JP4894513B2 - ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE - Google Patents

Description

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

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter referred to as organic EL elements). Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements. An organic EL device has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer and recombines them to generate excitons. An element that emits light by using light emission (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several V to several tens V, and is self-luminous. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type complete solid-state device, it has attracted attention from the viewpoints of space saving and portability.

  However, in organic EL elements for practical use in the future, development of organic EL elements that emit light efficiently and with high luminance with lower power consumption is desired.

  In Japanese Patent No. 3093796, a small amount of phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to achieve an improvement in light emission luminance and a longer device lifetime.

  Further, an element having an organic light-emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped thereto (for example, JP-A 63-264692), and an 8-hydroxyquinoline aluminum complex is used as a host compound. For example, an element having an organic light emitting layer doped with a quinacridone dye (for example, JP-A-3-255190) is known.

  As described above, when light emission from excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, and thus the generation probability of luminescent excited species is 25%. Since the efficiency is about 20%, the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, since Princeton University reported on organic EL devices using phosphorescence emission from excited triplets (MA Baldo et al., Nature, 395, 151-154 (1998)), at room temperature. Research on materials that exhibit phosphorescence has become active.

  For example, M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), US Pat. No. 6,097,147, and the like.

  When excited triplets are used, the upper limit of internal quantum efficiency is 100%, so that in principle the luminous efficiency is four times that of excited singlets, and there is a possibility that almost the same performance as cold cathode tubes can be obtained. Therefore, it is attracting attention as a lighting application.

  For example, S.M. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), etc., many compounds have been studied for synthesis centering on heavy metal complexes such as iridium complexes.

  In addition, the aforementioned M.I. A. Baldo et al. , Nature, Vol. 403, No. 17, pages 750-753 (2000), studies have been made using tris (2-phenylpyridine) iridium as a dopant.

In addition, M.M. E. Thompson et al. In The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) used L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac) as a dopant, J
Youn. 0 g, Tetsuo Tsutsui, etc., again, The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) in, as a dopant tris (2-(p-tolyl) pyridine) iridium (Ir (ptpy) _3), Studies using tris (benzo [h] quinoline) iridium (Ir (bzq) ₃ ) and the like are being conducted (note that these metal complexes are generally called orthometalated iridium complexes).

  In addition, S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), etc., attempts have been made to form devices using various iridium complexes.

  In order to obtain high luminous efficiency, in the 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. In addition, M.M. E. Thompson et al. Use various electron transporting materials as a host of a phosphorescent compound, doped with a novel iridium complex.

  Orthometalated complexes in which the central metal is platinum instead of iridium are also attracting attention. With regard to this type of complex, there are many known examples in which a ligand is characterized (see, for example, Patent Documents 1 to 5 and Non-Patent Document 1).

  In any case, the light emission luminance and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. There was a problem that it was lower than the conventional element. As described above, phosphorescent high-efficiency light-emitting materials are not capable of sufficiently achieving practical performance because it is difficult to shorten the emission wavelength and improve the light emission lifetime of the device.

In addition, regarding wavelength shortening, introduction of an electron withdrawing group such as a fluorine atom, a trifluoromethyl group, and a cyano group into phenylpyridine as a substituent, and picolinic acid and pyrazabole-based ligands as ligands Is known (for example, see Patent Documents 6 to 13 and Non-Patent Documents 1 to 4). However, with these ligands, the emission wavelength of the light-emitting material is shortened to achieve a blue color. While an efficient device can be achieved, the light emission lifetime of the device tends to deteriorate, and an improvement in the trade-off has been demanded.
JP 2002-332291 A JP 2002-332292 A JP 2002-338588 A JP 2002-226495 A JP 2002-234894 A International Publication No. 02/15645 Pamphlet JP 2003-123982 A JP 2002-117978 A JP 2003-146996 A International Publication No. 04/016711 Pamphlet International Publication No. 05/007767 Pamphlet International Publication No. 04/101707 Pamphlet JP 2005-053912 A Inorganic Chemistry, Vol. 41, No. 12, pp. 3055-3066 (2002) Applied Physics Letters, Volume 79, 2082 (2001) Applied Physics Letters, 83, 3818 (2003) New Journal of Chemistry, 26, 1171 (2002)

  An object of the present invention is to provide an organic EL element, an illuminating device, and a display device in which the emission wavelength is controlled, the emission efficiency is high, and the emission lifetime is long.

In order to achieve the above object, one aspect of the present invention is an organic electrolysis that is a metal complex represented by the following general formula (1) , (4), or (5): It is in the luminescence element material.

〔式中、Ｚ４１は、芳香族複素環を形成するのに必要な原子群を表す。Ｘ ₄₁ 、Ｘ ₄₂ は置換基を有してもよい炭素原子または窒素原子を表すが、その少なくとも１つは、窒素原子または−Ｎ（Ｒ ₄ ）−（ここで、Ｒ ₄ は、水素原子またはアルキル基、芳香族炭化水素基または芳香族複素環基を表す。）を表す。Ｍ ₄₁ は、イリジウム、または、白金を表す。Ｃ ₄₁ 、Ｃ ₄₂ 、Ｃ ₄₃ は、各々炭素原子を表す。Ｃ ₄₁ とＣ ₄₂ との間の結合、Ｃ ₄₁ とＸ ₄₂ との間の結合、Ｘ ₄₁ とＸ ₄₂ との間の結合、Ｘ ₄₁ とＣ ₄₃ との間の結合、Ｃ ₄₂ とＣ ₄₃ との間の結合は、単結合または二重結合を表す。ｎは２、または、３の整数を表す。〕

〔式中、Ｚ５１は、芳香族炭化水素環または芳香族複素環を形成するのに必要な原子群を表す。Ｘ ₅₁ は、酸素原子または硫黄原子を表す。Ｒ ₅₁ 、Ｒ ₅₂ は、水素原子またはアルキル基、芳香族炭化水素基または芳香族複素環基を表す。Ｍ ₅₁ は、イリジウム、または、白金を表す。ｎは２、または、３の整数を表す。〕

[Wherein, Z11 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group . M ₁₁ represents iridium or platinum. n represents an integer of 2 or 3. However, compounds represented by the following chemical formulas 1 and 2 are excluded. ]

[In formula, Z41 represents an atomic group required in order to form an aromatic heterocyclic ring. X ₄₁ and X ₄₂ each represent an optionally substituted carbon atom or nitrogen atom, at least one of which is a nitrogen atom or —N (R ₄ ) — (where R ₄ represents a hydrogen atom or Represents an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group. M ₄₁ represents iridium or platinum. C ₄₁ , C ₄₂ and C ₄₃ each represent a carbon atom. Bond between C ₄₁ and C _42, bond between C ₄₁ and X _42, coupling between X ₄₁ and X _42, coupling between X ₄₁ and C _43, and C ₄₂ and C ₄₃ The bond between represents a single bond or a double bond. n represents an integer of 2 or 3. ]

[In the formula, Z51 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. X ₅₁ represents an oxygen atom or a sulfur atom. R ₅₁ and R ₅₂ represent a hydrogen atom or an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group. M ₅₁ represents iridium or platinum. n represents an integer of 2 or 3. ]

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. 4 is a schematic diagram of a display unit A. FIG. It is an equivalent circuit diagram of the drive circuit which comprises a pixel. It is a schematic diagram of the display apparatus by a passive matrix system. It is a schematic diagram of the sealing structure of organic EL element OLED1-1. It is a schematic diagram of the illuminating device which comprises an organic EL element.

The above object of the present invention has been achieved by the following configurations 1 to 28.
(1) The following general formula (1) or a metal complex having the tautomer of the general formula (1) as a partial structure, the following general formula (2) or the tautomer of the general formula (2) A metal complex having a partial structure, a metal complex having the following general formula (3) or a tautomer of the general formula (3) as a partial structure, a following general formula (4) or a tautomer of the general formula (4) A metal complex having a mutant as a partial structure, the following general formula (5) or a metal complex having a tautomer of the general formula (5) as a partial structure, or the following general formula (6) or the general An organic electroluminescent element material, which is a metal complex having a tautomer of formula (6) as a partial structure.

