US20070292718A1 - Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds - Google Patents
Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds Download PDFInfo
- Publication number
- US20070292718A1 US20070292718A1 US11/830,550 US83055007A US2007292718A1 US 20070292718 A1 US20070292718 A1 US 20070292718A1 US 83055007 A US83055007 A US 83055007A US 2007292718 A1 US2007292718 A1 US 2007292718A1
- Authority
- US
- United States
- Prior art keywords
- formula
- occurrence
- different
- same
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- 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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/114—Poly-phenylenevinylene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
- H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
-
- 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
- This invention relates to electroluminescent complexes of iridium(III) which have emission spectra in the red-orange and red region of the visible spectrum. It also relates to electronic devices in which the active layer includes an electroluminescent Ir(III) complex.
- Organic electronic devices that emit light, such as light-emitting diodes that make up displays, are present in many different kinds of electronic equipment.
- an organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is light-transmitting so that light can pass through the electrical contact layer.
- the organic active layer emits light through the light-transmitting electrical contact layer upon application of electricity across the electrical contact layers.
- organic electroluminescent compounds As the active component in light-emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to show electroluminescence. Semiconductive conjugated polymers have also been used as electroluminescent components, as has been disclosed in, for example, Friend et al., U.S. Pat. No. 5,247,190, Heeger et al., U.S. Pat. No. 5,408,109, and Nakano et al., Published European Patent Application 443 861. Complexes of 8-hydroxyquinolate with trivalent metal ions, particularly aluminum, have been extensively used as electroluminescent components, as has been disclosed in, for example, Tang et al., U.S. Pat. No. 5,552,678.
- Electroluminescent devices with an active layer of polymer doped with organometallic complexes of iridium have been described by Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512. Most of these complexes have emission spectra with peaks in the green or blue-green region.
- the present invention is directed to a metal complex having a formula selected from Formula I and Formula II: IrL 3 (I) IrL 2 Z (II) Where:
- the present invention is directed to an organic electronic device having at least one active layer comprising a light-emitting layer having an emission maximum in the range of from 570 to 700 nm, wherein at least 20% by weight of the active layer comprises the above metal complex, or combinations of the above metal complexes.
- the term “compound” is intended to mean an electrically uncharged substance made up of molecules that further consist of atoms, wherein the atoms cannot be separated by physical means.
- ligand is intended to mean a molecule, ion, or atom that is attached to the coordination sphere of a metallic ion.
- L is used to designate a ligand having a nominal ( ⁇ 1) charge formed from the neutral parent compound, “HL”, by the loss of a hydrogen ion.
- the letter “Z” is used to designate a bidentate ligand having a nominal ( ⁇ 1) charge formed from the neutral parent compound, “HZ”, by the loss of a hydrogen ion.
- complex when used as a noun, is intended to mean a compound having at least one metallic ion and at least one ligand.
- ⁇ -dicarbonyl is intended to mean a neutral compound in which two ketone groups are present, separated by a CHR group.
- ⁇ -enolate is intended to mean the anionic form of the ⁇ -dicarbonyl in which the H from the CHR group between the two carbonyl groups has been abstracted.
- group is intended to mean a part of a compound, such a substituent in an organic compound or a ligand in a complex.
- the term “facial” is intended to mean one isomer of a complex, Ma 3 b 3 , having octahedral geometry, in which the three “a” groups are all adjacent, i.e. at the corners of one face of the octahedron.
- the term “meridional” is intended to mean one isomer of a complex, Ma 3 b 3 , having octahedral geometry, in which the three “a” groups occupy three positions such that two are trans to each other.
- the phrase “adjacent to,” when used to refer to layers in a device, does not necessarily mean that one layer is immediately next to another layer.
- adjacent R groups is used to refer to R groups that are next to each other in a chemical formula (i.e., R groups that are on atoms joined by a bond).
- photoactive refers to any material that exhibits electroluminescence and/or photosensitivity.
- the IUPAC numbering system is used throughout, where the groups from the Periodic Table are numbered from left to right as 1 through 18 (CRC Handbook of Chemistry and Physics, 81 st Edition, 2000).
- the letters A, E, L, R, Q, Y and Z are used to designate atoms or groups which are defined within. All other letters are used to designate conventional atomic symbols.
- emission maximum is meant the wavelength, in nanometers, at which the maximum intensity of electroluminescence is obtained. Electroluminescence is generally measured in a diode structure, in which the material to be tested is sandwiched between two electrical contact layers and a voltage is applied. The light intensity and wavelength can be measured, for example, by a photodiode and a spectrograph, respectively.
- FIG. 1 shows Formulae III through VII for the ligand L useful in the metal complex of the invention.
- FIG. 2 shows Formulae VII through X for the ligand L useful in the metal complex of the invention.
- FIG. 3 shows Formula XI for the ⁇ -enolate ligand and Formula XII for the phosphino alkoxide ligand, useful in the invention.
- FIG. 4 shows Equation (1) for synthesis of the parent ligand compounds, HL, useful in the invention.
- FIG. 5 shows Equations (2) through (4) for forming the complexes useful in the invention.
- FIG. 6 is a schematic diagram of a light-emitting device (LED).
- FIG. 7 is a schematic diagram of an LED testing apparatus.
- the metal complexes of the invention have one of Formulae I and II, given above, and are referred to as cyclometallated complexes.
- the iridium in Formulae I and II is in the +3 oxidation state and is hexacoordinate.
- the complex is a tris-cyclometallated complex with no additional ligands.
- the tris complexes may exhibit a facial or a meridional geometry, but most often the facial isomer is formed.
- the complex is a bis-cyclometallated complex with an additional monoanionic bidentate ligand, Z.
- These cyclometallated iridium complexes are neutral and non-ionic, and can be sublimed intact. Thin films of these materials obtained via vacuum deposition exhibit good to excellent electroluminescent properties.
- the complexes of the invention have emission spectra with maxima in the range of 570 to 700 nm, which is in the red-orange to red region of the visible spectrum.
- the preferred red emission is at 620 nm and above.
- Ligand L having Formula III, shown in FIG. 1 is derived from a thienyl-pyridine (when A is S) or pyrrolyl-pyridine (when A is NR 11 ) compound in which there is at least one fluorine-containing substituent on the pyridine ring.
- the R 3 through R 6 groups may be chosen from conventional substitutents for organic compounds, such as alkyl, alkoxy, halogen, nitro, and cyano groups, as well as deutero, fluoro, fluorinated alkyl and fluorinated alkoxy groups.
- the groups can be partially or fully fluorinated (perfluorinated). It is preferred that ⁇ is 0, and that R 3 and/or R 5 is a fluorine-containing substituent. Most preferred is CF 3 .
- A is NR 11
- R 11 is CH 3 .
- Ligand L having Formula IV is derived from a thienyl- or a pyrrolyl-quinoline compound.
- Ligand L having Formula V or Formula VI, shown in FIG. 1 is derived from a thienyl- or a pyrrolyl-isoquinoline compound. It is preferred that alpha is 0. When A is NR 11 , it is preferred that R 11 is CH 3 .
- Ligand L having Formula VII, shown in FIG. 1 is derived from a thienyl- or a pyrrolyl-diazine compound, or the analog with 3 or more nitrogens.
- A is NR 11
- R 11 is CH 3 .
- Ligand L having Formula VIII is derived from a phenyl-quinoline compound.
- Ligand L having Formulae IX or X, shown in FIG. 2 is derived from a phenyl-isoquinoline compound.
- the R 7 through R 10 groups may be chosen from conventional substitutents for organic compounds, such as alkyl, alkoxy, halogen, nitro, and cyano groups, as well as deutererium. It is preferred that the R 8 and/or R 10 is a substituent bonded through a heteroatom having non-bonding pi electrons, most preferably oxygen. It is preferred that the R 9 substituent is an alkyl, preferably a tertiary alkyl.
- the parent ligand compounds, HL can generally be prepared by standard palladium-catalyzed Suzuki or Kumada cross-coupling of the corresponding heterocyclic aryl chloride with an organoboronic acid or organomagnesium reagent, as described in, for example, O. Lohse, P. Thevenin, E. Waldvogel Synlett, 1999, 45-48. This reaction is illustrated for a phenyl-isoquinoline, where R and R′ represent substituents, in Equation (1) in FIG. 4 .
- the Z ligand is a monoanionic bidentate ligand.
- these ligands have N, O, P, or S as coordinating atoms and form 5- or 6-membered rings when coordinated to the iridium.
- Suitable coordinating groups include amino, imino, amido, alkoxide, carboxylate, phosphino, thiolate, and the like.
- Suitable parent compounds for these ligands include ⁇ -dicarbonyls ( ⁇ -enolate ligands), and their N and S analogs; amino carboxylic acids (aminocarboxylate ligands); pyridine carboxylic acids (iminocarboxylate ligands); salicylic acid derivatives (salicylate ligands); hydroxyquinolines (hydroxyquinolinate ligands) and their S analogs; and diarylphosphinoalkanols (diarylphosphinoalkoxide ligands).
- the ⁇ -enolate ligands generally have Formula XI shown in FIG. 3 , where R 13 is the same or different at each occurrence.
- the R 13 groups can be hydrogen, halogen, substituted or unsubstituted alkyl, aryl, alkylaryl or heterocyclic groups. Adjacent R 13 groups can be joined to form five- and six-membered rings, which can be substituted.
- Preferred R 13 groups are selected from H, F, C n (H+F) 2n+1 , —C 6 H 5 , —C 4 H 3 S, and —C 4 H 3 O, where n is an integer from 1 to 12, preferably from 1 to 6.
- Suitable ⁇ -enolate ligands, Z include the compounds listed below.
- the abbreviation for the ⁇ -enolate form is given below in brackets.
- the ⁇ -dicarbonyl parent compounds, HZ are generally available commercially.
- the parent compound of F7acac, 1,1,1,3,5,5,5-heptafluoro-2,4-pentanedione, CF 3 C(O)CFHC(O)CF 3 can be prepared using a two-step synthesis, based on the reaction of perfluoropentene-2 with ammonia, followed by a hydrolysis step. This compound should be stored and reacted under anyhydrous conditions as it is susceptible to hydrolysis.
- hydroxyquinoline parent compounds, HZ can be substituted with groups such as alkyl or alkoxy groups which may be partially or fully fluorinated. In general, these compounds are commercially available.
- suitable hydroxyquinolinate ligands, Z include:
- the phosphino alkoxide parent compounds, HZ generally have Formula XII, shown in FIG. 3 , where
- phosphino alkoxide ligands examples include phosphino alkoxide ligands listed below. The abbreviation for these ligands is given below in brackets.
- the parent phosphino alkanol compounds are generally available commercially.
- Complexes of Formulae I and II are generally prepared from the metal chloride salt by first forming the bridged chloride dimer. This reaction is illustrated for a thienyl-pyridine ligand in Equation (2) shown in FIG. 5 . Complexes of Formula I are then formed by adding an excess of the ligand parent compound HL, without a solvent, in the presence of 2 equivalents of silver trifluoroacetate, AgOCOCF 3 , per dimer. This reaction is illustrated in Equation (3) in FIG. 5 .
- Complexes of Formula II are formed by adding the sodium salt of the Z ligand to the bridged chloride dimer. This reaction is illustrated in Equation (4) in FIG. 5 .
- the complexes in Table 1 have electroluminescent emission maxima from about 570 nm, for compound 1-a, to about 670 nm, for compound 1-k.
- the present invention also relates to an electronic device comprising at least one photoactive layer positioned between two electrical contact layers, wherein the at least one photoactive layer of the device includes the complex of the invention.
- a typical device 100 has an anode layer 110 and a cathode layer 150 and layers 120 , 130 and optionally 140 between the anode 110 and cathode 150 .
- Layers 120 , 130 , and 140 are collectively referred to as the active layers.
- Adjacent to the anode is a hole injection/transport layer 120 .
- Adjacent to the cathode is an optional layer 140 comprising an electron transport material. Between the hole injection/transport layer 120 and the cathode (or optional electron transport layer) is the photoactive layer 130 .
- Layers 120 , 130 , and 140 are individually and collectively referred to as the active layers.
- the photoactive layer 130 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector).
- an applied voltage such as in a light-emitting diode or light-emitting electrochemical cell
- a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage
- photodetectors include photoconductive cells, photoresistors, photoswitches, phototransistors, and phototubes, and photovoltaic cells, as these terms are describe in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966).
- the complexes of the invention are particularly useful as the photoactive material in layer 130 , or as electron transport material in layer 140 .
- layer 130 it has been found that the complexes of the invention do not need to be in a solid matrix diluent in order to be effective.
- a diluent may also be added. Preferably, the diluent facilitates charge transport in the layer.
- the diluent can be a polymeric material, such as poly(N-vinyl carbazole) and polysilane. It can also be a small molecule, such as 4,4′-N,N′-dicarbazole biphenyl or tertiary aromatic amines. When a diluent is used, the metal complex is generally present in a small amount, usually less than 20% by weight, preferably less than 10% by weight, based on the total weight of the layer.
- One type of diluent which is useful with the iridium metal complexes of the invention is a conjugated polymer in which the triplet excited state of the polymer is at a higher energy level than the triplet excited state of the iridium complex.
