Shen, Kuo-hui (Kaohsiung County, TW)
Yeh, Shu-tang (Taichung County, TW)
Huang, Heh-lung (Taipei County, TW)
Shen, I-ho (Yunlin County, TW)
Chu, Miao-tsai (Taipei County, TW)
Shieh, Tien-shou (Taipei, TW)

Plaque It!

11/212796

11/04/2008

08/29/2005

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Industrial Technology Research Institute (Hsinchu, TW)

546/4

428/917, 257/E51.044, 313/504, 428/690, 257/40, 546/10, 549/3, 313/506

H01L51/54; C09K11/06

428/917, 546/4, 257/E51.044, 313/504, 428/690, 257/40, 546/10, 313/506, 549/3

20020024293	Light-emitting element and iridium complex	February, 2002	Igarashi et al.
20020034656	Organometallic complexes as phosphorescent emitters in organic LEDs	March, 2002	Thompson et al.
20020045061	Organic electroluminescence element	April, 2002	Hosokawa
20030017361	Organometallic complexes as phosphorescent emitters in organic LEDs	January, 2003	Thompson et al.
20030068526	Luminescence device and display apparatus	April, 2003	Kamatani et al.	428/690
20030072964	Phosphorescent compounds and devices comprising the same	April, 2003	Kwong et al.	428/690
20030092935	Metal complex carrying a 2-phospa-tricyclo[3.3.1.1(3.7)}}decyl radical as a ligand in hydroformylation	May, 2003	Ahlers
20030102800	Phosphorescent material	June, 2003	Kuo et al.
20040053071	Light emitting element and iridium complex	March, 2004	Igarashi et al.
20040086743	Organometallic compounds for use in electroluminescent devices	May, 2004	Brown et al.
20040102632	Organic light emitting materials with anionic ligand	May, 2004	Thompson et al.
20040110031	Organic electroluminescent element and display	June, 2004	Fukuda et al.

EP1434286	June, 2004			Phenyl pyridine-iridium metal complex compounds for organic electroluminescent device, process for preparing the compounds, and organic electroluminescent device using the compounds
JP2002226495	August, 2002			METAL COORDINATION COMPOUND, LIGHT EMITTING ELEMENT AND DISPLAY DEVICE
JP2002338588	November, 2002			METAL COORDINATED COMPOUND, ELECTROLUMINESCENT ELEMENT AND DISPLAY DEVICE
JP2003109758	April, 2003			ORGANIC ELECTROLUMINESCENT ELEMENT
JP2003113246	April, 2003			POLYMERIZABLE COMPOUND AND METHOD FOR PRODUCING THE SAME
JP2003119179	April, 2003			POLYMERIZABLE IRIDIUM COMPLEX, ITS POLYMER AND METHOD FOR PRODUCING THE SAME
JP2003123982	April, 2003			LIGHT EMITTING ELEMENT AND NOVEL IRIDIUM COMPLEX
JP2003147021	May, 2003			POLYMERIZABLE COMPOUND AND METHOD FOR PRODUCING THE SAME
JP2003171391	June, 2003			POLYMERIZABLE COMPOUND AND METHOD FOR PRODUCING THE SAME
JP2003206320	July, 2003			POLYMERIZABLE COMPOUND AND ITS MANUFACTURING METHOD
JP2003253128	September, 2003			LUMINESCENT COMPOSITION
JP2003253129	September, 2003			LUMINESCENT COMPOSITION
JP2003253145	September, 2003			LIGHT-EMITTING COMPOSITION
JP2004111379	April, 2004			LUMINESCENT ELEMENT AND IRIDIUM COMPLEX
WO-03040250	May, 2003
WO-2004026886	April, 2004
WO-2004028217	April, 2004
WO-2004037836	May, 2004
WO-2004048395	June, 2004
WO-2004055130	July, 2004

Baldo et al., Nature, vol. 395, Sep. 10, 1998, pp. 151-154.
Lamansky et al., J. Am. Chem. Soc. 2001, vol. 123, No. 18, pp. 4304-4312.
Tamayo et al., J. Am. Chem. Soc. 2003, vol. 125, No. 24, pp. 7377-7387.