[Wherein, Z11 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent. M ₁₁ represents a group 8 to group 10 metal in the periodic table. ]

[In formula, Z21 represents an atomic group required in order to form an aromatic-hydrocarbon ring or an aromatic heterocyclic ring. R ₂₁ , R ₂₂ and R ₂₃ each represents a hydrogen atom or a substituent. M ₂₁ represents a group 8 to group 10 metal in the periodic table. ]

[In formula, Z31 represents an atomic group required in order to form an aromatic-hydrocarbon ring or an aromatic heterocyclic ring. X ₃₁ , X ₃₂ and X ₃₃ each represent a carbon atom or a nitrogen atom which may have a substituent, and at least two are a nitrogen atom or —N (R ₃ ) — (where R ₃ is Represents a hydrogen atom or a substituent. C ₃₁ represents a carbon atom. M ₃₁ represents a group 8 to group 10 metal in the periodic table. Bond between C ₃₁ and N, bond between N and X ₃₃ , bond between X ₃₂ and X ₃₃ , bond between X ₃₁ and X ₃₂ , between C ₃₁ and X ₃₁ Each of the bonds represents a single bond or a double bond. ]

[In formula, Z41 represents an atomic group required in order to form an aromatic heterocyclic ring. X ₄₁ and X ₄₂ each represent an optionally substituted carbon atom or nitrogen atom, at least one of which is a nitrogen atom or —N (R ₄ ) — (where R ₄ represents a hydrogen atom or Represents a substituent). M ₄₁ represents a group 8 to group 10 metal in the periodic table. C ₄₁ , C ₄₂ and C ₄₃ each represent a carbon atom. M ₄₁ represents a group 8 to group 10 metal in the periodic table. Bond between C ₄₁ and C _42, bond between C ₄₁ and X _42, coupling between X ₄₁ and X _42, coupling between X ₄₁ and C _43, and C ₄₂ and C ₄₃ The bond between represents a single bond or a double bond. ]

[In the formula, Z51 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. X ₅₁ represents an oxygen atom or a sulfur atom. R ₅₁ and R ₅₂ represent a hydrogen atom or a substituent. M ₅₁ represents a group 8 to group 10 metal in the periodic table. ]

[Wherein, Z61 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. X ₆₁ , X ₆₂ and X ₆₃ each represents a carbon atom or a nitrogen atom which may have a substituent, and at least one represents a nitrogen atom. M ₆₁ represents a group 8 to group 10 metal in the periodic table. ]
(2) The organic electroluminescent element material according to (1) above, which is a metal complex having the partial structure of the general formula (1) or a tautomer of the general formula (1).
(3) In the metal complex having the above general formula (1) or a tautomer of the general formula (1) as a partial structure, Z11 represents an atomic group necessary for forming an aromatic heterocyclic ring The organic electroluminescence element material according to (2) above.
(4) The organic electroluminescent element material according to (1), which is a metal complex having the partial structure of the tautomer of the general formula (2) or the general formula (2).
(5) The organic electroluminescent element material according to (1) above, which is a metal complex having the above general formula (3) or a tautomer of the general formula (3) as a partial structure.
(6) In the metal complex having the above general formula (3) or a tautomer of the general formula (3) as a partial structure, X ₃₁ represents a carbon atom which may have a substituent, X ₃₂ , X ₃₃ is a nitrogen atom or -N (R ₃₎ - (wherein, R ₃ represents a hydrogen atom or a substituent.) the organic electroluminescence device material according to (5), characterized in that representing the.
(7) The organic electroluminescent element material according to (1) above, which is a metal complex having the partial structure of the general formula (4) or a tautomer of the general formula (4).
(8) The organic electroluminescent element material according to (1) above, which is a metal complex having the above general formula (5) or a tautomer of the general formula (5) as a partial structure.
(9) In the metal complex having the above general formula (5) or a tautomer of the general formula (5) as a partial structure, X ₅₁ represents a sulfur atom. Organic electroluminescence element material.
(10) The organic electroluminescent element material as described in (1) above, which is a metal complex having the general formula (6) or a tautomer of the general formula (6) as a partial structure.
(11) In the metal complex having the above general formula (6) or a tautomer of the general formula (6) as a partial structure, at least one of X ₆₁ and X ₆₃ represents a nitrogen atom, The organic electroluminescent element material according to (10) above.
(12) In the general formula (1), an organic electroluminescence device material according to (2), wherein the M ₁₁ is iridium or platinum.
(13) The organic electroluminescent element material as described in (12) above, wherein in the general formula (1), Z11 represents an atomic group necessary for forming an aromatic heterocyclic ring.
(14) In the general formula (2), an organic electroluminescence device material according to (4), wherein the M ₂₁ is iridium or platinum.
(15) In the general formula (3), an organic electroluminescence device material according to (5), characterized in that M ₃₁ is iridium or platinum.
(16) In the general formula (3), X ₃₁ represents a carbon atom which may have a substituent, and X ₃₂ and X ₃₃ are nitrogen atoms or —N (R ₃ ) — (where R ₃ is And represents a hydrogen atom or a substituent.) The organic electroluminescent element material according to (15), wherein
(17) In the general formula (4), M ₄₁ is iridium or platinum, The organic electroluminescence element material according to the above (7),
(18) The organic electroluminescent element material as described in (8) above, wherein, in the general formula (5), M ₅₁ is iridium or platinum.
(19) The organic electroluminescent element material as described in (18) above, wherein in the general formula (5), X ₅₁ represents a sulfur atom.
(20) The organic electroluminescent element material as described in (10) above, wherein in the general formula (6), M ₆₁ is iridium or platinum.
(21) In the above general formula (6), at least one of X ₆₁ and X ₆₃ represents a nitrogen atom, The organic electroluminescence element material according to the above (20),
(22) An organic electroluminescent element comprising the organic electroluminescent element material according to any one of (1) to (21).
(23) The light emitting layer as a constituent layer, wherein the light emitting layer contains the organic electroluminescent element material according to any one of (1) to (21). The organic electroluminescent element of description.
(24) It has a hole blocking layer as a constituent layer, and the hole blocking layer contains the organic electroluminescence element material according to any one of (1) to (21). (22) Or the organic electroluminescent element as described in (23).
(25) A light emitting layer is included as a constituent layer, and the light emitting layer has a ring structure in which at least one of carbon atoms of a carboline derivative or a hydrocarbon ring constituting a carboline ring of the carboline derivative is substituted with a nitrogen atom. The organic electroluminescence device according to any one of (22) to (24), wherein the organic electroluminescence device comprises a derivative.
(26) It has a hole blocking layer as a constituent layer, and at least one of the carbon atoms of the carboline derivative or the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom in the hole blocking layer. The organic electroluminescence device according to any one of (22) to (25), wherein the organic electroluminescence device comprises a derivative having a ring structure.
(27) A display device comprising the organic electroluminescence element according to any one of (22) to (26).
(28) An illumination device comprising the organic electroluminescence element according to any one of (22) to (26).

  In the organic EL element material of the present invention, the organic EL element material useful for the organic EL element has been successfully molecularly designed by the configuration defined in any one of the above (1) to (21). In addition, by using the organic EL element material, it was possible to provide an organic EL element, an illuminating device, and a display device that exhibit high luminous efficiency and have a long light emission lifetime.

  As a result of intensive studies on the above problems, the present inventors have found that phenylpyridine (a 6-membered ring and a 6-membered ring are connected by a carbon-carbon bond) that is generally used as a ligand of a metal complex. Of the “aromatic hydrocarbon ring or aromatic heterocycle (preferably 6-membered ring)” and “aromatic” as represented by the general formulas (1) to (6), respectively. An organic EL device comprising a metal complex having a specific partial structure, such as a group heterocycle (preferably a 5-membered ring) ”connected by a carbon-carbon bond or a carbon-nitrogen bond as an organic EL device material. The emission lifetime, which has been a problem of organic EL devices manufactured using conventional blue metal complexes, especially organic EL device materials whose emission wavelength has been controlled to the short wavelength side only by electron-withdrawing groups, has been greatly improved. I found out.

  Further, the molecular design for imparting the function of controlling the emission wavelength of the metal complex to a long wave region by introducing a substituent having a long wave emission wavelength as a substituent is a general formula according to the present invention. An appropriate partial structure can be selected by starting from the basic skeleton of each of the tautomers of (1) to (6) or the general formulas (1) to (6).