- suitable conjugated polymers include polyarylenevinylenes, polyfluorenes, polyoxadiazoles, polyanilines, polythiophenes, polypyridines, polyphenylenes, copolymers thereof, and combinations thereof.
- the conjugated polymer can be a copolymer having non-conjugated portions of, for example, acrylic, methacrylic, or vinyl, monomeric units. Particularly useful are homopolymers and copolymers of fluorene and substituted fluorenes.
- the metal complexes of the invention may be present in more than one isomeric form, or mixtures of different complexes may be present. It will be understood that in the above discussion of OLEDs, the term “the metal complex” is intended to encompass mixtures of complexes and/or isomers.
- the device generally also includes a support (not shown) which can be adjacent to the anode or the cathode. Most frequently, the support is adjacent the anode.
- the support can be flexible or rigid, organic or inorganic. Generally, glass or flexible organic films are used as a support.
- the anode 110 is an electrode that is particularly efficient for injecting or collecting positive charge carriers.
- the anode is preferably made of materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide. Suitable metals include the Group 11 metals, the metals in Groups 4, 5, and 6, and the Group 8-10 transition metals.
- the anode 110 may also comprise an organic material such as polyaniline as described in “Flexible light-emitting diodes made from soluble conducting polymers,” Nature vol. 357, pp 477-479 (11 Jun. 1992).
- the anode layer 110 is usually applied by a physical vapor deposition process or spin-cast process.
- physical vapor deposition refers to various deposition approaches carried out in vacuo.
- physical vapor deposition includes all forms of sputtering, including ion beam sputtering, as well as all forms of vapor deposition such as e-beam evaporation and resistance evaporation.
- a specific form of physical vapor deposition which is useful is rf magnetron sputtering.
- hole transport layer 120 There is generally a hole transport layer 120 adjacent the anode.
- Examples of hole transport materials for layer 120 have been summarized for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transporting molecules and polymers can be used.
- TPD 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane
- TAPC 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane
- ETPD N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine
- PDA tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine
- PDA a-phenyl-4-N,N-diphenylaminostyrene
- TPS p-(diethylamino)benzaldehyde diphenylhydrazone
- TPA triphenylamine
- hole transporting polymers are polyvinylcarbazole, (phenylmethyl)polysilane; poly(3,4-ethylendioxythiophene) (PEDOT); and polyaniline. It is also possible to obtain hole transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.
- Optional layer 140 can function both to facilitate electron transport, and also serve as a buffer layer or anti-quenching layer to prevent quenching reactions at layer interfaces. Preferably, this layer promotes electron mobility and reduces quenching reactions.
- electron transport materials for optional layer 140 include metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq 3 ); phenanthroline-based compounds, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA) or 4,7-diphenyl-1,10-phenanthroline (DPA), and azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ).
- the cathode 150 is an electrode that is particularly efficient for injecting or collecting electrons or negative charge carriers.
- the cathode can be any metal or nonmetal having a lower work function than the first electrical contact layer (in this case, an anode).
- Materials for the second electrical contact layer can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, the lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used.
- a layer between the conductive polymer layer 120 and the active layer 130 to facilitate positive charge transport and/or band-gap matching of the layers, or to function as a protective layer.
- additional layers between the active layer 130 and the cathode layer 150 to facilitate negative charge transport and/or band-gap matching between the layers, or to function as a protective layer.
- Layers that are known in the art can be used.
- any of the above-described layers can be made of two or more layers.
- inorganic anode layer 110 may be surface treated to increase charge carrier transport efficiency.
- the choice of materials for each of the component layers is preferably determined by balancing the goals of providing a device with high device efficiency.
- each functional layer may be made up of more than one layer.
- the device can be prepared by sequentially vapor depositing the individual layers on a suitable substrate.
- Substrates such as glass and polymeric films can be used.
- Conventional vapor deposition techniques can be used, such as thermal evaporation, chemical vapor deposition, and the like.
- the organic layers can be coated from solutions or dispersions in suitable solvents, using any conventional coating technique.
- the different layers will have the following range of thicknesses: anode 110, 500-5000 ⁇ , preferably 1000-2000 ⁇ ; hole transport layer 120 , 50-2500 ⁇ , preferably 200-2000 ⁇ ; light-emitting layer 130 , 10-1000 ⁇ , preferably 100-800 ⁇ ; optional electron transport layer 140 , 50-1000 ⁇ , preferably 100-800 ⁇ ; cathode 150 , 200-10,000 ⁇ , preferably 300-5000 ⁇ .
- the location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, is affected by the relative thickness of each layer.
- the electron-hole recombination zone can be in the Alq 3 layer.
- the emission would then be that of Alq 3 , and not the desired sharp lanthanide emission.
- the thickness of the electron-transport layer must be chosen so that the electron-hole recombination zone is in the light-emitting layer. The desired ratio of layer thicknesses will depend on the exact nature of the materials used.
- the efficiency of the devices of the invention made with metal complexes can be further improved by optimizing the other layers in the device.
- more efficient cathodes such as Ca, Ba, Mg/Ag, or LiF/Al can be used.
- Shaped substrates and novel hole transport materials that result in a reduction in operating voltage or increase quantum efficiency are also applicable.
- Additional layers can also be added to tailor the energy levels of the various layers and facilitate electroluminescence.
- the iridium complexes of the invention often are phosphorescent and photoluminescent and may be useful in other applications.
- organometallic complexes of iridium have been used as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts.
- the bis cyclometallated complexes can be used to sythesize tris cyclometalated complexes where the third ligand is the same or different.
- This example illustrates the preparation of a ligand parent compound (HL), 2-(2-thienyl)-5-(trifluoromethyl)pyridine.
- This example illustrates the preparation of the intermediate dichloro bridged dimer, [IrCl ⁇ 2-(2-thienyl)-5-(trifluoromethyl)pyridine ⁇ 2]2.
- This example illustrates the preparation of the ligand parent compound, 1-(4-tert-butylphenyl)-isoquinoline.
- the aqueous layer was extracted with 3 ⁇ 75 mL of diethyl ether, and the combined organic fractions were dried with sodium sulfate, filtered, and the filtrate was evaporated to dryness.
- the pure product fractions were collected and dried in vacuo, to afford 4.5 g (56% isolated yield) of a light yellow solid, >95% pure NMR spectroscopy.
- This example illustrates the preparation of the dichloro bridged dimer, IrCl ⁇ 1-(4-t-Bu-phenyl)-isoquinoline ⁇ 2 ] 2 .
- This example illustrates the preparation of the ligand parent compound, 1-(perdeuterophenyl)-isoquinoline.
- Perdeutero-benzeneboronic acid, dimethylester To a solution of bromobenzene-d5 (Aldrich Chemical Co., 10.0 g, 61.7 mmol) in dry diethyl ether (50 mL) at ⁇ 78° C. under nitrogen was added n-BuLi (Aldrich, 1.6 M in hexanes, 38.6 mL) slowly over two minutes. The stirred mixture was allowed to warm to room temperature for 2 hours, and then it was transferred to another flask which contained a stirred solution of trimethylborate (Aldrich, 50 mL, 494 mmol) and dry diethylether (200 mL) at ⁇ 78° C. under N 2 .
- n-BuLi Aldrich, 1.6 M in hexanes, 38.6 mL
- 1-(perdeuterophenyl)-isoquinoline 1-Chloroisoquinoline (Aldrich Chemical Co., 5.00 g, 30.6 mmol), perdeuterobenzeneboronic acid, dimethyl ester from the synthesis above (4.87 g, 31.4 mmol), potassium carbonate (EM Science, 8.4 g, 61.2 mmol), tetrakistriphenylphosphine palladium(0) (Aldrich, 707 mg, 0.611 mmol), dimethoxymethane (Aldrich, 100 mL) and water (100 mL) were combined under nitrogen, and the mixture was allowed to reflux for 15 hours.
- This example illustrates the preparation of the dichloro bridged dimer, [IrCl ⁇ 1-(perdeuterophenyl)-isoquinoline ⁇ 2 ] 2 .
- This example illustrates the preparation of a bis cyclometallated iridium complex, Ir(acac) ⁇ 1-(perdeuterophenyl)-isoquinoline ⁇ 2 , compound 1-m, from Table 1.
- This example illustrates the formation of OLEDs using the iridium complexes of the invention.
- Thin film OLED devices including a hole transport layer (HT layer), electroluminescent layer (EL layer) and at least one electron transport layer (ET layer) were fabricated by the thermal evaporation technique.
- An Edward Auto 306 evaporator with oil diffusion pump was used.
- the base vacuum for all of the thin film deposition was in the range of 10 ⁇ 6 torr.
- the deposition chamber was capable of depositing five different films without the need to break up the vacuum.
- ITO indium tin oxide coated glass substrate
- the substrate was first patterned by etching away the unwanted ITO area with 1N HCl solution, to form a first electrode pattern.
- Polyimide tape was used as the mask.
- the patterned ITO substrates were then cleaned ultrasonically in aqueous detergent solution.
- the substrates were then rinsed with distilled water, followed by isopropanol, and then degreased in toluene vapor for ⁇ 3 hours.
- patterned ITO from Thin Film Devices, Inc was used. These ITO's are based on Corning 1737 glass coated with 1400 ⁇ ITO coating, with sheet resistance of 30 ohms/square and 80% light transmission.
- the cleaned, patterned ITO substrate was then loaded into the vacuum chamber and the chamber was pumped down to 10 ⁇ 6 torr.
- the substrate was then further cleaned using an oxygen plasma for about 5-10 minutes.
- multiple layers of thin films were then deposited sequentially onto the substrate by thermal evaporation.
- patterned metal electrodes of Al were deposited through a mask.
- the thickness of the film was measured during deposition using a quartz crystal monitor (Sycon STC-200). All film thicknesses reported in the Examples are nominal, calculated assuming the density of the material deposited to be one.
- the completed OLED device was then taken out of the vacuum chamber and characterized immediately without encapsulation.
- the OLED samples were characterized by measuring their (1) current-voltage (I-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectra versus voltage.
- the apparatus used, 200 is shown in FIG. 7 .
- the I-V curves of an OLED sample, 220 were measured with a Keithley Source-Measurement Unit Model 237, 280.
- the electroluminescence radiance (in the unit of Cd/m 2 ) vs. voltage was measured with a Minolta LS-110 luminescence meter, 210 , while the voltage was scanned using the Keithley SMU.
- the electroluminescence spectrum was obtained by collecting light using a pair of lenses, 230 , through an electronic shutter, 240 , dispersed through a spectrograph, 250 , and then measured with a diode array detector, 260 . All three measurements were performed at the same time and controlled by a computer, 270 .
- the efficiency of the device at certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device. The unit is in Cd/A.
- This example illustrates the formation of OLED's using a red-emissive material of the invention as a dopant in a poly(fluorene) polymer matrix.
- the resulting blend will be used as the active red-emissive layer in an OLED.
- the iridium complex, [Ir(acac) ⁇ 1-(4-t-Bu-phenyl)-isoquinoline ⁇ 2 ], compound 1-j, from Table 1, will be prepared as described in Example 6.
- the polyfluorene polymer will be prepared as described in Yamamoto, Progress in Polymer Science, Vol.
- the organic film components in this OLED example will all be solution processed.
- a poly(ethylenedioxythiophene)-poly(styrenesufonic acid) (PEDOT-PSSA, Bayer Corp.) buffer layer (i.e. hole transport/injection layer) will then be spin-coated to a thickness of 90 nm.
- the film will be dried on a hotplate at 200° C. for 3 min.
- the substrate will be then transferred to a nitrogen-filled glovebox, at which point a solution of poly(fluorene) polymer, [Ir(acac) ⁇ 1-(4-t-Bu-phenyl)-isoquinoline ⁇ 2 ] (1.6 ⁇ mol), and anhydrous toluene (7.5 mL) will be spin coated on the substrate to a thickness of 70 nm.
- the substrate will be then transferred to a high vacuum chamber, where Ba (3.5 nm) followed by Al (400 nm) will be thermally deposited at 2.0 ⁇ 10 ⁇ 6 torr.
- the resulting OLED device will then be sealed from air by gluing a glass slide on top of the cathode with the use of a UV-curable epoxy resin.
- the device will be fully characterized by acquiring current-voltage, luminance-voltage, luminance-current, efficiency-voltage, and efficiency-current profiles. This will be accomplished with the use of a computer-driven (Labview software) Keithley Source-Measurement Unit and a photodiode, the latter which integrated light output over the entire 3 cm 2 device active area.
Abstract
The present invention is generally directed to electroluminescent Ir(III) complexes which have emission maxima in the red-orange to red region of the visible spectrum, and devices that are made with the Ir(III) complexes.
Description
- 1. Field of the Invention
- This invention relates to electroluminescent complexes of iridium(III) which have emission spectra in the red-orange and red region of the visible spectrum. It also relates to electronic devices in which the active layer includes an electroluminescent Ir(III) complex.
- 2. Description of the Related Art
- Organic electronic devices that emit light, such as light-emitting diodes that make up displays, are present in many different kinds of electronic equipment. In all such devices, an organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is light-transmitting so that light can pass through the electrical contact layer. The organic active layer emits light through the light-transmitting electrical contact layer upon application of electricity across the electrical contact layers.
