Organic electroluminescent element material, organic electroluminescent element, display device and lighting device

An organic electroluminescent element material represented by Formula (1), Formula (1): wherein Z is a heterocylcic ring comprising a substituent having a steric parameter value (Es) of −0.5 or less at the third atom of the ring counted from a nitrogen atom attached to Z, the nitrogen atom being counted as the first atom; and other symbols in Formula (1) are described in the specification.

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Description

This application is based on Japanese Patent Application No. 2006-042061 filed on Feb. 20, 2006 in Japan Patent Office, the entire content of which is hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to an organic electroluminescent element material, an organic electroluminescent element, a display device and an illumination device.

BACKGROUND

Conventionally, an emission type electronic display device includes an electroluminescence display (hereinafter, referred to as an ELD). A constituent element of ELD includes such as an inorganic electroluminescent element and an organic electroluminescent element (hereinafter, referred to as an organic EL element). An inorganic electroluminescent element has been utilized as a flat light source, however, requires a high voltage of alternating current to operate an emission element. An organic electroluminescent element is an element provided with a constitution comprising an emission layer containing a emitting substance being sandwiched with a cathode and an anode, and an exciton is generated by an electron and a positive hole being injected into the emission layer to be recombined, resulting emission utilizing light release (fluorescence•phosphorescence) at the time of deactivation of said exciton; the emission is possible at a voltage of approximately a few to a few tens volts, and an organic electroluminescent element is attracting attention with respect to such as superior viewing angle and high visual recognition due to a self-emission type as well as space saving and portability due to a completely solid element of a thin layer type.

However, in an organic electroluminescence in view of the future practical application, desired has been development of an organic EL element which efficiently emits at a high luminance with a low electric consumption.

In Japanese Patent No. 3093796, a slight amount of a fluorescent substance has been doped in a stilbene derivative, distyrylarylene derivative or a tristyrylarylene derivative, to achieve improved emission luminance and a prolonged life of an element.

Further, there are known such as an element having an organic emission layer comprising a 8-hydroxyquinoline aluminum complex as a host compound which is doped with a slight amount of a fluorescent substance (for example, JP-A 63-264692 (hereinafter, JP-A refers to Japanese Patent Publication Open to Public Inspection No.)) and an element having an organic emission layer comprising a 8-hydroxyquinoline aluminum complex as a host compound which is doped with quinacridone type dye (for example, JP-A 3-255190).

In the case of utilizing emission from an excited singlet as described above, since a generation ratio of a singlet exciton to a triplet exciton is 1/3, that is, a generation probability of an emitting exciton species is 25% and a light taking out efficiency is approximately 20%, the limit of a quantum efficiency (ηext) of taking out is said to be 5%.

However, since an organic EL element which utilizes phosphorescence from an excited triplet has been reported from Princeton University (M. A. Baldo et al., Nature vol. 395, pp. 151-154 (1998)), researches on materials exhibiting phosphorescence at room temperature have come to be active.

For example, it is also disclosed in A. Baldo et al., Nature, vol. 403, No. 17, pp. 750-753 (2000), and U.S. Pat. No. 6,097,147.

Since the upper limit of internal quantum efficiency becomes 100% by utilization of an excited triplet, which is principally 4 times of the case of an excited singlet, it may be possible to achieve almost the same ability as a cooled cathode ray tube to attract attention also for an illumination application.

For example, in such as S. Lamansky et al., J. Am. Chem. Soc., vol. 123, p. 4304 (2001), many compounds mainly belonging to heavy metal complexes such as iridium complexes have been synthesized and studied.

Further, in aforesaid, A. Baldo et al., Nature, vol. 403, No. 17, pp. 750-753 (2000), utilization of tris(2-phenylpyridine)iridium as a dopant has been studied.

In addition to these, M. E. Tompson et al., at The 10th International Workshops on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), have studied to utilize L2Ir(acac) such as (ppy)2Ir(acac) as a dopant, Moon-Jae Youn. Og., Tetsuo Tsutsui et al., also at The 10th International Workshops on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), have studied utilization of such as tris(2-(p-tolyl)pyridine)iridium (Ir(ptpy)3) and tris(benzo[h]quinoline)iridium (Ir(bzq)3) (herein, these metal complexes are generally referred to as orthometalated iridium complexes.).

Further, in also the aforesaid, S. Lamansky et al., J. Am. Chem. Soc., vol. 123, p. 4304 (2001), studies have been carried out to prepare an element utilizing various types of iridium complexes.

Further, to obtain high emission efficiency, Ikai et al., at The 10th International Workshops on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) utilized a hole transporting compound as a host of a phosphorescent compound. Further, M. E. Tompson et al. utilized various types of electron transporting materials as a host of a phosphorescent compound doped with a new iridium complex.

An orthometalated complex provided with platinum instead of iridium as a center metal is also attracting attention. With respect to these types of complexes, many examples having a characteristic ligand are known (for example, refer to Patent Documents 1-5 and Non-Patent Document 1.).

In any case, emission luminance and emission efficiency are significantly improved compared to conventional elements because the emitting light arises from phosphorescence, however, there has been a problem of a poor emission life of the element compared to conventional elements. It is hard to achieve an emission of a short wavelength and an improvement of an emission life of the element for a phosphorescent emission material provided with a high efficiency. At present state, it cannot be achieved a level of a practical use.

With respect to shortening of emission wavelength, heretofore, there have been known introduction of an electron attracting group such as a fluorine atom, a trifluoromethyl group, or a cyano group as a substituent group into phenylpyridine, and introduction of a ligand of such as picolinic acid or of a pyrazabole type. However, when an emission wavelength is shortened to achieve blue color by utilizing these substitution effects, a high efficiency may be achieved while emission life will be greatly deteriorated, which requires further improvement to overcome the trade-off relationship.

As a ligand, known are metal complexes having phenylpyrazole in which the phenyl group undergoes substitution (refer, for example, to Patent Documents 1 and 2). In the substitution mode of the phenyl group of phenylpyrazole, which is disclosed in the above, the lifetime of the luminescent element is improved but is still insufficient. Further, in view of luminescent efficiency, much room for improvement still remains. On the other hand, it has been known that ligands having a substituent exhibiting steric hindrance are appropriate for improvement of luminance, and there are examples of application to the phenylpyrazole mother nucleus (refer, for example, to Patent Document 3).

Examples of metal complexes, in which phenylimidazole as a ligand is employed as a basic skeleton, are disclosed (refer, for example, to Patent Documents 4,5, and 7). In the above patent documents, described is luminescent wavelength, driving characteristics of the elements, external quantum efficiency, and chromaticity, but not specifically described is the lifetime of the luminescent elements.

Further disclosed are examples of luminescent elements incorporating metal complexes in which phenylimidazole, phenyltriazole, or phenyltetrazole is employed as a basic skeleton (refer to Patent Document 6). In above patent document, the driving characteristics of elements, external quantum efficiency, and chromaticity are described, but the lifetime of luminescent elements is not specifically described.

[Patent Document 1] WO 04/085450

[Patent Document 2] JP-A 2005-53912

[Patent Document 3] JP-A 2003-109758

[Patent Document 4] WO 05/007767

[Patent Document 5] JP-A 2005-68110

[Patent Document 6] US-A 2006-0008670

[Patent Document 7] WO 06/009024

SUMMARY

This invention has been made in view of these problems, and an object of this invention is to provide an organic EL element material with a controlled emission wavelength which have high emission efficiency and long emission life, an illumination device and a display device by utilizing said element material.

The object of this invention described above has been achieved by the following constitutions.

  • (1) An organic electroluminescent element material represented by Formula (1),

wherein Z is a heterocyclic ring comprising a substituent having a steric parameter value (Es) of −0.5 or less at the third atom of the ring counted from a nitrogen atom attached to Z, the nitrogen atom being counted as the first atom;

each X and Y is independently a carbon atom or a nitrogen atom;

A is a group of atoms necessary to form a 5 or 6 membered hydrocarbon ring or heterocyclic ring with X—C;

B is —C(R01)═C(R02)—, —N═C(R02)—, —C(R01)═N—, or —N═N—, provided that each R01 and R02 is independently a hydrogen atom or a substituent;

X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;

m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and

M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

  • (2) An organic electroluminescent element material represented by Formula (1B),

wherein each X and Y is independently a carbon atom or a nitrogen atom;

A is a group of atoms necessary to form a 5 or 6 membered hydrocarbon ring or heterocyclic ring with X—C;

B is —C(R01)═C(R02)—, —N═C(R02)—, —C(R01)═N—, or —N═N—, provided that each R01 and R02 is independently a hydrogen atom or a substituent;

X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;

m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and

M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table; and

Zb is a group selected from the group consisting of:

provided that (*) indicates a position which binds to a nitrogen atom.

  • (3) The organic electroluminescent element material of the above-described item (2), wherein Zb in Formula (1B) has further a halogen atom.
  • (4) An organic electroluminescent element material comprising a polymer having a partial structure represented by Formula (1B) of the above-described item (2) in the molecule.
  • (5) An organic electroluminescent element material represented by Formula (2),

wherein R is a substituent having a steric parameter value (Es) of −0.5 or less,;

R1 is a hydrogen atom or a substituent, and n1 is an integer of 1 to 4;

R2 is a hydrogen atom or a substituent, and n2 is an integer of 1 or 2;

Z1 is a group of atoms necessary to form a 5 or 6 membered hydrocarbon ring or heterocyclic ring with C—C;

Z2 is a group of atoms necessary to form a hydrocarbon ring or a heterocyclic ring with C—C;

X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;

m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and

M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

  • (6) The organic electroluminescent element material of the above-described item (5), wherein in Formula (2), n1 is 2 or more and a plurality of R1s forms a ring by binding together.
  • (7) The organic electroluminescent element material of the above-described item (5), wherein R1 in Formula (2) is an aromatic hydrocarbon having a substituent.
  • (8) The organic electroluminescent element material of the above-described item (5), wherein R1 in Formula (2) is an aromatic heterocylic group or a non aromatic heterocylic group.
  • (9) The organic electroluminescent element material of the above-described item (5), wherein R1 in Formula (2) is an alkoxy group or an aryloxy group.
  • (10) The organic electroluminescent element material of the above-described item (5), wherein R2 in Formula (2) is a substituent.
  • (11) The organic electroluminescent element material of the above-described item (5), wherein Formula (2) is further represented by Formula (3),

wherein R is a substituent having a steric parameter value (Es) of −0.5 or less,;

R1 is a hydrogen atom or a substituent, and n1 is an integer of 1 to 4;

each R2 and R3 is independently a hydrogen atom or a substituent, n2 is an integer of 1 or 2 and n3 is an integer of 1 to 4;

X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;

m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and

M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

  • (12) The organic electroluminescent element material of the above-described item (11), wherein Formula (3) is further represented by Formula (4),

wherein R is a substituent having a steric parameter value (Es) of −0.5 or less,;

R1 is a hydrogen atom or a substituent, and n1 is an integer of 1 to 4;

each R2 and R3 is independently a hydrogen atom or a substituent, n2 is an integer of 1 or 2 and n3 is an integer of 1 to 3;

X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;

m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and

M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

  • (13) The organic electroluminescent element material of the above-described item (12), wherein R3 in Formula (4) is a hydrogen atom.
  • (14) The organic electroluminescent element material of the above-described item (5), wherein m2 in Formula (2) is 0.
  • (15) The organic electroluminescent element material of the above-described item (5), wherein R in Formula (2) is electron donative.
  • (16) The organic electroluminescent element material of the above-described item (5) exhibiting a first emission wavelength of 400 to 500 nm.
  • (17) An organic electroluminescent element comprising the organic electroluminescent element material of any one of the above-described items (1), (2) and (5).
  • (18) An organic electroluminescent element comprising an emission layer as a constituting layer of the element, wherein the emission layer comprises the organic electroluminescent element material of the above-described item (5).
  • (19) The organic electroluminescent element of the above-described item (18), wherein the emission layer further comprises:

(i) a carboline derivative; or

(ii) a condensed ring compound having a structure derived from carboline, wherein at least one of carbon atoms of a hydrocarbon ring in a carboline ring is substituted with a nitrogen atom.

  • (20) The organic electroluminescent element of the above-described item (17), comprising a positive hole inhibition layer as a constituting layer of the element, the positive hole layer containing:

(i) a carboline derivative; or

(ii) a condensed ring compound having a structure derived from carboline, wherein at least one of carbon atoms of a hydrocarbon ring in a carboline ring is substituted with a nitrogen atom.

  • (21) A display device comprising the organic electroluminescent element of the above-described item (17).
  • (22) A lighting device comprising the organic electroluminescent element of the above-described item (17).

This invention has been able to provide an organic EL element material for and an organic EL element having specific properties, and it has been achieved to provide an organic EL element, an illumination device and a display device having high emission efficiency and long emission life utilizing said organic EL element material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing to show an example of a display device constituted of an organic EL element.

FIG. 2 is a schematic drawing of display section A.

FIG. 3 is an equivalent circuit diagram of an image pixel.

FIG. 4 is a schematic drawing of a full color display device according to a passive matrix mode.

FIG. 5 is a schematic drawing of an illumination device.

FIG. 6 is a schematic drawing of an illumination device.

 DESCRIPTION OF THE PREFERRED EMBODIMENTS

In an organic electroluminescent element material of this invention, an organic EL element material, which is a metal complex having a specific ligand, could be obtained by adopting a constitution defined by any one of the embodiments of the present invention. An organic EL element having high emission efficiency and long emission life could be obtained by utilizing said organic EL element material. Further, by utilizing the aforesaid organic electroluminescent element, the display device described above and the illumination device described above each, exhibit high luminance as well as high durability, could be obtained.