  Hereinafter, details of each component according to the present invention will be sequentially described.

《Metal complex》
The metal complex which concerns on the organic EL element material of this invention is demonstrated.

  The metal complex-containing layer having the partial structure of each of the tautomers of the general formulas (1) to (6) or the general formulas (1) to (6) according to the present invention includes a light emitting layer and / or A hole blocking layer is preferred, and when it is contained in the light emitting layer, it can be used as a light emitting dopant in the light emitting layer to increase the efficiency of external extraction quantum efficiency of the organic EL device of the present invention (higher brightness) and light emission lifetime. Longer service life can be achieved.

<< General Formula (1) or Tautomer of General Formula (1) >>
In the general formula (1) or a tautomer of the general formula (1), the aromatic hydrocarbon ring represented by Z11 includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, Pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, Examples include perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring.

Of these, a benzene ring is preferably used. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁₁ , R ₁₂ , or R ₁₃ in the general formula (1) described later.

  In the general formula (1) or a tautomer of the general formula (1), the aromatic heterocycle represented by Z11 includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine. Ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, Examples thereof include a carboline ring and a ring in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom.

Of these, a pyridine ring is preferred. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁₁ , R ₁₂ , or R ₁₃ in the general formula (1) described later.

  In the general formula (1) or the tautomer of the general formula (1), the ring represented by R11 is preferably an aromatic heterocyclic ring. When a 5-membered heterocyclic ring as contained as a partial structure of the general formula (1) of the present invention is contained in the molecule, an aromatic ring (corresponding to Z11 in the present invention) linked to it is In the case of an aromatic heterocyclic ring, the stability of the molecule is improved and the emission wavelength becomes shorter.

In the general formula (1) or a tautomer of the general formula (1), examples of the substituent represented by R ₁₁ , R ₁₂ , and R ₁₃ include an alkyl group (for example, methyl group, ethyl group, isopropyl Group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.) , Aromatic hydrocarbon groups (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic groups (for example, furyl group) , Thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl Group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (Diazacarbazolyl group is any one of the carbon atoms constituting the carboline ring of the carbolinyl group replaced by a nitrogen atom. ), Phthalazinyl group etc.), alkoxyl group (eg ethoxy group, isopropoxy group, butoxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), cyano group, hydroxyl group, Examples include alkenyl groups (for example, vinyl group), styryl groups, halogen atoms (for example, chlorine atom, bromine atom, iodine atom, fluorine atom). These groups may be further substituted.

Among these, in the present invention, at least one of the groups represented by R ₁₁ , R ₁₂ and R ₁₃ is preferably the aromatic hydrocarbon group or the aromatic heterocyclic group.

In the general formula (1) or the tautomer of the general formula (1), M ₁₁ represents a group 8 to group 10 metal (a metal atom or an ion) in the periodic table of elements, and preferably used among them. Platinum (Pt) and iridium (Ir) are used. In the metal complex having the general formula (1) or an alternate isomer of the general formula (1) as a partial structure, M ₁₁ may be a metal or an ion.

In the present invention, a coordinate bond is formed between the above general formula (1) or a tautomer of the general formula (1) and a central metal (metal or ion) represented by M ₁₁ (complex formation). A metal complex is formed.

<< General Formula (2) or Tautomer of General Formula (2) >>
In the tautomer of the general formula (2) or the general formula (2), the aromatic hydrocarbon ring represented by Z21 is the general formula (1) or the tautomer of the general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by Z11.

  In the tautomer of the general formula (2) or the general formula (2), the aromatic heterocycle represented by Z21 is represented by Z11 in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic heterocyclic ring represented by these.

In the tautomer of the general formula (2) or the general formula (2), each of the substituents represented by R ₂₁ , R ₂₂ and R ₂₃ is represented by the general formula (1) or the general formula (1). In the tautomer, it is synonymous with the substituent represented by each of R ₁₁ , R ₁₂ and R ₁₃ .

In the tautomer of the general formula (2) or the general formula (2), the metal of group 8 to group 10 (which may be an ion) in the periodic table represented by M ₂₁ is represented by the general formula (1) or in tautomers general formula (1), represented by M _11, the same meaning as metal group 8-10 of the periodic table.

<< General Formula (3) or Tautomer of General Formula (3) >>
In the tautomer of the general formula (3) or the general formula (3), the aromatic hydrocarbon ring represented by Z31 is the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by Z11.

  In the tautomer of the general formula (3) or the general formula (3), the aromatic heterocycle represented by Z31 is represented by Z11 in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic heterocyclic ring represented by these.

In the general formula (3) or a tautomer of the general formula (3), a substituent represented by R ₃ of —N (R ₃ ) — represented by X ₃₁ , X ₃₂ , or X ₃₃ , respectively, In the general formula (1) or the tautomer of the general formula (1), it is synonymous with the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ .

In the tautomer of the general formula (3) or the general formula (3), the metal of group 8 to group 10 (which may be an ion) in the periodic table of elements represented by M ₃₁ is represented by the general formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

In the general formula (3) or a tautomer of the general formula (3), X ₃₁ is a carbon atom which may have a substituent, and X ₃₂ and X ₃₃ are a nitrogen atom or —N (R ₃ ). -(Wherein R ₃ represents a hydrogen atom or a substituent). Thereby, the emission wavelength becomes shorter and the ease of synthesis is improved.

<< General Formula (4) or Tautomer of General Formula (4) >>
In the tautomer of the general formula (4) or the general formula (4), the aromatic heterocycle represented by Z41 is represented by Z11 in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic heterocyclic ring represented by these.

In the general formula (4) or a tautomer of the general formula (4), a substituent represented by R ₄ of —N (R ₄ ) — represented by X ₄₁ and X ₄₂ is represented by the general formula ( In the tautomer of 1) or the general formula (1), it is synonymous with the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ .

In the general formula (4) or a tautomer of the general formula (4), a metal of group 8 to group 10 (which may be an ion) represented by M ₄₁ in the periodic table of elements is represented by the formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

<< General Formula (5) or Tautomer of General Formula (5) >>
In the tautomer of the general formula (5) or the general formula (5), the aromatic hydrocarbon ring represented by Z51 is the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by Z11.

  In the tautomer of the general formula (5) or the general formula (5), the aromatic heterocycle represented by Z51 is Z11 in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic heterocyclic ring represented by these.

In the general formula (5) or the tautomer of the general formula (5), the substituents represented by R ₅₁ and R ₅₂ are the general formula (1) or the tautomer of the general formula (1). Are the same as the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ .

In the general formula (5) or a tautomer of the general formula (5), a metal of group 8 to group 10 (which may be an ion) in the periodic table represented by M ₅₁ is represented by the formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

In the general formula (5) or a tautomer of the general formula (5), X ₅₁ is preferably a sulfur atom. In general, it is known that oxazole derivatives are susceptible to intramolecular ring opening and are unstable. In the general formula (5) of the present invention, although it is greatly improved, the molecule is more stable when it is a thiazole derivative.

<< General Formula (6) or Tautomer of General Formula (6) >>
In the tautomer of the general formula (6) or the general formula (6), the aromatic hydrocarbon ring represented by Z61 is the general formula (1) or the tautomer of the general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by Z11.

  In the general formula (6) or the tautomer of the general formula (6), the aromatic heterocycle represented by Z61 is the same as that of the general formula (1) or the tautomer of the general formula (1). It is synonymous with the aromatic heterocyclic ring represented by these.

In the general formula (6) or a tautomer of the general formula (6), a metal of group 8 to group 10 (which may be an ion) in the periodic table of elements represented by M ₆₁ is represented by the formula (1) or in tautomers general formula (1), represented by M _11, it is synonymous with the metal of group 8-10 of the periodic table.

In the general formula (6) or the tautomer of the general formula (6), it is preferable that at least one of X ₆₁ and X ₆₃ is a nitrogen atom. Thereby, the emission wavelength becomes shorter and the ease of synthesis is improved.

  Hereinafter, specific examples of the metal complex according to the present invention having the partial structures of the tautomers of the general formulas (1) to (6) or the general formulas (1) to (6) will be described. The invention is not limited to these.

