U.S. patent application number 12/838282 was filed with the patent office on 2010-11-04 for metal complex compound and organic electroluminescent element using the same.
This patent application is currently assigned to IDEMITSU KOSAN CO., LTD.. Invention is credited to Hidetsugu Ikeda, Masatoshi SAITOU.
Application Number | 20100277062 12/838282 |
Document ID | / |
Family ID | 36647593 |
Filed Date | 2010-11-04 |
United States Patent
Application |
20100277062 |
Kind Code |
A1 |
SAITOU; Masatoshi ; et
al. |
November 4, 2010 |
METAL COMPLEX COMPOUND AND ORGANIC ELECTROLUMINESCENT ELEMENT USING
THE SAME
Abstract
The present invention provides a novel metal complex compound
represented by the following general formula (1), and an organic
electroluminescence element which has a high efficiency of light
emission and a long lifetime, wherein one of organic thin film
layers including at least a light emitting layer between an anode
and a cathode, a least one of the organic thin film layers contains
the metal complex compounds. (L.sub.1).sub.mM(L.sub.2).sub.n (1)
wherein M represents Ir, Pt and Rh; L.sub.1 and L.sub.2 represents
mutually different bidentate ligands; (L.sub.1).sub.mM as a partial
structure is represented by general formula (2) and
M(L.sub.2).sub.n as a partial structure is represented by general
formula (3): and m and n are each an integer of 1 or 2, provided
that m+n is a integer of 2 or 3. ##STR00001## wherein ring A1
represents an aromatic, hetrocyclic ring group: and ring B1
represents an aryl group, provided that the ring A1 and the ring B1
are covalently linked to each other via Z which represents a single
bond or the like. ##STR00002## wherein R.sub.1, R.sub.2, R.sub.2'
and R.sub.3 each independently represent an alkyl group or the
like; R.sub.1 and R.sub.2, R.sub.1 and R.sub.2.sup.', R.sub.2 and
R.sub.2.sup.'. R.sub.2 and R.sub.3, and R.sub.2' and R.sub.3 may
combine with each other to form a cyclic structure; and Y
represents a group represented by O or S.
Inventors: |
SAITOU; Masatoshi; (Chiba,
JP) ; Ikeda; Hidetsugu; (Chiba, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
IDEMITSU KOSAN CO., LTD.
Tokyo
JP
|
Family ID: |
36647593 |
Appl. No.: |
12/838282 |
Filed: |
July 16, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11813516 |
Jul 9, 2007 |
7781960 |
|
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PCT/JP05/24079 |
Dec 28, 2005 |
|
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12838282 |
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Current U.S.
Class: |
313/504 ;
546/4 |
Current CPC
Class: |
H01L 51/0071 20130101;
H01L 51/5012 20130101; H01L 51/0068 20130101; H05B 33/14 20130101;
C09K 11/06 20130101; H01L 51/0081 20130101; C07D 401/10 20130101;
H01L 51/0085 20130101; H01L 51/0067 20130101; C09K 2211/1029
20130101; C07D 403/10 20130101; C09K 2211/185 20130101; H01L
51/0059 20130101; C07D 519/00 20130101; H01L 51/0087 20130101; C07D
403/14 20130101; H01L 51/0072 20130101; C07D 471/04 20130101; C07D
251/24 20130101; C07F 15/0086 20130101; C07F 15/0033 20130101; C09K
2211/1044 20130101; C07D 409/14 20130101; C07D 401/14 20130101 |
Class at
Publication: |
313/504 ;
546/4 |
International
Class: |
C07F 17/00 20060101
C07F017/00; H01J 1/63 20060101 H01J001/63 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 7, 2005 |
JP |
2005-002480 |
Claims
1. A metal complex compound represented by the following general
formula (1): (L.sub.1).sub.mM(L.sub.2).sub.n (1) wherein M
represents a metal atom selected from the group consisting of
iridium (Ir), platinum (Pt) and rhodium (Rh), L.sub.1 and L.sub.2
represent bidentate ligands which are different from each other,
the sectional structure (L.sub.1).sub.mM is represented by the
following general formula (2), the sectional structure
M(L.sub.2).sub.a is represented by the following general formula
(3), and m and n each represents an integer of 1 or 2, and m+n
represents an integer of 2 or 3; ##STR00075## wherein N and C each
represents a nitrogen atom and a carbon atom, A1 ring represents a
substituted or unsubstituted aromatic heterocyclic group having 3
to 50 ring carbon atoms which may contain a nitrogen atom, and B1
ring represents a substituted or unsubstituted aryl group having 6
to 50 ring carbon atoms, and the A1 ring and the B1 ring is linked
each other by a covalent bond via Z; wherein Z represents a single
bond, --O--, --S--, --CO--, --(CR'R'').sub.a--, --(SiR'R'').sub.a--
or --NR'--, in which R' and R'' each independently represents a
hydrogen atom, a substituted or unsubstituted aryl group having 6
to 50 ring carbon atoms, a substituted or unsubstituted aromatic
heterocyclic group having 3 to 50 ring atoms, or a substituted or
unsubstituted alkyl group having 1 to 50 carbon atoms, a represents
an integer of 1 to 10, and R' and R'' are the same with or
different from each other; ##STR00076## wherein N represents a
nitrogen atom, and R.sub.1, R.sub.2, R.sub.2' and R.sub.3 each
independently represents a substituted or unsubstituted alkyl group
having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl
group having 2 to 50 carbon atoms, or a substituted or
unsubstituted aryl group having 6 to 50 ring carbon atoms, R.sub.2'
may be a hydrogen atom, R.sub.1 and R.sub.2, R.sub.1 and R.sub.2',
R.sub.2, and R.sub.2' R.sub.2, and R.sub.3, and R.sub.2' and
R.sub.3 may be inked each other to form a saturated or unsaturated
ring structure, and Y represents a group represented by an oxygen
atom or a sulfur atom; with the proiso that the metal complex
compound is not one represented by the following general formula
(4) and (8) ##STR00077## wherein M and m are as defined in formula
(1), R.sub.4 to R.sub.11 each independently represents a hydrogen
atom, a substituted or unsubstituted alkyl group having 1 to 30
carbon atoms, a substituted or unsubstituted halogenated alkyl
group having 1 to 30 carbon atoms, a substituted or unsubstituted
alkoxy group having 1 to 30 carbon atoms, a substituted or
unsubstituted heterocyclic group having 3 to 20 ring atoms, a
substituted or unsubstituted aryl group having 6 to 40 ring carbon
atoms, a substituted or unsubstituted aryloxy group having 6 to 40
ring carbon atoms, a substituted or unsubstituted aralkyl group
having 7 to 40 carbon atoms, a substituted or unsubstituted alkenyl
group having 2 to 30 carbon atoms, a substituted or unsubstituted
arylamino group having 6 to 80 ring carbon atoms, a substituted or
unsubstituted alkylamino group having 1 to 60 carbon atoms, a
substituted or unsubstituted aralkylamino group having 7 to 80
carbon atoms, a substituted or unsubstituted alkylsilyl group
having 1 to 30 carbon atoms, a substituted or unsubstituted
arylsilyl group having 6 to 40 carbon atoms, a halogen atom, a
cyano group, a nitro group, --S(R)O.sub.2, or --S(R)O; wherein R
represents a substituent, and neighboring groups among R.sub.4 to
R.sub.11 may be linked to each other to form a saturated or
unsaturated ring structure; ##STR00078## wherein M and n are as
defined in formula (1), R.sub.31 to R.sub.34 each independently
represents a hydrogen atom, a substituted or unsubstituted alkyl
group having 1 to 30 carbon atoms, a substituted or unsubstituted
halogenated alkyl group having 1 to 30 carbon atoms, a substituted
or unsubstituted alkoxy group having 1 to 30 carbon atoms, a
substituted or unsubstituted heterocyclic group having 3 to 20 ring
atoms, a substituted or unsubstituted aryl group having 6 to 40
ring carbon atoms, a substituted or unsubstituted aryloxy group
having 6 to 40 ring carbon atoms, a substituted or unsubstituted
aralkyl group having 7 to 40 carbon atoms, a substituted or
unsubstituted alkenyl group having 2 to 30 carbon atoms, a
substituted or unsubstituted arylamino group having 6 to 80 ring
carbon atoms, a substituted or unsubstituted alkylamino group
having 1 to 60 carbon atoms, a substituted or unsubstituted
aralkylamino group having 7 to 80 carbon atoms, a substituted or
unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a
substituted or unsubstituted arylsilyl group having 6 to 40 carbon
atoms, a halogen atom, a cyano group, a nitro group, --S(R)O.sub.2,
or --S(R)O, wherein R represents a substituent, and neighboring
groups among R.sub.31 and R.sub.32, R.sub.32 and R.sub.33, and
R.sub.33 and R.sub.34 may be linked to each other to form a
saturated or unsaturated ring structure.
2. The metal complex compound according to claim 1, wherein the
sectional structure M(L.sub.2).sub.n of the above general formula
(1) is represented by the following general formula (3'):
##STR00079## wherein N represents a nitrogen atom, M, Y, R.sub.1,
R.sub.2 and R.sub.3 are the same with the aforementioned, R.sub.1
and R.sub.2, and R.sub.2 and R.sub.3 may be inked each other to
form a saturated or unsaturated ring structure.
3. The metal complex compound according to claim 1, wherein the
sectional structure (L.sub.1).sub.mM of the general formula (2) is
a metal complex compound represented by the general formula (4),
(5) or (6): ##STR00080## wherein M and m are the same with the
aforementioned, R.sub.4 to R.sub.26 each independently represents a
hydrogen atom, a substituted or unsubstituted alkyl group having 1
to 30 carbon atoms, a substituted or unsubstituted halogenated
alkyl group having 1 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 30 carbon atoms, a
substituted or unsubstituted heterocyclic group having 3 to 20 ring
atoms, a substituted or unsubstituted aryl group having 6 to 40
ring carbon atoms, a substituted or unsubstituted aryloxy group
having 6 to 40 ring carbon atoms, a substituted or unsubstituted
aralkyl group having 7 to 40 carbon atoms, a substituted or
unsubstituted alkenyl group having 2 to 30 carbon atoms, a
substituted or unsubstituted arylamino group having 6 to 80 ring
carbon atoms, a substituted or unsubstituted alkylamino group
having 1 to 60 carbon atoms, a substituted or unsubstituted
aralkylamino group having 7 to 80 carbon atoms, a substituted or
unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a
substituted or unsubstituted arylsilyl group having 6 to 40 carbon
atoms, a halogen atom, a cyano group, a nitro group, --S(R)O.sub.2,
or --S(R)O; wherein R represents a substituent, and neighboring
groups among R.sub.4 to R.sub.11, R.sub.12 to R.sub.19 and R.sub.20
to R.sub.26 may be inked each other to form a saturated or
unsaturated ring structure.
