WO2005076380A2 - Oleds utilizing multidentate ligand systems - Google Patents

Oleds utilizing multidentate ligand systems Download PDF

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Publication number
WO2005076380A2
WO2005076380A2 PCT/US2005/003107 US2005003107W WO2005076380A2 WO 2005076380 A2 WO2005076380 A2 WO 2005076380A2 US 2005003107 W US2005003107 W US 2005003107W WO 2005076380 A2 WO2005076380 A2 WO 2005076380A2
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group
formula
bidentate
aryl
alkyl
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PCT/US2005/003107
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French (fr)
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WO2005076380A3 (en
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Bin Ma
Robert Walters
Raymond Kwong
Jason Brooks
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Universal Display Corporation
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Publication of WO2005076380A3 publication Critical patent/WO2005076380A3/en

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    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/311—Phthalocyanine
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/917—Electroluminescent

Definitions

  • the present invention relates to efficient organic light emitting devices (OLEDs), and more specifically to phosphorescent organic materials used in such devices. More specifically, the present invention relates to phosphorescent emitting materials with improved stability and efficiency when incorporated into an OLED
  • OLEDs organic light emitting devices
  • organic phototransistors organic photovoltaic cells
  • organic pho ' todetectors examples include organic pho ' todetectors.
  • OLEDs organic light emitting devices
  • the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
  • organic includes polymeric materials as well as small molecule organic materials hat may be used to fabricate organic opto-electronic devices.
  • Small molecule refers to any organic material that is not a polymer, and "small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the "small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone.
  • Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety.
  • the core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter.
  • a dendrimer may be a "small molecule," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
  • OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Patent Nos.
  • OLED devices are generally (but not always) intended to emit light through at least one of the electrodes, and one or more transparent electrodes may be useful in organic opto- ⁇ lectronic devices.
  • a transparent electrode material such as indium tin oxide (ITO)
  • ITO indium tin oxide
  • a transparent top electrode such as disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, may also be used.
  • the top electrode does not need to be transparent, and may be comprised of a thick and reflective metal layer having a high electrical conductivity.
  • the bottom electrode may be opaque and / or reflective. Where an electrode does not need to be transparent, using a thicker layer may provide better conductivity, and using a reflective electrode may increase the amount of light emitted through the other electrode, by reflecting light back towards the transparent electrode.
  • Fully transparent devices may also be fabricated, where both electrodes are transparent. Side emitting OLEDs may also be fabricated, and one or both electrodes may be opaque or reflective in such devices.
  • top means furthest away from the substrate
  • bottom means closest to the substrate.
  • the bottom electrode is the electrode closest to the substrate, and is generally the first electrode fabricated.
  • the bottom electrode has two surfaces, a bottom surface closest to the substrate, and a top surface further away from the substrate.
  • a first layer is described as "disposed over” a second layer
  • the first layer is disposed further away from substrate.
  • a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
  • solution processible means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
  • Industry standards call for the lifetime of full color displays to be at least about 5000 hours.
  • high stability and efficiency are important characteristics of high quality displays. These requirements have helped generate a need for materials that exhibit longer lifetimes, higher stability, and higher efficiency than have been generally achieved in .the prior art.
  • the present invention provides an organic light emitting device that has an anode, a cathode and one or more organic layers between the anode and the cathode.
  • the present invention also provides materials having improved stability for use in an OLED.
  • the materials are metal complexes comprising a multidentate ligand system.
  • the organic layer comprises an emissive layer comprising an emissive material which is a phosphorescent organometallic emissive material.
  • the phosphorescent emissive material comprises a metal bound to two or more ligands wherein at least one ligand is a photoactive ligand and a wherein two or more of the ligands are covalentiy linked by one or more hhking groups.
  • the phosphorescent emissive material comprises a transition metal bound to two or three bidentate ligands, wherein two or more of the bidentate ligands are covalentiy linked by one or more linking groups.
  • Preferred emissive materials of the present invention may be represented by the formula I [X a -(L) b ]M (T) wherein M is a metal, L is a bidentate ligand, X is a linking group that links two or more L, a is 1 to 4, and ⁇ is 2 or 3.
  • the bidentate ligands are selected from bidentate photoactive ligands, and bidentate ancillary ligands.
  • the emissive materials comprise at least one bidentate photoactive ligand.
  • the device has an emissive layer comprising an emissive material which is a phosphorescent organometallic emissive material.
  • the phosphorescent organometallic emissive material comprises a transition metal, and two or three bidentate ligands, wherein two or more of the bidentate ligands are covalentiy linked by a linking group.
  • the bidentate ligands are selected from (i) bidentate photoactive ligands, wherein each bidentate photoactive ligand is bound to the transition metal through a carbon-metal bond and a nitrogen-metal bond to form a cyclometallated ring, and (ii) bidentate ancillary ligands, wherein at least one of the ligands is a bidentate photoactive ligand.
  • the invention provides an organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal complex having a first ligand, which is a bidentate ligand, a second ligand, and a linking group that covalentiy links the first ligand and the second ligand.
  • the linking group does not provide ⁇ -conjugation between the first ligand and the second ligand.
  • the non-conjugated linking group may comprise at least one atom in the linkage which contains no ⁇ -electrons, such as an sp 3 hybridized carbon or silicon.
  • the second ligand may be a bidentate ligand or may be a monodentate ligand.
  • the metal complex may further comprises an additional monodentate or bidentate ligand.
  • the additional ligand may also be linked to the first ligand, to second ligand, or to both the first ligand and the second ligand.
  • the invention provides an organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises an emissive material having the formula I [X fl -(L) ⁇ ]M (I) wherein, M is a transition metal having a molecular weight greater than 40;
  • X is a linking group that links two or more L, and is selected from the group consisting of - CR.2)d- > -[O(CR 2 ) e ]0- 3 or a group having the formula A A-B ⁇ A or A-B2-A wherein A is -(CR 2 ) ⁇ or -Z-(CR 2 V; Z is -O-, -NR-, or -SiR 2 -;
  • L is a bidentate ligand selected from the group consisting of (i) bidentate photoactive ligands having the formula II 4
  • R 2/ ⁇ C (ll) wherein Y is N or C, the dotted line represents an optional double bond
  • R 1 , R 2 , R 3 and R 4 are independently selected from H, alkyl, or aryl, and additionally or alternatively, one or more of R and R , R and R , and R and R together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cyclohetero alkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents Z; each substituent Z is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , NR 2 , NO 2 , OR, halo, and aryl, and additionally, or alternatively, two Z groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, and each R is independently selected from H, alky
  • the invention provides an organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a material of the formula Nil wherein Q is a bidentate ligand of the formula VIII
  • each R 7 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, C ⁇ , CF 3 , ⁇ R 2 , NO 2 , OR, halo, and aryl, and additionally, or alternatively, two R 7 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic ' group
  • each R 8 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , NR 2 , NO 2 , OR, halo, and aryl, and additionally, or alternatively, two R 8 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group
  • each R is independently selected from H, alkyl, aralkyl
  • Figure 1 shows an organic light emitting device having separate electron transport, hole transport, and emissive layers, as well as other layers.
  • Figure 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
  • Figure 3 shows the plot of current vs voltage for the device having the structure ITO/CuPc(100A)/NPD(300A)/CBP:dopant F/BAlq(100A)/Alq 3 (400A)/LiF(10A)/Al(1000A) in which the hexadentate emissive dopant, Dopant F, is doped into the CBP host at 4.5%, 6% and 9%.
  • Figure 4 shows the plot of external quantum efficiency vs current density for the device having the structure ITO/CuPc(l O ⁇ A)/NPD(30 ⁇ A)/CBP:dopant F/BAlq(l OOA) / Alq 3 (40 ⁇ A) /LiF(l ⁇ A)/Al(100 ⁇ A) in which the hexadentate emissive dopant, Dopant F, is doped into the CBP host at 4.5%, 6% and 9%.
  • Figure 5 shows the plot of liuninous efficiency vs luminance for the device having the structure ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP:dopant F/BAlq(10 ⁇ A) / Alq 3 (40 ⁇ A) /LiF(l ⁇ A)/Al(100 ⁇ A) in which the hexadentate emissive dopant, Dopant F, is doped into the CBP host at 4.5%, 6% and 9%.
  • Figure 6 shows the luminescent spectra for the devices having the structures (i) ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP:dopant F (9%, 30 ⁇ A)/BAlq(10 ⁇ A)/Alq 3 (40 ⁇ A) /LiF(l ⁇ A)/ Al(lOO ⁇ A), (ii) rTO/CuPc(100A)/NPD(300A)/CBP:dopant F(4.5%, 30 ⁇ A)/BAlq(10 ⁇ A)/Alq(400 A)/LiF(l ⁇ A)/Al(l 000 A), and (iii) ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP:dopant F(6%, 30 ⁇ A)/ B Alq(l O ⁇ A)/Alq(40 ⁇ A)/LiF(l ⁇ A)/Al(l OOOA).
  • Figure 7 shows the normalized luminance vs time for the devices having the structures ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP:dopant F(4.5%, 30 ⁇ A)/BAlq(10 ⁇ A)/Alq(400 A)/LiF(5A)/Al(100 ⁇ A) and ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP:Ir ppy) 3 (6%, 300A)/BAlq(l O ⁇ A)/Alq(400 A)/LiF(l ⁇ A)/Al(l OOOA).
  • Figure 8 shows the plot of current vs voltage(log scale) for devices having the structure ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP: dopant (4.5%, 30 ⁇ A) /BAlq(l O ⁇ A)/Alq 3 (40 ⁇ A)/LiF(l ⁇ A)/Al(l OOOA) in which 2 hexadentate linked emissive dopants, Dopant F and Dopant M ,and unlinked dopant Ir ppy) 3 doped into the CBP host at 4.5%, are compared.
  • Figure 9 shows the plot of external quantum efficiency vs current density for devices having the structure ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP: dopant (4.5%, 300A)
  • Figure 10 shows the luminescent spectra for devices having the structures (i)
  • ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP dopant F(4.5%, 30 ⁇ A) /BAlq(lO ⁇ A) / Alq 3 (40 ⁇ A)
  • ITO/CuPc(100A)/NPD(300A)/CBP dopant M(4.5%, 30 ⁇ A) BAlq(lO ⁇ A) / Alq 3 (400A) /LiF(l ⁇ A)/Al(100 ⁇ A) and ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP: fr(ppy) 3 (4.5%, 300A) /BAlq(lO ⁇ A) / Alq 3 (40 ⁇ A) /LiF(l ⁇ A)/Al(100 ⁇ A)
  • Figure 11 shows the normalized luminance vs time for devices having the stracture ITO/CuPc(100A)/NPD(300A)/CBP: dopant (4.5%, 30 ⁇ A) /BAlq(lO ⁇ A) / Alq 3 (40 ⁇ A)
  • Figure 12 shows the plot of current vs voltage(log scale) for devices having the structures ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/mCP:Dopant Q (6%, 30 ⁇ A)/BAlq(40 ⁇ A)/LiF(l ⁇ A)/Al(100 ⁇ A) and ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/ mCP:Ir(4,6- F 2 Ppy)s (6%, 30 ⁇ A)/BAlq(40 ⁇ A)/LiF(l ⁇ A)/Al(100 ⁇ A).
  • Figure 13 shows the plot of external quantum efficiency vs current density for devices having the structures ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/mCP:Dopant Q (6%, 3 O ⁇ A) BAlq(40 ⁇ A)/LiF(l ⁇ A)/Al(l OOOA) and ITO/CuPc(l O ⁇ A)/NPD(30 ⁇ A)/mCP :Ir(4,6- F 2 ppy) 3 (6%, 300A)/BAlq(400A)/LiF(10A)/Al(1000A).
  • Figure 14 shows the luminescent spectra for devices having the structures ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/mCP:Dopant Q (6%, 30 ⁇ A)/BAlq(40 ⁇ A)/LiF(l ⁇ A)/Al(100 ⁇ A) and ITO/CuPc(100A)/NPD(300A)/mCP:Ir(4,6-F 2 ppy) 3 (6%, 3 OOAVB Alq(40 ⁇ A)/LiF(l ⁇ A)/Al(l OOOA).
  • Figure 15 shows the normalized luminance vs time for devices having the structure ITO/CuPc(10 ⁇ A) PD(30 ⁇ A)/mCP:Dopant Q (6%, 30 ⁇ A)/BAlq(40 ⁇ A)/LiF(l ⁇ A)/Al(100 ⁇ A) and ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/mCP:Ir(4,6-F 2 ppy) 3 (6%, 30 ⁇ A)/BAlq(40 ⁇ A)/LiF(l ⁇ A)/Al(l OOOA).
  • the present invention provides an organic light emitting device that has an anode, a cathode and one or more organic layers between the anode and the cathode.
  • the present invention also provides materials having improved stability for use in an OLED.
  • the materials are metal complexes comprising a multidentate ligand system. By linking individual ligands together to form a multidentate ligand system, it is possible to increase the stability of the metal complexes formed using the ligands.
  • the device has an emissive layer comprising an emissive material which is a phosphorescent organometallic emissive material.
  • an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode.
  • an "exciton” which is a localized electron-hole pair having an excited energy state
  • Light is emitted when the exciton relaxes via a photoemissive mechanism.
  • the exciton may be localized on an excimer or an exciplex.
  • Non- radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
  • the initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence") as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
  • Phosphorescence may be referred to as a "forbidden" transition because the transition requires a change in spin states, and quantum mechanics indicates that such a transition is not favored.
  • phosphorescence generally occurs in a time frame exceeding at least 10 nanoseconds, and typically greater than 100 nanoseconds. If the natural radiative lifetime of phosphorescence is too long, triplets may decay by a non-radiative mechanism, such that no light is emitted.
  • Organic phosphorescence is also often observed in molecules containing heteroatoms with unshared pairs of electrons at very low temperatures. 2,2'-bipyridine is such a molecule.
  • Non-radiative decay mechanisms are typically temperature dependent, such that a material that exhibits phosphorescence at liquid nitrogen temperatures may not exhibit phosphorescence at room temperature. But, as demonstrated by Baldo, this problem may be addressed by selecting phosphorescent compounds that do phosphoresce at room temperature.
  • the excitons in an OLED are believed to be created in a ratio of about
  • OLEDs utihzing phosphorescent materials that emit from triplet excited states are disclosed, for example, in U.S. Patent No. 6,303,238, which is incorporated by reference in its entirety.
  • Phosphorescence may be preceded by a transition from a triplet excited state to an intermediate non-triplet state from which the emissive decay occurs.
  • organic molecules coordinated to lanthanide elements often phosphoresce from excited states localized on the lanthanide metal.
  • such materials do not phosphoresce directly from a triplet excited state but instead emit from an atomic excited state centered on the lanthanide metal ion.
  • the europium diketonate complexes illustrate one group of these types of species.
  • Phosphorescence from triplets can be enhanced over fluorescence by confining, preferably through bonding, the organic molecule in close proximity to an atom of high atomic number. This phenomenon, called the heavy atom effect, is created by a mechanism known as spin-orbit coupling. Such a phosphorescent transition may be observed from an excited metal-to-ligand charge transfer (MLCT) state of an organometallic molecule such as tris(2-phenylpyridine)iridium(III).
  • MLCT excited metal-to-ligand charge transfer
  • the term "triplet energy” refers to an energy corresponding to the highest energy feature discernable in the phosphorescence spectrum of a given material. The highest energy feature is not necessarily the peak having the greatest intensity in the phosphorescence spectrum, and could, for example, be a local maximum of a clear shoulder on the high energy side of such a peak
  • organometallic refers to compounds which have an organic group bonded to a metal through a carbon-metal bond. This class does not include per se coordination compounds, which are substances having only donor bonds from heteroatons, such as metal complexes of anines, halides, pseudohalides (CN, etc.), and the like. In practice organometallic compounds generally comprise, in addition to one or more carbon-metal bonds to an organic species, one or more donor bonds from a heteroatom.
  • FIG. 1 shows an organic light emitting device 100.
  • Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 160.
  • Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164.
  • Device 100 may be fabricated by depositing the layers described, in order.
  • Substrate 110 may be any suitable substrate that provides desired structural properties.
  • Substrate 110 may be flexible or rigid.
  • Substrate 110 may be transparent, translucent or opaque.
  • Plastic and glass are examples of preferred rigid substrate materials.
  • Plastic and metal foils are examples of preferred flexible substrate materials.
  • Substrate 110 may be a semiconductor material in order to facilitate the fabrication of circuitry.
  • substrate 110 may be a silicon wafer upon which circuits are fabricated, capable of controlling OLEDs subsequently deposited on the substrate. Other substrates may be used.
  • Anode 115 may be any suitable anode that is sufficiently conductive to transport holes to the organic layers.
  • the material of anode 115 preferably has a work function higher than about 4 eV (a "high work function material").
  • Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • AlZnO aluminum zinc oxide
  • Anode 115 (and substrate 110) may be sufficiently transparent to create a bottom-emitting device.
  • a preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate).
  • Anode 115 may be opaque and / or reflective.
  • a reflective anode 115 may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device.
  • the material and thickness of anode 115 may be chosen to obtain desired conductive and optical properties. Where anode 115 is transparent, there may be a range of thickness for a particular material that is thick enough to provide the desired conductivity, yet thin enough to provide the desired degree of transparency. Other anode materials and structures may be used.