In the following, the detail of each constituent element according to this invention will be successively explained.

Metal complexes related to the organic EL element materials of the present invention will now be described.

In view of the foregoing, the inventors of the present invention conducted diligent investigation and found that by employing organic EL elements incorporating the metal complex represented by each of above Formulas (1), (1B), (2) and (3), or Formula (4) as an organic EL element material, luminescent efficiency and luminescent lifetime are markedly improved.

The inventors of the present invention conducted further diligent investigation and also discovered that with regard to phenylimidazole derivatives, the stability of the complex varied to a great extent depending on effects of the substitution position and types of a substituent to phenylimidazole employed as a mother nucleus, whereby the above significantly affected the luminescent lifetime.

The inventors of the present invention discovered that as the metal complexes according to the present invention, by introducing a substituent having a specific steric or electronic parameter for imidazole into a heterocyclic ring, an aromatic heterocyclic ring, or an aromatic hydrocarbon ring, luminescent lifetime was markedly extended, which had caused problems for the organic EL element prepared by employing an organic EL element material which controlled the luminescent wavelength to the shorter wavelength side only by conventional metal complexes for blue, especially by an electron attractive group, whereby compatibility of the luminescent efficiency and the luminescent lifetime was realized. Further, it was discovered that by specifying the substitution position, size and electronic properties of an aromatic ring-shaped substituent, the lifetime of a luminescent element for blue, exhibiting excellent color purity, was further extended, whereby a significant extension of the luminescent lifetime of organic EL elements was realized.

The concept of the present invention will now be described. Description is made while referring to an example in which an aromatic hydrocarbon ring is introduced into the N position of 2-phenylimidazole. Namely, it is common knowledge that the introduction of a phenyl group into the N position of 2-phyenylimidazole is difficult in terms of synthesis, compared to the case in which a straight chain alkyl group is introduced into the N position. In addition, it has been featured that metal complexes employing the above ligand emit luminescence of a longer wavelength to broaden the waveform. The above suggests that the conjugated system is not cut off irrespective of the fact that the phenyl group on the N position is bonded via a nitrogen atom. It is possible to describe broadening of the luminescent wavelength due to a significant increase in probability of the presence of the vibration level due to rotation, compared to the ligand of the N-methylated compound. This assumption is supported by the molecular orbital calculation based on GAUSSIAN.

The inventors of the present invention conducted diligent investigation and achieved the present invention by discovering the following effects via introduction of a cyclic substituent having a bulky substituent in the ortho position onto the N position of phenylimidazole;

1) an increase in twist of the phenyl group to result in cutting of the conjugated system and in shortening the wavelength,

2) a decrease in probability of the vibration level due to retardation of free rotation via the presence of the bulky substituent,

3) significant enhancement of stability of molecules via protection of the N position, which tends to be oxidized, employing the bulky substituent, and

4) achieved compatibility of wavelength shortening with lifetime extension by combining the size of the substituted atom and the electronic effect.

Further, even in a ligand having the mother nucleus according to the present invention, by introducing an auxiliary ligand to be combined or a substituent itself which results in a longer wavelength, it is possible to control the emission wavelength of metal complexes within the desired region. Accordingly, it is possible to start a molecular design which provides a function to control the luminescence wavelength of metal complexes into the longer wavelength region (green-red) from the point in which Formulas (1), (1B), (2) or (3) according to the present invention, or Formula (4) is employed as a starting point for the basic skeleton design.

(Ligands)

In the metal complexes according to the present invention, for example, when description is made employing above Formula (1), when m1>m2, the partial structure represented in parenthesis having m1 or the partial structure represented by the tautomer is called a primary ligand, while the partial structure represented in parenthesis having m2 or the tautomer is called a secondary ligand.

In the present invention, as represented by Formula (1), the above metal complexes are composed of a primary ligand or its tautomer as well as a secondary ligand or its tautomer. However, as described below, m2=0 is allowed, namely all the ligands of the above metal complexes are composed of only the partial structure represented by the primary ligand or its tautomer.

Further, if desired, incorporated may be ligands (also called coordination compounds) well known as a so-called ligand by a person skilled in the art which is employed to form conventional metal complexes.

In view of achieving preferable results in desired effects of the present invention, the ligand in complexes is composed of 1 or 2 types, but is preferably composed of only one type.

Ligands employed in conventional metal complexes known in the art include various types. Examples include ligands (for example, halogen ligands, being preferably a chlorine ligand, and nitrogen containing heterocyclic ligands such as bipyridyl or phenanthroline, and diketone ligands) described, for example, in H. Yersin, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag Co., published in 1987, and in Akio Yamamoto, “Yuki Kinzoku Kagaku -Kiso to Oyo- (Organic Metal Chemistry -Bases and Applications-)” Shokabo Sha, published in 1982.

(Transition Metal Elements of Groups 8-10 of the Periodic Table of Elements)

Employed as a metal used to form the metal complexes represented by Formulas (1), (1B), (2) or (3) according to the present invention, or Formula (4) are the transition metal elements (also simply referred to as transition metals) of Groups 8-10 of the periodic table. Of these, iridium and platinum are listed as a preferable transition metal element.

Further, by employing such organic EL element materials, it became possible to provide organic EL elements which exhibit high luminescent efficiency and long luminescent lifetime, a lighting device and a display device.

Each of the constituting components according to the present invention will now be successively detailed.

Metal complexes which are organic EL element materials of the present invention will be described first.

Preferred as a layer incorporating the metal complexes represented by above Formulas (1), (1B), (2) or (3) according to the present invention, or Formula (4) is an emission layer and/or an electron inhibition layer. Further, when incorporated in the emission layer, by employing them as a emission dopant in the emission layer, it is possible to achieve an increase in the quantum efficiency (to realize high luminance) to be taken out and the extension of luminescent lifetime of the organic EL elements of the present invention.

The metal complexes represented by above Formula (1), (1B), (2) or (3), according to the present invention, or Formula (4) will be described next.

In Formula (1), Z represents a hydrocarbon ring or a heterocyclic ring (including each of the tautomers) in which a substituent of a steric parameter (being an Es value) of at most −0.5 is bound to at least one atom located in the third position from the nitrogen atom to be bound. “Es value”, as described herein, refers to a steric parameter derived from chemical reactivity. It is possible to describe that a decrease in this value indicates that the substituent becomes spatially more bulky.

Es value will now be described. It is common knowledge that in a hydrolysis reaction of esters under acidic conditions, effects for the progress of the reaction may be considered to be only caused by the steric hindrance. Based on this, the value which numerically expresses the steric hindrance is Es value.

Es value of substituent X may be obtainable as follows. Reaction rate constant kX of the following chemical reaction in which α-position mono-substituted acetate, which is derived from α-position mono-substituted acetic acid prepared by substituting one hydrogen atom of the methyl group of acetic acid with substituent X, undergoes hydrolysis under acidic conditions, is obtained.


X—CH2COORX+H2O→X—CH2COOH+RXOH

Reaction rate constant kH of the following reaction (RX is the same as RY) in which acetate corresponding to the above α-position mono-substituted acetate undergoes hydrolysis under acetic conditions, is also obtained.


CH3COORY+H2O→CH3COOH+RYOH

Subsequently, Es is obtained via the following formula.


Es=log(kX/kH)

The reaction rate decreases due to steric hindrance of substituent X. As a result, since kX<kH is held, Es value commonly becomes negative. In practice, when Es value is obtained, two reaction rate constants, namely kX and kH, are determined and it is calculated based on the above formula.

Specific examples of Es value are detailed in Unger, S. H., Hansch, C., Prog. Phys. Org. Chem. 12, 91 (1976). Further, specific numerical values are also described in “Yakubutsu no Kozo Kassei Sokan (Structural Activity Correlation)” (Kagaku no Ryoiki Zokan No. 122, Nanko Do), and “American Chemical Society Professional Reference Book, ‘Exploring QSAR’ p. 81, Table 3-3”. Table 1 below shows some of them.

TABLE 1 Substituent Es Value Substituent Es Value H 0 CH2OCH3 −1.43 F −0.46 CH2NO2 −2.71 Cl −0.97 CH2COCH3 −1.99 Br −1.16 CHF2 −1.91 I −1.4 CHCl2 −2.78 CH3 −1.24 CHBr2 −3.1 C2H5 −1.31 CHOHCH3 −1.15 n-C3H7 −1.6 CF3 −2.4 n-C4H9 −1.63 CCl3 −3.3 i-C4H9 −2.17 CBr3 −3.67 s-C4H9 −2.37 C(C6H5)3 −5.92 t-C4H9 −2.78 CHCH3 −2.84 cyclo-C4H7 −1.3 CN −0.51 n-C5H11 −1.64 OH −0.55 i-C5H11 −1.59 OCH3 −0.55 CH(C2H5) −3.22 SH −1.07 cyclo-C6H11 −2.03 SCH3 −1.07 CH2F −1.48 SF5 −2.91 CH2Cl −1.48 NH2 −0.61 CH2Br −1.51 CH2I −1.61 CH2OH −1.21

Further, it should be noted that the Es value, which is defined in the present invention, is not determined while a methyl group is 0, but is determined while a hydrogen atom to be 0, whereby the Es value of the present invention is a value which is obtained by subtracting 1.24 from the Es value determined while a methyl group is 0.

In one of the embodiments of n the present invention, the Es value is commonly at most −0.5, is preferably between −7.0 and −0.6, but is most preferably between −7.0 and −1.0.

Further, in the present invention, in the case of a substituent at a steric parameter (being a Es value) of at most −0.5, for example, in the case in which keto-enol tautomers are present in R and R′, the Es value of the keto portion is determined via conversion as an enol isomer. In cases in which other tautomers are present, Es values are determined based on the same conversion method. Further, a substituent at an Es value of at most −0.5 is preferably an electron donative group in terms of electronic effects. In the present invention, “a substituent is electron donating” means that Hammett σp value described below is a negative value and such substituent has a larger tendency to donate electrons to the bonded atoms when compared with a

Specific examples of an electron-donating substituent include: a hydroxyl group, a methoxy group, an acetyloxy group, an amino group, a dimethylamino group, an acetylamino group, alkyl groups (for example, a methyl group, an ethyl group, a propyl group and tert-butyl), and aryl groups (for example, a phenyl group) . The following literatures can be referred to for Hammett σp value, for example.

<<Hammett σp Value>>

Hammett σp value of the present invention represents Hammett substituent constant σp. Hammett σp value was determined from the electronic effect of the substituent exerted on hydrolysis of ethyl benzoate by Hammett et al. Groups shown in, for example, “Structure-activity relationship of a drug” (Nankodo Co., Ltd.: 1979), or “Substituent Constants for Correlation Analysis in chemistry and biology” (C. Hansch and A. Leo, John Wiley&Sons, New York, 1979) can be cited.

Preferred examples of Z in Formula (1) are listed below. Other than the listed examples below, Z may have substituent(s), whereby Z is not limited to these examples. Incidentally, * represents a binding position.

In Formula (1), Y represents a carbon atom or a nitrogen atom, but is preferably a carbon atom. B represents —C(R01)═C(R02)—, —N═C(R02)—, —C(R01)═N—, or —N═N—.

Preferred examples of nitrogen-containing heterocyclic groups incorporating Y include a 2-imidazoyl group, a 2-(1,3,4-triazolyl) group, a 2-(1,3,5-triazolyl) group, and a 2-tetrazolyl group. Of these nitrogen-containing heterocyclic groups, the 2-imidazolyl group is most preferred.