Shosho, Callie E.

Wilson, Michael

Birch, Stewart, Kolasch & Birch, LLP

What is claimed is:

1. An organometallic complex selected from the group consisting of wherein A3 is an acetylacetone group or a picolinic acid group.

2. The organometallic complex as claimed in claim 1, wherein the organometallic complex is a luminescent material.

3. The organometallic complex as claimed in claim 1, wherein the organometallic complex is an orange phosphorescent dopant.

4. The organometallic complex as claimed in claim 1, wherein A3 is the acetylacetone group.

5. The organometallic complex as claimed in claim 1, wherein A3 is the picolinic acid group.

6. An organic electroluminescent device, comprising: a pair of electrodes; and an organic electroluminescent layer installed between the electrodes, comprising an organometallic complex as claimed in claim 1.

7. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent layer comprises an emitting layer comprising the organometallic complex.

8. The organic electroluminescent device as claimed in claim 7, wherein the organometallic complex is an orange luminescent dopant.

9. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent layer comprises a hole transport layer, a hole blocking layer, an electron transport layer, or a buffer layer.

10. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent device has a drive voltage of about 4.66-5.55V.

11. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent device has a brightness of about 220-400 cd/m².

12. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent device has a brightness of about 20-45 cd/A.

13. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent device has a luminescent efficiency of about 12.4-26.1 lm/W.

14. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent device has a CIEx value of about 0.47-0.50 and a CIEy value of about 0.49-0.51.

15. The organic electroluminescent device as claimed in claim 6, wherein the organic electroluminescent device has a luminescent wavelength of about 560-580 nm.

BACKGROUND

The present invention relates to an organometallic complex, and more specifically to an organometallic complex used in an organic electroluminescent device.

Organic electroluminescent diode research began with Pope in 1962, providing single crystal luminescent naphthalene under application of an external voltage. A double-layer organic thin film device was then provided by Tan (Kodak Corporation) in 1982, significantly increasing brightness and luminescent efficiency and leading to follow-up research. Applications regarding organometallic complexes used in organic electroluminescent devices began in 1980, such as Pt(II), Ru(II), Os(II), Eu(III), and Ir(III) complexes, of which Ir(III) complexes were the most popular.

Initial doped red phosphorescent complexes were provided by M. E. Thompson and S. R. Forest as disclosed in Nature, 395, 1988, pages 151˜154, providing Pt as a metal center of a complex with a luminescent wavelength of 650 nm, quantum efficiency of 1.3%, and luminescent intensity of 0.15 lm/W under a current density of 100 cd/A. More types of Ir complexes were provided by M. E. Thompson in 2001 (J. Am. Chem. Soc. 2001, 123, 4304˜4312), with luminescent wavelengths across red, green, and blue light regions. In 2003, M. E. Thompson further provided a comparison of luminescent efficiency and lifetime between facial and meridional isomers of a Ir complex as disclosed in J. Am. Chem. Soc. 2003, 125, 7377˜7387. Other related technology is disclosed in U.S. Pre-Grant Pat. No. 2002024293, 2002034656, 2002045061, 2003017361, 2003092935, 2003102800, 2004053071, 2004102632, 2004086743, and 2004110031, in J. P. Pre-Grant Pat. No. 2002226495, 2002338588, 2003109758, 2003113246, 2003119179, 2003123982, 2003147021, 2003171391, 2003206320, 2003253128, 2003253129, 2003253145, and 2004111379, and in G. P Pre-Grant Pat. No. 2004026886, 2004028217, 2004037836, 2004048395, and 2004055130.

