connected by V, and the general formula (2) is a hexadentate structure in which the ligands L ₁ , L ₂ and L ₃ are connected by V. It is characterized by being a coordinate type ortho metal iridium complex, and at least one hydrogen atom in the complex molecule is substituted with deuterium.

By introducing V into the constituent element of the ligand, aggregation of metal complexes in the constituent layer of the organic EL element can be suppressed, and TT annihilation occurring between excitonic triplets of the metal complex can be suppressed. In addition to this, it was presumed that the lifetime of the device was improved as a result of suppression of bond dissociation with carbon atoms in the light emission process by replacing hydrogen atoms with deuterium and increasing CD bonds.
In addition, it seems that the reorientation energy is increased by the introduction of these substituents, but it was found that by combining each of the three ligands, the driving voltage of the device is lowered, and the luminance and lifetime are improved. .

《Orthometal Iridium Complex》
The ortho metal iridium complex used in the present invention will be described.
The ortho metal iridium complex can be used in any one of the constituent layers of the organic EL device of the present invention, but the effect of the present invention (light emission efficiency of the device (specifically, external extraction quantum efficiency, also simply referred to as efficiency)). From the standpoint of obtaining sufficient improvement in half life, increase in half-life, and decrease in driving voltage, it is preferably used as a light-emitting dopant (also simply referred to as a dopant) in the light-emitting layer of the device and further in the light-emitting layer.
The constituent layers of the organic EL element of the present invention will be described in detail later.

The ortho metal iridium complex is specifically represented by the general formula (1).
Here, in the general formula (1), V represents a divalent or trivalent linking group and represents a multidentate ligand of Ir covalently bonded to each of L _{1 to} L _3. (* Represents a bonding portion with L _{1 to} L _3, and n represents 1 to 2).

L _{1 to} L ₃ are each represented by the general formula (1-A), and X ₆ and Ir form a coordinate bond, and X ₈ and Ir form a covalent bond.
In the general formula (1-A), X _{1 to} X ₆ are an element group forming a nitrogen-containing 5-membered or _6- membered nitrogen-containing heterocyclic ring, selected from a carbon atom or a nitrogen atom, and X ₅ and X _6. At least one of them represents a nitrogen atom. However, if the X ₁ to X ₆ form a heterocyclic ring of 5-membered nitrogen-containing X ₃ represents a single bond.
Here, in at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is an aromatic hetero 6-membered ring A pyridine ring is preferred. Further, in at least one of L _{1 to} L ₃ , when the ring formed by X _{1 to} X ₆ of the general formula (1-A) is a hetero 5-membered ring, an imidazole ring, a pyrazole ring, or a triazole ring (Including deuterated ones) is preferable.

More specifically, at least one of X ₅ and X ₆ represents a nitrogen atom, and preferably represents an isoquinoline, pyridine, imidazole, pyrazole, or triazole ring (including deuterated ring). More preferably, it represents a pyridine ring or an imidazole ring. However, if the X ₁ to X ₆ form a heterocyclic ring of 5-membered nitrogen-containing X ₃ represents a single bond.

X < ₇ > -X < ₁₂ > is an element group which forms a 5-membered ring or a 6-membered ring, and is an atomic group which is chosen from a carbon atom or a nitrogen atom and forms a 5-membered ring or a 6-membered ring. Preferred examples of the 5-membered ring include a thiophene ring, an imidazole ring, a pyrazole ring, and a triazole ring (including deuterated ring), and examples of the 6-membered ring include a benzene ring and a pyridine ring, preferably benzene. Represents a ring. _However, if X 7 _{to X 12} form an aromatic 5-membered ring _{X 11} represents a single bond.
At least one of X _{2 to} X ₅ and X _{9 to} X ₁₂ is substituted with deuterium.

In the present invention, in the general formula (1), examples of the site where the hydrogen atom in the complex molecule is substituted with deuterium include L ₁ , L ₂ , and L ₃ . Or V is mentioned as a site | part substituted by deuterium. Further, all hydrogen atoms in the complex molecule may be substituted with deuterium.
The effect of the present invention is that a deuterium atom having a mass twice that of a hydrogen atom is replaced, whereby CH stretching in the molecule is converted to CD stretching, and the dissociation can be suppressed. It is presumed that the effect of improving the element lifetime was obtained.

The nitrogen-containing 5-membered or 6-membered heterocyclic ring represented by X _{1 to} X ₆ and the 5-membered or 6-membered ring represented by X _{7 to} X ₁₂ may further have a substituent. These substituents may be bonded to form a condensed ring.
Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, etc.), an alkynyl group (eg, ethynyl group, propargyl group, etc.), an aromatic hydrocarbon group (aromatic hydrocarbon). Also referred to as cyclic group, aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl Group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic compound A cyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2 , 3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, A dibenzothienyl group, an indolyl group, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), a quinoxalinyl group, a pyridazinyl group, Triazinyl group, quinazolinyl group, Razinyl group, etc.), heterocyclic groups (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group) Group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, Propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxy Sicarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.) ), Sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group) Naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, Nylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group) Butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonyl) Amino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenyl Carbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group) Octylureido group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, Tylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl Group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group) Etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, diphenylamino group, butylamino group, cyclopentylamino group, -Ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group) , Trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, tripyridyl group) Silyl group, phenyldiethylsilyl group, etc.), phosphono group and the like. Preferably, an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and an alkoxy group are mentioned. In addition, these substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring. These substituents include those that are deuterated.

  The general formula (1-A) is preferably the following general formula (1-B), (1-C), (1-D), (1-E), (1-F), (1-G) ).

In the general formula (1-B), the element group represented by X _{7 to} X ₁₂ and n 2 are the same as those in the general formula (1-A) described above. R _{1 to} R ₄ each represent a hydrogen atom, a deuterium atom, or a substituent, and the substituent may have an element group represented by X _{7 to} X ₁₂ in the general formula (1-A). The thing similar to a good substituent is mentioned.
The general formula (1-B) is preferably represented by the following general formula (1-BA).

In the general formula (1-BA), R _{1 to} R ₄ have the same meanings as those in the general formula (1-B). Rd represents a hydrogen atom, a deuterium atom or a substituent, and the substituent is the same as the substituent which the element group represented by X _{7 to} X ₁₂ in the general formula (1-A) may have. Can be mentioned. nd represents an integer of 0 to 4.

In General Formula (1-C), the element group represented by X _{7 to} X ₁₂ has the same meaning as that of General Formula (1-A) described above. R _{5 to} R ₇ each represent a hydrogen atom, a deuterium atom, or a substituent, and the substituent may include the element group represented by X _{7 to} X ₁₂ in the general formula (1-A). The thing similar to a good substituent is mentioned.
The general formula (1-C) is preferably represented by the following general formula (1-CA).