R01 and R02 each represents a hydrogen atom or a substituent. Examples of such a substituent include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group), a cycloalkyl group (for example, a cyclopentyl group and a cyclohexyl group), an alkenyl group (for example, a vinyl group and an allyl group), an alkynyl group (for example, an ethynyl group and a propargyl group), an aromatic hydrocarbon ring group (also called an aromatic carbon ring group or an aryl group such as a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthenyl group, fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, or a biphenyl group), an aromatic heterocyclic group (for example, a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a piradinyl group, a triazolyl group (for example, a 1,2,4-triazole-1-yl group and a 1,2,3-triazole-1-yl group), an oxazolyl group, a benzoxazolyl group, a thiazolyl group, an isooxazolyl group, an isothiazolyl group, a furazanyl group, a thienyl group, a quinolyl group, a benzofuryl group, a dibenzofuryl group, a benzothienyl group, a dibenzothienyl group, an indolyl group, a carbazolyl group, a carbolynyl group, a diazacarbazoyl group (which shows that one of the carbon atoms which constitute a carboline ring of the above carbolinyl group is replaced with a nitrogen atom), a quinoxythalinyl group, a pyridazinyl group, a triazinyl group, a quinazolinyl group, a phthalazinyl group), a heterocyclic group (for example, a pyrrolidinyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group), an alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group), a cycloalkoxy group (for example, a cyclopentyloxy group and a cyclohexyloxy group), an aryloxy group (for example, a phenoxy group and a naphthyloxy group), an alkylthio group (for example, a methylthio gropup, an ethylthio group, a propylthio group, a pentylthio group, a hexylthio group, an octylthio group, and a dodecylthio group), a cycloalkylthio group (for example, a cyclopentylthio group and a cyclohexylthio group), an arylthio group (for example, a phenylthio group and a naphthylthio group), an alkoxycarbonyl group (for example, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, a phenyloxycarbonyl group and a naphthyloxycarbonyl group), a sulfamoyl group (for example, an aminosulfonyl group, a methylaminosulfonyl group, a dimethylaminosulfonyl group, a butylaminosulfonyl group, a hexylaminosulfonyl group, a cyclohexylaminosulfonyl group, an octylaminosulfonyl group, a dodecylaminosulfonyl group, a phenylaminosulfonyl group, a naphthylaminosulfonyl group, and a 2-pyridylaminosulfonyl group), an acyl group (for example, an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a pentylcarbonyl group, a cyclohexylcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a dodecylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, a pyridylcarbonyl group), an acyloxy group (for example, an acetyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an octylcarbonyloxy group, a dodecylcarbonyloxy group, and a phenylcarbonyloxy group), an amido group (for example, a methylcarbonylamino group, an ethylcarbonylamino group, a dimethylcarbonylamino group, a propylcarbonylamino gropup, a pentylcarbonylamino group, a cyclohexylcarbonylamino group, a 2-ethylhexylcarbonylamino group, an octylcarbonylamino group, a dodecylcarbonylamino group, a phenylcarbonylamino group, and a naphthylcarbonylamino group), a carbamoyl group (for example, an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a propylaminocarbonyl group, a pentylaminocarbonyl group, a cyclohexylaminocarbonyl group, an octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, and a 2-pyridylaminocarbonyl group), an ureido group (for example, a methylureido group, an ethylureido group, a pentylureido group, a cyclohexylureido group, an octylureido group, a dodecylureido group, a phenylureido group, a naphthylureido group, and a 2-pyridylaminoureido group), a sulfinyl group (for example, a methylsulfinyl group, an ethylsulfinyl group, a butylsulfinyl group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, a docecylsulfinyl group, a phenylsulfinyl group, a naphthylsulfinyl group, and a 2-pyridylsulfinyl group), an alkylsulfonyl group (for example, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfinyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, and a dodecylsulfonyl group), an arylsulfonyl group or a heteroarylsulfonyl group (for example, a phenylsulfonyl group, a naphthylsulfonyl group, and a 2-pyridylsulfonyl group), an amino group (for example, an amino group, an ethylamino group, a dimethylamino group, a butylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, a dodecylamino group, an anilino group, a cyclopentylamino group, a 2-ethylhexylamino group, a dodecylamino group, an anilino group, a naphthylamino group, and a 2-pyridylamino group), a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a fluorinated hydrocarbon group (for example, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a pentafluorophenyl group), a cyano group, a nitro group, a hydroxyl group, a mercapto group, and a silyl group (for example, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, and a phenyldiethylsilyl group). These substituents may be substituted with the above substituents. Further, these substituents may be bound together to form a ring.

In the hydrocarbon ring or the heterocyclic group represented by A-C—X of Formula (1), X represents either a carbon atom or a nitrogen atom, but is preferably a carbon atom.

When the hydrocarbon ring represented by A-C—X is an aromatic hydrocarbon ring, it is one in which one hydrogen atom at an optional position is removed from the 4n+2π based aromatic hydrocarbon compound, and specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 1-anthryl group, a 9-phenanthryl group, a 2-triphenylenyl group, and a 3-perylenyl group. Further, the above hydrocarbon ring group may be substituted, for example with the substituent described in R01, and further, may form a condensed ring (for example, a 9-pyrenyl group which is prepared by condensing a hydrocarbon ring to a 9-phenanthryl group or a 8-quinolyl group which is prepared by condensing a heterocycle to a phenyl group).

When the heterocyclic group, represented by A-C—X, is an aromatic heterocyclic group, it is preferable that in the above aromatic heterocyclic group, at least one side contacting position of the portion bound to the nitrogen-containing aromatic heterocycle is a carbon atom, and though no particular limitation is made for the 4n+2π based aromatic group, both contacting positions of the portion bound to the nitrogen-containing aromatic heterocycle are carbon atoms. Specific examples include a 3-pyridyl group, a 5-pyrimidyl group, a 4-pyridadyl group, a 5-pyridadyl group, a 4-isooxazolyl group, a 4-isothiazolyl group, a 4-pyrazolyl group, a 3-pyrrolo group, a 3-furyl group, and a 3-thienyl group. Further, the above heterocycle may be substituted, for example, with the substituent described in R01, and still further, may form a condensed ring.

In Formula (1), X1-L1-X2 represents a bidentate ligand, and X1 and X2 each independently represents a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents a group of atoms which forms a bidentate ligand together with X2. Specific examples of the bidentate ligand represented by X1-L1-X2 include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabole, acetylacetone, and picolinic acid. “m1” represents an integer of 1, 2, or 3, while m2 represents an integer of 0, 1, or 2, wherein m1 plus m2 is 2 or 3. Of these, the case in which m2 is 0 is preferred.

In Formula (1B), each X and Y is independently a carbon atom or a nitrogen atom;

A is a group of atoms necessary to form a 5 or 6 membered hydrocarbon ring or heterocyclic ring with X—C;

B is —C(R01)═C(R02)—, —N═C(R02)—, —C(R01)═N—, or —N═N—, provided that each R01 and R02 is independently a hydrogen atom or a substituent;

X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;

m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and

M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table; and

Zb is a group selected from the group for the item (2) described above.

In Formula (2), R represents a substituent at a steric parameter (Es value) of at most −0.5, which is located in the ortho position of the ring composed of Z2 bound to the nitrogen atom of the imidazole ring. Es values are as detailed in Formula (1). Specific examples of R include substituents shown in Table 1 in the description of Formula (1).

R1 represents a hydrogen atom or a substituent, and n1 represents an integer of 1-4. R2 represents a hydrogen atom or a substituent and n2 represents an integer of 1 or 2.

Z2 represents a hydrocarbon ring or a heterocycle, or a group of atoms which is necessary to form a tautomer thereof. The above group of atoms may further have substituent(s), and examples of the substituents are as defined for R01 of Formula (1). When a plurality of substituents is further present, the plurality of substituents may be bound together other to form a ring. Preferable specific examples include substituents listed as Z of Formula (1).

In Formula (2), Z1 represents a group of atoms, which is necessary to form a 5- to 6-membered hydrocarbon ring or heterocycle together with C—C. Preferred as the hydrocarbon rings are aromatic hydrocarbon rings, while preferred as heterocycles are aromatic heterocycles.

The aromatic hydrocarbon group is one in which one hydrogen atom at an optional position is removed from a 4n+2 based aromatic hydrocarbon compound, and specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-antholyl group, a 1-antholyl group, a 9-phenantholyl group, a 2-triphenylenyl group, and a 3-perylenyl group. The above aromatic hydrocarbon group may further be substituted, for example, with the substituent described in R01 of Formula (1), and a condensed ring (for example, a 9-pyrenyl group prepared by condensing a 9-phenantolyl group to a hydrocarbon ring and a 8-quinolyl group prepared by condensing a heterocycle to a phenyl group, may be formed.

Aromatic heterocyclic groups are not particularly limited as long as at least one side contacting position of the portion bound to a nitrogen-containing heterocycle is a carbon atom and the above groups are 4n+2π based aromatic substituents, but dual side contacting positions of the portion bound to the nitrogen-containing aromatic heterocycle are carbon atoms. Specifically listed are a 3-pyridyl group, a 5-pyrimidyl group, a 4-pyridadyl group, a 4-isooxazoyl group, a 4-isothiazolyl group, a 4-pyrazolyl group, a 3-pyrrolo group, a 3-furyl group, and a 3-thienyl group. The above aromatic heterocycle may further be substituted with the substituent described in R01 of Formula (1), and may further form a condensed ring.

In Formula (2), R1 and R2 each represents a hydrogen atom or a substituent, while n1 represents an integer of 1-4 and n2 represents an integer of 1-2. However, when a plurality of substituents is present at R1 or R2, R1 and R2 each may be the same or different. Further, a plurality of substituents of R1 or R2 may be bound together to form a ring.

In Formula (2), X1-L1-X2 represents a bidentate ligand, and X1 and X2 each independently represents a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents a group of atoms which forms a bidentate ligand together with X2. Specific examples of the bidentate ligand represented by X1-L1-X2 include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabole, acetylacetone, and picolinic acid. “m1” represents an integer of 1, 2, or 3, while m2 represents an integer of 0, 1, or 2, wherein m1 plus m2 is 2 or 3. Of these, the case in which m2 is 0 is preferred.

In Formula (3), R represents a substituent at a steric parameter (Es value) of at most −0.5. Es values are as detailed in Formula (1). Specific examples of R include substituents shown in Table 1 in the description of Formula (1) .

R1 and R2 each represents a hydrogen atom or a substituent, and is defined as the description in Formula (2). R3 represents a hydrogen atom or a substituent, while n3 represents an integer of 1-4. However, when a plurality of substituents is present, each R3 may be the same or different. Further, a plurality of R3 may be bound together to form a ring.

In Formula (3), X1-L1-X2 represents a bidentate ligand, and X1 and X2 each independently represents a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents a group of atoms which forms a bidentate ligand together with X2. Specific examples of the bidentate ligand represented by X1-L1-X2 are as those described in Formula (2). “m1” represents an integer of 1, 2, or 3, while m2 represents an integer of 0, 1, or 2, wherein m1 plus m2 is 2 or 3. Of these, the case in which m2 is 0 is preferred.

In Formula (4), R represents a substituent at a steric parameter (Es value) of at most −0.5. Es values are as detailed in Formula (1). Specific examples of R include substituents shown in Table 1 in the description of Formula (1).

R1 and R2 each represents a hydrogen atom or a substituent, and is defined as the description in Formula (2). R3 represents a hydrogen atom or a substituent, while n3 represents an integer of 1-4. However, when a plurality of substituent R3 is present, each R3 may be the same or different. Further, a plurality of R3 may be bound together to form a ring.

In Formula (4), X1-L1-X2 represents a bidentate ligand, and X1 and X2 each independently represents a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents a group of atoms which forms a bidentate ligand together with X2. Specific examples of the bidentate ligand represented by X1-L1-X2 are as those described in Formula (2). “m1” represents an integer of 1, 2, or 3, while m2 represents an integer of 0, 1, or 2, wherein m1 plus m2 is 2 or 3. Of these, the case in which m2 is 0 is preferred.

In Formulas (2)-(4), R and R′ are preferably electron donative groups. The electron donative groups are as those described in Formula (1).

In Formulas (1)-(4), central metal M1 represents a metal in Groups 8-10 of the periodical table of elements. Of these, iridium or platinum is particularly preferred.

The specific examples represented by above Formulas (1), (1B), (2), and (3) according to the present invention, of Formula (4) will now be listed, however the present invention is not limited thereto.

Metal complexes according to an organic EL element material of this invention can be synthesized by applying a method described in such as Organic Letter, vol. 3, No. 16, pp. 2579-2581 (2001), Inorganic Chemistry vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Chem. Soc., vol. 123, p. 4304 (2001), Inorganic Chemistry vol. 40, No. 7, pp. 1704-1711 (2001), Inorganic Chemistry vol. 41, No. 12, pp. 3055-3066 (2002), New Journal of Chemistry, vol. 26, p. 1171 (2002), European Journal of Organic Chemistry Vol. 4, pp. 95-709 (12004), and reference documents described in these documents.

Synthesis examples of the representative compounds will now be described.

Further, the structure of the synthesized compound was confirmed via 1H-NMR and MS spectra.

SYNTHESIS EXAMPLE 1 Synthesis of 1-Phenylimidazole (Comparative Example)

Charged into a reaction vessel was 3.30 g (0.01734 mol) of phenanthroline monohydrate, the moisture of which was removed via heating while reducing pressure. After cooling, 1.32 g (0.006936 mol) of copper iodide, 10 g (0.06936 mol) of 2-phenylimidazole, 7.0 g of 4A molecular sieve, 20.1 g (0.1457 mol) of potassium carbonate, 50 ml of dimethylformamide, and 14.9 g (0.07283 mol) of iodobenzene were added, followed by reaction for 10 hours while refluxed. Thereafter, iodobenzene was further added and the reaction was performed at a reaction temperature of about 160° C. for 15 hours, while distilling off dimethylformamide. After cooling the reaction products, the resulting solution was diluted with ethyl acetate, and insoluble compounds were collected via filtration, followed by washing with well water. After concentrating the organic layer, the targeted compound was isolated via silica gel column chromatography (in which ethyl acetate/hexane was 1/4), whereby 9.52 g (65.3%) of 1-phenylimidazole was obtained.

SYNTHESIS EXAMPLE 2 Synthesis of 1-Phenylimidazole (Comparative Example)

Reaction was performed in the same manner as Synthesis Example 1, except that iodobenzene employed in Synthesis Example 1 was replaced with mesityl iodide. However, no reaction occurred, and then no targeted 1-phenylimidazole was obtained.

SYNTHESIS EXAMPLE 3 Synthesis of 2-Phenyl-1-(2,4,6-trimethylphenyl)-1H-imidazole (1) Synthesis of 1-(2,4,6-trimethylphenyl)1H-imidazole

Charged into a reaction vessel were 15.9 g (0.08813 mol) of phenanthroline, which was dehydrated in the same manner as Synthesis Example 1, 7.2 g (0.03781 mol) of copper iodide, 102.3 g (0.7402 mol) of potassium carbonate, 25.0 g of 4A molecular sieve, 24.0 g (0.3525 mol) of dimethylformamide, 25 g of mesityl iodide, and 78 g of mesityl bromide. When the interior temperature reached nearly 150° C., dimethylacetamide was distilled off, and reaction was performed for 14 hours at an interior temperate of approximately 170° C. The post-treatment and separation were carried out in the same manner as for Synthesis Example 1, whereby 35.4 g (54.9%) of targeted 1-(2,4,6-trimethylphenyl)-1H-imidazole was obtained.