4. The metal complex compound according to claim 1, wherein the
sectional structure M(L.sub.2).sub.n of the general formula (3) is
a metal complex compound represented by the following general
formula (7): ##STR00081## wherein M, Y and n are the same with
aforementioned, R.sub.27 to R.sub.30 each independently represents
the same with R.sub.4 to R.sub.26 of the aforementioned general
formulae (4) to (6), and R.sub.27 and R.sub.28, R.sub.28 and
R.sub.29, and R.sub.29 and R.sub.30 may be linked each other to
form a saturated or unsaturated ring structure.
5. The metal complex compound according to claim 1, wherein the
sectional structure (L.sub.1).sub.mM of the above general formula
(2) is a sectional structure represented by the following general
formula (4), (5) or (6), and the sectional structure
M(L.sub.2).sub.n of the above general formula (3) is a sectional
structure represented by the above general formula (7):
##STR00082## wherein M and m are the same with the afore mentioned,
R.sub.4 to R.sub.26 each independently represents a hydrogen atom,
a substituted or unsubstituted alkyl group having 1 to 30 carbon
atoms, a substituted or unsubstituted halogenated alkyl group
having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy
group having 1 to 30 carbon atoms, a substituted or unsubstituted
heterocyclic group having 3 to 20 ring atoms, a substituted or
unsubstituted aryl group having 6 to 40 ring carbon atoms, a
substituted or unsubstituted aryloxy group having 6 to 40 ring
carbon atoms, a substituted or unsubstituted aralkyl group having 7
to 40 carbon atoms, a substituted or unsubstituted alkenyl group
having 2 to 30 carbon atoms, a substituted or unsubstituted
arylamino group having 6 to 80 ring carbon atoms, a substituted or
unsubstituted alkylamino group having 1 to 60 carbon atoms, a
substituted or unsubstituted aralkylamino group having 7 to 80
carbon atoms, a substituted or unsubstituted alkylsilyl group
having 1 to 30 carbon atoms, a substituted or unsubstituted
arylsilyl group having 6 to 40 carbon atoms, a halogen atom, a
cyano group, a nitro group, --S(R)O.sub.2, or --S(R)O, wherein R
represents a substituent, and neighboring groups among R.sub.4 to
R.sub.11, R.sub.12 to R.sub.19 and R.sub.20 to R.sub.26 may be
linked each other to form a saturated or unsaturated ring
structure; ##STR00083## wherein M, Y and n are the same with
aforementioned, R.sub.27 to R.sub.30 each independently represents
the same with R.sub.4 to R.sub.26 of the aforementioned general
formulae (4) to (6), and R.sub.27 and R.sub.28, R.sub.28 and
R.sub.29, and R.sub.22 and R.sub.30 may be linked each other to
form a saturated or unsaturated ring structure.
6. The metal complex compound according to claim 1, wherein the
sectional structure (L.sub.1).sub.mM of the above general formula
(2) is a sectional structure represented by the following general
formula (5) or (6), and the sectional structure M(L.sub.2).sub.n of
the above general formula (3) is a sectional structure represented
by the following general formula (8): ##STR00084## wherein M and m
are the same with the aforementioned, R.sub.4 to R.sub.26 each
independently represents a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 30 carbon atoms, a
substituted or unsubstituted halogenated alkyl group having 1 to 30
carbon atoms, a substituted or unsubstituted alkoxy group having 1
to 30 carbon atoms, a substituted or unsubstituted heterocyclic
group having 3 to 20 ring atoms, a substituted or unsubstituted
aryl group having 6 to 40 ring carbon atoms, a substituted or
unsubstituted aryloxy group having 6 to 40 ring carbon atoms, a
substituted or unsubstituted aralkyl group having 7 to 40 carbon
atoms, a substituted or unsubstituted alkenyl group having 2 to 30
carbon atoms, a substituted or unsubstituted arylamino group having
6 to 80 ring carbon atoms, a substituted or unsubstituted
alkylamino group having 1 to 60 carbon atoms, a substituted or
unsubstituted aralkylamino group having 7 to 80 carbon atoms, a
substituted or unsubstituted alkylsilyl group having 1 to 30 carbon
atoms, a substituted or unsubstituted arylsilyl group having 6 to
40 carbon atoms, a halogen atom a cyano group a vitro group;
--S(R)O.sub.2, or --S(R)O, wherein R represents a substituent, and
neighboring groups among R.sub.4 to R.sub.11, R.sub.12 to R.sub.19
and R.sub.20 to R.sub.26 may be inked each other to form a
saturated or unsaturated ring structure; ##STR00085## wherein
R.sub.31 to R.sub.34 each independently is the same with R.sub.27
to R.sub.30 of the above general formula (7).
7. An organic electroluminescence device comprising at least any
one of organic thin layers including a light emitting layer between
an anode and a cathode, wherein at least any one of the organic
thin film layers contains a metal complex compound of claim 1.
8. The organic electroluminescence device according to claim 7,
wherein said light emitting layer contains the metal complex
compound as a light emitting material.
9. The organic electroluminescence device according to claim 7,
wherein said light emitting layer contains the metal complex
compound as a dopant.
10. The organic electroluminescence device according to claim 7,
wherein the device comprises at least any one of an electron
injecting layer and an electron transporting layer between said
light emitting layer and the cathode, and at least any one of the
electron injecting layer and the electron transporting layer
contains a .pi.-electron deficiency nitrogen-containing
heterocyclic derivative as the main component.
11. The organic electroluminescence device according to claim 7,
wherein a reductive dopant is added in an interface area between
the cathode and said organic thin film layer.
Description
TECHNICAL FIELD
[0001] The present invention relates to a metal complex compound
and an organic electroluminescence device using the same, in
particular, to an organic electroluminescence device having a high
efficiency of light emission and a long lifetime, and a novel metal
complex compound for producing the electroluminescence device.
BACKGROUND ART
[0002] An organic electroluminescence ("electroluminescence" will
be occasionally referred to as "EL", hereinafter) device is a
spontaneous light emitting device which utilizes the principle that
a fluorescent substance emits light by energy of recombination of
holes injected from an anode and electrons injected from a cathode
when an electric field is applied. Since an organic EL device of
the laminate type driven under a low electric voltage was reported
by C. W. Tang et al. of Eastman Kodak Company (C. W. Tang and S. A
Vanslyke, Applied Physics Letters, Volume 51, Pages 913, 1987),
many studies have been conducted on organic EL devices using
organic materials as the constituting materials. Tang et al. used a
laminate structure using tris(8-quinolinolato)aluminum for the
light emitting layer and a triphenyldiamine derivative for the hole
transporting layer. Advantages of the laminate structure are that
the efficiency of hole injection into the light emitting layer can
be increased, and that the efficiency of forming excitons which are
formed by blocking and recombining electrons injected from the
cathode can be increased, and that excitons formed among the light
emitting layer can be enclosed. As the structure of the organic EL
device, a two-layered structure having a hole transporting
(injecting) layer and an electron transporting and light emitting
layer or a three-layered structure having a hole transporting
(injecting) layer, a light emitting layer and an electron
transporting (injecting) layer are well known. To increase the
efficiency of recombination of injected holes and electrons in the
devices of the laminate type, the structure of the device and the
process for producing the device have been studied.
[0003] As the light emitting material of the organic EL device,
chelate complexes such as tris(8-quinolinolato)aluminum, coumarine
derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene
derivatives and oxadiazole derivatives are known. It is reported
that light in the visible region ranging from blue light to red
light can be obtained by using these light emitting materials, and
development of a device exhibiting color images is expected (refer
to, for example, Patent literatures 1, 2, and 3).
[0004] In addition, it has been recently proposed that an organic
phosphorescent material is applied to a light emitting layer
besides a light emitting material (refer to, for example,
non-Patent literatures 1 and 2). A high efficiency of light
emission has been achieved by utilizing a singlet state and a
triplet state of the organic phosphorescent materials in a light
emitting layer of an organic EL device. Since it has been
considered that singlet exciton and triplet exciton are formed at a
ratio of 1 to 3 due to difference of spin multiplicity thereof on
recombination of electrons and holes in an organic EL device, it
should be understood that three to four times higher efficiency of
light emission can be achieved by utilizing an phosphorescent light
emitting material than by utilizing only a fluorescent light
emitting material.
[0005] In the above organic EL devices, in order to avoid quenching
of triplet excited state or excitons in triplet state, a
construction comprised by laminating sequentially an anode, a hole
transporting layer, an organic light emitting layer, an electron
transporting layer (a hole blocking layer), an electron
transporting layer, a cathode and so forth has been employed, and a
host compound and a phosphorescent compound have been employed as
an organic light emitting layer (refer to, for example, Patent
literatures 4 and 5). The patent literatures relate to an organic
phosphorescent material emitting a light in the range of from red
to green. In addition, technologies relating to a material emitting
a blue light are disclosed (refer to, for example, Patent
literatures 6, 7 and 8). However, these have very short lifetimes.
Ligand-frameworks bonded with Ir metal and phosphorous atom are
described in Patent literatures 7 and 8. However, although they
emit blue light, the bond strengths are week so that the heat
resistances are extremely poor. Additionally, a complex, of which
the central metal is bonded with an oxygen atom and a nitrogen
atom, is described in Patent literature 9. However, there is no
description of any specific advantage of the group bonding to
oxygen atom. Further, the complex, of which the central metal
bonded with each nitrogen atom being contained in different ring
structures, is disclosed in Patent literature 10. Although a device
using it exhibits a blue light emission, the external quantum
efficiency is low as about 5%. [0006] Patent literature 1: Japanese
Patent Application Laid-open No. Heisei 8 (1996)-239655, [0007]
Patent literature 2: Japanese Patent Application Laid-open No.
Heisei 7 (1995)-183561, [0008] Patent literature 3: Japanese Patent
Application Laid-open No. Heisei 3 (1991)-200289, [0009] Patent
literature 4: U.S. Pat. No. 6,097,147, [0010] Patent literature 5:
International PCT publication No. WO01/41512, [0011] Patent
literature 6: U.S. Patent Application Laid-open No. 2001/0025108,
[0012] Patent literature 7: U.S. Patent Application Laid-open No.
2002/0182441, [0013] Patent literature 8: Japanese Patent
Application Laid-open No. 2002-170684, [0014] Patent literature 9:
Japanese Patent Application Laid-open No. 2003-123982, [0015]
Patent literature 10: Japanese Patent Application Laid-open No.
2003-133074, [0016] Non-patent literature 1: D. F. OBrien and M. A.
Baldo et al "Improved energy transfer in electrophosphorescent
devices" Vol. 74 No. 3, pp 442-444, Jan. 18, 1999, and [0017]
Non-patent literature 2: M. A. Baldo et al "Very high-efficiency
green organic light-emitting devices based in
electrophosphorescence" Applied Physics letters, Vol. 75 No. 1, pp
4-6, Jul. 5, 1999.
DISCLOSURE OF THE INVENTION
[0018] The present invention has been made to overcome the above
problems and has an objective of providing an organic EL device
having a high efficiency of light emission and a long lifetime, and
also a novel metal complex compound for producing the organic EL
device.