  • Hole transport layer 125 may include a material capable of fransporting holes.
  • Hole transport layer 130 may be mtrinsic (undoped), or doped. Doping may be used to enhance conductivity.
  • ⁇ -NPD and TPD are examples of intrinsic hole transport layers.
  • An example of a p-doped hole transport layer is m-MTDATA doped with F -TCNQ at a molar ratio of 50:1, as disclosed in United States Patent Application No. 10/173,682 to Forrest et al., which is incorporated by reference in its entirety. Other hole transport layers may be used.
  • Emissive layer 135 comprises an organic dopant material capable of emitting light when a current is passed between anode 115 and cathode 160.
  • emissive layer 135 contains a phosphorescent emissive material, although fluorescent emissive materials may also be used. Phosphorescent materials are preferred because of the higher luminescent efficiencies associated with such materials.
  • Emissive layer 135 may also comprise a host material. The host material may be capable of fransporting electrons and / or holes, and is doped with the emissive material that may trap electrons, holes, and / or excitons, such that excitons relax from the emissive material via a photoemissive mechanism.
  • Emissive layer 135 may comprise a single material that combines transport and emissive properties.
  • emissive layer 135 may comprise other materials, such as dopants that tune the emission of the emissive material.
  • Emissive layer 135 may include a plurality of emissive materials capable of, in combination, emitting a desired spectrum of light. Examples of fluorescent emissive materials include DCM and DMQ . Examples of host materials include Alq 3 , CBP and mCP. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. Emissive material may be included in emissive layer 135 in a number of ways.
  • Electron transport layer 140 may include a material capable of transporting electrons. Electron transport layer 140 may be mtrinsic (undoped), or doped. Doping may be used to enhance conductivity. Alq 3 is an example of an intrinsic electron transport layer. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1 : 1 , as disclosed in United States Patent Application Publication No. 2002-0071963 Al to Forrest et al., which is incorporated by reference in its entirety. Other electron transport layers may be used.
  • the charge carrying component of the electron transport layer may be selected such that electrons can be efficiently injected from the cathode into the LUMO (Lowest Unoccupied Molecular Orbital) level of the electron transport layer.
  • the "charge carrying component” is the material responsible for the LUMO that actually transports electrons. This component may be the base material, or it may be a dopant.
  • the LUMO level of an organic material may be generally characterized by the electron affinity of that material and the relative electron injection efficiently of a cathode may be generally characterized in terms of the work function of the cathode material.
  • the preferred properties of an electron transport layer and the adjacent cathode may be specified in terms of the electron affinity of the charge carrying component of the ETL and the work function of the cathode material.
  • the work function of the cathode material is preferably not greater than the electron affinity of the charge carrying component of the electron transport layer by more than about 0.75 eV, more preferably, by not more than about 0.5 eV. Similar considerations apply to any layer into which electrons are being injected.
  • Cathode 160 may be any suitable material or combination of materials known to the art, such that cathode 160 is capable of conducting electrons and injecting them into the organic layers of device 100.
  • Cathode 160 may be transparent or opaque, and may be reflective. Metals and metal oxides are examples of suitable cathode materials. Cathode 160 may be a single layer, or may have a compound structure. Figure 1 shows a compound cathode 160 having a thin metal layer 162 and a thicker conductive metal oxide layer 164. In a compound cathode, preferred materials for the thicker layer 164 include ITO, IZO, and other materials known to the art. U.S. Patent Nos.
  • cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer.
  • the part of cathode 160 that is in contact with the underlying organic layer, whether it is a single layer cathode 160, the thin metal layer 162 of a compound cathode, or some other part, is preferably made of a material having a work function lower than about 4 eN (a "low work function material").
  • Other cathode materials and structures may be used.
  • Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and / or excitons that leave the emissive layer.
  • An electron blocking layer 130 may be disposed between emissive layer 135 and the hole transport layer 125, to block electrons from leaving emissive layer 135 in the direction of hole transport layer 125.
  • a hole blocking layer 140 may be disposed between emissive layerl35 and electron transport layer 145, to block holes from leaving emissive layer 135 in the direction of electron transport layer 140.
  • Blocking layers may also be used to block excitons from diffusing out of the emissive layer. The theory and use of blocking layers is described in more detail in United States Patent No.
  • blocking layer means that the layer provides a barrier that significantly inhibits transport of charge carriers and/or excitons through the device, without suggesting that the layer necessarily completely blocks the charge carriers and/or excitons.
  • the presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer.
  • a blocking layer may be used to confine emission to a desired region of an OLED.
  • injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or an organic layer, into an adjacent organic layer. Injection layers may also perform a charge transport function.
  • hole injection layer 120 may be any layer that improves the injection of holes from anode 115 into hole transport layer 125.
  • CuPc is an example of a material that may be used as a hole injection layer from an ITO anode 115, and other anodes.
  • electron injection layer 150 may be any layer that improves the injection of electrons into electron transport layer 145.
  • LiF / Al is an example of a material that may be used as an electron injection layer into an electron transport layer from an adjacent layer.
  • a hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, e.g., PEDOT:PSS, or it may be a vapor deposited small molecule material, e.g., CuPc or MTDATA.
  • a hole injection layer may planarize or wet the anode surface so as to provide efficient hole injection from the anode into the hole injecting material.
  • a hole injection layer may also have a charge carrying component having HOMO (Highest Occupied Molecular Orbital) energy levels that favorably match up, as defined by their herein-described relative ionization potential (IP) energies, with the adjacent anode layer on one side of the HIL and the hole transporting layer on the opposite side of the HIL.
  • the "charge carrying component” is the material responsible for the HOMO that actually transports holes. This component may be the base material of the HIL, or it may be a dopant. Using a doped HIL allows the dopant to be selected for its electrical properties, and the host to be selected for morphological properties such as wetting, flexibility, toughness, etc.
  • the charge carrying component of the HIL preferably has an IP not more than about 0.7 eV greater that the LP of the anode material. More preferably, the charge carrying component has an LP not more than about 0.5 eV greater than the anode material. Similar considerations apply to any layer into which holes are being injected.
  • HIL materials are further distinguished from conventional hole fransporting materials that are typically used in the hole transporting layer of an OLED in that such HIL materials may have a hole conductivity that is substantially less than the hole conductivity of conventional hole fransporting materials.
  • the thickness of the HIL of the present invention may be thick enough to help planarize or wet the surface of the anode layer.
  • an HIL thickness of as little as 10 nm maybe acceptable for a very smooth anode surface.
  • a thickness for the HIL of up to 50 nm may be desired in some cases.
  • a protective layer may be used to protect underlying layers during subsequent fabrication processes.
  • the processes used to fabricate metal or metal oxide top electrodes may damage organic layers, and a protective layer may be used to reduce or eliminate such damage.
  • protective layer 155 may reduce damage to underlying organic layers during the fabrication of cathode 160.
  • a protective layer has a high carrier mobility for the type of carrier that it transports (electrons in device 100), such that it does not significantly increase the operating voltage of device 100.
  • CuPc, BCP, and various metal phthalocyanines are examples of materials that may be used in protective layers. Other materials or combinations of materials may be used.
  • protective layer 155 is preferably thick enough that there is little or no damage to underlying layers due to fabrication processes that occur after organic protective layer 160 is deposited, yet not so thick as to significantly increase the operating voltage of device 100.
  • Protective layer 155 may be doped to increase its conductivity.
  • a CuPc or BCP protective layer 160 may be doped with Li.
  • a more detailed description of protective layers may be found in U.S. Patent Application Serial No. 09/931,948 to Lu et al., which is incorporated by reference in its entirety.
  • Figure 2 shows an inverted OLED 200.
  • the device includes a substrate 210, an cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230.
  • Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. Figure 2 provides one example of how some layers may be omitted from the structure of device 100. [0054] The simple layered structure illustrated in Figures 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used.
  • Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the la3'ers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer.
  • an OLED may be described as having an "organic layer" disposed between a cathode and an anode.
  • This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to Figures 1 and 2.
  • Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190, Friend et al., which is incorporated by reference in its entirety.
  • OLEDs having a single organic layer may be used.
  • OLEDs may be stacked, for example as described in U.S. Patent No.
  • the OLED structure may deviate from the simple layered structure illustrated in Figures 1 and 2.
  • the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.
  • any of the layers of the various embodiments may be deposited by any suitable method.
  • preferred methods include thermal evaporation, ink-jet, such as described in U.S.
  • Patent Nos. 6,013,982 and 6,087,196 which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Patent No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Patent Application No. 10/233,470, which is incorporated by reference in its entirety.
  • OVPD organic vapor phase deposition
  • Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere.
  • preferred methods include thermal evaporation.
  • Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Patent Nos.
  • 6,294,398 and 6,468,819 which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and ONJD. Other methods may also be used.
  • the materials to be deposited may be modified to make them compatible with a particular deposition method.
  • substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range.
  • Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize.
  • Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
  • Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign.
  • PDAs personal digital assistants
  • Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix.
  • the materials and structures described herein may have applications in devices other than OLEDs.
  • other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures.
  • organic devices such as organic transistors, may employ the materials and structures.
  • the emissive materials are phosphorescent organometallic emissive materials.
  • the phosphorescent emissive material is composed of a heavy metal atom and a multidentate, for example a tefradentate or hexadentate ligand system.
  • the phosphorescent emissive material comprises a transition metal bound to two or three bidentate ligands, wherein two or more of the bidentate ligands are covalentiy linked by one or more linking groups.
  • the emissive materials of the present invention may be represented by the formula I K L M (I) wherein M is a metal, L is a bidentate Hgand, X is a linking group that Hnks two or more L, a is 1 to 4, and b is 2 or 3.
  • the bidentate ligands are selected from bidentate photoactive ligands, and bidentate ancillary ligands.
  • the emissive materials comprise at least one bidentate photoactive ligand.
  • the metal, M is selected from the transition metals having an atomic weight greater than 40.
  • Preferred metals include Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag. More preferably, the metal is Ir or Pt. Most preferably, the metal is Ir.
  • the emissive materials of the present invention may comprise carbene-metal complexes including those disclosed in the application entitled “Luminescent Compounds with Carbene Ligands,” filed May 18, 2004, by Thompson et al., U.S. Application No. (not yet assigned), which is incorporated in its entirety by reference, wherein a carbene ligand is preferably linked to another ligand by a hnking group.
  • the emissive materials of the present invention comprise at least one photoactive ligand. This ligand is referred to as "photoactive" because it is believed that it contributes to the photoactive properties of the emissive material.
  • a photoactive ligand may be represented by the formula II R 4 R3 -
  • Y is N or C
  • the dotted line represents an optional double bond
  • R 1 , R 2 , R 3 and R 4 are independently selected from H, alkyl, .or aryl, and additionally or alternatively, one or more of R and R , R and R , and R and R together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cycHc group is optionally substituted by one or more substituents Z; each substituent Z is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , NR , NO 2 , OR, halo, and aryl, and additionally, or alternatively, two Z groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, and each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl.
  • the photoactive ligand of the formula II is a bidentate ligand that is bound to the transition metal through a carbon-metal bond and a nitrogen-metal bond to form a cyclometallated ring as shown in the partial structure III
  • R 1 and R 2 or R 3 and R 4 together form a 5 or 6-membered aryl ring.
  • both R 1 and R 2 together form a 5 or 6-membered aryl ring
  • R 3 and R 4 together from a 5 or 6-member aryl ring.
  • R 1 and R 2 together form a phenyl ring
  • R 3 and R 4 together form a heteroaryl group to give a bidentate photoactive ligand of the formula IV
  • ring A is an aromatic heterocyclic ring or a fused aromatic heterocyclic ring with at least one nitrogen atom that coordinates to the metal M
  • Y is selected from carbon or nitrogen
  • each R 5 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , NR 2 , N0 2 , OR, halo, and aryl, and additionally, or alternatively, two R 5 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group
  • each R is independently selected from the group consisting of alkyl, alkenj , alkynyl, aralkyl, CN, CF 3 , NR 2 , N0 2 , OR, halo, and aryl
  • two R 6 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group
  • each R is independently selected from H, alkyl, aralkyl,
  • Ring A in formula IN is an aromatic heterocycHc ring or a fused aromatic heterocyclic ring with at least one nitrogen atom that is coordinated to the metal M, wherein the ring can be optionally substituted.
  • A is pyridine, pyrimidine, quinoline, or isoquinoline. Most preferable, A is pyridine.
  • Optional substituents on the Ring A include of alkyl, alkenyl, alkynyl, aralkyl, C ⁇ , CF 3 , ⁇ R 2 , NO 2 , OR, halo, and aryl.
  • a particularly preferred photoactive ligand is phenylpyridine, and derivatives thereof.
  • the number of photoactive ligands may be any integer from 1 to the maximum number of ligands that may be attached to the metal. For example, for Ir the maximum number of bidentate ligands bound to the metal would 3, at least one of which would be a photoactive ligand. When more that one photoactive ligand is present, each photoactive ligand may be the same or may be different.
  • the emissive materials of the present invention may comprise one or more ancillary ligands. These ligands are referred to as "ancillary" because it is believed that they may modify the photoactive properties of the molecule, as opposed to directly contributing to the photoactive properties. The definitions of photoactive and ancillary are intended as non-limiting theories.
  • Ancillary ligands for use in the emissive material may be selected from those known in the art.
  • Non-limiting examples of ancillary ligands may be found in PCT Application Publication WO 02/15645 Al to Lamansky et al. at pages 89-90, which is incorporated herein by reference.
  • Preferred ancillary Hgands include acetylacetonate (acac) and picolinate (pic), and derivatives thereof.
  • the preferred ancillary ligands have the foUowing structures:
  • the number of "ancillary" ligands of a particular type may be any integer from zero to one less than the maximum number if Hgands that may be attached to the metal.
  • the linking group, X, Hnks two bidentate Hgands to give a tefradentate ligand system.
  • the tefradentate Hgand system may be represented by the formula (V) L-X-L (V) wherein each L is independently selected from a bidentate photoactive Hgand and a bidentate ancillary ligand, and X is a linking group.
  • the tefradentate Hgand system may be comprised of two photoactive ligands, two ancillary ligands, or a photoactive ligand and an ancillary ligand.
  • the tefradentate ligand system binds to the metal through four chemical bonds in the emissive material.
  • the emissive material may further comprise an additional bidentate ligand that is not linked to the tefradentate ligand system, and which may be a bidentate ancillary ligand, or a bidentate photoactive ligand.
  • the emissive material comprising the tefradentate ligand system further comprises a separate photoactive Hgand bound to the metal.
  • the linking group, X may be connected to each bidentate ligand, L, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligands ability to bind to the metal, M, and form a tefradentate system.
  • the tefradentate ligand system is comprised of two phenylpyridine Hgands linked by a linking group, X, is depicted below:
  • the linking group may be covalentiy bound to any atom of the phenylpyridine that does not interfere with each ligand's ability to bind to the metal in a bidentate fashion to form a terra dentate Hgand system.
  • the linking group may not be bound to the pyridine nitrogen.
  • the emissive material comprises a hexadentate ligand system.
  • the linking group may link two tridentate Hgands or three bidentate ligands or a bidentate and a tefradentate Hgand to form a hexadentate Hgand system.
  • the hexadentate ligand system comprises one or more Ifriking groups, X, that link three bidentate Hgands.
  • Such hexadentate ligand systems may be represented by the formula L-X-L I -X-L-X-L L (Nla) (VIb)
  • each X is independently selected from a linking group
  • each L is independently selected from a bidentate photoactive ligand and a bidentate ancillary ligand, with the proviso that at least one L is selected from a bidentate photoactive ligand.
  • the hexadentate ligand system may be comprised of three photoactive ligands, two photoactive ligands and an ancillary ligand, or one photoactive ligand and two anciUary ligands. The hexadentate ligand system binds to the metal through six chemical bonds in the emissive material.
  • the linking group(s), X may be connected to each bidentate Hgand, L, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligand's ability to bind to the metal, M, and form a hexadentate system. Examples of the case where the hexadentate ligand system is comprised of three phenylpyridine ligands linked by a linking group(s), X, are depicted below:
  • the emissive material comprises a hexadentate ligand system having three phenylpyridine ligands linked by a linking group(s), X, through the phenyl rings as depicted below:
  • the emissive material comprises a hexadentate ligand system having three phenylpyridine ligands linked by a Unking group(s), X, through the pyridine rings as depicted below:
  • other structures with multidentate ligands can be useful in OLED applications.
  • electron transporters using derivatives of duminum 8-hydroxyquinolates, such as Alq and BAlq can be ligand-interhnked, preferably by non-conjugated linking groups.
  • Such materials may be used in an OLED as an electron transporting material and/or as a host material in an emissive layer.
  • Linking according to the present invention may improve the stability of devices containing these compounds as compared to devices containing the non-ligand-interlinked analogs. These materials may be represented by the formula VII AltQ ⁇ L] (VII)
  • Q is a bidentate Hgand
  • J is a monodentate ligand
  • X is a linking group
  • h is 2 or 3
  • i is 1 to 4
  • j is 0 to 2.
  • the linking group X links two or more of the Hgands, Q or J, wherein at least one of the ligands linked by the linking group X is a bidentate Hgand Q.