1-27

  The metal complex according to the organic EL device material of the present invention is described in, for example, Organic Letter, vol. 16, p 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. MoI. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, pages 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, pages 3055-3066 (2002) , New Journal of Chemistry. 26, page 1171 (2002), and further by applying a method such as a reference described in these documents.

<< Application of organic EL element material containing metal complex to organic EL element >>
When producing an organic EL element using the organic EL element material of the present invention, it is preferably used for a light emitting layer or a hole blocking layer in the constituent layers (details will be described later) of the organic EL element. Moreover, in a light emitting layer, it is preferably used as a light emitting dopant.

(Light emitting host and light emitting dopant)
The mixing ratio of the light-emitting dopant to the light-emitting host, which is the host compound as the main component in the light-emitting layer, is preferably adjusted to a range of 0.1% by mass to less than 30% by mass.

  However, the light-emitting dopant may be a mixture of a plurality of types of compounds, and the partner to be mixed may be another metal complex having a different structure, or a phosphorescent dopant or a fluorescent dopant having another structure.

  Here, the dopant (phosphorescent dopant, fluorescent dopant, etc.) that may be used in combination with the metal complex used as the luminescent dopant will be described.

  The light-emitting dopant is roughly classified into two types: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

  Representative examples of the former (fluorescent dopant) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, Examples include perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Typical examples of the latter (phosphorescent dopant) are preferably complex compounds containing metals of Groups 8, 9, and 10 in the periodic table of elements, more preferably iridium compounds and osmium compounds. Of these, iridium compounds are most preferred.

  Specifically, it is a compound described in the following patent publications.

  WO 00/70655 pamphlet, JP 2002-280178, JP 2001-181616, JP 2002-280179, JP 2001-181617, JP 2002-280180, JP 2001-247859, JP 2002-299060, JP 2001-313178, JP 2002-302671, JP 2001-345183, JP 2002-324679, International Publication No. 02/15645 pamphlet, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-2002 A. No. 117978, JP 20 JP-A-2-338588, JP-A-2002-170684, JP-A-2002-352960, WO01 / 93642, JP-A-2002-50483, JP-A-2002-1000047, JP-A-2002. No. -173744, JP-A No. 2002-359082, JP-A No. 2002-175484, JP-A No. 2002-363552, JP-A No. 2002-184582, JP-A No. 2003-7469, JP 2002-525808 A. Gazette, JP2003-7471, JP2002-525833, JP2003-31366, JP2002-226495, JP2002-234894, JP2002-2335076 JP 2002-241751 A JP 2001-319779, JP 2001-319780, JP 2002-62824, JP 2002-1000047, JP 2002-203679, JP 2002-343572, JP 2002-203678 gazette etc.

  Some examples are shown below.

(Light emitting host)
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more compounds. For other compounds, “dopant compound ( Simply referred to as a dopant). " For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, if a light emitting layer is comprised from 3 types of compound A, compound B, and compound C, and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, Compound C is a host compound.

  The light-emitting host used in the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, an oligo Those having a basic skeleton such as an arylene compound, or a carboline derivative or diazacarbazole derivative (herein, a diazacarbazole derivative is a nitrogen atom in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is a nitrogen atom) And the like.) And the like.

  Of these, carboline derivatives, diazacarbazole derivatives and the like are preferably used.

  Specific examples of carboline derivatives, diazacarbazole derivatives and the like are given below, but the present invention is not limited thereto. These compounds may be used as hole blocking materials.

  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 (evaporation polymerizable light emitting host). .

  As the light-emitting host, a compound having a hole transporting ability and an electron transporting ability and preventing a long wavelength of light emission and having a high Tg (glass transition temperature) is preferable.

  As specific examples of the light-emitting host, compounds described in the following documents are suitable. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Next, a configuration of a typical organic EL element will be described.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described.

Although the preferable specific example of the layer structure of the organic EL element of this invention is shown below, this invention is not limited to these. (I) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode (ii) Anode / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode (iii) anode / Hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode (iv) anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode ( v) Anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode / anode buffer layer / hole transport layer / electron blocking layer / light emitting layer / Hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode buffer layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode 《Blocking layer (electron blocking layer, hole blocking layer)》
The blocking layer (for example, electron blocking layer, hole blocking layer) according to the present invention will be described.

  In the present invention, it is preferable to use the organic EL element material of the present invention for the hole blocking layer, the electron blocking layer, etc., and particularly preferably for the hole blocking layer.

  When the organic EL element material of the present invention is contained in a hole blocking layer or an electron blocking layer, the metal complex according to any one of claims 1 to 17 is converted into a hole blocking layer or an electron. It may be contained in a state of 100% by mass as a layer constituent component such as a blocking layer, or may be mixed with other organic compounds (for example, a compound used for a constituent layer of the organic EL device of the present invention). .

  The thickness of the blocking layer according to the present invention is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.

《Hole blocking layer》
The hole blocking layer has the function of an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons but has a very small ability to transport holes, and blocks holes while transporting electrons. Thus, the probability of recombination of electrons and holes can be improved.

  Examples of the hole blocking layer include those disclosed in JP-A-11-204258, JP-A-11-204359, and “Organic EL device and its forefront of industrialization (issued by NTS, Inc. on November 30, 1998)”. The hole blocking (hole block) layer described in page 237 and the like can be applied as the hole blocking layer according to the present invention. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

《Electron blocking layer》
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.

  In the present invention, the organic EL element material of the present invention is preferably used for the adjacent layer adjacent to the light emitting layer, that is, the hole blocking layer and the electron blocking layer, and particularly used for the hole blocking layer. Is preferred.

《Hole transport layer》
The hole transport layer includes a 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 is not particularly limited, and is conventionally used as a hole charge injection / transport material in an optical transmission material or a well-known material used for a hole injection layer or a hole transport layer of an EL element. Any one can be selected and used.

  The hole transport material has 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, stilbenes Derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers, and the like can be given.

  As the hole transport material, those described above can be used, 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-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type (MTDATA).

  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. The hole transport material preferably has a high Tg.

  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, an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, it is about 5 nm-5000 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

《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 multiple layers.

  Conventionally, in the case of a single-layer electron transport layer and a plurality of layers, the following materials are used as the electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the cathode side with respect to the light emitting layer. Are known.

  Further, the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material can be selected from conventionally known compounds. .

  Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimides, Examples include fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, and oxadiazole derivatives. Furthermore, in the above 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.

  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, 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), etc., and the central metals of these metal complexes are In, Mg, Cu Metal complexes replaced with Ca, Sn, Ga, or Pb can also be used as electron transport materials. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and similarly to the hole injection layer and the hole transport layer, inorganic such as n-type-Si and n-type-SiC. A semiconductor can also be used as an electron transport material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, it is about 5-5000 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Next, an injection layer used as a constituent layer of the organic EL element of the present invention will be described.

<< Injection layer >>: Electron injection layer, hole injection layer The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, between the anode and the light emitting layer or the hole transport layer, and You may exist between a cathode, a light emitting layer, or an electron carrying layer.

  An injection layer is a layer provided between an electrode and an organic layer in order to lower drive voltage or improve light emission luminance. “Organic EL element and its forefront of industrialization (issued on November 30, 1998 by NTS Corporation) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, 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. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  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 or aluminum Metal buffer layer represented by lithium fluoride, alkali metal compound buffer layer represented by lithium fluoride, alkaline earth metal compound buffer layer represented by magnesium fluoride, oxide buffer layer represented by aluminum oxide, etc. It is done.

  The buffer layer (injection layer) is preferably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 100 nm.

  This injection layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an injection | pouring layer, Usually, it is about 5-5000 nm. This injection layer may have a single layer structure composed of one or more of the above materials.

"anode"
As the anode according to the organic EL device of the present invention, an electrode having a work function (4 eV or more) metal, alloy, electrically conductive compound and a mixture thereof as an electrode material 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, a thin film may be formed by depositing these electrode materials 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 the pattern accuracy is not required (100 μm or more) Degree), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance is 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.

"cathode"
On the other hand, as the cathode according to the present invention, a cathode 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 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, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, such as a magnesium / silver mixture, magnesium, from the viewpoint of electron injectability and durability against oxidation, etc. / 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 the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 1000 nm, preferably 50 nm to 200 nm. In order to transmit 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.