- It is well known to use organic electroluminescent compounds as the active component in light-emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to show electroluminescence. Semiconductive conjugated polymers have also been used as electroluminescent components, as has been disclosed in, for example, Friend et al., U.S. Pat. No. 5,247,190, Heeger et al., U.S. Pat. No. 5,408,109, and Nakano et al., Published European Patent Application 443 861. Complexes of 8-hydroxyquinolate with trivalent metal ions, particularly aluminum, have been extensively used as electroluminescent components, as has been disclosed in, for example, Tang et al., U.S. Pat. No. 5,552,678.
- Electroluminescent devices with an active layer of polymer doped with organometallic complexes of iridium have been described by Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512. Most of these complexes have emission spectra with peaks in the green or blue-green region.
- There is a continuing need for efficient electroluminescent compounds which emit light in the red region of the visible spectrum (625-700 nm)
- The present invention is directed to a metal complex having a formula selected from Formula I and Formula II:
IrL3 (I)
IrL2Z (II)
Where: - Z is selected from β-dienolates, aminocarboxylates, iminocarboxylates, salicylates, hydroxyquinolates, and diarylphosphinoalkoxides; and
- L is selected from Formula III, Formula IV, Formula V, Formula VI, and Formula VII in
FIG. 1 , and Formula VIII, Formula IX and Formula X inFIG. 2 , where:
In Formula III:- R3 through R6 are the same or different and at least one of R3 through R6 is selected from D, F, CnF2n+1, OCnF2n+1, and OCF2Y;
At each Occurrence in any of Formulae III Through VII: - R1 is the same or different at each occurrence and is selected from D, CnH2n+1, OR11, SR11, N(R11)2, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y, or adjacent pairs of R1 can be joined to form a five- or six-membered ring;
- Y is H, Cl, or Br; and
- A is S or NR11;
At each Occurrence in any of Formulae III Through X: - R11 is the same or different at each occurrence and is H or CnH2n+1;
- n is an integer from 1 through 12; and
- α is 0, 1 or 2;
At each Occurrence in any of Formulae IV Through X: - δ is 0 or an integer from 1 through 4;
In Formula VII: - E1 through E4 are the same or different and are N or CR12, with the proviso that at least one E is N; and
- R12 is the same or different at each occurrence and is selected from H, D, SR11, N(R11)2, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y, or adjacent pairs of R12 can be joined to form a five- or six-membered ring, with the proviso that at least one of R12 is selected from D, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y;
At each Occurrence in Any of Formulae VIII Through X: - R2 and R7 through R10 are the same or different at each occurrence and are selected from H, D, CnH2n+1, OR11, SR11, and N(R11)2, or adjacent pairs of R groups can be joined to form a five- or six-membered ring.
- R3 through R6 are the same or different and at least one of R3 through R6 is selected from D, F, CnF2n+1, OCnF2n+1, and OCF2Y;
- In another embodiment, the present invention is directed to an organic electronic device having at least one active layer comprising a light-emitting layer having an emission maximum in the range of from 570 to 700 nm, wherein at least 20% by weight of the active layer comprises the above metal complex, or combinations of the above metal complexes.
- As used herein, the term “compound” is intended to mean an electrically uncharged substance made up of molecules that further consist of atoms, wherein the atoms cannot be separated by physical means. The term “ligand” is intended to mean a molecule, ion, or atom that is attached to the coordination sphere of a metallic ion. The letter “L” is used to designate a ligand having a nominal (−1) charge formed from the neutral parent compound, “HL”, by the loss of a hydrogen ion. The letter “Z” is used to designate a bidentate ligand having a nominal (−1) charge formed from the neutral parent compound, “HZ”, by the loss of a hydrogen ion. The term “complex”, when used as a noun, is intended to mean a compound having at least one metallic ion and at least one ligand. The term “β-dicarbonyl” is intended to mean a neutral compound in which two ketone groups are present, separated by a CHR group. The term “β-enolate” is intended to mean the anionic form of the β-dicarbonyl in which the H from the CHR group between the two carbonyl groups has been abstracted. The term “group” is intended to mean a part of a compound, such a substituent in an organic compound or a ligand in a complex. The term “facial” is intended to mean one isomer of a complex, Ma3b3, having octahedral geometry, in which the three “a” groups are all adjacent, i.e. at the corners of one face of the octahedron. The term “meridional” is intended to mean one isomer of a complex, Ma3b3, having octahedral geometry, in which the three “a” groups occupy three positions such that two are trans to each other. The phrase “adjacent to,” when used to refer to layers in a device, does not necessarily mean that one layer is immediately next to another layer. On the other hand, the phrase “adjacent R groups,” is used to refer to R groups that are next to each other in a chemical formula (i.e., R groups that are on atoms joined by a bond). The term “photoactive” refers to any material that exhibits electroluminescence and/or photosensitivity. In addition, the IUPAC numbering system is used throughout, where the groups from the Periodic Table are numbered from left to right as 1 through 18 (CRC Handbook of Chemistry and Physics, 81st Edition, 2000). In the Formulae and Equations, the letters A, E, L, R, Q, Y and Z are used to designate atoms or groups which are defined within. All other letters are used to designate conventional atomic symbols. The term “(H+F)” is intended to mean all combinations of hydrogen and fluorine, including completely hydrogenated, partially fluorinated or perfluorinated substituents. By “emission maximum” is meant the wavelength, in nanometers, at which the maximum intensity of electroluminescence is obtained. Electroluminescence is generally measured in a diode structure, in which the material to be tested is sandwiched between two electrical contact layers and a voltage is applied. The light intensity and wavelength can be measured, for example, by a photodiode and a spectrograph, respectively.
-
FIG. 1 shows Formulae III through VII for the ligand L useful in the metal complex of the invention. -
FIG. 2 shows Formulae VII through X for the ligand L useful in the metal complex of the invention. -
FIG. 3 shows Formula XI for the β-enolate ligand and Formula XII for the phosphino alkoxide ligand, useful in the invention. -
FIG. 4 shows Equation (1) for synthesis of the parent ligand compounds, HL, useful in the invention. -
FIG. 5 shows Equations (2) through (4) for forming the complexes useful in the invention. -
FIG. 6 is a schematic diagram of a light-emitting device (LED). -
FIG. 7 is a schematic diagram of an LED testing apparatus. - The metal complexes of the invention have one of Formulae I and II, given above, and are referred to as cyclometallated complexes. The iridium in Formulae I and II is in the +3 oxidation state and is hexacoordinate. In Formula I, the complex is a tris-cyclometallated complex with no additional ligands. The tris complexes may exhibit a facial or a meridional geometry, but most often the facial isomer is formed. In Formula II, the complex is a bis-cyclometallated complex with an additional monoanionic bidentate ligand, Z. These cyclometallated iridium complexes are neutral and non-ionic, and can be sublimed intact. Thin films of these materials obtained via vacuum deposition exhibit good to excellent electroluminescent properties.
- The complexes of the invention have emission spectra with maxima in the range of 570 to 700 nm, which is in the red-orange to red region of the visible spectrum. The preferred red emission is at 620 nm and above.
- Ligand L having Formula III, shown in
FIG. 1 , is derived from a thienyl-pyridine (when A is S) or pyrrolyl-pyridine (when A is NR11) compound in which there is at least one fluorine-containing substituent on the pyridine ring. The R3 through R6 groups may be chosen from conventional substitutents for organic compounds, such as alkyl, alkoxy, halogen, nitro, and cyano groups, as well as deutero, fluoro, fluorinated alkyl and fluorinated alkoxy groups. The groups can be partially or fully fluorinated (perfluorinated). It is preferred that α is 0, and that R3 and/or R5 is a fluorine-containing substituent. Most preferred is CF3. When A is NR11, it is preferred that R11 is CH3. - Ligand L having Formula IV, shown in
FIG. 1 , is derived from a thienyl- or a pyrrolyl-quinoline compound. Ligand L having Formula V or Formula VI, shown inFIG. 1 , is derived from a thienyl- or a pyrrolyl-isoquinoline compound. It is preferred that alpha is 0. When A is NR11, it is preferred that R11 is CH3. - Ligand L having Formula VII, shown in
FIG. 1 , is derived from a thienyl- or a pyrrolyl-diazine compound, or the analog with 3 or more nitrogens. There is at least one substituent on the 6-membered ring that is selected from D, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y, most preferably CF3. It is preferred that α is 0. When A is NR11, it is preferred that R11 is CH3. - Ligand L having Formula VIII, shown in
FIG. 2 , is derived from a phenyl-quinoline compound. Ligand L having Formulae IX or X, shown inFIG. 2 , is derived from a phenyl-isoquinoline compound. The R7 through R10 groups may be chosen from conventional substitutents for organic compounds, such as alkyl, alkoxy, halogen, nitro, and cyano groups, as well as deutererium. It is preferred that the R8 and/or R10 is a substituent bonded through a heteroatom having non-bonding pi electrons, most preferably oxygen. It is preferred that the R9 substituent is an alkyl, preferably a tertiary alkyl. - The parent ligand compounds, HL, can generally be prepared by standard palladium-catalyzed Suzuki or Kumada cross-coupling of the corresponding heterocyclic aryl chloride with an organoboronic acid or organomagnesium reagent, as described in, for example, O. Lohse, P. Thevenin, E. Waldvogel Synlett, 1999, 45-48. This reaction is illustrated for a phenyl-isoquinoline, where R and R′ represent substituents, in Equation (1) in
FIG. 4 . - The Z ligand is a monoanionic bidentate ligand. In general these ligands have N, O, P, or S as coordinating atoms and form 5- or 6-membered rings when coordinated to the iridium. Suitable coordinating groups include amino, imino, amido, alkoxide, carboxylate, phosphino, thiolate, and the like. Examples of suitable parent compounds for these ligands include β-dicarbonyls (β-enolate ligands), and their N and S analogs; amino carboxylic acids (aminocarboxylate ligands); pyridine carboxylic acids (iminocarboxylate ligands); salicylic acid derivatives (salicylate ligands); hydroxyquinolines (hydroxyquinolinate ligands) and their S analogs; and diarylphosphinoalkanols (diarylphosphinoalkoxide ligands).
- The β-enolate ligands generally have Formula XI shown in
FIG. 3 , where R13 is the same or different at each occurrence. The R13 groups can be hydrogen, halogen, substituted or unsubstituted alkyl, aryl, alkylaryl or heterocyclic groups. Adjacent R13 groups can be joined to form five- and six-membered rings, which can be substituted. Preferred R13 groups are selected from H, F, Cn(H+F)2n+1, —C6H5, —C4H3S, and —C4H3O, where n is an integer from 1 to 12, preferably from 1 to 6. - Examples of suitable β-enolate ligands, Z, include the compounds listed below. The abbreviation for the β-enolate form is given below in brackets.
- 2,4-pentanedionate [acac]
- 1,3-diphenyl-1,3-propanedionate [DI]
- 2,2,6,6-tetramethyl-3,5-heptanedionate [TMH]
- 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate [TTFA]
- 7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octanedionate [FOD]
- 1,1,1,3,5,5,5-heptafluoro-2,4-pentanedionate [F7acac]
- 1,1,1,5,5,5-hexaflouro-2,4-pentanedionate [F6acac]
- 1-phenyl-3-methyl-4-i-butyryl-pyrazolinonate [FMBP]
- The β-dicarbonyl parent compounds, HZ, are generally available commercially. The parent compound of F7acac, 1,1,1,3,5,5,5-heptafluoro-2,4-pentanedione, CF3C(O)CFHC(O)CF3, can be prepared using a two-step synthesis, based on the reaction of perfluoropentene-2 with ammonia, followed by a hydrolysis step. This compound should be stored and reacted under anyhydrous conditions as it is susceptible to hydrolysis.
- The hydroxyquinoline parent compounds, HZ, can be substituted with groups such as alkyl or alkoxy groups which may be partially or fully fluorinated. In general, these compounds are commercially available. Examples of suitable hydroxyquinolinate ligands, Z, include:
-
- 8-hydroxyquinolinate [8hq]
- 2-methyl-8-hydroxyquinolinate [Me-8hq]
- 10-hydroxybenzoquinolinate [10-hbq]
The parent hydroxyquinoline compounds are generally available commercially.
- The phosphino alkoxide parent compounds, HZ, generally have Formula XII, shown in
FIG. 3 , where -
- R14 can be the same or different at each occurrence and is selected from Cn(H+F)2n+1 and C6(H+F)5,
- R15 can be the same or different at each occurrence and is selected from H and Cn(H+F)2n+1, and
- λ is 2 or 3.
- Examples of suitable phosphino alkoxide ligands listed below. The abbreviation for these ligands is given below in brackets.
- 3-(diphenylphosphino)-1-oxypropane [dppO]
- 1,1-bis(trifluoromethyl)-2-(diphenylphosphino)-ethoxide [tfmdpeO]
- The parent phosphino alkanol compounds are generally available commercially.
