Patent Grant
8115379
This is a submission pursuant to 35 U.S.C. 154(d)(4) to enter the national stage under 35 U.S.C. 371 for PCT/DE2006/002330 filed Dec. 22, 2006. Priority is claimed under 35 U.S.C. 119(a) and 35 U.S.C. 365(b) to European Patent Application No. 05028570.9 filed Dec. 28, 2005. The subject matters of PCT/DE2006/002330 and European Patent Application No. 05028570.9 are hereby expressly incorporated herein by reference.
The present invention relates to the use of metal complexes as emitter in an electronic component and this electronic component.
As is known in the art, electroluminescent compounds are the main feature of organic light emitting diodes. They are generally embedded in or chemically bound to monomeric, oligomeric or polymeric materials, which are generally of that kind, that in these materials suitable charge carriers are created and can be transported, with the provision that, upon collision of oppositely charged charge carriers, excitones are formed, which can transfer its excess energy to the respective electroluminescent compound. This electroluminescent compound can thereafter be transformed into a certain electronic excitation condition, which is then converted, preferably completely and with avoidance of radiationless deactivation processes, by light emission into the respective ground condition. As electronic excitation condition, which can be also formed by transmission of energy from a suitable precursor-exciton, a singlet or triplet-condition is considered, having only a few exceptions. As both conditions are, according to spin statistic, occupied generally in a ratio of 1:3, this results in the fact that in an emission from a singlet-condition, which is called fluorescence and predominantly occurs for organic, heavy metal free compounds, only a maximum of 25% of the excitation energy can be emitted. In contrast to that, in a triplet-emission, which is called phosphorescence and occurs predominantly for transition metal organyl-compounds, the whole amount of the excitation energy can be emitted (triplet-harvesting) so that in this case the light efficiency can reach 100%, as far as the simultaneously formed singlet condition lying energetically above the triplet condition is also emitted, is completely converted into the triplet condition and radiationless competition processes are without significance. Thus, triplet-emitters should be in general the more efficient luminophores, which are suitable to provide for a high light efficiency in organic light-emitting diodes.
As is known, despite intensive search for high efficient triplet emitters, only a few compounds are known, whose light efficiency is nearly 100%, as nearly always radiationless competition processes are simultaneously present with the desired phosphorescence. The known high efficient triplet-emitters are almost complexes of some heavy metals from the groups 6-10 of the Periodic System with specific, predominantly π-electron containing ligands, wherein these ligands are both bound to the respective heavy metal via primary—and secondary valences. It was found that for the known complexes the kind and strength of the metal-ligand bonding has an important influence to the interplay between radiationless and radiating desactivation and thus to the respective luminescence quantum efficiency, however, these features are hardly predictable for a specific compound.
As a consequence, the search for suitable triplet-emitters with luminescence quantum efficiency is more or less empiric. Thus, in most of the patent applications of the prior art all possible and suitable compounds of a specific structural type were contained.
In DE 102 51 986 A1 high efficient triplet-emitters are claimed, consisting of a central heavy metal atom, such as iridium or platin, being complexed with a different number of different 2-aryl or 2-heteroarylpyridines, respectively, as well as being partly complexed with additional bi- or monodentate ligands, wherein for the claimed 2-heteroarylpyridines 2-(2-thienyl)-pyridine is explicitly disclosed as ligand. However, an advantage of the use of this type of ligand in contrast to the ligands also disclosed is not explicitly disclosed. Detailed spectroscopic data for compounds of the above mentioned structural type were published from H. Yersin and D. Douges in Topics in Curr. Chem. 2001, 214, 81.
It is an object of the present invention, to overcome the advantages of the prior art, especially to provide electronic components, which can use high efficient emitter compounds. Especially the use of respective compounds with high luminescence quantum efficiency shall be possible, so that with these compounds organic light emitting diodes with high radiation performance and low degradation under long term conditions can be constructed.
This object is achieved by the use of a metal complex containing 2-(3-thienyl)-pyridine ligands as the emitter in an organic light-emitting component, wherein the metal complex is of general formula 1 or 2:
wherein M is a heavy metal, X, Y and LL are ligands, which independently of one another are charged or uncharged and from which essentially no emission comes, R1 and R2 independently of one another may be present one or more times on the respective cycle and are independently selected from F, Cl, Br, I, NO2, CN, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by —O—, —SiR32—, —S—, —NR3— or —CONR3— and wherein one or more H atoms may be replaced by F, or an aryl or heteroaryl group with 4 to 14 C atoms, which may be substituted with one or more non-aromatic radicals R1 or R2; wherein a number of substituents R1 and/or R2, both on the same ring and on the two different rings, may together form a further monocyclic or polycyclic ring system;
R3 is identical or different each time it occurs and is selected from H or an aliphatic or aromatic hydrocarbon radical with 1 to 20 carbon atoms; n=1-3, m and l independently of one another are 0-4 where 2n+m+1=4 or 6, or p=0−2 where 2n+2p=4 or 6.