  • the compound of formula NLT comprise two or three bidentate ligands, Q, that may be represented by the formula Nm
  • each R is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, C ⁇ , CF 3 , ⁇ R 2 , NO 2j OR, halo, and aryl, and additionally, or alternatively, two R 7 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , NR 2 , NO 2 , OR, halo, and aryl, and additionally, or alternatively, two R 8 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, C ⁇ , CF 3 , ⁇ R 2 , NO 2j OR, halo, and aryl, and additionally, or alternatively, two R 7 groups on adjacent ring atoms form a fused 5-
  • the bidentate Hgand Q is bound to the aluminum through an oxygen-metal bond and a nitrogen-metal bond to form the partial structure LX
  • ring B is a phenyl ring and ring C is a pyridine ring providing a bidentate ligand of formula X
  • the ligand J is selected from monodentate ligands having the formula wherein each R' is mdependently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , NO 2 , O-alkyl, halo, and aryl, and z is 0 to 5.
  • the linking group, X links two bidentate Hgands Q to give a tefradentate ligand system.
  • the tefradentate Hgand system may be represented by the formula (XI) Q-X-Q (XI)
  • Each bidentate ligand Q may be the same or may be different.
  • the complex may further comprise an additional bidentate ligand Q that is not linked to the tefradentate ligand system.
  • the complex may further comprise a monodentate ligand J that is not linked to the tefradentate ligand system.
  • the linking group, X may be connected to each bidentate Hgand, Q, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the Hgan 's ability to bind to the Al, and form a tefradentate system.
  • the tefradentate ligand system is comprised of two 8-hydroxyquinolinato ligands linked by a linking group, X, is depicted below:
  • the linking group, X links a bidentate ligands Q to a monodentate ligand J to give a tridentate ligand system.
  • the tridentate ligand system may be represented by the formula (XII) Q-X-J (XII)
  • the complex may further comprise an additional bidentate ligand Q that is not linked to the tridentate ligand system.
  • the linking group, X may be connected to each ligand in the tridentate ligand system by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligand' s ability to bind to the Al, and form a tridentate system.
  • the tridentate ligand system is comprised of a 8-hydroxyquinolinato Hgand linked by a linking group, X, to a 4-phenylphenolate ligand is depicted below:
  • one or more linking groups, X link three bidentate Hgands Q to give a hexadentate ligand system that may be represented by the formula Xm a andXm Q-X- Q Q— X— -X— Q Q (xm a ) (xm t ) wherein each X is independently selected form a linking group, and each bidentate ligand Q may be the same or may be different.
  • the linking group(s), X may be connected to each bidentate Hgand, Q, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the Hgand's ability to bind to the Al and form a hexadentate system. Examples of the case where the hexadentate ligand system is comprised of three 8-hy ⁇ roxyquinolinato Hgands linked by a linking group(s), X, are depicted below:
  • one or more linking groups X link two bidentate ligands Q and one monodentate ligand J to give a pentadentate Hgand system that may be represented by the formula XIV a , XLV and XLV C Q— — J Q— X—Q— — J Q— — J— X— Q Q (X V a ) (XTV b ) (XLV C )
  • each X is independently selected form a Hn ing group, and each bidentate ligand Q may be the same or may be different.
  • the linking group(s), X may be connected to each bidentate ligand Q or monodentate Hgand J by a covalent bond to any carbon or heteroatorn of the Hgand that does not interfere with the Hgand's ability to bind to the Al and form a pentadentate system. Examples of the case where the pentadentate ligand system is comprised of two 8-hydroxy- quinolinato Hgands Hnked by a linking group(s), X, to a 4-phenylphenolate ligand are depicted below:
  • the compounds of invention may be prepared by methods known in the art.
  • the multidentate Hgand systems are prepared by the metal catalyzed coupling of the linking group to the ligand. See, for example, Beeston et al., Inorg. Chem. 1998, 37, 4368-4379.
  • Metal complexes of the formula VII may be prepared, for example, according to the synthesis provided in Scheme I:
  • the materials of the present invention comprise one or more linking groups, X, that Hnks together two or more ligands (L, Q, or J).
  • the linking group, X may be connected to a ligand by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the Hgands ability to bind to the metal.
  • the linking group may be any group that is covalentiy bound to two or more of the ligands, and which does not interfere with the Hgand's individual abilities to bind to the same metal.
  • Linking groups may include, for example, organic, organometaHic and other metal containing groups.
  • linking group X is bivalent and trivalent alkyl groups, aryl groups, silanes, ethers, and polyethers.
  • the ligands connected by the linking group X may be the same or different.
  • the Hnking group, X may link two tridentate ligands or three bidentate ligands or a bidentate and a tefradentate ligand to form a hexadentate ligand system.
  • three bidentate ligands are joined by a common linking group X.
  • three bidentate ligands are each independently connected to a first linking group and a second linking group wherein the first and the second linking group may be the same or different.
  • the linking group X provides no ⁇ -conjugation between the linked ligands. Having ⁇ -conjugation between the linked ligands may change the electronic properties of the Hgands and the resulting metal complexes, such as a red-shift in the luminescence. It is desirable to link the ligands together to without significantly altering the electronic properties of the Hgands and the resulting metal complex.
  • a non-conjugated linking group may comprise at least one atom in the linkage which contains no ⁇ -electrons, such as an sp 3 hybridized carbon or sihcon.
  • the linking group, X is connected by a covalent bond to a phenyl moiety in a first Hgand and links the first ligand to at least a second ligand via a covalent bond to a phenyl moiety in the second ligand.
  • three ligands are linked together by a linking group covalentiy bound to a phenyl moiety on each
  • X is connected by a covalent bond to a pyridyl moiety of a first ligand and connects the first ligand to at least a second ligand via a covalent bond to a pyridyl moiety on the second ligand.
  • three ligands are linked together by a linking group covalentiy bound to a pyridyl moiety on each Hgand.
  • the Hnking group, X is selected from the group consisting of -(CR 2 )r, -[O(CR 2 ) e ]O-, or a group having the formula A A-B -A or A-B2-A wherein Z is -O-, -NR-, or -SiR 2 -;
  • B 2 is — i — , — C i R— , alkyl, aryl, heteroaryl, cycloalkyl, or a heterocyclic group; each R is independentiy selected from H, alkyl, aralkyl, aryl and heteroaryl, d is 1 to 6, e is 1 to 6, fis 1 to 4, and g is 1 to 4.
  • the metal complexes with multidentate Hgands may have improved chemical, thermochemical, elecfrochemical and photochemical stability compared to the fraditional bidentate ligand analogs.
  • the improvement in stability may be attributed, at least in part, to what is known as the "chelate effect" such as described in Inorganic Chemistry (2nd Edition), Gary L. Miessler, Donald A. Tarr (Prentice Hall, 1998) pp 396-397.
  • Linking two or more ligands to one another may render the resulting ligand system less labile than the corresponding non-linked ligands.
  • the mass specfroscopy (El, 70 eV) of Dopant F (described herein below)
  • Dopant F there is no fragmentation of the molecular ion whereas significant fragmentation is observed in Ir(ppy) 3 .
  • metal complexes with multidentate ligands can have increased photoluminescence quantum yields compared to the traditional bidentate ligand analogs because the complexes with multidentate ligands are more rigid, i.e., with decreased vibrational and rotational freedom, which can be pathways for non-radiative decay.
  • structural isomers may result from the synthesis. For example, in Ir(phenylpyridine) 3 type complexes, both facial and meridional isomers can form. Separation of these isomers may be difficult. Through suitable interHnking of the ligands, selective structural isomeric configuration can be achieved.
  • alkyl as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionaUy substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR.
  • cycloalkyl as used herein contemplates cyclic alkyl radicals.
  • Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. AdditionaUy, the cycloalkyl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic- amino, NO2, and OR.
  • alkenyl as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms.
  • alkenyl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cycHc-amino, NO 2 , and OR.
  • alkynyl as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optional' substituted with one or more substituents selected from halo, CN, C0 2 R, C(0)R, NR 2 , cyclic-amino, N0 2 , and OR.
  • aralkyl as used herein contemplates an alkyl group which has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted on the aryl with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic- amino, NO 2 , and OR. [00100]
  • heterocyclic group as used herein contemplates non-aromatic cyclic radicals.
  • Preferred heterocyclic groups are those containing 5 or 6 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tefrahydrofuran, tefrahydropyran, and the like.
  • aryl or "aromatic group” as used herein contemplates single- ring aromatic groups (for example, phenyl, pyridyl, pyrazole, etc.) and polycyclic ring systems (naphthyl, quinoline, etc.).
  • the polycyclic rings may have two or more rings in which two atoms are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls.
  • heteroaryl as used herein contemplates single-ring hetero- aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like.
  • heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls.
  • All value ranges, for example those given for n and m, are inclusive over the entire range. Thus, for example, a range of 0 to 4 would include the values 0, 1, 2, 3 and 4.
  • ITO indium tin oxide
  • NPD N,N'-diphenyl-N-N'-di(l-naphmyl)-be ⁇ zidine
  • TPD N,N'-diphenyl-N-N'-di(3-toly)-benzidine
  • BAlq alum um(III)bis(2-methyl-8-hycfroxyquinolinato)4-phenylphenolate mCP: 1 ,3 -N,N-dicarbazole-benzene
  • PEDOT:PSS an aqueous dispersion of poly(3,4-ethylenedioxythiophene) with polystyrenesulfonate (PSS)
  • solvents and reagents were purchased from Aldrich Chemical Company. The reagents were of the highest purity and used as received.
  • mCP was prepared by the palladium-catalyzed cross coupling of aryl halides and arylamines. (T. Yamamoto, M. Nishiyama, Y. Koie Tet. Lett., 1998, 39, 2367- 2370).
  • Example 4 Device fabrication and measurement All devices are fabricated by high vacuum ( ⁇ 10 "7 Torr) thermal evaporation.
  • the anode electrode is -1200 A of indium tin oxide (ITO).
  • the cathode consists of 10 A of LiF followed by 1,000 A of Al. All devices are encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box ( ⁇ 1 ppm of H 2 O and O 2 ) immediately after fabrication, and a moisture getter was incorporated inside the package.
  • the current- voltage-luminance (LVL) characteristics and operational Hfetime are measured and summarized in the Table 1. A typical display brightness level of 600 cd/m 2 for green emitting devices is chosen for the comparison between different devices. Table 1
  • the organic stack consists of 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l-naphthyl)-N-phenylamino]biphenyl ( ⁇ - NPD), as the hole fransporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 4.5, 6 or 9 wt% of Dopant F as the emissive layer (EML).
  • the ETL2 is 100 A of aluminum(III)bis(2-methyl-8-hydroxyqumolinato)4-phenylphenolate (BAlq).
  • the ETL1 is 400 A of tris(8-hydroxyquinolinato)aluminum (Alq 3 ).
  • Comparative Example 1 [00124] The organic stack consists of 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l-naphthyl)-N-phenylamino]biphenyl ( - NPD), as the hole fransporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 6 wt% of Oc-tris(2-phenylpyridine)iridium [Ir(ppy) 3 ] as the emissive layer (EML).
  • CuPc copper phthalocyanine
  • HIL hole injection layer
  • HTL hole fransporting layer
  • CBP 4,4'-bis(N-carbazolyl)biphenyl
  • EML emissive layer
  • the ETL2 is 100 A of aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate (BAlq).
  • the ETL1 is 400 A of tris(8-hydroxyquinol ato)alu ⁇ unum (Alq 3 ).
  • the linked ligand devices of Example 4 were characterized. The device characteristics are shown in Figures 3-6. The plot of current density vs voltage is shown in Figure 3.
  • Figure 4 shows the plot of the external quantum efficiency at various current densities for these devices.
  • Figure 5 shows the plots of luminous efficiency for these devices. The devices show high quantum efficiency and luminous efficiencies. The device having a dopant concentration of 4.5% gave a maximum quantum efficiency of 10% and a maximum luminous efficiency of 36 cd/A.
  • Figure 6 shows the luminescent spectra for the device having dopant concentration of 4.5%, 6% and 9%.
  • the operational stability of the 4.5% doped linked Hgand device was tested at room temperature under a constant direct current drive to achieve an initial luminance of 955 cd/m 2 .
  • a comparison of stability was made to the comparative example 1 (unlinked ligand device) which was driven at a lower initial luminance of 600 cd/m 2 ( Figure 7). Without the enhanced stability provided by the present invention, one would have expected the device which was driven at higher initial luminance, to degrade more rapidly.
  • the Hnked ligands of the present invention exhibit enhanced stability since the linked Hgand device of Example 4 degraded less than the unlinked ligand device (comparative Example 1) when operating at a 37% higher brightness.
  • the linked ligand device utilizing Dopant F retains 91% of 955 cd/m 2 after 1000 hours of operation whereas comparative Example 1 utilizing unlinked Ir(ppy) 3 retains only 89% of 600 cd/m 2 , after 1,000 hrs of continuous operation.
  • Example 6 Device Comparison [00131] Linked hexadentate molecules, Dopant M and Dopant F and the analogous unlinked tris ligand Ir(ppy) 3 (Comparative Example 1) were compared as phosphorescent dopants in OLED devices. Devices were fabricated similarly to those in Example 4.
  • test device structure for each was ITO/CuPc(10 ⁇ A)/NPD(30 ⁇ A)/CBP: Dopant (4.5%, 30 ⁇ A) /BAlq(lO ⁇ A) / Alq 3 (40 ⁇ A) /LiF(loA)/Al(1000A) where the dopant was Dopant F, Dopant M, or the unlinked analog ligand Ir(ppy) 3 (Comparative Example 1).
  • a comparison of the device data for the three dopants is shown in Figures 8-10.
  • the plot of current density vs voltage is shown in Figure 8.
  • Figure 9 shows the plot of the external quantum efficiency as a function of current density for these devices.
  • Figure 10 shows the electroluminescent spectra for these devices.
  • Dopant M is a hexadentate iridium 2-phenylpyridine (ppy) complex analogous to Dopant F except that Dopant M is linked through the phenyl rings while Dopant F is linked through the pyridine rings.
  • ppy hexadentate iridium 2-phenylpyridine
  • the organic stack consisted of 100 A thick of copper phthalocyanine (CuPc) as the hole mjec ⁇ on layer (HIL), 300 A of 4,4 ' - bis[N-(l-naphthyl)-N-phenylamino]biphenyl ( ⁇ -NPD), as the hole fransporting layer (HTL), 300 A of N,N'-dicarbazolyl-3,5-benzene (mCP) doped with 6 wt% of Dopant Q as the emissive layer (EML).
  • CuPc copper phthalocyanine
  • HIL hole mjec ⁇ on layer
  • ⁇ -NPD 4,4 ' - bis[N-(l-naphthyl)-N-phenylamino]biphenyl
  • HTL hole fransporting layer
  • mCP N,N'-dicarbazolyl-3,5-benzene
  • the ETL2 is 400 A of alummum( ⁇ i)bis(2-methyl-8-quinolinato)4- phenylphenolate (BAlq). There was no ETL1.
  • Comparative example 2 [00140] In the unlinked comparative example, the organic stack consisted of 100 A thick of copper ph alocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l - naphthyl)-N-phenylamino]biphenyl ( -NPD), as the hole fransporting layer (HTL), 300 A of N,N'-dicarbazolyl-3,5-benzene (mCP) doped with 6 wt% of Ir(4,6-F 2 ppy) 3 as the emissive layer (EML).
  • CuPc copper ph alocyanine
  • HIL hole injection layer
  • HTL hole -NPD
  • HTL hole fransporting layer
  • mCP N,N'-
  • the ETL2 is 400 A of aluminum(m)bis(2-methyl-8-quinolinato)4- phenylphenolate (BAlq). There was no ETL1.
  • Devices were fabricated similarly to those in Example 4. The current- voltage plot, external quantum efficiency vs current density, elecfroluminescence spectra, and room temperature operational stability (constant current of 5 mA/cm 2 ) in terms of normalized elecfroluminescence vs time of the Dopant Q device and Comparative Example 2 [Ir(4,6- F ppy) 3 ] are shown in Figure 12, Figure 13, Figure 14 and Figurel5 respectively.
  • the efficiency of the devices containing the ligand-linked complex (Dopant Q) is lower than that of the unlinked analog Comparative Example 2 [Ir(4,6-F 2 ppy) 3 ].
  • the operational stability the devices containing the Hgand-linked complex (Dopant Q) is similar to that of the unlinked analog Comparative Example 2 [Ir(4,6-F 2 ppy) 3 ]. In this case, there is very little or no improvement in lifetime between devices containing the linked and unlinked complexes.
  • devices containing the Hnked versions of the Ir(ppy)3 type complex clearly exhibit enhanced stability compared to the unlinked Ir(ppy) 3 .
  • the lack of improvement in the Ir(4,6-F 2 ⁇ py) 3 type complex may be due to the electrochemical instability of fluorine substituents, which perhaps results in ligand degradation due to the reductive elimination of fluorine upon device operation.
  • the enhanced chelating effect of the ligand to the metal center which is believed to improve the stability of the complex may not have a significant effect in such a degradation mechanism.
  • a further possibility is that the degradation mechanism occurs primarily through the cleavage of the Ir-C bond.
  • Dopant M where the Hgands are linked through the phenyl ring, are more stable than devices using dopant F, with ligands Hnked through the pyridine ring.