In the general formula (1-CA), Ra, Rb and Rc each represents a substituent, and the substituent which the element group represented by X _{7 to} X ₁₂ in the general formula (1-A) may have. The same thing is mentioned. Ra and Rb are preferably alkyl groups (methyl group, ethyl group, isopropyl group, etc.), cycloalkyl groups (cyclohexyl group, etc.) and aryl groups (phenyl group, etc.). These substituents include those that are deuterated. Rd and nd have the same meaning as that of the general formula (1-BA). nc represents an integer of 0 to 3.
The general formula (1-CA) is preferably represented by the following general formula (1-CB).

  In the general formula (1-CB), Ra and Rb have the same meanings as those in the general formula (1-CA). Rd and nd have the same meaning as that of the general formula (1-BA). Ar represents a substituted or unsubstituted aryl group, and examples of the aryl group include a phenyl group, a mesityl group, a xylyl group, a naphthyl group, a biphenyl group, and a terphenyl group, and a phenyl group is preferable. Examples of the substituent substituted on the phenyl group include an alkyl group (methyl group, ethyl group, trifluoromethyl group, isopropyl group, etc.), an alkoxy group (methoxy group, ethoxy group, etc.), a halogen atom (fluorine atom, etc.), and a cyano group. , Nitro group, dialkylamino group (such as dimethylamino group), trialkylsilyl group (such as trimethylsilyl), triarylsilyl group (such as triphenylsilyl group), triheteroarylsilyl group (such as tripyridylsilyl group), benzyl group An aryl group (such as a phenyl group) and a heteroaryl group (such as a pyridyl group and a carbazolyl group), and an alkyl group and an aryl group are preferable. These substituents include those that are deuterated.

In General Formula (1-D), the element group represented by X _{7 to} X ₁₂ has the same meaning as that of General Formula (1-A) described above. R _{8 to} R ₁₀ each represent a hydrogen atom, a deuterium atom, or a substituent, and the substituent may include the element group represented by X _{7 to} X ₁₂ in the general formula (1-A). The thing similar to a good substituent is mentioned.
The general formula (1-D) is preferably represented by the following general formula (1-DA).

In general formula (1-DA), R < ₈ > -R < ₁₀ > is synonymous with that of general formula (1-D). Rd and nd are synonymous with those of the general formula (1-BA).

In General Formula (1-E), the element group represented by X _{7 to} X ₁₂ has the same meaning as that of General Formula (1-A) described above. R _{11 to} R ₁₃ each represent a hydrogen atom, a deuterium atom, or a substituent, and the substituent may have an element group represented by X _{7 to} X ₁₂ in the general formula (1-A). The thing similar to a good substituent is mentioned.
The general formula (1-E) is preferably represented by the following general formula (1-EA).

In the general formula (1-EA), R _{11 to} R ₁₃ have the same meanings as those in the general formula (1-E). Rd and nd are synonymous with those of the general formula (1-BA).

In General Formula (1-F), the element group represented by X _{7 to} X ₁₂ has the same meaning as that of General Formula (1-A) described above. R ₁₄ and R ₁₅ each represent a hydrogen atom, a deuterium atom or a substituent, and the substituent may be an atom group represented by X _{7 to} X ₁₂ in the general formula (1-A). The thing similar to a good substituent is mentioned.
The general formula (1-F) is preferably represented by the following general formula (1-FA).

In the general formula (1-FA), R _{14 and} R ₁₅ have the same meanings as those in the general formula (1-F). Rd and nd are synonymous with the general formula (1-BA).

In General Formula (1-G), the element group represented by X _{7 to} X ₁₂ has the same meaning as that of General Formula (1-A) described above. R ₁₆ and R ₁₇ each represent a hydrogen atom, a deuterium atom, or a substituent, and the substituent may have an atomic group represented by X _{7 to} X ₁₂ in the general formula (1-A). The thing similar to a good substituent is mentioned.
The general formula (1-G) is preferably represented by the following general formula (1-GA).

In the general formula (1-GA), R ₁₆ and R ₁₇ have the same meanings as those in the general formula (1-G). Rd and nd are synonymous with the general formula (1-BA).

  The general formula (1) is preferably the general formula (2).

In the general formula (2), V represents a trivalent linking group and is covalently bonded to each of L _{1 to} L ₃ to represent a multidentate ligand of Ir, but L _{1 to} L in the general formula (1) Synonymous with ₃ . In the general formula (1-A), X ₆ and Ir are coordinated, and X ₈ and Ir form a covalent bond.

Hereinafter, although the specific example of the ortho metal iridium complex represented by either of the said general formula of this invention is shown below, this invention is not limited to these. Note that "number" in the table shows the number of _compounds, L _1, L _{2, L} 3, V are respectively the general formula _{(1), L 1, L} 2, L 3, the compound of V (2) Corresponding to

These metal complexes can be synthesized with reference to, for example, US Patent Application Publication No. 2010/176390, International Publication No. 2007/97149, and the like. Furthermore, it can synthesize | combine by applying methods, such as a reference document described in these literature.
Next, a synthesis example of the ortho metal iridium complex represented by the general formula (1) will be described.

The synthesis example of a typical compound is shown below.
[Synthesis of Compound Example 1C-27]
As shown below, ligand A1 was synthesized, and then Compound Example 1C-27 was synthesized.

<< Synthesis of Ligand A1 >>
(Process 1)
20 g of Compound (I-1) was dissolved in 300 ml of toluene, 25 ml of triethylamine was added, and a solution of 18 g of p-bromobenzoic acid chloride dissolved in 20 ml of toluene was added dropwise under water cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 1.5 hours, and insoluble matters were collected by filtration. The white crystals taken after that were placed in 1 L of water and suspended for 1 hour, and the water was filtered off to obtain 30 g of compound (I-2) as white crystals.

(Process 2)
15 g of the compound (I-2) obtained in Step 1 was dissolved in 200 ml of toluene, 6 ml of phosphoryl chloride was added, and the mixture was stirred at an internal temperature of 90 ° C. for 2 hours and then allowed to cool. Next, 15 g of aminoacetaldehyde diethyl acetal was dissolved in 100 ml of acetonitrile to prepare a solution to which 45 ml of triethylamine was added, and the previously cooled solution was added dropwise at an internal temperature of 50 ° C. or lower. Then, 200 ml of ethyl acetate and 50 ml of saturated brine were added. After separation, the organic layer was dried over magnesium sulfate, removed, and the solvent was concentrated to obtain intermediate amidine and compound (I-3) as crude crystals. It was.

