U.S. patent application number 11/563118 was filed with the patent office on 2007-06-21 for light-emitting element and iridium complex.
This patent application is currently assigned to CHI MEI OPTOELECTRONICS CORP.. Invention is credited to Tai-Yen Chen, Chien-Hong Cheng, Huai-Ting Shih, Hung-Hsin Shih, Kuan-Che Wang, Chien-Te Wu, Chin-In Wu.
Application Number | 20070141394 11/563118 |
Document ID | / |
Family ID | 38197908 |
Filed Date | 2007-06-21 |
United States Patent
Application |
20070141394 |
Kind Code |
A1 |
Cheng; Chien-Hong ; et
al. |
June 21, 2007 |
LIGHT-EMITTING ELEMENT AND IRIDIUM COMPLEX
Abstract
An indium complex is disclosed, which has a structure
represented by the following formula (I): ##STR1## wherein each of
Z.sub.1 and Z.sub.3 represents an atomic group for forming a
nitrogen-containing heteroaryl group or a nitrogen-containing
heterocycloalkenyl group; Z.sub.2 represents an atomic group for
forming an aryl group, a heteroaryl group, a cycloalkenyl group or
a heterocycloalkenyl group; Y represents an atomic group for
forming a 5-membered nitrogen-containing heterocycloalkenyl group;
each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represents a hydrogen
atom or a substituent; m is 1 or 2; a, b and d is 0 or any positive
integer; and c is an integer of from 0 to 2.
Inventors: |
Cheng; Chien-Hong;
(Hsin-Chu, TW) ; Chen; Tai-Yen; (Hsinchu, TW)
; Shih; Hung-Hsin; (Hsichu, TW) ; Wu;
Chien-Te; (Tainan Science-Based Industrial Park, TW)
; Wang; Kuan-Che; (Tainan Science-Based Industrial Park,
TW) ; Wu; Chin-In; (Tainan Science-Based Industrial
Park, TW) ; Shih; Huai-Ting; (Tainan Science-Based
Industrial Park, TW) |
Correspondence
Address: |
LOWE HAUPTMAN BERNER, LLP
1700 DIAGONAL ROAD
SUITE 300
ALEXANDRIA
VA
22314
US
|
Assignee: |
CHI MEI OPTOELECTRONICS
CORP.
TAINAN COUNTY
TW
NATIONAL TSING HUA UNIVERSITY
HSINCHU
TW
|
Family ID: |
38197908 |
Appl. No.: |
11/563118 |
Filed: |
November 24, 2006 |
Current U.S.
Class: |
428/690 ;
257/E51.044; 313/504; 313/506; 428/917; 544/225; 546/2; 546/4;
548/101; 548/103 |
Current CPC
Class: |
H05B 33/14 20130101;
C09K 2211/185 20130101; C07F 15/0033 20130101; C09K 2211/1044
20130101; C09K 2211/1059 20130101; H01L 51/5016 20130101; C09K
11/06 20130101; H01L 51/0085 20130101; C09K 2211/1037 20130101;
C09K 2211/1029 20130101 |
Class at
Publication: |
428/690 ;
428/917; 313/504; 313/506; 257/E51.044; 546/002; 546/004; 544/225;
548/101; 548/103 |
International
Class: |
H01L 51/54 20060101
H01L051/54; C09K 11/06 20060101 C09K011/06 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 25, 2005 |
TW |
94141584 |
Claims
1. A light-emitting material comprising a compound represented by a
following formula (I): ##STR29## wherein each of Z.sub.1 and
Z.sub.3 represents an atomic group for forming a
nitrogen-containing heteroaryl group or a nitrogen-containing
heterocycloalkenyl group; Z.sub.2 represents an atomic group for
forming an aryl group, a heteroaryl group, a cycloalkenyl group or
a heterocycloalkenyl group; Y represents an atomic group for
forming a 5-membered nitrogen-containing heterocycloalkenyl group;
each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represents a hydrogen
atom or a substituent; m is 1 or 2; a is 0 or any positive integer
depending upon a size of the Z.sub.1 atomic group; b is 0 or any
positive integer depending upon a size of the Z.sub.2 atomic group;
c is an integer of from 0 to 2; and d is 0 or any positive integer
depending upon a size of the Z.sub.3 atomic group.
2. The light=emitting material according to claim 1, wherein a net
effect of the (R.sub.3).sub.c group is not electron donating.
3. The light-emitting material according to claim 1, wherein a net
effect of the (R.sub.4).sub.d group is not electron
withdrawing.
4. The light-emitting material according to claim 1, wherein the
aryl group is selected from the group consisting of a phenyl group,
a naphthyl group, a diphenyl group, an anthryl group, a pyrenyl
group, a phenanthryl group and fluorene.
5. The light-emitting material according to claim 1, wherein the
cycloalkenyl group is selected from the group consisting of
cyclohexene, cyclohexadiene, cyclopentane and cyclopentadiene.
6. The light-emitting material according to claim 1, wherein the
hetrocycloalkenyl group is selected from the group consisting of
pyrane, pyrroline, furan, benzofuran, thiophene, benzothiophene,
pyridine, quinoline, isoquinoline, pyrazine, pyrimidine, pyrrole,
pyrazole, imidazole, indole, thiazole, isothiazole, oxazole,
isoxazole, benzothiazole, benzoxazole, 1,2,4-triazole,
1,2,3-triazole, tetrazole, and phenanthroline.
7. The light-emitting material according to claim 1, wherein each
of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is selected from the group
consisting of a hydrogen atom, a halogen atom, an aryl group, a
C.sub.1-C.sub.20 alkyl group, an aryl substituted C.sub.1-C.sub.20
alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20
alkynyl group, a halogen substituted C.sub.1-C.sub.20 alkyl group,
a C.sub.1-C.sub.20 alkoxy group, A C.sub.1-C.sub.20 substituted
amino group, a C.sub.1-C.sub.20 acyl group, a C.sub.1-C.sub.20
ester group, a C.sub.1-C.sub.20 amide group, a halogen-substituted
aryl group, a halogen-substituted aryl alkyl group, an alkyl
halide-substituted aryl group, an alkyl halide-substituted aryl
alkyl group, a cyano group and a nitro group.
8. The light-emitting material according to claim 1, wherein the
compound is represented by following formula II-1, II-2, II-3,
II-4, II-5, II-6 or II-31: ##STR30## ##STR31##
9. The light-emitting material according to claim 1, wherein the
compound is represented by following formulas II-7, II-8, II-9,
II-10, II-11, II-12, II-13, II-14, II-15, II-16, II-17, II-18,
II-19, II-20, II-21, II-22, II-23, II-24, II-25, II-26, II-27,
II-28, II-29 or II-30. ##STR32## ##STR33## ##STR34## ##STR35##
##STR36## ##STR37## ##STR38##
10. A light-emitting material comprising a compound represented by
a following formula (III); ##STR39## wherein Z.sub.3 represents an
atomic group for forming a nitrogen-containing heteroaryl group or
a nitrogen-containing heterocycloalkenyl group; Y represents an
atomic group for forming a 5-membered nitrogen-containing
heterocycloalkenyl group; each of R.sub.3 and R.sub.4 represents a
hydrogen atom or a substituent; R.sub.5 represents a
C.sub.1-C.sub.6 alkyl group; R.sub.6 represents an
electron-withdrawing group; R.sub.7 represents an aryl group, a
C.sub.1-C.sub.20 alkyl group or a phenyl group; R.sub.8 represents
a alkyl group, a tert-butyl group or a trifluoromethyl group; m is
1 or 2; c is an integer of from 0 to 2; and d is 0 or any positive
integer depending upon a size of the Z.sub.3 atomic group.