  • linking the ligands through the pyridine rings may not show a significant improvement in stability for high energy dopants substituted with fluorine, such as Dopant Q.

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Abstract

The present invention relates to an organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a phosphorescent organometallic emissive material comprising a metal bound or two or three bidentate ligands, wherein two or more of the bidentate ligands are covalently linked by one or more linking groups.

Description

OLEDS UTILIZING MULTIDENTATE LIGAND SYSTEMS
Reference to Related Application [0001] This application is a continuation-in-part of co-pending U.S. application serial number 10/771,423 filed February 3, 2004.
Field of the Invention [0002] The present invention relates to efficient organic light emitting devices (OLEDs), and more specifically to phosphorescent organic materials used in such devices. More specifically, the present invention relates to phosphorescent emitting materials with improved stability and efficiency when incorporated into an OLED
Background [0003] Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices axe relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic pho'todetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants. [0004] As used herein, the term "organic" includes polymeric materials as well as small molecule organic materials hat may be used to fabricate organic opto-electronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a "small molecule," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules. [0005] OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Patent Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety. [0006] OLED devices are generally (but not always) intended to emit light through at least one of the electrodes, and one or more transparent electrodes may be useful in organic opto-εlectronic devices. For example, a transparent electrode material, such as indium tin oxide (ITO), may be used as the bottom electrode. A transparent top electrode, such as disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, may also be used. For a device intended to emit light only through the bottom electrode, the top electrode does not need to be transparent, and may be comprised of a thick and reflective metal layer having a high electrical conductivity. Similarly, for a device intended to emit' light only through the top electrode, the bottom electrode may be opaque and / or reflective. Where an electrode does not need to be transparent, using a thicker layer may provide better conductivity, and using a reflective electrode may increase the amount of light emitted through the other electrode, by reflecting light back towards the transparent electrode. Fully transparent devices may also be fabricated, where both electrodes are transparent. Side emitting OLEDs may also be fabricated, and one or both electrodes may be opaque or reflective in such devices.
[0007] As used herein, "top" means furthest away from the substrate, while "bottom" means closest to the substrate. For example, for a device having two electrodes, the bottom electrode is the electrode closest to the substrate, and is generally the first electrode fabricated. The bottom electrode has two surfaces, a bottom surface closest to the substrate, and a top surface further away from the substrate. Where a first layer is described as "disposed over" a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is "in physical contact with" the second layer. For example, a cathode may be described as "disposed over" an anode, even though there are various organic layers in between. [0008] As used herein, "solution processible" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form. [0009] Industry standards call for the lifetime of full color displays to be at least about 5000 hours. In addition, high stability and efficiency are important characteristics of high quality displays. These requirements have helped generate a need for materials that exhibit longer lifetimes, higher stability, and higher efficiency than have been generally achieved in .the prior art.
Summary of the Invention [0010] The present invention provides an organic light emitting device that has an anode, a cathode and one or more organic layers between the anode and the cathode. The present invention also provides materials having improved stability for use in an OLED. The materials are metal complexes comprising a multidentate ligand system. [0011] . In one embodiment, the organic layer comprises an emissive layer comprising an emissive material which is a phosphorescent organometallic emissive material. The phosphorescent emissive material comprises a metal bound to two or more ligands wherein at least one ligand is a photoactive ligand and a wherein two or more of the ligands are covalentiy linked by one or more hhking groups. Preferably, the phosphorescent emissive material comprises a transition metal bound to two or three bidentate ligands, wherein two or more of the bidentate ligands are covalentiy linked by one or more linking groups. Preferred emissive materials of the present invention may be represented by the formula I [Xa-(L)b]M (T) wherein M is a metal, L is a bidentate ligand, X is a linking group that links two or more L, a is 1 to 4, and ό is 2 or 3. The bidentate ligands are selected from bidentate photoactive ligands, and bidentate ancillary ligands. The emissive materials comprise at least one bidentate photoactive ligand. [0012] In one embodiment, the device has an emissive layer comprising an emissive material which is a phosphorescent organometallic emissive material. The phosphorescent organometallic emissive material comprises a transition metal, and two or three bidentate ligands, wherein two or more of the bidentate ligands are covalentiy linked by a linking group. The bidentate ligands are selected from (i) bidentate photoactive ligands, wherein each bidentate photoactive ligand is bound to the transition metal through a carbon-metal bond and a nitrogen-metal bond to form a cyclometallated ring, and (ii) bidentate ancillary ligands, wherein at least one of the ligands is a bidentate photoactive ligand. [0013] In one embodiment, the invention provides an organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal complex having a first ligand, which is a bidentate ligand, a second ligand, and a linking group that covalentiy links the first ligand and the second ligand. The linking group does not provide π-conjugation between the first ligand and the second ligand. The non-conjugated linking group may comprise at least one atom in the linkage which contains no π-electrons, such as an sp3 hybridized carbon or silicon. The second ligand may be a bidentate ligand or may be a monodentate ligand. The metal complex may further comprises an additional monodentate or bidentate ligand. The additional ligand may also be linked to the first ligand, to second ligand, or to both the first ligand and the second ligand.
[0014] In another embodiment, the invention provides an organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises an emissive material having the formula I [Xfl-(L)έ]M (I) wherein, M is a transition metal having a molecular weight greater than 40; X is a linking group that links two or more L, and is selected from the group consisting of - CR.2)d-> -[O(CR2)e]0-3 or a group having the formula A A-B^A or A-B2-A wherein A is -(CR2)Λ or -Z-(CR2V; Z is -O-, -NR-, or -SiR2-; B1 is -O-, -NR-, -CR=CR-, aryl, heteroaryl, cycloalkyl, or a heterocyclic group, B 9 is — N i — , — C i R— , alkyl, aryl, heteroaryl, cycloalkyl, or a heterocyclic group; each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, d is 1 to 6, e is 1 to 6, /is 1 to 4, and g is 1 to 4;
L is a bidentate ligand selected from the group consisting of (i) bidentate photoactive ligands having the formula II 4
R2/^C (ll) wherein Y is N or C, the dotted line represents an optional double bond, R1, R2, R3 and R4 are independently selected from H, alkyl, or aryl, and additionally or alternatively, one or more of R and R , R and R , and R and R together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cyclohetero alkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents Z; each substituent Z is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two Z groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, and each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl. (ii) bidentate ancillary ligands, a is 1 to 4; b is 2 or 3; and at least one L is selected from a bidentate photoactive ligand.
[0015] In another embodiment, the invention provides an organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a material of the formula Nil
Figure imgf000007_0001
wherein Q is a bidentate ligand of the formula VIII
Figure imgf000007_0002
wherein ring B is a 5- or 6-membered aromatic group, ring C is a 5- or 6-membered aromatic heterocyclic ring with at least one nitrogen atom that coordinates to the Al, each R7 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CΝ, CF3, ΝR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R7 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic ' group, each R8 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R8 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, x is 0 to 3, and is 0 to 3; J is selected from monodentate ligands having the formula
Figure imgf000008_0001
wherein eachR9 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NO2, O-alkyl, halo, and aryl, and z is 0 to 5; X is a linking group as defined for Formula I that links two or more of the ligands Q or J ■ wherein at least one of the ligands linked by the linking group X is a bidentate ligand Q; h is 2 or 3; i is 1 to 4; and j is 0 to 2.
Brief Description of the Drawings [0016] Figure 1 shows an organic light emitting device having separate electron transport, hole transport, and emissive layers, as well as other layers. [0017] Figure 2 shows an inverted organic light emitting device that does not have a separate electron transport layer. ' [0018] Figure 3 shows the plot of current vs voltage for the device having the structure ITO/CuPc(100A)/NPD(300A)/CBP:dopant F/BAlq(100A)/Alq3(400A)/LiF(10A)/Al(1000A) in which the hexadentate emissive dopant, Dopant F, is doped into the CBP host at 4.5%, 6% and 9%. [0019] Figure 4 shows the plot of external quantum efficiency vs current density for the device having the structure ITO/CuPc(l OθA)/NPD(30θA)/CBP:dopant F/BAlq(l OOA) / Alq3(40θA) /LiF(lθA)/Al(100θA) in which the hexadentate emissive dopant, Dopant F, is doped into the CBP host at 4.5%, 6% and 9%. [0020] Figure 5 shows the plot of liuninous efficiency vs luminance for the device having the structure ITO/CuPc(10θA)/NPD(30θA)/CBP:dopant F/BAlq(10θA) / Alq3(40θA) /LiF(lθA)/Al(100θA) in which the hexadentate emissive dopant, Dopant F, is doped into the CBP host at 4.5%, 6% and 9%. [0021] Figure 6 -shows the luminescent spectra for the devices having the structures (i) ITO/CuPc(10θA)/NPD(30θA)/CBP:dopant F (9%, 30θA)/BAlq(10θA)/Alq3(40θA) /LiF(lθA)/ Al(lOOθA), (ii) rTO/CuPc(100A)/NPD(300A)/CBP:dopant F(4.5%, 30θA)/BAlq(10θA)/Alq(400 A)/LiF(lθA)/Al(l 000 A), and (iii) ITO/CuPc(10θA)/NPD(30θA)/CBP:dopant F(6%, 30θA)/ B Alq(l OθA)/Alq(40θA)/LiF(l θA)/Al(l OOOA). [0022] Figure 7 shows the normalized luminance vs time for the devices having the structures ITO/CuPc(10θA)/NPD(30θA)/CBP:dopant F(4.5%, 30θA)/BAlq(10θA)/Alq(400 A)/LiF(5A)/Al(100θA) and ITO/CuPc(10θA)/NPD(30θA)/CBP:Ir ppy)3(6%, 300A)/BAlq(l OθA)/Alq(400 A)/LiF(l θA)/Al(l OOOA). [0023] Figure 8 shows the plot of current vs voltage(log scale) for devices having the structure ITO/CuPc(10θA)/NPD(30θA)/CBP: dopant (4.5%, 30θA) /BAlq(l OθA)/Alq3(40θA)/LiF(l θA)/Al(l OOOA) in which 2 hexadentate linked emissive dopants, Dopant F and Dopant M ,and unlinked dopant Ir ppy)3 doped into the CBP host at 4.5%, are compared. [0024] Figure 9 shows the plot of external quantum efficiency vs current density for devices having the structure ITO/CuPc(10θA)/NPD(30θA)/CBP: dopant (4.5%, 300A)
/BAlq(10θA) / Alq3(400A) /LiF(lθA)/Al(100θA) in which 2 hexadentate linked emissive dopants, Dopant F and Dopant M ,and unlinked dopant Ir ppy)3 doped into the CBP host at
4.5%, are compared. [0025] Figure 10 shows the luminescent spectra for devices having the structures (i)
ITO/CuPc(10θA)/NPD(30θA)/CBP: dopant F(4.5%, 30θA) /BAlq(lOθA) / Alq3(40θA)
/LiF(lθA)/Al(100θA), (ii) ITO/CuPc(100A)/NPD(300A)/CBP: dopant M(4.5%, 30θA) BAlq(lOθA) / Alq3(400A) /LiF(lθA)/Al(100θA) and (iii) ITO/CuPc(10θA)/NPD(30θA)/CBP: fr(ppy)3 (4.5%, 300A) /BAlq(lOθA) / Alq3(40θA) /LiF(lθA)/Al(100θA)
[0026] Figure 11 shows the normalized luminance vs time for devices having the stracture ITO/CuPc(100A)/NPD(300A)/CBP: dopant (4.5%, 30θA) /BAlq(lOθA) / Alq3(40θA)
/LiF(lθA)/Al(100θA) in which 2 hexadentate linked emissive dopants, Dopant F and Dopant
M .and unlinked dopant Ir ppy)3 doped into the CBP host at 4.5%, are compared when driven at a constant current of 40 mA/cmP [0027] Figure 12 shows the plot of current vs voltage(log scale) for devices having the structures ITO/CuPc(10θA)/NPD(30θA)/mCP:Dopant Q (6%, 30θA)/BAlq(40θA)/LiF(lθA)/Al(100θA) and ITO/CuPc(10θA)/NPD(30θA)/ mCP:Ir(4,6- F2Ppy)s (6%, 30θA)/BAlq(40θA)/LiF(lθA)/Al(100θA). [0028] Figure 13 shows the plot of external quantum efficiency vs current density for devices having the structures ITO/CuPc(10θA)/NPD(30θA)/mCP:Dopant Q (6%, 3 OθA) BAlq(40θA)/LiF(l θA)/Al(l OOOA) and ITO/CuPc(l OθA)/NPD(30θA)/mCP :Ir(4,6- F2ppy)3 (6%, 300A)/BAlq(400A)/LiF(10A)/Al(1000A). [0029] Figure 14 shows the luminescent spectra for devices having the structures ITO/CuPc(10θA)/NPD(30θA)/mCP:Dopant Q (6%, 30θA)/BAlq(40θA)/LiF(lθA)/Al(100θA) and ITO/CuPc(100A)/NPD(300A)/mCP:Ir(4,6-F2ppy)3 (6%, 3 OOAVB Alq(40θA)/LiF(l θA)/Al(l OOOA). [0030] Figure 15 shows the normalized luminance vs time for devices having the structure ITO/CuPc(10θA) PD(30θA)/mCP:Dopant Q (6%, 30θA)/BAlq(40θA)/LiF(lθA)/Al(100θA) and ITO/CuPc(10θA)/NPD(30θA)/mCP:Ir(4,6-F2ppy)3 (6%, 30θA)/BAlq(40θA)/LiF(l θA)/Al(l OOOA).
Detailed Description [0031] The present invention provides an organic light emitting device that has an anode, a cathode and one or more organic layers between the anode and the cathode. The present invention also provides materials having improved stability for use in an OLED. The materials are metal complexes comprising a multidentate ligand system. By linking individual ligands together to form a multidentate ligand system, it is possible to increase the stability of the metal complexes formed using the ligands. In one embodiment, the device has an emissive layer comprising an emissive material which is a phosphorescent organometallic emissive material. Previously used phosphorescent emissive materials, such as Ir(ppy)3, use individual bidentate Hgands. The phosphorescent emissive material in the present invention is composed of a heavy metal atom and a multidentate ligand system such as a tetradentate or hexadentate ligand system formed, for example, by hnking bidentate ligands. [0032] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an "exciton," which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non- radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable. [0033] The initial OLEDs used emissive molecules that emitted light from their singlet states ("fluorescence") as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds. [0034] More recently, OLEDs having emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. Baldo et al., 'Ηighly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-ϋ"), which are incorporated by reference in their entireties. Phosphorescence may be referred to as a "forbidden" transition because the transition requires a change in spin states, and quantum mechanics indicates that such a transition is not favored. As a result, phosphorescence generally occurs in a time frame exceeding at least 10 nanoseconds, and typically greater than 100 nanoseconds. If the natural radiative lifetime of phosphorescence is too long, triplets may decay by a non-radiative mechanism, such that no light is emitted. Organic phosphorescence is also often observed in molecules containing heteroatoms with unshared pairs of electrons at very low temperatures. 2,2'-bipyridine is such a molecule. Non-radiative decay mechanisms are typically temperature dependent, such that a material that exhibits phosphorescence at liquid nitrogen temperatures may not exhibit phosphorescence at room temperature. But, as demonstrated by Baldo, this problem may be addressed by selecting phosphorescent compounds that do phosphoresce at room temperature.