(Process 3)
The total amount of compound (I-3) obtained in step 2 was dissolved in 150 ml of toluene, 25 g of phosphoric acid and 60 ml of water were added, and the mixture was refluxed for 2 hours with an ester tube attached. Next, a solution prepared by dissolving 36 g of potassium hydroxide in 57 ml of water was added dropwise over 30 minutes under ice-cooling, 200 ml of ethyl acetate and 50 ml of saturated brine were added, and the mixture was separated through diatomaceous earth, and the organic layer was separated into sulfuric acid. 7 g of compound (I-4) was obtained as a white solid by recrystallizing what was dried with magnesium, removed, and concentrated the solvent and then heptane-ethyl acetate.

(Process 4)
Under a nitrogen atmosphere, 5 g of the compound (I-4) obtained in Step 3 was dissolved in dehydrated toluene, dehydrated diisopropylamine and 1,3,5-triethynylbenzene were added, and tetrakistriphenylphosphine palladium ( 0) and copper (I) iodide were added, and the mixture was stirred at an internal temperature of 60 ° C. for 2 days. Thereafter, 50 ml of ethyl acetate and 50 ml of saturated brine were added, and the mixture was separated. The organic layer was dried over magnesium sulfate, and after removal, the solvent was concentrated and purified by silica gel column chromatography to obtain 2.2 g of compound (I-5 )

(Process 5)
500 mg of the compound (I-5) obtained in Step 4 was dissolved in 50 ml of tetrahydrofuran and 20 ml of ethanol, 0.25 g of palladium-carbon (5%) was added, and hydrogenation was performed to obtain 500 mg of ligand A1.
The structure of the ligand A1 was confirmed by mass spectrum and ¹ H-NMR.

<< Synthesis of Compound Example 1C-27 >>
(Step 6)
Under a nitrogen atmosphere, 180 mg of tris (acetylacetonato) iridium (III), 35 ml of ethylene glycol and 10 ml of glycerin were added to 500 mg of the ligand A1 obtained in Step 5, and the mixture was heated at an internal temperature of 160 ° C. for 15 hours. After returning to room temperature, it was diluted with 50 ml of methanol and the precipitate was collected by filtration. Further, the obtained precipitate was washed with methanol and dried to obtain 80 mg of Compound Example 1C-27.
The structure of Compound Example 1C-27 was confirmed by mass spectrum and ¹ H-NMR.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.
(I) Anode / light emitting layer unit / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer unit / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer unit / hole blocking Layer / electron transport layer / cathode (iv) anode / hole transport layer / light emitting layer unit / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) anode / anode buffer layer / hole transport layer / light emission Layer unit / hole blocking layer / electron transport layer / cathode buffer layer / cathode

Furthermore, the light emitting layer unit may have a non-light emitting intermediate layer between a plurality of light emitting layers, and may have a multi-photon unit configuration in which the intermediate layer is a charge generation layer. In this case, the charge generation layer includes ITO (indium tin oxide), IZO (indium zinc oxide), ZnO ₂ , TiN, ZrN, HfN, TiO _x , VO _x , CuI, InN, GaN, CuAlO _2. , CuGaO ₂ , SrCu ₂ O ₂ , LaB ₆ , RuO ₂ and other conductive inorganic compound layers, Au / Bi ₂ O _{3 and} other two-layer films, SnO ₂ / Ag / SnO ₂ , ZnO / Ag / ZnO, Bi ₂ O ₃ / Au / Bi ₂ O ₃ , TiO ₂ / TiN / TiO ₂ , TiO ₂ / ZrN / TiO _{2 and} other multilayer films, C60 and other fullerenes, conductive organic layers such as oligothiophene, metal phthalocyanine , Conductive organic compound layers such as metal-free phthalocyanines, metal porphyrins, metal-free porphyrins, and the like. The light emitting layer in the organic EL device of the present invention is preferably a white light emitting layer, and an illumination device using these is preferable. If it is a white light emitting layer, the organic EL element emits white light.
In addition to the hole blocking layer, an electron blocking layer can be used as the blocking layer.

Each layer which comprises the organic EL element of this invention is demonstrated.
<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 nm to 200 nm, and particularly preferably in the range of 5 nm to 100 nm.

  For the production of the light emitting layer, a light emitting dopant or host compound described later is used, for example, a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, Examples thereof include an inkjet method, a printing method, a spray coating method, a curtain coating method, and an LB method (Langmuir Brodgett method). (When the compound of the present invention is used for a light emitting layer, it is preferably produced by a wet process).

In the light emitting layer of the organic EL device of the present invention, a light emitting dopant (phosphorescent dopant (also referred to as phosphorescent dopant or phosphorescent dopant group) or fluorescent dopant) compound and a host compound (also referred to as light emitting host compound) are used. ).
(Luminescent dopant compound)
A light-emitting dopant compound (a light-emitting dopant, also simply referred to as a dopant) will be described.
As the light-emitting dopant, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used.

(Phosphorescent dopant (also called phosphorescent dopant))
The phosphorescent dopant according to the present invention will be described.
The phosphorescent dopant compound according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.

The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
There are two types of light emission of the phosphorescent dopant in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the luminescent host compound, and this energy is used as the phosphorescent dopant. It is an energy transfer type in which light emission from a phosphorescent dopant is obtained by moving to. The other is a carrier trap type in which a phosphorescent dopant serves as a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant compound is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

In the organic EL device of the present invention, at least one of the light-emitting layers contains a phosphorescent organometallic complex (also referred to as a phosphorescent dopant or a phosphorescent dopant). Preferably contains a hexadentate ortho metal iridium complex represented by the general formula (1) or (2), which is a material of the organic EL device of the present invention.
Moreover, you may use together the conventionally well-known compound etc. which are described in the following patent gazettes in the light emitting layer which concerns on this invention.

  For example, WO 00/70655 pamphlet, JP 2002-280178 A, JP 2001-181616 A, JP 2002-280179 A, JP 2001-181617 A, JP 2002-280180 A. JP, 2001-247859, JP, 2002-299060, JP, 2001-313178, JP, 2002-302671, JP, 2001-345183, JP, 2002-324679, International, Publication No. 02/15645, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-117978, JP 2002-338588, JP 2002-170684, JP 2002-352960, WO 01/93642, JP 2002-50483, JP 2002-1000047, JP JP 2002-173684 A, JP 2002-359082 A, JP 2002-17584 A, JP 2002-363552 A, JP 2002-184582 A, JP 2003-7469 A, Special Table 2002. No. 525808, JP 2003-7471, JP 2002-525833, JP 2003-31366, JP 2002-226495, JP 2002-234894, JP 2002-233506 Japanese Patent Laid-Open No. 2002-24175 JP, JP 2001-319779, JP 2001-319780, JP 2002-62824, JP 2002-1000047, JP 2002-203679, 2002-343572. JP-A-2002-203678.

(Fluorescent dopant (also called fluorescent compound))
As fluorescent dopants, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, rare earth complex phosphors, and the like, and compounds having a high fluorescence quantum yield such as laser dyes.
The light emitting dopant may be used in combination of a plurality of types of compounds, or may be a combination of phosphorescent dopants having different structures or a combination of a phosphorescent dopant and a fluorescent dopant.
Here, although the specific example of the conventionally well-known light emission dopant which may be used in combination with the metal complex represented by General formula (1) used for this invention as a light emission dopant is given, this invention is not limited to these.