11. The light-emitting material according to claim 10, wherein a
net effect of the (R.sub.3).sub.c group is not electron
donating.
12. The light-emitting material according to claim 10, wherein a
net effect of the (R.sub.4).sub.d group is not electron
withdrawing.
13. The light-emitting material according to claim 10, wherein the
R.sub.6 group is selected from the group consisting of a halogen
atom, a nitrile group, a nitro group, a carbonyl group, a cyano
group and a trifluoromethyl group.
14. The light-emitting material according to claim 10, wherein the
aryl group is selected from the group consisting of a phenyl group,
a naphthyl group, a diphenyl group, an anthryl group, a pyrenyl
group, a phenanthryl group and fluorene.
15. The light-emitting material according to claim 10, wherein the
cycloalkenyl group is selected from the group consisting of
cyclohexene, cyclohexadiene, cyclopentene and cyclopentadiene.
16. The light-emitting material according to claim 10, wherein the
heterocycloalkenyl group is selected from the group consisting of
pyrane, pyrroline, furan, benzofuran, thiophene, benzothiophene,
pyridine, quinoline, isoquinoline, pyrazine, pyrimidine, pyrrole,
pyrazole, imidazole, indole, thiazole, isothiazole, oxazole,
isoxazole, benzothiazole, benzoxazole, 1,2,4-triazole,
1,2,3-triazole, tetrazole, and phenanthroline.
17. An organic light-emitting diode (OLED) device which includes an
anode, a cathode and an electroluminescent region interposed
between the anode and the cathode, wherein the electroluminescent
region includes an emitter layer comprising a phosphorescent
iridium complex represented by a following formula (I): ##STR40##
wherein each of Z.sub.1 and Z.sub.3 represents an atomic group for
forming a nitrogen-containing heteroaryl group or a
nitrogen-containing heterocycloalkenyl group; Z.sub.2 represents an
atomic group for forming an aryl group, a heteroaryl group, a
cycloalkenyl group or a heterocycloalkenyl group; Y represents an
atomic group for forming a 5-membered nitrogen-containing
heterocycloalkenyl group; each of R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 represents a hydrogen atom or a substituent; m is 1 or 2; a
is 0 or any positive integer depending upon a size of the Z.sub.1
atomic group; b is 0 or any positive integer depending upon a size
of the Z.sub.2 atomic group; c is an integer of from 0 to 2, and d
is 0 or any positive integer depending upon a size of the Z.sub.3
atomic group.
18. The OLED device according to claim 17, wherein a net effect of
the (R.sub.3).sub.c group is not electron donating.
19. The OLED device according to claim 17, wherein a net effect of
the (R.sub.4).sub.d is not electron withdrawing.
20. The OLED device according to claim 17, wherein the aryl group
is selected from the group consisting of a phenyl group, a naphthyl
group, a diphenyl group, an anthryl group, a pyrenyl group, a
phenanthryl group and fluorene.
21. The OLED device according to claim 17, wherein the cycloalkenyl
group is selected from the group consisting of cyclohexene,
cyclohexadiene, cyclopentene and cyclopentadiene.
22. The OLED device according to claim 17, wherein the
heterocycloalkenyl group is selected from the group consisting of
pyrane, pyrroline, furan, benzofuran, thiophene, benzothiophene,
pyridine, quinoline, isoquinoline, pyrazine, pyrimidine, pyrrole,
pyrazole, imidazole, indole, thiazole, isothiazole, oxazole,
isoxazole, benzothiazole, benzoxazole, 1,2,4-triazole,
1,2,3-triazole, tetraazole, and phenanthroline.
23. The OLED device according to claim 17, wherein each of R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 is selected from the group consisting
of a hydrogen atom, a halogen atom, an aryl group, a
C.sub.1-C.sub.20 alkyl group, an aryl substituted C.sub.1-C.sub.20
alkyl group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20
alkynyl group, a halogen substituted C.sub.1-C.sub.20 alkyl group,
A C.sub.1-C.sub.20 alkoxy group, a C.sub.1-C.sub.20 substituted
amino group, a C.sub.1-C.sub.20 acyl group, a C.sub.1-C.sub.20
ester group, a C.sub.1-C.sub.20 amide group, a halogen-substituted
aryl group, a halogen-substituted aryl alkyl group, an alkyl
halide-substituted aryl group, an alkyl halide-substituted aryl
alkyl group, a cyano group and a nitro group.
24. The OLED device according to claim 17, wherein the emitter
layer includes the compound represented by following formulas II-1,
II-2, II-3, II-4, II-5 or II-6: ##STR41## ##STR42##
25. The OLED device according to claim 17, wherein the emitter
layer includes the compound represented by following formulas II-7,
II-8, II-9, II-10, II-11, II-12, II-13, II-14, II-15, II-16, II-17,
II-18, II-19, II-20, II-21, II-22, II-23, II-24, II-25, II-26,
II-27, II-28, II-29, or II-30; ##STR43## ##STR44## ##STR45##
##STR46## ##STR47## ##STR48## ##STR49##
26. The OLED device according to claim 17, wherein the emitter
layer further includes a host luminescent compound doped with the
iridium complex.
27. The OLED device according to claim 26, wherein the host
luminescent compound is represented by a following structural
formula: ##STR50##
28. The OLED device according to claim 17, wherein the
electroluminescent region further includes a hole transfer layer
interposed between the anode and the emitter layer, and the hole
transfer layer comprises a compound represented by a following
structural formula of H1 or H2; ##STR51##
29. The OLED device according to claim 17, wherein the
electroluminescent region further includes a hole-blocking layer
interposed between the cathode and the emitter layer and in contact
with the emitter layer, and the hole-blocking layer comprises a
compound represented by a following structural formula: ##STR52##
wherein the Ph group is a phenyl group, and the Me group is a
methyl group.
30. The OLED device according to claim 17, wherein the
electroluminescent region further includes an electron-transporting
layer interposed between the hole-blocking layer and the cathode,
and the hole-blocking layer comprises a compound represented by a
following structural formula: ##STR53##
31. An OLED device which includes an anode, a cathode and an
electroluminescent region interposed between the anode and the
cathode, wherein the electroluminescent region includes an emitter
layer comprising a phosphorescent iridium complex represented by a
following formula (III): ##STR54## wherein Z.sub.3 represents an
atomic group for forming a nitrogen-containing heteroaryl group or
a nitrogen-containing heterocycloalkenyl group; Y represents an
atomic group for forming a 5membered nitrogen-containing
heterocycloalkenyl group; each of R.sub.3 and R.sub.4 represents a
hydrogen atom or a substituent; R.sub.5 represents a
C.sub.1-C.sub.6 alkyl group; R.sub.6 represents an
electron-withdrawing group; R.sub.7 represents an aryl group, a
C.sub.1-C.sub.20 alkyl group or a phenyl group; R.sub.8 represents
a alkyl group, a tert-butyl group or a trifluoromethyl group; m is
1 or 2; c is an integer of from 0 to 2; and d is 0 or any positive
integer depending upon a size of the Z.sub.3 atomic group.
32. The OLED device according to claim 31, wherein a net effect of
the (R.sub.3).sub.c group is not electron donating.
33. The OLED device according to claim 31, wherein a net effect of
the (R.sub.4).sub.d is not electron withdrawing.
34. The OLED device according to claim 31, wherein the R.sub.6
group is selected from the group consisting of a halogen atom, a
nitrile group, a nitro group, a carbonyl group, a cyano group and a
trifluoromethyl group.