[0035] Generally, the excitons in an OLED are believed to be created in a ratio of about
3:1, i.e., approximately 75% triplets and 25% singlets. See, Adachi et al., "Nearly 100% Internal Phosphorescent Efficiency In An Organic Light Emitting Device," J. Appl. Phys., 90, 5048 (2001), which is incorporated by reference in its entirety. In many cases, singlet excitons may readily transfer their energy to triplet excited states via "intersystem crossing," whereas triplet excitons may not readily transfer their energy to singlet excited states. As a result, 100% internal quantum efficiency is theoretically possible with phosphorescent OLEDs. In a fluorescent device, the energy of triplet excitons is generally lost to radiationless decay processes that heat-up the device, resulting in much lower internal quantum efficiencies. OLEDs utihzing phosphorescent materials that emit from triplet excited states are disclosed, for example, in U.S. Patent No. 6,303,238, which is incorporated by reference in its entirety. [0036] Phosphorescence may be preceded by a transition from a triplet excited state to an intermediate non-triplet state from which the emissive decay occurs. For example, organic molecules coordinated to lanthanide elements often phosphoresce from excited states localized on the lanthanide metal. However, such materials do not phosphoresce directly from a triplet excited state but instead emit from an atomic excited state centered on the lanthanide metal ion. The europium diketonate complexes illustrate one group of these types of species. [0037] Phosphorescence from triplets can be enhanced over fluorescence by confining, preferably through bonding, the organic molecule in close proximity to an atom of high atomic number. This phenomenon, called the heavy atom effect, is created by a mechanism known as spin-orbit coupling. Such a phosphorescent transition may be observed from an excited metal-to-ligand charge transfer (MLCT) state of an organometallic molecule such as tris(2-phenylpyridine)iridium(III). [0038] As used herein, the term "triplet energy" refers to an energy corresponding to the highest energy feature discernable in the phosphorescence spectrum of a given material. The highest energy feature is not necessarily the peak having the greatest intensity in the phosphorescence spectrum, and could, for example, be a local maximum of a clear shoulder on the high energy side of such a peak
[0039] The term "organometallic" as used herein is as generally understood by one of ordinary skill in the art and as given, for example, in "Inorganic Chemistry" (2nd Edition) by Gary L. Miessler and Donald A. Tarr, Pentice-Hall (1998). Thus, the term organometallic refers to compounds which have an organic group bonded to a metal through a carbon-metal bond. This class does not include per se coordination compounds, which are substances having only donor bonds from heteroatons, such as metal complexes of anines, halides, pseudohalides (CN, etc.), and the like. In practice organometallic compounds generally comprise, in addition to one or more carbon-metal bonds to an organic species, one or more donor bonds from a heteroatom. The carbon-metal bond to an organic species refers to a direct bond between a metal and a carbon atom of an organic group, such as phenyl, alkyl, alkenyl, etc., but does not refer to a metal bond to an "inorganic carbon," such as the carbon of CN. [0040] Figure 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 160. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. [0041] Substrate 110 may be any suitable substrate that provides desired structural properties. Substrate 110 may be flexible or rigid. Substrate 110 may be transparent, translucent or opaque. Plastic and glass are examples of preferred rigid substrate materials. Plastic and metal foils are examples of preferred flexible substrate materials. Substrate 110 may be a semiconductor material in order to facilitate the fabrication of circuitry. For example, substrate 110 may be a silicon wafer upon which circuits are fabricated, capable of controlling OLEDs subsequently deposited on the substrate. Other substrates may be used. The material and thickness of substrate 110 may be chosen to obtain desired structural and optical properties. [0042] Anode 115 may be any suitable anode that is sufficiently conductive to transport holes to the organic layers. The material of anode 115 preferably has a work function higher than about 4 eV (a "high work function material"). Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. Anode 115 (and substrate 110) may be sufficiently transparent to create a bottom-emitting device. A preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate). A flexible and transparent substrate-anode combination is disclosed in United States Patent No. 5,844,363, which is incorporated by reference in its entirety. Anode 115 may be opaque and / or reflective. A reflective anode 115 may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. The material and thickness of anode 115 may be chosen to obtain desired conductive and optical properties. Where anode 115 is transparent, there may be a range of thickness for a particular material that is thick enough to provide the desired conductivity, yet thin enough to provide the desired degree of transparency. Other anode materials and structures may be used. [0043] Hole transport layer 125 may include a material capable of fransporting holes. Hole transport layer 130 may be mtrinsic (undoped), or doped. Doping may be used to enhance conductivity. α-NPD and TPD are examples of intrinsic hole transport layers. An example of a p-doped hole transport layer is m-MTDATA doped with F -TCNQ at a molar ratio of 50:1, as disclosed in United States Patent Application No. 10/173,682 to Forrest et al., which is incorporated by reference in its entirety. Other hole transport layers may be used. [0044] Emissive layer 135 comprises an organic dopant material capable of emitting light when a current is passed between anode 115 and cathode 160. Preferably, emissive layer 135 contains a phosphorescent emissive material, although fluorescent emissive materials may also be used. Phosphorescent materials are preferred because of the higher luminescent efficiencies associated with such materials. Emissive layer 135 may also comprise a host material. The host material may be capable of fransporting electrons and / or holes, and is doped with the emissive material that may trap electrons, holes, and / or excitons, such that excitons relax from the emissive material via a photoemissive mechanism. Emissive layer 135 may comprise a single material that combines transport and emissive properties. Whether the emissive material is a dopant or a major constituent, emissive layer 135 may comprise other materials, such as dopants that tune the emission of the emissive material. Emissive layer 135 may include a plurality of emissive materials capable of, in combination, emitting a desired spectrum of light. Examples of fluorescent emissive materials include DCM and DMQ . Examples of host materials include Alq3, CBP and mCP. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. Emissive material may be included in emissive layer 135 in a number of ways. For example, an emissive small molecule may be incorporated into a polymer. Other emissive layer materials and structures may be used. [0045] Electron transport layer 140 may include a material capable of transporting electrons. Electron transport layer 140 may be mtrinsic (undoped), or doped. Doping may be used to enhance conductivity. Alq3 is an example of an intrinsic electron transport layer. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1 : 1 , as disclosed in United States Patent Application Publication No. 2002-0071963 Al to Forrest et al., which is incorporated by reference in its entirety. Other electron transport layers may be used. [0046] The charge carrying component of the electron transport layer may be selected such that electrons can be efficiently injected from the cathode into the LUMO (Lowest Unoccupied Molecular Orbital) level of the electron transport layer. The "charge carrying component" is the material responsible for the LUMO that actually transports electrons. This component may be the base material, or it may be a dopant. The LUMO level of an organic material may be generally characterized by the electron affinity of that material and the relative electron injection efficiently of a cathode may be generally characterized in terms of the work function of the cathode material. This means that the preferred properties of an electron transport layer and the adjacent cathode may be specified in terms of the electron affinity of the charge carrying component of the ETL and the work function of the cathode material. In particular, so as to achieve high electron injection efficiency, the work function of the cathode material is preferably not greater than the electron affinity of the charge carrying component of the electron transport layer by more than about 0.75 eV, more preferably, by not more than about 0.5 eV. Similar considerations apply to any layer into which electrons are being injected. [0047] Cathode 160 may be any suitable material or combination of materials known to the art, such that cathode 160 is capable of conducting electrons and injecting them into the organic layers of device 100. Cathode 160 may be transparent or opaque, and may be reflective. Metals and metal oxides are examples of suitable cathode materials. Cathode 160 may be a single layer, or may have a compound structure. Figure 1 shows a compound cathode 160 having a thin metal layer 162 and a thicker conductive metal oxide layer 164. In a compound cathode, preferred materials for the thicker layer 164 include ITO, IZO, and other materials known to the art. U.S. Patent Nos. 5,703,436, 5,707,745, 6,548,956 B2, and 6,576,134 B2, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The part of cathode 160 that is in contact with the underlying organic layer, whether it is a single layer cathode 160, the thin metal layer 162 of a compound cathode, or some other part, is preferably made of a material having a work function lower than about 4 eN (a "low work function material"). Other cathode materials and structures may be used. [0048] Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and / or excitons that leave the emissive layer. An electron blocking layer 130 may be disposed between emissive layer 135 and the hole transport layer 125, to block electrons from leaving emissive layer 135 in the direction of hole transport layer 125. Similarly, a hole blocking layer 140 may be disposed between emissive layerl35 and electron transport layer 145, to block holes from leaving emissive layer 135 in the direction of electron transport layer 140. Blocking layers may also be used to block excitons from diffusing out of the emissive layer. The theory and use of blocking layers is described in more detail in United States Patent No. 6,097,147 and United States Patent Application Publication No. 2002-0071963 Al to Forrest et al., which are incorporated by reference in their entireties. [0049] As used herein, the term "blocking layer" means that the layer provides a barrier that significantly inhibits transport of charge carriers and/or excitons through the device, without suggesting that the layer necessarily completely blocks the charge carriers and/or excitons. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. [0050] Generally, injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or an organic layer, into an adjacent organic layer. Injection layers may also perform a charge transport function. In device 100, hole injection layer 120 may be any layer that improves the injection of holes from anode 115 into hole transport layer 125. CuPc is an example of a material that may be used as a hole injection layer from an ITO anode 115, and other anodes. In device 100, electron injection layer 150 may be any layer that improves the injection of electrons into electron transport layer 145. LiF / Al is an example of a material that may be used as an electron injection layer into an electron transport layer from an adjacent layer. Other materials or combinations of materials may be used for injection layers. Depending upon the configuration of a particular device, injection layers may be disposed at locations different than those shown in device 100. More examples of injection layers are provided in U.S. Patent Application Serial No. 09/931,948 to Lu et al., which is incorporated by reference in its entirety. A hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, e.g., PEDOT:PSS, or it may be a vapor deposited small molecule material, e.g., CuPc or MTDATA. [0051] A hole injection layer (HIL) may planarize or wet the anode surface so as to provide efficient hole injection from the anode into the hole injecting material. A hole injection layer may also have a charge carrying component having HOMO (Highest Occupied Molecular Orbital) energy levels that favorably match up, as defined by their herein-described relative ionization potential (IP) energies, with the adjacent anode layer on one side of the HIL and the hole transporting layer on the opposite side of the HIL. The "charge carrying component" is the material responsible for the HOMO that actually transports holes. This component may be the base material of the HIL, or it may be a dopant. Using a doped HIL allows the dopant to be selected for its electrical properties, and the host to be selected for morphological properties such as wetting, flexibility, toughness, etc. Preferred properties for the HIL material are such that holes can be efficiently injected from the anode into the HIL material. In particular, the charge carrying component of the HIL preferably has an IP not more than about 0.7 eV greater that the LP of the anode material. More preferably, the charge carrying component has an LP not more than about 0.5 eV greater than the anode material. Similar considerations apply to any layer into which holes are being injected. HIL materials are further distinguished from conventional hole fransporting materials that are typically used in the hole transporting layer of an OLED in that such HIL materials may have a hole conductivity that is substantially less than the hole conductivity of conventional hole fransporting materials. The thickness of the HIL of the present invention may be thick enough to help planarize or wet the surface of the anode layer. For example, an HIL thickness of as little as 10 nm maybe acceptable for a very smooth anode surface. However, since anode surfaces tend to be very rough, a thickness for the HIL of up to 50 nm may be desired in some cases.
[0052] A protective layer may be used to protect underlying layers during subsequent fabrication processes. For example, the processes used to fabricate metal or metal oxide top electrodes may damage organic layers, and a protective layer may be used to reduce or eliminate such damage. In device 100, protective layer 155 may reduce damage to underlying organic layers during the fabrication of cathode 160. Preferably, a protective layer has a high carrier mobility for the type of carrier that it transports (electrons in device 100), such that it does not significantly increase the operating voltage of device 100. CuPc, BCP, and various metal phthalocyanines are examples of materials that may be used in protective layers. Other materials or combinations of materials may be used. The thickness of protective layer 155 is preferably thick enough that there is little or no damage to underlying layers due to fabrication processes that occur after organic protective layer 160 is deposited, yet not so thick as to significantly increase the operating voltage of device 100. Protective layer 155 may be doped to increase its conductivity. For example, a CuPc or BCP protective layer 160 may be doped with Li. A more detailed description of protective layers may be found in U.S. Patent Application Serial No. 09/931,948 to Lu et al., which is incorporated by reference in its entirety. [0053] Figure 2 shows an inverted OLED 200. The device includes a substrate 210, an cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. Figure 2 provides one example of how some layers may be omitted from the structure of device 100. [0054] The simple layered structure illustrated in Figures 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the la3'ers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to Figures 1 and 2. [0055] Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190, Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Patent No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in Figures 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties. [0056] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Patent No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Patent Application No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and ONJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing. [0057] Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C to 30 degrees C, and more preferably at room temperature (20 - 25 degrees C). [0058] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures. [0059] In one embodiment of the invention, the emissive materials are phosphorescent organometallic emissive materials. The phosphorescent emissive material is composed of a heavy metal atom and a multidentate, for example a tefradentate or hexadentate ligand system. By linking two or three bidentate ligands together to give tefradentate or hexadentate ligand systems, it is possible to increase the stability of the metal complexes formed using the ligands. [0060] The phosphorescent emissive material comprises a transition metal bound to two or three bidentate ligands, wherein two or more of the bidentate ligands are covalentiy linked by one or more linking groups. The emissive materials of the present invention may be represented by the formula I K L M (I) wherein M is a metal, L is a bidentate Hgand, X is a linking group that Hnks two or more L, a is 1 to 4, and b is 2 or 3. The bidentate ligands are selected from bidentate photoactive ligands, and bidentate ancillary ligands. The emissive materials comprise at least one bidentate photoactive ligand. [0061] The metal, M, is selected from the transition metals having an atomic weight greater than 40. Preferred metals include Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag. More preferably, the metal is Ir or Pt. Most preferably, the metal is Ir. [0062] The emissive materials of the present invention may comprise carbene-metal complexes including those disclosed in the application entitled "Luminescent Compounds with Carbene Ligands," filed May 18, 2004, by Thompson et al., U.S. Application No. (not yet assigned), which is incorporated in its entirety by reference, wherein a carbene ligand is preferably linked to another ligand by a hnking group. [0063] The emissive materials of the present invention comprise at least one photoactive ligand. This ligand is referred to as "photoactive" because it is believed that it contributes to the photoactive properties of the emissive material. [0064] In one embodiment of the invention, a photoactive ligand may be represented by the formula II R4 R3 -
R2/^C R1 (ID wherein
Y is N or C, the dotted line represents an optional double bond,
'"R1, R2, R3 and R4 are independently selected from H, alkyl, .or aryl, and additionally or alternatively, one or more of R and R , R and R , and R and R together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cycHc group is optionally substituted by one or more substituents Z; each substituent Z is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR , NO2, OR, halo, and aryl, and additionally, or alternatively, two Z groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, and each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl.
[0065] The photoactive ligand of the formula II is a bidentate ligand that is bound to the transition metal through a carbon-metal bond and a nitrogen-metal bond to form a cyclometallated ring as shown in the partial structure III
Figure imgf000022_0001
wherein Y, M, R1, R2, R3 and R4 are as described above for formula II.
[0066] In a preferred embodiment, at least one of R1 and R2 or R3 and R4 together form a 5 or 6-membered aryl ring. In a more preferred embodiment, both R1 and R2 together form a 5 or 6-membered aryl ring, and R3 and R4 together from a 5 or 6-member aryl ring. [0067] In a further embodiment, R1 and R2 together form a phenyl ring, and R3 and R4 together form a heteroaryl group to give a bidentate photoactive ligand of the formula IV
Figure imgf000022_0002
wherein: ring A is an aromatic heterocyclic ring or a fused aromatic heterocyclic ring with at least one nitrogen atom that coordinates to the metal M, Y is selected from carbon or nitrogen, each R5 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, N02, OR, halo, and aryl, and additionally, or alternatively, two R5 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from the group consisting of alkyl, alkenj , alkynyl, aralkyl, CN, CF3, NR2, N02, OR, halo, and aryl, and additionally, or alternatively, two R6 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, n is 0 to 4, and m is 0 to 4.
[0068] Ring A in formula IN is an aromatic heterocycHc ring or a fused aromatic heterocyclic ring with at least one nitrogen atom that is coordinated to the metal M, wherein the ring can be optionally substituted. In a preferred embodiment, A is pyridine, pyrimidine, quinoline, or isoquinoline. Most preferable, A is pyridine. Optional substituents on the Ring A include of alkyl, alkenyl, alkynyl, aralkyl, CΝ, CF3, ΝR2, NO2, OR, halo, and aryl. A particularly preferred photoactive ligand is phenylpyridine, and derivatives thereof. [0069] The number of photoactive ligands may be any integer from 1 to the maximum number of ligands that may be attached to the metal. For example, for Ir the maximum number of bidentate ligands bound to the metal would 3, at least one of which would be a photoactive ligand. When more that one photoactive ligand is present, each photoactive ligand may be the same or may be different. [0070] The emissive materials of the present invention may comprise one or more ancillary ligands. These ligands are referred to as "ancillary" because it is believed that they may modify the photoactive properties of the molecule, as opposed to directly contributing to the photoactive properties. The definitions of photoactive and ancillary are intended as non-limiting theories. Ancillary ligands for use in the emissive material may be selected from those known in the art. Non-limiting examples of ancillary ligands may be found in PCT Application Publication WO 02/15645 Al to Lamansky et al. at pages 89-90, which is incorporated herein by reference. Preferred ancillary Hgands include acetylacetonate (acac) and picolinate (pic), and derivatives thereof. The preferred ancillary ligands have the foUowing structures:
Figure imgf000023_0001
acac
The number of "ancillary" ligands of a particular type, may be any integer from zero to one less than the maximum number if Hgands that may be attached to the metal. [0071] In one embodiment, the linking group, X, Hnks two bidentate Hgands to give a tefradentate ligand system. The tefradentate Hgand system may be represented by the formula (V) L-X-L (V) wherein each L is independently selected from a bidentate photoactive Hgand and a bidentate ancillary ligand, and X is a linking group. The tefradentate Hgand system may be comprised of two photoactive ligands, two ancillary ligands, or a photoactive ligand and an ancillary ligand. The tefradentate ligand system binds to the metal through four chemical bonds in the emissive material. The emissive material may further comprise an additional bidentate ligand that is not linked to the tefradentate ligand system, and which may be a bidentate ancillary ligand, or a bidentate photoactive ligand. In the case where the tefradentate ligand system is comprised of two ancillary ligands, the emissive material comprising the tefradentate ligand system further comprises a separate photoactive Hgand bound to the metal. The linking group, X, may be connected to each bidentate ligand, L, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligands ability to bind to the metal, M, and form a tefradentate system. For example, the case where the tefradentate ligand system is comprised of two phenylpyridine Hgands linked by a linking group, X, is depicted below:
Figure imgf000024_0001
The linking group may be covalentiy bound to any atom of the phenylpyridine that does not interfere with each ligand's ability to bind to the metal in a bidentate fashion to form a terra dentate Hgand system. Thus, for example, the linking group may not be bound to the pyridine nitrogen.