[0019] As a result of intensive researches and studies to achieve
the above objectives by the present inventors, it was found that
employing a metal complex compound represented by the general
formula (1) enables to provide an organic electroluminescence
device having a great efficiency of light emission and a long
lifetime. [0020] Namely, the present invention is: [0021] (a) a
metal complex compound represented by the following general formula
(1):
[0021] (L.sub.1).sub.mM(L.sub.2).sub.n (1)
[0022] wherein M represents a metal atom selected from the group
consisting of iridium (Ir), platinum (Pt) and rhodium (Rh), L1 and
L2 represent bidentate ligands which are different from each other,
the sectional structure (L.sub.1).sub.mM is represented by the
following general formula (2), and the sectional structure
M(L2).sub.n is represented by the following general formula (3), m
and n each represents an integer of 1 or 2, and m+n represents an
integer of 2 or 3;
##STR00003##
[0023] wherein N and C each represents a nitrogen atom and a carbon
atom, A1 ring represents a substituted or unsubstituted aromatic
heterocyclic group having 3 to 50 ring carbon atoms containing
nitrogen atom, B1 ring represents a substituted or unsubstituted
aryl group, containing a nitrogen atom, having 6 to 50 ring carbon
atoms, and the A1 ring and the B1 ring is linked each other by a
covalent bond via Z. Z represents a single bond, --O--, --S--,
--CO--, --(CR'R'').sub.a--, --(SiR'R'').sub.a-- or --NR'--; wherein
R' and R'' each independently represents a hydrogen atom, a
substituted or unsubstituted aryl group having 6 to 50 ring carbon
atoms, a substituted or unsubstituted aromatic heterocyclic group
having 3 to 50 ring atoms, or a substituted or unsubstituted alkyl
group having 1 to 50 carbon atoms, and a represents an integer of 1
to 10, and R' and R'' are the same with or different from each
other,
##STR00004##
[0024] wherein N represents a nitrogen atom, and R.sub.1, R.sub.2,
R.sub.2' and R.sub.3 each independently represents a substituted or
unsubstituted alkyl group having 1 to 50 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 50 carbon
atoms, or a substituted or unsubstituted aryl group having 6 to 50
ring carbon atoms. R.sub.2' may be a hydrogen atom. R.sub.1 and
R.sub.2, R.sub.1 and R.sub.2', R.sub.2 and R.sub.2', R.sub.2 and
R.sub.3, and R.sub.2' and R.sub.3 may be linked each other to form
a saturated or unsaturated ring structure. Y represents a group
represented by an oxygen atom or a sulfur atom, [0025] (b) The
metal complex compound in (a) in which the sectional structure
M(L.sub.2).sub.n of the general formula (1) is represented by the
following general formula (3'):
##STR00005##
[0026] wherein N represents a nitrogen atom, M, Y, R.sub.1, R.sub.2
and R.sub.3 are the same with the aforementioned. R.sub.1 and
R.sub.2, and R.sub.2 and R.sub.3 may be linked each other to form a
saturated or unsaturated ring structure, [0027] (c) The metal
complex compound in (a) in which the sectional structure
(L.sub.1).sub.mM of the general formula (2) is represented by the
general formula (4), (5) or (6):
##STR00006##
[0028] wherein M and m are the same with the aforementioned.
R.sub.4 to R.sub.26 each independently represents a hydrogen atom,
a substituted or unsubstituted alkyl group having 1 to 30 carbon
atoms, a substituted or unsubstituted halogenated alkyl group
having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy
group having 1 to 30 carbon atoms, a substituted or unsubstituted
heterocyclic group having 3 to 20 ring atoms, a substituted or
unsubstituted aryl group having 6 to 40 ring carbon atoms, a
substituted or unsubstituted aryloxy group having 6 to 40 ring
carbon atoms, a substituted or unsubstituted aralkyl group having 7
to 40 carbon atoms, a substituted or unsubstituted alkenyl group
having 2 to 30 carbon atoms, a substituted or unsubstituted
arylamino group having 6 to 80 ring carbon atoms, a substituted or
unsubstituted alkylamino group having 1 to 60 carbon atoms, a
substituted or unsubstituted aralkylamino group having 7 to 80
carbon atoms, a substituted or unsubstituted alkylsilyl group
having 1 to 30 carbon atoms, a substituted or unsubstituted
arylsilyl group having 6 to 40 carbon atoms, a halogen atom, a
cyano group, a nitro group, --S(R)O.sub.2, or --S(R)O; wherein R
represents a substituent, and neighboring groups among R.sub.4 to
R.sub.11, R.sub.12 to R.sub.19 and R.sub.20 to R.sub.26 may be
linked each other to form a saturated or unsaturated ring
structure, [0029] (d) The metal complex compound of (a), wherein
the sectional structure M(L.sub.2).sub.n represented by the general
formula (3) is a sectional structure represented by the following
general formula (7):
##STR00007##
[0030] wherein M, Y and n are the same with aforementioned.
R.sub.27 to R.sub.30 each independently represents the same with
R.sub.4 to R.sub.26 of the aforementioned general formulae (4) to
(6). R.sub.27 and R.sub.29, R.sub.28 and R.sub.29, and R.sub.29 and
R.sub.30 may be linked each other to form a saturated or
unsaturated ring structure, [0031] (e) The metal complex compound
of (a), wherein the sectional structure (L.sub.1).sub.mM
represented by the above general formula (2) is a sectional
structure represented by the above general formula (4), (5) or (6),
and the sectional structure M(L.sub.2).sub.n represented by the
above general formula (3) is a sectional structure represented by
the above general formula (7), [0032] (f) The metal complex
compound of (a), wherein the sectional structure (L.sub.1).sub.mM
represented by the above general formula (2) is a sectional
structure represented by the above general formula (4), (5) or (6),
and the sectional structure M(L.sub.2).sub.n represented by the
above general formula (3) is a sectional structure represented by
the following general formula (8), in represents 2, n represents 1
and M represents Ir:
##STR00008##
[0033] wherein R.sub.31 to R.sub.34 each independently is the same
with R.sub.27 to R.sub.30 of the above general formula (7), [0034]
(g) an organic EL device comprising at least any one of organic
thin film layers including a light emitting layer between an anode
and a cathode, wherein at least any one of the organic thin film
layers contains a metal complex compound of (a) to (f), [0035] (h)
an organic EL device described in (g) wherein said light emitting
layer contains the metal complex compound of (a) to (f) as a light
emitting material. [0036] (i) an organic EL device described in (g)
wherein said light emitting layer contains the metal complex
compound of claim 1 as a dopant. [0037] (j) an organic EL device
described in (g) wherein the device comprises at least any one of
an electron injecting layer and an electron transporting layer
between said light emitting layer and the cathode, and at least any
one of the electron injecting layer and the electron transporting
layer contains a n-electron deficiency nitrogen-containing
heterocyclic derivative as the main component, and [0038] (k) an
organic EL device described in (g) comprising a reductive dopant
added into an interface area between a cathode and said organic
thin film layer are provided.
[0039] The present invention provides an organic EL device having a
high efficiency of light emission and a long lifetime, and also a
novel metal complex compound for producing the organic EL
device.
THE PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION
[0040] The metal complex compound of the present invention is
represented by the following general formula (1):
(L.sub.1).sub.mM(L.sub.2).sub.n (1)
[0041] wherein M represents a metal atom selected from the group
consisting of iridium (Ir), platinum (Pt) and rhodium (Rh), L.sub.1
and L.sub.2 represent bidentate ligands which are different from
each other, the sectional structure of (L.sub.1).sub.mM is
represented by the following general formula (2), and the sectional
structure of M(L.sub.2).sub.n is represented by the following
general formula (3); wherein in and n each represents an integer of
1 or 2, and m+n represents an integer of 2 or 3.
##STR00009##
[0042] wherein N and C each represent a nitrogen atom and a carbon
atom, A1 ring represents a substituted or unsubstituted
nitrogen-containing aromatic heterocyclic group having 3 to 50
carbon ring atoms, and B1 ring represents a substituted or
unsubstituted aryl group having 6 to 50 ring carbon atoms.
[0043] The nitrogen-containing aromatic heterocyclic group includes
preferably the group having 3 to 20 ring atoms, more preferably the
group having 3 to 10 ring atoms. Examples of the
nitrogen-containing aromatic heterocyclic group include pyrazinyl
group, pyridyl group, pyrimidinyl group, pyrazolyl group,
imidazolyl group, indolidinyl group, imidazopyridinyl group,
quinolyl group, isoquinplyl group, quinoxalinyl group and the
like.
[0044] Among those, pyrazinyl group, pyridyl group, pyrimidinyl
group, pyrazolyl group, imidazolyl group, quinolyl group and
isoquinolyl are preferable.
[0045] The aryl group of the above B1 ring includes preferably the
group having 6 to 50 ring carbon atoms, more preferably the group
having 6 to 24 ring carbon atoms. The aryl group includes phenyl
group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group,
2-anthryl group, 9-anthryl group, 1-phenanthryl group,
2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group,
9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group,
9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl
group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group,
p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl
group, m-terphenyl-4-yl group, m-terphenyl-3-yl group,
m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl
group, p-t-butylphenyl group, p-(2-phenylpropyl) phenyl group,
3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group,
4-methyl-1-anthryl group, 4'-methylbiphenyl-yl group,
4''-t-butyl-p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl
group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl
group, mesityl group and the like.
[0046] Among those, phenyl group, 1-naphthyl group, 2-naphthyl
group, 9-phenanthryl group, 2-biphenylyl group, 3-biphenylyl group,
4-biphenylyl group, p-tolyl group and 3,4-xylyl group are
preferable.
[0047] In the general formula (2), A1 ring and B1 ring is linked
each other by a covalent bond via Z. Z represents a single bond,
--O--, --S--, --CO--, --(CR'R'').sub.a--, --(SiR'R'').sub.a-- or
--NR'--, wherein R' and R'' each independently represents a
hydrogen atom, a substituted or unsubstituted aryl group having 6
to 50 ring carbon atoms, a substituted or unsubstituted aromatic
heterocyclic group having 3 to 50 ring atoms, or a substituted or
unsubstituted alkyl group having 1 to 50 carbon atoms, a represents
an integer of from 1 to 10, and R' and R'' are the same with or
different from each other.
[0048] Examples of an aryl group represented by R' and R'' include
the similar ones mentioned in the above B1 ring, and examples of
the aromatic heterocyclic group include the similar ones mentioned
in the above Al ring.
[0049] Substituted or unsubstituted alkyl group having 1 to 50
carbon atoms includes preferably the group having 1 to 10 carbon
atoms. Examples of the alkyl group include methyl group, ethyl
group, propyl group, isopropyl group, n-butyl group, s-butyl group,
isobutyl group, t-butyl group, n-pentyl group, n-hexyl group,
n-heptyl group, n-octyl group, n-nonyl group, n-decyl group,
n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl
group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group,
n-octdecyl group, neopentyl group, 1-metylpentyl group,
2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group,
1-heptyloctyl group, 3-metylpentyl group, hydroxymethyl group,
1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl
group, 1,2-dihydroxyethyl group, 1,3-dihyroxyisopropyl group,
2,3-dihyroxy-t-butyl group, 1,2,3-trihydroxypropyl group,
aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,
2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl
group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group,
cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,
2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoethyl
group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group,
nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,
1,2-dinitroethyl group, 2,3-dinitro-t-butyl group,
1,2,3-trinitropropyl group, cyclopentyl group, cyclohexyl group,
cyclooctyl group, 3,5-dimethylcyclohexyl group,
3,3,5,5-tetramethylcyclohexyl group and the like.
