WO2011158204A1 - Organic electronic devices comprising the layer containing at least one metal organic compound and at least one metal oxide - Google Patents

Organic electronic devices comprising the layer containing at least one metal organic compound and at least one metal oxide Download PDF

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WO2011158204A1
WO2011158204A1 PCT/IB2011/052625 IB2011052625W WO2011158204A1 WO 2011158204 A1 WO2011158204 A1 WO 2011158204A1 IB 2011052625 W IB2011052625 W IB 2011052625W WO 2011158204 A1 WO2011158204 A1 WO 2011158204A1
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alkyl
aryl
substituted
organic
metal
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PCT/IB2011/052625
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English (en)
French (fr)
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Soichi Watanabe
Christian Schildknecht
Gerhard Wagenblast
Christian Lennartz
Evelyn Fuchs
Oliver Molt
Thomas Gessner
Korinna Dormann
Nicolle Langer
Junichi Tanabe
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Basf Se
Basf (China) Company Limited
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Priority to JP2013514830A priority Critical patent/JP6014938B2/ja
Priority to CN201180039004.5A priority patent/CN103068950B/zh
Priority to EP11795282.0A priority patent/EP2582770A4/en
Priority to KR1020137001283A priority patent/KR101806586B1/ko
Publication of WO2011158204A1 publication Critical patent/WO2011158204A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • H—ELECTRICITY
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
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    • C09B69/008—Dyes containing a substituent, which contains a silicium atom
    • 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
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    • 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
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/156—Hole transporting layers comprising a multilayered structure
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to an organic electronic device including a first electrode, a second electrode and a first organic layer interposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide.
  • the present invention further relates to an apparatus comprising the organic electronic device according to the present invention.
  • Organic electronics is a subfield of electronics and uses electronic circuits which comprise polymers or smaller organic compounds. Fields of use of organic electronics are the use of polymers or smaller organic compounds in organic light-emitting diodes (OLEDs), use in organic solar cells (organic photovoltaics) and in switching elements such as organic transistors, for example organic FETs and organic TFTs.
  • OLEDs organic light-emitting diodes
  • organic solar cells organic photovoltaics
  • switching elements such as organic transistors, for example organic FETs and organic TFTs.
  • a preferred field of use according to the present application is the use of relatively small organic compounds in organic light-emitting diodes.
  • OLEDs Organic light-emitting diodes
  • OLEDs exploit the property of materials of emitting light when they are excited by electrical current.
  • OLEDs are of particular interest as an alternative to cathode ray tubes and liquid-crystal displays for producing flat visual dis- play units.
  • the devices comprising OLEDs are suitable especially for mobile applications, for example for applications in cellphones, laptops, etc., and for illumination.
  • the light-emitting materials (emitters) used may, as well as fluorescent materials (fluorescence emitters), be phosphorescent materials (phosphorescence emitters).
  • the phosphorescence emitters are typically organometallic complexes which, in contrast to the fluorescence emitters which exhibit singlet emission, exhibit triplet emission (M. A. Baldow et al., Appl. Phys. Lett. 1999, 75, 4 to 6).
  • the phosphorescence emitters are used, up to four times the quantum efficiency, energy efficiency and power efficiency is possible.
  • organic light-emitting diodes with long operative lifetime, good efficiency, high stability to thermal stress and a low use and operating voltage.
  • Such device compositions may, for example, comprise specific matrix materials in which the actual light emitter is present in distributed form.
  • the compositions may comprise blocker materials, it being possible for hole blockers, exciton blockers and/or electron blockers to be present in the device compositions.
  • the device compositions may further comprise hole injection materials and/or electron injection materials and/or charge transport materials such as hole transport materials and/or electron transport materials.
  • Suitable organic materials are organic compounds comprising an arylamine skeleton and having hole transporting properties, e.g. 4,4'-bis(N- ⁇ 4-[N,N'-bis(3-methylphenyl)amino]phenyl ⁇ -N- phenylaminojbiphenyl (DNTPD) and N,N'-bis(spiro-9,9'-bifluorene-2-yl)-N,N'- diphenylbenzidine (BSPB).
  • Suitable inorganic materials are metal oxides, especially molybdenum oxide, vanadium oxide, ruthenium oxide, and tungsten oxide.
  • US 2008/0008905 A1 discloses an electrode of a pixel or a pixel portion with a light transmitting conductive film containing a hole-transporting organic compound and a metal oxide which shows an electron accepting property with respect to the hole- transporting organic compound.
  • the organic compounds are aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons and high molecular compounds.
  • the inorganic compounds are transition metal oxides, whereby molybdenum oxide is particularly preferred.
  • DE 10 2008 051 132 A1 discloses an organic electronic device having a specific layer sequence.
  • the device comprises a charge transport layer comprising a matrix material comprising a dopant, wherein the matrix material and the dopant form a charge transfer complex.
  • suitable matrix materials for a hole transport layer are mentioned. All materials mentioned are organic materials, especially aromatic amino compounds. Suitable dopants are for example metal oxides.
  • US 2006/0008740 A1 discloses an organic device, including an organic compound having charge transporting ability.
  • the device comprising a charge transfer complex- contained layer having a charge transfer complex formed upon contact of an organic hole transporting compound and a molybdenum trioxide via a manner of lamination or mixing; wherein the organic hole transporting compound is in a state of radical cations in the charge transfer complex-contained layer.
  • Suitable organic hole-transporting compounds are arylamine compounds.
  • reduction of power consumption is achieved by using a hole transport layer comprising an organic compound, especially an arylamine compound, and a metal oxide, especially (in most cases) molybdenum oxide.
  • OLEDs organic light-emitting diodes
  • an organic electronic device including a first electrode, a second electrode and a first organic layer interposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide.
  • Organic electronic devices of the present invention having a first organic layer comprising at least one metal organic compound and at least one metal oxide show superior power efficiency, lifetime, quantum efficiency and/or a low operating voltage.
  • the first organic layer comprises at least one metal oxide, preferably one or two metal oxides, more preferably one metal oxide.
  • the metal oxide is preferably a transition metal oxide, more preferably an oxide of a metal belonging to Groups 4, 5, 6, 7 or 8 of the periodic table. Even more preferably, the metal oxide is selected from rhenium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, niobium oxide, tantalum oxide, chromium oxide and manganese oxide.
  • the metal may be present in said oxides in every suitable oxidation state. Most pref- erably, the metal oxide is molybdenum oxide (MoO x ) or rhenium oxide (ReO x ), especially Mo0 3 or Re0 3 .
  • Re0 3 is particularly preferably. It has been found by the inventors that by using Re0 3 electronic devices having superior operative lifetimes are obtained.
  • the metal oxide is employed in the first organic layer usually in an amount of from 0.1 to ⁇ 10 wt%, preferably 1 to 8 wt%, more preferably 3 to 5 wt% based on the total amount of the first organic layer (which is 100 wt%). It has been found by the inventors that there is an optimum amount of metal oxides. If more than the optimum amount is used, the operative lifetime of the electronic device is high but clearly reduced com- pared with the optimum amount.
  • the first organic layer comprises at least one metal organic compound, preferably one or two metal organic compounds, more preferably one metal organic compound.