(2) Synthesis of 2-Bromo-1-(2,4,6-trimethylphenyl)-1H-imidazole

Charged into a reaction vessel was 1-mesitylimidazole, and subsequently, under a flow of nitrogen, 500 ml of dehydrated tetrahydrofuran was added. Further, under a flow of nitrogen, the interior temperature was lowered to at most −60° C., and 180 ml n-butyl lithium (being a hexane solution at a concentration of 1.57 mol) was dripped.

Thereafter, after elevating the interior temperature to −30° C. over 30 minutes, the interior temperature was again lowered to at most −60° C., and 14.5 ml of bromine was dripped. After the dripping, the inner temperature was elevated to room temperature. Thereafter, a 5% aqueous sodium thiosulfate solution, an aqueous sodium hydrogencarbonate solution, and ethyl acetate were added. After separation of the organic layer followed by concentration, the targeted compound was isolated via silica gel column chromatography (in which ethyl acetate/hexane was 2/3), whereby 49.7 g (69.8%) of 2-bromo-1-(2,4,6-trimethylphenyl)-1H-imidazole was obtained.

(3) Synthesis of 2-Phenyl-1-(2,4,6-trimethylphenyl)-1H-imidazole

After stirring 6.5 g (0.01131 mol) of bis (dibenzylideneacetone)palladium, 6.3 g of 1,1-bis(diphenylphosphino)ferrocene, and 30 ml of ethylene glycol dimethyl ether at 50° C. for 30 minutes under a flow of nitrogen, 50.0 g (0.1885 mol) of 2-bromo-1-(2,4,6-trimethylphenyl)-1H-imidazole, 27.6 g of phenylboronic acid, and 1.3 L of ethylene glycol dimethyl ether were added. Further, an aqueous solution prepared by dissolving 62.5 g (0.4526 mol) of potassium carbonate in 300 ml of water was added. Further, under a flow of nitrogen, reaction was performed for 12 hours while maintaining the interior temperature at approximately 80° C. After cooling the reaction products, the solution was diluted with ethyl acetate. After collecting insoluble compounds via filtration, washing was carried out employing well water. After concentrating the organic layer, the targeted compound was isolated via silica gel column chromatography (in which ethyl acetate/hexane was 1/4), whereby 30.6 g (61.8%) of targeted 2-phenyl-1-(2,4,6-trimethylphenyl)-1H-imidazole was obtained.

Synthesis of Exemplified Compound (154)

Under a nitrogen atmosphere, 8.1 g (0.02297 mol) of iridium trichloride trihydrate and 100 ml of water were added to a solution prepared by dissolving 18 g (0.06861 mol) of 2-phenyl-(2,4,6-trimethylphenyl)-1H-imidazole in 350 ml of 2-ethoxymethanol, and the resulting mixture was refluxed for 5 hours under a nitrogen atmosphere. The reaction liquor was cooled, followed by the addition of 500 ml of methanol, and deposited crystals were collected via filtration. The resulting crystals were washed with methanol and subsequently dried, whereby 15.2 g (at a yield of 88.4%) of Complex A was obtained.

Under a nitrogen atmosphere, 14.5 g (0.00966 mol) of Complex A and 14.5 g of sodium carbonate were suspended into 350 ml of 2-ethoxyethanol. Subsequently, 3.9 g (0.03895 mol) of acetylacetone was added to the above suspension and the resulting mixture was refluxed for two hours under a nitrogen atmosphere. After cooling the reaction liquor, sodium carbonate and inorganic salts were removed via vacuum filtration. After concentrating solvents under vacuum, 1 L of water was added to the resulting solids to form a suspension, followed by collection of solids via filtration. The resulting crystals were washed with a solution prepared by blending methanol and water at a ratio of 1/1 and subsequently dried, whereby 14.7 g (at a yield of 93.6%) of Complex B was obtained.

Under a nitrogen atmosphere, 7.5 g (0.009214 mol) of Complex B and 6.0 g (0.02287 mol) of 2-phenyl-(2,4,6-trimethylphenyl)-1H-imidazole were dispersed into 400 ml of glycerin. Under a nitrogen atmosphere, the resulting mixture underwent reaction for two hours at a reaction temperature of 150-160° C., and the reaction was terminated upon confirmation of the absence of Complex B. The reaction liquor was cooled, followed by the addition of 500 ml of methanol, and further followed by collection of deposited crystals via filtration. The resulting crystals were further washed with methanol and dried, whereby 7.1 g (at a yield of 78.9%) as a crude product was obtained. The resulting crude product was dissolved in a small amount of methylene, followed by purification (methylene chloride) employing silica gel column chromatography, whereby 6.5 g (at a yield of 72.2%) of Exemplified Compound (154) was obtained.

The wavelength of phosphorescence of Exemplified Compound (154) in a solution was determined employing F-4500, produced by Hitachi, Ltd., resulting in 466 nm (in 2-methyltetrahydrofuran).

<Application of Organic EL Element Material Containing Metal Complex to Organic EL Element>

In the case of preparing an organic EL element by utilizing an organic EL element material of this invention, said material is preferably utilized in an emission layer or an electron inhibition layer among constituent layers (details will be described later) of the organic EL element. Further, the material is preferably utilized as an emission dopant in an emission layer as described above.

(Emission Host and Emission Dopant)

A mixing ratio of an emission dopant against an emission host as a primary component in an emission layer, is preferably adjusted to a range of 0.1-30 weight %.

However, plural types of compounds may be utilized in combination as an emission dopant, and the partner to be mixed may be a metal complex having a different structure, and a phosphorescent dopant or a fluorescent dopant having other structures.

Here, a dopant (such as a phosphorescent dopant and a fluorescent dopant) which may be utilized together with a metal complex employed as an emission dopant will be described. An emission dopant is roughly classified into two types, that is, a fluorescent dopant which emits fluorescence and a phosphorescent dopant which emits phosphorescence.

A typical example of the former (a fluorescent dopant) includes coumarin type dye, pyran type dye, cyanine type dye, chroconium type dye, squalium type dye, oxobenzanthracene type dye, fluorescein type dye, rhodamine type dye, pyrylium type dye, perylene type dye, stilbene type dye, polythiophene type dye or rare earth complex type fluorescent substances.

A typical example of the latter (a phosphorescent dopant) is preferably a complex type compound containing metal of the 8th-10th groups of the periodic table, more preferably an iridium compound and an osmium compound and most preferable among them is an iridium compound.

Specifically, listed are compounds described in the following patent publication:

Such as WO 00/70655, JP-A Nos. 2002-280178, 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859, 2002-299060, 2001-313178, 2002-302671, 2001-345183 and 2002-324679, WO 02/15645, JP-A Nos. 2002-332291, 2002-50484, 2002-322292 and 2002-83684, Japanese Translation of PCT International Application Publication No. 2002-540572, JP-A Nos. 2002-117978, 2002-338588, 2002-170684 and 2002-352960, WO 01/93642 pamphlet, JP-A Nos. 2002-50483, 2002-100476, 2002-173674, 2002-359082, 2002-175884, 2002-363552, 2002-184582 and 2003-7469, Japanese Translation of PCT International Application Publication No. 2002-525808, JP-A 2003-7471, Japanese Translation of PCT International Application Publication No. 2002-525833, JP-A Nos. 2003-31366, 2002-226495, 2002-234894, 2002-235076, 2002-241751, 2001-319779, 2001-319780, 2002-62824, 2002-100474, 2002-203679, 2002-343572 and 2002-203678.

A part of examples thereof will be shown below.

(Emission Hosts)

A host compound, employed in the present invention, refers to a compound, among those incorporated in the emission layer, which results in a phosphorescent quantum yield of less than 0.01 during emitting phosphorescence.

Structures of the emission host employed in the present invention are not particularly limited. Representative compounds include those having a basic skeleton such as carbazole derivatives, triarylamine derivatives, aromatic borane derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, or oligoarylene compounds, or derivatives having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring, which constitutes carboline derivatives and the carboline ring of the above carboline derivatives, is substituted with a nitrogen atom. Of these, preferably employed are derivatives having a ring structure in which carbazole derivatives carboline derivatives or the hydrocarbon ring constituting carbazole derivatives and carboline derivatives or the carboline ring of the above carboline derivatives is substituted with a nitrogen atom. Of these, derivatives are preferably employed which have a structure in which at least one carbon atom of carbazole derivatives, and carboline derivatives, and the hydrocarbon ring constituting the carboline ring of the above carboline derivatives.

Specific examples of emission hosts will now be listed, however the present invention is not limited thereto. It is also preferable to employ these compounds as a positive hole inhibition material.

In the emission layer according to the present invention, prior art host compounds may be employed in combinations of a plurality of types. The use of a plurality of host compounds enables regulation of migration of electrons to make organic EL elements more efficient. Preferred as these prior art host compounds are those which exhibit positive hole transportability and electron transportability, minimize the variation of luminescent wavelength to a longer wavelength, and attain a high Tg (being a glass transition temperature).

Further, an emission host of this invention may be either a low molecular weight compound or a polymer compound having a repeating unit, in addition to a low molecular weight compound provided with a polymerizing group such as a vinyl group and an epoxy group (an evaporation polymerizing emission host).

An emission host is preferably a compound having a positive hole transporting ability and an electron transporting ability, as well as preventing elongation of an emission wavelength and having a high Tg (a glass transition temperature).

As specific examples of an emission host, compounds described in the following Documents are preferable: For example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227, 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, 2002-299060, 2002-302516, 2002-305083, 2002-305084 and 2002-308837. Specific examples of an emission host are shown below; however, this invention is not limited thereto.

The emission layer may further incorporate, as a host compound, a compound which exhibits a maximum fluorescent wavelength. In such a case, luminescence is also generated from the other host compound, resulting in the maximum fluorescent wavelength in the form of electromagnetic luminescence as an organic EL element due to energy transfer from the other host compound and a phosphorescent compound to the fluorescent compound. Preferred as such host compounds resulting in the maximum fluorescent wavelength are those which attain a high fluorescent quantum yield. Herein, the fluorescent quantum yield is preferably at least 10%, but is more preferably at least 30%. Specific examples of host compounds resulting in the maximum fluorescent wavelength include coumarin based dyes, pyran based dyes, cyanine based dyes, croconium based dyes, suqualium based dyes, oxobenzanthracene based dyes, fluorescein based dyes, ROHDAMINE based dyes, pyrylium based dyes, perylene based dyes, stilbene based dyes, and polythiophene based dyes. The fluorescent quantum yield can be determined based on the method described on page 362 of Bunko (Spectroscopy) II of aforesaid Zikken Kagaku Koza (Lecture on Experimental Chemistry) 7, 4th Edition (published by Maruzen, 1992).

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

<Constituent Layers of Organic EL Element>

Constituent layers of an organic EL element of this invention will now be explained.

Specific examples of a preferable layer constitution of an organic EL element of this invention are shown below; however, this invention is not limited thereto.

  • (i) anode/positive hole transport layer/emission layer/positive hole inhibition layer/electron transport layer/cathode,
  • (ii) anode/electron inhibition layer/emission layer/positive hole inhibition layer/electron transport layer/cathode,
  • (iii) anode/positive hole transport layer/electron inhibition layer/emission layer/positive hole inhibition layer/electron transport layer/cathode,
  • (iv) anode/anode buffer layer/positive hole transport layer/electron inhibition layer/emission layer/positive hole inhibition layer/electron transport layer/cathode,
  • (v) anode/positive hole transport layer/electron inhibition layer/emission layer/positive hole inhibition layer/electron transport layer/cathode buffer layer/cathode,
  • (vi) anode/anode buffer layer/positive hole transport layer/electron inhibition layer/emission layer/positive hole inhibition layer/electron transport layer/cathode buffer layer/cathode,
  • (vii) anode/anode buffer layer/positive hole transport layer/electron inhibition layer/emission layer/positive hole inhibition layer/electron transport layer/cathode buffer layer/cathode.

<Inhibition Layer (Electron Inhibition Layer, Positive Hole Inhibition Layer)>

An inhibition layer (such as an electron inhibition layer, a positive hole inhibition layer) according to this invention will now be explained.

In this invention, an organic EL element material of this invention is preferably utilized in such as a positive hole inhibition layer and an electron inhibition layer, and specifically preferably in a positive hole inhibition layer.

In the case of an organic EL element material of this invention being contained in a positive hole inhibition layer and an electron inhibition layer, a metal complex according to this invention, which is described in any one of the above-described embodiments 1-7, may be contained in a state of 100 weight % as a layer constituent component of such as a positive hole inhibition layer and an electron inhibition layer, or may be contained by being mixed with another organic compound (such as compounds utilized in a constituent layer of an organic EL element of this invention).

The layer thickness of an inhibition layer according to this invention is preferably 3-100 nm and more preferably 5-30 nm.

<Positive Hole Inhibition Layer>

A positive hole inhibition layer, in a broad meaning, is provided with a function of electron transport layer, being comprised of a material having a function of transporting an electron but a very small ability of transporting a positive hole, and can improve the recombination probability of an electron and a positive hole by inhibiting a positive hole while transporting an electron.

As a positive hole inhibition layer, for example, a positive inhibition layer described in such as JP-A Nos. 11-204258 and 11-204359 and p. 273 of “Organic EL Elements and Idustrialization Front Thereof (Nov. 30 (1998), published by N. T. S Corp.)” is applicable to a positive hole inhibition (hole block) layer according to this invention. Further, a constitution of an electron transport layer described later can be appropriately utilized as a positive hole inhibition layer according to this invention.