[0050] Among those, methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, s-butyl group, isobutyl group,
t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group,
n-octyl group, n-nonyl group, n-decyl group, n-undecyl group,
n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl
group, n-hexadecyl group, n-heptadecyl group, n-octdecyl group,
neopentyl group, 1-metylpentyl group, 1-pentylhexyl group,
1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group,
cyclooctyl group, 3,5-dimethylcyclohexyl group,and
3,3,5,5-tetramethylcyclohexyl group are preferable.
##STR00010##
[0051] In the general formula (3), N represents a nitrogen atom,
and R.sub.1, R.sub.2, R.sub.2' and R.sub.3 each independently
represents a substituted or unsubstituted alkyl group having 1 to
50 carbon atoms, a substituted or unsubstituted alkenyl group
having 2 to 50 carbon atoms, or a substituted or unsubstituted aryl
group having 6 to 50 ring carbon atoms. R.sub.2' may be a hydrogen
atom. R.sub.1 and R.sub.2, R.sub.1 and R.sub.2', R.sub.2 and
R.sub.2', R.sub.2 and R.sub.3, and R.sub.2' and R.sub.3 may he
linked each other to form a saturated or unsaturated ring
structure. Y represents a group represented by an oxygen atom or a
sulfur atom.
[0052] The metal complex compound of the present invention is the
compound which the sectional structure M(L.sub.2).sub.n of the
above general formula (1) is represented by the following general
formula (3'):
##STR00011##
[0053] wherein N represents a nitrogen atom, M, Y, R.sub.1, R.sub.2
and R.sub.3 are the same with the aforementioned. R.sub.1 and
R.sub.2, and R.sub.2 and R.sub.3 may be linked each other to form a
saturated or unsaturated ring structure.
[0054] Examples of a substituted or unsubstituted alkyl group
having 1 to 50 carbon atoms for R.sub.1, R.sub.2, R.sub.2' and
R.sub.3 include the similar ones to the examples of R' and R''
mentioned in the above Z. Examples of a substituted or
unsubstituted aryl group having 6 to 50 ring carbon atoms for
R.sub.1, R.sub.2, R.sub.2' and R.sub.3 include perfluorophenyl
group as well as the examples mentioned for the above B1 ring, and
also preferable ones are the similar ones as well.
[0055] An alkenyl group having 2 to 50 carbon atoms for R.sub.1,
R.sub.2, R.sub.2' and R.sub.3 includes the group having 2 to 16
carbon atoms preferably. Examples of the alkenyl group include
vinyl group, allyl group, 1-butenyl group, 2-butenyl group,
3-butenyl group, 1,3-butandienyl group, 1-methylvinyl group, styryl
group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group,
1-metylallyl group, 1,1-dimetylallyl group, 2-methylally group,
1-phenylallyl group, 2-phenylallyl group, 3-phenyallyl group,
3,3-diphenylallyl group, 1,2-dimetylallyl group, 1-phenyl-1-butenyl
group, 3-phenyl-1-butenyl group and the like. Styryl group,
2,2-diphenylvinyl group and 1,2-diphenylvinyl group are
preferable.
[0056] In the general formula (3), R.sub.1 and R.sub.2, R.sub.1 and
R.sub.2', R.sub.2 and R.sub.2', R.sub.2 and R.sub.3, and R.sub.2'
and R.sub.3 may be linked each other to form a saturated or
unsaturated ring structure. In addition, R.sub.1 and R.sub.2, and
R.sub.2 and R.sub.3 in the general formula (3') may be linked each
other to form a saturated or unsaturated ring structure.
[0057] The saturated or unsaturated ring structures formed by
bonding each other include, for example, a cycloalkane having 4 to
12 carbon atoms such as cyclobutane, cyclopentane, cyclohexane,
adamantane and norbornane, a cycloalkene having having 4 to 12
carbon atoms such as cyclobutene, cyclopentene, cyclohexene,
cycloheptene and cyclooctene, a cycloalkadiene having 6 to 12
carbon atoms such as cyclohexadiene, cycloheptadiene and
cyclooctadiene, an aromatic ring having 6 to 50 carbon atoms such
as benzene, naphthalene, phenanthrene, anthracene, pyrene, chrysene
and acenaphthylene and the like.
[0058] The metal complex compound of the general formula (1) of the
present invention is the compound which the sectional structure
(L.sub.1).sub.mM of the above general formula (2) is represented by
the following general formula (4), (5) or (6):
##STR00012##
[0059] M and n in the general formulae (4), (5) and (6) are the
same with aforementioned. R4 to R26 each independently includes
hydrogen atom, a substituted or unsubstituted alkyl group having 1
to 30 carbon atoms, a substituted or unsubstituted halogenated
alkyl group having 1 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 30 carbon atoms, a
substituted or unsubstituted heterocyclic group having 3 to 20 ring
atoms, a substituted or unsubstituted aryl group having 6 to 40
ring carbon atoms, a substituted or unsubstituted aryloxy group
having 6 to 40 ring carbon atoms, a substituted or unsubstituted
aralkyl group having 7 to 40 carbon atoms, a substituted or
unsubstituted alkenyl group having 2 to 30 carbon atoms, a
substituted or unsubstituted arylamino group having 6 to 80 carbon
atoms, a substituted or unsubstituted alkylamino group having 1 to
60 carbon atoms, a substituted or unsubstituted arallylamino group
having 7 to 80 carbon atoms, a substituted or unsubstituted
alkylsilyl group having 1 to 30 carbon atoms, a substituted or
unsubstituted arylsilyl group having 6 to 40 carbon atoms, a
halogen atom, a cyano group, a nitro group, -S(R)02, or -S(R)O;
wherein R represents a substituent.
[0060] Examples of the substituted or unsubstituted alkyl group
having 1 to 30 carbon atoms, the substituted or unsubstituted aryl
group having 6 to 40 ring carbon atoms and the substituted or
unsubstituted alkenyl group having 2 to 30 carbon atoms include the
similar groups to aforementioned.
[0061] The substituted or unsubstituted halogenated alkyl group
having 1 to 30 carbon atoms is preferably the group having 1 to 10
carbon atoms. Examples of the halogenated alkyl group include
chloromethyl group, 1-chloroethyl group, 2-chloroethyl group,
2-chloroisobutyl group, 1,2-dichloroethyl group,
1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group,
1,2,3-trichloropropyl group, 1-bromoethyl group, 2-bromoethyl
group, 2-bromoisobutyl group, 1,2-dibromoethyl group,
1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group,
1,2,3-tribromopropyl group, iodometyl group, 1-iodoethyl group,
2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl
group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group,
fluoromethyl group, 1-fluoromethyl group, 2-fluoromethyl group,
2-fluoroisobutyl group, 1,2-difluoroethyl group, difluoromethyl
group, trifluoromethyl group, pentafluoroethyl group,
perfluoroisopropyl group, perfluorobutyl group, perfluorocyclohexyl
group, and the like.
[0062] Among those, fluoromethyl group, trifluoromethyl group,
pentafluoroethyl group, perfluoroisopropyl group, perfluorobutyl
group and perfluorocyclohexyl group are preferable.
[0063] The substituted or unsubstituted alkoxy group having 1 to 30
carbon atoms is represented by --OX.sub.1, and examples of X.sub.1
include the similar groups to those mentioned in the alkyl group
and the halogenated alkyl group above.
[0064] The substituted of unsubstituted heterocyclic group having 3
to 20 ring carbon atoms includes preferably the group having 3 to
10 ring carbon atoms. Specific examples thereof include 1-pyrrolyl
group, 2-pyrrolyl group, 3-pyrrolyl group, pyradinyl group,
2-pyridinyl group, 1-imidazolyl group, 2-imidazolyl group,
1-pyrazolyl group, 1-indolyzinyl group, 2-indolyzinyl group,
3-indolyzinyl group, 5-indolyzinyl group, 6-indolyzinyl group,
7-indolyzinyl group, 8-indolyzinyl group, 2-imidazopyridinyl group,
3-imidazopyridinyl group, 5-imidazopyridinyl group,
6-imidazopyridinyl group, 7-imidazopyridinyl group,
8-imidazopyridinyl group, 3-pyridinyl group, 4-pyridinyl group,
1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group,
5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl
group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group,
5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl
group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group,
4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group,
7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl
group, 4-isobenzofuranyl group, 5-isobenzofuranyl group,
6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group,
3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl
group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group,
3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group,
6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group,
2-quinoxanyl group, 5-quinoxanyl group, 6-quinoxanyl group,
1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group,
4-carbazolyl group, 9-carbazolyl group, .beta.-carboline-1-yl
group, .beta.-carboline-3-yl group, .beta.-carboline-4-yl group,
.beta.-carboline-5-yl group, .beta.-carboline-6-yl group,
.beta.-carboline-7-yl group, .beta.-carboline-8-yl group,
.beta.-carboline-9-yl group, 1-phenanthridinyl group,
2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl
group, 6-phenanthridinyl group, 7-phenanthridinyl group,
8-phenanthridinyl group, 9-phenanthridinyl group,
10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group,
3-acridinyl group, 4-acridinyl group, 9-acridinyl group,
1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group,
1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group,
1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group,
1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group,
1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group,
1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group,
1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group,
1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group,
1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group,
1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group,
1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group,
1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group,
1,10-phenanthrolin-2-yl group, 1,10-phennthrolin-3-yl group,
1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group,
2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group,
2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group,
2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group,
2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group,
2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group,
2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group,
2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group,
2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group,
2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group,
2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group,
2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group,
2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group,
1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,
2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl
group, 10-phenothiazinyl group, 1-phenoxazinyl group,
2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group,
10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group,
5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group,
3-furazanyl group, 2-thienyl group, 3-thienyl group,
2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group,
2-methylpyrrol-4-yl group, 2-methylpyrrole-5-yl group,
3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group,
3-methylpyrrole-4-yl group, 3-methylpyrrole-5-yl group,
2-t-butylpyrrole-4-yl group, 3-(2-phenylpropyl)pyrrole-1-yl group,
2-methyl-1-indolyl group, 4-methyl-1-indolyl group,
2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl
1-indolyl group, 4-t-butyl 1-indolyl group, 2-t-butyl 3-indolyl
group, 4-t-butyl 3-indolyl group and the like.
[0065] Among those, 2-pyriclinyl group, 1-indolyzinyl group,
2-indolyzinyl group, 3-indolyzinyl group, 5-indolyzinyl group,
6-indolyzinyl group, 7-indolyzinyl group, 8-indolyzinyl group,
2-imidazopyridinyl group, 3-imidazopyridinyl group,
5-imidazopyridinyl group, 6-imidazopyridinyl group,
7-imidazopyridinyl group, 8-imidazopyridinyl group, 3-pyridinyl
group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group,
3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group,
7-indolyl group, 1-isoindolyl group, 2-isoindolyl group,
3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group,
6-isoindolyl group, 7-isoindolyl group, 1-carbazolyl group,
2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group and
9-carbazolyl group are preferable.