  • metal organic compound (or organometallic compound) is generally understood by one of ordinary skill. According to the present invention, the term is understood as defined in Inorganic Chemistry (2nd edition) by Gary L. Miesler and Donald A. Tarr, Prentice-Hall (1998), page 422, chapter 13, first paragraph.
  • Preferred metal organic compounds are metal organic compounds having hole transporting properties.
  • the band gap of the at least one metal organic compound with hole transporting property generally greater than the band gap of the emitter material used.
  • band gap is understood to mean the triplet energy.
  • carbene complexes are, for example, carbene complexes as described in WO 2005/019373, WO 2006/056418, WO 2005/1 13704, WO 2007/1 15970, WO 2007/1 15981 and WO 2008/000727.
  • Examples for particularly preferred carbene complexes are compound of the following formula (I)
  • M 1 is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt,
  • Carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;
  • K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a ⁇ complex with M 1 ;
  • n is the number of carbene ligands, where n is at least 1 and when n > 1 the carbene ligands in the complex of the formula I can be identical or different;
  • m is the number of ligands L, where m can be 0 or ⁇ 1 and when m > 1 the ligands L can be identical or different;
  • o is the number of ligands K, where o can be 0 or ⁇ 1 and when o > 1 the ligands K can be identical or different;
  • n + m + o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n is at least 1 .
  • carbene complexes are described in WO 2005/19373.
  • a suitable carbene complex is fac-iridium-tris(1 ,3- diphenylbenzimidazoline-2-ylidene-C,C2') (lr(dpbic) 3 ) having the formula (la)
  • the at least one metal organic compound, preferably the carbene complex, is employed in the first organic layer usually in an amount of from >90 to 99.9 wt%, prefera- bly 92 to 99 wt%, more preferably 95 to 97 wt% based on the total amount of the first organic layer (which is 100 wt%).
  • the first organic layer comprises at least one metal organic compound and at least one metal oxide.
  • Preferred metal organic compounds and preferred metal oxides and suitable amounts of metal organic compounds and metal oxides are mentioned before.
  • the first organic layer is preferably a hole transport layer or a hole injection layer, more preferably a hole transport layer.
  • the first organic layer preferably comprises:
  • a metal oxide preferably a metal oxide selected from rhenium oxide, molybde- num oxide, vanadium oxide, tungsten oxide, niobium oxide, tantalum oxide, chromium oxide and manganese oxide in every suitable oxidation state, more preferably, molybdenum oxide (MoO x ) or rhenium oxide (ReO x ), especially Mo0 3 or Re0 3 , most preferably Re0 3 ; and
  • the first organic layer comprises:
  • the first organic layer is prepared by any method, for example by a wet method or a dry method.
  • the first organic layer can for example be prepared by co-evaporation of the above mentioned metal organic compound and metal oxide. Since especially Re0 3 is easily vaporized in vacuum, the co-evaporation method mentioned before is a preferred method. However, it is also possible to prepare the first organic layer in such a way that a solution including the above mentioned metal organic compound and metal alkoxide is coated and baked. As a coating method, for example an ink-jet method or a spin coating method can be used.
  • the further organic layers of the electronic device of the present invention mentioned below can be prepared in the same way as the first organic layer.
  • the first organic layer has usually a thickness of from 5 to 100 nm, preferably 20 to 80 nm.
  • the present invention relates to an organic layer, preferably a hole transport layer or a hole injection layer, comprising at least one metal organic compound and at least one metal oxide. Suitable metal organic compounds and metal oxides as well as suitable amounts are mentioned before.
  • the hole transport layer or the hole injection layer is a hole transport layer or hole injection layer in an organic light-emitting diode (OLED).
  • the organic electronic device additionally comprises a second organic layer comprising at least one compound of formula (II)
  • R 1 and R 2 are independenly of each other F, CrC 8 alkyl, or C 6 -Ci 4 aryl, which may optionally be substituted by one, or more CrC 8 alkyl groups, or
  • R 1 and/or R 2 combine to form a fused benzene ring group, which may optionally be substituted by one, or more CrC 8 alkyl groups, a and b are independently of each other 0, or an integer 1 to 3,
  • M is an alkali metal atom, or an earth alkaline metal atom
  • p is 1 , if M is an alkali metal atom, p is 2, if M is an earth alkaline metal atom.
  • the most preferred metal complex is (Liq), which can exist as the single species, or in other forms such as LigQg, where g is an integer, for example LigQg.
  • Q represents 8-hydroxyquinolate ligand or a derivative of 8-hydroxyquinolate.
  • the second organic layer additionally comprises at least one compound of formula (II I), (IVa) and/or (IVb)
  • R 81 , R 82 , R 83 , R 84 , R 81 ' , R 82' , R 83' , and R 84' are independently of each other H, C Ci 8 alkyl, CrCi 8 alkyl which is substituted by E and/or interrupted by D, C 6 -C24aryl, C 6 - C 2 4aryl which is substituted by G, C2-C 2 oheteroaryl, or C 2 -C2oheteroaryl which is substituted by G,
  • Q is an arylene or heteroarylene group, each of which may optionally be substituted by G;
  • E is -OR 29 ; -SR 29 ; -NR 25 R 26 ; -COR 28 ; -COOR 27 ; -CONR 25 R 26 ; -CN; or F;
  • G is E, C Ci 8 alkyl, d-Ci 8 alkyl which is interrupted by D, Ci-Ci 8 perfluoroalkyl, Ci-Ci 8 alkoxy, or CrCi 8 alkoxy which is substituted by E and/or interrupted by D, wherein
  • R 23 and R 24 are independently of each other H, C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -0-;
  • R 25 and R 26 are independently of each other C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -0-; or R and R together form a five or six membered ring, R and R are independently of each other C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by CrCi 8 alkyl, or CrCi 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -O-,
  • R 29 is C 6 -Ci 8 aryl; C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; d- Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -0-,
  • R 30 and R 31 are independently of each other Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl,
  • R 32 is Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl.
  • Preferred compounds of formula (III) are compounds of formula (Ilia)
  • R 89 is phenanthryl, pyrenyl, triphenylenyl, 1 ,10-phenanthrolinyl, triazinyl, dibenzothio- phenyl, or pyrimidinyl, each of which may optionally be substituted by one, or more C Ci 8 alkyl, C 6 -Ci 4 aryl, or C 2 -C 2 oheteroaryl groups,
  • R 90 is phenanthryl, pyrenyl, triphenylenyl, 1 ,10-phenanthrolinyl, triazinyl, dibenzothio- phenyl, or pyrimidinyl, each of which may optionally be substituted by one, or more C Ci 8 alkyl, C 6 -Ci 4 aryl, or C 2 -C 2 oheteroaryl groups,
  • R 91 is phenanthryl, pyrenyl, triphenylenyl, 1 ,10-phenanthrolinyl, triazinyl, dibenzothio- phenyl, pyrimidinyl, or dibenzofuranyl, each of which may optionally be substituted by one, or more CrCi 8 alkyl, C 6 -Ci 4 aryl, or C 2 -C 2 oheteroaryl groups,
  • R 92 is H, phenanthryl, pyrenyl, triphenylenyl, 1 ,10-phenanthrolinyl, triazinyl, diben- zothiophenyl, or pyrimidinyl, each of which may optionally be substituted by one, or more CrCi 8 alkyl, C 6 -Ci 4 aryl, or C 2 -C 2 oheteroaryl groups,
  • A is a single bond, arylene, or heteroarylene group, each of which may optionally be substituted by one, or more CrCi 8 alkyl groups; or -SiR 87 R 88 -, wherein R 87 and R 88 are independently of each other Ci-Ci 8 alkyl, or C 6 -Ci 4 aryl groups, which may optionally be substituted by one, or more Ci-Ci 8 alkyl groups.