[0072] In another embodiment of the invention, the emissive material comprises a hexadentate ligand system. The linking group may link two tridentate Hgands or three bidentate ligands or a bidentate and a tefradentate Hgand to form a hexadentate Hgand system. In one. embodiment, the hexadentate ligand system, comprises one or more Ifriking groups, X, that link three bidentate Hgands. Such hexadentate ligand systems may be represented by the formula
Figure imgf000025_0001
L-X-L I -X-L-X-L L (Nla) (VIb)
wherein each X is independently selected from a linking group, and each L is independently selected from a bidentate photoactive ligand and a bidentate ancillary ligand, with the proviso that at least one L is selected from a bidentate photoactive ligand. The hexadentate ligand system may be comprised of three photoactive ligands, two photoactive ligands and an ancillary ligand, or one photoactive ligand and two anciUary ligands. The hexadentate ligand system binds to the metal through six chemical bonds in the emissive material. The linking group(s), X, may be connected to each bidentate Hgand, L, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligand's ability to bind to the metal, M, and form a hexadentate system. Examples of the case where the hexadentate ligand system is comprised of three phenylpyridine ligands linked by a linking group(s), X, are depicted below:
Figure imgf000025_0002
[0073] In another embodiment, the emissive material comprises a hexadentate ligand system having three phenylpyridine ligands linked by a linking group(s), X, through the phenyl rings as depicted below:
Figure imgf000025_0003
[0074] In another embodiment, the emissive material comprises a hexadentate ligand system having three phenylpyridine ligands linked by a Unking group(s), X, through the pyridine rings as depicted below:
Figure imgf000026_0001
[0075] In other embodiments of the invention, other structures with multidentate ligands can be useful in OLED applications. For example, electron transporters using derivatives of duminum 8-hydroxyquinolates, such as Alq and BAlq, can be ligand-interhnked, preferably by non-conjugated linking groups. Such materials may be used in an OLED as an electron transporting material and/or as a host material in an emissive layer. Linking according to the present invention may improve the stability of devices containing these compounds as compared to devices containing the non-ligand-interlinked analogs. These materials may be represented by the formula VII AltQ^L] (VII)
wherein Q is a bidentate Hgand, J is a monodentate ligand, X is a linking group, h is 2 or 3, i is 1 to 4 andj is 0 to 2. The linking group X links two or more of the Hgands, Q or J, wherein at least one of the ligands linked by the linking group X is a bidentate Hgand Q.
[0076] The compound of formula NLT comprise two or three bidentate ligands, Q, that may be represented by the formula Nm
Figure imgf000027_0001
Nm wherein ring B is a 5- or 6-membered aromatic group, ring C is a 5- or 6-membered aromatic heterocycHc ring with at least one nitrogen atom that coordinates to the metal M, each R is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CΝ, CF3, ΝR2, NO2j OR, halo, and aryl, and additionally, or alternatively, two R7 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R8 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, x is 0 to 3, and y is 0 to 3.
[0077] The bidentate Hgand Q is bound to the aluminum through an oxygen-metal bond and a nitrogen-metal bond to form the partial structure LX
Figure imgf000027_0002
<TX) 7 & wherein R , R . x and y are as described above for formula VTIL [0078] In a preferred embodiment, ring B is a phenyl ring and ring C is a pyridine ring providing a bidentate ligand of formula X
Figure imgf000028_0001
(X)
[0079] The ligand J is selected from monodentate ligands having the formula
Figure imgf000028_0002
wherein each R' is mdependently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NO2, O-alkyl, halo, and aryl, and z is 0 to 5.
[0080] In one embodiment, the linking group, X, links two bidentate Hgands Q to give a tefradentate ligand system. The tefradentate Hgand system may be represented by the formula (XI) Q-X-Q (XI)
Each bidentate ligand Q may be the same or may be different. The complex may further comprise an additional bidentate ligand Q that is not linked to the tefradentate ligand system. Alternatively the complex may further comprise a monodentate ligand J that is not linked to the tefradentate ligand system. The linking group, X, may be connected to each bidentate Hgand, Q, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the Hgan 's ability to bind to the Al, and form a tefradentate system. For example, the case where the tefradentate ligand system is comprised of two 8-hydroxyquinolinato ligands linked by a linking group, X, is depicted below:
Figure imgf000029_0001
[0081] In another embodiment, the linking group, X, links a bidentate ligands Q to a monodentate ligand J to give a tridentate ligand system. The tridentate ligand system may be represented by the formula (XII) Q-X-J (XII)
The complex may further comprise an additional bidentate ligand Q that is not linked to the tridentate ligand system. The linking group, X, may be connected to each ligand in the tridentate ligand system by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligand' s ability to bind to the Al, and form a tridentate system. For example, the case where" the tridentate ligand system is comprised of a 8-hydroxyquinolinato Hgand linked by a linking group, X, to a 4-phenylphenolate ligand is depicted below:
Figure imgf000029_0002
[0082] In another embodiment of the invention, one or more linking groups, X, link three bidentate Hgands Q to give a hexadentate ligand system that may be represented by the formula Xma andXm Q-X- Q Q— X— -X— Q Q (xma) (xmt) wherein each X is independently selected form a linking group, and each bidentate ligand Q may be the same or may be different. The linking group(s), X, may be connected to each bidentate Hgand, Q, by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the Hgand's ability to bind to the Al and form a hexadentate system. Examples of the case where the hexadentate ligand system is comprised of three 8-hyάroxyquinolinato Hgands linked by a linking group(s), X, are depicted below:
Figure imgf000030_0001
[0083] In another embodiment of the invention, one or more linking groups X link two bidentate ligands Q and one monodentate ligand J to give a pentadentate Hgand system that may be represented by the formula XIVa, XLV and XLVC Q— — J Q— X—Q— — J Q— — J— X— Q Q (X Va) (XTVb) (XLVC)
wherein each X is independently selected form a Hn ing group, and each bidentate ligand Q may be the same or may be different. The linking group(s), X, may be connected to each bidentate ligand Q or monodentate Hgand J by a covalent bond to any carbon or heteroatorn of the Hgand that does not interfere with the Hgand's ability to bind to the Al and form a pentadentate system. Examples of the case where the pentadentate ligand system is comprised of two 8-hydroxy- quinolinato Hgands Hnked by a linking group(s), X, to a 4-phenylphenolate ligand are depicted below:
Figure imgf000031_0001
[0084] The compounds of invention may be prepared by methods known in the art. In preferred embodiments, the multidentate Hgand systems are prepared by the metal catalyzed coupling of the linking group to the ligand. See, for example, Beeston et al., Inorg. Chem. 1998, 37, 4368-4379. Metal complexes of the formula VII may be prepared, for example, according to the synthesis provided in Scheme I:
Figure imgf000032_0001
Compound A
Figure imgf000032_0002
Scheme 1: a) NBS, acetic acid; b) Fe, HCI, ethanol c) H2SO4, H2O, 220°C ; d) Pd(PPh3)4, Cul, diisopropyl amine, toluene, 60°C e) cyclohexene, Pd 10% on Carbon, THF; f) aluminum isopropoxide, toluene.
[0085] The materials of the present invention comprise one or more linking groups, X, that Hnks together two or more ligands (L, Q, or J). The linking group, X, may be connected to a ligand by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the Hgands ability to bind to the metal. The linking group may be any group that is covalentiy bound to two or more of the ligands, and which does not interfere with the Hgand's individual abilities to bind to the same metal. Linking groups may include, for example, organic, organometaHic and other metal containing groups. Representative groups suitable for use as a linking group are bivalent and trivalent alkyl groups, aryl groups, silanes, ethers, and polyethers. [0086] The ligands connected by the linking group X may be the same or different. For example the Hnking group, X, may link two tridentate ligands or three bidentate ligands or a bidentate and a tefradentate ligand to form a hexadentate ligand system. In one preferred embodiment, three bidentate ligands are joined by a common linking group X. In another embodiment, three bidentate ligands are each independently connected to a first linking group and a second linking group wherein the first and the second linking group may be the same or different. [0087] In a preferred embodiment, the linking group X provides no π-conjugation between the linked ligands. Having π-conjugation between the linked ligands may change the electronic properties of the Hgands and the resulting metal complexes, such as a red-shift in the luminescence. It is desirable to link the ligands together to without significantly altering the electronic properties of the Hgands and the resulting metal complex. A non-conjugated linking group may comprise at least one atom in the linkage which contains no π-electrons, such as an sp3 hybridized carbon or sihcon. [0088] In one preferred embodiment, the linking group, X, is connected by a covalent bond to a phenyl moiety in a first Hgand and links the first ligand to at least a second ligand via a covalent bond to a phenyl moiety in the second ligand. In a more preferred embodiment, three ligands are linked together by a linking group covalentiy bound to a phenyl moiety on each
Hgand.
[0089] In an alternative embodiment, X is connected by a covalent bond to a pyridyl moiety of a first ligand and connects the first ligand to at least a second ligand via a covalent bond to a pyridyl moiety on the second ligand. In a preferred alternative embodiment, three ligands are linked together by a linking group covalentiy bound to a pyridyl moiety on each Hgand. [0090] In a preferred embodiment of the invention, the Hnking group, X, is selected from the group consisting of -(CR2)r, -[O(CR2)e]O-, or a group having the formula A A-B -A or A-B2-A wherein
Figure imgf000034_0001
Z is -O-, -NR-, or -SiR2-; B1 is -O-, -NR-, -CR=CR-, aryl, heteroaryl, cycloalkyl, or a heterocyclic group, B 2 is — i — , — C i R— , alkyl, aryl, heteroaryl, cycloalkyl, or a heterocyclic group; each R is independentiy selected from H, alkyl, aralkyl, aryl and heteroaryl, d is 1 to 6, e is 1 to 6, fis 1 to 4, and g is 1 to 4.
[0091] It is believed that the metal complexes with multidentate Hgands may have improved chemical, thermochemical, elecfrochemical and photochemical stability compared to the fraditional bidentate ligand analogs. As would be understood by those of skill in the art, the improvement in stability may be attributed, at least in part, to what is known as the "chelate effect" such as described in Inorganic Chemistry (2nd Edition), Gary L. Miessler, Donald A. Tarr (Prentice Hall, 1998) pp 396-397. Linking two or more ligands to one another may render the resulting ligand system less labile than the corresponding non-linked ligands. As indicated in the mass specfroscopy (El, 70 eV) of Dopant F (described herein below), for example, there is no fragmentation of the molecular ion whereas significant fragmentation is observed in Ir(ppy)3.
[0092] It is believed that the metal complexes with multidentate ligands can have increased photoluminescence quantum yields compared to the traditional bidentate ligand analogs because the complexes with multidentate ligands are more rigid, i.e., with decreased vibrational and rotational freedom, which can be pathways for non-radiative decay. [0093] In metal-Hgand complexes, structural isomers may result from the synthesis. For example, in Ir(phenylpyridine)3 type complexes, both facial and meridional isomers can form. Separation of these isomers may be difficult. Through suitable interHnking of the ligands, selective structural isomeric configuration can be achieved. For example, in Dopant F, as the ligands are interlinked through the pyridine rings, the only structural isomer possible is the facial isomer. Similariy, in Dopant M (also described herein below), as the ligands are interlinked through the phenyl rings, the only structural isomer possible is the facial isomer. This can significantly improve the synthesis yield and simplify the purification process.
[0094] The term "halo" or "halogen" as used herein includes fluorine, chlorine, bromine and iodine. [0095] The term "alkyl" as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionaUy substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR. [0096] The term "cycloalkyl" as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. AdditionaUy, the cycloalkyl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic- amino, NO2, and OR. [0097] The term "alkenyl" as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cycHc-amino, NO2, and OR. [0098] The term "alkynyl" as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optional' substituted with one or more substituents selected from halo, CN, C02R, C(0)R, NR2, cyclic-amino, N02, and OR. [0099] The term "aralkyl" as used herein contemplates an alkyl group which has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted on the aryl with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic- amino, NO2, and OR. [00100] The term "heterocyclic group" as used herein contemplates non-aromatic cyclic radicals. Preferred heterocyclic groups are those containing 5 or 6 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tefrahydrofuran, tefrahydropyran, and the like. [00101] The term "aryl" or "aromatic group" as used herein contemplates single- ring aromatic groups (for example, phenyl, pyridyl, pyrazole, etc.) and polycyclic ring systems (naphthyl, quinoline, etc.). The polycyclic rings may have two or more rings in which two atoms are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls. [00102] The term "heteroaryl" as used herein contemplates single-ring hetero- aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls. [00103] All value ranges, for example those given for n and m, are inclusive over the entire range. Thus, for example, a range of 0 to 4 would include the values 0, 1, 2, 3 and 4. [00104] It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. It is understood that various theories as to why the invention works are not intended to be limiting. For example, theories relating to charge transfer are not intended to be limiting. [00105] -Material Definitions: [00106] As used herein, abbreviations refer to materials as follows: CBP: 4,4'-N,N-dicarbazolebiphenyl m-MTDATA 4,4',4"-tris(3-memylphenylphenlyanιino)triphenylamine Alq3: 8-tris-hyάroxyqtιinoline alumhmm Bphen: 4, 7-diphenyl- 1 , 10-phenanthroline n-BPhen: n-doped BPhen (doped with lithium) F4-TCNQ:tefrafluoro-tefracyano-quinodimethane p-MTDATA: p-doped m-MTDATA (doped with F4-TCNQ) Ir(ppy)3: fris(2-phenylpvridine)-iridium Ir(pρz)3: tris(l-phenylpyrazoloto,N,C(2')iridium(iri) BCP: 2,9-dimethyl-4,7-diphenyl- 1 , 10-phenanthroline TAZ: 3 -phenyl-4-(l '-naphthyl)-5-phenyl- 1 ,2,4-triazole CuPc: copper phthalocyanine. ITO: indium tin oxide NPD: N,N'-diphenyl-N-N'-di(l-naphmyl)-beιιzidine TPD: N,N'-diphenyl-N-N'-di(3-toly)-benzidine
BAlq: alum um(III)bis(2-methyl-8-hycfroxyquinolinato)4-phenylphenolate mCP: 1 ,3 -N,N-dicarbazole-benzene
DCM: 4-(dicyanoethylene)-6-(4-dimethylammos1yryl-2-methyl)-4H-pyran
DMQA: N,N'-dimethylquinacridone
PEDOT:PSS : an aqueous dispersion of poly(3,4-ethylenedioxythiophene) with polystyrenesulfonate (PSS)
Ir(4,6-F2ppy)3: tris[2-(4,6-difluorophenyl)pyridme]iridium(III) mCP: 3,5-N,N'-dicarbazolebenzene
EXPERIMENTAL: [00107] Specific representative embodiments of the invention wfll now be described, including how such embodiments may be made. It is understood that the specific methods, materials, conditions, process parameters, apparatus and the like do not necessarily limit the scope of the invention.
[00108] Where available, solvents and reagents were purchased from Aldrich Chemical Company. The reagents were of the highest purity and used as received.
[00109] mCP was prepared by the palladium-catalyzed cross coupling of aryl halides and arylamines. (T. Yamamoto, M. Nishiyama, Y. Koie Tet. Lett., 1998, 39, 2367- 2370).
Example 1 - Synthesis of Dopant F
[00110] Compound A
Figure imgf000038_0001
Approximately 300 mL of 1,2-dimethoxy ethane and 150 mL of distilled water were added to a 1000 mL round bottom flask. To this mixture 25. Og of 2-bromo-5-methyl pyridine, 17.7 g of phenylboronic acid, 0.81 g of palladium (II) acetate, 3.8 g of friphenylphosphine, and 41.5 g of sodium carbonate were added. This mixture was heated to reflux under nitrogen atmosphere for 16 hours. After the reaction was cooled, 200 mL water and 150 mL ethyl acetate were added. The mixture was added to a separatory funnel and the organic and aqueous layers were allowed to separate. The organic layer was then washed with brine and dried over magnesium sulfate. After removal of the solvents by rotary evaporation, the crude mixture was purified by silica get column chromatography using 10% EtOAc/Hexanes as the eluent. The fractions containing the desired product were combined and solvent was removed by rotary evaporation. About 100 mL of hexane was added to the obtained oil and cooled in ice water after which crystaUization occurred. The crystals were isolated by vacuum filfration. Fifteen grams of white sofid was obtained. [00111] Compound C
Figure imgf000039_0001
A mixture of 500 mL of methyl formate, 20.4 g of mesitylene, 100 grams of n- bromosuccimide, and 0.2 g of 2,2'-azobisisobutyronitrile were added to a 1000 mL round bottom flask. This mixture was heated to reflux for 16 hours and then extracted with a saturated solution of sodium bicarbonate twice. The organic layer was then dried over magnesium sulfate and the solvent removed by rotary evaporation. About 300 mL of hexane was added to the resulting oil and heated to reflux until a clear solution was obtained. Cooling to room temperature caused the formation of white crystals that were then vacuum filtered. This crystallization technique was repeated twice more to yield 7 g of white solid. [00112] Compound D
Figure imgf000039_0003
Compound A
Figure imgf000039_0002
Compound D To an oven dried 250 mL round bottom flask, 20 mL of dry tefrahydrofuran and 4.18 g of dusopropylamine were added. This mixture was cooled in an ice bath and 25.9 mL of 1.6M n-butyl Hthium was added drop wise. The mixture was stirred for 30 minutes and then 7.41 g of hexamethylphosphoramide was added drop wise. After stirring for 30 minutes, 7.0 g of compound A in 15 mL of dry tefrahytfrofuran was added drop wise. This mixture was allowed to stir at room temperature for 18 hours. After cooling in a dry ice/acetone bath, 1.85 g of compound C in 15 mL of dry tefrahydrofuran was added drop wise.