It is preferable that the organic EL layer of the present invention incorporates a positive hole layer, which incorporates derivatives having a ring structure, in which at least one carbon atom of the hydrocarbon ring constituting the above carboline derivative or the carboline ring of the above carboline derivative is substituted with a nitrogen atom.

<Electron Inhibition Layer>

On the other hand, an electron inhibition layer is, in a broad meaning, provided with a function of a positive hole transport layer, being comprised of a material having a function of transporting a positive hole but a very small ability of transporting an electron, and can improve the recombination probability of an electron and a positive hole by inhibiting an electron while transporting a positive hole. Further, a constitution of a positive hole transport layer described later can be appropriately utilized as an electron inhibition layer.

Further, in this invention, it is preferable to utilize an organic EL element material of this invention described above in an adjacent layer neighboring to an emission layer, that is in a positive hole inhibition layer and an electron inhibition layer, and specifically preferably in a positive hole inhibition layer.

<Positive Hole Transport Layer>

A positive hole transport layer contains a material having a function of transporting a positive hole, and in a broad meaning, a positive hole injection layer and an electron inhibition layer are also included in a positive hole transport layer. A single layer of or plural layers of a positive hole transport layer may be provided.

A positive hole transport material is not specifically limited and can be arbitrary selected from those such as generally utilized as a charge injection transporting material of a positive hole in a conventional photoconductive material and those which are well known in the art and utilized in a positive hole injection layer and a positive hole transport layer of an EL element.

A positive hole transport material is those having any one of a property to inject or transport a positive hole or a barrier property to an electron, and may be either an organic substance or an inorganic substance. For example, listed are a triazole derivative, an oxadiazole derivative, an imidazole derivative, a polyallylalkane derivative, a pyrazolone derivative, a phenylenediamine derivative, a allylamine derivative, an amino substituted chalcone derivative, an oxazole derivatives, a styrylanthracene derivative, a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aniline type copolymer, or conductive polymer oligomer and specifically preferably such as thiophene oligomer.

As a positive hole transport material, those described above can be utilized, however, it is preferable to utilized a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, and specifically preferably an aromatic tertiary amine compound.

Typical examples of an aromatic tertiary amine compound and a styrylamine compound include N,N,N′,N′-tetraphenyl-4,4′-diaminophenyl; N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TDP); 2,2-bis(4-di-p-tolylaminophenyl)propane; 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane; N,N,N′,N′-tetra-p-tolyl4,4′-diaminobiphenyl; 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane; bis(4-dimethylamino-2-metyl)phenylmethane; bis(4-di-p-tolylaminophenyl)phenylmethane; N,N′-diphenyl-N,N′-di(4-methoxyphenyl)-4,4′-diaminobiphenyl; N,N,N′,N′-tetraphenyl-4,4′-diaminophenylether; 4,4′-bis(diphenylamino)quarterphenyl; N,N,N-tri(p-tolyl)amine; 4-(di-p-tolylamino)-4′-[4-(di-p-triamino)styryl]stilbene; 4-N,N-diphenylamino-(2-diphenylvinyl)benzene; 3-methoxy-4′-N,N-diphenylaminostilbene; and N-phenylcarbazole, in addition to those having two condensed aromatic rings in a molecule described in U.S. Pat. No. 5,061,569, such as 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NDP), and 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MDTDATA), in which three of triphenylamine units are bonded in a star burst form, described in JP-A 4-308688.

Polymer materials, in which these materials are introduced in a polymer chain or constitute the main chain of polymer, can be also utilized. Further, an inorganic compound such as a p type-Si and a p type-SiC can be utilized as a positive hole injection material and a positive hole transport material

This positive hole transport layer can be prepared by forming a thin layer made of the above-described positive hole transport material according to a method well known in the art such as a vacuum evaporation method, a spin coating method, a cast method, an inkjet method and a LB method. The layer thickness of a positive hole transport layer is not specifically limited, however, is generally 5-5,000 nm. This positive transport layer may have a single layer structure comprised of one or not less than two types of the above described materials.

<Electron Transport Layer>

An electron transfer layer is comprised of a material having a function to transfer an electron, and an electron injection layer and a positive hole inhibition layer are included in an electron transfer layer in a broad meaning. A single layer or plural layers of an electron transfer layer may be provided.

Conventionally, as an electron transfer material utilized in a single layer of an electron transfer layer, and in an electron transfer layer adjacent to the cathode side against an emission layer in the case of utilizing plural electron transfer layers, the following materials are known.

Further, an electron transfer layer is provided with a function to transmit an electron injected from a cathode to an emission layer, and compounds conventionally well known in the art can be utilized by arbitrarily selection as a material thereof.

Examples of a material utilized in this electron transfer layer (hereinafter, referred to as an electron transfer material) include such as a nitro-substituted fluorene derivative, a diphenylquinone derivative, a thiopyradineoxide derivative, a heterocyclic tetracarbonic acid anhydride such as naphthaleneperylene, carbodiimide, a fluorenylidenemethane derivative, anthraquinonedimethane and anthrone derivatives, and an oxadiazole derivative. Further, a thiazole derivative in which an oxygen atom in the oxadiazole ring of the above-described oxadiazole derivative is substituted by a sulfur atom, and a quinoxaline derivative having a quinoxaline ring which is known as an electron attracting group can be utilized as an electron transfer material.

Polymer materials, in which these materials are introduced in a polymer chain or these materials form the main chain of polymer, can be also utilized.

Further, a metal complex of a 8-quinolinol derivative 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 and bis(8-quinolinol)zinc (Znq); and metal complexes in which a central metal of the aforesaid metal complexes is substituted by In, Mg, Cu, Ca, Sn, Ga or Pb, can be also utilized as an electron transfer material. Further, metal-free or metal phthalocyanine, or those the terminal of which is substituted by an alkyl group and a sulfonic acid group, can be preferably utilized as an electron transfer material. Further, distyrylpyrazine derivative, which has been exemplified as a material of an emission layer, can be also utilized as an electron transfer material, and, similarly to the case of a positive hole injection layer and a positive hole transfer layer, an inorganic semiconductor such as an n-type-Si and an n-type-SiC can be also utilized as an electron transfer material.

This electron transport layer can be prepared by forming a thin layer made of the above-described electron transport material according to a method well known in the art such as a vacuum evaporation method, a spin coating method, a cast method, an inkjet method and a LB method. The layer thickness of an electron transport layer is not specifically limited; however, is generally 5-5,000 nm. This electron transport layer may have a single layer structure comprised of one or not less than two types of the above described materials.

Next, an injection layer which is known as a constituent layer of an organic EL element of this invention will be explained.

<Injection Layer>: Electron Injection Layer, Positive Hole Injection Layer

An injection layer is appropriately provided and includes an electron injection layer and a positive hole injection layer, which may be arranged between an anode and an emission layer or a positive transfer layer, and between a cathode and an emission layer or an electron transfer layer, as described above.

An injection layer is a layer which is arranged between an electrode and an organic layer to decrease an operating voltage and to improve an emission luminance, which is detailed in volume 2, chapter 2 (pp. 123-166) of “Organic EL Elements and Industrialization Front thereof (Nov. 30th 1998, published by N. T. S Corp.)”, and includes a positive hole injection layer (an anode buffer layer) and an electron injection layer (a cathode buffer layer).

An anode buffer layer (a positive hole injection layer) is also detailed in such as JP-A 9-45479, 9-260062 and 8-288069, and specific examples include such as a phthalocyanine buffer layer comprising such as copper phthalocyanine, an oxide buffer layer comprising such as vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer employing conductive polymer such as polythiophene.

A cathode buffer layer (an electron injection layer) is also detailed in such as JP-A 6-325871, 9-17574 and 10-74586, and specific examples include a metal buffer layer comprising such as strontium and aluminum, an alkali metal compound buffer layer comprising such as lithium fluoride, an alkali earth metal compound buffer layer comprising such as magnesium fluoride, and an oxide buffer layer comprising such as aluminum oxide.

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

This injection layer can be prepared by forming a thin layer made of the above-described material according to a method well known in the art such as a vacuum evaporation method, a spin coating method, a cast method, an inkjet method and a LB method. The layer thickness of an injection layer is not specifically limited; however, is generally 5-5,000 nm. This injection layer may have a single layer structure comprised of one or not less than two types of the above described materials.

<Anode>

As an anode according to an organic EL element of this invention, those comprising metal, alloy, a conductive compound, which is provided with a large work function (not less than 4 eV), and a mixture thereof as an electrode substance are preferably utilized. Specific examples of such an electrode substance include a conductive transparent material such as metal like Au, CuI, indium tin oxide (ITO), SnO2 and ZnO. Further, a material such as IDIXO (In2O3—ZnO), which can prepare an amorphous and transparent electrode, may be also utilized. As for an anode, these electrode substances may be made into a thin layer by a method such as evaporation or spattering and a pattern of a desired form may be formed by means of photolithography, or in the case of requirement of pattern precision is not so severe (not less than 100 μm), a pattern may be formed through a mask of a desired form at the time of evaporation or spattering of the above-described substance. When emission is taken out of this anode, the transmittance is preferably set to not less than 10% and the sheet resistance as an anode is preferably not more than a few hundreds Ω/□. Further, although the layer thickness depends on a material, it is generally selected in a range of 10-1,000 nm and preferably of 10-200 nm.

<Cathode>

On the other hand, as a cathode according to this invention, metal, alloy, a conductive compound and a mixture thereof, which have a small work function (not more than 4 eV), are utilized as an electrode substance. Specific examples of such an electrode substance includes such as sodium, sodium-potassium alloy, magnesium, lithium, a magnesium/copper mixture, a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al2O3) mixture, indium, a lithium/aluminum mixture and rare earth metal. Among them, with respect to an electron injection property and durability against such as oxidation, preferable are a mixture of electron injecting metal with the second metal which is stable metal having a work function larger than electron injecting metal, such as a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al2O3) mixture and a lithium/aluminum mixture, and aluminum. As for a cathode, these electrode substances may be made into a thin layer by a method such as evaporation or spattering. Further, the sheet resistance as a cathode is preferably not more than a few hundreds Ω/□ and the layer thickness is generally selected in a range of 10-1,000 nm and preferably of 10-200 nm. Herein, to transmit emission, either one of an anode or a cathode of an organic EL element is preferably transparent or translucent to improve the mission luminance.

<Substrate (Also Referred to as Base Plate, Base Material or Support)>

A substrate according to an organic EL element of this invention is not specifically limited with respect to types of such as glass and plastics provided being transparent, however, a substrate preferably utilized includes such as glass, quartz and transparent resin film. A specifically preferable substrate is resin film capable of providing an organic EL element with a flexible property.

Resin film includes such as film comprised of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulphone (PES), polyether imide, polyether etherketone, polyphenylene sulfide, polyallylate, polyimide, polycarbonate (PC) and cellulose acetate propionate (CAP).

On the surface of resin film, an inorganic or organic cover layer or a hybrid cover layer comprising the both may be formed, and the film is preferably provided with a high barrier ability having a vapor transmittance of not more than 0.01 g/m2·day·at a temperature of 25±0.5° C., relative humidity (90±2)% RH, measured based on JIS K 7129-1992.

The taking out efficiency of emission of an organic EL element of this invention at room temperature is preferably not less than 1% and more preferably not less than 2%. Herein, taking out quantum efficiency (%)=photon number emitted out of organic EL element/electron number flown into organic EL element×100.

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

In the case of an illumination application, roughening processed film (such as anti-glare film) can be also utilized in combination to decrease emission unevenness.

In the case of an application as a multi-color display device, the display is comprised of at least two types of organic EL elements having different emission maximum wavelengths, and a preferable example to prepare an organic EL element will now be explained.

<Preparation Method of Organic EL Element>

As an example of a preparation method of an organic EL element of this invention, a preparation method of an organic EL element, comprising anode/positive hole injection layer/positive hole transport layer/emission layer/positive hole inhibition layer/electron transport layer/cathode buffer layer/cathode, will be explained.

First, on an appropriate substrate, a thin layer comprising a desired electrode substance such as an anode electrode substance is formed by means of evaporation or spattering so as to make a layer thickness of not more than 1 μm and preferably of 10-200 nm, whereby an anode is prepared. Next, on this layer, thin layers containing organic substances of such as a positive hole injection layer, a positive hole transport layer, an emission layer, a positive hole inhibition layer and an electron transport layer are formed.

A thin layer forming method of these layers containing the organic substances includes such as a spin coat method, a cast method, an inkjet method, an evaporation method and a printing method as described before, however, a vacuum evaporation method or a spin coat method is specifically preferable with respect to easy preparation of a homogeneous layer and bare generation of pinholes. Further, a different layer forming method depending on each layer may be applied. In the case of employing an evaporation method in layer formation, the evaporation condition depends on such as the type of a utilized compound, however, is generally appropriately selected in a range of 50-450° C. as a boat heating temperature, 10−6-10−2 Pa as a vacuum degree, 0.01-50 nm/sec as a deposition rate, −50-300° C. as a substrate temperature and 1 nm-5 μm as a layer thickness.

After formation of these layers, a thin layer comprising a cathode electrode substance is formed thereon by means of such as evaporation or spattering so as to make a layer thickness in a range of 50-200 nm to provide a cathode, whereby a desired organic EL element can be prepared. This preparation of an organic EL element is preferably carried out with one time evacuation to prepare all through from a positive hole injection layer to a cathode, however, different layer forming method may be also applied by taking out the element on the way. At that time, it is preferable to take consideration such as to perform the operation under a dry inert gas environment.