  • Preferred compounds of formula (IVa) and (IVb) are:
  • CrCi 8 alkyl is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1 -methylhexyl, 1 ,1 ,3,3,5,5- hexamethylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1 -methylheptyl, 3- methylheptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl
  • d- C 8 alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl.
  • CrC 4 alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.
  • C 6 -Ci 4 aryl which optionally can be substituted, is typically phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1 -naphthyl, or 2-naphthyl, biphenylyl, ter- phenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted.
  • C 2 -C 2 oheteroaryl represents a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated ⁇ -electrons such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridaz- inyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinoliz
  • the C 6 -Ci 4 aryl and C 2 -C 2 oheteroaryl groups are preferably substituted by one, or more CrC 8 alkyl groups.
  • arylene radicals are phenylene, naphthylene, phenalenylene, antracylene and phenantrylene, which may optionally be substituted by one or more C Cisalkyl groups.
  • Preferred arylene radicals are 1 ,3-phenylene, 3,6-naphthylene, and 4,9- phenalenylene, which may optionally be substituted by one or more C Cisalkyl groups.
  • heteroarylene radicals are 1 ,3,4-thiadiazol-2,5-ylene, 1 ,3-thiazol-2,4- ylene, 1 ,3-thiazol-2,5-ylene, 2,4-thiophenylene, 2,5-thiophenylene, 1 ,3-oxazol-2,4- ylene, 1 ,3-oxazol-2,5-ylene and 1 ,3,4-oxadiazol-2,5-ylene, 2,5-indenylene, 2,6- indenylene, especially pyrazinylene, pyridinylene, pyrimidinylene, and triazolylene, which may optionally be substituted by one or more C Cisalkyl groups.
  • Preferred heteroarylene radicals are 2,6-pyrazinylene, 2,6-pyridinylene, 4,6-pyrimidinylene, and 2,6-triazolylene, which may optionally be substituted by one or more C Cisalkyl groups.
  • the second organic layer comprises a mixture of
  • the organic metal complex of formula (II) is contained in the second organic layer in an amount of 99 to 1 % weight, preferably 75 to 25 % by weight, more preferably about 50 % by weight, wherein the amount of compound of formula (II) and (III), or (IVa) or (IVb) sums up to 100 % by weight.
  • the synthesis of the compounds of formula (II) is described, for example, in Christoph Schmitz et al. Chem. Mater. 12 (2000) 3012-3019 and WO00/32717, or can be done in analogy to the methods described therein.
  • the second organic layer is preferably an electron transport layer.
  • the organic electronic device of the present invention includes a first electrode, a sec- ond electrode and a first organic layer interposed between the first electrode and the second electrode, wherein the first organic layer comprises at least one metal organic compound and at least one metal oxide.
  • the first organic layer comprises at least one metal organic compound and at least one metal oxide.
  • Preferred embodiments of the first organic layer are mentioned above. Suitable first and second electrodes are known to those skilled in the art.
  • the organic electronic device of the present invention is, for example, an organic solar cell (organic photovoltaics), a switching element such as an organic transistor, for example an organic field effect transistor (FET) or an organic thin-film transistor (TFT), an organic light emitting field effect transistor (OLEFET), or an organic light-emitting diode (OLED), preference being given to OLEDs.
  • a switching element such as an organic transistor, for example an organic field effect transistor (FET) or an organic thin-film transistor (TFT), an organic light emitting field effect transistor (OLEFET), or an organic light-emitting diode (OLED), preference being given to OLEDs.
  • FET organic field effect transistor
  • TFT organic thin-film transistor
  • OEFET organic light emitting field effect transistor
  • OLED organic light-emitting diode
  • Suitable structures of organic electronic devices are known to those skilled in the art and are specified below.
  • the organic transistor generally includes a semiconductor layer formed from an organic layer with hole transport capacity and/or electron transport capacity; a gate electrode formed from a conductive layer; and an insulating layer introduced between the semicon- ductor layer and the conductive layer. A source electrode and a drain electrode are mounted on this arrangement in order thus to produce the transistor element.
  • the organic layer with hole transport capacity comprises at least one metal organic compound and at least one metal oxide. Suitable metal organic compounds and metal oxides as well as suitable amounts are mentioned before.
  • the organic solar cell (photoelectric conversion element) generally comprises an organic layer present between two plate-type electrodes arranged in parallel.
  • the organic layer may be configured on a comb-type electrode.
  • at least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode.
  • the organic layer is formed from two sublayers, i.e. a layer with p-type semiconductor properties or hole transport capacity, and a layer formed with n-type semiconductor properties or electron transport capacity.
  • the layer with hole transport capacity comprises at least one metal organic compound and at least one metal oxide. Suitable metal organic compounds and metal oxides as well as suitable amounts are mentioned before.
  • OLED Organic light-emitting diode
  • the present invention further relates to an organic light-emitting diode comprising an anode An and a cathode Ka, a light-emitting layer E arranged between the anode An and the cathode Ka, a hole transport layer and/or a hole injection layer arranged between the light-emitting layer E and the anode An, and if appropriate at least one fur- ther layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for electrons/excitons, at least one electron transport layer and at least one electron injection layer, wherein the hole transport layer and/or the hole injection layer comprises at least one metal organic compound and at least one metal oxide. Suitable metal organic compounds and metal oxides as well as suitable amounts are mentioned before.
  • the inventive organic light-emitting diode thus generally has the following structure: an anode (An) and a cathode (Ka) and a light-emitting layer E arranged between the anode (An) and the cathode (Ka) and an hole transport layer and/or hole injection layer arranged between the light-emitting layer E and the anode An.
  • the inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:
  • the OLED does not have all of the layers mentioned; for example, OLEDs which have layers (1 ), (2), (3), (4) and (6), are likewise suitable.
  • the OLEDs may have a blocking layer for electrons/excitons between the hole transport layer (2) and the light-emitting layer (3).
  • the OLEDs may have a hole injection layer between the hole transport layer (2) and the light-emitting layer.
  • a plurality of the aforementioned functions are combined in one layer and are assumed, for example, by a single material present in this layer.
  • a material used in the hole transport layer in one embodiment, may simultaneously block excitons and/or electrons.
  • the individual layers of the OLED among those specified above may in turn be formed from two or more layers.
  • the hole transport layer may be formed from a layer into which holes are injected from the electrode, and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer.
  • the electron transport layer may likewise consist of a plurality of layers, for example a layer in which electrons are injected by the electrode, and a layer which receives electrons from the electron injection layer and transports them into the light-emitting layer.