35. The OLED device according to claim 31, wherein the aryl group
is selected from the group consisting of a phenyl group, a naphthyl
group, a diphenyl group, an anthryl group, a pyrenyl group, a
phenanthryl group and fluorene.
36. The OLED device according to claim 31, wherein the cycloalkenyl
group is selected from the group consisting of cyclohexene,
cyclohexadiene, cyclopentene and cyclopentadiene.
37. The OLED device according to claim 31, wherein the
heterocycloalkenyl group is selected from the group consisting of
pyrane, pyrroline, furan, benzofuran, thiophene, benzothiophene,
pyridine, quinoline, isoquinoline, pyrazine, pyrimidine, pyrrole,
pyrazole, imidazole, indole, thiazole, isothiazole, oxazole,
isoxazole, benzothiazole, benzoxazole, 1,2,4,-triazole,
1,2,3-triazole, tetrazole, and phenanthroline.
38. The OLED device according to claim 31, wherein the emitter
layer further includes a host luminescent compound doped with the
iridium complex.
39. The OLED device according to claim 31, wherein the host
luminescent compound is represented by a following structural
formula: ##STR55##
40. The OLED device according to claim 31, wherein the
electroluminescent region further includes a hole transfer layer
interposed between the anode and the emitter layer, and the hole
transfer layer comprises a compound represented by a following
structural formula of H1 or H2: ##STR56##
41. The OLED device according to claim 31, wherein the
electroluminescent region further includes a hole-blocking layer
interposed between the cathode and the emitter layer and in contact
with the emitter layer, and the hole-blocking layer comprises a
compound represented by a following structural formula: ##STR57##
wherein the Ph group is a phenyl group, and the Me group is a
methyl group.
42. The OLED device according to claim 31, wherein the
electroluminescent region further includes an electron-transporting
layer interposed between the hole-blocking layer and the cathode,
and the hole-blocking layer comprises a compound represented by a
following structural formula: ##STR58##
Description
RELATED APPLICATIONS
[0001] The present application is based on, and claims priority
from, Taiwan Application Serial Number 94141584, filed Nov. 25,
2005, the disclosure of which is hereby incorporated by reference
herein in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates generally to a novel iridium complex
and a light-emitting element using the same material as phosphor,
and more particularly, to a novel iridium complex and a
light-emitting device using the same material for applying in
display devices, displays, backlight sources and the like.
BACKGROUND OF THE INVENTION
[0003] Electroluminescent (EL) devices using organic luminescent
materials are being actively researched recently because of the
ability of displays fabricated using EL devices to exhibit wider
viewing angle and faster response time than conventional liquid
crystal displays. More particularly, flat panel displays fabricated
using EL devices made from organic luminescent materials are
expected to use spontaneous light emission and the resultant flat
panel displays have high response speed no matter what the vision
angle is. Furthermore, EL devices using organic luminescent
materials can exhibit advantages such as low power consumption,
high brightness, and light and thin design, which can be useful in
consumer electronic devices such as digital cameras, personal
digital assistants (PDA), and videophones.
[0004] An example of a light-emitting device is an organic
light-emitting diode (OLED) device. In general, an OLED device,
which can include an organic thin film containing a luminescent
material formed between an optically transparent anode and a
metallic cathode, emits light when an external voltage is applied
to the luminescent material. To produce a full-color EL display
panel using OLEDs, it is useful to have highly efficient red,
green, and blue EL materials with appropriate chromaticity and
luminance efficiency.
[0005] OLEDs exhibiting high luminance efficiency can be fabricated
using electroluminescent materials containing heavy metal
complexes, and the electroluminescent materials attract attention
in applications and researches. For example, electroluminescent
materials comprising complexes of platinum (PT), osmium (Os), and
iridium (Ir) can be used to form an electroluminescent layer in
OLEDs, wherein the iridium complexes exhibit the highest
efficiency. Iridium complexes exhibiting high luminance efficiency
typically have an octahedral structure with the iridium center in a
+3 oxidation state. The mechanism of luminance emission of these
iridium complexes is based on a triplet-.sup.3MLCT (metal to ligand
charge transfer) transition between the metal and the ligand, or a
triplet-.sup.3.pi.-.pi.* ligand-centered luminescence. The strong
spin-orbit coupling of the heavy metal complexes produces high
phosphorescence efficiency.
[0006] One of the best known t riplet-state blue phosphorescent
light-emitting material is
Iridium(III)bis(4,6-difluorophenylpyridinato)picolate (FIrpic), and
its exteneral quantum efficiency can achieve approximately 10% (or
10 lm/W) in some reports. However, the blue light of FIrpic is not
enough saturated, the CIE (Commission International D'Eclairage)
chromaticity of which is (0.17, 0.34), so the light of FIrpic is
merely defined as cyan or greenish blue.
SUMMARY OF THE INVENTION
[0007] It is an aspect of the present invention to provide a novel
phosphorescent iridium complex serving as an emitter layer of a
light-emitting element. The resultant light-emitting element
possesses high brightness, high external quantum efficiency, high
current efficiency and excellent CIE chromaticity coordinates.
[0008] It is another aspect of the present invention to provide an
iridium complex serving as an emitter layer of a blue
phosphorescent light-emitting element.
[0009] According to the aforementioned aspects of the present
invention, a phosphorescent iridium complex is provided, which is
represented by a flowing formula I or III: ##STR2##
[0010] in which each of Z.sub.1 and Z.sub.3 represents an atomic
group for forming a nitrogen-containing heteroaryl group or a
nitrogen-containing heterocycloalkenyl group; Z.sub.1 represents an
atomic group for forming an aryl group, a heteroaryl group, a
cycloalkenyl group or a hetrocycloalkenyl groups; Y represents an
atomic group for forming a 5-membered nitrogen-containing
heterocycloalkenyl group, each of R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 represents a hydrogen atom or a substituent; R.sub.5
represents a C.sub.1-C.sub.6 alkyl group; R.sub.6 represents an
electron-withdrawing group; R.sub.7 represents an aryl group, a
C.sub.1-C.sub.20 alkyl group or a phenyl group; R.sub.8 represents
a alkyl group (e.g. a methyl group or a tert-butyl group) or a
trifluoromethyl group (--CF.sub.3); m is 1 or 2; a is 0 or any
positive integer depending upon a size of the Z.sub.1 atomic group;
b is 0 or any positive integer depending upon a size of the Z.sub.2
atomic group; c is an integer of from 0 to 2; and d is 0 or any
positive integer depending upon a size of the Z.sub.3 atomic
group.
[0011] According to another aspect of the present invention, a
light-emitting element produced by using a compound represented by
the above formula I or III is provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The foregoing aspects and many of the attendant advantages
of this invention will become more readily appreciated as the same
becomes better understood by reference to the following detailed
description, when taken in conjunction with the accompanying
drawing, wherein:
[0013] FIG. 1 is a cross-sectional diagram of an OLED device
according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0014] The present invention relates a light-emitting material,
which comprises a novel phosphorescent iridium complex. The present
invention is further clarified by following figures. It can be
comprehended that, these embodiments are intended to illustrate,
rather than to limit the present invention.
[0015] According to an embodiment of the present invention, the
phosphorescent iridium complex has a following formula I or III,
which is an octahedral structure for hexa-coordinated complex
formed from three bidentate chelating ligands: ##STR3##
[0016] In the above formula I or III, each of Z.sub.1 and Z.sub.3
represents an atomic group for forming a nitrogen-containing
heteroraryl group or a nitrogen-containing heterocycloalkenyl
group. The appropriate nitrogen-containing heteroaryl group or
nitrogen-containing heterocycloalkenyl group may be pyrroline,
pyridine, quinoline, isoquinoline, pyrazine, pyrimidine, pyrrole,
pyrazole, imidazole, indole, thiazole, isothiazole, oxazole,
isoxazole, benzothiazole, benzoxazole, or phenanthroline.
[0017] In the above formula I or III, Y represents an atomic group
for forming a 5-membered nitrogen-containing heterocycloalkenyl
group. The appropriate 5-membered nitrogen-containing
heterocycloalkenyl group may be pyrroline, pyrrole, pyrazole,
imidazole, indole, thiazole, isothiazole, oxazole, isoxazole,
1,2,4-triazole, 1,2,3-triazole or tetraazole,
[0018] In the above formula I or III, Z.sub.2 represents an atomic
group for forming an aryl group, a heteroaryl group, a cycloalkenyl
group or a heterocycloalkenyl group.
[0019] In the above formula I or III, R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 may be the same with or different from one another, each of
which represents a hydrogen atom, a halogen atom (e.g. fluorene,
chlorine, bromine, iodine), a C.sub.1-C.sub.20 alkyl group (e.g.
methyl group, ethyl group, butyl group, cyclohexyl group), a
C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a
halogen substituted C.sub.1-C.sub.20 alkyl group (e.g.
trifluoromethyl group), a C.sub.1-C.sub.20 alkoxy group, a
C.sub.1-C.sub.20 substituted amino group, a C.sub.1-C.sub.20 acyl
group, a C.sub.1-C.sub.20 ester group, a C.sub.1-C.sub.20 amide
group, an aryl group, a halogen-substituted aryl group, a
halogen-substituted aryl alkyl group, an alkyl halide-substituted
aryl group an alkyl halide-substituted aryl alkyl group, an aryl
substituted C.sub.1-C.sub.20 alkyl group (e.g. benzyl group), a
cyano group, a nitro group or other type of substitute.
[0020] The aforementioned aryl group may comprise phenyl group,
napthyl group, diphenyl group, anthryl group, pyrenyl group,
phenanthryl group, florene or other type of polyphenyl
substitute.
[0021] The aforementioned cycloalkenyl group may be cyclohexene,
cyclohexadiene, cyclopentene or cyclopentadiene.
[0022] The aforementioned heterocyclic group may be pyrane,
pyrroline, furan, benzofuran, thiophene, benzothiophene, pyridine,
quinoline, isoquinoline, pyrazine, pyrimidine, pyrrole, pyrazole,
imidazole, indole, thiazole, isothiazole, oxazole, isoxazole,
benzothiazole, benzoxazole, 1,2,4-triazole, 1,2,3-triazole,
tetrazole, phenanthroline other type of heteronuclear aromatic
ring.
[0023] IN the above formula III, R.sub.5 represents a
C.sub.1-C.sub.6 alkyl group, for example, a methyl group, an ethyl
group, a butyl group or a cyclohexyl group.
[0024] In the above formula III, R.sub.6 represents an
electron-withdrawing group, for example, a halogen atom, a nitrile
group, a nitro group, a carbonyl group, a cyano group, or a
trifluoromethyl group.
[0025] In the above formula III, R.sub.7 represents an aryl group,
a C.sub.1-C.sub.20 alkyl group or a phenyl group.
[0026] In the above formula III, R.sub.8 represents an alkyl group
(e.g. a methyl group or a tert-butyl group) or a trifluoromethyl
group (--CF.sub.3).
[0027] In the above formula I or III, m is 1 or 2; a is 0 or any
positive integer depending upon a size of the Z.sub.1 atomic group;
b is 0 or any positive integer depending upon a size of the Z.sub.2
atomic group; c is an integer of from 0 to 2; and d is 0 or any
positive integer depending upon a size of the Z.sub.3 atomic
group.
[0028] Preferably, in the above formula I or III, the R.sub.3 group
includes no electron donating group. If the complex represented by
the formula I or III includes several R.sub.3 groups, their
preferred net effect is not electron donating. The R.sub.3 group is
preferably an electron withdrawing group, for example, a halogen
atom, a nitrile group, a nitro group, a carbonyl group, a cyano
group, or a trifluoromethyl group.
[0029] Preferably, in the above formula I or III, the R.sub.4 group
includes no electron withdrawing group. If the complex represented
by the formula I or III includes several R.sub.4 groups, their
preferred net effect is not electron withdrawing. The R.sub.4 group
is preferably an electron donating group, for example, a
C.sub.1-C.sub.20 alkyl group (e.g. methyl group, ethyl group, butyl
group, cyclohexyl group), a C.sub.1-C.sub.20 alkoxy group, or a
sulfur, nitrogen, or phosphor-containing substituent [e.g. a
hydroxyl group (--OH), an amino group (--NH.sub.2) or aniline].
[0030] The phosphorescent iridium complexes produced by the present
invention are exemplary shown as follows, but are not intended to
limit the present invention therein. ##STR4## ##STR5## ##STR6##
##STR7## ##STR8## ##STR9## ##STR10## ##STR11## ##STR12##
[0031] The phosphorescent iridium complex may serve as a emitter
layer of an OLED. The OLED of the present invention may comprise a
emittter layer or a plurality of organic compound layer containing
the emitter layer, wherein the pair of the electrodes includes a
cathode and an anode. In addition, a light-emitting device may be
further provided by the present invention, wherein a emitter layer
is formed by the indium complex of the present invention and is
interposed between an electron-transporting layer and a hold
transfer layer. The light-emitting device is not limited by its
system, its driving way and its application way, but includes the
compound of the present invention. A typical example of the
light-emitting device is an OLED device. The phosphorescent iridium
complex of the present invention is particularly suitable for being
a phosphorescent light-emitting material of the OLED.
[0032] In general, the structure of the OLED is classified into a
bottom emission type and a top emission type. The bottom emission
type device employs an anode of a transparent electrode such as
ITO, and employs a cathode of an opaque or reflective metal having
low work function, such as Al or Mg:Ag alloy, resulting in light
transmission from the side of the transparent anode. However, the
top emission type device employs an anode of an opaque or
reflective metal, such as Al/Ni or Al/TiO alloys, and a cathode of
a transparent electrode having low work function in thin thickness,
such as Ca, Al, Mg:Ag alloy, ITO and so on, resulting in light
transmission from the side of the transparent cathode.
[0033] The bottom emission type device is produced as follows. A
transparent anode, an optional hole injection/modification layer, a
hole transfer layer, an emitter layer, a hole-blocking layer, an
electron-transporting layer, an optional electron injection layer
(KF) and a cathode are formed in turn on a substrate such as glass.
Before performing evaporation of an organic layer, the ITO glass
substrate is cleaned by a commercial detergent and an organic
solvent, followed by treatment of an UV-ozone cleaner.
[0034] Reference is made to FIG. 1, which depicts a cross-sectional
diagram of a bottom emission type OLED device according to one
preferred embodiment of the present invention, and the actual
dimension of each layer is not drawn to scale. The OLED device
comprises a substrate 100, an anode 102, a hole
injection/modification layer 110, a hole transfer layer 120, an
electron-blocking layer (not shown), a emitter layer 130, a
hole-blocking layer 140, an electron-transporting layer 150 and a
cathode 104. The OLED device may include the electron-blocking
layer and the hole injection/modification layer 110 or not,
depending on the requirement of the OLED device, wherein the layers
disposed between the anode 102 and the cathode 104 from an
electroluminescent medium 400. The emitter layer 130 is formed by
doping the phosphorescent materials of the present invention as
dopants doped in the host luminescent compound. The substrate 100
may be made of glass, plastic or other suitable materials. The
anode 102 may be a conductive metal oxide (e.g. ITO), and may be
made of the mixture of metal and conductive metal oxide or be made
by stacking the laminate thereof. According to the aspect of
manufacture, electrical conductivity and transparency, the metal
oxide is preferably ITO. The material suitable for the cathode 104
comprises metal, alloy or the mixture thereof. The example of the
above material may comprise Au, Ag, Pb, Al, Mg:Ag alloy and the
mixture thereof. The cathode 104 may be not only a monolayer of the
above compound or mixture, but also a laminated structure
thereof.
[0035] The top emission type device is produced as follows. A
opaquely reflective anode, an optional hole injection/modification
layer, a hole transfer layer, an emitter layer, a hole-blocking
layer; an electron-transporting layer, an optional electron
injection layer (KF) and a transparent cathode are formed in turn
on a substrate such as glass. The anode is made of conductive Al/Ni
or Al/TiO in approximately 100 nm of a total thickness. Doping the
phosphorescent indium complex of the present invention, which
serves as a dopant, in the host luminescent compound, forms the
emitter layer. Using a thermal evaporation in high vacuum, in which
Al, Ni or Al, TiO are coated in turn and respectively on the glass
substrate, forms the opaquely reflective anode. Before forming the
anode substrate, the surface of the anode is treated by oxygen
plasma or UV-O.sub.3. The cathode of the top emission OLED device
is made of low work metal, such as Ca, Mg and so on, in
approximately 20 nm of a total thickness. In order to protect the
low work metal of the cathode, an inorganic or organic material
having high refractive index serves as a protection layer to cover
the cathode, and increases the penetrated light, thereby elevating
the light emission efficiency and prolonging the device lifespan.
The material of the protection layer having high refractive index
may be an inorganic material such as ZnSe, ZnS, TiO2, ITO and so
on, or an organic material such as 2-TNATA, IDE320 and so on.
[0036] The material applied in the hole injection/modification
layer of the device of the present invention may be a compound
represented by a formula group G1 of following members, for
example, m-MTDATA
(4,4',4''-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine),
2-TNATA (4,4',4''-tris [2-naphthylphenylamino]triphenylamine), CuPc
(copper phthalocyanine), or IDE406 (manufactured by Idemitsu
Kosen). ##STR13##
[0037] The material applied in the hole transfer layer of the
device of the present invention may be a aniline compound
represented by a formula group G2 of following members, for example
NPB (4,4'-bis[1-naphthylphenylamino]biphenyl), TPD
(4,4'-bis[m-tolylphenylamino]biphenyl), NCB
(4-[N-carbazolyl]-4'-[N-phenylnaphthylamino]biphenyl), PPB
(4,4'-bis [9-phenanthrylphenylamino] biphenyl), TCTA
(4,4',4''-tri[N-carbazolyl] triphenylamin), MPMP
(bis{4-[N,N-diethylamino]-2-[methylphenyl]}-[4-methylpheny]methane,
HMTPD (4,4'-bis{N,N'-[3-tolyl]amino}-3,3'-dimethylbiphenyl) or
IDE320(manufactured by Idemitsu Kosen). ##STR14## ##STR15##
[0038] The host luminescent compound applied in the present
invention may be TCTA of the above formula group G2. Moreover, the
host luminescent compound may be a compound capable of hole
transfer and represented by a formula group G3 of following
members, for example, CBP (4,4'-N,N'-dicarbazole-biphenyl), CCP
(1,4-bis [carbazolyl]benzene), TCPB (1,3,5-tris
[4-(N-carbazolyl)phenyl]benzene), mCP (N,
N'-dicarbazolyl-3,5-benzene), TCB(1,3,5-tris [carbazolyl]benzene)
or CDBP(4,4'-bis[9-carbazolyl]-2,2'-dimethyl-biphenyl).
Furthermore, the host luminescent compound may be a compound
capable of electron transfer and represented by a formula group G4
of following members, for example, TPBI (1,3,5-tris
[N-phenylbenzimidazol-2-yl]benzene), TAZ-I
(3-pheny-4-[1'-naphthyl]-5-phenyl-1,2,4-triazole),
TAZ-2(3-[4-biphenylyl]-4-phenyl-5-tert-butylphenyl-1,2,4-triazole),
TAZ-3(3-phenyl-4-[1'-phenyl]-5-phenyl-1,2,4-triazole),
PBD(2-[4-biphenyl]-5-[4-tert-butylphenyl]-1,3,4-oxadiazole) or
TMM004(manufactured by Covion). ##STR16## ##STR17##
[0039] The material applied in the hole blocking layer of the
device of the present invention may be a compound represented by a
formula group G5 of following members, for example, BCP
(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline),
BAlq(aluminum[III]bis[2-methyl-8-quinolinato][-4phenylphenolate]),
PAlq (aluminum[III]bis[2-methyl-8-quinolinato]-[4-phenolate]), or
Salq
aluminum[III]bis[2-methyl-8-quinolinato][triphenylsilanolate]).
Moreover, the material applied in the electron transfer layer of
the device of the present invention may be a compound represented
by TPBI, TAZ-1, TAZ-2, TAZ-3, PBD of the above formula group G4, or
a formula group G5 of following members, for example, Alq3
(tris[8-hydroxyquinolinato]aluminum), DPA
(4,7-diphenyl-1,10-phenanthroline), or TYE704(manufactured by Toyo
Ink). ##STR18## ##STR19##
[0040] In the above formula groups G2 to G5, "Ph" refers to phenyl
group, "Me" refers to methyl group, "Et" refers to ethyl group, and
"Bu" refers to butyl group.
EXAMPLE 1
Synthesis of EFPMPZ
[0041] The reaction scheme of synthesizing
3-(2-ethoxy-4-fluoro-phenyl)-1-methyl-1H-pyrazole (EFPMPz) is shown
as Scheme 1, 1.90 g (36 mmole) of sodium methoxide (NaOCH.sub.3)
was added into a 250-ml two-neck flask and purged with nitrogen gas
in several times, followed by adding 30 ml of tetrahydrofuran (THF)
with stirring well. And then, 4.68 g (30 mmole) of
2,4-difluoroacetophonene and 3.30 g (45 mmole) of ethyl formate
were added thereto in turn in cold bath. After completion the
reaction, the reaction mixture was continuously stirred for 2 hours
so as to ensure the reaction completion. Following that, water was
added into the reaction mixture to remove nonreactive NaOCH.sub.3,
and 1.8 g (60 mmole) of hydrazine was added thereto for 15 minutes
of reaction. The reactor mixture was extracted several times with
acetyl acetate, concentrated and dried and then an intermediated
product was obtained in a yield of 70%. After adding 0.9 g (5
mmole) of the intermediated product into 20 ml of acetone, 5 ml
(4%) of sodium hydroxide solution and 0.72 ml (5 mmole) of methyl
iodide were added thereto. After stirring for 30 minutes, the
reaction mixture was extracted several times with acetyl acetate,
concentrated and dried. The final product was separated by column
chromatography using n-hexane/ethyl acetate in a ratio of 5/1 (v/v)
as the eluent. The EFPMPZ was isolated in a yield of 80%. .sup.1H
NMR (400 MHz, CDCl.sub.3): .delta.7.90 (J=1.2 Hz, J=7.2 Hz, 1 H),
7.34 (d,J=2.4 Hz, 1H), 6.76 (d, J=2 Hz, 1 H) 6.70-6.62 (m, 2 H),
4.05 (q, J=6.8 Hz, 2 H), 3.91 (s, 3 H), 1.45 (t, 3 H).
##STR20##
EXAMPLE 2
Synthesis of TFPZPY
[0042] The reaction scheme of synthesizing
2-(5-trifluoromethyl-2H-pyrazol-3-yl)-pyridine (TFPZPY) is shown as
Scheme 2. 1.90 g (36 mmole) of sodium methoxide (NaOCH.sub.3) was
added into a 250-ml two-neck flask and purged with nitrogen gas in
several times, followed by adding 30 ml of THF with stirring well.
And then, 3.63 g (30 mmole) of 2-acetylpyridine and 6.39 g (45
mmole) of ethyltrifluoroacetate were added thereto in turn in cold
bath. After completion the reaction, the reaction mixture was
continuously stirred for 2 hours so as to ensure the reaction
completion. Following that, water was added into the reaction
mixture to remove nonreactive NaOCH.sub.3, and 1.8 g (60 mmole) of
hydrazine was added thereto for 15 minutes of reaction. The
reaction mixture was extracted several times with acetyl, acetate,
concentrated and dried, and then an intermediated product was
obtained in a yield of 64%. .sup.1H NMR (400 MHz, CDCl.sub.3):
.delta. 12.41 (br, 1 H), 8.66 (d, J=4 Hz, 1 H), 7.82 (dd, J=6 Hz,
1.6 Hz, 1 H),7.74 (m, 1 H), 7.33 (m, 1 H), 6.95 (s, 1 H).
##STR21##
EXAMPLE 3
Synthesis of TFPZMI
[0043] The reaction scheme of synthesizing
5-(1-methyl-1H-imidazol-2yl)-3-trifluorometh-yl-1H-pyrazole
(TFPZMI) is shown as Scheme 3. The process of synthesizing the
TFPZMI was similar to the method disclosed in EXAMPLE 2, resulting
in a yield of 72%. .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.30
(s, 1 H), 7.29 (s, 1 H), 7.02 (s, 1 H), 3.88 (s, 3 H).
##STR22##
EXAMPLE 4
Synthesis of PZPY
[0044] The reaction scheme of synthesizing PZPY is shown as Scheme
4. The process of synthesizing the PZPY was similar to the method
disclosed in EXAMPLE 2, resulting in a yield of 65%. .sup.1H NMR
(400 MHz, CDCl.sub.3): .delta. 8.61 (d, J=5.2 Hz, 1 H), 7.72 (dd,
J=1.2 Hz, J=6 Hz, 2 H), 7.64 (d, J=2 Hz, 1 H), 7.22 (m, 1 H), 6.78
(d, J=1.6 Hz, 1H). ##STR23##
EXAMPLE 5
Synthesis of PZP
[0045] The reaction scheme of synthesizing PZP is shown as Scheme
5. The process of synthesizing the PZP was similar to the method
disclosed in EXAMPLE 2, resulting in a yield of 60%. .sup.1H NMR
(400 MHz, CDCl.sub.3): .delta. 9.11 (s, 1 H), 8.55 (d, J=2 Hz, 1
H), 8.45 (d, J=2.5 Hz, 1 H), 7.68 (d, J=2 Hz, 1H), 6.22 (d, J=2.5
Hz, 1H). ##STR24##
EXAMPLE 6
Synthesis of PZTH
[0046] The reaction scheme of synthesizing PZTH is shown as Scheme
6. The process of synthesizing the PZTH was similar to the method
disclosed in EXAMPLE 2, resulting in a yield of 60%. .sup.1H NMR
(400 MHz, CDCl.sub.3): .delta. 7.87 (d, J=3.2 Hz), .delta. 7.68 (d,
J=2 Hz), .delta. 7.32 (d, J=3.6 Hz), .delta. 6.86 (d, J=2 Hz).
##STR25##
EXAMPLE 7
Synthesis of DIPY
[0047] The reaction scheme of synthesizing DIPY is shown as Scheme
7. The process of synthesizing the DIPY was similar to the method
disclosed in EXAMPLE 2, resulting in a yield of 50%. .sup.1H NMR
(400 MHz, CDCl.sub.3): .delta. 8.435 (d, J=4.8 Hz, 1H), .delta.
8.063 (d, J=8 Hz, 1H), .delta.7.698 (td, J=7.8 Hz, J=2 Hz, 1H),
.delta. 7.152 (m, 1H), .delta. 2.216 (s, 6H). ##STR26##
EXAMPLE 8
Synthesis of EFPTBPZ
[0048] The reaction scheme of synthesizing
5-tert-butyl-3-(2,4-difluoro-phenyl)-1-methyl-1H-pyrazole (EFPTBPZ)
is shown as Scheme 8. 1.90 g (36 mmole) of NaOCH.sub.3 was added
into a 250-ml two-neck flask and purged with nitrogen gas in
several times, followed by adding 30 ml of THF with stirring well.
And then, 3.0 g (30 mmole) of 3,3-dimethyl-butan-2-one and 8.37 g
(45 mmole) of 2,4-difluoro-benzoic acid ethyl ester were added
thereto in turn in cold bath. After completion the reaction, the
reaction mixture was continuously stirred for 2 hours so as to
ensure the reaction completion. Following that, water was added
into the reaction mixture to remove nonreactive NaOCH.sub.3, and
1.8 g (60 mmole) of hydrazine was added thereto for 15 minutes of
reaction. The reaction mixture was extracted several times with
acetyl acetate, concentrated and dried, and then an intermediated
product was obtained in a yield of 50%. After adding 1.12 g (5
mmole) of the intermediated product into 20 ml of acetone, 5 ml
(4%) of sodium hydroxide solution and 0.721 ml (5 mmole) of methyl
iodide were added thereto. After stirring for 30 minutes, the
reaction mixture was extracted several times with acetyl acetate,
concentrated and dried. The final product was separated by column
chromatography using n-hexane/ethyl acetate in a ratio of 5/1 (v/v)
as the eluent. The EFPTBPZ was isolated in a yield of 50%. .sup.1H
NMR (400 MHz, CDCl.sub.3): .delta. 7.88 (dd, J=6.8 Hz, J=1.6 Hz, 1
H), 6.68-6.61 (m, 2 H), 6.58 (s, 1 H), 4.06 (q, 2 H), 3.99 (s, 3
H), 1.48 (t, 3 H), 1.39 (t, 9 H). ##STR27##
EXAMPLE 9
Synthesis of TFPYTZ
[0049] The reaction scheme of synthesizing
2-(5-(trifluoromethyl)-4H-1,2,4-triazol-3-yl)pyridine (TFPYTZ) is
shown as Scheme 8 1.04 g (10.0 mmole) of 2-cyanopyridine was added
into a 25-ml round-bottomed bottle and added with little ethanol
thereto for dissolving 2-cyanopyridine. After adding 0.96 g (30
mmole) of hydrazine thereto, the reaction was performed for 1 hour
at room temperature, so as to obtain while solid. The white solid
was rinsed with ethanol to remove nonreactive hydrazine. The rinsed
white solid was added into a 50-ml round-bottomed bottle, added
with 1.42 g (10.0 mmole), and heated under reflux of 5.0 ml of
ethanol for 1 hour. After completion of the reaction, the reaction
mixture was extracted with ethanol, and the organic layer was
concentrated to obtain while solid. Afterwards, the final product
TFPYTZ was separated by silica column chromatography in a yield of
50%. .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 8.78 (m, 1 H), 8.31
(d, 1 H, J=8.0 Hz), 7.97-7.94 (m, 1 H), 7.53-7.50 (m, 1 H). HRMS
(EI) m/z calcd for C.sub.8H.sub.5F.sub.3N.sub.4 214.0466; found
214.0469.
EXAMPLE 10
Synthesis of Iridium Complex II-7 (EFPMPZ).sub.2Ir(TFPZPY)
[0050] The reaction scheme of synthesizing (EFPMPZ).sub.2Ir(TFPZPY)
is shown as Scheme 9. (1) 2.2 mmole of the compound EFPMPZ of
EXAMPLE 1 was added into a reaction bottle and added with 1 mmole
of IrCl.sub.3.nH.sub.2O thereto, and they were carried put a
reaction under reflux using the mixture of 2-ethoxyethanol and
water as solvent for 12 hours. The reaction solution was filtrated
to collect the solid, and the solid was rinsed several times with
n-hexane and dried, thereby obtaining cyclometalated
Ir(III)-.mu.-chloro-bridged dipolymer. (2) 0.5 mmole of the above
dipolymer was added into a reaction bottle, and 2.2 mmole of
potassium carbonate (K.sub.2CO.sub.3) and the compound TFPZPY of
EXAMPLE 2 were added thereto. After mixing them well, they were
reacted under stable reflux of 5 ml of 2-ethoxyethanol for 12
hours. The reaction solution was filtrated to collect the solid,
following by inactivating the solid with triethylamine. Afterwards,
the iridium complex II-7 was separated by silica column
chromatography in a yield of 60%. Before manufacturing the device,
the indium complex II-7 is necessary to be sublimed at temperature
ranging from 230.degree. C. to 280.degree. C. under pressure
4-8*10.sup.-3 Pa for further purification. .sup.1H NMR (400 MHz,
CDCl.sub.3): .delta. 8.08-8.06 (m, 1 H), 7.96-7.92 (m, 2 H), 7.62
(dd, J=2.8 Hz), J=4.8 Hz, 2 H), 7.24-7.19 (m, 2 H),6.73 (dd, J=1.6
Hz), J=2.8 Hz, 2 H), 6.34 (dd, J=9.6 Hz, J=2.4 Hz, 1 H), 6.23 (dd,
J=9.6 Hz, J=2.0 Hz, 1 H), 5.50 (dd, J=6.8 Hz, J=2.0 Hz, 1 H), 5.34
(dd, J=7.2 Hz, J=2.4 Hz, 1 H), 4.14 (m, 4 H), 3.2 (s, 3H), 3.14 (s,
3 H), 1.51-1.31 (m, 6 H). ##STR28##
EXAMPLE 11
Synthesis of Iridium Complex II-8 (EFPMPZ).sub.2Ir(TFPZMI)
[0051] The process of synthesizing (EFPMPZ).sub.2Ir(TFPZMI) was
similar to the method disclosed in EXAMPLE 8, but the ligand was
TFPZMI of EXAMPLE 2 instead of TFPZPY, resulting in a yield of 60%.
.sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 7.6 (dd, J=7.2 Hz, J=2.8
Hz, 2 H), 7.18 (d, J=1.6 Hz, 1 H), 6.95 (s, 1 H), 6.71-6.70 (m, 2
H), 6.37 (d, J=1.6 Hz, 1 H), 6.27 (dd, J=9.2 Hz, J=2.4 Hz, 1 H),
6.18 (dd, J=9.6 Hz, J=20 Hz, 1 H), 5.48 (dd, J=7.2 Hz, J=2.0 Hz, 1
H), 5.41 (dd, J=7.6 Hz, J=2.0 Hz, 2 H), 4.10 (m, 7 H), 3.28 (s, 3
H), 3.12 (s, 3 H), 1.48-1.44 (m, 6 H).
EXAMPLE 12
Synthesis of Iridium Complex II-1 (DFPPY).sub.2Ir(TFPZPY)
[0052] 0.2 mmole of [Ir(DFPPY).sub.2Cl].sub.2 was added into a
reaction bottle, and 0.44 mmole of K.sub.2CO.sub.3 and the compound
TFPZPY of EXAMPLE 2 were added thereto. After mixing them well,
they were reacted under stable reflux of 5 ml of 2-ethoxyethanol
for 12 hours. The reaction solution was filtrated to collect the
solid, following by inactivating the solid with triethylamine.
Afterwards the iridium complex II-1 was separated by silica column
chromatography in a yield of 50%. .sup.1H NMR (400 MHz,
CDCl.sub.3): .delta. 8.25 (d, J=8.4 Hz, 1H), .delta. 8.19 (d, J=8.4
Hz, 1H), .delta. 7.77-7.60 (m, 6H), .delta. 7.47 (d, J=6 Hz, 1 H),
.delta. 7.02-6.92 (m, 3H), .delta. 6.85 (t, J=6.4 Hz, 1H), .delta.
6.49-6.37 (m, 2H), .delta. 5.74 (dd, J=2.8 Hz, J=5.6 Hz, 1H),
.delta. 5.67 (dd, J=2 Hz, J=6.8 Hz 1 Hz).
EXAMPLE 13
Synthesis of Iridium Complex II-2 (DFPPY).sub.2Ir(PZPY)
[0053] The process of synthesizing (DFPPY).sub.2Ir(PZPY) was
similar to the method disclosed in EXAMPLE 12, but the ligand was
PZPY of EXAMPLE 4 instead of TFPZPY, resulting in a yield of 60%.
.sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 9.24 (d, J=8.8 Hz, 1H),
.delta. 8.18 (d, J=8.4 Hz, 1 Hz), .delta. 7.23-7.61 (m, 6H),
.delta. 7.54 (t, J=6 Hz, 2H), .delta. 6.95-6.84 (m, 2H), .delta.
6.84-6.82 (m, 1H), .delta. 6.70 (d, J=2 Hz, 1H), .delta. 6.45-6.38
(m, 2H), .delta. 5.78 (dd, J=2.4 Hz, J=6 Hz, 1H), .delta. 5.71 (dd,
J=2.4 Hz, J=6.4 Hz, 1H).
EXAMPLE 14
Synthesis of Iridium Complex II-3 (DFPPY).sub.2Ir(PZP)
[0054] The process of synthesizing (DFPPY).sub.2Ir(PZP) was similar
to the method disclosed in EXAMPLE 12, but the ligand was PZP of
EXAMPLE 5 instead of TFPZPY, resulting in a yield of 62%. .sup.1H
NMR (400 MHz, CDCl.sub.3): .delta. 9.04 (s, 1H), .delta. 8.26 (d,
J=8.8 Hz, 1H), .delta. 8.21-8.18 (m, 2H), .delta. 7.75 (d, J=2 Hz,
1H), .delta. 7.68 (dd, J=8 Hz, J=7.6 Hz, 2H), .delta. 7.56-7.58 (m,
1H), .delta. 7.5 (dd, J=5.2 Hz, J=4.4 Hz, 2H), .delta. 6.94 (t,
J=6.4 Hz, 1H), .delta. 6.88 (t, J=7.2 Hz, 1H),.delta. 6.82 (d, J=2
Hz, 1H), .delta. 6.51-6.39 (m, 2H), .delta. 5.78 (dd, J=2.4 Hz, J=6
Hz, 1H), .delta. 5.68 (dd, J=2.4 Hz, J=6.4 Hz, 1H).
EXAMPLE 15
Synthesis of Iridium Complex II-4 (DFPPY).sub.2Ir(PZTH)
[0055] The process of synthesizing (DFPPY).sub.2Ir(PZTH) was
similar to the method disclosed in EXAMPLE 12, but the ligand was
PZTH of EXAMPLE 6 instead of TFPZPY, resulting in a yield of 65%.
.sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 8.24 (d, J=8.4 Hz, 1H),
.delta. 8.17 (d, J=9.2 Hz, 1H), .delta. 7.69-7.6 (m, 3H), .delta.
7.57 (d, J=11.2 Hz, 1H), .delta. 7.54 (d, J=6 Hz), .delta.
7.16-7.15 (m, 1H), .delta. 6.95-6.88 (m, 3H), .delta. 6.70-6.69 M,
1H), .delta. 6.46-6.36 (m, 2H), .delta. 5.80 (d, J=8.4 Hz, 1H),
.delta. 5.73 (d, J=10.4 Hz, 1H).
EXAMPLE 16
Synthesis of Iridium Complex II-5 (DFPPY).sub.2Ir(DIPY)
[0056] The process of synthesizing (DFPPY).sub.2Ir(DIPY) was
similar to the method disclosed in EXAMPLE 12, but the ligand was
DIPY of EXAMPLE 7 instead of TFPZPY, resulting in a yield of 63%.
.sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 8.25 (t, J=9.6 Hz, 2H),
.delta. 7.75-7.71 (m, 4H), .delta. 7.52 (m, 2H), .delta. 7.02-6.93
(m, 3H), .delta. 6.50-6.40 (m, 2H), .delta. 5.76-5.66 (m, 2H),
.delta. 2.24 (s, 3H), .delta. 1.27 (s, 3H).
EXAMPLE 17
Synthesis of Iridium Complex II-6 (DFPPY).sub.2Ir(TFPZMI)
[0057] The process of synthesizing (DFPPY).sub.2Ir (TFPZMI) was
similar to the method disclosed in EXAMPLE 12, but the ligand was
TFPZMI of EXAMPLE 7 instead of TFPZPY, resulting in a yield of 60%.
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.23 (d, J=6.4 Hz, 1H),
.delta. 8.17 (d, J=9.2 Hz, 1H), .delta. 7.66-7.61 (m, 4H), .delta.
6.98-6.81 (m, 2H), .delta. 6.8 (d, J=4.4 Hz, 1H), .delta. 6.72 (s,
1H), .delta. 6.44-6.35 (m, 2H), .delta. 6.32 (d, J=1.6 Hz, 1H),
.delta. 5.76-5.72 (m, 2H), .delta. 3.90 (s, 3H).
EXAMPLE 18
Synthesis of Iridium Complex II-9 (EFPTBPZ).sub.2Ir(TFTZPY)
[0058] The process of synthesizing (EFPTBPZ).sub.2Ir(TFTZPY) was
similar to the method disclosed in EXAMPLE 10, but the ligands were
EFPTBPZ and TFTZPY instead of EFPMPZ and TFPZPY, resulting in a
yield of 60%. .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 8.2 (d,
J=8 Hz, 1H), .delta. 8.10-8.06 (m, 1H), .delta. 7.98 (d, J=5.2 Hz,
4H, .delta. 7.47-7.43 (m, 1H), .delta. 6.63 (s, 1H), .delta. 6.62
(s, 1H), .delta. 6.36 (dd, J=2 Hz, J=9.6 Hz, 1H), .delta. 6.26 (dd,
J=2.4 Hz, J=9.6 Hz, 1H), .delta. 5.42 (dd, J=2.4 Hz, J=6.8 Hz, 1H),
.delta. 5.32 (dd, J=2 Hz, J=7.6, 1H), .delta. 4.15-4.05 (m, 4H),
.delta. 3.218 (s, 3H), .delta. 3.215 (s, 3H), .delta. 2.08-2.03 (m,
3H), .delta. 1.50-1.46 (m, 3H), .delta. 1.35 (s, 3H), .delta. 1.34
(s, 3H).
EXAMPLE 19
Synthesis of Iridium Complex II-10 (EFPTBPZ).sub.2Ir(TFPZPY)
[0059] The process of synthesizing (EFPTBPZ).sub.2Ir(TFPZPY) was
similar to the method disclosed in EXAMPLE 12, resulting in a yield
of 65%. .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 8.04-8.02 (m,
1H), .delta. 7.94-7.88 (m, 2H), .delta. 7.22-7.19 (m, 1H), .delta.
7.16 (s, 1H), .delta. 6.62 (d, J=1.2 Hz, 2H), .delta. 6.32 (dd, J=2
Hz, J=9.6 Hz, 1H), .delta. 6.21 (dd, J=2.4 Hz, J=9.6 Hz, 1H),
.delta. 5.40 (dd, J=2.4 Hz, J=6.8 Hz, 1H), .delta. 5.33 (dd, J=2
Hz, J=7.6 Hz, 1H), .delta. 4.15-4.01 (m, 4H), .delta. 3.24 (s, 3H),
.delta. 3.22 (s, 3H), .delta. 2.07-2.03 (m, 3H), .delta. 1.50-1.46
(m, 3H, .delta. 1.35 (s, 9H), .delta. 1.31 (s, 9H).
Manufacture of OLED Device
[0060] During manufacturing the OLED device, the chamber used for
evaporating organic substances, phosphorescent iridium complex and
metal was preferable under pressure less than 5*10.sup.-6 tort,
wherein the organic substances was evaporated in a speed of 1.5-2.5
.ANG./sec, the phosphorescent iridium complex was evaporated in a
speed of 0.05-0.2 .ANG./sec, the hole transfer layer had a
thickness ranging from 10 nm to 50 nm, the hole blocking layer had
a thickness ranging from 10 nm to 20 nm, and the electron transfer
layer had a thickness ranging from 10 nm to 50 nm. If the cathode
was a material of Mg:Ag alloy, Mg was plated as a film in a speed
of 5 .ANG./sec, Ag was plated as a film in a speed of 0.5
.ANG./sec, and Mg and Ag were co-evaporated in a ratio of 10:1.
Results of All Devices Were Shown in TAB 1, Wherein the Structure
of Each Device Was Shown as Follows:
[0061] EXAMPLE 16: ITO/NPB(40 nm)/II-1;CBP(7%, 30 nm)/BCP(10
nm)/Alq.sub.3(40 mm)/Mg:Ag
[0062] EXAMPLE 17: ITO/TCTA(40 nm)/II-1:CBP(7%, 30 nm)/BCP(10
nm)/Alq.sub.3(40 nm)/Mg:Ag TABLE-US-00001 TABLE 1 EXAMPLE 16
EXAMPLE 17 Threshold Voltage (V) 4.5 4.5 Maximum External Quantum
Efficiency 0.95 1.16 (%) Maximum Brightness (cd/m.sup.2) 5569 5236
Maxinmm Efficiency (cd/A) 1.97 2.41 CIE chromaticity coordinates (8
V) (0.16, 0.29) (0.15, 0.30) (x, y) Maximum Emission Wavelength
(mm) 466 464
[0063] According to the result of TAB. 1, the phosphorescent
iridium complex prepared by the present invention can serve as
phosphorescent material for applying in manufacture of OLED device.
The resultant device can emit blue phosphorescence, and the device
has excellent CIE chromaticity coordinates.
[0064] As is understood by a person skilled in the art, the
foregoing preferred embodiments of the present invention are
illustrated of the present invention rather than limiting of the
present invention. It is intended to cover various modifications
and similar arrangements included within the spirit and scope of
the appended claims. Therefore, the scope of which should be
accorded to the broadest interpretation so as to encompass all such
modifications and similar structure.
* * * * *