<Display Device>

A display device of this invention will now be explained. The display device of this invention includes the above-described organic EL element.

A display device of this invention may be either monochromatic or multi-colored. Here explained will be a multicolor display device. In the case of a multicolor display device, a shadow mask is provided only at the time of emission layer formation, and layers can be formed all over the surface by such as an evaporation method, a cast method, a spin coat method, an inkjet method and a printing method.

When patterning is performed only with an emission layer, the method is not specifically limited; however, preferable are an evaporation method, an inkjet method and a printing method. And patterning employing a shadow mask is preferred in the case of an evaporation method.

Further, reversing the preparation order, it is also possible to prepare layers in the order of a cathode, an electron transport layer, a positive hole inhibition layer, an emission layer, a positive hole transport layer and an anode.

When a direct current voltage is applied on the multicolor display device thus prepared, emission can be observed by application of a voltage of approximately 2-40 V setting an anode to + polarity and a cathode to − polarity. Further, no current flows and no emission generate at all even when a voltage is applied with a reversed polarity. Further, in the case of alternate current voltage being applied, emission generates only in a state of an anode being + and a cathode being −. Herein, the wave shape of alternate current may be arbitrary.

A multicolor display device can be utilized as a display device, a display and various types of emission light sources. In a display device and a display, full-colored display is possible by employing three types of organic EL elements providing blue, red and green emissions.

A display device and a display include a TV, a personal computer, a mobile instrument, an AV instrument, a character broadcast display and an information display in a car. Particularly, the display device and the display may be also utilized as a display to playback still images and moving images, and may adopt either a simple matrix (a passive matrix) mode or an active matrix mode when being utilized as a display device for moving image playback.

An illumination light source includes a home use illumination, a car room illumination, a backlight of a watch or a liquid crystal, a panel advertisement, a signal, a light source of an optical memory medium, a light source for an electrophotographic copier, a light source for an optical telecommunication processor and a light source for a photo-sensor, however, is not limited thereto.

<Illumination Device>

An illumination device (or a lighting device) of this invention will now be explained. The illumination device of this invention includes the above-described organic EL element.

An organic EL element of this invention can be utilized as an organic EL element provided with a resonator structure, and a utilization purpose of such an organic EL element provided with a resonator structure includes such as a light source for an optical memory medium, a light source for an electrophotographic copier, a light source for a optical telecommunication processor and a light source for a photo-sensor, however, is not limited thereto. Further, the organic EL element may be utilized for the above-described applications by being made to perform laser emission.

Further, an organic EL element of this invention may be utilized as one type of a lamp like an illumination and an exposure light, and may be also utilized as a display device of a projector of an image projecting type and a display device (a display) of a type to directly view still images and moving images. An operating mode in the case of being utilized as a display device for playback of moving images may be either a simple matrix (a passive matrix) mode or an active matrix mode. In addition, a full-color display device can be prepared by utilizing at least two types of organic EL elements of this invention which emit different emitting colors.

In the following, one example of a display device provided with an organic EL element of this invention will be explained.

FIG. 1 is a schematic drawing to show an example of a display device constituted of an organic EL element. It is a schematic drawing of a display, which displays image information by emission of an organic EL element, such as a mobile phone.

Display 1 is constituted of such as display section A having plural number of pixels and control section B which performs image scanning of display section A based on image information.

Control section B, which is electrically connected to display section A, sends a scanning signal and an image data signal to plural number of pixels based on image information from the outside and pixels of each scanning line successively emit depending on the image data signal by a scanning signal to perform image scanning, whereby image information is displayed on display section A.

FIG. 2 is a schematic drawing of display section A.

Display section A is provided with such as a wiring part, which contains plural scanning lines 5 and data lines 6, and plural pixels 3 on a substrate. Primary part materials of display section A will be explained in the following.

In the drawing, shown is the case that light emitted by pixel 3 is taken out along the white allow (downward).

Scanning lines 5 and plural data lines 6 in a wiring part each are comprised of a conductive material, and scanning lines 5 and data lines 6 are perpendicular in a grid form and are connected to pixels 3 at the right-angled crossing points (details are not shown in the drawing).

Pixel 3 receives an image data from data line 6 when a scanning signal is applied from scanning line 5 and emits according to the received image data. Full-color display device is possible by appropriately arranging pixels having an emission color in a red region, pixels in a green region and pixels in a blue region, side by side on the same substrate.

Next an emission process of a pixel will be explained.

FIG. 3 is a schematic drawing of a pixel.

A pixel is equipped with such as organic EL element 10, switching transistor 11, operating transistor 12 and condenser 13. Red, green and blue emitting organic EL elements are utilized as organic EL element 10 for plural pixels, and full-color display device is possible by arranging these side by side on the same substrate.

In FIG. 3, an image data signal is applied on the drain of switching transistor 11 via data line 6 from control section B. Then, when a scanning signal is applied on the gate of switching transistor 11 via scanning line 5 from control section B, operation of switching transistor is on to transmit the image data signal applied on the drain to the gates of condenser 13 and operating transistor 12.

Operating transistor 12 is on, simultaneously with condenser 13 being charged depending on the potential of an image data signal, by transmission of an image data signal. In operating transistor 12, the drain is connected to electric source line 7 and the source is connected to the electrode of organic EL element 10, and an electric current is supplied from electric source line 7 to organic EL element 10 depending on the potential of an image data applied on the gate.

When a scanning signal is transferred to next scanning line 5 by successive scanning of control section B, operation of switching transistor 11 is off. However, since condenser 13 keeps the charged potential of an image data signal even when operation of switching transistor 11 is off, operation of operating transistor 12 is kept on to continue emission of organic EL element 10 until the next scanning signal is applied. When the next scanning signal is applied by successive scanning, operating transistor 12 operates depending on the potential of an image data signal synchronized to the scanning signal and organic EL element 10 emits.

That is, emission of each organic EL element 10 of plural pixels 3 is performed by providing switching transistor 11 and operating transistor 12 against each organic EL element 10 of plural pixels 3. Such an emission method is called as an active matrix mode.

Herein, emission of organic EL element 10 may be either emission of plural gradations based on a multiple-valued image data signal having plural number of gradation potentials or on and off of a predetermined emission quantity based on a binary image data signal. Further, potential hold of condenser 13 may be either continuously maintained until the next scanning signal application or discharged immediately before the next scanning signal application.

In this invention, emission operation is not necessarily limited to the above-described active matrix mode but may be a passive matrix mode in which organic EL element is emitted based on a data signal only when a scanning signal is scanned.

FIG. 4 is a schematic drawing of a display device based on a passive matrix mode. In FIG. 4, plural number of scanning lines 5 and plural number of image data lines 6 are arranged grid-wise, opposing to each other and sandwiching pixels 3.

When a scanning signal of scanning line 5 is applied by successive scanning, pixel 3 connected to scanning line 5 applied with said signal emits depending on an image data signal.

Since pixel 3 is provided with no active element in a passive matrix mode, decrease of manufacturing cost is possible.

An organic EL element material of this invention can be also applied to an organic EL element to generate emission of practically white color as an illumination device. Plural emission colors are simultaneously emitted by plural number of emission materials to obtain white light by mixing colors. A combination of plural emission colors may be either the one, in which three emission maximum wavelengths of three primary colors of blue, green and red are contained, or the other, in which two emission maximum wavelengths, utilizing a relationship of complimentary colors such as blue and yellow, or blue and orange, are contained.

Further, a combination of emission materials to obtain plural number of emission colors may be either a combination comprising plural number of materials which emit phosphoresce or fluorescence, or a combination of a material which emits phosphoresce or fluorescence and a dye material which emits by light from an emission material as exiting light, however, in a white organic electroluminescent element according to this invention, it is enough only to mix plural emission dopants in combination. A mask is provided only at the time of forming such as an emission layer, a positive hole transport layer or an electron transport layer, to only simply arrange the plural emission dopants such as by separately painting through the mask, while other layers are commonly utilized to require no patterning such as a mask. Therefore, such as an electrode can be formed all over the plane by such as an evaporation method, a cast method, a spin coat method, an inkjet method and a printing method, resulting in improvement of productivity. According to this method, different from a white organic EL device in which plural colors of emission elements are arranged parallel in an alley form, an element itself is white emitting.

An emission material utilized in an emission layer is not specifically limited, and in the case of a backlight of a liquid crystal display element, any combination by arbitrary selection among platinum complexes according to this invention or emission materials well known in the art can be utilized so as to be fitted to the wavelength range corresponding to CF (color filter) characteristics, whereby white emission can be obtained.

In this manner, a white emitting organic EL element of this invention is usefully utilized as one type of a lamp such as a home use illumination, a car room illumination or an exposure light source as various emission light sources or illumination devices, in addition to the aforesaid display device and a display, and is further usefully applied for a display as such as a backlight of a liquid crystal display.

In addition to these, listed is a wide range of applications such as a backlight of a watch, an advertising board, a signal, a light source of an optical memory medium, a light source of an electrophotographic copier, a light source of an optical telecommunication processor and a light source of an optical sensor, and further general home use electric instruments which require a display device.

EXAMPLES

In the following, this invention will be explained with reference to examples, however, is not limited thereto.

Example 1 <Preparation of Organic EL Element 1-1>

After a substrate, in which ITO had been deposited at 150 nm on a glass plate as an anode (NA-45 produced by NH Techno Glass Co. Ltd.) was subjected to patterning, the transparent support substrate was washed with isopropyl alcohol by use of ultrasonic waves, followed by being dried with a dry nitrogen gas, and was subjected to UV ozone washing for 5 minutes. This transparent support substrate was fixed on a substrate holder of a vacuum evaporation system available on the market, and on the other hand, each of five resistance heating boats made of tantalum was charged with α-NPD, H4, Ir-12, BCP and Alq3, respectively, which was attached in the vacuum evaporation system (in the first vacuum chamber).

Further, a resistance heating boat made of tantalum was charged with lithium fluoride and a resistance heating boat made of tungsten was charged with aluminum, respectively, and these boats were attached in the second chamber of the vacuum evaporation system.

First, after the first vacuum chamber was evacuated down to 4×10−4 Pa, the aforesaid heating boat charged with α-NPD was heated with an electric current to deposit α-NPD on a support substrate at a deposition rate of 0.1-0.2 nm/sec so as to make a layer thickness of 20 nm, whereby a positive hole injection/transport layer was formed.

Further, the aforesaid heating boat charged with H4 and the boat charged with Ir-12 were independently supplied with an electric current to deposit H4 as an emission host and Ir-12 as an emission dopant so as to make a layer thickness of 30 nm while adjusting the deposition rates thereof to 100:6, whereby an emission layer was formed.

Next, the aforesaid heating boat charged with BCP was heated with an electric current to provide a positive hole inhibition layer having a layer thickness of 10 nm at a deposition rate of 0.1-0.2 nm/sec. Further, the aforesaid heating boat charged with Alq3 was heated with an electric current to provide an electron transport layer having a layer thickness of 20 nm at a deposition rate of 0.1-0.2 nm/sec.

Next, after an element having been deposited with up to an electron injection layer as described before was transferred into the second vacuum chamber while keeping vacuum, a mask, which was made of stainless steel and had rectangular holes, was arranged on the electron injection layer by means of remote control from outside of the system.

After the second vacuum chamber was evacuated down to 2×10−4 Pa, a boat charged with lithium fluoride was supplied with an electric current to provide a cathode buffer layer having a layer thickness of 0.5 nm at a deposition rate of 0.01-0.02 nm/sec, and then a boat charged with aluminum was supplied with an electric current to provide a cathode having a layer thickness of 150 nm at a deposition rate of 1-2 nm/sec to obtain Organic EL Element 1-1.

<Preparation of Organic EL Elements 1-2-1-21>

Organic EL Elements 1-2-1-21 each were prepared in a similar manner to preparation of organic EL element 1-1 described above, except that an emission dopant was changed as shown in table 2.

<<Evaluation of Organic EL Elements>>

When resulting Organic EL Elements 1-1-1-21 were evaluated, after their preparation, the non-luminescent side was covered with a glass case, and a 300 μm thick glass substrate was employed as a sealing substrate. Further, an epoxy based radiation curable type adhesive (LAXTRACK C0629B, produced by TOAGOSEI Co., Ltd.) was applied to the periphery as a sealing agent. The resulting substrate was overlapped onto the above anode to come into close contact with the above transparent supporting substrate. Subsequently, UV radiation was exposed to the glass substrate side to result in curing and sealing. Thus, the lighting device as shown in FIGS. 5 and 6 was formed and evaluation was then carried out.

FIG. 5 is a schematic view of a lighting device. Organic EL element 101 is covered with glass cover 102 (sealing operation employing the glass cover was carried out in a globe box (under an atmosphere of high purity nitrogen gas at a purity of at least 99.999%) without contact with atmospheric air). FIG. 6 is a sectional view of the lighting device, in which numeral 105 represents a cathode, 106 represents an organic EL layer, and 107 represents a glass substrate fitted with a transparent electrode. Further, nitrogen gas 108 is fed into glass cover 102, and desiccant 109 is provided.

<Quantum Efficiency of Taking Out>

Each of organic EL elements was lighted under a constant current condition of 2.5 mA/cm2 at room temperature (approximately 23-25° C.), and an emission luminance (L) [cd/m2] immediately after turning on was measured, whereby a quantum efficiency of taking out (η) was calculated. Herein, CS-1000 (produced by Konica Minolta Sensing Inc.) was utilized for measurement of emission luminance. Further, each of the quantum efficiency of taking out was expressed as a relative value when that of organic EL element 1-1 was set to 100.