  • These layers mentioned are each selected according to factors such as energy level, thermal resistance and charge carrier mobility, and also energy difference of the layers specified with the organic layers or the metal electrodes.
  • the person skilled in the art is ca- pable of selecting the structure of the OLEDs such that it is matched optimally to the organic compounds used as emitter substances in accordance with the invention.
  • the HOMO (highest occupied molecular orbital) of the hole transport layer should be matched to the work func- tion of the anode
  • the LUMO (lowest unoccupied molecular orbital) of the electron transport layer should be matched to the work function of the cathode, provided that the aforementioned layers are present in the inventive OLEDs.
  • the anode (1 ) is an electrode which provides positive charge carriers. It may be formed, for example, from materials which comprise a metal, a mixture of various metals, a metal alloy, a metal oxide or a mixture of various metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise metals and alloys of the metals of the main groups, transition metals and of the lanthanoids, especially the metals of groups lb, IVa, Va and Via of the periodic table of the elements, and the transi- tion metals of group Villa.
  • the anode When the anode is to be transparent, generally mixed metal oxides of groups lib, 1Mb and IVb of the periodic table of the elements (lUPAC version) are used, for example indium tin oxide (ITO). It is likewise possible that the anode (1 ) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (June 1 1 , 1992). At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed.
  • the material used for the anode (1 ) is preferably ITO.
  • Suitable hole transport materials for layer (2) of the inventive OLEDs - in the case that the hole transport layer does not comprise at least one metal organic compound and at least one metal oxide or in addition to the at least one metal organic compound and at least one metal oxide - are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, Vol. 18, pages 837 to 860, 1996. Both hole-transport molecules and polymers can be used as the hole transport material.
  • Hole-transport molecules typically used are selected from the group consisting of tris[N-(1 -naphthyl)- N-(phenylamino)]triphenylamine (1 -NaphDATA), 4,4'-bis[N-(1 -naphthyl)-N- phenylamino]biphenyl (a-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1 ,1 '-biphenyl]- 4,4'-diamine (TPD), 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), te
  • Hole-transporting polymers typically used are selected from the group consisting of polyvinylcarbazoles, (phenylmethyl)polysilanes and polyanilines. It is likewise possible to obtain hole-transporting polymers by doping hole-transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole-transporting molecules are the molecules already mentioned above.
  • it is possible to use carbene complexes as hole transport materials the band gap of the at least one hole transport material generally being greater than the band gap of the emitter material used. Suitable carbene complexes are mentioned before.
  • the hole transport layer (2) comprises at least one metal organic compound and at least one metal oxide, wherein suitable metal organic compounds and suitable metal oxides as well as suitable amounts of metal organic compounds and suitable metal oxides are mentioned above.
  • the light-emitting layer (3) comprises at least one emitter material.
  • it may be a fluroescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art.
  • the at least one emitter material is preferably a phosphorescence emitter.
  • the phosphorescence emitter compounds used with preference are based on metal complexes, and especially the complexes of the metals Ru, Rh, Ir, Pd and Pt, in particular the complexes of Ir, have gained significance.
  • Suitable metal complexes for use in the inventive OLEDs are described, for example, in documents WO 02/60910 A1 , US 2001/0015432 A1 , US 2001/0019782 A1 , US 2002/0055014 A1 , US 2002/0024293 A1 , US 2002/0048689 A1 , EP 1 191 612 A2, EP 1 191 613 A2, EP 1 21 1 257 A2, US 2002/0094453 A1 , WO 02/02714 A2, WO 00/70655 A2, WO 01/41512 A1 , WO 02/15645 A1 , WO 2005/019373 A2, WO 2005/1 13704 A2, WO 2006/1 15301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 200612181 1 A1 , WO 20070951 18 A2, WO 2007/1 15970, WO 2007/1 15981 and WO 2008/000727.
  • metal complexes are the commercially available metal complexes tris(2-phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C 2 '), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l -phenylisoquinoline), irid- ium(lll) bis(2,2'-benzothienyl)pyridinato-N,C 3 ')(acetylacetonate), tris(2- phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-
  • N,C 2 )picolinate iridium(lll) bis(1 -phenylisoquinoline)(acetylacetonate), bis(2- phenylquinoline)(acetylacetonato)iridium(lll), iridium(lll) bis(di- benzo[f,h]quinoxaline)(acetylacetonate), iridium(lll) bis(2-methyldi- benzo[f,h]quinoxaline)(acetylacetonate) and tris(3-methyl-1 -phenyl-4-trimethylacetyl-5- pyrazolino)terbium(lll), bis[1 -(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline](acetyl- acetonato)iridium(lll), bis(2-phenylbenzothiazolato)(acetylacetonato)iridium(lll), bis
  • Preferred triplet emitters are carbene complexes. Suitable carbene complexes are known to those skilled in the art and are described, for example, in WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/1 13704, WO 2007/1 15970, WO 2007/1 15981 and WO 2008/000727. Preferred carbene complexes are carbene complexes of the formula (I) mentioned above. Particularly preferred carbene complexes are carbene complexes of the formula la) as mentioned above and (lb).
  • the light-emitting layer may comprise further components in addition to the emitter material.
  • a fluroescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material.
  • a matrix material can be used.
  • This matrix material may be a polymer, for example poly(N-vinylcarbazole) or polysilane.
  • Suitable matrix materials are - in addition to the aforementioned matrix materials - in principle the materials specified hereinafter as hole and electron transport materials, and also carbon complexes, for example the carbene complexes mentioned in WO 2005/019373.
  • Particularly suitable are carbazole derivatives, for example 4,4'- bis(carbazol-9-yl)-2,2'-dimethylbiphenyl (CDBP), 4,4'-bis(carbazol-9-yl)biphenyl (CBP), 1 ,3-bis(N-carbazolyl)benzene (mCP), and the matrix materials specified in the following applications: WO2008/034758, WO2009/003919.
  • Dibenzofurans are additionally suitable as matrix materials, for example the dibenzofurans disclosed in US 2007/0224446 A1 , for example those dibenzofurans in which at least one of the R1 to R8 radicals is a heterocyclic group, for example compound A-15, and the dibenzofurans disclosed in WO 2009/069442 A1 , WO 2010/090077 A1 and JP 2006/321750 A.
  • Additional matrix materials on basis of dibenzofurane are, for example, described in US2009066226, EP1885818B1 , EP1970976, EP1998388 and EP2034538.
  • WO2007108459 H-1 to H-37
  • H-20 to H-22 and H-32 to H-37 most preferably H-20, H-32, H-36, H-37,
  • WO2008035571 A1 Host 1 to Host 6
  • JP2010135467 compounds 1 to 46 and Host-1 to Host-39 and Host-43
  • WO2009008100 compounds No.1 to No.67 preferably No.3, No.4, No.7 to No. 12, No.55, No.59, No. 63 to No.67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No.64, No.65, and No. 67, WO2009008099 compounds No.