(Luminescent host compound (also referred to as luminescent host))
In the present invention, the host compound has a mass ratio of 20% or more among the compounds contained in the light emitting layer, and a phosphorescence quantum yield of phosphorescence emission is 0 at room temperature (25 ° C.). Defined as less than 1 compound. The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
The light emitting host compound is preferably contained in at least one layer of the light emitting layer. Furthermore, it is preferable that at least one hydrogen atom of the luminescent host compound is substituted with a deuterium atom, and it is more preferable that all the hydrogen atoms are substituted with a deuterium atom.

There is no restriction | limiting in particular as a light emission host which can be used for this invention, The compound conventionally used with an organic EL element can be used. Typically, a carbazole derivative, a triarylamine derivative, an aromatic derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, an oligoarylene compound or the like having a basic skeleton, or a carboline derivative or a diazacarbazole derivative (here And the diazacarbazole derivative represents one in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom.
As the known light-emitting host that can be used in the present invention, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature) is preferable.

In the present invention, conventionally known light-emitting hosts may be used alone or in combination of two or more.
By using a plurality of types of light-emitting hosts, the movement of charges can be adjusted, and the organic EL element can be made highly efficient.
Moreover, it becomes possible to mix different light emission by using multiple types of the metal complex of this invention used as said phosphorescence dopant, and / or a conventionally well-known compound, and, thereby, arbitrary luminescent colors can be obtained.

In addition, the light emitting host used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (polymerizable light emitting host). Of course, one or more of such compounds may be used.
Specific examples of the known light-emitting host include compounds described in the following documents.
JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Hereinafter, although the specific example used as a light emission host of the light emitting layer of the organic EL element of this invention is given, this invention is not limited to these.

  Furthermore, a compound represented by the following general formula (B) is particularly preferable as a light emitting host of the light emitting layer of the organic EL device of the present invention.

[Wherein, Xa represents O or S, and Xb, Xc, and Xd each represents a hydrogen atom, a substituent, or a group represented by the following general formula (C), and at least one of Xb, Xc, and Xd Represents the following general formula (C), and in at least one of the groups represented by the general formula (C), Ar represents a carbazolyl group. ]

General formula (C)
Ar- _{(L 4)} n - *
[Wherein L ₄ represents a divalent linking group derived from an aromatic hydrocarbon ring or an aromatic heterocyclic ring. n represents 0 or an integer of 1 to 3, and when n is 2 or more, the plurality of L ₄ may be the same or different. * Represents a linking site with the general formula (B). Ar represents a group represented by the following general formula (D). ]

[Wherein, Xf represents N (R ″), O or S, E _{1 to} E ₈ represent C (R ″ ₁ ) or N, and R ″ and R ″ ₁ represent a hydrogen atom, a substituent or L _4. Represents the linking site. * Represents a linking site of the _{L 4.} ]

In the compound represented by the general formula (B), preferably at least two of Xb, Xc and Xd are represented by the general formula (C), and more preferably Xb is represented by the general formula (C). And Ar in the general formula (C) represents a carbazolyl group which may have a substituent, more preferably Xb is represented in the general formula (C) and Ar in the general formula (C) is It represents a carbazolyl group linked to L ₄ at the N-position which may have a substituent.
Xc is preferably represented by the general formula (C), and Xd is preferably a hydrogen atom.

  Specific examples of the compound represented by the general formula (B) preferably used as a host compound (also referred to as a light emitting host) of the light emitting layer of the organic EL device of the present invention are shown below, but the present invention is not limited thereto.

  In addition, a compound represented by the following general formula (B ′) is also particularly preferably used as a light-emitting host of the light-emitting layer of the organic EL device of the present invention.

  In the formula, Xa represents O or S, Xb and Xc each represent a substituent or a group represented by the following general formula (C), and at least one of Xb or Xc represents the following general formula (C) And at least one of the groups represented by formula (C) represents Ar as a carbazolyl group.

General formula (C)
Ar- _{(L 2)} n - *
In the formula, L ₂ represents a divalent linking group derived from an aromatic hydrocarbon ring or an aromatic heterocyclic ring. n represents 0 or an integer of 1 to 3, and when n is 2 or more, the plurality of L ₂ may be the same or different. * Represents a linking site with the general formula (B). Ar represents a group represented by the following general formula (D). ]

In the formula, Xe represents N (R ″), O or S, E1 to E8 represent C (R ″ 1) or N, and R ″ and R ″ 1 are linked to a hydrogen atom, a substituent or L _2. Represents a site. * Represents a linking site of the _{L 2.}

In the compound represented by the general formula (B ′), preferably at least one of Xb and Xc is represented by the general formula (C), and more preferably, Ar in the general formula (C) is a substituent. Represents a carbazolyl group that may have a carbazolyl group, and more preferably, Ar in the general formula (C) represents a carbazolyl group linked to L ₂ at the N-position that may have a substituent.
The compound represented by the general formula (B ′) that is preferably used as the host compound (also referred to as a light-emitting host) of the light-emitting layer of the organic EL device of the present invention is specifically a specific example that is previously used as a light-emitting host Examples include OC-9, OC-11, OC-12, OC-14, OC-18, OC-18, OC-29, OC-30, OC-31, OC-32, and OC-33. It is not limited to these.

  The host compound of the present invention may be deuterated. Specific examples include those in which the hydrogen atoms of the compounds OC-1 to OC-33 and 1 to 56 of the host compounds mentioned in the present invention are all replaced with deuterium atoms, or partially replaced with deuterium. Is mentioned.

In the general formula (1) of the present invention, the deuterium substitution purity of the hexadentate ortho metal iridium complex is preferably 80% or more, more preferably 90% or more, and most preferably 99% or more. It is.
In the present invention, deuterium substitution purity refers to the proportion of all hydrogen atoms in a molecule that are deuterium atoms. Therefore, the ratio (deuterium substitution purity) of deuterium atoms present in all hydrogen atoms in the compound represented by the general formula in the present invention.
The deuterium substitution purity can be determined by proton NMR using an external standard solution. In addition, a method using a mass spectrometer dedicated to deuterium, gas chromatography, hydrogen carrier ganomo molecular sieve method, It can also be determined by utilizing the carrier gas batch alumina method.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided with a single layer or a plurality of layers.
The electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer. As a constituent material of the electron transport layer, any conventionally known compound may be selected and used in combination. Is possible.