- Complexes of Formulae I and II are generally prepared from the metal chloride salt by first forming the bridged chloride dimer. This reaction is illustrated for a thienyl-pyridine ligand in Equation (2) shown in
FIG. 5 . Complexes of Formula I are then formed by adding an excess of the ligand parent compound HL, without a solvent, in the presence of 2 equivalents of silver trifluoroacetate, AgOCOCF3, per dimer. This reaction is illustrated in Equation (3) inFIG. 5 . Complexes of Formula II are formed by adding the sodium salt of the Z ligand to the bridged chloride dimer. This reaction is illustrated in Equation (4) inFIG. 5 . - Examples of metal complexes of the invention are given in Table 1 below. At each occurrence, α and δ are zero.
TABLE 1 Complex Ligand R Complex Formula Formula A substituents Z 1-a I III S R5 = CF3 — 1-b I V S none — 1-c I IX — R9 = t-butyl — 1-d I IX — R8 = OCH3 — 1-e I IX — R8 = OH — 1-f I VIII — R9 = t-butyl — 1-g II III N—CH3 R5 = CF3 acac 1-h II V S none acac 1-i II IX — none acac 1-j II IX — R9 = t-butyl acac 1-k II IX — R8 = OCH3 acac 1-l II VIII — R9 = t-butyl acac 1-m II IX — R7 = R8 = R9 = acac R10 = D - The complexes in Table 1 have electroluminescent emission maxima from about 570 nm, for compound 1-a, to about 670 nm, for compound 1-k.
- Electronic Device
- The present invention also relates to an electronic device comprising at least one photoactive layer positioned between two electrical contact layers, wherein the at least one photoactive layer of the device includes the complex of the invention. As shown in
FIG. 6 , atypical device 100 has ananode layer 110 and acathode layer 150 andlayers anode 110 andcathode 150.Layers transport layer 120. Adjacent to the cathode is anoptional layer 140 comprising an electron transport material. Between the hole injection/transport layer 120 and the cathode (or optional electron transport layer) is thephotoactive layer 130.Layers - Depending upon the application of the
device 100, thephotoactive layer 130 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector). Examples of photodetectors include photoconductive cells, photoresistors, photoswitches, phototransistors, and phototubes, and photovoltaic cells, as these terms are describe in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966). - The complexes of the invention are particularly useful as the photoactive material in
layer 130, or as electron transport material inlayer 140. When used inlayer 130, it has been found that the complexes of the invention do not need to be in a solid matrix diluent in order to be effective. A layer that is greater than 20% by weight metal complex, based on the total weight of the layer, up to 100% metal complex, can be used as the emitting layer. Additional materials can be present in the emitting layer with the metal complex. For example, a fluorescent dye may be present to alter the color of emission. A diluent may also be added. Preferably, the diluent facilitates charge transport in the layer. The diluent can be a polymeric material, such as poly(N-vinyl carbazole) and polysilane. It can also be a small molecule, such as 4,4′-N,N′-dicarbazole biphenyl or tertiary aromatic amines. When a diluent is used, the metal complex is generally present in a small amount, usually less than 20% by weight, preferably less than 10% by weight, based on the total weight of the layer. - One type of diluent which is useful with the iridium metal complexes of the invention, is a conjugated polymer in which the triplet excited state of the polymer is at a higher energy level than the triplet excited state of the iridium complex. Examples of suitable conjugated polymers include polyarylenevinylenes, polyfluorenes, polyoxadiazoles, polyanilines, polythiophenes, polypyridines, polyphenylenes, copolymers thereof, and combinations thereof. The conjugated polymer can be a copolymer having non-conjugated portions of, for example, acrylic, methacrylic, or vinyl, monomeric units. Particularly useful are homopolymers and copolymers of fluorene and substituted fluorenes.
- In some cases the metal complexes of the invention may be present in more than one isomeric form, or mixtures of different complexes may be present. It will be understood that in the above discussion of OLEDs, the term “the metal complex” is intended to encompass mixtures of complexes and/or isomers.
- The device generally also includes a support (not shown) which can be adjacent to the anode or the cathode. Most frequently, the support is adjacent the anode. The support can be flexible or rigid, organic or inorganic. Generally, glass or flexible organic films are used as a support. The
anode 110 is an electrode that is particularly efficient for injecting or collecting positive charge carriers. The anode is preferably made of materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide. Suitable metals include the Group 11 metals, the metals inGroups 4, 5, and 6, and the Group 8-10 transition metals. If the anode is to be light-transmitting, mixed-metal oxides ofGroups 12, 13 and 14 metals, such as indium-tin-oxide, are generally used. Theanode 110 may also comprise an organic material such as polyaniline as described in “Flexible light-emitting diodes made from soluble conducting polymers,” Nature vol. 357, pp 477-479 (11 Jun. 1992). - The
anode layer 110 is usually applied by a physical vapor deposition process or spin-cast process. The term “physical vapor deposition” refers to various deposition approaches carried out in vacuo. Thus, for example, physical vapor deposition includes all forms of sputtering, including ion beam sputtering, as well as all forms of vapor deposition such as e-beam evaporation and resistance evaporation. A specific form of physical vapor deposition which is useful is rf magnetron sputtering. - There is generally a
hole transport layer 120 adjacent the anode. Examples of hole transport materials forlayer 120 have been summarized for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transporting molecules and polymers can be used. Commonly used hole transporting molecules, in addition to TPD and MPMP mentioned above, are: 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC); N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine (ETPD); tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA); a-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline (PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB); and porphyrinic compounds, such as copper phthalocyanine. Commonly used hole transporting polymers are polyvinylcarbazole, (phenylmethyl)polysilane; poly(3,4-ethylendioxythiophene) (PEDOT); and polyaniline. It is also possible to obtain hole transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate. -
Optional layer 140 can function both to facilitate electron transport, and also serve as a buffer layer or anti-quenching layer to prevent quenching reactions at layer interfaces. Preferably, this layer promotes electron mobility and reduces quenching reactions. Examples of electron transport materials foroptional layer 140 include metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3); phenanthroline-based compounds, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA) or 4,7-diphenyl-1,10-phenanthroline (DPA), and azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ). - The
cathode 150 is an electrode that is particularly efficient for injecting or collecting electrons or negative charge carriers. The cathode can be any metal or nonmetal having a lower work function than the first electrical contact layer (in this case, an anode). Materials for the second electrical contact layer can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, the lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used. - It is known to have other layers in organic electronic devices. For example, there can be a layer (not shown) between the
conductive polymer layer 120 and theactive layer 130 to facilitate positive charge transport and/or band-gap matching of the layers, or to function as a protective layer. Similarly, there can be additional layers (not shown) between theactive layer 130 and thecathode layer 150 to facilitate negative charge transport and/or band-gap matching between the layers, or to function as a protective layer. Layers that are known in the art can be used. In addition, any of the above-described layers can be made of two or more layers. Alternatively, some or all ofinorganic anode layer 110, theconductive polymer layer 120, theactive layer 130, andcathode layer 150, may be surface treated to increase charge carrier transport efficiency. The choice of materials for each of the component layers is preferably determined by balancing the goals of providing a device with high device efficiency. - It is understood that each functional layer may be made up of more than one layer.
- The device can be prepared by sequentially vapor depositing the individual layers on a suitable substrate. Substrates such as glass and polymeric films can be used. Conventional vapor deposition techniques can be used, such as thermal evaporation, chemical vapor deposition, and the like. Alternatively, the organic layers can be coated from solutions or dispersions in suitable solvents, using any conventional coating technique. In general, the different layers will have the following range of thicknesses:
anode 110, 500-5000 Å, preferably 1000-2000 Å;hole transport layer 120, 50-2500 Å, preferably 200-2000 Å; light-emittinglayer 130, 10-1000 Å, preferably 100-800 Å; optionalelectron transport layer 140, 50-1000 Å, preferably 100-800 Å;cathode 150, 200-10,000 Å, preferably 300-5000 Å. The location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, is affected by the relative thickness of each layer. For examples, when an emitter, such as Alq3 is used as the electron transport layer, the electron-hole recombination zone can be in the Alq3 layer. The emission would then be that of Alq3, and not the desired sharp lanthanide emission. Thus the thickness of the electron-transport layer must be chosen so that the electron-hole recombination zone is in the light-emitting layer. The desired ratio of layer thicknesses will depend on the exact nature of the materials used. - It is understood that the efficiency of the devices of the invention made with metal complexes, can be further improved by optimizing the other layers in the device. For example, more efficient cathodes such as Ca, Ba, Mg/Ag, or LiF/Al can be used. Shaped substrates and novel hole transport materials that result in a reduction in operating voltage or increase quantum efficiency are also applicable. Additional layers can also be added to tailor the energy levels of the various layers and facilitate electroluminescence.
- The iridium complexes of the invention often are phosphorescent and photoluminescent and may be useful in other applications. For example, organometallic complexes of iridium have been used as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts. The bis cyclometallated complexes can be used to sythesize tris cyclometalated complexes where the third ligand is the same or different.
- The following examples illustrate certain features and advantages of the present invention. They are intended to be illustrative of the invention, but not limiting. All percentages are mole percents, unless otherwise indicated.
- This example illustrates the preparation of a ligand parent compound (HL), 2-(2-thienyl)-5-(trifluoromethyl)pyridine.
- 2-thienylboronic acid (Lancaster Synthesis, Inc., 1.00 g, 7.81 mmmol), 2-chloro-5-trifluoromethylpyrdine (Aldrich Chemical Co., 1.417 g, 7.81 mmol), tetrakistriphenylphosphine palladium(0) (Aldrich, 451 mg, 0.391 mmol), potassium carbonate (EM Science, 3.24 g, 23.4 mmol), water (20 mL), and dimethoxyethane (Aldrich, 20 mL) were allowed to stir at reflux for 20 hours under N2, after which time the mixture was cooled to room temperature and the organic and aqueous layers were separated. The aqueous layer was extracted with 3×50 mL of diethyl ether, and the combined organic fractions were dried with sodium sulfate, filtered, and the filtrate was evaporated to dryness. The crude product was purified by silica gel flash chromatography with CH2Cl2/hexanes (1:1) as the eluent (product Rf=0.5), to afford the product as a white crystalline solid (yield=5.2 g, 73% isolated yield). 1H NMR (CDCl3, 296 K, 300 MHz): δ=7.73-7.57 (2H, m), 7.55 (1H, d, J=8.5 Hz), 7.34 (1H, d, J=4.8 Hz), 6.88 (1H d, J=4.8 Hz) ppm. 19F NMR (CDCl3, 296K, 282 MHz) δ=−62.78 ppm.
- This example illustrates the preparation of the intermediate dichloro bridged dimer, [IrCl{2-(2-thienyl)-5-(trifluoromethyl)pyridine}2]2.
- 2-(2-thienyl)-5-(trifluoromethyl)pyridine from Example 1 (555 mg, 2.42 mmol), iridium trichloride (Strem Chemicals, 401 mg, 1.13 mmol), 2-ethoxyethanol (Aldrich Chemical Co., 10 mL) and water (1 mL) were allowed to reflux under nitrogen for 15 hours, after which time the reaction was allowed to cool to room temperature. The resulting precipitated product was collected by filtration, washed with hexanes, and dried in vacuo, to afford 575 mg (37%) of the product as a red-orange solid. 1H NMR (CDCl3, 296 K, 300 MHz): δ=9.30 (4H, d, J=1.5 Hz), 7.80 (4H, dd, J=2.0 Hz and 8.5 Hz), 7.59 (4H, d, J=8.5 Hz), 7.21 (8H, d, J=4.8 Hz), 5.81 (d, 4H, J=4.9 Hz). 19F NMR (CDCl3, 296K, 282 MHz) δ=−62.07 ppm.
- This example illustrates the preparation of a tris-cyclometallated iridium complex, [Ir{2-(2-thienyl)-5-(trifluoromethyl)pyridine}3], compound 1-a from Table 1.
- [IrCl{2-(2-thienyl)-5-(trifluoromethyl)pyridine}2]2 from Example 2 (100 mg, 0.073 mmol), 2-(2-thienyl)-5-(trifluoromethyl)pyridine from Example 1 (201 mg, 0.88 mmol), and silver trifluoroacetate (Aldrich, 40 mg, 0.18 mmol) were combined and allowed to stir at 170-180° C. under nitrogen for 10 min. Then the mixture was allowed to cool to room temperature and it was redissolved in a minimum amount dichloromethane. The solution was passed through a silica gel column with dichloromethane/hexanes (1:1) as the eluting solvent. The first red-orange fraction to come down the column (product Rf=0.5) was collected and evaporated to dryness. The residue was suspended in hexanes, and the precipitated product was filtered and washed with excess hexanes to remove any residual 2-(2-thienyl)-5-(trifluoromethyl)pyridine, to afford the product as a red-orange solid. Isolated yield ≈50 mg (39%). 1H NMR (CDCl3, 296 K, 300 MHz): δ=7.73-7.57 (6H, m), 7.55 (3H, d, J=8.5 Hz), 7.34 (3H, d, J=4.8 Hz), 6.88 (3H, d, J=4.8 Hz). 19F NMR (CDCl3, 296K, 282 MHz) δ=−62.78.
- Compounds 1-b through 1-f in Table 1 were made using a similar procedure.
- This example illustrates the preparation of the ligand parent compound, 1-(4-tert-butylphenyl)-isoquinoline.