  • WO20081401 14 compounds 1 -1 to 1 - 50, WO2008090912 compounds OC-7 to OC-36 and the polymers of Mo-42 to Mo-51 , JP2008084913 H-1 to H-70, WO2007077810 compounds 1 to 44, preferably 1 , 2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers of monomers 1 -1 to 1 - 9, preferably of 1 -3, 1 -7, and 1 -9, WO2008029729 the (polymers of) compounds 1 -1 to 1 -36, WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298 the (co)polymers based on the monomers 1 to 75, JP2009170764, JP2009135183 the (co)polymers based on the monomers 1 -14, WO2009063757 pre-
  • one or more compounds of the general formula (X) specified hereinafter are used as matrix material.
  • Preferred embodiments of the compounds of the general formula (X) are likewise specified hereinafter.
  • the present invention therefore relates to an organic electronic device, preferably an OLED, according to the present invention comprising at least one compound of the general formula (X), particularly preferable in combination with carbene complexes as triplet emitters
  • T is NR , S, O or PR , preferably S or O, more preferably O;
  • R ,57 is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
  • Q' is -NR 58 R 59 , -SiR 70 R 71 R 72 , -P(O)R 60 R 61 , -PR 62 R 63 , -S(0) 2 R 64 , -S(0)R 65 , -SR 1 or -OR 67 , preferably -NR 58 R 59 ; more preferably
  • R 68 , R 69 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or di- benzothienyl;
  • y, z are each independently 0, 1 , 2, 3 or 4, preferably 0 or 1 ;
  • R 55 , R 56 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl,
  • SiR 70 R 71 R 72 a Q' group or a group with donor or acceptor action; a" is 0, 1 , 2, 3 or 4;
  • b' is 0, 1 , 2 or 3;
  • R 58 , R 59 form, together with the nitrogen atom, a cyclic radical which has 3 to 10 ring atoms and may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action, and/or may be fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action;
  • T is S or O, preferably O, and
  • alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or di- benzothienyl;
  • T is O or S, preferably O;
  • a" is 1 ;
  • y. z are each independently 0 or 1 ;
  • R 68 are each independently methyl, carbazolyl, dibenzofuryl or dibenzothienyl
  • R 55 is substituted phenyl, carbazolyl, dibenzofuryl or dibenzothienyl. Further very particularly preferred compounds of the formula (X) have the formula (Xab)
  • T O or S preferably O;
  • a particularly preferred compound of formula (Xab) is the following compound:
  • T is O or S, preferably O.
  • the compounds of the formula (X) may be for example prepared as described in WO2010079051 , WO2007/077810, JP2009267255 respectively US20090017331 A1 and WO2009/003898 or analogeous to the preparation processes described in the documents mentioned before.
  • At least one compound of the formula (V) is used as matrix material, particularly preferable with carbene complexes as triplet emitters.
  • X is NR, S, O or PR
  • R is aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyl
  • A is -NR 6 R 7 , -P(0)R 8 R 9 , -PR 10 R 11 , -S(0) 2 R 12 , -S(0)R 13 , -SR 14 , or -OR 15 ;
  • R 1 , R 2 and R 3 are independently of each other aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyl, wherein at least on of the groups R 1 , R 2 , or R 3 is aryl, or heteroaryl;
  • R 4 and R 5 are independently of each other alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a group A, or a group having donor, or acceptor characteristics;
  • n and m are independently of each other 0, 1 , 2, or 3;
  • R 6 , R 7 form together with the nitrogen atom a cyclic residue having 3 to 10 ring atoms, which can be unsubstituted, or which can be substituted with one, or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group having donor, or acceptor characteristics; and/or which can be annulated with one, or more further cyclic residues having 3 to 10 ring atoms, wherein the annulated residues can be unsubstituted, or can be substituted with one, or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group having donor, or accep- tor characteristics; and
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 und R 15 are independently of each other aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyl.
  • aryl radical or group, heteroaryl radical or group, alkyl radical or group, cyc- loalkyl radical or group, heterocycloalkyl radical or group, alkenyl radical or group, al- kynyl radical or group, and groups with donor and/or acceptor action are each defined as follows:
  • An aryl radical is understood to mean a radical having a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is formed from an aromatic ring or a plurality of fused aromatic rings.
  • Suitable base skeletons are, for example, phenyl, naphthyl, anthracenyl or phenanthrenyl, indenyl or fluorenyl.
  • This base skeleton may be unsubstituted (which means that all carbon atoms which are substitutable bear hydrogen atoms), or may be substituted at one, more than one or all substitutable posi- tions of the base skeleton.
  • Suitable substituents are, for example, deuterium, alkoxy radicals, aryloxy radicals, alkylamino groups, arylamino groups, carbazolyl groups, silyl groups, SiR 78 R 79 R 80 , suitable silyl groups SiR 78 R 79 R 80 being specified below, alkyl radicals, preferably alkyl radi- cals having 1 to 8 carbon atoms, more preferably methyl, ethyl or i-propyl, aryl radicals, preferably C 6 -aryl radicals, which may in turn be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which comprise at least one nitrogen atom, more preferably pyridyl radicals and carbazolyl radicals, alkenyl radicals, preferably alkenyl radicals which bear one double bond, more preferably alkenyl radicals having one double bond and 1 to 8 carbon atoms, alkynyl radicals, preferably alky
  • the substituted aryl radicals most preferably bear substituents selected from the group consisting of methyl, ethyl, isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen and amino, preferably arylamino.
  • the aryl radical or the aryl group is preferably a C 6 -Ci 8 -aryl radical, more preferably a C 6 -aryl radical, which is optionally substituted by at least one or more than one of the aforementioned substituents.
  • the C 6 -Ci 8 -aryl radical, preferably C 6 -aryl radical more preferably has none, one, two, three or four, most preferably none, one or two, of the aforementioned substituents.
  • a heteroaryl radical or a heteroaryl group is understood to mean radicals which differ from the aforementioned aryl radicals in that at least one carbon atom in the base skeleton of the aryl radicals is replaced by a heteroatom, and in that the base skeleton of the heteroaryl radicals preferably has 5 to 18 ring atoms.
  • Preferred heteroatoms are N, O and S.
  • Heteroaryl radicals suitable with particular preference are nitrogen-containing heteroaryl radicals. Most preferably, one or two carbon atoms of the base skeleton are replaced by heteroatoms, preferably nitrogen.
  • the base skeleton is especially preferably selected from systems such as pyridine, pyrimidine and five-membered heteroaro- matics such as pyrrole, furan, pyrazole, imidazole, thiophene, oxazole, thiazole, tri- azole.
  • the heteroaryl radicals may be fused ring systems, for example ben- zofuryl, benzothienyl, benzopyrrolyl, dibenzofuryl, dibenzothienyl, phenanthrolinyl, car- apelolyl radicals, azacarbazolyl radicals or diazacarbazolyl radicals.
  • the base skeleton may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the same as have already been specified for the aryl groups.
  • alkyl radical or an alkyl group is understood to mean a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8, most preferably 1 to 4 carbon atoms.
  • This alkyl radical may be branched or unbranched and optionally be interrupted by one or more heteroatoms, preferably Si, N, O or S, more preferably N, O or S.
  • this alkyl radical may be substituted by one or more of the substituents specified for the aryl groups.
  • the alkyl radicals present in accordance with the invention may have at least one halogen atom, for example F, CI, Br or I, especially F.