The ligands X, Y und LL are such that from these essentially no emission comes, which, however, significantly influence the wave length of emission, duration of emission and quantum efficiency of emission as well as stability of the resulting complexes.
By specific combinations of ligands also negatively charged complexes of formula [(3-thienylpyridine)nMXmYl]q− and [(3-thienylpyridine)nM(LL)p]r− can be formed. For balancing the charge, metal cations Mes+ (s=1−3) as well as ammonium and phosphonium salts can be utilized. The negatively charged complexes shall be enclosed within the scope of the present invention according to the formulas 1 and 2 as illustrated above.
Preferably, the heavy metal is selected from Pt(II), Pt(IV), Re(I), Os(II), Ru(II), Ir(I), Ir(III), Au(I), Au(III), Hg(I), Hg(II) and Cu(I).
In a further embodiment it is provided that X and Y independently of one another or ligands with a single negative charge or neutral monodentate ligand.
In this regard it is preferred that X and Y independently of one another are selected from F−, Cl−, Br−, I−, CN−, NCO−, SCN−, R4S−, R4O−, R4C═C−, R4COO−, NO3−, amine, phosphane, arsane, nitrile, isonitrile, CO, carbon, ether and thioether, wherein R4 is an organic radical having 1 to 15 carbons, preferably alkyl.
In a further embodiment of the invention LL, preferably with single negative charge, is a chelating ligand and/or a cyclometallating ligand.
Especially preferred is that LL is selected from β-diketonate, β-diketoiminate, [(pyrazolyl)2H]−, [(pyrazolyl)2BR52]—, [pyrazolyl3BH]−, [pyrazolyl4B]−, (triazolyl)2BH2−, (triazolyl)3BH−, (triazolyl)4B−, (Ph2PCH2)2BR52−, R5COO−, NO3−, diamine, diphosphane, diarsane, dinitrile, diisonitrile, dialkylether and dialkyl(thio)ethers, wherein R5 is an organic radical with 1-15 carbon atoms, preferably alkyl.
Especially preferred is that the metal complex is used as a triplet emitter
According to the invention is also an electronic component, which contains a metal complex as described above.
It is preferably an electronic component in the form of an organic light-emitting diode (OLED).
Further, an electronic component is provided, wherein the organic light-emitting diode contains the complex, preferably in an electron transporting layer, in a concentration of 2-20 weight percent, preferably 5-8 weight percent.
Surprisingly it was found that by the use of the disclosed heavy metal complexes with 2-(3-thienyl)-pyridine ligands instead of 2-(2-thienyl)-pyridine especially in organic light-emitting diodes significantly improved luminescence quantum efficiencies are possible and thus the radiation performance of the organic light-emitting diode can be significantly improved. Additional advantages of the disclosed heavy metal complexes are the good sublimability as well as the possibility to vary the emission range and thus the detectible colours of the light emitting diodes in a great extent by the structural variation of the organyl-ligands.
The metal complexes according to the general formulas 1 and 2 used as emitters can be prepared according to known methods, starting from a suitable heavy metal compound, such as a heavy metal halide, heavy metal acetate or heavy metal nitrate, wherein this compound is either directly reacted with 2-(3-thienyl)-pyridine or is reacted after its preceding activation in the form of a suitable alkali metal compound or a respective metal organic derivative, such as a trialkyl stannyl, alkyl cupryl or alkyl zincate compound. Depending on the type of the starting components utilized, the reaction conditions chosen and the respective stoichiometric ratio of the respective components, complexes can be obtained which have due to this specific structural feature an extremely high phosphorescence quantum efficiency.