Examples of conventionally known materials used for the electron transport layer (hereinafter referred to as electron transport materials) include polycyclic aromatic hydrocarbons such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, Ring tetracarboxylic anhydride, carbodiimide, fluorenylidenemethane derivative, anthraquinodimethane and anthrone derivative, oxadiazole derivative, carboline derivative, or at least carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative Derivatives having a ring structure, one of which is substituted with a nitrogen atom, hexaazatriphenylene derivatives and the like.
Furthermore, in the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material.
It is also possible to use a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.
In addition, metal-free or metal phthalocyanine, or those having the terminal substituted with an alkyl group or a sulfonic acid group can also be used as the electron transport material.
In addition, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.

The electron transport layer is made of an electron transport material such as a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, an ink jet method, a printing method, or a spraying method. The film is preferably formed by thinning by a coating method, a curtain coating method, an LB method (such as Langmuir Brodgett method)).
The method for forming the constituent layers of the organic EL element will be described in detail in the section of the method for manufacturing the organic EL element.
Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, about 5 nm-5000 nm, Preferably it is 5 nm-200 nm. This electron transport layer may have a single layer structure composed of one or more of the above materials.
Further, an n-type dopant such as a metal compound such as a metal complex or a metal halide may be doped.

  Hereinafter, although the specific example of the conventionally well-known compound (electron transport material) preferably used for formation of the electron carrying layer of the white organic EL element of this invention is given, this invention is not limited to these.

"cathode"
As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.
In addition, a transparent or semi-transparent cathode can be produced by producing a conductive transparent material mentioned in the explanation of the anode described later after producing the metal with a thickness of 1 nm to 20 nm on the cathode. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

<< Injection layer: hole injection layer (anode buffer layer), electron injection layer (cathode buffer layer) >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.
An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166), and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Representative phthalocyanine buffer layer, hexaazatriphenylene derivative buffer layer, oxide buffer layer typified by vanadium oxide, amorphous carbon buffer layer, polyaniline as described in JP-T-2003-519432 and JP-A-2006-135145 Examples thereof include a polymer buffer layer using a conductive polymer such as (emeraldine) or polythiophene, an ortho-metalated complex layer represented by tris (2-phenylpyridine) iridium complex, and the like.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by, alkali metal compound buffer layer typified by lithium fluoride and potassium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride and cesium fluoride, typified by aluminum oxide Examples thereof include an oxide buffer layer. The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.
The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
Moreover, the structure of the electron carrying layer mentioned above can be used as a hole-blocking layer concerning this invention as needed.

The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
The hole blocking layer includes a carbazole derivative, a carboline derivative, a diazacarbazole derivative (the diazacarbazole derivative is a nitrogen atom in which any one of carbon atoms constituting the carboline ring is mentioned as the host compound described above. It is preferable to contain (represented by).

Further, in the present invention, when a plurality of light emitting layers having different emission colors are provided, the light emitting layer having the shortest wavelength of the light emission maximum wavelength (shortest wave layer) is closest to the anode among all the light emitting layers. preferable. In such a case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the shortest wave layer. Further, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at this position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

The ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied orbital) level of the compound to the vacuum level, and can be determined by, for example, the following method.
(1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA As a value (eV unit converted value) calculated by performing structure optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
(2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
Further, azatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.

The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbene; N-phenylcarbazole and also two condensations described in US Pat. No. 5,061,569 Having an aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308688 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units described in the publication are linked in a starburst type Etc.

Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.
The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.

Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.
Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.
Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc., and it is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 ⁻³ ml / (m ² · 24 h · atm) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.
The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.
The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.
Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.
In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<< Method for producing organic EL element >>
As an example of a method for producing an organic EL element, anode / hole injection layer / hole transport layer / light emitting layer unit (light emitting layer) / anode buffer layer (hole blocking layer) / electron transport layer / cathode buffer layer (electron injection) A method for manufacturing an element composed of (layer) / cathode will be described.
First, a desired electrode material, for example, a thin film made of a material for an anode is formed on a suitable substrate so as to have a thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode.
Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, which is a device material, is formed thereon.
As a method for forming the thin film, for example, the thin film can be formed by a vacuum deposition method, a wet method (also referred to as a wet process), or the like.
Wet methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, and LB, but precise thin films can be formed. In view of high productivity, a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable. Different film formation methods may be applied for each layer.

Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.
After the formation of these layers, a thin film made of a cathode material is formed thereon so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a desired organic EL device can be obtained by providing a cathode. .
Alternatively, the cathode, electron injection layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in this order in the reverse order.
When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.
The organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.
As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.
Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
Examples of the polymer plate include those formed from polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like.

Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned.
Furthermore, the polymer film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less measured by a method according to JIS K 7126-1987, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.
Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate and the like), and anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.
As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.
When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.
The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.
However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface. By condensing in the front direction, the luminance in a specific direction can be increased.
As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
As the shape of the prism sheet, for example, a substrate may be formed by forming a triangle (triangular) stripe with a vertex angle of 90 degrees and a pitch of 50 μm, a shape with a rounded vertex, and a pitch. The shape may be changed at random, or other shapes.
Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Examples include, but are not limited to, a sensor light source. However, it can be effectively used particularly as a backlight of a liquid crystal display device and an illumination light source.
In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do. The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total CS-1000 (Konica Minolta Sensing Co., Ltd.) is applied to the CIE chromaticity coordinates.
When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

≪Display device≫
The display device of the present invention will be described. The display device of the present invention comprises the organic EL element of the present invention.
Although the display device of the present invention may be single color or multicolor, the multicolor display device will be described here. In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.
In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.
The configuration of the organic EL element provided in the display device is selected from the above-described configuration examples of the organic EL element as necessary.
Moreover, the manufacturing method of an organic EL element is as having shown to the one aspect | mode of manufacture of the organic EL element of said invention.

In the case of applying a DC voltage to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2V to 40V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.
The multicolor display device can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. The present invention is not limited to these examples.
Hereinafter, an example of a display device having the organic EL element of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal. The image information is sequentially emitted to scan the image and display the image information on the display unit A.

FIG. 2 is a schematic diagram of the display unit A.
The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below.
In the figure, the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not)
When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.
Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.

Next, the light emission process of the pixel will be described. FIG. 3 is a schematic diagram of a pixel.
The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
In FIG. 3, an image data signal is applied from the control unit B (see FIG. 1) to the drain of the switching transistor 11 through the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues. When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

That is, the light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels. It is carried out. Such a light emitting method is called an active matrix method.
Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good. The potential of the capacitor 13 may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

FIG. 4 is a schematic diagram of a passive matrix display device. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.
In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

≪Lighting device≫
The lighting device of the present invention will be described. The illuminating device of this invention comprises the said organic EL element.
In the illumination device of the present invention, the organic EL element of the present invention may be used as an organic EL element having a resonator structure. Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.
Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).
The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

The organic EL material used in the present invention can be applied to an organic EL element that emits substantially white light as a lighting device. This organic EL element emits a plurality of emission colors simultaneously with a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of red, green and blue, or two using the complementary colors such as blue and yellow, blue green and orange. The thing containing the light emission maximum wavelength may be used.
In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.