<< Substrate (also referred to as substrate, substrate, support, etc.) >>
The substrate of the organic EL device of the present invention is not particularly limited to the type of glass, plastic, etc., and is not particularly limited as long as it is transparent. Examples of substrates that are preferably used include glass, quartz, A light transmissive resin film can be mentioned. A particularly preferable substrate is a resin film that can give flexibility to the organic EL element.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate. Examples thereof include films made of (TAC), cellulose acetate propionate (CAP) and the like.

An inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film, and the film should be a high barrier film having a water vapor transmission rate of 0.01 g / m ² · day · atm or less. preferable.

  The external extraction efficiency at room temperature for light emission of the organic electroluminescence device of the present invention is preferably 1% or more, more preferably 2% 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.

  Further, a hue improving filter such as a color filter may be used in combination.

  When used in lighting applications, a film (such as an antiglare film) that has been roughened to reduce unevenness in light emission can be used in combination.

  When used as a multicolor display device, it is composed of organic EL elements having at least two different light emission maximum wavelengths. A suitable example for producing an organic EL element will be described.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode. Will be described.

  First, a thin film made of a desired electrode material, for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode. To do. 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, or an electron transport layer, which is an element material, is formed thereon.

As described above, there are spin coating method, casting method, ink jet method, vapor deposition method, printing method and the like as a method for thinning the thin film containing the organic compound, but it is easy to obtain a uniform film and has pinholes. From the viewpoint of difficulty in formation, vacuum deposition or spin coating is particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 ° C. to 450 ° C., a vacuum degree of 10 ⁻⁶ Pa to 10 ⁻² Pa, and a vapor deposition rate of 0 It is desirable to select appropriately within a range of 0.01 nm to 50 nm / second, a substrate temperature of −50 ° C. to 300 ° C., and a thickness of 0.1 nm to 5 μm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 nm to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained. The organic EL element is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

<Display device>
The display device of the present invention will be described.

  The display device of the present invention may be single color or multicolor, but here, the multicolor display device will be described. 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 a vapor deposition method, a casting method, a spin coating method, an ink jet method, a printing method, or the like.

  When patterning is performed only on the light emitting layer, the method is not limited. However, a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.

  Moreover, it is also possible to reverse the production order to produce the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, and the anode in this 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 to 40 V 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, or various light emission sources. In a display device or a 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. For example, but not limited to.

《Lighting device》
The lighting device of the present invention will be described.

  The organic EL element of the present invention may be used as an organic EL element having a resonator structure. The use of the organic EL element having such a resonator structure is as a light source for an optical storage medium, an electrophotographic copying machine, and the like. Light sources, optical communication processor light sources, optical sensor light sources, and the like. 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 type for directly viewing a still image or a moving image. It may be used as a display device (display). When used as a display device for reproducing moving images, the driving method 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.

  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 diagram illustrating an example of a display device including 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 the plurality of pixels based on image information from the outside. The pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display 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 drawing, the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning lines 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 lattice shape and are connected to the pixels 3 at the orthogonal positions (details are shown in FIG. Not shown).

  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 that emit light 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 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 organic EL element 10 emits light by the switching transistor 11 and the driving transistor 12 that are active elements for the organic EL elements 10 of the plurality of pixels, and the organic EL elements 10 of the plurality of pixels 3 emit light. 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 on / off of a predetermined light emission amount by a binary image data signal. But you can.

  The potential of the capacitor 13 may be held continuously 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 view 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.

  The organic EL material according to the present invention can also be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. As a combination of a plurality of luminescent colors, those containing three luminescence maximum wavelengths of three primary colors of blue, green, and blue may be used. 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 includes a combination of a plurality of phosphorescent or fluorescent materials (light emitting dopants), a light emitting material that emits fluorescent or phosphorescent light, and the light emission. Any combination of a dye material that emits light from the material as excitation light may be used, but in the white organic electroluminescence device according to the present invention, a method of combining a plurality of light-emitting dopants is preferable.

  As a layer structure of an organic electroluminescence device for obtaining a plurality of emission colors, a method of having a plurality of emission dopants in one emission layer, a plurality of emission layers, and an emission wavelength in each emission layer And a method of forming minute pixels emitting light having different wavelengths in a matrix.

  In the white organic electroluminescence device according to the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like at the time of film formation, if necessary. When patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire element layer may be patterned.

  The light emitting material used for the light emitting layer is not particularly limited. For example, in the case of a backlight in a liquid crystal display element, the platinum complex according to the present invention is known so as to be suitable for the wavelength range corresponding to the CF (color filter) characteristics. Any one of the light emitting materials may be selected and combined to be whitened.

  Thus, in addition to the display device and display, the white light-emitting organic EL element of the present invention can be used as various light sources, lighting devices, household lighting, interior lighting, and a kind of lamp such as an exposure light source. It is also useful for display devices such as backlights for liquid crystal display devices.

  Others such as backlights for watches, signboard 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. There are a wide range of uses such as household appliances.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Moreover, the compound used for an Example is shown below.

Example 1
<< Production of Organic EL Element OLED1-1 >>
After patterning on a substrate (made by NH Techno Glass Co., Ltd .: NA-45) having a 150 nm ITO film formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with iso-propyl alcohol. Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. The transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while α-NPD, CBP, Ir-12, BCP, and Alq ₃ are placed in five tantalum resistance heating boats, respectively. It was attached to the (first vacuum chamber).

  Further, lithium fluoride was placed in a resistance heating boat made of tantalum, and aluminum was placed in a resistance heating boat made of tungsten, and attached to the second vacuum tank of the vacuum evaporation apparatus.

First, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD is energized and heated, and transparent at a deposition rate of 0.1 nm / second to 0.2 nm / second. It vapor-deposited so that it might become a film thickness of 25 nm on the support substrate, and provided the positive hole injection / transport layer.

  Further, the heating boat containing CBP and the boat containing Ir-12 are energized independently to adjust the deposition rate of CBP as a light emitting host and Ir-12 as a light emitting dopant to 100: 7. A light emitting layer was provided by vapor deposition so as to have a thickness of 30 nm.

Then, the heating boat containing BCP was energized and heated to provide a 10 nm thick hole blocking layer at a deposition rate of 0.1 m / sec to 0.2 nm / sec. Further, the heating boat containing Alq ₃ was heated by energization to provide an electron transport layer having a film thickness of 40 nm at a deposition rate of 0.1 nm / second to 0.2 nm / second.

  Next, after the element formed up to the electron transport layer as described above is transferred to the second vacuum chamber in a vacuum state, a stainless steel rectangular perforated mask is disposed on the electron transport layer from the outside of the apparatus. Installed with remote control.

After reducing the pressure in the second vacuum chamber to 2 × 10 ⁻⁴ Pa, a cathode buffer layer having a film thickness of 0.5 nm was formed at a deposition rate of 0.01 nm / second to 0.02 nm / second by energizing a boat containing lithium fluoride. Then, a boat containing aluminum was energized to attach a cathode having a film thickness of 150 nm at a deposition rate of 1 nm / second to 2 nm / second. Further, the organic EL element was transferred to a glove box under nitrogen atmosphere (a glove box substituted with high-purity nitrogen gas with a purity of 99.999% or more) without being brought into contact with the atmosphere, and the interior as shown in FIG. An organic EL element OLED1-1 was produced with a substituted sealing structure.

  In addition, barium oxide 105 which is a water trapping agent is a glass-sealed can 104 made of high-purity barium oxide powder manufactured by Aldrich with a fluororesin-based semipermeable membrane (Microtex S-NTF8031Q made by Nitto Denko) with an adhesive. The material pasted on was prepared and used in advance. An ultraviolet curable adhesive 107 was used for bonding the sealing can and the organic EL element, and both were bonded to each other by irradiation with an ultraviolet lamp to produce a sealing element.

  In FIG. 5, 101 is a glass substrate provided with a transparent electrode, 102 is an organic EL layer composed of the hole injection / transport layer, light emitting layer, hole blocking layer, electron transport layer, and the like, and 103 is a cathode.