- 4-tert-butylphenylboronic acid (Aldrich Chemical Co., 5.00 g, 30.56 mmmol), 1-chloroisoquinoline (Aldrich Chemical Co., 5.44 g, 30.56 mmol), tetrakistriphenylphosphine palladium(0) (Aldrich, 800 mg, 0.69 mmol), potassium carbonate (EM Science, 12.5 g, 23.4 mmol), water (50 mL), and dimethoxyethane (Aldrich, 75 mL) were allowed to stir at reflux for 20 h under N2, after which time the mixture was cooled to room temperature and the organic and aqueous layers were separated. The aqueous layer was extracted with 3×75 mL of diethyl ether, and the combined organic fractions were dried with sodium sulfate, filtered, and the filtrate was evaporated to dryness. The crude material was chromatographed on a silica gel column, first by eluting the catalyst byproduct with 4:1 hexanes/dichloromethane, and finally the product was eluted with dichloromethane/MeOH (9.5:0.5, product Rf=0.7). The pure product fractions were collected and dried in vacuo, to afford 4.5 g (56% isolated yield) of a light yellow solid, >95% pure NMR spectroscopy. 1H NMR (CDCl3, 296 K, 300 MHz): δ=8.58 (1H, d, J=5.70 Hz), 8.15 (1H, d, J=8.5 Hz), 7.83 (1H, d, J=8.5 Hz), 7.5-7.7 (7H, m), 1.38 (9H, s) ppm.
- This example illustrates the preparation of the dichloro bridged dimer, IrCl{1-(4-t-Bu-phenyl)-isoquinoline}2]2.
- 1-(4-t-Bu-phenyl)-isoquinoline from Example 4 (1.00 g, 3.82 mmol), IrCl3(H2O)3 (Strem Chemicals, 633 mg, 1.79 mmol), and 2-ethoxyethanol (Aldrich Chemical Co., 40 mL) were allowed to stir at reflux for 15 h, after which time the mixture was poured into an equal volume of water. The resulting orange precipitate was isolated by filtration, washed with water, and allowed to dry in vacuo. Then the solid was re-dissolved in dichloromethane and passed through a silica gel pad. The red eluted dichloromethane solution was evaporated to dryness, and the resulting solid was suspended in hexanes. The solid was isolated by filtration to afford 650 mg (49%) of a red-orange solid, >95% pure by NMR spectroscopy.1H NMR (CD2Cl2, 296 K, 300 MHz): δ=9.37 (4H, d, J=6.5 Hz), 8.95 (4H, d, J=8.2 Hz), 8.07 (4H, d, J=8.5 Hz), 7.90 (4H, dd, J=1.4 and 8.2 Hz), 7.7-7.9 (8H, m), 6.94 (4H, dd, J=2.0 and 8.4 Hz), 6.86 (4H, d, J=6.4 Hz), 5.92 (4 H, d, J=2.0 Hz), 0.81 (36H, s) ppm.
- This example illustrates the preparation of a bis cyclometallated iridium complex, [Ir(acac){1-(4-t-Bu-phenyl)-isoquinoline}2], compound 1-j, from Table 1.
- [IrCl{1-(4-t-Bu-phenyl)-isoquinoline}2]2 from Example 5 (200 mg, 0.135 mmol), sodium acetylacetonate (Aldrich, 80 mg, 0.656 mmol), and 2-ethoxyethanol (Aldrich, 5 mL) were allowed to stir at 120° C. for 10 min, then the volatile components were removed in vacuo. The residue was redissolved in dichloromethane and passed through a pad of silica gel on a sintered glass funnel with CH2Cl2 as the eluting solvent. The red-luminescent filtrate was evaporated to dryness to afford 190 mg (87% isolated yield) of the desired product, >95% by 1H NMR. 1H NMR (CDCl3, 296 K, 300 MHz): δ=8.94 (2H, dd, J=2.1 and 8.2 Hz), 8.49 (2H, d, J=6.4 Hz), 8.11 (2H, d, J=8.50 Hz), 7.98 (2H, d, J=3.9 and 9.6 Hz), 7.6-7.8 (4H, m), 7.55 (2H, d, J=6.4 Hz), 6.99 (2H, d, J=2.1 and 8.5 Hz), 6.21 (2H, d, J=2.0 Hz), 5.35 (1H, s), 1.84 (6H, s), 0.95 (18H, s) ppm.
- Compounds 1-g through 1-i and 1-k through1-l in Table 1 were made using a similar procedure.
- This example illustrates the preparation of the ligand parent compound, 1-(perdeuterophenyl)-isoquinoline.
- Perdeutero-benzeneboronic acid, dimethylester: To a solution of bromobenzene-d5 (Aldrich Chemical Co., 10.0 g, 61.7 mmol) in dry diethyl ether (50 mL) at −78° C. under nitrogen was added n-BuLi (Aldrich, 1.6 M in hexanes, 38.6 mL) slowly over two minutes. The stirred mixture was allowed to warm to room temperature for 2 hours, and then it was transferred to another flask which contained a stirred solution of trimethylborate (Aldrich, 50 mL, 494 mmol) and dry diethylether (200 mL) at −78° C. under N2. The resulting mixture was allowed to warm to room temperature and stirred for 15 hours, after which time ice-cold 2 M HCl (50 mL) was added to quench the reaction mixture. The organic phase was separated, dried with sodium sulfate, filtered, and evaporated to dryness, to afford 4.9 g (52% yield) of the desired product as a white solid. 1H NMR (CDCl3, 296 K, 300 MHz) δ 3.73 (br s) ppm.
- 1-(perdeuterophenyl)-isoquinoline: 1-Chloroisoquinoline (Aldrich Chemical Co., 5.00 g, 30.6 mmol), perdeuterobenzeneboronic acid, dimethyl ester from the synthesis above (4.87 g, 31.4 mmol), potassium carbonate (EM Science, 8.4 g, 61.2 mmol), tetrakistriphenylphosphine palladium(0) (Aldrich, 707 mg, 0.611 mmol), dimethoxymethane (Aldrich, 100 mL) and water (100 mL) were combined under nitrogen, and the mixture was allowed to reflux for 15 hours. After this time, the organic layer was separated, and the aqueous layer was extracted with 3×50 mL of diethyl ether. The combined organic components were dried with sodium sulfate, filtered, and evaporated to dryness. The resulting crude product was purified by silica gel chromatography. The phosphine catalyst was first eluted with 4:1 dichloromethane/hexanes, and then the desired product was eluted with 100% dichloromethane and then dichloromethane/methanol (95:5, product Rf=0.6). The product fractions were combined and evaporated to dryness, to afford 4.5 g (70%) of the desired product as a white solid. 1H NMR (CDCl3, 296 K, 300 MHz): δ=8.60 (1H, d, J=5.7 Hz), 8.10 (1H, d, J=8.5 Hz), 7.88 (1H, d, J=8.4 Hz), 7.67 (2H, m), 7.53 (1H, m) ppm.
- This example illustrates the preparation of the dichloro bridged dimer, [IrCl{1-(perdeuterophenyl)-isoquinoline}2]2.
- 1-(Perdeuterophenyl)-isoquinoline from Example 7 (3.00 g, 14.3 mmol), IrCl3(H2O)3 (Strem Chemicals, Inc.) 2.42 g, 6.80 mmol), 2-ethoxyethanol (Aldrich Chemical Co., 45 mL), and water (5 mL) were allowed to stir at reflux for 15 hours under nitrogen, after which time the resulting precipitated product was isolated via filtration. It was then washed with excess methanol, then diethyl ether, and finally dried in vacuo, to afford the desired product as a red-orange solid. Yield=2.12 g (48%).
- This example illustrates the preparation of a bis cyclometallated iridium complex, Ir(acac){1-(perdeuterophenyl)-isoquinoline}2, compound 1-m, from Table 1.
- [IrCl{1-(perdeuterophenyl)-isoquinoline}2]2 from Example 8 (300 mg, 0.232 mmol), acetylacetone, sodium salt (Aldrich Chemical Co., 71 mg, 0.581 mmol), and 2-ethoxyethanol (Aldrich, 15 mL) were allowed to stir at 120° C. for 45 min, after which time the volatile components were removed in vacuo. The resulting residue was taken up in dichloromethane and passed through a silica gel pad with dichloromethane as the eluting solvent. The first red fraction (Rf=1.0) was collected and evaporated to dryness, to afford the desired product as a red-orange solid. Yield=230 (70%). 1H NMR (CDCl3, 296 K, 300 MHz) δ=8.99 (1H, m), 8.45 (1H, d, J=6.4 Hz), 7.98 (1H, m), 7.75 (2H, m), 7.55 (1H, d, J=6.3 Hz), 5.29 (1H, s), 1.79 (6H, s) ppm. Additional signals observed that are due to small amounts of H/D exchange that occurred in the cyclometallation reaction: 8.24 (0.5 H, m), 6.96 (0.20 H, d, J=9.8 Hz).
- This example illustrates the formation of OLEDs using the iridium complexes of the invention.
- Thin film OLED devices including a hole transport layer (HT layer), electroluminescent layer (EL layer) and at least one electron transport layer (ET layer) were fabricated by the thermal evaporation technique. An Edward Auto 306 evaporator with oil diffusion pump was used. The base vacuum for all of the thin film deposition was in the range of 10−6 torr. The deposition chamber was capable of depositing five different films without the need to break up the vacuum.
- An indium tin oxide (ITO) coated glass substrate was used, having an ITO layer of about 1000-2000 Å. The substrate was first patterned by etching away the unwanted ITO area with 1N HCl solution, to form a first electrode pattern. Polyimide tape was used as the mask. The patterned ITO substrates were then cleaned ultrasonically in aqueous detergent solution. The substrates were then rinsed with distilled water, followed by isopropanol, and then degreased in toluene vapor for ˜3 hours. Alternatively, patterned ITO from Thin Film Devices, Inc was used. These ITO's are based on Corning 1737 glass coated with 1400 Å ITO coating, with sheet resistance of 30 ohms/square and 80% light transmission.
- The cleaned, patterned ITO substrate was then loaded into the vacuum chamber and the chamber was pumped down to 10−6 torr. The substrate was then further cleaned using an oxygen plasma for about 5-10 minutes. After cleaning, multiple layers of thin films were then deposited sequentially onto the substrate by thermal evaporation. Finally, patterned metal electrodes of Al were deposited through a mask. The thickness of the film was measured during deposition using a quartz crystal monitor (Sycon STC-200). All film thicknesses reported in the Examples are nominal, calculated assuming the density of the material deposited to be one. The completed OLED device was then taken out of the vacuum chamber and characterized immediately without encapsulation.
- A summary of the device layers and thicknesses are given in Table 2. In all cases the anode was ITO as discussed above, and the cathode was Al having a thickness in the range of 700-760 Å.
TABLE 2 HT layer EL layer ET layer Cathode Sample Thickness, Å thickness, Å thickness, Å thickness, Å 1 MPMP Compound 1-a DPA Al 504 411 418 737 2 MPMP Compound 1-i DPA Al 513 420 412 737 3 MPMP Compound 1-j DPA Al 513 414 400 721 4 MPMP Compound 1-k DPA Al 530 407 407 732 5 MPMP Compound 1-l DPA Al 533 411 414 727 6 MPMP Compound 1-f DPA Al 563 305 408 725 7 MPMP Compound 1-h DPA Al 538 409 418 734 8 MPMP Compound 1-c DPA Al 526 428 402 728 9 MPMP Compound 1-m DPA Al 530 404 415 725
DPA = 4,7-diphenyl-1,10-phenanthroline
ET = electron transport
EL = electroluminescence
HT = hole transport
MPMP = bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane
- The OLED samples were characterized by measuring their (1) current-voltage (I-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectra versus voltage. The apparatus used, 200, is shown in
FIG. 7 . The I-V curves of an OLED sample, 220, were measured with a Keithley Source-Measurement Unit Model 237, 280. The electroluminescence radiance (in the unit of Cd/m2) vs. voltage was measured with a Minolta LS-110 luminescence meter, 210, while the voltage was scanned using the Keithley SMU. The electroluminescence spectrum was obtained by collecting light using a pair of lenses, 230, through an electronic shutter, 240, dispersed through a spectrograph, 250, and then measured with a diode array detector, 260. All three measurements were performed at the same time and controlled by a computer, 270. The efficiency of the device at certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device. The unit is in Cd/A. - The results are given in Table 3 below.
TABLE 3 Electroluminescent Properties of Iridium Compounds Approximate Peak Peak Peak Radiance, efficiency, Wavelengths, Sample Cd/m2 Cd/A nm 1 200 Cd/m2 1.5 570 at 25 V 2 100 Cd/m2 0.65 620 at 22 V 3 200 1.2 625 at 22 V 4 1 0.04 >670 at 21 V 5 400 1.6 605 and 640 at 22 V 6 5 0.3 585 at 20 V 7 7 0.06 620 at 23 V 8 2.5 0.3 625 at 23 V 9 350 0.6 625 at 19 V - This example illustrates the formation of OLED's using a red-emissive material of the invention as a dopant in a poly(fluorene) polymer matrix. The resulting blend will be used as the active red-emissive layer in an OLED. The iridium complex, [Ir(acac){1-(4-t-Bu-phenyl)-isoquinoline}2], compound 1-j, from Table 1, will be prepared as described in Example 6. The polyfluorene polymer will be prepared as described in Yamamoto, Progress in Polymer Science, Vol. 17, p 1153 (1992), where the dihalo, preferably dibromo, derivatives of the monomeric units are reacted with a stoichiometric amount of a zerovalent nickel compound, such as bis(1,5-cyclooctadiene)nickel(0).