It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, for example, an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved.
According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.
There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.

<< One Embodiment of Lighting Device of the Present Invention >>
One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.
The non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material. LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and an illumination device as shown in FIGS. Can be formed.
FIG. 5 shows a schematic diagram of a lighting device, and the organic EL element 101 of the present invention is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is to bring the organic EL element 101 into contact with the atmosphere. And a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more).
FIG. 6 shows a cross-sectional view of the lighting device. In FIG. 6, 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

Hereinafter, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
The structure of the compound used for preparation of an organic EL element is shown below.

[Example 1]
[Production of Organic EL Element 1-1]
Patterning was performed on a substrate (NAV-45, manufactured by AvanStrate Co., Ltd.) in which an ITO (indium tin oxide) film having a thickness of 100 nm was formed on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) to 70% with pure water is spin-coated. After that, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

  On the first hole transport layer, a hole transport material Poly (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl)) benzidine (manufactured by American Dye Source, ADS- 254) was formed into a film by spin coating. It heat-dried at 150 degreeC for 1 hour, and provided the 2nd hole transport layer with a film thickness of 40 nm.

On this 2nd hole transport layer, the host compound OC-11 and the butyl acetate solution of the comparison 1 which is a dopant compound were formed into a film by the spin coat method, and it heat-dried at 120 degreeC for 1 hour, and the light emitting layer with a film thickness of 30 nm Was established.
On this light emitting layer, the 1-butanol solution of electron transport material ET-11 was formed into a film by the spin coat method, and the 20-nm-thick electron transport layer was provided.
This was attached to a vacuum deposition apparatus, and the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa. Subsequently, lithium fluoride 1.0nm was vapor-deposited as an electron injection layer, and aluminum 110nm was vapor-deposited as a cathode, and the organic EL element 1-1 was produced.

[Production of Organic EL Elements 1-2 to 1-23]
In the production of the organic EL element 1-1, each of the organic EL elements 1-2 to 1-23 was similarly performed except that the host compound OC-11 and dopant compound comparison 1 in the light emitting layer were replaced with the compounds shown in Table 1. Produced.

<Evaluation of organic EL element>
When evaluating the obtained organic EL elements 1-1 to 1-23, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the periphery, and this is placed on the cathode so as to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, after curing and sealing, an illumination device as shown in FIGS. 5 and 6 was formed and evaluated as follows.

(Luminescence efficiency (external extraction quantum efficiency (also simply referred to as efficiency)))
By lighting the organic EL element under a constant current condition of room temperature (about 23 to 25 ° C.) and ^2.5 mA / cm ² , and measuring the light emission luminance (L) [cd / m ² ] immediately after the start of lighting, The external extraction quantum efficiency (η) was calculated.
Here, the measurement of light emission luminance was performed using CS-1000 (manufactured by Konica Minolta Sensing), and the external extraction quantum efficiency was expressed as a relative value with the organic EL element 1-1 (comparative example) as 100.

(Drive voltage)
Each voltage was measured when the organic EL device was driven at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and the measurement result was calculated by the following formula. The results obtained are shown in Table 1.
The organic EL element 1-1 (comparative example) is taken as 100 and each is shown as a relative value.
Drive voltage (relative value) = (drive voltage of each element / drive voltage of organic EL element 1-1 (comparative example)) × 100
A smaller value indicates a lower drive voltage for comparison.

(Half life)
The half-life was evaluated according to the measurement method shown below.
Each organic EL device driven with a constant current at a current giving an initial luminance 1000 cd / ^{m 2,} obtains the time to be 1/2 (500cd / ^{m 2)} of the initial luminance, which was used as a measure of the half-life.
The half life was expressed as a relative value when the comparative organic EL element 1-1 (comparative example) was set to 100.
The obtained results are shown in Table 1.

  From Table 1, the element of the present invention exhibits high efficiency as compared with the comparative example, the half-life is improved, the drive voltage is also lowered, and the characteristics as the element are improved.

[Example 2]
[Production of Organic EL Element 2-1]
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
A solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, manufactured by HC Starck Co., Ltd., CLEVIO P VP AI 4083) to 70% with pure water on the transparent support substrate. After forming a thin film by spin coating at 3000 rpm for 30 seconds, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 20 nm.
This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was put in a molybdenum resistance heating boat, and 200 mg of OC-30 as a host compound was put in another molybdenum resistance heating boat, 200 mg of ET-8 was put into another molybdenum resistance heating boat, and 100 mg of Comparative Compound 1 as a dopant compound was put into another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.

Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, evaporated onto the transparent support substrate at a deposition rate of 0.1 nm / second, and the second positive electrode of 20 nm. A hole transport layer was provided.
Further, the heating boat containing the host compound OC-30 and the comparison compound 1 as a dopant compound was energized and heated, and on the second hole transport layer at a deposition rate of 0.1 nm / second and 0.006 nm / second, respectively. A 40 nm light emitting layer was provided by co-evaporation.
Furthermore, it supplied with electricity to the said heating boat containing ET-8, and heated, and it vapor-deposited on the said light emitting layer with the vapor deposition rate of 0.1 nm / sec, and provided the electron carrying layer with a film thickness of 30 nm.
In addition, the substrate temperature at the time of vapor deposition was room temperature.
Then, 0.5 nm of lithium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 110nm was vapor-deposited, the cathode was formed, and the organic EL element 2-1 was produced.

[Production of Organic EL Elements 2-2 to 2-23]
In the production of the organic EL element 2-1, the organic EL elements 2-2 to 2-2 were prepared in the same manner except that the host compound OC-30 of the light emitting layer and the comparative compound 1 as the dopant compound were replaced with the compounds shown in Table 2. 23 were prepared respectively.

<Evaluation of organic EL element>
When evaluating the obtained organic EL elements 2-1 to 2-23, sealing was performed in the same manner as the organic EL element 1-1 of Example 1, and an illumination device as shown in FIGS. 5 and 6 was formed. The following evaluation was performed.

(Luminance brightness)
The light emission luminance (L) [cd / m ² ] when a temperature of 23 ° C. and a DC voltage of 10 V were applied to the organic EL element was measured. The light emission luminance was expressed as a relative value with the organic EL element 2-1 (comparative example) as 100. The light emission luminance was measured using CS-1000 (manufactured by Konica Minolta Sensing).

(Initial deterioration)
According to the measurement method shown below, initial deterioration was evaluated and used as an index of durability. When the half-life was measured, the time required for the luminance to reach 90% was measured and used as a measure of initial deterioration. The initial deterioration was 100 for the comparative organic EL element 2-1. The initial deterioration was calculated based on the following formula.
Initial deterioration = (luminance 90% arrival time of organic EL element 2-1) / (luminance 90% arrival time of each element) × 100
That is, the smaller the initial deterioration value, the smaller the initial deterioration.