[0066] The substituted or unsubstituted aryloxy group having 6 to
40 ring atoms is represented by --OAr, and examples of Ar include
the similar groups to those mentioned in the aryl group.
[0067] The substituted or unsubstituted aralkyl group having 7 to
40 carbon atoms is preferably the group having 7 to 18 carbon
atoms. Examples of the aralkyl group include benzyl group,
1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group,
2-phenylisopropyl group, phenyl-t-butyl group,
.alpha.-naphthylmethyl group, 1-.alpha.-naphtylethyl group,
2-.alpha.-naphtylisopropyl group, .beta.-naphthylmethyl group,
1-.beta.-naphtylethyl group, 2-.beta.-naphtylethyl group,
1-.beta.-naphtylisopropyl group, 2-.beta.-naphtylisopropyl group,
1-pyrrolylmethyl group, 2-(1-pyrrolyl)ethyl group, p-methylbenzyl
group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl
group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl
group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl
group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl
group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl
group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl
group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl
group, m-cyanobenzyl group, o-cyanobenzyl group,
1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group
and the like. Benzyl group, p-cyanobenzyl group, m-cyanobenzyl
group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl
group, 1-phenylisopropyl group and 2-phenylisopropyl group are
preferable.
[0068] The substituted or unsubstituted arylamino group having 6 to
80 ring carbon atoms, the substituted or unsubstituted alkylamino
group having 1 to 60 carbon atoms and the substituted or
unsubstituted aralkylamino group having 7 to 80 carbon atoms are
represented by --NQ.sub.1Q.sub.1. Q.sub.1 and Q.sub.2 each
independently is preferably the groups having 1 to 20 carbon atoms,
and a hydrogen atom and the similar examples to those mentioned in
the aryl group, the alkyl group and the aralkyl group are
mentioned.
[0069] The substituted or unsubstituted alkylsilyl group having 1
to 30 carbon atoms includes trimethylsilyl group, triethylsilyl
group, t-butyldimethylsilyl group, vinyldimethylsilyl group,
propyldimethlsilyl and the like.
[0070] The substituted or unsubstituted alkylsilyl group having 6
to 40 carbon atoms includes triphenylsilyl group,
phenyldimethylsilyl group, t-butyldiphenylsilyl group and the
like.
[0071] The halogen atom includes, for example, fluorine, chlorine,
bromine, iodine and the like. The substituent R of --S(R)O.sub.2
and --S(R)O includes the similar groups to those of the above R4 to
R26. In the general formulae (4), (5) and (6), neighboring groups
among R.sub.4 to R.sub.11, R.sub.12 to R.sub.19 and R.sub.20 to
R.sub.26 may be linked each other to form a saturated or
unsaturated ring structure. The ring structures include the similar
structures to aforementioned.
[0072] The metal complex compound of the general formula (1) of the
present invention is the compound which the sectional structure
M(L.sub.2).sub.n of the above general formula (3) is represented by
the following general formula (7):
##STR00013##
[0073] M, Y and n in the general formulae (7) are the same with the
aforementioned. R.sub.27 to R.sub.30 each independently is the same
with R.sub.4 to R.sub.26 in the above general formulae (4) to (6).
R.sub.27 and R.sub.28, R.sub.28 and R.sub.29, and R.sub.29 and
R.sub.30 each independently may be linked each other to form a
saturated or unsaturated ring structure.
[0074] The metal complex compounds represented by the general
formula (1) of the present invention comprise the sectional
structure (L.sub.1).sub.mM of the above general formula (2) which
is represented by the above general formula (4), (5) or (6), and
the sectional structure M(L.sub.2).sub.n of the above general
formula (3) which is represented by the above general formula
(7).
[0075] The metal complex compounds represented by the general
formula (1) of the present invention comprise the sectional
structure (L.sub.1).sub.mM of the above general formula (2) which
is represented by the above general formula (4), (5) or (6), and
the sectional structure M(L.sub.2).sub.n of the above general
formula (3) which is represented by the above general formula (8),
in which m represents 2, n represents 1 and M represents Ir.
##STR00014##
[0076] R.sub.31 to R.sub.34 in the general formula (8) each
independently is the same with R.sub.27 to R.sub.30 in the above
general formula (7).
[0077] The organic EL device of the present invention is an organic
EL device comprising at least any one of organic thin film layers
containing at least any one of a light emitting layers between an
anode and a cathode, wherein at least any one of the layers of the
organic thin film layers comprises a metal complex compound having
any one of the chemical structures or of the sectional structures
of the general formulae (1) to (8).
[0078] The organic EL device of the present invention comprises the
above light emitting layer containing any one of the above metal
complex compounds as a light emitting material.
[0079] The organic EL device of the present invention comprises the
above light emitting layer containing any one of the above metal
complex compounds as a dopant.
[0080] The organic EL device of the present invention comprises at
least any one of an electron injecting layer and an electron
transporting layer between the light emitting layer and a cathode,
and at least any one of the electron injecting layer and the
electron transporting layer contains a .pi.-electron deficiency
nitrogen-containing heterocyclic derivative as the main
component.
[0081] The organic EL device of the present invention is the device
comprising a reductive dopant added into an interface area between
a cathode and the above organic thin film layer.
[0082] Examples of the metal complex compound represented by the
general formula (1) of the present invention will be shown as
follows, which do not limit the scope of it. Here, Me represents a
methyl group.
##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019##
##STR00020## ##STR00021## ##STR00022##
[0083] The organic EL device of the present invention is the device
comprising at least one of the organic thin film layers containing
at least any one of a light emitting layers between an anode and a
cathode, wherein at least any one of the layers of the organic thin
film layers comprises a metal complex compound of the present
invention.
[0084] The content of a metal complex compound of the present
invention in the above organic thin film layer is generally in the
range of from 0.1 to 100% by weight, preferably 1 to 30% by weight
in the total weight of the light emitting layer.
[0085] In the organic EL device of the present invention, it is
preferable that the light emitting layer comprises a metal complex
compound of the present invention as the light emitting material.
In general, the light emitting layer is formed as a thin layer in
accordance with the vacuum vapor deposition process or the coating
process. It is preferable that the layer comprising the metal
complex compound of the present invention is formed as a thin layer
in accordance with the coating process since the production process
can be simplified by using the coating process.
[0086] In the organic EL device of the present invention, an
organic thin film layer, which is a monolayer type, is a light
emitting layer, and the light emitting layer contains a metal
complex compound of the present invention. Additionally, an organic
EL device of a multilayer type includes "an anode/a hole injecting
layer (a hole transporting layer)/a light emitting layer/a
cathode", "an anode/a light emitting layer/an electron injecting
layer (an electron transporting layer)/a cathode", "an anode/a hole
injecting layer (a hole transporting layer)/a light emitting
layer/an electron injecting layer (an electron transporting
layer)/a cathode, and the like.
[0087] It is effective for the anode of the organic EL device of
the present invention to have a work function of 4.5 eV or larger
as it has a role of supplying holes into a hole injecting layer, a
hole transporting layer, a light emitting layer and the like.
Materials for the anode include metal, alloy, metal oxide, a
conductive material or a mixture thereof. Specific examples of the
material for the anode include a conductive metal oxide such as tin
oxide, zinc oxide, indium oxide and indium tin oxide (ITO), a metal
such as gold, silver, chromium and nickel, a mixture or lamination
of the conductive material and the metals, an inorganic conductive
metal oxide such as copper iodide and copper sulfide, an organic
conductive metal oxide such as polyaniline, polythiophene and
polypyrrole, and lamination of ITO and those materials. It is
preferable to employ the conductive metal oxides, and more
preferable to employ ITO due to its productivity, higher
conductivity, transparency and the like. It is possible to select a
film thickness of the anode appropriately depending on a kind of
the materials.
[0088] The cathode of the organic EL device of the present
invention has a role of supplying electron into an electron
injecting layer, an electron transporting layer, a light emitting
layer and the like. Materials for the cathode include metal, alloy,
metal halide, metal oxide, a conductive compound or a mixture
thereof. Specific examples of the material for the cathode include
an alkaline metal such as Li, Na and K, fluoride or oxide thereof,
an alkaline earth metal such as Mg and Ca, fluoride or oxide
thereof, gold, silver, zinc, aluminum, sodium-potassium alloy or
mixed metal, lithium-aluminum alloy or mixed metal,
magnesium-silver alloy or mixed metal, or rare earth metal such as
indium and ytterbium. Among those, aluminum, lithium-aluminum alloy
or mixed metal, magnesium-silver alloy or mixed metal, and the like
are preferable. The cathode may be a monolayer structure of the
aforementioned materials or a layered structure containing those
materials. For example, the layered structures of aluminum/lithium
fluoride and aluminum / lithium oxide are preferable. It is
possible to select a thickness of the cathode appropriately
depending on a kind of the materials.
[0089] It is possible to use the hole injecting layer and the hole
transporting layer of the organic EL device when they have a role
of injecting holes from the anode, transporting holes from the
anode or blocking electrons injected from the cathode. Specific
examples thereof include a carbazol derivative, a triazole
derivative, an oxazole derivative, an imidazole derivative, a
polyarylalkane derivative, a pyrazoline derivative, a pyrazolon
derivative, a phenylenediamine derivative, an arylamine derivative,
an amino-substituted chalcone derivative, a stylylanthracene
derivative, a fluorenone derivative, a hydrazone derivative, a
stilbene derivative, a silazane derivative, an aromatic
tertiary-amine compound, a stylylamine compound, an aromatic
dimethylidyne-based compound, a porphyrin-based compound, a
polysilane-based compound, poly(N-vinylcarbazol) derivative, an
aniline-based coplymer, conductive polymeric oligomer such as a
thiophene oligomer and polythiophene, an organic silane derivative,
the metal complex compounds of the present invention and the like.
In addition, the aforementioned hole injecting layer and the
aforementioned hole transporting layer may be a monolayer structure
comprising at least one or more material of the aforementioned
materials or a multilayered structure comprising a plural layer of
the same composition or the different composition thereof.
[0090] It is possible to use the electron injecting layer and the
electron transporting layer of the organic EL device when they have
a role of injecting electrons from the cathode, transporting the
electrons, or blocking holes injected from the anode. Specific
examples thereof include a triazole derivative, an oxazole
derivative, an oxadiazole derivative, an imidazole derivative, a
fluorenone derivative, an anthraquino-dimetane drivative, an
anthrone derivative, a diphenylquinone derivative, a
thiopyrandioxide derivative, a carbodiimide derivative, a
fluorenylidene methane derivative, a distyrylpyradine derivative,
an aromatic tetracarboxylic acid anhydride of naphthalene or
perylene, a phthalocyanine derivative, a metal complex of a
8-quinolinol derivative, a metal complex represented by the metal
complex coordinated with metal phthalocyanine, benzoxazole or
benzothiazole, an organic silane derivative, a metal complex
compound of the present invention and the like. In addition, the
aforementioned electron injecting layer and the aforementioned
electron transporting layer may be a monolayer structure comprising
at least one or more material of the aforementioned materials or a
multilayered structure comprising a plural layer of the same
composition or the different composition thereof.