This is for example given for the compounds Ir(3-thpy)3 and Pt(3-thpy)2. The iridium compound can be prepared according to the disclosure of K. M. Lo et al. in J. Organometal. Chem. 1992, 430, 149 in that 2-(3-thienyl)-pyridine is converted by reaction with butyllithium into the respective lithium compound, which is subsequently reacted in situ with anhydrous IrCl3 in THF, resulting in the desired iridium complex, which is subsequently isolated by precipitation with water and purified by column chromatography using silicagel and toluene as eluent. The iridium complex formed is provided as orange-yellow solid which thermally stable up to 250° C., and which can be evaporated without any decomposition under high vacuum at a temperature of less than 220° C. The structure thereof is confirmed as fac-Ir(3-thpy)3 by its mass number of m/z=655 and 1H-NMR-spektrum with signals at 8.63, 8.43, 8.14, 7.85, 7.77 and 7.4 ppm. It seems that for preparing the compounds which are suitable for the intended use special reaction conditions are necessary, for example lithium organic intermediates.
In an analogous manner, according to the disclosures of L. Chassot and A. von Zelewsky in Inorg. Chem. 1987, 26, 281, the compound trans-PtCl2(SEt)2 can be prepared from one equivalent of trans-PtCl2(SEt)2 and two equivalents of the above disclosed lithiated 2-(3-thienyl)-pyridine, which is obtained as dark red solid having a maximum in the red spectral range at about 600 mm, which is intensively luminescent and which can be evaporated thermally up to a temperature of about 300° C. under high vacuum without any decomposition. The compound crystallizes in a monocline lattice of room group P 21/n with lattice constants of a=1217.74 pm, b=1043.77 pm, c=1225.36 pm, a=90°, β=100, 141° and γ=90°. Using this compound an organic light-emitting diode was constructed and the characteristics were tested.
The present invention is now further illustrated with a detailed description of one embodiment in conjunction with the drawings as enclosed, in which
Organic light emitting diodes having the following configuration were designed and the properties tested.
A 100 nm layer of 4,4′,4″-tris-[phenyl-(3-tolyl)-amino]-triphenylamine (mMTDATA), doped with 2% of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4-TCNQ), a 20 nm layer of 4,4′,4″-tris-(N-carbazolyl)-triphenylamine (TCTA), doped with 7% Ppt(3-thienylpyridine)2, a 40 nm layer of 3-(4-biphenyl)-4-phenyl-5-tert.-butylphenyl-1,2,4-triazole (TAZ), and a 0.5 nm layer of lithium fluoride and finally an aluminium electrode were successively evaporated on a glass support having a 50 nm ITO-layer.
The electroluminescence spectrum of the component obtained according to the design as disclosed above was measured and is provided in
The features disclosed in the foregoing description, in the drawings or in the claims may, both separately, and in any combination thereof, be material for realizing the invention in divers forms thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 05028570 | Dec 2005 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/DE2006/002330 | 12/22/2006 | WO | 00 | 11/10/2008 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2007/073728 | 7/5/2007 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 5792568 | Emoto et al. | Aug 1998 | A |
| 6908783 | Kuehl et al. | Jun 2005 | B1 |
| 6984591 | Buchanan et al. | Jan 2006 | B1 |
| 20020042174 | Kunugi et al. | Apr 2002 | A1 |
| 20020179885 | Che et al. | Dec 2002 | A1 |
| 20030186080 | Kamatani et al. | Oct 2003 | A1 |
| 20030205707 | Chi-Ming et al. | Nov 2003 | A1 |
| 20040065544 | Igarashi et al. | Apr 2004 | A1 |
| 20040121184 | Thompson et al. | Jun 2004 | A1 |
| 20040241492 | Tokuda | Dec 2004 | A1 |
| 20040262576 | Thompson et al. | Dec 2004 | A1 |
| 20050221115 | Tsuboyama et al. | Oct 2005 | A1 |
| 20050260449 | Walters et al. | Nov 2005 | A1 |
| 20060071206 | Spreitzer et al. | Jun 2006 | A1 |
| 20060208252 | Wessels et al. | Sep 2006 | A1 |
| 20060258043 | Bold et al. | Nov 2006 | A1 |
| 20070111025 | Lennartz et al. | May 2007 | A1 |
| 20070135635 | Stoessel et al. | Jun 2007 | A1 |
| 20070264524 | Gessner et al. | Nov 2007 | A1 |
| 20080121870 | Seth et al. | May 2008 | A1 |
| Number | Date | Country |
|---|---|---|
| 4112793 | Oct 1992 | DE |
| 1436230 | May 1976 | GB |
| 03208689 | Sep 1991 | JP |
| WO 2004017043 | Feb 2004 | WO |
| WO 2005086251 | Sep 2005 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20090318698 A1 | Dec 2009 | US |