<< Production of Organic EL Elements OLED1-2 to 1-24 >>
In preparation of said organic EL element OLED1-1, as described in Table 1, except having changed each of the light emission host, the light emission dopant, and the hole blocking material, it is the same, and organic EL element OLED1-2-1- 24 was produced.

  The following evaluation was performed about obtained organic EL element OLED1-1 to 1-24.

<< External quantum efficiency >>
The organic EL elements OLED1-1 to 1-24 are turned on at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and light emission luminance (L) [cd / m immediately after the start of lighting] ² ] was measured to calculate the external extraction quantum efficiency (η). Here, CS-1000 (manufactured by Minolta) was used for measurement of light emission luminance.

  The external extraction quantum efficiency was expressed as a relative value when the organic EL element OLED1-1 was set to 100.

<Luminescent life>
At room temperature the organic EL element OLED1-1～1-24, performs continuous lighting by constant current condition of 2.5 mA / cm ^2, the time required to becomes half of the initial luminance (τ _1/2) It was measured. Moreover, the light emission lifetime was represented by the relative value when the organic EL element OLED1-1 was set to 100.

  The obtained results are shown in Table 1.

From Table 1, the organic EL element OLED1-4~1-24 compared to the organic EL element OLED1-1～1-3, high luminous efficiency, it is clear that the lifetime of the emission lifetime can be achieved.

  Furthermore, by using a carboline derivative or a derivative having a ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom in the light emitting layer, the carboline derivative Alternatively, a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom is used for the hole blocking layer. The improvement of the effect was seen.

Example 2
<< Production of Organic EL Element OLED2-1 >>
After patterning on a substrate (made by NH Techno Glass Co., Ltd .: NA-45) having a 150 nm ITO film formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with iso-propyl alcohol. Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

The transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while α-NPD, CBP, Ir-12, BCP, and Alq ₃ are placed in five tantalum resistance heating boats, respectively. It was attached to the (first vacuum chamber).

  Further, lithium fluoride was placed in a resistance heating boat made of tantalum, and aluminum was placed in a resistance heating boat made of tungsten, and attached to the second vacuum tank of the vacuum evaporation apparatus.

First, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD is energized and heated, and transparent at a deposition rate of 0.1 nm / second to 0.2 nm / second. It vapor-deposited so that it might become a film thickness of 30 nm on the support substrate, and provided the positive hole injection / transport layer.

  Further, the heating boat containing CBP and the boat containing Ir-12 are energized independently to adjust the deposition rate of CBP as a light emitting host and Ir-12 as a light emitting dopant to 100: 7. A light emitting layer was provided by vapor deposition so as to have a thickness of 30 nm.

Then, the heating boat containing BCP was energized and heated to provide a 10 nm thick hole blocking layer at a deposition rate of 0.1 nm / sec to 0.2 nm / sec. Further, the heating boat containing Alq ₃ was heated by energization to provide an electron transport layer having a film thickness of 30 nm at a deposition rate of 0.1 nm / second to 0.2 nm / second.

  Next, after the element formed up to the electron transport layer as described above is transferred to the second vacuum chamber in a vacuum state, a stainless steel rectangular perforated mask is disposed on the electron transport layer from the outside of the apparatus. Installed with remote control.

After reducing the pressure in the second vacuum chamber to 2 × 10 ⁻⁴ Pa, a cathode buffer layer having a film thickness of 0.5 nm was formed at a deposition rate of 0.01 nm / second to 0.02 nm / second by energizing a boat containing lithium fluoride. Then, a boat containing aluminum was energized to attach a cathode having a film thickness of 150 nm at a deposition rate of 1 to 2 nm / second. Further, the organic EL element was transferred to a glove box under nitrogen atmosphere (a glove box substituted with high-purity nitrogen gas with a purity of 99.999% or more) without being brought into contact with the atmosphere, and the interior as shown in FIG. An organic EL element OLED1-1 was produced with a substituted sealing structure. In addition, barium oxide 105 which is a water trapping agent is a glass-sealed can 104 made of high-purity barium oxide powder manufactured by Aldrich with a fluororesin-based semipermeable membrane (Microtex S-NTF8031Q made by Nitto Denko) with an adhesive. The material pasted on was prepared and used in advance. An ultraviolet curable adhesive 107 was used for bonding the sealing can and the organic EL element, and both were bonded to each other by irradiation with an ultraviolet lamp to produce a sealing element. In FIG. 5, 101 is a glass substrate provided with a transparent electrode, 102 is an organic EL layer composed of the hole injection / transport layer, light emitting layer, hole blocking layer, electron transport layer, and the like, and 103 is a cathode.

<< Production of Organic EL Elements OLED2-2 to 2-19 >>
In preparation of said organic EL element OLED2-1, as described in Table 1, except having changed each of the light emission host, the light emission dopant, and the hole-blocking material, it is the same, and organic EL element OLED2-2-2-2 19 was produced.

  About the obtained organic EL element OLED2-1 to 2-19, it evaluated by the method similar to Example 1 about external extraction quantum efficiency.

<Luminescent life>
At room temperature the organic EL element OLED2-1~2-19, 2.5mA / cm ² of make continuous lighting by constant current conditions, the time required to become 90% of the initial luminance (τ _1/9) Was measured. The external extraction quantum efficiency was expressed as a relative value when the organic EL element OLED2-1 was 100, and the emission lifetime was expressed as a relative value when the organic EL element OLED2-1 was 100.

  The obtained results are shown in Table 2.

From Table 2, the organic EL element OLED2-4~2-19 compared to the organic EL element OLED2-1～2-3, high luminous efficiency, it is clear that the lifetime of the emission lifetime can be achieved.

  Furthermore, by using a carboline derivative or a derivative having a ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom in the light emitting layer, the carboline derivative Alternatively, a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom is used for the hole blocking layer. The improvement of the effect was seen.

Example 3
<< Preparation of organic EL element OLED3-1 >>
After patterning on a substrate (made by NH Techno Glass Co., Ltd .: NA-45) having a 150 nm ITO film formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with iso-propyl alcohol. Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

The transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while m-MTDATXA, H1, Ir-12, BCP, and Alq ₃ are placed in five tantalum resistance heating boats, respectively. It was attached to the (first vacuum chamber).

  Further, lithium fluoride was placed in a resistance heating boat made of tantalum, and aluminum was placed in a resistance heating boat made of tungsten, and attached to the second vacuum tank of the vacuum evaporation apparatus.

First, after reducing the pressure of the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing m-MTDATXA was energized and heated, and transparent at a deposition rate of 0.1 nm / sec to 0.2 nm / sec. It vapor-deposited so that it might become a film thickness of 40 nm in the support substrate, and provided the positive hole injection / transport layer.

  Further, the heating boat containing H1 and the boat containing Ir-12 are energized independently to adjust the deposition rate of H1 as a light emitting host and Ir-12 as a light emitting dopant to 100: 7. A light emitting layer was provided by vapor deposition so as to have a thickness of 30 nm.

Subsequently, the heating boat containing BCP was energized and heated to provide a hole blocking layer having a thickness of 10 nm at a deposition rate of 0.1 to 0.2 nm / second. Further, the heating boat containing Alq ₃ was heated by energization to provide an electron transport layer having a film thickness of 20 nm at a deposition rate of 0.1 nm / second to 0.2 nm / second.

  Next, after the element formed up to the electron transport layer as described above is transferred to the second vacuum chamber in a vacuum state, a stainless steel rectangular perforated mask is disposed on the electron transport layer from the outside of the apparatus. Installed with remote control.

After reducing the pressure in the second vacuum chamber to 2 × 10 ⁻⁴ Pa, a cathode buffer layer having a film thickness of 0.5 nm was formed at a deposition rate of 0.01 nm / second to 0.02 nm / second by energizing a boat containing lithium fluoride. Then, a boat containing aluminum was energized to attach a cathode having a film thickness of 150 nm at a deposition rate of 1 nm / second to 2 nm / second. Further, the organic EL element was transferred to a glove box under nitrogen atmosphere (a glove box substituted with high-purity nitrogen gas with a purity of 99.999% or more) without being brought into contact with the atmosphere, and the interior as shown in FIG. An organic EL element OLED3-1 was produced with a substituted sealing structure. In addition, barium oxide 105 which is a water trapping agent is a glass-sealed can 104 made of high-purity barium oxide powder manufactured by Aldrich with a fluororesin-based semipermeable membrane (Microtex S-NTF8031Q made by Nitto Denko) with an adhesive. The material pasted on was prepared and used in advance. An ultraviolet curable adhesive 107 was used for bonding the sealing can and the organic EL element, and both were bonded to each other by irradiation with an ultraviolet lamp to produce a sealing element. In FIG. 5, 101 is a glass substrate provided with a transparent electrode, 102 is an organic EL layer composed of the hole injection / transport layer, light emitting layer, hole blocking layer, electron transport layer, and the like, and 103 is a cathode.