[0091] Further, en electron transporting material for the electron
injecting layer and the electron transporting layer includes the
following compounds:
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027##
##STR00028## ##STR00029##
[0092] It is preferable in the organic EL device that at least any
one of the electron injecting layer and the electron transporting
layer contains a .pi.-electron deficiency nitrogen-containing
heterocyclic derivative as the main component.
[0093] Examples of the n-electron deficiency nitrogen-containing
heterocyclic derivative include preferably a nitrogen-containing
5-members ring derivative such as a benzimidazole ring, a
benztriazole ring, a pyridinoimidazole ring, a pyrimidinoimidazole
ring and a pyridazinoimidazole ring, and a nitrogen-containing 6
members ring derivative such as a pyridine ring, a pyrimidine ring,
a pyrazine ring and a triazine ring. A structure represented by the
following general formula B-I is preferable for the
nitrogen-containing 5-members ring derivative, and a structure
represented by the following general formulae C-I, C-II, C-III,
C-VI, C-V and C-VI is preferable for the nitrogen-containing
6-members ring derivative, in particular, the structure represented
the general formulae C-I and C-II are is more preferable.
##STR00030##
[0094] In the general formula (B-I), L.sup.B represents a
connecting group having bivalent or more, and a connecting group
formed by carbon, silicon, nitrogen, boron, oxygen, sulfur, metal,
metal ion or the like is preferable, and a carbon atom, a nitrogen
atom, a silicone atom, a boron atom, an oxygen atom, a sulfur atom,
an aromatic hydrocarbon ring and an aromatic heterocyclic ring are
more preferable, a carbon atom, a silicon atom, an aromatic
hydrocarbon ring and an aromatic heterocyclic ring are particularly
preferable.
[0095] L.sup.B may have a substituent, and a preferable substituent
includes an alkyl group, an alkenyl group, an alkynyl group, an
aromatic hydrocarbon group, an amino group, an alkoxy group, an
aryloxy group, an acyl group, an alkoxycarbonyl group, an
aryloxycarbonyl group, an acyloxy group, an acylamino group, an
alkoxycarbonylamino group, an aryloxycarbonylamino group, a
sulfonylamino group, a sulfamoyl group, a carbamoyl group, an
alkylthio group, an arylthio group, a sulfonyl group, a halogen
atom, a cyano group and an aromatic heterocyclic group. More
preferable one includes an alkyl group, an aryl group, an alkoxy
group, an aryloxy group, a halogen atom, an cyano group and an
aromatic heterocyclic group, and further more preferable one
includes an alkyl group, an aryl group, an alkoxy group, an aryloxy
group and an aromatic heterocyclic group, particularly preferable
one includes an alkyl group, an aryl group and an aromatic
heterocyclic group.
[0096] Examples of the connecting group represented by L.sup.B
include the following:
##STR00031## ##STR00032##
[0097] In the general formula (B-I), X.sup.B2 represents --O--,
--S-- or .dbd.N--R.sup.B2. R.sup.B2 represents a hydrogen atom, an
aliphatic hydrocarbon group, an aryl group and a heterocyclic
group.
[0098] An aliphatic hydrocarbon group represented by R.sup.B2
includes a linear, branched or cyclic alkyl group having preferably
1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms and in
particular preferably 1 to 8 carbon atoms. Specific examples
include methyl, ethyl isopropyl, t-butyl, n-octyl, n-decyl,
n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. An
alkenyl group thereof includes the group having preferably 2 to 20
carbon atoms, more preferably 2 to 12 carbon atoms, in particular
preferably 2 to 8 carbon atoms. Specific examples include a vinyl
group, an aryl group, 2-butenyl group, 3-pentenyl group and the
like. An alkynyl group thereof includes the group having preferably
2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, in
particular preferably 2 to 8 carbon atoms. Specific examples
thereof include a propargyl group, a 3-pentyl group and the like.
An alkyl group is more preferable.
[0099] An aryl group represented by R.sup.B2 include a monocyclic
or a condensed cyclic aryl group having preferably 6 to 30 carbon
atoms, more preferably 6 to 20 carbon atoms, and further more
preferably 6 to 12 carbon atoms. Specific examples thereof include
phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl,
2-methoxyphenyl, 3-trifluoromethylphenyl, pentafluorophenyl,
1-naphtyl, 2-naphtyl and the like.
[0100] A heterocyclic group represented by R.sup.B2 include the
group of a monocyclic or condensed cyclic ring having preferably 1
to 20 carbon atoms, more preferably 1 to 12 carbon atoms, further
more preferably 2 to 10 carbon numbers, and preferably an aromatic
heterocyclic group containing at least one selected from the group
consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a
selenium atom. Specific examples thereof include pyrrolidine,
piperidine, piperadine, morpholine, thiophene, selenophen, furan,
pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine,
pyrimidine, triazole, triazine, indole, indazole, purine,
thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole,
quinoline, isoquinoline, phthalazine, naphthylizine, quinoxaline,
quinazoline, cinnoline, pteridine, acridine, phenanthroline,
phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole,
benztriazole, tetraazainndene, carbazol, azepine and the like.
Among those, furan, thiophen, pyridine, pyrazine, pyrimidine,
pyridazine, triazine, quinoline, phthalazine, naphthylizine,
quinoxaline and quinazoline are preferable, furan, thiophen,
pyridine and quinoline are more preferable, and quinoline is
further more preferable.
[0101] The aliphatic hydrocarbon group, the aryl group and the
heterocyclic group represented by R.sup.B2 may have substituent and
include the similar ones to the aforementioned in the L.sup.B.
[0102] R.sup.B2 includes preferably an alkyl group, an aryl group
and an aromatic heterocyclic group, more preferably an aryl group
and an heterocyclic group, and further more preferably an aryl
group.
[0103] X.sup.B2 includes preferably --O-- and .dbd.N--R.sup.B2,
more preferably .dbd.N--R.sup.B2, further more preferably
.dbd.N--Ar.sup.B2: wherein Ar.sup.B2 includes an aryl group having
6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and
further more preferably 6 to 12 carbon atoms, and an aromatic
heterocyclic group having preferably 1 to 20 carbon numbers, more
preferably 1 to 12 carbon atoms and further more preferably 2 to 10
carbon atoms, and preferably an aryl group.
[0104] Z.sup.B2 represents an atomic family required to form an
aromatic ring. The aromatic rings formed by Z.sup.B2 may be any one
of an aromatic hydrocarbon ring and an aromatic heterocycle.
Specific examples include, for example, a benzene ring, a pyridine
ring, a pyradine ring, a pyrimidine ring, a pyridazine ring, a
triazine ring, a pyrrole ring, a furan ring, a thiophene ring, a
selenophene ring, a tellurophene ring, an imidazole ring, a
thiazole ring, a selenazole ring, a tellurazole ring, a thiadiazole
ring, an oxadiazole ring, and a pyrazole ring, preferably a benzene
ring, a pyridine ring, a pyradine ring, a pyrimidine ring, and a
pyridazine ring, more preferably a benzene ring, a pyridine ring
and a pyradine ring, further more preferably a benzene ring and a
pyridine ring, in particular preferably a pyridine ring. The
aromatic rings formed by Z.sup.B2 may be linked further to another
ring to form a condensed ring and may have substituent. Examples of
the substituent include preferably an alkyl group, an alkenyl
group, an alkynyl group, an aryl group, an amino group, an alkoxy
group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an
aryloxycarbonyl group, an acyloxycarbonyl group, an acylamino
group, an alkoxycarbonylamino group, an aryloxycarbonylamino group,
a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an
alkylthio group, an arylthio group, a sulfonyl group, a halogen
atom, a cyano atom and a heterocyclic group, more preferably an
alkyl group, an aryl group, an alkoxy group, an aryloxy group, a
halogen atom, a cyano group and a heterocyclic group, further more
preferably an alkyl group, an aryl group, an alkoxy group, an
aryloxy group and an aromatic heterocyclic group, in particular
preferably an alkyl group, an aryl group, an alkoxy group and an
aromatic heterocyclic group.
[0105] n.sup.B2 is an integer of from 1 to 4, and preferably from 2
to 3.
[0106] The compounds represented by the following general formula
(B-II) are preferable among the compounds represented the above
general formula (B-I):
##STR00033##
[0107] wherein R.sup.B71, R.sup.B72 and R.sup.B73 each in the
general formula (B-II) is the same with R.sup.B72 in the general
formula (B-I), and also the preferable range thereof is similar
thereto. Z.sup.B71, Z.sup.B72 and Z.sup.B73 each is similar to
Z.sup.B2 in the general formula (B-I), and also the preferable
range thereof is similar thereto. L.sup.B71, L.sup.B72 and
L.sup.B73 each represents a connecting group, and includes bivalent
derivatives derived from the examples of L.sup.B in the general
formula (B-I). Preferable one is a connecting bond consisting of a
single bond, a bivalent aromatic hydrocarbon ring group, a bivalent
aromatic heterocyclic group and a combination thereof, and more
preferable one is a single bond. L.sup.B71, L.sup.B72 and L.sup.B73
may have substituents, and the substituents include the similar
ones to those of L.sup.B in the general formula (B-I). Y represents
a nitrogen atom, a 1,3,5-benzenetriyl group or a
2,4,6-triazinetriyl group. The 1,3,5-benzentriyl group may have
substituent at 2,4,6-positions thereof, and the substituent
includes, for example, an alkyl group, an aromatic hydrocarbon ring
group, a halogen atom and the like.
[0108] Specific examples of the nitrogen-containing 5-members
derivatives represented by the general formulae (B-I) or (B-II)
will be shown as follows, which do not limit the scope of it.
##STR00034## ##STR00035## ##STR00036## ##STR00037##
(Cz-).sub.nA(C-I)
Cz(-A).sub.m(C-II)
[0109] wherein Cz represents a substituted or unsubstituted
carbazolyl group, an arylcarbazolyl group or a carbazolylalkylene
group, and A represents a group formed from a moiety represented by
the following general formula (A), n and m each represents an
integer from 1 to 3.
(M).sub.p-(L).sub.q-(M').sub.r (A)
[0110] wherein, M and M' each independently represents a
nitrogen-containing heteroaromatic ring having 2 to 40 carbon atoms
of forming a ring, and the ring may have a substituent. In
addition, M and M' may be the same with or different from each
other. L represents a single bond, an arylene group having 6 to 30
carbon atoms, a cycloalkylene having 5 to 30 carbon atoms or a
heteroaromatic ring having 2 to 30 carbon atoms, and may has a
substituent bonding to the ring. p represents an integer from 0 to
2, q represents an integer from 1 to 2 and r represents an integer
from 0 to 2, with the proviso that p+r is 1 or larger.