  • the alkyl radicals present in accordance with the invention may be fully fluorinated. It is likewise possible that the alkyl radical bears one or more (hetero)aryl groups. In the context of the present application, for example, benzyl radicals are thus substituted alkyl radicals. In this context, all of the (hetero)aryl groups listed above are suitable.
  • the alkyl radicals are more preferably selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl and tert- butyl, very particular preference being given to methyl and ethyl.
  • a cycloalkyi radical or a cycloalkyi group is understood to mean a radical having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms.
  • This base skeleton may be unsubstituted (which means that all carbon atoms which are substitutable bear hydrogen atoms) or substituted at one, more than one or all substitutable positions of the base skeleton.
  • Suitable substituents are the groups already mentioned above for the aryl radicals. It is likewise possible that the cycloalkyi radical bears one or more (hetero)aryl groups. Examples of suitable cycloalkyi radicals are cyclopropyl, cyclopentyl and cyclohexyl.
  • a heterocycloalkyi radical or a heterocycloalkyi group is understood to mean radicals which differ from the aforementioned cycloalkyi radicals in that at least one carbon atom in the base skeleton of the cycloalkyi radicals is replaced by a heteroatom.
  • Preferred heteroatoms are N, O and S.
  • Most preferably, one or two carbon atoms of the base skeleton of the cycloalkyi radicals are replaced by heteroatoms.
  • suitable heterocycloalkyl radicals are radicals derived from pyrrolidine, piperidine, pipe- razine, tetrahydrofuran, dioxane.
  • alkenyl radical or an alkenyl group is understood to mean a radical which corres- ponds to the aforementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C-C single bond of the alkyl radical is replaced by a C-C double bond.
  • the alkenyl radical preferably has one or two double bonds.
  • alkynyl radical or an alkynyl group is understood to mean a radical which corres- ponds to the aforementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C-C single bond of the alkyl radical is replaced by a C-C triple bond.
  • the alkynyl radical preferably has one or two triple bonds.
  • SiR 78 R 79 R 80 group is understood to mean a silyl radical in which
  • R 78 , R 79 and R 80 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, hete- roaryl or OR 73 .
  • SiR 74 R 75 R 76 group is understood to mean a silyl radical in which
  • R 74 , R 75 and R 76 are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, hete- roaryl or OR 73 .
  • a group or a substituent with donor or accep- tor action is understood to mean the following groups:
  • Groups with donor action are understood to mean groups which have a +l and/or +M effect, and groups with acceptor action are understood to mean groups which have a -I and/or -M effect.
  • R81 ", R82” and R83" radicals mentioned in the aforementioned groups with donor or acceptor action are each independently: substituted or unsubstituted CrC 2 o-alkyl or substituted or unsubstituted C 6 -C3o-aryl, or OR 76 , suitable and preferred alkyl and aryl radicals having been specified above.
  • the R81 ", R82” and R83" radicals are more preferably CrC 6 -alkyl, e.g. methyl, ethyl or i- propyl, or phenyl.
  • SiR81 "R82”R83" - R81 ", R82” and R83" are preferably each independently substituted or unsubstituted Ci-C 20 - alkyl or substituted or unsubstituted aryl, preferably phenyl.
  • Preferred substituents with donor or acceptor action are selected from the group consisting of:
  • CF 3 CH 2 F, CHF 2 or C 2 F 5 ; amino, preferably dimethylamino, diethylamino or diarylamino, more preferably diary- lamino; pseudohalogen radicals, preferably CN, -C(0)OCrC 4 -alkyl, preferably - C(0)OMe, P(0)R 2 , preferably P(0)Ph 2 .
  • Very particularly preferred substituents with donor or acceptor action are selected from the group consisting of methoxy, phenyloxy, halogenated Ci-C 4 -alkyl, preferably CF 3 , CH 2 F, CHF 2 , C 2 F 5 , halogen, preferably F, CN, SiR81 "R82”R83", suitable R81 ", R82” and R83" radicals already having been specified, diarylamino (NR84"R85” where R84", R85" are each C 6 -C 3 o-aryl), -C(0)OC C 4 -alkyl, preferably -C(0)OMe, P(0)Ph 2 .
  • Halogen groups are preferably understood to mean F, CI and Br, more preferably F and CI, most preferably F.
  • Pseudohalogen groups are preferably understood to mean CN, SCN and OCN, more preferably CN.
  • the aforementioned groups with donor or acceptor action do not rule out the possibility that further radicals and substituents mentioned in the present application, but not in- eluded in the above list of groups with donor or acceptor action, have donor or acceptor action.
  • the aryl radicals or groups, heteroaryl radicals or groups, alkyl radicals or groups, cyc- loalkyl radicals or groups, heterocycloalkyl radicals or groups, alkenyl radicals or groups and groups with donor and/or acceptor action may - as mentioned above - be substituted or unsubstituted.
  • an unsubstituted group is understood to mean a group in which the substitutable atoms of the group bear hydrogen atoms.
  • a substituted group is understood to mean a group in which one or more substitutable atom(s) bear(s) a substituent in place of a hydrogen atom at least at one position.
  • Suitable substituents are the substituents specified above for the aryl radicals or groups.
  • radicals having the same numbering occur more than once in the compounds according to the present application, these radicals may each independently have the definitions specified.
  • the T radical in the compounds of the formula (X) is NR 57 , S, O or PR 57 , preferably NR 57 , S or O, more preferably O or S, most preferably O.
  • the X radical in formula (V) is NR, S, O or PR, more preferably O or S, most preferably O;
  • the R 57 radical is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl, heteroaryl or alkyl, more preferably aryl, where the aforementioned radicals may be unsubstituted or substituted. Suitable substituents have been specified above. R 57 is more preferably phenyl which may be substituted by the aforementioned substituents or unsubstituted. R 57 is most preferably unsubstituted phenyl.
  • R radical is aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyl, , where the aforementioned radicals may be unsubstituted or substituted. Suitable substituents have been specified above. R is more preferably phenyl which may be substituted by the aforementioned substituents or unsubstituted. R is most preferably unsubstituted phenyl.
  • the Q' group in the compounds of the formula (X) is -NR 58 R 59 , -P(O)R 60 R 61 , -PR 62 R 63 , -S(0) 2 R 64 , -S(0)R 65 , -SR 66 or -OR 67 ; preferably NR 58 R 59 , -P(O)R 60 R 61 or -OR 67 , more preferably -NR 58 R 59 .
  • the A group in the compounds of the formula (V) is -NR 6 R 7 , -P(0)R 8 R 9 , -PR 10 R 11 , - S(0) 2 R 12 , -S(0)R 13 , -SR 14 , or -OR 15 , preferably -NR 6 R 7 , -P(0)R 8 R 9 or -OR 15 , more preferably -NR 6 R 7 .
  • the R 58 to R 67 and R 74 to R 76 and the R 6 to R 15 radicals radicals are each defined as follows:
  • R 6 , R 7 form, together with the nitrogen atom, a cyclic radical which has 3 to 10 ring atoms and may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action and/or may be fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action;
  • D 11 D 12 D 13 D 14 D 15 are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl or heteroaryl, where the radicals may be unsubstituted or substituted by one or more of the radicals selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with donor or acceptor action, more preferably unsubstituted or substituted phenyl, suitable substituents having been specified above, for example tolyl or a group of the formula
  • R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 and R 67 and R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 are most preferably each independently phenyl, tolyl or a group of the formula
  • T is NPh, S or O.