- The organic film components in this OLED example will all be solution processed. Device assembly will be as follows: ITO/glass substrate (Applied Films) will be patterned (device active area=entire 3 cm2) and cleaned as described in Example 10. The substrate will then be further cleaned by placing in a 300 W plasma oven for 15 min. A poly(ethylenedioxythiophene)-poly(styrenesufonic acid) (PEDOT-PSSA, Bayer Corp.) buffer layer (i.e. hole transport/injection layer) will then be spin-coated to a thickness of 90 nm. The film will be dried on a hotplate at 200° C. for 3 min. The substrate will be then transferred to a nitrogen-filled glovebox, at which point a solution of poly(fluorene) polymer, [Ir(acac){1-(4-t-Bu-phenyl)-isoquinoline}2] (1.6 μmol), and anhydrous toluene (7.5 mL) will be spin coated on the substrate to a thickness of 70 nm. The substrate will be then transferred to a high vacuum chamber, where Ba (3.5 nm) followed by Al (400 nm) will be thermally deposited at 2.0×10−6 torr. The resulting OLED device will then be sealed from air by gluing a glass slide on top of the cathode with the use of a UV-curable epoxy resin.
- The device will be fully characterized by acquiring current-voltage, luminance-voltage, luminance-current, efficiency-voltage, and efficiency-current profiles. This will be accomplished with the use of a computer-driven (Labview software) Keithley Source-Measurement Unit and a photodiode, the latter which integrated light output over the entire 3 cm2 device active area.
Claims (14)
1. An organic electronic device comprising an active layer comprising a light-emitting layer having an emission maximum in the range of 570 to 700 nm, wherein the active layer comprises at least one compound having a formula according to Formula I:
IrL3 (I)
where:
L is selected from Formula III, Formula IV, Formula V, Formula VI, and Formula VII in FIG. 1 , and Formula VIII, Formula IX and Formula X in FIG. 2 , where:
in Formula III:
R3 through R6 are the same or different and at least one of R3 through R6 is selected from D, F, CnF2n+1, OCnF2n+1, and OCF2Y;
at each occurrence in any of Formulae III through VII:
R1 is the same or different at each occurrence and is selected from D, CnH2n+1, OR11, SR11, N(R11)2, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y, or adjacent pairs of R1 can be joined to form a five- or six-membered ring;
Y is H, Cl, or Br; and
A is S or NR11;
at each occurrence in any of Formulae III through X:
R11 is the same or different at each occurrence and is H or CnH2n+1;
n is an integer from 1 through 12; and
α is 0, 1 or 2;
at each occurrence in any of Formulae IV through X:
δ is 0 or an integer from 1 through 4;
in Formula VII:
E1 through E4 are the same or different and are N or CR12, with the proviso that at least one E is N; and
R12 is the same or different at each occurrence and is selected from H, D, SR11, N(R11)2, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y, or adjacent pairs of R12 can be joined to form a five- or six-membered ring, with the proviso that at least one of R12 is selected from D, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y;
at each occurrence in any of Formulae VIII through X:
R2 and R7 through R10 are the same or different at each occurrence and are selected from H, D, CnH2n+1, OR11, SR11, and N(R11)2, or adjacent pairs of R groups can be joined to form a five- or six-membered ring
provided that, where the active layer contains less than 20% by weight of the at least one compound, a diluent is also present.
2. The device of claim 1 wherein R5 is CF3.
3. The device of claim 1 wherein R8 is selected from OCH3 and OH.
4. The device of claim 1 wherein R9 is t-butyl.
5. The device of claim 1 wherein the diluent is selected from poly(N-vinyl carbazole); polysilane; 4,4′-N,N′-dicarbazole biphenyl; and tertiary aromatic amines.
6. The device of claim 1 , further comprising a hole transport layer selected from N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine; 1,1-bis[(di-4-tolylamino) phenyl]cyclohexane; N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine; tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine; α-phenyl-4-N,N-diphenylaminostyrene; p-(diethylamino)benzaldehyde diphenylhydrazone; triphenylamine; bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane; 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline; 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane; N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine; porphyrinic compounds; and combinations thereof.
7. The device of claim 1 , further comprising an electron transport layer selected from tris(8-hydroxyquinolato)aluminum; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; 4,7-diphenyl-1,10-phenanthroline; 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole; 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole; and combinations thereof.
8. A compound selected from complex 1-a through 1-f, as shown in Table 1.
9. An organic electronic device comprising an active layer that comprises a compound selected from complex 1-a through 1-f, as shown in Table 1.
10. The device of claim 9 wherein the active layer further comprises a diluent.
11. The device of claim 10 wherein the diluent is selected from poly(N-vinyl carbazole); polysilane; 4,4′-N,N′-dicarbazole biphenyl; and tertiary aromatic amines.
12. The device of claim 1 wherein the diluent is a conjugated polymer selected from polyarylenevinylenes, polyfluorenes, polyoxadiazoles, polyanilines, polythiophenes, polypyridines, polyphenylenes, copolymers thereof, and combinations thereof.
13. The device of claim 12 wherein the diluent is a conjugated polymer selected from polyarylenevinylenes, polyfluorenes, polyoxadiazoles, polyanilines, polythiophenes, polypyridines, polyphenylenes, copolymers thereof, and combinations thereof.
14. An active layer comprising at least one compound having a formula according to Formula I:
IrL3 (I)
where:
L is selected from Formula III, Formula IV, Formula V, Formula VI, and Formula VII in FIG. 1 , and Formula VIII, Formula IX and Formula X in FIG. 2 , where:
in Formula III:
R3 through R6 are the same or different and at least one of R3 through R6 is selected from D, F, CnF2n+1, OCnF2n+1, and OCF2Y;
at each occurrence in any of Formulae III through VII:
R1 is the same or different at each occurrence and is selected from D, CnH2n+1, OR11, SR11, N(R11)2, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y, or adjacent pairs of R1 can be joined to form a five- or six-membered ring;
Y is H, Cl, or Br; and
A is S or NR11;
at each occurrence in any of Formulae III through X:
R11 is the same or different at each occurrence and is H or CnH2n+1;
n is an integer from 1 through 12; and
α is 0, 1 or 2;
at each occurrence in any of Formulae IV through X:
δ is 0 or an integer from 1 through 4;
in Formula VII:
E1 through E4 are the same or different and are N or CR12, with the proviso that at least one E is N; and
R12 is the same or different at each occurrence and is selected from H, D, SR11, N(R11)2, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y, or adjacent pairs of R12 can be joined to form a five- or six-membered ring, with the proviso that at least one of R12 is selected from D, F, Cn(H+F)2n+1, OCn(H+F)2n+1, and OCF2Y;
at each occurrence in any of Formulae VIII through X:
R2 and R7 through R10 are the same or different at each occurrence and are selected from H, D, CnH2n+1, OR11, SR11, and N(R11)2, or adjacent pairs of R groups can be joined to form a five- or six-membered ring
provided that, where the active layer contains less than 20% by weight of the at least one compound, a diluent is also present.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/830,550 US20090162694A9 (en) | 2001-11-07 | 2007-07-30 | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US34791101P | 2001-11-07 | 2001-11-07 | |
US10/284,593 US7250512B2 (en) | 2001-11-07 | 2002-10-31 | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
US11/830,550 US20090162694A9 (en) | 2001-11-07 | 2007-07-30 | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/284,593 Division US7250512B2 (en) | 2001-11-07 | 2002-10-31 | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
US20070292718A1 true US20070292718A1 (en) | 2007-12-20 |
US20090162694A9 US20090162694A9 (en) | 2009-06-25 |
Family
ID=23365814
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/284,593 Expired - Lifetime US7250512B2 (en) | 2001-11-07 | 2002-10-31 | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
US11/830,550 Abandoned US20090162694A9 (en) | 2001-11-07 | 2007-07-30 | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/284,593 Expired - Lifetime US7250512B2 (en) | 2001-11-07 | 2002-10-31 | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
Country Status (10)
Country | Link |
---|---|
US (2) | US7250512B2 (en) |
EP (3) | EP2034000B1 (en) |
JP (3) | JP3981079B2 (en) |
KR (4) | KR101138095B1 (en) |
CN (1) | CN1705730A (en) |
AT (1) | ATE515550T1 (en) |
CA (1) | CA2466143A1 (en) |
IL (1) | IL160836A0 (en) |
TW (1) | TWI306447B (en) |
WO (1) | WO2003040256A2 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060063026A1 (en) * | 2002-04-26 | 2006-03-23 | Andrew Holmes | Solution-processable phosphorescent materials |
US20110073853A1 (en) * | 2008-06-26 | 2011-03-31 | E.I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110101316A1 (en) * | 2009-10-29 | 2011-05-05 | E.I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110127501A1 (en) * | 2009-10-29 | 2011-06-02 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode lminaires |
US20110204340A1 (en) * | 2009-08-24 | 2011-08-25 | E.I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110204339A1 (en) * | 2009-08-24 | 2011-08-25 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260144A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260143A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260140A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260142A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110266524A1 (en) * | 2009-10-29 | 2011-11-03 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110266525A1 (en) * | 2009-10-29 | 2011-11-03 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
Families Citing this family (103)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE261483T1 (en) | 1998-05-05 | 2004-03-15 | Massachusetts Inst Technology | LIGHT EMITTING POLYMERS AND DEVICES CONTAINING SAME |
US20050147534A1 (en) | 1998-05-05 | 2005-07-07 | Massachusetts Institute Of Technology | Emissive sensors and devices incorporating these sensors |
US6821645B2 (en) * | 1999-12-27 | 2004-11-23 | Fuji Photo Film Co., Ltd. | Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex |
US20020121638A1 (en) * | 2000-06-30 | 2002-09-05 | Vladimir Grushin | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds |
JP4006335B2 (en) * | 2000-11-30 | 2007-11-14 | キヤノン株式会社 | Light emitting element and display device |
EP1348711B1 (en) * | 2000-11-30 | 2018-06-13 | Canon Kabushiki Kaisha | Luminescent element and display |
US7998595B2 (en) * | 2001-02-14 | 2011-08-16 | Sanyo Electric Co., Ltd. | Organic electroluminescent device, luminescent material and organic compound |
JP3650082B2 (en) * | 2001-06-04 | 2005-05-18 | 三洋電機株式会社 | Organic electroluminescence device, light emitting material, and organic compound |
US7166368B2 (en) * | 2001-11-07 | 2007-01-23 | E. I. Du Pont De Nemours And Company | Electroluminescent platinum compounds and devices made with such compounds |
US7250512B2 (en) * | 2001-11-07 | 2007-07-31 | E. I. Du Pont De Nemours And Company | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
JP3969132B2 (en) * | 2002-03-12 | 2007-09-05 | コニカミノルタホールディングス株式会社 | Organic electroluminescence element and display device using the same |
US6995445B2 (en) * | 2003-03-14 | 2006-02-07 | The Trustees Of Princeton University | Thin film organic position sensitive detectors |
DE10320103A1 (en) | 2003-05-05 | 2004-12-02 | Basf Ag | Process for the preparation of phenylpyridine metal complexes and use of such complexes in OLEDs |
GB0311234D0 (en) | 2003-05-16 | 2003-06-18 | Isis Innovation | Organic phosphorescent material and organic optoelectronic device |