58 After stirring for 1 hour the reaction was quenched with water and extracted with ethyl acetate. The organic layer was washed with brine and then dried over magnesium sulfate. Removal of the solvent by rotary evaporation resulted in a brown oil which was purified by siHca gel column chromatography using 40% EtOAc/hexanes as the eluent. The fractions containing the desired product were combined and the solvent removed to yield 1 gram of yellow oil. [00116] Dopant F
+ lrCI3 + AgOCOCF3
Figure imgf000040_0001
Figure imgf000040_0002
To a 250 mL round bottom flask 40 mL 1,2-dichlorobenzene, 2 mL water, 0.9 g of compound D, 0.52 g of IrCl3, and 1.28 g of silver trifluoroacetate were added. This mixture was heated to reflux under nitrogen for 4 hours. After cooling to room temperature, the reaction mixture was passed through a silica gel plug with 50%CH2Cl2/hexanes as the solvent system. The good fractions were combined and the solvent was removed. YeUow crystals were collected from a dichloromethane/methanol mixture. The product was further purified by sublimation. The desired product was confirmed by mass specfroscopy and 1H NMR. λmax (emission) of the compound was 508 nm in diphloromethane.
Example 2 - Synthesis of Dopant G
[00117] Compound B
Pd OQAc TPP. NasCC,
Figure imgf000040_0003
Figure imgf000040_0004
Compound B Approximately 250 mL of 1,2-dimethoxyethane and 100 mL of distilled water were added to a 1000 mL round bottom flask. To this mixture 15.0 g of 2-bromo-5-methyl pyridine, 12.2g of 4-fluorophenylboronic acid, 0.48 g of palladium (II) acetate, 2.3 g of triphenylphosphine and 23.0 g of sodium carbonate were added. This mixture was heated to reflux under nitrogen atmosphere for 16 hours. After the reaction was cooled, 150 mL. water and 150 mL ethyl acetate were added. The mixture was added to a separatory funnel and the organic and aqueous layers were allowed to separate. The organic layer was then washed with brine and dried over magnesium sulfate. After removal of the solvents by rotary evaporation, the crude mixture was purified by silica gel column chromatography using 10% EtOAc/hexanes as the eluent. The fractions containing the desired product were combined and the solvent was removed by rotary evaporation. About 100 mL of hexane was added to the obtained oil and cooled in ice water after which crystallization occurred. The crystals were isolated by vacuum filtration. Ten grams of white soHd was obtained. [00118] Compound E
Figure imgf000041_0002
Compound B
Figure imgf000041_0001
Compound E
To an oven dried 100 mL round bottom flask 10 mL of dry tefrahydrofuran and 0.54 g of diisopropylarnine were added. This mixture was cooled in an ice bath and 3.3 mL of 1.6 M n- butyl lithium was added drop wise. The mixture was stirred for 30 minutes and then 0.95 g of hexamethylphosphoramide were added drop wise. After stirring for 30 minutes, the reaction mixture was cooled to -78°C and then 1.0 g of compound B in 10 mL of dry tefrahydrofuran was added drop wise. After stirring for 4 hours at -78 °C, 1.85 g of compound C in 15 mL of dry tefrahydrofuran was added drop wise. After stirring for 1 hour the reaction was quenched with water and extracted with ethyl acetate. The organic layer was then washed with brine and dried over magnesium sulfate. Removal of the solvent by rotary evaporation resulted in a brown oil which was purified by silica get column chromatography using 30% EtOAc/hexanes as the eluent. The fractions containing the desired product were combined and the solvent removed to yield 0.3 grams of white sohd.
[00119] Dopant G
+ lrCI3 + AgOCOCF3
Figure imgf000042_0002
Compound E
Figure imgf000042_0001
To a 100 mL round flask, 15 mL 1,2-dichlorobenzene, 1 mL water, 0.1 g of compound E, 0.05 g of IrCl3, and 0.13 g of silver trifluoro acetate were added. This mixture was heated to reflux under nitrogen for 5 hours. After cooling to room temperature the reaction mixture was passed through a silica gel plug with 50% MeCl2/hexanes as the eluent. The desired fractions were combined and the solvent removed in vacuo. Yellow crystals were collected from a dichloromethane/methanol mixture. The desired product was confirmed by mass specfroscopy. Emission of the material in dichloromethane gave a λmax at 480 nm.
Example 3 - Synthesis of Dopant H [00120] Dopant H
+ RhCl3 + AgOCOCF3
Figure imgf000043_0002
Compound E
Figure imgf000043_0001
To a 100 mL round bottom flask 15 mL 1,2-dichlorobenzene, 1 mL water, 0.1 g of compound E, 0.04 g RhCl3 g of silver trifluoroacetate were added. This mixture was heated to reflux under nitrogen for 5 hours. After cooling to room temp the reaction mixture was passed through a silica gel plug with 50% CH2Cl2 hexanes as the eluent. The desired fractions were combined and the solvent removed in vacuo. White crystals were collected from a dichloromethane/methanol mixture. The desired product was confirmed by mass specfroscopy. Emission of the material in dichloromethane gave a λmax at 456 nm.
Example 4 - Device Comparison [00121] Device fabrication and measurement All devices are fabricated by high vacuum (<10"7 Torr) thermal evaporation. The anode electrode is -1200 A of indium tin oxide (ITO). The cathode consists of 10 A of LiF followed by 1,000 A of Al. All devices are encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication, and a moisture getter was incorporated inside the package. [00122] The current- voltage-luminance (LVL) characteristics and operational Hfetime are measured and summarized in the Table 1. A typical display brightness level of 600 cd/m2 for green emitting devices is chosen for the comparison between different devices. Table 1
Figure imgf000044_0001
Linked Ligand Device [00123] The organic stack consists of 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l-naphthyl)-N-phenylamino]biphenyl (α- NPD), as the hole fransporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 4.5, 6 or 9 wt% of Dopant F as the emissive layer (EML). The ETL2 is 100 A of aluminum(III)bis(2-methyl-8-hydroxyqumolinato)4-phenylphenolate (BAlq). The ETL1 is 400 A of tris(8-hydroxyquinolinato)aluminum (Alq3). Comparative Example 1 [00124] The organic stack consists of 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l-naphthyl)-N-phenylamino]biphenyl ( - NPD), as the hole fransporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 6 wt% of Oc-tris(2-phenylpyridine)iridium [Ir(ppy)3] as the emissive layer (EML). The ETL2 is 100 A of aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate (BAlq). The ETL1 is 400 A of tris(8-hydroxyquinol ato)aluπunum (Alq3). [00125] The linked ligand devices of Example 4 were characterized. The device characteristics are shown in Figures 3-6. The plot of current density vs voltage is shown in Figure 3. Figure 4 shows the plot of the external quantum efficiency at various current densities for these devices. Figure 5 shows the plots of luminous efficiency for these devices. The devices show high quantum efficiency and luminous efficiencies. The device having a dopant concentration of 4.5% gave a maximum quantum efficiency of 10% and a maximum luminous efficiency of 36 cd/A. Figure 6 shows the luminescent spectra for the device having dopant concentration of 4.5%, 6% and 9%. [00126] The operational stability of the 4.5% doped linked Hgand device was tested at room temperature under a constant direct current drive to achieve an initial luminance of 955 cd/m2. A comparison of stability was made to the comparative example 1 (unlinked ligand device) which was driven at a lower initial luminance of 600 cd/m2 (Figure 7). Without the enhanced stability provided by the present invention, one would have expected the device which was driven at higher initial luminance, to degrade more rapidly. The results indicate, however, that the Hnked ligands of the present invention exhibit enhanced stability since the linked Hgand device of Example 4 degraded less than the unlinked ligand device (comparative Example 1) when operating at a 37% higher brightness. As shown, the linked ligand device utilizing Dopant F retains 91% of 955 cd/m2 after 1000 hours of operation whereas comparative Example 1 utilizing unlinked Ir(ppy)3 retains only 89% of 600 cd/m2, after 1,000 hrs of continuous operation.
Example 5 - Synthesis of Dopant M [00127] Compound J
Compound J
Figure imgf000045_0001
Approximately 250 mL of 1,2-dimethoxyethane and 170 mL of a 2 M sodium carbonate solution were added to a 1000 mL round bottom flask. To this mixture, 39.0 g of 2- bromopyridine, 25.0 g of 4-bromophenylboronic acid, 0.70 g of palladium (II) acetate, and 3.26 g of friphenylphosphine were added. This mixture was heated to reflux under nitrogen atmosphere for 16 hours. After the reaction was cooled, 200 mL of water and 150 mL of ethyl acetate were added. The mixture was added to a separatory funnel and the organic and aqueous layers were allowed to separate. The organic layer was then washed with brine and dried over magnesium sulfate. After removal of the solvents by rotary evaporation, the crude mixture was purified by silica gel column chromatography using 10% EtOAc/Hexanes as the eluent. The fractions containing the desired product were combined and the solvent was removed by rotary evaporation. 22.0 g of white solid was obtained. [00128] Compound K
Figure imgf000046_0001
Approximately 70 mL of dry toluene, 70 mL dry diisopropylamine, 10.0 g of Compound J, and 1.5 g of tefraMs(triphenylphosphine)palladium were added to a 500 mL round bottom flask. This mixture was heated to 60°C for 30 minutes and then 2.14 g of 1,3,5 triethynylbenzene and 0.16 gr of copper(I) iodide were added. The reaction was maintained at 60°C for 16 hours and then allowed to cool. The solids were filtered and the solvent was removed from the filtrate by rotary evaporation. The product was purified by silica gel column chromatography using 80% dichloromethane/ethyl acetate as the eluent. The fractions containing the desired product were combined and the solvent was removed by rotary evaporation. The product was crystallized from a dichloromethane/methanol mixture to yield 6 g of white needle crystals. [00129] Compound L
Cyclohexene, Pd on Carbon Compound K -
Figure imgf000046_0002
Compound L Approximately 60 mL of cyclohexene, 60 mL of tefrahydrofuran, 3.0 g of 10%> Pd on carbon, and 6 g of Compound K were added to a 250 mL round bottom flask. The reaction mixture was heated to reflux for 20 hours and then allowed to cool. The solids were removed by filtration and the solvent removed from the filtrate by rotary evaporation. The product was purified by silica gel column chromatography using 60%> hexanes/ethyl acetate as the eluent. The fractions containing the desired product were combined and the solvent was removed by rotary evaporation. The pure product was crystallized from ethyl acetate/hexanes and filtered to yield 4.6 g of a white solid. [00130] Dopant M
Compound L
Figure imgf000047_0001
Dopant M
Approximately 200 mL of ethylene glycol, 1.85 g of Ir(AcAc)3, and 2.5 g of compound L were added to a 500 mL round bottom flask. The reaction was heated to 160°C under N2 for 18 hours and then allowed to cool. Methanol was added arid the yellow solids were filtered. These solids were dissolved in dichloromethane and filtered through a silica gel plug. The fractions containing the desired product were combined and the solvent was removed by rotary evaporation. The yellow solids were recrystalHzed from dichlormethane/methanol and filtered to yield 1.5 g of the desired product, which was characterized by mass specfroscop}'' and NMR. The product was further purified by sublimation. Example 6 - Device Comparison [00131] Linked hexadentate molecules, Dopant M and Dopant F and the analogous unlinked tris ligand Ir(ppy)3 (Comparative Example 1) were compared as phosphorescent dopants in OLED devices. Devices were fabricated similarly to those in Example 4. The test device structure for each was ITO/CuPc(10θA)/NPD(30θA)/CBP: Dopant (4.5%, 30θA) /BAlq(lOθA) / Alq3(40θA) /LiF(loA)/Al(1000A) where the dopant was Dopant F, Dopant M, or the unlinked analog ligand Ir(ppy)3 (Comparative Example 1). A comparison of the device data for the three dopants is shown in Figures 8-10. The plot of current density vs voltage is shown in Figure 8. Figure 9 shows the plot of the external quantum efficiency as a function of current density for these devices. Figure 10 shows the electroluminescent spectra for these devices. These devices were found to have high external quantum efficiency with emission characteristic of the dopant. All of these dopants have nearly identical green emission at -510 nm. This demonstrates that the hexadentate linkage does not have a considerable effect on the color of emission. [00132] A comparison of the lifetime data can be seen in Figure 11. The devices were driven to 50% initial luminance at a constant direct current drive of 40mA/cm2 at room temperature. The Dopant M and Dopant F devices were found to have lifetimes of -300 hrs and -200 hrs, respectively, compared to a lifetime -130 hrs of the Ir(ppy)3 device. As in Example 4, the results indicate that the complexes with linked ligands of the present invention exhibit enhanced stability since the Dopant F and Dopant M devices both degraded less than the device doped with a complex with unlinked ligands of Comparative Example 1. [00133] Dopant M is a hexadentate iridium 2-phenylpyridine (ppy) complex analogous to Dopant F except that Dopant M is linked through the phenyl rings while Dopant F is linked through the pyridine rings. In general, it is beHeved that tethering the ligands of metal chelate complexes improves the stability with respect to Hgand dissociation degradation pathways. These pathways may occur both thermally (for example, during fabrication at temperatures compatible with OLED manufacturing processes) and electrochemically (for example, oxidation reduction during device operation). In this Example, a comparison of these two analogous hexadentate ligands indicates that linking through the phenyl rings may lower the rate of ligand dissociation even more effectively than Hnking through the pyridine rings. These observations may indicate a ligand dissociation pathway through Ir-C (phenyl ring) bond cleavage. Example 7 - Synthesis of Dopant Q
[00134] CompoundN
Compound K
Figure imgf000049_0001
Approximately 300 mL of 1,2-dimethoxyethane and 200 mL of water were added to a 1000 mL round bottom flask. To this mixture, 30.0 g of 2,5-dibromopyridine, 20.0 g of 2,4- difluorophenylboronic acid, 0.71 g of palladium (II) acetate, and 3.3 g of triphenylphosphine, and 36.3 g of sodium carbonate were added. This mixture was heated to reflux under nitrogen atmosphere for 16 hours. After the reaction was cooled, 200 mL water and 200 mL ethyl acetate were added. The mixture was added to a separatory funnel and the organic and aqueous layers were allowed to separate. The organic layer was then washed with brine and dried over magnesium sulfate. After removal of the solvents by rotary evaporation, the crude mixture was purified by silica gel column chromatography using 10% EtOAc Hexanes as the eluent. The fractions containing the desired product were combined and the solvent was removed by rotary evaporation. The product was crystaUized from dichloromethane and hexanes. 20 g of a white solid was obtained. [00135] Compound O
Figure imgf000050_0001
Approximately "100 mL of dry toluene, 100 mL dry diisopropylamine, 15.0 g of Compound N, and 1.9 g of tefrakis (friphenylphosphine) palladium were added to a 500 mL round bottom flask. This mixture was heated to 60°C for 30 minutes and then 2.8 grams of 1,3,5 triethynylbenzene and 0.21 grams of copper (I) iodide were added. The reaction was maintained at 60°C for 12 hours and then allowed to cool. The soHds were filtered and redispersed in refluxing dichloromethane. The slurry was filtered and dried to yield 12 g of a white solid. [00136] Compound P
Compound O
Figure imgf000050_0002
Compound P
[00137] Approximately 100 mL cyclohexene, 100 mL tefrahydrofuran, 6.0 g of 10% Pd on Carbon, and 12 g of Compound O were added to a 250 mL round bottom flask. The reaction mixture was heated to reflux for 24 hours and then allowed to cool. The solids were removed by filfration and the solvent removed from the filtrate by rotary evaporation. The product was purified by silica gel column chromatography using 60% hexanes/ethyl acetate as the eluent. The fractions containing the desired product were combined and the solvent was removed by rotary evaporation. The pure product was crystallized from ethyl acetate / hexanes and filtered to yield 8.0 g of a white solid. [00138] Dopant Q
Compound P
Figure imgf000051_0001
Approximately 250 mL of ethylene glycol, 1.55 g of Ir(AcAc)3, and 2.3 grams of compound P were added to a 500 mL round bottom flask. The reaction was heated to reflux under N2 for 18 hours and then allowed to cool. Methanol was added and the yellow solids were filtered. The solids were dissolved in refluxing 1,2-dichlorobenzene and allowed to cool. The solids were filtered to yield 1.5 g of yellow product, which was confirmed by mass specfroscopy and NMR. The product was further purified by sublimation.