  • -NR 58 R 59 groups and -NR 6 R 7 groups suitable with preference are selected from the group consisting of pyrrolyl, 2,5-dihydro-1 -pyrrolyl, pyrrolidinyl, indolyl, indolinyl, isoindolinyl, carbazolyl, azacarbazolyl, diazacarbazolyl, imidazolyl, imidazo- linyl, benzimidazolyl, pyrazolyl, indazolyl, 1 ,2,3-triazolyl, benzotriazolyl, 1 ,2,4-triazolyl, tetrazolyl, 1 ,3-oxazolyl, 1 ,3-thiazolyl, piperidyl, morpholinyl, 9,10-dihydroacridinyl and 1 ,4-oxazinyl, where the aforementioned groups may be unsubstituted
  • Particularly preferred -NR 58 R 59 and -NR 6 R 7 groups are:
  • R 68 , R 69 are each independently alkyl, cycloalkyi, heterocydoalkyi, aryl or heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;
  • y, z are each independently 0, 1 , 2, 3 or 4, preferably 0 or 1 ;
  • X and T are independently NPh, S or O;
  • T is NPh, S or O
  • R 55 , R 56 in the compounds of the formula (X) and R 4 , R 5 in the compounds of formula (V) are each independently alkyl, cycloalkyi, heterocycloalkyi, aryl, heteroaryl, a further A group or a group with donor or acceptor action; preferably each independently alkyl, aryl, heteroaryl or a group with donor or acceptor action.
  • R 55 or R 56 or R 4 or R 5 may each independently be:
  • a" R groups and/or b' R groups may be present, where a" and b' are: a" is 0, 1 , 2, 3 or 4; preferably independently 0, 1 or 2;
  • b' is 0, 1 , 2 or 3; preferably independently 0, 1 or 2.
  • At least a" or b' is 0, very especially preferably a" and b' are each 0 or a" is 1 and b' is 0.
  • m R 4 groups and/or n' R 5 groups may be present, where m and n are: m is 0, 1 , 2, 3 or 4; preferably independently 0, 1 or 2;
  • n 0, 1 , 2 or 3; preferably independently 0, 1 or 2. Most preferably at least m or n is 0, very especially preferably m and n are each 0 or m is 1 and n is 0.
  • R 70 , R 71 , R 72 are each independently aryl, heteroaryl, alkyl, cycloalkyi or heterocyc- loalkyl.
  • Preferred examples of compounds of formula (V) are:
  • the light emitting layer may comprise further carbene complexes as additional or sole matrix material and/or as additional emitter material. Suitable further carbene complexes are the same carbene complexes as mentioned before, especially carbene complexes of formula (I).
  • the light-emitting layer is formed from 2 to 70% by weight, preferably 5 to 40% by weight, of at least one of the aforementioned emitter materials and 30 to 98% by weight, preferably 60 to 95% by weight, of at least one of the afore- mentioned matrix materials - in one embodiment at least one compound of the formula (V) - where the sum total of the emitter material and of the matrix material adds up to 100% by weight.
  • the light-emitting layer comprises at least one of the afore- mentioned matrix materials - in one embodiment a compound of formula (V) -, such as,
  • the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of
  • the compound of formula (V) - adds up to 100% by weight.
  • the light-emitting layer comprises at least one of the afore- mentioned matrix materials - in one embodiment a compound of formula (V) - as described below as matrix material and one or two carbene complexes, preferably of formula (la) and/or (lb).
  • the at least one of the aforementioned matrix materials - in one embodiment the compounds of the formula (V) - are used as hole/exciton blocker material, preferably together with carbene complexes as triplet emitters.
  • the at least one of the aforementioned matrix materials - in one embodiment the compounds of the formula (V) - may also be used both as matrix materials and as hole/exciton blocker materials together with carbene complexes as triplet emitters.
  • the OLED has - if a blocking layer for holes is present - hole blocker materials typically used in OLEDs, such as 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline (bathocuproin, (BCP)), bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll) (BAIq), phenothiazine S,S- dioxide derivates and 1 ,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-conducting material.
  • mCPy 2,6-bis(N-carbazolyl)pyridine
  • BCP 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline
  • BAIq bis(2- methyl-8-quinolinato)-4-phenylpheny
  • hole blockers and/or electron transport materials are 2,2',2"-(1 ,3,5-benzenetriyl)tris(1 -phenyl-1 -H- benzimidazole), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole, 8- hydroxyquinolinolatolithium, 4-(naphthalen-1 -yl)-3,5-diphenyl-4H-1 ,2,4-triazole, 1 ,3- bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4-oxadiazo-5-yl]benzene, 4,7-diphenyl-1 ,10- phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1 ,2,4-triazole, 6,6'-bis[5- (biphenyl-4-yl)-1
  • disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, disilylben- zothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and disilylben- zothiophene S,S-dioxides, as specified, for example, in WO2009003919 (PCT/EP2008/058207) and WO2009003898 (PCT/EP2008/058106) and disilyl com- pounds as disclosed in WO2008/034758, as a blocking layer for holes/excitons (4) or as matrix materials in the light-emitting layer (3).
  • the present invention relates to an inventive OLED comprising the layers (1 ) anode, (2) hole transport layer, (3) light-emitting layer, (4) blocking layer for holes/excitons, (5) electron transport layer and (6) cathode, and if appropriate further layers, wherein the hole transport layer comprises at least one metal organic compound and at least one metal oxide. Suitable metal organic compounds and metal oxides as well as suitable amounts are mentioned before.
  • the layer (5) may serve both to facilitate electron transport and as a buffer layer or barrier layer in order to prevent quenching of the exci- ton at the interfaces of the layers of the OLED.
  • the layer (5) preferably improves the mobility of the electrons and reduces quenching of the exciton.
  • TPBI is used as the electron conductor material.
  • the electron conductor layer comprises at least one compound of the formula (V) as electron conductor material.
  • the electron transport layer (5) of the inventive OLEDs comprises an organic metal complex of formula (II) and preferably additionally a compound of formula (III), (IVa) or (IVb).
  • the layer (5) preferably improves the mobility of the electrons.
  • the compounds of formulae (II), (III), (IVa) and (IVb) as well as suitable amounts of said compounds in an organic layer, especially in an electron transport layer, are mentioned above.
  • hole transport materials and electron transport materials some may fulfil several functions.
  • some of the electron- transporting materials are simultaneously hole-blocking materials when they have a low-lying HOMO. These can be used, for example, in the blocking layer for holes/excitons (4).
  • the charge transport layers can also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • the hole transport materials can be doped with electron acceptors; for example, phthalocyanines or arylamines such as TPD or TDTA can be doped with tetrafluorotetracyanquinodimethane (F4-TCNQ) or with Mo0 3 or W0 3 .
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No.
  • the cathode (6) is an electrode which serves to introduce electrons or negative charge carriers.
  • Suitable materials for the cathode are selected from the group consisting of alkali metals of group la, for example Li, Cs, alkaline earth metals of group lla, for example calcium, barium or magnesium, metals of group lib of the periodic table of the elements (old lUPAC version), comprising the lanthanides and actinides, for example samarium.
  • metals such as aluminum or indium, and combinations of all metals mentioned.
  • lithium-comprising organometal- lic compounds or potassium fluoride (KF) can be applied between the organic layer and the cathode in order to reduce the operating voltage.
  • the OLED according to the present invention may additionally comprise further layers which are known to those skilled in the art.
  • a layer which facilitates the transport of the positive charge and/or matches the band gaps of the layers to one another may be applied between the layer (2) and the light-emitting layer (3).
  • this further layer may serve as a protective layer.
  • additional layers may be present between the light-emitting layer (3) and the layer (4) in order to facilitate the transport of negative charge and/or to match the band gaps between the layers to one another.
  • this layer may serve as a protective layer.
  • the inventive OLED in addition to layers (1 ) to (6), com- prises at least one of the following layers mentioned below:
  • a hole injection layer between the anode (1 ) and the hole-transport layer (2); a blocking layer for electrons between the hole-transport layer (2) and the light- emitting layer (3);
  • Materials for a hole injection layer may be selected from copper phthalocyanine, 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris- (N-(2-naphthyl)-N-phenylamino)triphenylamine (2T-NATA), 4,4',4"-tris(N-(1 -naphthyl)- N-phenylamino)triphenylamine (1T-NATA), 4,4',4"-tris(N,N- diphenylamino)triphenylamine (NATA), titanium oxide phthalocyanine, 2,3,5,6- tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), pyrazino[2,3- f][1 ,10]phenanthroline-2,3-dicarbonitrile (PPDN), N,N,N'
  • KF As a material for the electron injection layer, KF, or Liq, for example, can be selected. KF is more preferred than Liq.
  • Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
  • the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport.
  • the selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.
  • the inventive OLED can be produced by methods known to those skilled in the art.
  • the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate.
  • Suitable substrates are, for example, glass, inorganic semitransports, typically ITO, or IZO, or polymer films.
  • ITO inorganic semitransports
  • IZO inorganic semitransports
  • polymer films polymer films.
  • customary techniques such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
  • the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art.
  • the different layers have the following thicknesses: anode (1 ) 50 to 500 nm, preferably 100 to 200 nm; hole-conducting layer (2) 5 to 100 nm, preferably 20 to 80 nm, light-emitting layer (3) 1 to 100 nm, preferably 10 to 80 nm, blocking layer for holes/excitons (4) 2 to 100 nm, preferably 5 to 50 nm, electron-conducting layer (5) 5 to 100 nm, preferably 20 to 80 nm, cathode (6) 20 to 1000 nm, preferably 30 to 500 nm.
  • the relative position of the recombination zone of holes and electrons in the inventive OLED in relation to the cathode and hence the emission spectrum of the OLED can be influenced, among other factors, by the relative thickness of each layer.
  • the ratio of the layer thicknesses of the individual layers in the OLED depends on the materials used. The layer thicknesses of any additional layers used are known to those skilled in the art. It is possible that the electron-conducting layer and/or the hole-conducting layer have greater thicknesses than the layer thicknesses specified when they are electrically doped.
  • the first organic layer, especially the hole transport layer or hole injection layer, of the present application makes it possible to obtain OLEDs with high efficiency and with low operating voltage.
  • the OLEDs obtained by the use of the the first organic layer, especially the hole transport layer or hole injection layer, of the present application additionally have high lifetimes.
  • the efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs. Shaped substrates and novel electron-transport materials which bring about a reduction in the operating voltage or an increase in the quantum efficiency are likewise usable in the inventive OLEDs.
  • additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence.
  • the OLEDs may further comprise at least one second light-emitting layer.
  • the overall emission of the OLEDs may be composed of the emission of the at least two light- emitting layers and may also comprise white light.
  • the OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Further devices in which the inventive OLEDs can be used are, for example, keyboards; items of clothing; furniture; wall- paper.
  • the electron transport layer of the present application can be used in OLEDs with inverse structure.
  • the structure of inverse OLEDs and the materials typically used therein are known to those skilled in the art.
  • the present invention relates to an apparatus selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising the inventive organic electronic device, or the inventive organic layer, especially electron transport layer.
  • stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels
  • mobile visual display units such as visual display units in cellphones, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains
  • illumination units keyboards
  • items of clothing furniture
  • wallpaper comprising the inventive organic electronic device, or the inventive organic layer, especially electron transport layer.
  • the ITO substrate used as the anode is first cleaned with commercial detergents for LCD production (Deconex ® 20NS, and 250RGAN-ACID ® neutralizing agent) and then in an acetone/isopropanol mixture in an ultrasound bath. To eliminate any possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for a further 25 minutes. This treatment also improves the hole injection properties of the ITO.
  • the organic materials specified below are applied by vapor deposition to the clean substrate at a rate of approx. 0.5-5 nm/min at about 10 "8 mbar.
  • Ir(dpbic) 3 (V1 ) is a lied to the substrate with a thickness of 80 nm.
  • V1 doped with a metal oxide especially doped with Re0 3 , is much higher than the conductivity of V1 alone.
  • the ITO substrate used as the anode is first cleaned with commercial detergents for LCD production (Deconex ® 20NS, and 250RGAN-ACID ® neutralizing agent) and then in an acetone/isopropanol mixture in an ultrasound bath. To eliminate any possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for a further 25 minutes. This treatment also improves the hole injection proper- ties of the ITO. Then AJ20-1000 (commercially available from Plexcore) is spin-coated and dried to form an hole injection layer (-40 nm).
  • the organic materials specified below are applied by vapor deposition to the clean substrate at a rate of approx. 0.5-5 nm/min at about 10 "8 mbar.
  • lr(dpbic) 3 (V1 ) is applied to the substrate with a thickness of 40 nm.
  • lr(dpbic) 3 for preparation, see Ir complex (7) in the application
  • V3 described in PCT/EP2009/067120
  • compound V2 functioning as an emitter material
  • compounds V1 and V3 as a matrix material.
  • the material (V3) is applied by vapor deposition with a thickness of 5 nm as exciton and hole blocker.
  • (Liq)) and 75 % by weight of (V4) is applied as electron transport layer by vapor deposition in a thickness of 40 nm, as are a 2 nm- thick potassium fluoride layer (electron injection layer) and finally a 100 nm-thick Al electrode.
  • EQE External quantum efficiency
  • HT Layer Hole Transport Layer.

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JP2016197744A (ja) 2016-11-24
CN103068950A (zh) 2013-04-24
EP2582770A1 (en) 2013-04-24
CN107698622B (zh) 2021-06-29
JP6408519B2 (ja) 2018-10-17
CN107698622A (zh) 2018-02-16
EP2582770A4 (en) 2014-06-18
CN103068950B (zh) 2016-08-24
KR101806586B1 (ko) 2017-12-07
JP6014938B2 (ja) 2016-10-26
KR20130118858A (ko) 2013-10-30
JP2013537701A (ja) 2013-10-03

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