<Emission Life>

Each of organic EL elements was continuously lighted under a constant current condition of 2.5 mA/cm2 at room temperature (approximately 23-25° C.), and time to reach a half of the initial luminance (τ½) was measured. Further, each emission life was expressed as a relative value when that of organic EL element 1-1 was set to 100.

<Luminescent Color>

Each of organic EL elements was continuously lighted under a constant current condition of 2.5 mA/cm2 at room temperature (approximately 23-25° C.). The luminescent color was visibly observed and evaluated.

The obtained results are shown in table 2.

TABLE 2 Organic Taking- EL Emis- out Lumines- Lumines- Element sion Emission Quantum cent cent Re- No. host dopant Yield Lifetime Color marks 1-1 H4 Ir-12 100 100 Bluish Comp. green 1–2 H4 Compar- 75 95 yellowish Comp. ative 1 green 1–3 H4 Compar- 109 113 yellow Comp. ative 2 1–4 H4 Compar- 112 40 pale Comp. ative 3 bluish white 1–5 H4  (3) 128 325 pure blue Inv. 1–6 H4 (17) 133 488 pure blue Inv. 1–7 H4 (23) 129 342 pure blue Inv. 1–8 H4 (34) 134 470 pure blue Inv. 1–9 H4 (42) 129 445 pure blue Inv. 1–10 H4 (54) 135 538 blue Inv. 1–11 H6 (68) 141 501 blue Inv. 1–12 H6 (83) 139 529 pure blue Inv. 1–13 H6 (95) 135 520 pure blue Inv. 1–14 H6 (97) 142 649 bluish Inv. green 1–15 H6 (123)  145 588 pure blue Inv. 1–16 H6 (133)  141 613 blue Inv. 1–18 H30 (154)  149 688 blue Inv. 1–19 H30 (176)  143 632 blue Inv. 1–20 H30  (3) 135 362 blue Inv. 1–21 H30 (97) 150 678 bluish Inv. green Comp.: Comparative Example, Inv.: Present Invention

Based on Table 2, it is clear that the organic EL elements prepared via the metal complexes according to the present invention attain high luminescent efficiency and extended luminescent lifetime, compared to the EL element of the Comparative Examples. In addition, compared to the organic EL elements of the Comparative Examples, it was found that the purity of blue color is higher, resulting in a more useful blue luminescent element. Further, it was noticed that by simultaneously employing, in the emission layer, a derivative having the ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline derivative or the carboline ring of the carboline derivative was substituted with a nitrogen atom, targeted effects of the present invention were further enhanced.

Example 2 <Preparation of Organic EL Element 2-1>

After a substrate, in which ITO had been deposited at 150 nm on a glass plate as an anode (NA-45 produced by NH Techno Glass Co. Ltd.) was subjected to patterning, the transparent support substrate was washed with isopropyl alcohol by use of ultrasonic waves, followed by being dried with a dry nitrogen gas, and was subjected to UV ozone washing for 5 minutes.

This transparent support substrate was fixed on a substrate holder of a vacuum evaporation system available on the market, and on the other hand, each of five resistance heating boats made of tantalum was charged with A-NPD, H2, Ir-13, BCP and Alq3, respectively, which was attached in the vacuum evaporation system (in the first vacuum chamber).

Further, a resistance heating boat made of tantalum was charged with lithium fluoride and a resistance heating boat made of tungsten was charged with aluminum, respectively, and these boats were attached in the second chamber of the vacuum evaporation system.

First, after the first vacuum chamber was evacuated down to 4×10−4 Pa, the aforesaid heating boat charged with α-NPD was heated with an electric current to deposit α-NPD on a support substrate at a deposition rate of 0.1-0.2 nm/sec so as to make a layer thickness of 20 nm, whereby a positive hole injection/transport layer was formed.

Further, the aforesaid heating boat charged with H2 and the boat charged with Ir-13 were independently supplied with an electric current to deposit H2 as an emission host and Ir-13 as an emission dopant so as to make a layer thickness of 30 nm while adjusting the deposition rates thereof to 100:6, whereby an emission layer was formed.

Next, the aforesaid heating boat charged with BCP was heated with an electric current to provide a positive hole inhibition layer having a layer thickness of 10 nm at a deposition rate of 0.1-0.2 nm/sec. Further, the aforesaid heating boat charged with Alq3 was heated with an electric current to provide an electron transport layer having a layer thickness of 20 nm at a deposition rate of 0.1-0.2 nm/sec.

Next, after an element having been deposited with up to an electron injection layer as described before was transferred into the second vacuum chamber while keeping vacuum, a mask, which was made of stainless steel and had rectangular holes, was arranged on the electron injection layer by means of remote control from outside of the system.

After the second vacuum chamber was evacuated down to 2×10−4 Pa, a boat charged with lithium fluoride was supplied with an electric current to provide a cathode buffer layer having a layer thickness of 0.5 nm at a deposition rate of 0.01-0.02 nm/sec, and then a boat charged with aluminum was supplied with an electric current to provide a cathode having a layer thickness of 150 nm at a deposition rate of 1-2 nm/sec to obtain Organic EL Element 2-1.

<Preparation of Organic EL Elements 2-2-2-31>

Organic EL Elements 2-2-2-31 each were prepared in a similar manner to preparation of organic EL element 2-1 described above, except that an emission dopant was changed as shown in table 3.

<<Evaluation of Organic EL elements>>

When resulting Organic EL Elements 2-1-2-31 were evaluated, after their preparation, the non-luminescent side was covered with a glass case, and a 300 μm thick glass substrate was employed as a sealing substrate. Further, an epoxy based radiation curable type adhesive (LAXTRACK C0629B, produced by TOAGOSEI Co., Ltd.) was applied to the periphery as a sealing agent. The resulting substrate was overlapped onto the above anode to come into close contact with the above transparent supporting substrate. Subsequently, UV radiation was exposed to the glass substrate side to result in curing and sealing. Thus, the lighting device as shown in FIGS. 5 and 6 was formed and evaluation was then carried out.

Taking-out quantum efficiency, luminescent lifetime, and luminescent color were evaluated in the same manner as for Example 1. The taking-out quantum efficiency and the luminescent lifetime were expressed by relative values when each value of Organic EL Element 2-1 was 100. Table 3 shows the results.

TABLE 3 Organic Taking- EL out Element Emission Emission Quantum Luminescent Luminescent No. host dopant *1 Yield Lifetime Color Remarks 2-1 H2 Ir-13 BCP 100 100 yellowish Comp. green 2-2 H2 Comparative 1 BCP 83 95 yellowish Comp. green 2-3 H2 Comparative 4 BCP 110 65 blue Comp. 2-4 H2 Comparative 5 BCP 73 70 blue Comp. 2-5 H2 Comparative 6 BCP 90 69 blue Comp. 2-6 H2 Comparative 7 BCP 94 100 bluish Comp. green 2-7 H2 Comparative 8 BCP 108 94 yellow Comp. 2-8 H2 Comparative 9 BCP 125 889 yellow Comp. 2-9 H2 (7) BCP 135 360 pure blue Inv. 2-10 H2 (27) BCP 140 372 pure blue Inv. 2-11 H2 (38) BCP 142 368 pure blue Inv. 2-12 H4 (56) BCP 151 582 blue Inv. 2-13 H4 (77) BCP 153 603 blue Inv. 2-14 H4 (97) BCP 156 707 bluish Inv. green 2-15 H4 (106) BCP 149 668 blue Inv. 2-16 H6 (113) BCP 154 692 blue Inv. 2-17 H6 (119) BCP 148 671 blue Inv. 2-18 H6 (139) BCP 159 721 blue Inv. 2-19 H6 (146) BCP 157 764 pure blue Inv. 2-20 H10 (150) BCP 155 738 pure blue Inv. 2-21 H10 (154) BCP 158 756 blue Inv. 2-22 H10 (159) BCP 156 744 pure blue Inv. 2-23 H10 (161) BCP 152 715 pure blue Inv. 2-24 H2 (7) H5 141 399 pure blue Inv. 2-25 H4 (56) H5 156 615 blue Inv. 2-26 H4 (97) H5 161 738 bluish Inv. green 2-27 H6 (119) H5 154 698 blue Inv. 2-28 H6 (146) H5 164 822 pure blue Inv. 2-29 H10 (154) H26 166 798 blue Inv. 2-30 H10 (159) H26 163 801 pure blue Inv. 2-31 H10 (161) H26 159 745 pure blue Inv. Comp.: Comparative Example, Inv.: Present Invention *1: Positive Hole Blocking Material

Based on Table 3, it is apparent that the organic EL elements prepared via the metal complexes according to the present invention attained high luminescent efficiency and extended luminescent lifetime, compared to the EL element of Comparative Examples. In addition, compared to the organic EL elements resulting in long wavelength by employing Comparative 9, it is clear that when the organic EL element materials of the present invention are employed, satisfactory effects to shorten the wavelength were realized.

Further, it was noticed that by simultaneously employing, in the emission layer, a derivative having the ring structure in which at least one carbon atom of the hydrocarbon ring constituting the carboline derivative or the carboline ring of the carboline derivative was substituted with a nitrogen atom, targeted effects of the present invention were further enhanced.

Example 3

A cathode (at a thickness of 200 nm) composed of an indium tin oxide (ITO at an indium/tin=95/5 mol ratio) was formed on a 25 mm×25 mm×0.5 mm glass substrate under application of a direct electric current, employing a sputtering method. The surface resistance of the resulting cathode was 10Ω/□. The above surface was coated with a dichloroethane solution in which polyvinylcarbazole (being a positive hole transporting binder polymer)/Ir-13 (being a blue fluorescent ortho metal complex)/2-(4-biphenylyl-5(4-t-butylphenyl)-1,3,4-oxazole (being an electron transport material)=200/2/50 mole ratio were dissolved, employing a spin coater, whereby a 100 nm emission layer was prepared. On the resulting organic compound layer, a mask (being a mask resulting in a luminescent area of 5 mm×5 mm), which was subjected to patterning, was arranged and an anode was arranged in such a manner that in a vacuum evaporation device, 0.5 mm lithium fluoride was evaporated as an anode buffer layer and 150 nm aluminum as a cathode was evaporated, whereby Blue Luminescent Organic EL Element 3-1 was prepared.

<<Evaluation of Organic EL Elements>>

Organic EL Elements 3-2-3-11 were prepared in the same manner as Organic EL Element 3-1, except that the emission dopant was changed as described in Table 4.

When resulting Organic EL Elements 3-1-3-11 were evaluated, after their preparation, the non-luminescent side was covered with a glass case, and a 300 μm thick glass substrate was employed as a sealing substrate. Further, an epoxy based radiation curable type adhesive (LAXTRACK C0629B, produced by TOAGOSEI Co., Ltd.) was applied to the periphery as a sealing agent. The resulting substrate was overlapped onto the above anode to come into close contact with the above transparent supporting substrate. Subsequently, UV radiation was exposed to the glass substrate side to result in curing and sealing. Thus, the lighting device as shown in FIGS. 5 and 6 was formed and evaluation was then carried out.

Subsequently, luminance and luminescent efficiency were determined as described below.

(Luminance and Luminescent Efficiency)

By employing SOURCE MAJOR UNIT Type 2400, produced by Toyo Technica Inc., DC voltage was applied to an organic EL element to result in luminescence. Luminance (cd/m2) in the case in which 10 V DC voltage was applied, was determined and luminescent efficiency (lm/W). In the case in which an electric current of 2.5 mA/cm2 was run, was also determined. Table 4 shows the results.

TABLE 4 Organic EL Luminescent Element Emission Luminance Efficiency No. dopant (cd/m2) (lm/W) Remarks 3-1 Ir-13 100 100 Comparative Example 3-2 (7) 132 134 Present Invention 3-3 (39) 139 141 Present Invention 3-4 (57) 142 142 Present Invention 3-5 (68) 140 141 Present Invention 3-6 (95) 138 140 Present Invention 3-7 (97) 144 147 Present Invention 3-8 (116) 146 150 Present Invention 3-9 (146) 153 156 Present Invention  3-10 (154) 155 157 Present Invention  3-11 (169) 154 155 Present Invention

Based on Table 4, it is evident that the organic EL elements prepared by employing the metal complexes according to the present invention attained high luminescent efficiency and high luminance, compared to the EL element of the Comparative Example.

Example 4 <Preparation of Full-color Display Device> (Preparation of Blue Emission Element)

Organic EL Element 1-18 of example 1 was utilized as a blue emission element.

(Preparation of Green Emission Element)

A green emission element was prepared by substituting Ir-13 used in Organic EL element 2-1 of Example 2 with Ir-1.

(Preparation of Red Emission Element)

A red emission element was prepared by substituting Ir-13 used in Organic EL element 2-1 of Example 2 with Ir-9.

Each of red, green and blue organic EL elements prepared above was arranged parallel on the same substrate to prepare an active matrix mode full-color having a form as described in FIG. 1, and only display section A of said display device is schematically shown in FIG. 2. That is, a wiring section containing plural lines of scanning line 5 and data line 6, and plural pixels 3 (such as a pixel having an emission color of a red region, a pixel of a green region and a pixel of a blue region) arranged parallel are provided on the same substrate, and scanning lines 5 and data lines 6 in a wiring section, which are comprised of a conductive material, respectively, cross each other at a right angle in a grid form to be connected to pixels 3 at the right-angled crossing points (details being not shown in the drawing). The aforesaid plural pixels 3 each are operated in an active matrix mode, in which an organic EL element, a switching transistor and an operating transistor are provided corresponding to each emission color, and receive an image data signal from data line 6 when a scanning signal is applied from scanning line 5 to emit based on the received image data. Each red, green and blue pixel was appropriately arranged parallel in this manner, whereby a full-color display device was prepared.