Example 8 - Device Comparison
[00139] Linked Ligand Device. In the Dopant Q device, the organic stack consisted of 100 A thick of copper phthalocyanine (CuPc) as the hole mjecύon layer (HIL), 300 A of 4,4 ' - bis[N-(l-naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole fransporting layer (HTL), 300 A of N,N'-dicarbazolyl-3,5-benzene (mCP) doped with 6 wt% of Dopant Q as the emissive layer (EML). The ETL2 is 400 A of alummum(πi)bis(2-methyl-8-quinolinato)4- phenylphenolate (BAlq). There was no ETL1. Comparative example 2 [00140] In the unlinked comparative example, the organic stack consisted of 100 A thick of copper ph alocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l - naphthyl)-N-phenylamino]biphenyl ( -NPD), as the hole fransporting layer (HTL), 300 A of N,N'-dicarbazolyl-3,5-benzene (mCP) doped with 6 wt% of Ir(4,6-F2ppy)3 as the emissive layer (EML). The ETL2 is 400 A of aluminum(m)bis(2-methyl-8-quinolinato)4- phenylphenolate (BAlq). There was no ETL1. [00141] Devices were fabricated similarly to those in Example 4. The current- voltage plot, external quantum efficiency vs current density, elecfroluminescence spectra, and room temperature operational stability (constant current of 5 mA/cm2) in terms of normalized elecfroluminescence vs time of the Dopant Q device and Comparative Example 2 [Ir(4,6- F ppy)3] are shown in Figure 12, Figure 13, Figure 14 and Figurel5 respectively. The efficiency of the devices containing the ligand-linked complex (Dopant Q) is lower than that of the unlinked analog Comparative Example 2 [Ir(4,6-F2ppy)3]. However, the operational stability the devices containing the Hgand-linked complex (Dopant Q) is similar to that of the unlinked analog Comparative Example 2 [Ir(4,6-F2ppy)3]. In this case, there is very little or no improvement in lifetime between devices containing the linked and unlinked complexes. However, as shown in Examples 4 and 6, devices containing the Hnked versions of the Ir(ppy)3 type complex clearly exhibit enhanced stability compared to the unlinked Ir(ppy)3. The lack of improvement in the Ir(4,6-F2ρpy)3 type complex may be due to the electrochemical instability of fluorine substituents, which perhaps results in ligand degradation due to the reductive elimination of fluorine upon device operation. The enhanced chelating effect of the ligand to the metal center which is believed to improve the stability of the complex may not have a significant effect in such a degradation mechanism. A further possibility is that the degradation mechanism occurs primarily through the cleavage of the Ir-C bond. As shown in Example 6, Dopant M, where the Hgands are linked through the phenyl ring, are more stable than devices using dopant F, with ligands Hnked through the pyridine ring. If this is the case, linking the ligands through the pyridine rings may not show a significant improvement in stability for high energy dopants substituted with fluorine, such as Dopant Q. [00142] ' While the present invention is described with respect to particular examples and preferred embodiments, it is understood that the present invention is not limited to these examples and embodiments. The present invention as claimed therefore includes variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art.

Claims

WHAT IS CLAIMED IS:
1. An organic Hght emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a phosphorescent organometaUic emissive material comprising a transition metal, and two or three bidentate ligands, wherein two or more of the bidentate Hgands are covalentiy linked by a linking group, wherein, the bidentate ligands are selected from bidentate photoactive ligands, wherein each bidentate photoactive ligand is bound to the transition metal through a carbon-metal bond and a nitrogen-metal bond to form a cyclometallated ring, and bidentate ancHlary ligands, wherein at least one of the bidentate Hgands is a bidentate photoactive Hgand.
2. The organic light entitling device of claim 1 ,■ wherein the linking group provides no %- conjugation between the linked bidentate Hgands.
3. An organic Hght emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises an emissive material having the formula I
Figure imgf000054_0001
wherein, M is a transition metal having a molecular weight greater than 40; X is a linking group that links two or more L, and is selected from the group consisting of -(CR2)d-, -[O(CR2)e]O-, or a group having the formula A A-Bx-A or A-B^-A wherein A is -(CRa) -, or -Z-(CR2) ; Z is -0-, -NR-, or -SiR2-;
33 B1 is -O-, -NR-, -CR=CR-, aryl, heteroaryl, cycloalkyl, or aheterocycHc group, ? i I B is -N- , — CR— , alkyl, aryl, heteroaryl, cycloalkyl, or a heterocyclic group; each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, d is 1 to 6, e is 1 to 6, fis 1 to 4, and g is 1 to 4;
L is a bidentate ligand selected from the group consisting of (i) bidentate photoactive ligands having the formula II R4
R2^^C (ID wherein the bidentate photoactive ligand is bound to the transition metal through a carbon- metal bond and a nitrogen-metal bond to form a cyclometallated ring, Y is N or C, the dotted line represents an optional double bond, R1, R2, R3 and R4 are independently selected from H, alkyl, or aryl, and additionally or alternatively, one or more of R1 and R2, R2 and R3, and R3 and R4 together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cyclohetero alkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents Z; each substituent Z is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR23 NO2, OR, halo, and aryl, and additionally, or alternatively, two Z groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, and each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl; and (ii) bidentate ancillary ligands, a is 1 to 4; b is 2 or 3; and at least one L is selected from a bidentate photoactive Hgand.
4. The organic light ermtting device of claim 3, wherein the photoactive ligands are selected from compounds of the formula LV
Figure imgf000056_0001
wherein: ring A is an aromatic heterocyclic ring or a fused aromatic heterocychc ring with at least one nitrogen atom, that coordinates to the metal M, Y is selected from carbon or nitrogen, each R5 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CΝ, CF3, ΝR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R5 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R6 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R6 groups on adjacent ring atoms form a fused 5- or- 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, n is'O to 4, and m is o 4.
5. The organic Hght emitting device of claim 3, wherein [Xa-(L)j] has the formula:
Figure imgf000057_0001
Figure imgf000057_0002
6. The organic Hght emitting device of claim 3 , wherein the emissive material is a compound having the formula
Figure imgf000057_0003
7. The organic light emitting device of claim 3, wherein the emissive material is a compound having the formula
Figure imgf000058_0001
8. The organic light emitting device of claim 3, wherein the emissive material is a compound having the formula
Figure imgf000058_0002
9. A compound of the formula I [Xfl-(L)6]M (I) wherein, M is a fransition metal having a molecular weight greater than 40; X is a linking group that links two or more L, and is selected from the group consisting of -(CR2)<r, -[O(CR2)JO-, or a group having the formula A A-B^A or A-B^-A wherein A is -(CR2) -, or -Z-(CR2) ; Z is -O-, -NR-, or -SiR2-; B1 is -0-, -NR-, -CR=CR-, aryl, heteroaryl, cycloalkyl, or a heterocycli-c group, B 2 is — N I — , — C ' R— , alkyl, aryl, heteroaryl, cycloalkyl, or a heterocyclic group; each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, d is 1 to 6, e is 1 to 6, /is 1 to 4, and g is 1 to 4; L is a bidentate Hgand selected from the group consisting of (i) bidentate photoactive ligands having the formula II R4
R2/ ^C R1 (n) wherein the bidentate photoactive Hgand is bound to the fransition metal through a carbon- metal bond and a nitrogen-metal bond to form a cyclometallated ring, Y is N or C, the dotted line represents an optional double bond, R1, R2, R3 and R4 are independently selected from H, alkyl, or aryl, and additionally or alternatively, one or more of R1 and R2, R2 and R3, and R3 and R4 together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionaHy substituted by one or more substituents Z; each substituent Z is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two Z groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, and (ii) bidentate ancillary ligands, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl; a is 1 to 4; b is 2 or 3; and at least one L is selected from a bidentate photoactive ligand.
10. The compound of claim 9, wherein the photoactive ligands are selected from compounds of the formula LV
Figure imgf000060_0001
wherein: ring A is an aromatic heterocyclic ring or a fused aromatic heterocychc ring with at least one nitrogen atom that coordinates to the metal M, Y is selected from carbon or nitrogen, each R5 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CΝ, CF3, ΝR2, NO2, OR, halo, and aryl, and additionaUy, or alternatively, two R5 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R6 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, N02, OR, halo, and aryl, and additionally, or alternatively, two R6 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independentiy selected from H, alkyl, aralkyl, aryl and heteroaryl, n is 0 to 4, and m is 0 to 4.
11. The compound of claim 9, wherein [Xα-(L)έ] has the formula:
Figure imgf000061_0001
12. The compound of claim 9, having the formula
Figure imgf000061_0002
13. The compound of claim 9, having the formula
Figure imgf000062_0001
14. The compound of claim 9, having the formula
Figure imgf000062_0002
15. An organic Hght emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a material of the formula VLI A1[Q/,(XH-] (VII) wherein Q is a bidentate ligand of the formula VLII
Figure imgf000063_0001
(VIII) wherein ring B is a 5- or 6-membered aromatic group, ring C is a 5- or 6-membered aromatic heterocyclic ring with at least one nitrogen atom that coordinates to the Al, each R7 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO , OR, halo, and aryl, and additionally, or alternatively, two R7 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R8 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R groups on adjacent rirϊg atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, x is 0 to 3, and y is 0 to 3; J is selected from monodentate Hgands having the formula
Figure imgf000063_0002
wherein each R9 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NO2, O-alkyl, halo, and aryl, and z is 0 to 5; X is a hnking group that links two or more of the ligands Q or I, wherein at least one of the ligands linked by the linking group X is a bidentate ligand Q; h is 2 or 3; i is 1 to 4; and j is 0 to 2.
16. The organic light emitting device of claim 15, wherein the linking group provides no π- conjugation between the linked bidentate ligands.
17. The organic light emitting device of claim 15, wherein the linking group X is selected from the group consisting of -(CR2 , -[O(CR2)JO-, or a group having the formula A A-BJ-A or A-B2-A wherein A is -(CR2V-, or -Z-(CR2) ; Z is -O-, -NR-, or -SiR2-; B1 is -O-, -NR-, -CR=CR-, aryl, heteroaryl, cycloalkyl, or a heterocyclic group, B 2 is — ' — , — C ' R— , alkyl, aryl, heteroaryl, cycloalkyl, or a heterocyclic group; each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, d is 1 to 6, e is 1 to 6, fis 1 to 4, and g is 1 to 4.
18. The organic Hght emitting device of claim 15, wherein the bidentate ligand Q has the formula
Figure imgf000065_0001
19. The organic Hght emitting device of claim 15, wherein/ is 0 and h is 3.
20. The organic Hght emitting device of claim 15, wherein j is 1 and h is 2.
21. The organic light emitting device of claim 15, wherein [QΛ ] has the formula
Figure imgf000065_0002
22. The organic Hght emitting device of claim 15, wherein the organic layer comprises a material of the formula
Figure imgf000066_0001
23. A compound of the formula VII Al[Q»(X)|J] (VH) wherein
Q is a bidentate ligand of the formula VIII
Figure imgf000066_0002
(vm) wherein ring B is a 5- or 6-membered aromatic group, ring C is a 5- or 6-membered aromatic heterocyclic ring with at least one nifrogen atom that coordinates to the Al, each R7 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionaUy, or alternatively, two R7 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R8 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionaUy, or alternatively, two R8 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, is 0 to 3, and y is 0 to 3; I is a monodentate ligands having the formula
Figure imgf000067_0001
wherein each R9 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NO2, O-alkyl, halo, and aryl, and z is 0 to 5; X is a linking group that links two or more of the ligands Q or I wherein at least one of the ligands Hnked by the liriking group X is a bidentate ligand Q; h is 2 or 3; i is 1 to 4; and j is 0 to 2.
24. The compound of claim 23, wherein the linking group provides no π-conjugation between the linked bidentate ligands.
25. The compound of claim 23, wherein the linking group X is selected from the group consisting of -(CR2)i-, -[O(CR2)JO-, or a group having the formula A A-B3-A or A-B2-A wherein A is -(CR2)r, or -Z-(CR2V; Z is -O-, -NR-, or -SiR2-; B1 is -O-, -NR-, -CR=CR-, aryl, heteroaryl, cycloalkyl, or a heterocyclic group, B ? is — N ' — , — C I R— , alkyl, aryl, heteroaryl, cycloalkyl, or a heterocyclic group; each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, d is 1 to 6, e is 1 to 6, /is 1 to 4, and g is 1 to 4.
26. The compound of claim 23, wherein the bidentate ligand Q has the formula
Figure imgf000068_0001
27. The compound of claim 23, whereiny is 0 and h is 3.
28. The compound of claim 23, whereiny is 1 and h is 2.
29. The compound of claim 23, wherein [QA(X)ZJ,-] has the formula
Figure imgf000068_0002
Figure imgf000069_0001
30. The compound of claim 23, having the formula
Figure imgf000069_0002
31. An organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal complex comprising: a metal; a first Hgand bound to the metal, wherein the first Hgand is a bidentate Hgand; a second Hgand bound to the metal; and a linking group that covalentiy links the first Hgand and the second ligand, wherein the linking group provides no π-conjugation between the first ligand and the second Hgand.
32. The organic light enntting device of claim 31, wherein the metal complex is a phosphorescent organometallic emissive material.
33. The organic light emitting device of claim 31, wherein the metal complex further comprises an additional bidentate ligand.
34. The organic light emitting device of claim 31, wherein the second ligand is a bidentate ligand.
35. The organic Hght emitting device of claim 31, wherein the second ligand is a monodentate ligand.
36. The organic Hght emitting device of claim 31, wherein the metal is duminum.
37. The organic light ernitting device of claim 3, wherein [Xα-(L)j] has the formula:
Figure imgf000070_0001
Figure imgf000071_0001
38. The organic light emitting device of claim 3 , wherein [Xfl-(L)&] has the formula:
Figure imgf000071_0002
39. The organic light enntting device of claim 3, wherein [Xa-(L)b] has the formula:
Figure imgf000071_0003
40. The organic light einitting device of claim 3, wherein the emissive material is a compound having the formula
Figure imgf000071_0004
41. The compound of claim 9, wherein [Xα-(L)&] has the formula:
Figure imgf000072_0001
Figure imgf000072_0002
42. The compound of claim 9, wherein [Xfl-(L)J has the formula:
Figure imgf000072_0003
43. The compound claim 9, wherein [Xα-(L)i] has the formula:
Figure imgf000072_0004
44. The compound of claim 9, having the formula:
Figure imgf000073_0001
45. The organic Hght enutting device of claim 3, wherein the emissive material is a compound having the formula:
Figure imgf000073_0002
46. The compound of claim 9 having the formula:
Figure imgf000074_0001
47. The.organic light emitting device of claim 3, wherein two or more L comprise a phenyl moiety and X is a linking group that links the two or more L via a covalent bond to the phenyl moiety in each of the two or more L.
48. The organic light emitting device of claim 3, wherein Xa-(L)b] has the formula
Figure imgf000074_0002
(R )n
Figure imgf000074_0003
wherein each R5 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively two R5 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R6 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, N02, OR, halo, and aryl, and additionally, or alternatively, two R1 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, n is 0 to 4, and m is 0 to 4.
49. The organic light emitting device of claim 48, wherein [Xa-(L) b] has the formula:
Figure imgf000075_0001
50. The organic light emitting device of claim 48, wherein fXβ-(L),&] has the formula:
Figure imgf000075_0002
(R5)π
51. The compound of claim 9, wherein X is linked to each L via a covalent bond to a pyridyl moiety in each L.
52. The compound of claim 9, wherein [Xα-(L)J has the formula:
Figure imgf000076_0001
each R5 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R5 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R6 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, NR2, NO2, OR, halo, and aryl, and additionally, or alternatively, two R6 groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group, each R is independently selected from H, alkyl, aralkyl, aryl and heteroaryl, n is 0 to 4, and m is 0 to 4.
53. The compound of claim 52, wherein [Xα-(L)J has the formula:
Figure imgf000077_0001
54. The compound of claim 52, wherein [Xα-(L)&] has the formula:
Figure imgf000077_0002
(R5)π
55. An organic light emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a phosphorescent organometallic emissive material comprising a metal bound to two or three bidentate ligands, wherein two or more of the bidentate ligands are covalentiy linked by one or more linking groups.
56. The organic light emitting device of claim 55 wherein the organometallic emissive material comprises a compound represented by the formula [Xa-(L)b]M wherein M is a transition metal, L is a bidentate ligand, X is a linking group that links two or more L, a is 1 to 4, b is 2 or 3 wherein the bidentate Hgands are selected from bidentate photoactive Hgands, and bidentate ancillary ligands wherein at least one of the bidentate ligands is a bidentate photoactive Hgand.
57. A compound of the formula [Xa-(L)b]M wherein M is a fransition metal, L is a bidentate ligand, X is a linking group that links two or more L, a is 1 to 4, b is 2 or 3 wherein the bidentate Hgands are selected from bidentate photoactive ligands, and bidentate ancillary ligands wherein at least one of the bidentate ligands is a bidentate photoactive ligand bound to the transition metal through a carbon-metal bond.
58. The organic Hght entitling device of claim 1 wherein the transition metal is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
59. The organic light entitling device of claim 1 wherein the transition metal is Ir.
60. The organic light emitting device of claim 3 wherein the transition metal is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, Hi, Sn, Sb, Te, Au, and Ag.
61. The organic light emitting device of claim 3 wherein the fransition metal is Ir.
62. The compound of claim 9 wherein the fransition metal is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
63. The compound of claim 9 wherein the transition metal is Ir.
64. The organic light emitting device of claim 56 wherein the fransition metal is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
65. The organic light enfrtting device of claim 56 wherein the transition metal is Ir.
66. The compound of claim 57 wherein the transition metal is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
67. The compound of claim 57 wherein the fransition metal is Ir.
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