<< Preparation of Organic EL Element OLED3-2-3-23 >>
In the production of the organic EL element OLED3-1, as described in Table 3, the organic EL elements OLED3-2 to 3- 23 was produced.

  About the obtained organic EL element OLED3-1 to 3-23, it evaluated by the method similar to Example 1 about external extraction quantum efficiency.

《Voltage increase》
The organic EL elements OLED3-1 to 3-23 are continuously lit under a constant current condition of 25 ° C. and 2.5 mA / cm ² , and the initial drive voltage is the drive voltage when the brightness becomes half the initial brightness. The rise from was measured.

  Note that the external extraction quantum efficiency and voltage increase are expressed as relative values when the organic EL element OLED3-1 is set to 100.

  The obtained results are shown in Table 3.

From Table 3, the organic EL element OLED3-4~3-23 compared to the organic EL element 31 to 33, a high emission efficiency, it is clear that the low voltage rise can be achieved.

  Furthermore, by using a carboline derivative or a derivative having a ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom in the light emitting layer, the carboline derivative Alternatively, a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom is used for the hole blocking layer. The improvement of the effect was seen.

Example 4
<< Preparation of organic EL element OLED4-1 >>
An organic EL device was prepared in the same manner as in Example 3 except that the vapor deposition rate of H1 as a light emission host and Ir-12 as a light emission dopant was changed from 100: 7 to 100: 4 in the production of the light emitting layer in Example 3. OLED4-1 was created.

<< Production of Organic EL Elements OLED4-2 to 4-19 >>
In preparation of said organic EL element OLED4-1, as described in Table 4, except having changed each of the light emission host, the light emission dopant, and the hole-blocking material, it is the same, and organic EL element OLED4-2-4-4- 11 was produced.

  The following evaluation was performed about obtained organic EL element OLED4-1 to 4-19.

<< External quantum efficiency >>
The organic EL elements OLED4-1 to 4-19 are turned on at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and light emission luminance (L) [cd / m immediately after the start of lighting] ² ] was measured to calculate the external extraction quantum efficiency (η). Here, CS-1000 (manufactured by Minolta) was used for measurement of light emission luminance. The external extraction quantum efficiency was expressed as a relative value when the organic EL element OLED4-1 was set to 100.

<Luminescent life>
At room temperature the organic EL element OLED4-1～4-19, performs continuous lighting by constant current condition of 2.5 mA / cm ^2, the time required to becomes half of the initial luminance (τ _1/2) It was measured. Moreover, the light emission lifetime was represented by the relative value by setting the organic EL element OLED4-1 to 100.

  Table 4 shows the obtained results.

From Table 4, the organic EL element OLED4-4~4-19 compared to the organic EL element OLED4-1～4-3, high luminous efficiency, it is clear that the lifetime of the emission lifetime can be achieved. Furthermore, by using a carboline derivative or a derivative having a ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom in the light emitting layer, the carboline derivative Alternatively, a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom is used for the hole blocking layer. The improvement of the effect was seen.

Example 5
<< Production of Organic EL Element OLED5-1 >>
After patterning on a substrate (made by NH Techno Glass Co., Ltd .: NA-45) having a 150 nm ITO film formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with iso-propyl alcohol. Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

The transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while m-MTDATXA, H1, Ir-12, BCP, and Alq ₃ are placed in five tantalum resistance heating boats, respectively. It was attached to the (first vacuum chamber).

  Further, lithium fluoride was placed in a resistance heating boat made of tantalum, and aluminum was placed in a resistance heating boat made of tungsten, and attached to the second vacuum tank of the vacuum evaporation apparatus.

First, after reducing the pressure of the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing m-MTDATXA was energized and heated, and transparent at a deposition rate of 0.1 nm / sec to 0.2 nm / sec. It vapor-deposited so that it might become a film thickness of 30 nm on the support substrate, and provided the positive hole injection / transport layer.

  Further, the heating boat containing H1 and the boat containing Ir-12 are energized independently to adjust the deposition rate of H1 as a light emitting host and Ir-12 as a light emitting dopant to 100: 7. A light emitting layer was provided by vapor deposition so as to have a thickness of 30 nm.

Then, the heating boat containing BCP was energized and heated to provide a 10 nm thick hole blocking layer at a deposition rate of 0.1 nm / sec to 0.2 nm / sec. Further, the heating boat containing Alq ₃ was heated by energizing to provide an electron transport layer having a film thickness of 30 nm at a deposition rate of 0.1 nm / second to 0.2 nm / second.

  Next, after the element formed up to the electron transport layer as described above is transferred to the second vacuum chamber in a vacuum state, a stainless steel rectangular perforated mask is disposed on the electron transport layer from the outside of the apparatus. Installed with remote control.

After reducing the pressure in the second vacuum chamber to 2 × 10 ⁻⁴ Pa, a cathode buffer layer having a film thickness of 0.5 nm was formed at a deposition rate of 0.01 nm / second to 0.02 nm / second by energizing a boat containing lithium fluoride. Next, a boat containing aluminum was energized to attach a cathode having a film thickness of 150 nm at a deposition rate of 1 nm / second to 2 nm / second. Further, the organic EL element was transferred to a glove box under nitrogen atmosphere (a glove box substituted with high-purity nitrogen gas with a purity of 99.999% or more) without being brought into contact with the atmosphere, and the interior as shown in FIG. An organic EL element OLED1-1 was produced with a substituted sealing structure.

  In addition, barium oxide 105 which is a water catching agent is a glass sealed can 104 made of high-purity barium oxide powder manufactured by Aldrich with a fluororesin semi-permeable membrane (Microtex S-NTF8031Q manufactured by Nitto Denko) with an adhesive. The material pasted on was prepared and used in advance. An ultraviolet curable adhesive 107 was used for bonding the sealing can and the organic EL element, and both were bonded to each other by irradiation with an ultraviolet lamp to produce a sealing element. In FIG. 5, 101 is a glass substrate provided with a transparent electrode, 102 is an organic EL layer composed of the hole injection / transport layer, light emitting layer, hole blocking layer, electron transport layer, and the like, and 103 is a cathode.

<< Production of Organic EL Elements OLED5-2 to 5-25 >>
In preparation of said organic EL element OLED5-1, as described in Table 5, except having changed each of the light emission host, the light emission dopant, and the hole-blocking material, it is the same, and organic EL element OLED5-2-5-5 25 was produced.

  About the obtained organic EL element OLED5-1 to 5-25, it evaluated by the method similar to Example 1 about external extraction quantum efficiency.

<Luminescent life>
At room temperature the organic EL element OLED5-1~5-25, 2.5mA / cm ² of make continuous lighting by constant current conditions, the time required to become 90% of the initial luminance (τ _1/9) Was measured. The external extraction quantum efficiency was expressed as a relative value when the organic EL element OLED5-1 was set to 100, and the emission lifetime was expressed as a relative value when the organic EL element OLED5-1 was set as 100.

  The results obtained are shown in Table 5.

Table 5, the organic EL element OLED5-4~5-25 compared to the organic EL element OLED5-1～5-3, high luminous efficiency, it is clear that the lifetime of the emission lifetime can be achieved. Furthermore, by using a carboline derivative or a derivative having a ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom in the light emitting layer, the carboline derivative Alternatively, a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom is used for the hole blocking layer. The improvement of the effect was seen.

Example 6
<< Production of Organic EL Element OLED6-1 >>
In the production of the organic EL element 3-1 of Example 3, the same thing except that the vapor deposition rate of H1 as the light emitting host and Ir-12 as the light emitting dopant was changed from 100: 7 to 100: 5 at the time of forming the light emitting layer. Thus, an organic EL element OLED6-1 was produced.

<< Production of Organic EL Elements OLED6-2 to 6-20 >>
In preparation of said organic EL element OLED6-1, as described in Table 6, except having changed each of the light emission host, the light emission dopant, and the hole blocking material, it is the same, and organic EL element OLED6-2-6-6 20 was produced. About the obtained organic EL element OLED6-1 to 6-20, it evaluated by the method similar to Example 1 about external extraction quantum efficiency.

《Voltage increase》
The organic EL elements OLED6-1 to 6-20 are continuously lit under a constant current condition of 25 ° C. and 2.5 mA / cm ² , and the initial driving voltage of the driving voltage when the luminance becomes half of the initial luminance is obtained. The rise from was measured.

  The external extraction quantum efficiency and the voltage increase are expressed as relative values when the organic EL element OLED6-1 is 100.

From Table 6, the organic EL element OLED6-4~6-20 compared to the organic EL element OLED6-1～6-3, high luminous efficiency, it is clear that the low voltage rise can be achieved. Furthermore, by using a carboline derivative or a derivative having a ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom in the light emitting layer, the carboline derivative Alternatively, a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is further substituted with a nitrogen atom is used for the hole blocking layer. The improvement of the effect was seen.

Example 7
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL element OLED1-7 of Example 1 was used as a blue light emitting element.

(Production of green light emitting element)
Ir-1 was used as a green light emitting element.

(Production of red light emitting element)
Ir-9 was used as a red light emitting element.

  Each of the red, green, and blue light emitting organic EL elements produced above was juxtaposed on the same substrate to produce an active matrix type full color display device having the form as shown in FIG. 1, and FIG. Only the schematic diagram of the display section A of the display device is shown. That is, a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of juxtaposed pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) The scanning lines 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 lattice shape and are connected to the pixels 3 at the orthogonal positions ( Details are not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was produced by appropriately juxtaposing the red, green, and blue pixels.

  It has been found that by driving the full-color display device, a clear full-color moving image display having high luminance, high durability, and clearness can be obtained.

Example 8
<Production of full-color display device>
A full-color display device was produced in the same manner as in the production of the blue light-emitting element of Example 7, except that the organic EL element OLED1-7 was changed to the organic EL element OLED2-7.

  It has been found that by driving the full-color display device, a clear full-color moving image display having high luminance, high durability, and clearness can be obtained.

Example 9
<Production of full-color display device>
In the production of the blue light-emitting device of Example 7, the organic EL device OLED1-7 was replaced with the organic EL device OLED3-4.
A full-color display device was produced in the same manner except that it was changed to.

  It has been found that by driving the full-color display device, a clear full-color moving image display having high luminance, high durability, and clearness can be obtained.

Example 10
<Production of full-color display device>
A full-color display device was produced in the same manner as in the production of the blue light-emitting element of Example 7, except that the organic EL element OLED1-7 was changed to the organic EL element OLED4-4.

  It has been found that by driving the full-color display device, a clear full-color moving image display having high luminance, high durability, and clearness can be obtained.

Example 11
<Production of full-color display device>
A full-color display device was produced in the same manner as in the production of the blue light-emitting element of Example 7, except that the organic EL element OLED1-7 was changed to the organic EL element OLED5-4.

  It has been found that by driving the full-color display device, a clear full-color moving image display having high luminance, high durability, and clearness can be obtained.

Example 12
<Production of full-color display device>
A full-color display device was produced in the same manner as in the production of the blue light-emitting element of Example 7, except that the organic EL element OLED1-7 was changed to the organic EL element OLED6-5.

  It has been found that by driving the full-color display device, a clear full-color moving image display having high luminance, high durability, and clearness can be obtained.

Example 13
<< Preparation of white light emitting element and white lighting device >>
The electrode of the transparent electrode substrate of Example 1 was patterned to 20 mm × 20 mm, and α-NPD was formed as a hole injection / transport layer with a thickness of 25 nm thereon as in Example 1, containing said heating boat and of compound 1-5 of containing boat and Ir-9 of containing and the boat is a light emitting host energized independently CBP with emission dopant der Ru of compound 1-5 and Ir The light emitting layer was provided by adjusting the vapor deposition rate of −9 to 100: 5: 0.6 and depositing it to a thickness of 30 nm.

Next, a hole blocking layer was provided by depositing BCP to a thickness of 10 nm. Furthermore, Alq ₃ was deposited at 40 nm to provide an electron transport layer.

  Next, as in Example 1, a square perforated mask having the same shape as the transparent electrode made of stainless steel was placed on the electron injection layer, lithium fluoride 0.5 nm as the cathode buffer layer and aluminum 150 nm as the cathode. Was deposited.

  This element was provided with a sealing can having the same method and the same structure as in Example 1 to produce a flat lamp. FIG. 6 shows a schematic diagram of a flat lamp. FIG. 6A shows a schematic plan view, and FIG. 6B shows a schematic cross-sectional view.

  When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 14
<< Preparation of white light emitting element and white lighting device >>
A white lighting device was produced in the same manner as in Example 13 except that the compound 1-5 of the present invention was changed to 2-7 in the production of the white light emitting device of Example 13.

  When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 15
<< Preparation of white light emitting element and white lighting device >>
In the preparation of the white light emitting device of Example 13, to prepare a white illumination device except for changing the reduction compound 1-5 3-2 in the same manner as in Example 13.

  When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 16
<< Preparation of white light emitting element and white lighting device >>
A white lighting device was produced in the same manner as in Example 13 except that Compound 1-5 was changed to 4-4 in the production of the white light emitting device of Example 13.

  When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 17
<< Preparation of white light emitting element and white lighting device >>
A white lighting device was produced in the same manner as in Example 13 except that Compound 1-5 was changed to 5-1 in the production of the white light emitting device of Example 13.

  When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 18
<< Preparation of white light emitting element and white lighting device >>
A white lighting device was produced in the same manner as in Example 13 except that Compound 1-5 was changed to 6-5 in the production of the white light emitting device of Example 13.

  When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 19
<< Production of Organic EL Elements OLED7-1 to 7-13 >>
Organic EL elements OLED7-1 to 7-13 were produced in the same manner as in Example 1 except that the luminescent dopant was changed to Ir-1 and the hole blocking material was changed as shown in Table 7.

  Measurement of the external extraction quantum efficiency and the light emission lifetime of each of the obtained devices was performed in the same manner as in the method described in Example 1.

  At this time, the value of OLED7-1 was set to 100, and the value of each organic EL element sample was represented by the relative value. The results obtained are shown in Table 7.

From Table 7, the organic EL element OLED7-2~7-13 compared to the organic EL element OLED7-1, a high luminous efficiency, it was found that the emission life can be obtained. The emission color of the organic EL elements OLEDs 7-2 to 7-13 was all green.

  According to the present invention, an organic EL element material useful for an organic EL element is obtained. By using the organic EL element material, an emission wavelength is controlled, high emission efficiency is exhibited, and an emission lifetime is long. An illumination device and a display device can be provided.

Claims (1)

An organic electroluminescent element material, which is a metal complex represented by the following general formula (1), (4), or (5) .

[Wherein, Z11 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group . M ₁₁ represents iridium or platinum. n represents an integer of 2 or 3. However, compounds represented by the following chemical formulas 1 and 2 are excluded. ]

[In formula, Z41 represents an atomic group required in order to form an aromatic heterocyclic ring. X ₄₁ and X ₄₂ each represent an optionally substituted carbon atom or nitrogen atom, at least one of which is a nitrogen atom or —N (R ₄ ) — (where R ₄ represents a hydrogen atom or Represents an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group . M ₄₁ represents iridium or platinum. C ₄₁ , C ₄₂ and C ₄₃ each represent a carbon atom. Bond between C ₄₁ and C _42, bond between C ₄₁ and X _42, coupling between X ₄₁ and X _42, coupling between X ₄₁ and C _43, and C ₄₂ and C ₄₃ The bond between represents a single bond or a double bond. n represents an integer of 2 or 3. ]

[In the formula, Z51 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. X ₅₁ represents an oxygen atom or a sulfur atom. R ₅₁ and R ₅₂ represent a hydrogen atom or an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group . M ₅₁ represents iridium or platinum. n represents an integer of 2 or 3. ]

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