(Drive voltage)
The same procedure as described in Example 1 was performed. In addition, the drive voltage was each shown by the relative value by making the organic EL element 2-1 (comparative example) 100.

  From Table 2, even when the element was manufactured by the vapor deposition method, the element of the present invention exhibited high emission luminance, the initial deterioration was suppressed, and the drive voltage was decreased, as compared with the comparative example. Has improved. In this case, the deuterium-substituted compound of the present invention was compared with the effect of binding the ligands of Comparative 1 to Comparative 2 having a phenylpyridine-based ligand. The effect is clearly great.

[Example 3]
[Production of Organic EL Elements 3-1 to 3-6]
In the production of the organic EL element 1-1, each of the organic EL elements 3-1 to 3-6 was similarly performed except that the host compound OC-11 of the light emitting layer and the dopant compound comparison 1 were replaced with the compounds shown in Table 3. Produced.

<Evaluation of organic EL elements 3-1 to 3-6>
When evaluating the obtained organic EL elements 3-1 to 3-6, sealing was performed in the same manner as the organic EL element 1-1 of Example 1, and an illumination device as shown in FIGS. 5 and 6 was formed. The following evaluation was performed.

(Deuterium substitution purity)
Deuterium substitution purity was measured by proton NMR using an external standard.

(Luminescence efficiency)
The same procedure as described in Example 1 was performed. The light emission luminance is expressed as a relative value when the organic EL element 3-1 (comparative example) is 100.

(Half life)
The same procedure as described in Example 1 was performed. The half-life was shown as a relative value with the organic EL element 3-1 (comparative example) as 100.

(Drive voltage)
The same procedure as described in Example 1 was performed. In addition, the drive voltage was each shown by the relative value by making the organic EL element 3-1 (comparative example) 100.
The obtained results are shown in Table 3.

  From Table 3, compared with the comparative organic EL element 3-1, the organic EL elements 3-2 to 3-6 of the present invention produced using the organic EL element material having high deuterium substitution purity of the present invention It is apparent that various characteristics as an element are improved, such as high luminous efficiency, half-life, and low driving voltage.

[Example 4]
[Production of White Light-Emitting Organic EL Element 4-1]
Patterning was performed on a substrate (NAV-45, manufactured by AvanStrate Co., Ltd.) in which an ITO (indium tin oxide) film having a thickness of 100 nm was formed on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) to 70% with pure water is spin-coated. After that, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.
On the first hole transport layer, a hole transport material Poly (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl)) benzidine (manufactured by American Dye Source, ADS- 254) was formed into a film by spin coating. It heat-dried at 150 degreeC for 1 hour, and provided the 2nd hole transport layer with a film thickness of 40 nm.

Next, using a solution obtained by dissolving host compound 24 (100 mg), dopant materials 1D-1 (3 mg) and 1D-10 (3 mg) in 10 ml of toluene, a film was formed by spin coating under conditions of 2000 rpm and 30 seconds. . The first light emitting layer was formed by vacuum drying at 60 ° C. for 1 hour.
Furthermore, on this 1st light emitting layer, it spins on 2000 rpm and 30 second conditions using the solution which melt | dissolved host compound OC-11 (100 mg) and dopant material 1C-6 (16 mg) in 6 ml hexafluoroisopropanol (HFIP). A film was formed by a coating method and vacuum-dried at 60 ° C. for 1 hour to form a second light emitting layer.
This substrate is fixed to the substrate holder of the vacuum evaporation apparatus, and the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa. Then, the electron transport material ET-9 is formed on the second light emitting layer as a cathode buffer layer by 30 nm. A cathode was formed by vapor-depositing lithium fluoride at 0.5 nm and further using aluminum as a cathode at 110 nm to prepare an organic EL element 4-1.
When this element was energized, almost white light was obtained, and it was found that it could be used as a lighting device. In addition, it turned out that white light emission is obtained similarly even if it replaces with the other compound of illustration.

[Example 5]
[Production of White Light-Emitting Organic EL Element 5-1]
Patterning was performed on a substrate (NAV-45, manufactured by AvanStrate Co., Ltd.) in which an ITO (indium tin oxide) film having a thickness of 100 nm was formed on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) to 70% with pure water is spin-coated. After that, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.
On the first hole transport layer, a hole transport material Poly (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl)) benzidine (manufactured by American Dye Source, ADS- 254) was formed into a film by spin coating. It heat-dried at 150 degreeC for 1 hour, and provided the 2nd hole transport layer with a film thickness of 40 nm.

Next, using a solution of host compound 7 (100 mg), dopant material 1D-1 (3 mg) and 1D-6 (3 mg), 1F-3 (16 mg) dissolved in 10 ml of toluene, under the conditions of 2000 rpm and 30 seconds, A film was formed by spin coating. A light emitting layer was formed by vacuum drying at 60 ° C. for 1 hour.
This substrate is fixed to a substrate holder of a vacuum deposition apparatus, and the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, and then the electron transport material ET-15 is 30 nm on the light emitting layer, followed by lithium fluoride as a cathode buffer layer. The organic EL element 5-1 was produced by depositing aluminum with a thickness of 0.5 nm and further depositing 110 nm of aluminum as the cathode.
When this element was energized, almost white light was obtained, and it was found that it could be used as a lighting device. In addition, it turned out that white light emission is obtained similarly even if it replaces with the other compound of illustration.

[Example 6]
[Production of White Light-Emitting Organic EL Element 6-1]
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD is put in a molybdenum resistance heating boat, and 200 mg of 1 as a host compound is put in another resistance heating boat made of molybdenum. Put 200 mg of ET-11 into a resistance heating boat made of molybdenum, put 100 mg of 1C-12 as a dopant compound into another resistance heating boat made of molybdenum, and put 100 mg of 1D-10 as a dopant compound into another resistance heating boat made of molybdenum And attached to a vacuum deposition apparatus.
Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, each of the heating boats containing α-NPD was separately energized, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A hole transport layer was provided.

Further, the host boat 1 and the dopant compound 1C-12, and the heating boat containing the dopant compound 1D-10 were energized, and the host compound 1 and the dopant compounds 1C-12 and 1D-10. The vapor deposition rate was adjusted to 100: 5: 0.6, vapor deposition was performed to a thickness of 30 nm, and a light emitting layer was provided.
Furthermore, it supplied with electricity to the said heating boat containing ET-11, it heated, and it vapor-deposited on the said light emitting layer with the vapor deposition rate of 0.1 nm / second, and provided the electron carrying layer with a film thickness of 30 nm.
In addition, the substrate temperature at the time of vapor deposition was room temperature.
Then, 0.5 nm of lithium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 110nm was vapor-deposited, the cathode was formed, and the organic EL element 6-1 was produced.
When this element was energized, almost white light was obtained, and it was found that it could be used as a lighting device. In addition, it turned out that white light emission is obtained similarly even if it replaces with the other compound of illustration.

1. Display device (display)
3 pixels 5 scanning lines 6 data lines 7 power supply lines 10 organic EL elements 11 switching transistors 12 drive transistors 13 capacitors 101 organic EL elements 102 glass covers 105 cathodes 106 organic EL layers 107 glass substrates with transparent electrodes 108 nitrogen gas 109 water catching agents A Display unit B Control unit

Claims (27)

In an organic electroluminescence device having at least one light emitting layer between an anode and a cathode,
The organic electroluminescence element contains a hexadentate ortho metal iridium complex represented by the following general formula (1), and at least one hydrogen atom in the complex molecule is substituted with deuterium. An organic electroluminescence device characterized.

[Wherein, V represents a divalent or trivalent linking group and is linked to L ₁ and L _{2 through a} covalent bond. A dotted line connecting V and L ₃ represents a covalent bond or a non-bond. It is assumed that at least one hydrogen atom in the general formula (1) is substituted with deuterium. L _{1 to} L ₃ are represented by the following general formula (1-A), wherein X ₆ and Ir are coordinated and X ₈ and Ir form a covalent bond. ]

[Wherein, X _{1 to} X ₆ are an element group forming a nitrogen-containing 5-membered or _6- membered nitrogen-containing heterocyclic ring, selected from a carbon atom or a nitrogen atom, and at least one of X ₅ and X ₆ is Represents a nitrogen atom. X ₃ and X ₁₁ each represent a carbon atom, and n 1 and n 2 each represents an integer of 0 or 1. X < ₇ > -X < ₁₂ > is an element group which forms a 5-membered ring or a 6-membered ring, and is selected from a carbon atom or a nitrogen atom. It is assumed that at least one of X _{2 to} X ₅ and X _{9 to} X ₁₂ is substituted with deuterium. ] In the general formula (1), an organic electroluminescence device according to claim 1, part of the hydrogen atoms in the complex molecule is deuterated is characterized in that it is a L _1, L 2 or L _3,.   3. The organic electroluminescence device according to claim 1, wherein in the general formula (1), a site where a hydrogen atom in the complex molecule is substituted with deuterium is V. 4.   In the said General formula (1), all the hydrogen atoms in a complex molecule are substituted with deuterium, The organic electroluminescent element of Claim 1 characterized by the above-mentioned. In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is an aromatic hetero 6-membered ring, and the aromatic The organic electroluminescent device according to any one of claims 1 to 4, wherein the group 6-membered ring is a pyridine ring. In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is a hetero 5-membered ring, and the complex 5-membered The organic electroluminescence device according to any one of claims 1 to 4, wherein the ring is an imidazole ring. In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is a hetero 5-membered ring, and the complex 5-membered The organic electroluminescence device according to any one of claims 1 to 4, wherein the ring is a pyrazole ring. In at least one of L _{1 to} L ₃ of the general formula (1), the ring formed by X _{1 to} X ₆ of the general formula (1-A) is a hetero 5-membered ring, and the complex 5-membered The organic electroluminescence device according to any one of claims 1 to 4, wherein the ring is a triazole ring. The said general formula (1-A) is represented by the following general formula (1-B), The organic electroluminescent element of any one of Claim 1 to 4 characterized by the above-mentioned.

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, a deuterium atom or a substituent. ] The said general formula (1-A) is represented by the following general formula (1-C), The organic electroluminescent element of any one of Claims 1-4 characterized by the above-mentioned.

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₅ , R ₆ and R ₇ each represent a hydrogen atom, a deuterium atom or a substituent. ] The said general formula (1-A) is represented by the following general formula (1-D), The organic electroluminescent element of any one of Claims 1-4 characterized by the above-mentioned.

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom, a deuterium atom or a substituent. ] The said general formula (1-A) is represented by the following general formula (1-E), The organic electroluminescent element of any one of Claim 1 to 4 characterized by the above-mentioned.

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, a deuterium atom or a substituent. ] The said general formula (1-A) is represented by the following general formula (1-F), The organic electroluminescent element of any one of Claims 1-4 characterized by the above-mentioned.

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁₄ and R ₁₅ each represent a hydrogen atom, a deuterium atom or a substituent. ] The said general formula (1-A) is represented by the following general formula (1-G), The organic electroluminescent element of any one of Claims 1-4 characterized by the above-mentioned.

[Wherein, the element group represented by X _{7 to} X ₁₂ , n 2 has the same meaning as in the general formula (1-A). R ₁₆ and R ₁₇ each represent a hydrogen atom, a deuterium atom or a substituent. ] The organic electroluminescence device according to claim 1, wherein the element group represented by X _{7 to} X ₁₂ is a benzene ring. 16. The organic electro of any one of claims 1 to 15, wherein the general formula (1) is a hexadentate ortho metal iridium complex represented by the following general formula (2). Luminescence element.

[Wherein, V represents a trivalent linking group and is linked to L _{1 to} L _{3 through a} covalent bond. L _{1 to} L ₃ are each represented by the general formula (1-A) in claim 1, wherein X ₆ and Ir are coordinated, and X ₈ and Ir form a covalent bond. ]   The organic electroluminescence device according to any one of claims 1 to 16, wherein the V is any one of compounds having the structures shown below.
[In the compound having the structure shown below, * represents L ₁ ~ L ₃ And n represents 1-2. ]

In the general formula (1), an organic electroluminescence according to any one of claims 1 to 17, wherein the deuterated purity hexa-coordinated ortho-metal iridium complex is 80% or more Luminescence element. In the general formula (1), an organic electroluminescence according to any one of claims 1 to 17 for deuterated purity of hexa-coordinated ortho-metal iridium complex is characterized in that less than 90% Luminescence element. In the general formula (1), an organic electroluminescence according to any one of claims 1 to 17 for deuterated purity of hexa-coordinated ortho-metal iridium complex is characterized in that less than 99% Luminescence element. The organic electroluminescence device according to any one of claims 1 to 20 , wherein the hexadentate ortho metal iridium complex is contained in at least one of the light emitting layers. The organic electroluminescent element according to any one of claims 1 to 21 , wherein a host compound is contained in at least one of the light emitting layers. The organic electroluminescence device according to claim 22 , wherein at least one hydrogen atom of the host compound is substituted with a deuterium atom. The organic electroluminescence device according to claim 22 , wherein all the hydrogen atoms of the host compound are substituted with deuterium atoms. The organic electroluminescence device according to any one of claims 1 to 24 , which emits white light. A display device comprising the organic electroluminescence element according to any one of claims 1 to 25 . An illuminating device comprising the organic electroluminescence element according to any one of claims 1 to 25 .

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