Various Ir complexes have been provided, such as Ir complexes coordinating with acetyl acetone as disclosed in E.P. Pat. No. 1434286 and a blue phosphorescent Ir complex with an emission wavelength exceeding 500 nm and quantum efficiency exceeding 5% as disclosed in U.S. Pat. No. 2002024293. Orange phosphorescent Ir complexes, however, have yet to be effectively provided, regarding compounds such as Bt₂Ir(acac) with an emission wavelength of about 560 nm provided by Thompson as disclosed in J. Am. Chem. Soc. 2001, 123, 4304˜4312 and an orange phosphorescent Ir complex with emission wavelength of about 570 nm as disclosed in G.P. Pat. No. 2003040250.

SUMMARY

The invention provides an organometallic complex having formula (I):

wherein A1 is a substituted or non-substituted aromatic heterocyclic group, A2 is a substituted or non-substituted aryl group, A3 is an acetylacetone group or picolinic acid group, and X is selected from the group consisting of fluorine atom, trifluoromethyl, alkoxy, thioalkyl, and amino.

The invention also provides an organic electroluminescent device comprising a pair of electrodes and an organic electroluminescent layer installed therebetween, utilizing the disclosed organometallic complex.

A detailed description is given in the following embodiments with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:

FIG. 1 is a cross section of an organic electroluminescent device of the invention.

DETAILED DESCRIPTION

The invention provides an organometallic complex having formula (I):

In formula (I), A1 is a substituted or non-substituted aromatic heterocyclic group such as thiophenyl, benzothiophenyl, furanyl, or pyridinyl, preferably thiophenyl or benzothiophenyl. A2 is a substituted or non-substituted aryl group such as benzene, benzothiophene, or naphthalene. A3 is an acetylacetone group or picolinic acid group. X may comprise fluorine atom, trifluoromethyl, alkoxy, thioalkyl, or amino groups.

The specific organometallic complexes provided by the invention comprise

wherein A3 is an acetylacetone group or picolinic acid group.

The compound of formula (I) is prepared as follows. First, a coordination compound such as phenyl thienopyridine, naphthalenyl thienopyridine, or phenyl benzothienopyridine is prepared by general synthesis. Next, the coordination compound, a metal halide, solvent, and deionized water are added to a flask with thermal reflux for about 45˜50 hours. The metal halide may be IrCl₃*H₂O, and the solvent may be 2-ethoxy ethanol. After cooling to room temperature, and filtration, collected solids are washed with a small quantity of solvent such as water or methanol. An organometallic dimer is prepared after drying. Next, the organometallic dimmer and a salt, such as Na₂CO₃, a bidentate compound, and solvent, such as 2-ethoxy ethanol, are mixed in a flask and stirred with heating for about 20˜25 hours. The bidentate compound comprises acetyl acetone or picolinic acid. After cooling to room temperature, and filtration, collected solids are washed with a small quantity of solvent such as water or methanol, an organometallic complex (formula (I)) containing two coordination groups and a bidentate group is prepared.

Due to strong spin-orbital coupling, electrons of a d⁶ Ir complex may span multiple energy levels to form a triplet excited state by Metal to Ligand Charge Transfer (MLCT) and mixed π-π* coordination orbits, resulting in increased phosphorescent luminescent efficiency with low drive voltage requirement. Emission wavelength of the phosphorescent complex appears in an orange or yellow light region of about 530˜600 nm. Electroluminescent devices comprising the Ir complex can more easily meet the NTSC standard.

The invention also provides an organic electroluminescent device comprising a pair of electrodes and an organic electroluminescent layer installed therebetween, utilizing the disclosed organometallic complex as formula (I).

The organic electroluminescent layer comprises an emitting layer comprising the disclosed organometallic complex used as a red luminescent dopant. Hosts of the emitting layer comprise CBP, TCTA, CzTT, TPBI, TAZ, BAlq, MCP, UGHI, UGH2, or UGH3. The organic electroluminescent layer further comprises a hole transport layer, a hole blocking layer, an electron transport layer, or a buffer layer. The hole transport layer comprises HTM2, TPD, NPB, PPD, TBPB, spiro-TAD, spiro-NPB, TPTE2, TPTE1, NTPA, or DNPD. The hole blocking layer comprises BPhen BCP, BAlq, CF-X, TAZ, or CF-Y. The electron transport layer comprises t-Bu-PBD, Alq₃, BeBq, TAZ, Almq3, BAlq, or TPBI. The buffer layer may comprise LiF or Li₂O. The foregoing abbreviations represent the following structures.

A method of fabricating an organic electroluminescent device is further provided. An anode is provided on a substrate and a hole transport layer is evaporated on the anode to a thickness of about 400˜600 Å. A Ir complex (dopant) and host are then co-evaporated on the hole transport layer to form an emitting layer at a thickness of about 150˜250 Å, with dopant/host volume ratio about 5˜10%. Next, a hole blocking layer is evaporated on the emitting layer to a thickness of about 100˜200 Å. An electron transport layer is evaporated on the hole blocking layer to a thickness of about 100˜200 Å. A buffer layer is evaporated on the electron transport layer to a thickness of about 3˜10 Å. Finally, a cathode is evaporated on the buffer layer to a thickness of about 1000˜1400 Å.

The organic electroluminescent device has a drive voltage of about 4.66˜5.55V, brightness of about 220˜400 cd/m² or 20˜45 cd/A, luminescent efficiency of about 12.4˜26.1 lm/W, a CIEx value of about 0.47˜0.50, a CIEy value of about 0.49˜0.51, and a luminescent wavelength of about 560˜580 nm.

EXAMPLES

Example 1

Preparation of Compound 1

• (1) 1 g phenyl-thiophen-3-yl-methanone (compound 1a), 1.03 g 2,2-dimethoxy-ethylamine, and 15 ml toluene were added to a 50 ml round-bottomed flask and stirred at 110° C. for 12 hours. After returning to room temperature, 2,2-dimethoxy-ethylamine was removed by low-pressure distillation. Remaining solution was then purified by a column (ethyl acetate:n-hexane=1:4) to finally form 1.12 g yellow compound 1b with yield of 83%. The reaction according to step (1) was

• (2) 2.75 g compound 1b and 10 g PPA were added to a 50 ml round-bottomed flask and stirred at 120° C. for 6 hours. After returning to room temperature, 200 ml water was added. A proper quantity of KOH was then added to neutralize the solution to a basic condition. Organo-layer was extracted by adding 120 ml ethyl acetate. Remaining water in the organo-layer was then removed by adding 2 g MgSO₄. After the organo-layer condensed, 1.79 g white compound 1c solids were prepared with yield of 85%. The reaction according to step (2) was

• (3) 0.725 g compound 1c, 0.57 g IrCl₃*H₂O, 15 ml 2-ethoxy ethanol, and 5 ml water were added to a flask with reflux at 110° C. for 48 hours. After returning to room temperature, solvent was distilled by a low-pressured distillation. 0.743 g yellow compound 1d powders were prepared after drying with yield of 81%. The reaction according to step (3) was

• (4) 1.46 g compound 1d, 1.12 g acetic acetone, 0.59 g Na₂CO₃, and 20 ml 2-ethoxy ethanol were added to a flask and stirred at 120° C. for 24 hours. After returning to room temperature, solvent was distilled by a low-pressured distillation. 1.6 g yellow compound 1 powders were prepared after drying with yield of 68%. The reaction according to step (3) was

Example 2

Preparation of Compound 2

• (1) 1 g phenyl-thiophen-2-yl-methanone (compound 2a), 1.03 g 2,2-dimethoxy-ethylamine, and 15 ml toluene were added to a 50 ml round-bottomed flask and stirred at 110° C. for 12 hours. After returning to room temperature, 2,2-dimethoxy-ethylamine was removed by low-pressure distillation. Remaining solution was then purified by a column (ethyl acetate:n-hexane=1:4) to finally form 1.09 g yellow compound 2b with yield of 81%. The reaction according to step (1) was

• (2) 2.5 g compound 2b and 9 g PPA were added to a 50 ml round-bottomed flask and stirred at 120° C. for 6 hours. After returning to room temperature, 200 ml water was added. A proper quantity of KOH was then added to neutralize the solution to a basic condition. Organo-layer was extracted by adding 120 ml ethyl acetate. Remaining water in the organo-layer was then removed by adding 2 g MgSO₄. After the organo-layer condensed, 1.53 g white compound 2c solids were prepared with yield of 80%. The reaction according to step (2) was

• (3) 0.8 g compound 2c, 0.62 g IrCl₃, 15 ml 2-ethoxy ethanol, and 5 ml water were added to a flask with reflux at 110° C. for 48 hours. After returning to room temperature, solvent was distilled by a low-pressured distillation. 0.79 g yellow compound 2d powders were prepared after drying with yield of 78%. The reaction according to step (3) was

• (4) 1.5 g compound 2d, 1.21 g acetic acetone, 0.6 g Na₂CO₃, and 20 ml 2-ethoxy ethanol were added to a flask and stirred at 120° C. for 24 hours. After returning to room temperature, solvent was distilled by a low-pressured distillation. 1.43 g yellow compound 2 powders were prepared after drying with yield of 61%. The reaction according to step (3) was

Example 3

Fabrication of Organic Electroluminescent Device

Referring to FIG. 1, a method of fabricating an organic electroluminescent device is disclosed according to the following example, in which an ITO anode 100 was provided on a substrate and washed with cleaning agent and deionized water. After drying, NPB was evaporated on the ITO anode 100 to form a hole transport layer 110 at a thickness of 500 Å. Ir complex (compound 1, dopant) and CBP (host) were then co-evaporated on the hole transport layer 110 to form an emitting layer 120 at a thickness of 200 Å. The dopant/host volume ratio thereof was 6%. Next, BCP was evaporated on the emitting layer 120 to form a hole blocking layer 130 at a thickness of 150 Å. Next, Alq₃ was evaporated on the hole blocking layer 130 to form an electron transport layer 140 at a thickness of 200 Å. Next, LiF was evaporated on the electron transport layer 140 to form a buffer layer 150 at a thickness of 5 Å. Finally, A1 was evaporated on the buffer layer 150 to form a cathode 160 at a thickness of 1200 Å.

The invention also provides three devices utilizing various dopants and concentrations in emitting layers, for example, doping with 6% compound 2, 9% compound 1, and 9% compound 2, respectively, in emitting layers.

Referring to Table 1, various drive voltages, brightness, CIE values, and wavelengths of the foregoing devices were compared.

< td>21.9Luminescent< td>(nm)

TABLE 1
	Compound 1	Compound 1	Compound 2	Compound 2
dopant	(6%)	(9%)	(6%)	(9%)
Drive	5.21	4.66	5.55	5.46
voltage
(Volts)
Brightness	399	390	222	288
(cd/m2)
Brightness	40.3	38.7	28.7
(cd/A)
24.3	26.1	12.4	16.5
efficiency
(lm/W)
CIE (x, y)	(0.48, 0.50)	(0.49, 0.50)	(0.49, 0.50)	(0.49, 0.50)
values
Wavelength	560	560	564	564

The data in Table 1, such as drive voltages, brightness, and luminescent efficiency, were measured at current density of merely 1 mA/cm. Clearly, the organic electroluminescent devices of the invention provide low drive voltage requirements and high luminescent efficiency.

While the invention has been described by way of example and in terms of preferred embodiment, it is to be understood that the invention is not limited thereto. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.