TWI287567B (en) * | 2003-07-30 | 2007-10-01 | Chi Mei Optoelectronics Corp | Light-emitting element and iridium complex |
CN102181281A (en) * | 2003-09-12 | 2011-09-14 | 住友化学株式会社 | Luminescent material and luminescent element comprising the same |
EP1687859B1 (en) * | 2003-11-25 | 2013-08-07 | Merck Patent GmbH | Organic electroluminescent element |
US7084425B2 (en) | 2003-12-05 | 2006-08-01 | Eastman Kodak Company | Organic electroluminescent devices |
US6835835B1 (en) * | 2003-12-05 | 2004-12-28 | Eastman Kodak Company | Synthesis for organometallic cyclometallated transition metal complexes |
US6870054B1 (en) * | 2003-12-05 | 2005-03-22 | Eastman Kodak Company | Synthesis for organometallic cyclometallated transition metal complexes |
GB0329364D0 (en) | 2003-12-19 | 2004-01-21 | Cambridge Display Tech Ltd | Optical device |
ATE332305T1 (en) * | 2004-01-13 | 2006-07-15 | Lg Electronics Inc | PHENYL PYRIDINE-IRIDIUM METAL COMPLEX COMPOUNDS FOR ORGANIC ELECTROLUMINIZING DEVICE, METHOD FOR PRODUCING THE COMPOUNDS, AND ORGANIC ELECTROLUMINIZING DEVICE USING THESE COMPOUNDS |
KR100615215B1 (en) * | 2004-04-13 | 2006-08-25 | 삼성에스디아이 주식회사 | Iridium compound and organic electroluminescent display using the same |
US7598388B2 (en) | 2004-05-18 | 2009-10-06 | The University Of Southern California | Carbene containing metal complexes as OLEDs |
US7154114B2 (en) * | 2004-05-18 | 2006-12-26 | Universal Display Corporation | Cyclometallated iridium carbene complexes for use as hosts |
US7534505B2 (en) * | 2004-05-18 | 2009-05-19 | The University Of Southern California | Organometallic compounds for use in electroluminescent devices |
US7601436B2 (en) | 2004-05-18 | 2009-10-13 | The University Of Southern California | Carbene metal complexes as OLED materials |
US7655323B2 (en) * | 2004-05-18 | 2010-02-02 | The University Of Southern California | OLEDs utilizing macrocyclic ligand systems |
US7393599B2 (en) | 2004-05-18 | 2008-07-01 | The University Of Southern California | Luminescent compounds with carbene ligands |
US7445855B2 (en) * | 2004-05-18 | 2008-11-04 | The University Of Southern California | Cationic metal-carbene complexes |
US7491823B2 (en) | 2004-05-18 | 2009-02-17 | The University Of Southern California | Luminescent compounds with carbene ligands |
US7279704B2 (en) | 2004-05-18 | 2007-10-09 | The University Of Southern California | Complexes with tridentate ligands |
WO2006034081A2 (en) * | 2004-09-17 | 2006-03-30 | Massachusetts Institute Of Technology | Polymers for analyte detection |
WO2006067074A1 (en) | 2004-12-23 | 2006-06-29 | Ciba Specialty Chemicals Holding Inc. | Electroluminescent metal complexes with nucleophilic carbene ligands |
JP4548121B2 (en) * | 2005-01-14 | 2010-09-22 | セイコーエプソン株式会社 | Method for manufacturing light emitting device |
KR100676965B1 (en) * | 2005-03-05 | 2007-02-02 | 주식회사 두산 | Novel iridium complex and organic electroluminescence device using the same |
KR100803125B1 (en) | 2005-03-08 | 2008-02-14 | 엘지전자 주식회사 | Red phosphorescent compounds and organic electroluminescence devices using the same |
KR100797469B1 (en) * | 2005-03-08 | 2008-01-24 | 엘지전자 주식회사 | Red phosphorescent compounds and organic electroluminescence devices using the same |
CA2617213C (en) | 2005-07-29 | 2014-01-28 | Resverlogix Corp. | Pharmaceutical compositions for the prevention and treatment of complex diseases and their delivery by insertable medical devices |
US8501328B2 (en) | 2005-11-07 | 2013-08-06 | Lg Display Co., Ltd. | Red phosphorescent compounds and organic electroluminescent devices using the same |
US9023489B2 (en) | 2005-11-07 | 2015-05-05 | Lg Display Co., Ltd. | Red phosphorescent compounds and organic electroluminescent devices using the same |
KR100662378B1 (en) * | 2005-11-07 | 2007-01-02 | 엘지전자 주식회사 | Red phosphorescene compounds and organic electroluminescence devices using the same |
TWI331484B (en) * | 2006-03-15 | 2010-10-01 | Au Optronics Corp | Organic emmitting material for oled |
KR20070097139A (en) * | 2006-03-23 | 2007-10-04 | 엘지전자 주식회사 | Red phosphorescene compounds and organic electroluminescence devices using the same |
US9118020B2 (en) * | 2006-04-27 | 2015-08-25 | Global Oled Technology Llc | Electroluminescent devices including organic eil layer |
GB2440368A (en) * | 2006-07-26 | 2008-01-30 | Oled T Ltd | Cathode coating for an electroluminescent device |
US7691292B2 (en) * | 2006-07-28 | 2010-04-06 | General Electric Company | Organic iridium compositions and their use in electronic devices |
US7718087B2 (en) * | 2006-07-28 | 2010-05-18 | General Electric Company | Organic iridium compositions and their use in electronic devices |
US7608677B2 (en) * | 2006-07-28 | 2009-10-27 | General Electric Company | Method for preparing polymeric organic iridium compositions |
US7691494B2 (en) * | 2006-07-28 | 2010-04-06 | General Electric Company | Electronic devices comprising organic iridium compositions |
US7704610B2 (en) * | 2006-07-28 | 2010-04-27 | General Electric Company | Electronic devices comprising organic iridium compositions |
US7718277B2 (en) * | 2006-07-28 | 2010-05-18 | General Electric Company | Electronic devices comprising organic iridium compositions |
US7695640B2 (en) * | 2006-07-28 | 2010-04-13 | General Electric Company | Organic iridium compositions and their use in electronic devices |
US8283423B2 (en) | 2006-09-29 | 2012-10-09 | Massachusetts Institute Of Technology | Polymer synthetic technique |
US8802447B2 (en) * | 2006-10-05 | 2014-08-12 | Massachusetts Institute Of Technology | Emissive compositions with internal standard and related techniques |
US20090215189A1 (en) * | 2006-10-27 | 2009-08-27 | Massachusetts Institute Of Technology | Sensor of species including toxins and chemical warfare agents |
JP5262104B2 (en) | 2006-12-27 | 2013-08-14 | 住友化学株式会社 | Metal complexes, polymer compounds, and devices containing them |
NZ579355A (en) | 2007-02-01 | 2012-03-30 | Resverlogix Corp | 2-(Aryl)-4-oxo-quinazoline derivatives |
CN101657518A (en) | 2007-03-08 | 2010-02-24 | 通用显示公司 | phosphorescent materials |
US9130177B2 (en) | 2011-01-13 | 2015-09-08 | Universal Display Corporation | 5-substituted 2 phenylquinoline complexes materials for light emitting diode |
JP2008270737A (en) * | 2007-03-23 | 2008-11-06 | Fujifilm Corp | Organic electroluminescent element |
JP4775297B2 (en) * | 2007-03-29 | 2011-09-21 | コニカミノルタホールディングス株式会社 | Organic electroluminescence element and display device using the same |
JP5202864B2 (en) * | 2007-03-29 | 2013-06-05 | コニカミノルタホールディングス株式会社 | Organic electroluminescence element and display device using the same |
US20080284317A1 (en) * | 2007-05-17 | 2008-11-20 | Liang-Sheng Liao | Hybrid oled having improved efficiency |
US20080284318A1 (en) * | 2007-05-17 | 2008-11-20 | Deaton Joseph C | Hybrid fluorescent/phosphorescent oleds |
US8034465B2 (en) * | 2007-06-20 | 2011-10-11 | Global Oled Technology Llc | Phosphorescent oled having double exciton-blocking layers |
US8067100B2 (en) * | 2007-10-04 | 2011-11-29 | Universal Display Corporation | Complexes with tridentate ligands |
US8383249B2 (en) * | 2007-10-04 | 2013-02-26 | Universal Display Corporation | Complexes with tridentate ligands |
KR100910153B1 (en) * | 2007-11-20 | 2009-07-30 | (주)그라쎌 | Novel red electroluminescent compounds and organic electroluminescent device using the same |
JP5258271B2 (en) * | 2007-11-28 | 2013-08-07 | キヤノン株式会社 | Organometallic complex, light emitting element and display device using the same |
CN101998983B (en) | 2007-12-17 | 2015-01-14 | 通用电气公司 | Emissive polymeric materials for optoelectronic devices |
US7973126B2 (en) * | 2007-12-17 | 2011-07-05 | General Electric Company | Emissive polymeric materials for optoelectronic devices |
US20090191427A1 (en) * | 2008-01-30 | 2009-07-30 | Liang-Sheng Liao | Phosphorescent oled having double hole-blocking layers |
EP2346837B8 (en) | 2008-06-26 | 2015-04-15 | Resverlogix Corporation | Methods of preparing quinazolinone derivatives |
JP5353509B2 (en) * | 2008-07-16 | 2013-11-27 | 国立大学法人群馬大学 | NOVEL COMPLEX COMPOUND, AND OXYGEN CONCENTRATION REAGENT USING THE SAME AND CANCER DIAGNOSIS |
US7989580B2 (en) | 2008-10-29 | 2011-08-02 | General Electric Company | Phosphorescent iridium complexes |
EP2660238B1 (en) | 2009-01-08 | 2015-05-06 | Resverlogix Corporation | Compounds for the prevention and treatment of cardiovascular disease |
KR101803259B1 (en) | 2009-03-18 | 2017-11-30 | 리스버로직스 코퍼레이션 | Novel anti-inflammatory agents |
BRPI1014956B8 (en) | 2009-04-22 | 2021-05-25 | Resverlogix Corp | anti-inflammatory agents |
JP5523016B2 (en) * | 2009-08-20 | 2014-06-18 | キヤノン株式会社 | Heterocyclic compound and organic light emitting device using the same |
EP2471121A4 (en) * | 2009-08-24 | 2013-10-30 | Du Pont | Organic light-emitting diode luminaires |
EP2471118A2 (en) * | 2009-08-24 | 2012-07-04 | E. I. du Pont de Nemours and Company | Organic light-emitting diode luminaires |
WO2011028471A2 (en) * | 2009-08-24 | 2011-03-10 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260603A1 (en) * | 2009-10-29 | 2011-10-27 | E.I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US10008677B2 (en) | 2011-01-13 | 2018-06-26 | Universal Display Corporation | Materials for organic light emitting diode |
JP5532020B2 (en) * | 2011-06-28 | 2014-06-25 | コニカミノルタ株式会社 | Organic electroluminescence element and display device using the same |
LT2773354T (en) | 2011-11-01 | 2019-08-12 | Resverlogix Corp. | Oral immediate release formulations for substituted quinazolinones |
CN107814821A (en) | 2012-01-12 | 2018-03-20 | Udc 爱尔兰有限责任公司 | Metal complex with dibenzo [F, H] quinoxaline |
CN103204880B (en) * | 2012-11-12 | 2016-01-20 | 吉林奥来德光电材料股份有限公司 | A kind of organophosphorus luminescent material, its preparation method and the organic electroluminescence device be made up of it |
WO2014080291A2 (en) | 2012-11-21 | 2014-05-30 | Rvx Therapeutics Inc. | Biaryl derivatives as bromodomain inhibitors |
WO2014080290A2 (en) | 2012-11-21 | 2014-05-30 | Rvx Therapeutics Inc. | Cyclic amines as bromodomain inhibitors |
CN102977152B (en) * | 2012-12-07 | 2014-12-10 | 太原理工大学 | Preparation method of orange-red phosphor powder |
MX2015007921A (en) | 2012-12-21 | 2016-03-03 | Zenith Epigenetics Corp | Novel heterocyclic compounds as bromodomain inhibitors. |
CN103936792B (en) * | 2013-12-12 | 2017-04-26 | 石家庄诚志永华显示材料有限公司 | Compound containing pyrazole structural unit |
KR101706203B1 (en) | 2014-11-10 | 2017-02-27 | 부산대학교 산학협력단 | Novel Red-emitting Iridium(III) Complexes with Hole Transporting Substitutent and Organic Light-Emitting Diodes Containing the Same |
EP3268007B1 (en) | 2015-03-13 | 2022-11-09 | Resverlogix Corp. | Compositions and therapeutic methods for the treatment of complement-associated diseases |
CN104987859A (en) * | 2015-06-24 | 2015-10-21 | 电子科技大学 | Organic electrophosphorescence luminescent material, preparation method thereof and luminescent device |
EP3689887A4 (en) | 2017-09-29 | 2021-06-09 | Sumitomo Chemical Company Limited | Composition and light-emitting device using same |
CN111909212B (en) | 2019-05-09 | 2023-12-26 | 北京夏禾科技有限公司 | Organic luminescent material containing 6-silicon-based substituted isoquinoline ligand |
CN111909213B (en) | 2019-05-09 | 2024-02-27 | 北京夏禾科技有限公司 | Metal complex containing three different ligands |
CN111909214B (en) | 2019-05-09 | 2024-03-29 | 北京夏禾科技有限公司 | Organic luminescent material containing 3-deuterium substituted isoquinoline ligand |
DE102021100230A1 (en) | 2020-01-10 | 2021-07-15 | Beijing Summer Sprout Technology Co., Ltd. | Organic light emitting material |
CN113105507B (en) * | 2020-01-10 | 2023-09-12 | 北京夏禾科技有限公司 | Organic light-emitting material |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3718488A (en) * | 1971-03-02 | 1973-02-27 | Du Pont | Precious metal decorating compositions containing bis-chelate derivatives of palladium |
US5552678A (en) * | 1994-09-23 | 1996-09-03 | Eastman Kodak Company | AC drive scheme for organic led |
US20010019782A1 (en) * | 1999-12-27 | 2001-09-06 | Tatsuya Igarashi | Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex |
US6303238B1 (en) * | 1997-12-01 | 2001-10-16 | The Trustees Of Princeton University | OLEDs doped with phosphorescent compounds |
US20010053462A1 (en) * | 2000-05-02 | 2001-12-20 | Masayuki Mishima | Light-emitting device |