[0111] The bonding mode of the general formulae (C-I) and (C-II) is
shown as follows depending on the number of index n and m;
TABLE-US-00001 TABLE 1 n = m = 1 n = 2 n = 3 m= 2 m= 3 Cz--A
Cz--A--Cz ##STR00038## A--Cz--A ##STR00039##
[0112] In addition, the bonding mode of the group represented by
the general formulae (A) is shown as (1) to (16) in the Tables
depending on the number of index p, q and r;
TABLE-US-00002 TABLE 2 No p q r Bonding mode (1) 0 1 1 L--M' (2) 0
1 2 L--M'--M', M'--L--M' (3) 0 2 1 L--L--M', L--M'--L (4) 0 2 2
L--L--M'--M', M'--L--L--M', ##STR00040## ##STR00041## ##STR00042##
(5) 1 1 0 the same as (1) (replacing M' with M) (6) 1 1 1 M--L--M'
(7) 1 1 2 M--L--M'--M', ##STR00043## (8) 1 2 0 the same as (3)
(replacing M' with M) (9) 1 2 1 M--L--L--M', L--M--L--M',
M--L--M'--L
TABLE-US-00003 TABLE 3 (10) 1 2 2 M--L--L--M'--M', M'--L--M--L--M',
M'--M'--L--M--L, ##STR00044## ##STR00045## ##STR00046##
##STR00047## ##STR00048## (11) 2 1 0 the same as (2) (replacing M'
with M) (12) 2 1 1 the same as (7) (replacing M' with M) (13) 2 1 2
M--M--L--M'--M', ##STR00049## ##STR00050## (14) 2 2 0 the same as
(4) (replacing M' with M) (15) 2 2 1 the same as (10) (replacing M'
with M) (16) 2 2 2 M--M--L--L--M'--M', ##STR00051## ##STR00052##
##STR00053## ##STR00054## ##STR00055## ##STR00056##
[0113] In the above general formulae (C-I) and (C-II), Cz may be
linked to any part of M, L and M' representing A when Cz bonds to
A. For example, in the case of Cz-A of m=n=1 and of p=q=r=1 ((6) in
Table), A is M-L-M', and tree bonding modes of Cz-M-L-M',
M-L(-Cz)-M' and M-L-M'-Cz can be shown. Similarly, for example, in
Cz-A-Cz which is n=2 of the general formula (C-I), and in the case
of p=q=1 and r=2 ((7) in Table), A is M-L-M'-M or M-L(-M')-M' and
represented by the following bonding modes:
##STR00057##
[0114] Specific examples represented by the above general formulae
(C-I) and (C-II) include the following structures, but not limited
thereto;
##STR00058## ##STR00059## ##STR00060## ##STR00061##
##STR00062##
[0115] wherein, Ar.sub.11 to Ar.sub.13 each represents the similar
groups to those of R.sup.B2 in the general formula (B-I), and
specific examples thereof are similar thereto. Ar.sub.1 to Ar.sub.3
represent bivalent derivatives derived from the groups similar to
those of R.sup.B2 in the general formula (B-I) and specific
examples thereof are similar thereto.
[0116] Example of the general formula (C-III) is shown as follows,
but not limited thereto;
##STR00063##
[0117] wherein, R.sub.56 to R.sub.62 each represents the similar
groups to those of R.sup.B2 in the general formula (B-I), and
specific examples thereof are similar thereto.
[0118] Example of the general formula (C-IV) is shown as follows,
but not limited thereto;
##STR00064##
[0119] wherein, Ar.sub.5 to Ar.sub.7 each represents the similar
groups to those of R.sup.B2 in the general formula (B-I), and
specific examples thereof are similar thereto.
[0120] Example of the general formula (C-V) is shown as follows,
but not limited thereto;
##STR00065##
[0121] wherein, Ar.sub.7 to Ar.sub.10 each represents the similar
groups to those of R.sup.B2 in the general formula (B-I), and
specific examples thereof are similar thereto.
[0122] Example of the general formula (C-VI) is shown as follows,
but not limited thereto;
##STR00066##
[0123] In addition, it is preferable to employ an inorganic
compound of insulator or semiconductor as a material constituting
an electron injecting or transporting layer in the organic EL
device of the present invention. When the electron injecting or
transporting layer comprises the above insulator or semiconductor,
it is possible to prevent the leakage of the electric current
effectively and the electron injecting capability can be improved.
It is preferable that at least one metal compound selected from the
group consisting of alkali metal chalcogenides, alkaline earth
metal chalcogenides, alkali metal halides and alkaline earth metal
halides is used as the insulator. It is preferable that the
electron injecting or transporting layer comprises the above alkali
metal chalcogenide and the like since the electron injecting
capability can be improved.
[0124] Preferable examples of the alkali metal chalcogenide include
Li.sub.2O, Na.sub.2S, Na.sub.2Se and the like. Preferable examples
of the alkaline earth metal chalcogenide include CaO, BaO, SrO,
BeO, BaS and CaSe. Preferable examples of the alkali metal halide
include LiF, NaF, KF, LiCl, KCl, NaCl and the like. Preferable
examples of the alkaline earth metal halide include fluorides such
as CaF.sub.2, BaF.sub.2, SrF.sub.2, MgF.sub.2 and BeF.sub.2 and
halides other than the fluorides.
[0125] Examples of the semiconductor constituting the electron
injecting or transporting layer include oxides, nitrides and oxide
nitrides containing at least one element selected from Ba, Ca, Sr,
Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn, which are used
singly or in combination of two or more. It is preferable that the
inorganic compound constituting the electron transporting layer is
in the form of a microcrystalline or amorphous insulating thin
film. When the electron transporting layer comprises the above
insulating thin film, a more uniform thin film can be formed and
pixel defect such as dark spots can be decreased. Examples of the
inorganic compound include the alkali metal chalcogenides, the
alkaline earth metal chalcogenides, the alkali metal halides and
the alkaline earth metal halides which are described above.
[0126] In addition, at least any one of the electron injecting
layer and electron transporting layer of the organic EL device of
the present invention may contain a reductive dopant with the work
function of 2.9 eV or less. In the present invention, the reductive
dopant means compounds which increase the electron injecting
efficiency.
[0127] Further, it is preferable in the present invention that a
reductive dopant is added into an interface area between the
cathode and the organic thin film layer. The dopant reduces at
least one part of the organic layer contained in the interface area
to form anion. Preferable examples of the reductive dopant include
at least one compound selected from the group consisting of alkali
metals, alkali metal oxides, alkaline earth metals, rare earth
metals, alkali metal oxides, alkali metal halides, alkaline earth
metal oxides, alkaline earth metal halides, rare earth metal
oxides, rare earth metal halides, alkali metal complexes, alkaline
earth metal complexes and rare earth metal complexes. Specific
examples of the preferable reductive dopant include at least an
alkali metal selected from the group consisting of Na (the work
function: 2.36 eV), K (the work function: 2.28 eV), Rb (the work
function: 2.16 eV) and Cs (the work function: 1.95 eV),or at least
an alkaline earth metal selected from the group consisting of Ca
(the work function: 2.9 eV), Sr (the work function: 2.0 to 2.5 eV)
and Ba (the work function: 2.52 eV), and whose work function of 2.9
eV is particularly preferable. Among those dopants, an alkali metal
selected from the group consisting of K, Rb and Cs is more
preferable, and Rb and Cs are further more preferable. Cs is most
preferable. The alkali metals have particularly high reducing
capability so that addition of them in small quantity into an
electron injecting zone results in improvement of luminance of
emitted light as well as a longer lifetime.
[0128] The alkaline earth metal oxides include preferably, for
example, BaO, SrO, CaO, and the mixtures thereof having the
structures of Ba.sub.xSr.sub.1-xO (0<x<1) and
Ba.sub.xCa.sub.1-xO (o<x<1). The alkali oxides or alkali
fluorides include LiF, Li.sub.2O, NaF and the like. It is not
limited for the alkali metal complexes, alkaline earth metal
complexes and rare earth metal complexes when these complexes
contain at least a metal ion of alkali metal ion, alkaline earth
metal ion and rare earth metal ion. In addition, examples of the
ligand include, for example, quinolinol, benzoquinolinol,
acridinol, phenanthridinol, hydroxyphenyloxazole,
hydroxyphenylthiazol, hydroxydiaryloxazole, hydroxydiarylthiazol,
hydroxyphenylpyridine, hydoxyphenylbenzimidazole,
hydroxybenztriazole, hydroxyfluborane, bipyridyl, phenanthroline,
phthalocyanine, porphyrin, cyclopentadiene, .beta.-diketones,
azomethine and derivatives thereof, but not limited thereto.
[0129] It is preferable to form the reductive dopants in a layer
shape or in an island shape. The preferable thickness of the layer
shape is from 0.05 to 8 nm.
[0130] As a forming process of the electron injecting or
transporting layer containing a reductive dopant thereof, it is
preferable that organic materials of a light emitting material or
an electron injecting material forming an interface area are
deposited while depositing a reductive dopant by a resistive
heating vapor deposition process and the reductive dopant is
dispersed into the organic materials. The dispersion concentration
is in the range from 100:1 to 1:100, preferably 5:1 to 1:5 by mole
ratio. When forming the reductive dopant in a layer shape, a light
emitting material or an electron injecting material is formed in a
layer shape, followed by depositing the reductive dopant singly by
a resistive heating vapor deposition process so as to form the
layer having preferably a thickness of 0.1 to 15 nm. When forming
the reductive dopant in a island shape, a light emitting material
or an electron injecting material of an organic layer at the
interface is formed, followed by depositing the reductive dopant
singly by a resistive heating vapor deposition process so as to
form the layer having preferably a thickness of 0.05 to 1 nm.
[0131] When an electric field is applied to the organic EL device
of the present invention, the light emitting layer has the function
of injecting holes from the anode or the hole injecting layer, the
function of injecting electrons from the cathode or the electron
injecting layer, the function of transporting injected charges
(electrons and holes) by the force of the electric field, and the
function of providing the field for recombination of electrons and
holes in order to lead the recombination to the emission of light.
It is preferable for the light emitting layer of the organic EL
device to contain at least a metal complex compound of the present
invention and also a host material, of which a guest material is
the metal complex compound. The above host material includes, for
example, a compound having a carbazole framework, a diarylamine
framework, a pyridine framework, a pyrazine famework, a triazine
framework, an arylsilane framework and the like. It is preferable
for T1, which is a energy level at the minimum triplet excited
state, of the host materials is larger than T1 of the guest
materials. The host materials may be a low molecular weight
compound or a high molecular weight compound. In addition, it is
possible to form a light emitting layer having the light emitting
material doped in the host material by a co-deposition or the like
with the host material and a light emitting material of the metal
complex compounds and the like.
[0132] In the organic EL device of the present invention, there is
no limitation for a forming process of the layers described above,
but it is possible to employ various processes such as a vacuum
vapor deposition process, a LB process, a resistive heating vapor
deposition process, an electron beam process, a sputtering process,
a molecular lamination process, a conventional coating process such
as the spin coating process, the casting process, the dipping
coating process and the like, an inkjet process and a printing
process. The coating process as an application process is
preferable for the present invention.
[0133] In addition, the organic thin film layer comprising the
metal complex compound of the present invention can be formed in
accordance with the vacuum vapor deposition process, the molecular
beam epitaxy process (the MBE process) or, using a solution
prepared by dissolving the compound into a solvent, in accordance
with a conventional coating process such as the dipping process,
the spin coating process, the casting process, the bar coating
process and the roller coating process.
[0134] In the above coating processes, it is possible to prepare an
embrocation by dissolving the metal complex compound into a
solvent, followed by applying it on the desired layer or the
electrode and dried. It is possible to have a resin contained in
the embrocation, and the resin may be dissolved or dispersed in the
solvent. A non-conjugated type polymer such a polyvinylcarbazole
and a conjugated type polymer such as polyolefine may be used.
Specific examples thereof include, for example, polyvinylchloride,
polycarbonate, polystyrene, polymethylmethacrylate,
polybutylmethacrylate, polyester, polysulfone, polyphenyleneoxide,
polybutadiene, poly(N-vinylcarbazole), hydrocarbon resin, ketone
resine, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate,
ABS resin, polyurethane, melamine resin, unsaturated polyester
resin, alkyd resin, epoxy resin, and silicone resin.
[0135] Additionally, the film thickness of each organic layer in
the organic EL device of the present invention is not particularly
limited, but, there is a general tendency of causing defects such
as a pin-hole when it is too thin, adversely there is a tendency of
lowing efficiency due to high voltage charged when it is too thick;
therefore, a thickness in the range of from several nanometers to 1
.mu.m is preferable.
Example
[0136] This invention will be described in further detail with
reference to the examples.
Synthesis Example 1
##STR00067##
[0137] Synthesis of Compound (A1)
[0138] 2.00 g of iridium chloro-bridged dimer A, 0.34 g of
2-acetylpyrrole, 1.57 g of sodium carbonate and 50 ml of
2-ethoxyethanol were placed in a three neck flask of 200 ml,
followed by the argon gas displacement, and the resultant was
refluxed under heating for 10 hours while stirring. The resultant
was cooled to a room temperature, followed by filtration. The
obtained-solid substance was added dichloromethane and water,
followed by dichloromethane extraction. The organic solvent layer
was dried with the use of sodium sulfate anhydride, followed by
evaporation. The obtained was purified with 100 g of silica gel
column chromatography and as a result, slightly yellow colored
solid of 2.0 g was obtained. Further, it was purified by
sublimation under the vacuum of 5.0.times.10.sup.-6 Torr at 250
degC., and 1.93 g of the compound (A1) was obtained. The structure
was identified by FD-MS measurement (Field Desorption Mass
Spectrometry). The result of the measurement is shown as
follows:
[0139] FD-MS: calcd. for IrC.sub.32H.sub.19F.sub.12N.sub.30=881,
found, m/z=881 (100)
Synthesis Example 2
##STR00068##
[0140] Synthesis of Compound (A4)
[0141] 2.40 g of iridium chloro-bridged dimer B, 0.36 g of
2-acetylpyrrole, 1.60 g of sodium carbonate and 50 ml of
2-ethoxyethanol were placed in a three neck flask of 200 ml,
followed by the argon gas displacement, and the resultant was
refluxed under heating for 9 hours while stirring. The resultant
was cooled to a room temperature, followed by filtration. The
obtained-solid substance was added dichloromethane and water,
followed by dichloromethane extraction. The organic layer was dried
with the use of sodium sulfate anhydride, followed by evaporation.
The obtained was purified with 100 g of silica gel column
chromatography and as a result, slightly yellow colored solid of
1.75 g was obtained. Further, it was purified by sublimation under
the vacuum of 4.0.times.10.sup.-6 Torr at 280 degC., and 1.41 g of
the compound (A4) was obtained. The structure was identified by
FD-MS measurement. The result of THE measurement is shown as
follows:
[0142] FD-MS: calcd. for IrC.sub.28H.sub.22IrN.sub.30=609, found,
m/z=609 (100)
Synthesis Example 3
##STR00069##
[0143] Synthesis of Compound (A12)
[0144] 2.20 g of iridium chloro-bridged dimer B, 0.42 g of
2-acetyl-5-methylpyrrole, 1.60 g of sodium carbonate and 50 ml of
2-ethoxyethanol were placed in a three neck flask of 200 ml,
followed by the argon gas displacement, and the resultant was
refluxed under heating for 16 hours while stirring. The resultant
was cooled to a room temperature, followed by filtration. The
obtained-solid substance was added dichloromethane and water,
followed by dichloromethane extraction. The organic layer was dried
with the use of sodium sulfate anhydride, followed by evaporation.
The obtained was purified with 100 g of silica gel column
chromatography and as a result, slightly yellow colored solid of
1.60 g was obtained. Further, it was purified by sublimation under
the vacuum of 3.6.times.10.sup.-6 Torr at 260 degC., and 1.38 g of
the compound (A12) was obtained. The structure was identified by
FD-MS measurement. The result of the measurement is shown as
follows:
[0145] FD-MS: calcd. for C.sub.29H.sub.24IrN.sub.30=623, found,
m/z=623 (100)
Example 1
Fabrication Example 1 of an Organic EL Device
[0146] A glass substrate of 25 mm.times.75 mm.times.0.7 mm
thickness having an ITO transparent electrode was cleaned by
application of ultrasonic wave in isopropyl alcohol for 5 minutes,
and then exposed to ozone generated by ultraviolet light for 30
minutes. The cleaned glass substrate having the ITO transparent
electrode was fixed to a substrate holder of a vacuum deposition
apparatus, and on a surface of the substrate, on which the ITO
transparent electrode was formed, a film of TPD232 of the following
formula was formed so as to cover the transparent electrode. The
film thickness was 85 nm. The TPD232 film performs as a hole
injecting layer. Subsequently, on the TPD232 film, a layer having
layer thickness of 10 nm of
4,4',4''-tris(carbazole-9-yl)-triphenylamine (TCTA) of the
following formula was formed. The TCTA film performs as a hole
transporting layer. Subsequently, on the TCTA film, a film having a
film thickness of 30 nm of the following compound (H) as a host
material was formed for a light emitting layer by vapor deposition.
As a phosphorescent Ir metal complex dopant, the metal complex
compound (A1) was added together. The content of the metal complex
compound (A1) in the light emitting layer was 7.5% by weight. The
film performs as a light emitting layer. On the film, a BAlq film
of the following formula having a film thickness of 25 nm was
formed. The BAlq film performs as an electron transporting layer.
Subsequently, on the film, an Alq film of the following formula
having a film thickness of 5 nm was formed. The Alq film performs
as an electron injecting layer. Then, lithium fluoride was
deposited thereon to be a thickness of 0.1 nm, followed by
deposition of aluminum of a thickness of 150 nm. The Al/LiF
performs as the cathode. Thus an organic EL device was
fabricated.
[0147] The sealed-device was tested by applying electric current,
and the luminance of 102 cd/m.sup.2 and a blue-green colored
emission of CIE chromaticity (0.17, 0.36) were observed and the
current efficiency was 17.3 cd/A at the voltage of 6.8 V and the
current density of 0.59 mA/cm.sup.2.
##STR00070## ##STR00071##
Comparative Example 1
[0148] An organic EL device was fabricated similarly as Example 1
except that Compound D was used in place of (A1) as a dopant.
[0149] The sealed-device was tested by applying electric current,
and the luminance of 102 cd/m.sup.2 and a blue-green colored
emission of CIE chromaticity (0.18, 0.38) were observed and the
current efficiency was 12.8 cd/A at the voltage of 7.5 V and the
current density of 0.80 mA/cm.sup.2.
##STR00072##
Example 2
Fabrication Example 2 of an Organic EL Device
[0150] A glass substrate of 25 mm.times.75 mm.times.0.7 mm
thickness having an ITO transparent electrode was cleaned by
application of ultrasonic wave in isopropyl alcohol for 5 minutes,
and then exposed to ozone generated by ultraviolet light for 30
minutes. The cleaned glass substrate having an ITO transparent
electrode was fixed to a substrate holder of a vacuum deposition
apparatus, and on a surface of the substrate, on which the ITO
transparent electrode was formed, a film of TPD232 of the following
formula was formed so as to cover the transparent electrode. The
film thickness was 60 nm. The film of TPD232 performs as a hole
injecting layer. Subsequently, on the TPD232 film, a layer having
layer thickness of 30 nm of TBDB was formed. The TBDB film performs
as a hole transporting layer. Subsequently, on the TBDB film, a
film having a film thickness of 30 nm of the compound (H) as a host
material was formed for a light emitting layer by vapor deposition.
As a phosphorescent Ir metal complex dopant, the metal complex
compound (A4) was added together. The content of the metal complex
compound (A4) in the light emitting layer was 5% by weight. The
film performs as a light emitting layer. On the film, the BAlq film
having a film thickness of 10 nm was formed. The BAlq film performs
as an electron transporting layer. Subsequently, on the film, the
Alq film having a film thickness of 40 nm was formed. The Alq film
performs as an electron injecting layer. Then, LiF of alkali
halides was deposited thereon to be a thickness of 0.2 nm, followed
by deposition of aluminum of a thickness of 150 nm. The Al/LiF
performs as the cathode. Thus an organic EL device was fabricated.
The sealed-device was tested by applying electric current, and the
luminance of 105 cd/m.sup.2 and a green colored emission of the
chromaticity coordinates (0.30, 0.60) were observed and the current
efficiency was 35 cd/A at the voltage of 5.4 V and the current
density of 0.30 mA/cm.sup.2.
##STR00073##
Example 3
Fabrication Example 3 of an Organic EL Device
[0151] An organic EL device was fabricated similarly as Example 2
except that the above metal complex compound (A12) was used in
place of the metal complex compound (A4) as the Ir metal complex
dopant of the light emitting layer.
[0152] The sealed-device was tested by applying electric current,
and the luminance of 101 cd/m.sup.2 and a green colored emission of
the chromaticity coordinates (0.30, 0.59) were observed and the
current efficiency was 37 cd/A at the voltage of 5.6 V and the
current density of 0.27 mA/cm.sup.2.
Comparative Example 2
[0153] An organic EL device was fabricated similarly as Example 2
except that the following compound D2 was used in place of the
metal complex compound (A4) as the Ir metal complex dopant of the
light emitting layer. The sealed-device was tested by applying
electric current, and the luminance of 102 cd/m.sup.2 and a green
colored emission of the chromaticity coordinates (0.30, 0.63) were
observed and the current efficiency was 31 cd/A at the voltage of
5.7 V and the current density of 0.33 mA/cm.sup.2.
##STR00074##
[0154] As explained above, the organic EL device having high
efficiency and heat resistance can be produced by employing the
metal complexes compounds comprising a pyrrole framework as the
ligand of dopant.
INDUSTRIAL APPLICABILITY
[0155] As aforementioned, the EL device employing the metal complex
compounds exhibits high efficiency of light emission and the
compounds can be suitable for a material of an organic EL device.
Therefore, it is useful for using in the field of a various display
devices, a display, a back-light, a light source, a sign,
advertising display, interior and the like. It is particularly
suitable for a display device for a color display.
* * * * *