It has been proved that a full-color moving image display device exhibiting a high luminance, a high durability and a highly visibility can be achieved by operating said full-color display.

Example 5 <Preparation of White Emitting Element and White Illumination>

A transparent electrode substrate of example 1 was subjected to patterning of an electrode having an area of 20 mm×20 mm, and α-NPD was deposited thereon at a layer thickness of 25 nm as a positive hole injection/transport layer in a similar manner to example 1; and further the aforesaid heating boat charged with H4, boat containing Example compound (159) and boat containing Ir-9 were supplied with an electric current to deposit an emission layer having a layer thickness of 30 nm, while adjusting the evaporation rates of CBP as an emission host, Example compound (159) and Ir-9 as emission dopants to be 100:5:0.6.

Successively, BCP was deposited at 10 nm to provide a positive hole inhibition layer. Further, Alq3 was deposited at 40 nm to provide an electron transport layer.

Next, similar to example 1, a mask with square holes having a shape nearly same as a transparent electrode made of stainless steel was arranged on an electron injection layer, and 0.5 nm of lithium fluoride as a cathode buffer layer and 150 nm of aluminum as a cathode were deposited.

This element was equipped with a sealed can, which had a similar structure and was prepared in a similar method to example 1, to prepare flat lamps shown in FIGS. 5 and 6.

Nearly white light was obtained when these lamps were supplied with an electric current to prove that said lamp can be utilized as an illumination.

Example 6 <<Preparation of Organic EL Element 6-1>>: Present Invention

After carrying out patterning on a substrate (NA-45, produced by NH Techno Glass Co.) prepared in such a manner that ITO (being indium tin oxide) was applied at a thickness of 100 nm onto, a 100 mm×100 mm×1.1 mm glass substrate as an anode, the resulting transparent substrate fitted with the above ITO transparent electrode was subjected to ultrasonic washing employing isopropyl alcohol and dried via desiccated nitrogen gas, and then subjected to UV ozone cleaning for 5 minutes.

A solution prepared by diluting poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT/PSS, produced by Bayer Co., BASYTRON P A1 4083) with pure water to 70% by weight was applied to the resulting transparent substrate at 3,000 rpm over 30 seconds, employing a spin coating method, and subsequently dried at 200° C. over 1 hour, whereby a 30 nm thick positive hole injection transport layer was resulted.

A solution prepared by dissolving 30 mg of PO-1 of the present invention in 3 ml of toluene was applied onto the resulting positive hole injection transport layer at 1,000 rpm over 30 seconds, employing a spin coating method, and subsequently dried for one hour under vacuum, whereby a 80 mm thick emission layer was prepared.

The resulting layer was placed in a vacuum deposition apparatus, and subsequently, the pressure of the vacuum tank was reduced to 4×10−4 Pa. Subsequently, 10 nm calcium as a cathode buffer layer was deposited, while 110 nm aluminum as a cathode was deposited, whereby Organic EL Element 6-1 was prepared.

<<Preparation of Organic EL Elements 6-2-6-17>>: Present Invention

Each of Organic EL Elements 6-2-6-17 was prepared in the same manner as Organic Element 6-1, except that “PO-1” employed to prepare the luminance layer was replaced with each of PO-2, PO-3, PO-7, PO-8, PO-10, PO-11, PO-13, PO-15, PO-17, PO-20, PO-22, PO-23, PO-24, PO-25, PO-29, and PO-30.

<<Preparation of Organic EL Element 6-18>>: Comparative Example

Organic EL Element 6-18 was prepared in the same manner as Organic EL Element 6-1, except that 3 ml of the solution of PO-1 of the present invention was replaced with the solution described in following (A).

  • (A): Solution prepared by dissolving 30 mg of polyvinylcarbazole and 1.5 mg of Ir-13 (being a blue luminescent orthometalated complex)

<<Evaluation of Organic EL Elements 6-1-6-18>>

When resulting Organic EL Elements 6-1 through 6-18 were evaluated, after their preparation, the non-luminescent side of each Organic EL element was covered with a glass case, and a 300 μm thick glass substrate was employed as a sealing substrate. Further, an epoxy based radiation curing type adhesive (LAXTRUCK C0629B, produced by TOA Synthetic Co.) was applied to the periphery as a sealing agent. The resulting substrate was overlapped onto the above anode to come into close contact with the above transparent supporting substrate. Subsequently, UV radiation was exposed to the glass substrate side to result in curing and sealing. Thus, the lighting device as shown in FIGS. 5 and 6 was formed and evaluation was carried out.

Subsequently, taking-out quantum efficiency and luminescent lifetime were determined as follows.

<<Taking-Out Quantum Efficiency>>

Under a desiccated nitrogen gas atmosphere at 23° C., 2.5 mA/cm2 constant-current was applied to each of Organic EL Elements prepared as above and taking-out quantum efficiency (in %) was determined. Determination was carried out employing a spectral radiance meter CS-1000 (produced by Konica Minolta Holdings, Inc.).

<<Luminescent Lifetime>>

Under a desiccated nitrogen gas atmosphere at 23° C., 2.5 mA/cm2 constant-current was applied to each of Organic EL Elements, and the time, which was required for the change in which the luminance just after luminance initiation (being initial luminance) was halved, was determined. The determined value was designated the half lifetime (τ1/2) and employed as an index for lifetime. Determination was carried out also employing a spectral radiance meter CS-1000 (produced by Konica Minolta Holdings, Inc.).

Measurement results of the taking-out quantum efficiency and the luminescent lifetime of Organic EL Elements 6-1-6-18 were subjected to relative evaluation when each value of Organic EL Element 6-18 was to be 100. Table 5 shows the results.

TABLE 5 Taking-out Organic Material Quantum EL in Yield Lumines- Lumines- Element emission (relative cent cent No. Layer value) Lifetime Color Remarks 6-1 PO-1 139 529 blue Inv. 6-2 PO-2 48 685 blue Inv. 6-3 PO-3 152 531 blue Inv. 6-4 PO-7 160 458 blue Inv. 6-5 PO-8 141 624 blue Inv. 6-6 PO-10 155 652 blue Inv. 6–7 PO-11 121 418 blue Inv. 6–8 PO-13 172 713 blue Inv. 6–9 PO-15 154 851 blue Inv. 6–10 PO-17 132 366 blue Inv. 6–11 PO-19 115 584 blue Inv. 6–12 PO-20 128 759 blue Inv. 6–13 PO-22 168 611 blue Inv. 6–14 PO-24 188 763 blue Inv. 6–15 PO-25 176 826 blue Inv. 6–16 PO-29 180 701 green Inv. 6–17 PO-30 168 274 red Inv. 6–18 PVCz/Ir-13 100 100 blue Comp.

As can be seen from Table 5, by employing the polymer compound of the present invention in the emission layer, the taking-out quantum efficiency was significantly enhanced and electrical consumption was markedly reduced, while the luminescent lifetime was also improved.

Further, Element (6-16) employing PO-29 of the present invention resulted in green luminescence, while Element (6-17) employing PO-30 of the present invention resulted in red luminescence. Organic EL Elements other than those resulted in blue luminescence.

Claims

1. An organic electroluminescent element material represented by Formula (1),

wherein Z is a heterocyclic ring comprising a substituent having a steric parameter value (Es) of −0.5 or less at the third atom of the ring counted from a nitrogen atom attached to Z, the nitrogen atom being counted as the first atom;
each X and Y is independently a carbon atom or a nitrogen atom;
A is a group of atoms necessary to form a 5 or 6 membered hydrocarbon ring or heterocyclic ring with X—C;
B is —C(R01)═C(R02)—, —N═C(R02)—, —C(R01)═N—, or —N═N—, provided that each R01 and R02 is independently a hydrogen atom or a substituent;
X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;
m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and
M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

2. An organic electroluminescent element material represented by Formula (1B),

wherein each X and Y is independently a carbon atom or a nitrogen atom;
A is a group of atoms necessary to form a 5 or 6 membered hydrocarbon ring or heterocyclic ring with X—C;
B is —C(R01)═C(R02)—, —N═C(R02)—, —C(R01)═N—, or —N═N—, provided that each R01 and R02 is independently a hydrogen atom or a substituent;
X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;
m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and
M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table; and
Zb is a group selected from the group consisting of:
provided that (*) indicates a position which binds to a nitrogen atom.

3. The organic electroluminescent element material of claim 2, wherein Zb in Formula (1B) has further a halogen atom.

4. An organic electroluminescent element material comprising a polymer having a partial structure represented by Formula (1B) of claim 2 in the molecule.

5. An organic electroluminescent element material represented by Formula (2),

wherein R is a substituent having a steric parameter value (Es) of −0.5 or less,;
R1 is a hydrogen atom or a substituent, and n1 is an integer of 1 to 4;
R2 is a hydrogen atom or a substituent, and n2 is an integer of 1 or 2;
Z1 is a group of atoms necessary to form a 5 or 6 membered hydrocarbon ring or heterocyclic ring with C—C;
Z2 is a group of atoms necessary to form a hydrocarbon ring or a heterocyclic ring with C—C;
X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;
m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and
M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

6. The organic electroluminescent element material of claim 5, wherein in Formula (2), n1 is 2 or more and a plurality of R1s forms a ring by binding together.

7. The organic electroluminescent element material of claim 5, wherein R1 in Formula (2) is an aromatic hydrocarbon having a substituent.

8. The organic electroluminescent element material of claim 5, wherein R1 in Formula (2) is an aromatic heterocylic group or a non aromatic heterocylic group.

9. The organic electroluminescent element material of claim 5, wherein R1 in Formula (2) is an alkoxy group or an aryloxy group.

10. The organic electroluminescent element material of claim 5, wherein R2 in Formula (2) is a substituent.

11. The organic electroluminescent element material of claim 5, wherein Formula (2) is further represented by Formula (3),

wherein R is a substituent having a steric parameter value (Es) of −0.5 or less,;
R1 is a hydrogen atom or a substituent, and n1 is an integer of 1 to 4;
each R2 and R3 is independently a hydrogen atom or a substituent, n2 is an integer of 1 or 2 and n3 is an integer of 1 to 4;
X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;
m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and
M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

12. The organic electroluminescent element material of claim 11, wherein Formula (3) is further represented by Formula (4),

wherein R is a substituent having a steric parameter value (Es) of −0.5 or less,;
R1 is a hydrogen atom or a substituent, and n1 is an integer of 1 to 4;
each R2 and R3 is independently a hydrogen atom or a substituent, n2 is an integer of 1 or 2 and n3 is an integer of 1 to 3;
X1-L1-X2 is a bidentate ligand, provided that each X1 and X2 is independently a carbon atom, a nitrogen atom or an oxygen atom, and that L1 is a group of atoms necessary to form the bidentate ligand with X1 and X2;
m1 is an integer of 1 to 3, and m2 is an integer of 0 to 2, provided that a sum of m1 and m2 is 2 or 3; and
M1 is a metal element selected from the group consisting of Groups 8 to 10 in the periodic table.

13. The organic electroluminescent element material of claim 12, wherein R3 in Formula (4) is a hydrogen atom.

14. The organic electroluminescent element material of claim 5, wherein m2 in Formula (2) is 0.

15. The organic electroluminescent element material of claim 5, wherein R in Formula (2) is electron donative.

16. The organic electroluminescent element material of claim 5 exhibiting a first emission wavelength of 400 to 500 nm.

17. An organic electroluminescent element comprising the organic electroluminescent element material of claim 1.

18. An organic electroluminescent element comprising the organic electroluminescent element material of claim 2.

19. An organic electroluminescent element comprising the organic electroluminescent element material of claim 5.

20. An organic electroluminescent element comprising an emission layer as a constituting layer of the element, wherein the emission layer comprises the organic electroluminescent element material of claim 5.

21. The organic electroluminescent element of claim 20, wherein the emission layer further comprises:

(i) a carboline derivative; or
(ii) a condensed ring compound having a structure derived from carboline, wherein at least one of carbon atoms of a hydrocarbon ring in a carboline ring is substituted with a nitrogen atom.

22. The organic electroluminescent element of claim 19, comprising a positive hole inhibition layer as a constituting layer of the element, the positive hole layer containing:

(i) a carboline derivative; or
(ii) a condensed ring compound having a structure derived from carboline, wherein at least one of carbon atoms of a hydrocarbon ring in a carboline ring is substituted with a nitrogen atom.

23. A display device comprising the organic electroluminescent element of claim 17.

24. A display device comprising the organic electroluminescent element of claim 18.

25. A display device comprising the organic electroluminescent element of claim 19.

26. A lighting device comprising the organic electroluminescent element of claim 17.

27. A lighting device comprising the organic electroluminescent element of claim 18.

28. A lighting device comprising the organic electroluminescent element of claim 19.

Patent History
Publication number: 20070196690
Type: Application
Filed: Feb 15, 2007
Publication Date: Aug 23, 2007
Inventors: Dai Ikemizu (Tokyo), Hiroshi Kita (Tokyo), Masato Nishizeki (Tokyo), Eisaku Katoh (Tokyo), Tomohiro Oshiyama (Tokyo)
Application Number: 11/707,232