US20020064681A1 (en) * | 2000-09-26 | 2002-05-30 | Takao Takiguchi | Luminescence device, display apparatus and metal coordination compound |
US20020063516A1 (en) * | 2000-09-26 | 2002-05-30 | Akira Tsuboyama | Limuninescence device, display apparatus and metal coordination compound |
US20020182441A1 (en) * | 2000-08-11 | 2002-12-05 | Trustee Of Princeton University | Organometallic compounds and emission-shifting organic electrophosphorescence |
US20030059646A1 (en) * | 2000-11-30 | 2003-03-27 | Canon Kabushiki Kaisha | Luminescence device and display apparatus |
US20030068628A1 (en) * | 1990-02-12 | 2003-04-10 | Aventis Pharma S.A. | Nucleotide sequences coding for variable regions of beta chains of human T lymphocyte receptors, corresponding peptide segments and the diagnostic and therapeutic uses |
US20030072984A1 (en) * | 2001-10-17 | 2003-04-17 | Saloka George Steve | System and method for rapid preheating of an automotive fuel cell |
US20030108771A1 (en) * | 2001-11-07 | 2003-06-12 | Lecloux Daniel David | Electroluminescent platinum compounds and devices made with such compounds |
US6670645B2 (en) * | 2000-06-30 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds |
US7147935B2 (en) * | 2000-11-30 | 2006-12-12 | Canon Kabushiki Kaisha | Luminescence device and display apparatus |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8909011D0 (en) | 1989-04-20 | 1989-06-07 | Friend Richard H | Electroluminescent devices |
EP0443861B2 (en) | 1990-02-23 | 2008-05-28 | Sumitomo Chemical Company, Limited | Organic electroluminescence device |
US5408109A (en) | 1991-02-27 | 1995-04-18 | The Regents Of The University Of California | Visible light emitting diodes fabricated from soluble semiconducting polymers |
WO2000070655A2 (en) | 1999-05-13 | 2000-11-23 | The Trustees Of Princeton University | Very high efficiency organic light emitting devices based on electrophosphorescence |
JP3949363B2 (en) * | 1999-10-26 | 2007-07-25 | 富士フイルム株式会社 | Aromatic fused ring compound, light emitting device material, and light emitting device using the same |
EP3379591A1 (en) | 1999-12-01 | 2018-09-26 | The Trustees of Princeton University | Complexes of form l2mx |
JP3929689B2 (en) * | 2000-03-28 | 2007-06-13 | 富士フイルム株式会社 | Highly efficient red light emitting device, light emitting device material comprising iridium complex and novel iridium complex |
JP3929690B2 (en) | 1999-12-27 | 2007-06-13 | 富士フイルム株式会社 | Light emitting device material, light emitting device and novel iridium complex comprising orthometalated iridium complex |
JP2001284049A (en) * | 2000-03-31 | 2001-10-12 | Fuji Photo Film Co Ltd | Color conversion membrane and light emitting device using it |
US20020121638A1 (en) | 2000-06-30 | 2002-09-05 | Vladimir Grushin | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds |
DE60143106D1 (en) | 2000-07-17 | 2010-11-04 | Fujifilm Corp | Light-emitting element and azole compound |
CN102041001B (en) | 2000-08-11 | 2014-10-22 | 普林斯顿大学理事会 | Organometallic compounds and emission-shifting organic electrophosphorescence |
JP4344494B2 (en) * | 2000-08-24 | 2009-10-14 | 富士フイルム株式会社 | Light emitting device and novel polymer element |
JP4154145B2 (en) * | 2000-12-01 | 2008-09-24 | キヤノン株式会社 | Metal coordination compound, light emitting device and display device |
WO2002064700A1 (en) * | 2001-02-14 | 2002-08-22 | Sanyo Electric Co., Ltd. | Organic electroluminescence device, lumincescent material, and organic compound |
JP4438042B2 (en) * | 2001-03-08 | 2010-03-24 | キヤノン株式会社 | Metal coordination compound, electroluminescent element and display device |
JP2002359079A (en) * | 2001-05-31 | 2002-12-13 | Canon Inc | Light emitting element and display device |
JP3650082B2 (en) * | 2001-06-04 | 2005-05-18 | 三洋電機株式会社 | Organic electroluminescence device, light emitting material, and organic compound |
JP4285947B2 (en) * | 2001-06-15 | 2009-06-24 | 三洋電機株式会社 | Luminescent organometallic compound and light emitting device |
WO2002104080A1 (en) * | 2001-06-15 | 2002-12-27 | Canon Kabushiki Kaisha | Organic electroluminescnece device |
JP4208492B2 (en) * | 2001-06-15 | 2009-01-14 | キヤノン株式会社 | Light emitting element |
JP2003073387A (en) * | 2001-09-04 | 2003-03-12 | Canon Inc | Metal coordination compound and organic luminescent element |
US6835469B2 (en) * | 2001-10-17 | 2004-12-28 | The University Of Southern California | Phosphorescent compounds and devices comprising the same |
US7250512B2 (en) * | 2001-11-07 | 2007-07-31 | E. I. Du Pont De Nemours And Company | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds |
IL158314A0 (en) | 2001-12-26 | 2004-05-12 | Du Pont | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds |
-
2002
- 2002-10-31 US US10/284,593 patent/US7250512B2/en not_active Expired - Lifetime
- 2002-11-04 EP EP20080017886 patent/EP2034000B1/en not_active Expired - Lifetime
- 2002-11-04 JP JP2003542296A patent/JP3981079B2/en not_active Expired - Fee Related
- 2002-11-04 AT AT02786655T patent/ATE515550T1/en not_active IP Right Cessation
- 2002-11-04 KR KR1020117005913A patent/KR101138095B1/en active IP Right Grant
- 2002-11-04 WO PCT/US2002/035429 patent/WO2003040256A2/en active Application Filing
- 2002-11-04 EP EP10012661A patent/EP2325279A3/en not_active Withdrawn
- 2002-11-04 CN CNA02822163XA patent/CN1705730A/en active Pending
- 2002-11-04 IL IL16083602A patent/IL160836A0/en unknown
- 2002-11-04 KR KR1020047006848A patent/KR20050043757A/en not_active Application Discontinuation
- 2002-11-04 KR KR1020117020302A patent/KR101106874B1/en active IP Right Grant
- 2002-11-04 CA CA002466143A patent/CA2466143A1/en not_active Abandoned
- 2002-11-04 KR KR1020107012388A patent/KR20100066592A/en not_active Application Discontinuation
- 2002-11-04 EP EP02786655A patent/EP1442094B1/en not_active Expired - Lifetime
- 2002-11-07 TW TW091132776A patent/TWI306447B/en not_active IP Right Cessation
-
2007
- 2007-05-28 JP JP2007141159A patent/JP2007314792A/en active Pending
- 2007-05-28 JP JP2007141160A patent/JP4971034B2/en not_active Expired - Lifetime
- 2007-07-30 US US11/830,550 patent/US20090162694A9/en not_active Abandoned
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3718488A (en) * | 1971-03-02 | 1973-02-27 | Du Pont | Precious metal decorating compositions containing bis-chelate derivatives of palladium |
US20030068628A1 (en) * | 1990-02-12 | 2003-04-10 | Aventis Pharma S.A. | Nucleotide sequences coding for variable regions of beta chains of human T lymphocyte receptors, corresponding peptide segments and the diagnostic and therapeutic uses |
US5552678A (en) * | 1994-09-23 | 1996-09-03 | Eastman Kodak Company | AC drive scheme for organic led |
US6303238B1 (en) * | 1997-12-01 | 2001-10-16 | The Trustees Of Princeton University | OLEDs doped with phosphorescent compounds |
US20010019782A1 (en) * | 1999-12-27 | 2001-09-06 | Tatsuya Igarashi | Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex |
US20010053462A1 (en) * | 2000-05-02 | 2001-12-20 | Masayuki Mishima | Light-emitting device |
US6670645B2 (en) * | 2000-06-30 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds |
US20020182441A1 (en) * | 2000-08-11 | 2002-12-05 | Trustee Of Princeton University | Organometallic compounds and emission-shifting organic electrophosphorescence |
US20020064681A1 (en) * | 2000-09-26 | 2002-05-30 | Takao Takiguchi | Luminescence device, display apparatus and metal coordination compound |
US20020063516A1 (en) * | 2000-09-26 | 2002-05-30 | Akira Tsuboyama | Limuninescence device, display apparatus and metal coordination compound |
US20030059646A1 (en) * | 2000-11-30 | 2003-03-27 | Canon Kabushiki Kaisha | Luminescence device and display apparatus |
US7147935B2 (en) * | 2000-11-30 | 2006-12-12 | Canon Kabushiki Kaisha | Luminescence device and display apparatus |
US20030072984A1 (en) * | 2001-10-17 | 2003-04-17 | Saloka George Steve | System and method for rapid preheating of an automotive fuel cell |
US20030108771A1 (en) * | 2001-11-07 | 2003-06-12 | Lecloux Daniel David | Electroluminescent platinum compounds and devices made with such compounds |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060063026A1 (en) * | 2002-04-26 | 2006-03-23 | Andrew Holmes | Solution-processable phosphorescent materials |
US9023978B2 (en) | 2002-04-26 | 2015-05-05 | Cambridge Enterprise Ltd. | Solution-processable phosphorescent materials |
US20110073853A1 (en) * | 2008-06-26 | 2011-03-31 | E.I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US8546844B2 (en) | 2008-06-26 | 2013-10-01 | E I Du Pont De Nemours And Company | Process for forming an organic light-emitting diode luminaires having a single light-emitting layer with at least two light-emitting dopants |
US8772767B2 (en) | 2009-08-24 | 2014-07-08 | E I Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110204340A1 (en) * | 2009-08-24 | 2011-08-25 | E.I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110204339A1 (en) * | 2009-08-24 | 2011-08-25 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US8476620B2 (en) | 2009-08-24 | 2013-07-02 | E I Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US8471247B2 (en) | 2009-08-24 | 2013-06-25 | E I Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110266524A1 (en) * | 2009-10-29 | 2011-11-03 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260142A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110266525A1 (en) * | 2009-10-29 | 2011-11-03 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260140A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260143A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US20110260144A1 (en) * | 2009-10-29 | 2011-10-27 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US8669547B2 (en) * | 2009-10-29 | 2014-03-11 | E I Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
US8674343B2 (en) * | 2009-10-29 | 2014-03-18 | E I Du Pont De Nemours And Company | Organic light-emitting diodes having white light emission |
US8716700B2 (en) * | 2009-10-29 | 2014-05-06 | E I Du Pont De Nemours And Company | Organic light-emitting diodes having white light emission |
US8716699B2 (en) * | 2009-10-29 | 2014-05-06 | E I Du Pont De Nemours And Company | Organic light-emitting diodes having white light emission |
US20110127501A1 (en) * | 2009-10-29 | 2011-06-02 | E. I. Du Pont De Nemours And Company | Organic light-emitting diode lminaires |
US20110101316A1 (en) * | 2009-10-29 | 2011-05-05 | E.I. Du Pont De Nemours And Company | Organic light-emitting diode luminaires |
Also Published As
Publication number | Publication date |
---|---|
JP2005508437A (en) | 2005-03-31 |
EP2325279A3 (en) | 2012-05-30 |
KR20100066592A (en) | 2010-06-17 |
KR101138095B1 (en) | 2012-04-24 |
EP1442094B1 (en) | 2011-07-06 |
US20030096138A1 (en) | 2003-05-22 |
KR101106874B1 (en) | 2012-01-25 |
US7250512B2 (en) | 2007-07-31 |
EP2034000A2 (en) | 2009-03-11 |
JP4971034B2 (en) | 2012-07-11 |
KR20110112454A (en) | 2011-10-12 |
WO2003040256A2 (en) | 2003-05-15 |
CA2466143A1 (en) | 2003-05-15 |
WO2003040256A3 (en) | 2003-09-18 |
EP2034000A3 (en) | 2011-01-12 |
ATE515550T1 (en) | 2011-07-15 |
EP1442094A2 (en) | 2004-08-04 |
EP2034000B1 (en) | 2015-05-06 |
TWI306447B (en) | 2009-02-21 |
EP2325279A2 (en) | 2011-05-25 |
JP2007314792A (en) | 2007-12-06 |
KR20110032008A (en) | 2011-03-29 |
CN1705730A (en) | 2005-12-07 |
IL160836A0 (en) | 2004-08-31 |
TW200300128A (en) | 2003-05-16 |
JP2007270155A (en) | 2007-10-18 |
US20090162694A9 (en) | 2009-06-25 |
KR20050043757A (en) | 2005-05-11 |
JP3981079B2 (en) | 2007-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7250512B2 (en) | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds | |
US7517594B2 (en) | Electroluminescent platinum compounds and devices made with such compounds | |
EP1295514B1 (en) | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds | |
US6924047B2 (en) | Luminescent lanthanide complexes with imine ligands and devices made with such complexes | |
WO2005075601A1 (en) | Electroluminescent platinum compounds and devices made with such compounds | |
US7132681B2 (en) | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds | |
AU2002350128A1 (en) | Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds | |
AU2002354028A1 (en) | Electroluminescent platinum compounds and devices made with such compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |