EP2100339A1 - Émetteur contenant des lanthanides utilisé dans des applications pour des diodes électroluminescentes organiques (odel) - Google Patents

Émetteur contenant des lanthanides utilisé dans des applications pour des diodes électroluminescentes organiques (odel)

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Publication number
EP2100339A1
EP2100339A1 EP07818927A EP07818927A EP2100339A1 EP 2100339 A1 EP2100339 A1 EP 2100339A1 EP 07818927 A EP07818927 A EP 07818927A EP 07818927 A EP07818927 A EP 07818927A EP 2100339 A1 EP2100339 A1 EP 2100339A1
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EP
European Patent Office
Prior art keywords
formula
emitter
light
emitting device
complexes
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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.)
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Application number
EP07818927A
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German (de)
English (en)
Inventor
Hartmut Yersin
Uwe Monkowius
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Merck Patent GmbH
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Merck Patent GmbH
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Publication date
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Publication of EP2100339A1 publication Critical patent/EP2100339A1/fr
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    • 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
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • 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
    • 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
    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
    • 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
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • 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
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
    • 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
    • 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
    • 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
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3

Definitions

  • the present invention relates to light emitting devices, and more particularly to organic light emitting devices (OLEDs).
  • OLEDs organic light emitting devices
  • the invention relates to the use of luminescent lanthanoid complexes as emitters in such devices.
  • OLEDs Organic Light Emitting Devices or Organic Light Emitting Diodes
  • OLEDs represent a new technology that will dramatically change the screen and lighting technology.
  • OLEDs consist mainly of organic layers, which are also flexible and inexpensive to manufacture.
  • OLED components can be designed over a large area as lighting fixtures, but also as small pixels for displays.
  • OLEDs The function of OLEDs has also been described in C. Adachi et al., Appl. Phys. Lett. 2001, 78, 1622; X.H. Yang et al., Appl. Phys. Lett. 2004, 84, 2476; J. Shinar, "Organic Light Emitting Devices - A Survey", AIP-Press, Springer, New York 2004, W. Sotoyama et al., Appl. Phys. Lett., 2005, 86, 153505, S. Okada et al. , Dalton Trans., 2005, 1583 and Y. L. Tung et al., J. Mater. Chem., 2005, 15, 460-464.
  • OLEDs Since the first reports on OLEDs (see, for example, Tang et al., Appl. Phys. Lett. 51 (1987) 913), these devices have been further developed, in particular with regard to the emitter materials used, and in particular so-called phosphorescent emitters have recently been of interest .
  • LCDs liquid crystal displays
  • CRTs cathode ray tubes
  • OLEDs have numerous advantages, such as low operating voltage, flat design, high-efficiency self-luminous pixels, high contrast, and a good resolution as well as the possibility to display all colors.
  • an OLED emits light when applying electrical voltage instead of just modulating it.
  • emitters can be significantly greater than for purely organic materials. Because of this property, the further development of organometallic materials is of major importance. Emitters are described, for example, in WO 2004/017043 A2 (Thompson), WO 2004/016711 A1 (Thompson), WO 03/095587 (Tsuboyama), US 2003/0205707 (Chi-Ming Che), US 2002/0179885 (Chi-Ming Che), US 2003/186080 A1 (J. Kamatani), DE 103 50 606 A1 (pestle), DE 103 38 550 (Bold), DE 103 58 665 A1 (Lennartz).
  • Lanthanoid compounds have also been used as emitter materials.
  • the advantage of lanthanoid compounds is their high color purity, which is due to the narrow line widths of their photo or Electroluminescence is due.
  • Lanthanoid complexes and their use in OLEDs are described, for example, in WO 98/55561 A1, WO 2004/016708 A1, WO 2004/058912 A2, EP 0 744 451 A1, WO 00/44851 A2, WO 98/58037 A1 and US Pat. No. 5,128,587 A.
  • these compounds for example the compounds described in WO 98/55561, have the drawbacks frequently observed for lanthanide compounds.
  • An object of the present invention was to provide new emitter materials, in particular for OLEDs, as well as novel light-emitting devices which at least partially overcome the disadvantages of the prior art and which in particular are stable to water and air.
  • a light emitting device comprising (i) an anode, (ii) a cathode and (iii) an emitter layer disposed between and in direct or indirect contact with the anode and the cathode comprising at least one complex of the formula (I) or (II)
  • R 5 R 1 or H
  • R 2 , R 3 , R 4 , R 6 , R 7 H, halogen or a hydrocarbon group which may optionally contain heteroatoms, in particular alkyl, aryl or heteroaryl.
  • the groups R 2 - R 7 may be fluorinated.
  • the compounds according to the invention are particularly preferably compounds having a homoleptic substitution pattern on the boron atom, in particular since these are the most easily obtainable synthetically.
  • the compounds have the preferred formulas (Ia) or (IIa).
  • R 1 and R 5 may also be another organic group, in particular alkyl, aryl, heteroaryl, alkoxy, phenolate, amine or amide groups.
  • the essential advantage of the compounds according to the invention is their good solubility in virtually all polar solvents, for example in H 2 O, MeOH,
  • Solvents must be worked.
  • the complexes can also be varied by substitution or / and modification of the ligands, which offers a variety of possibilities for modifying or controlling the emission properties (eg color, quantum efficiency, decay time, etc.) ⁇ rg ⁇ u ⁇ .
  • Another object of the invention are therefore complexes of the formulas
  • the light-emitting device contains as emitter at least one Ln complex of the formula (I) or (II).
  • the compounds according to the invention are in particular homoleptic complexes in which the borate ligands adequately shield the Ln center by at least ninefold coordination. This prevents decomposition.
  • (II) are eminently suitable as emitter molecules for light emitting devices and, in particular, for organic light emitting devices (OLEDs).
  • the compounds according to the invention are outstandingly suitable, in particular, for use in light-generating systems, such as, for example, displays or illuminations.
  • Ln complexes of the formula (I) or (II) as emitter materials in OLEDs results in a number of advantages.
  • 100% or highly concentrated emitter layers with materials according to the invention of formula (I) and / or formula (II), no concentration fluctuations can occur in the manufacture of the devices.
  • high luminance densities can be achieved at high current densities.
  • a relatively high efficiency can be achieved even at high current densities. This is especially true for Ce 3+ complexes that exhibit short-lived fluorescence emission (* 60 ns).
  • the complexes of the formulas (I) and (II) can also be used according to the invention dissolved in suitable matrices in small doping (for example 2 to 10%).
  • complexes of the formula (I) or / and of the formula (II) are employed in low concentration in the emitter layer, whereby a monomer emission in the emitter layer
  • the complexes of the formula (I) or / and (II) are in the emitter layer in particular more than 2 wt .-%, in particular more than 4 wt .-% and up to 10 wt .-%, in particular up to 8 wt .-%, based on the total weight of the emitter layer before.
  • three or at least two different complexes of the formula (I) or (II) are used according to the invention in the light-emitting device.
  • mixed-colored light can be obtained by means of such emitter layers having a plurality of complexes.
  • the complexes of the formula (I) or (II) used according to the invention as emitter molecules are, in particular, luminescent compounds.
  • the complexes have a central atom, which is a lanthanide.
  • the central atom is preferably Ce 3+ , Eu 3+ , Tb 3+ or Nd 3+ .
  • complexes with Nd 3+ as the central atom give emitters for the infrared range.
  • By appropriate selection of the central atom can be cover interesting regions of the spectrum according to the invention.
  • blue emitters in particular with Ce 3+ as the central atom.
  • R 1 is preferably a pyrazolyl radical. While R 5 may be H, it is preferred that R 5 represent a residue other than H. R 5 is particularly preferably a triazolyl radical.
  • radicals R 2 , R 3 , R 4 , R 6 and R 7 are each independently of one another hydrogen, halogen or a hydrocarbon group which may optionally contain heteroatoms and / or be substituted.
  • the heteroatoms are in particular selected from O, S, N, P, Si, Se, F, Cl, Br and / or I.
  • the radicals R 1 to R 7 preferably each have 0 to 50, in particular 0 to 10, and even more preferably 0 to 5 heteroatoms. In some embodiments, the radicals R 1 to R 7 each have at least 1, in particular at least 2 heteroatoms.
  • the heteroatoms may be present in the framework or as part of substituents.
  • the radicals R 1 to R 7 are a hydrocarbon group having one or more substituents (functional groups).
  • Suitable substituents or functional groups are, for example, halogen, in particular F, Cl, Br or I, alkyl, in particular Ci to C 2 o, more preferably Ci to C 6 alkyl, aryl, O-alkyl, O-aryl, S-aryl , S-alkyl, P-alkyl 2) P-aryl 2 , N-alkyl 2 or N-aryl 2 or other donor or acceptor groups.
  • at least one of R 1 to R 7 contains at least one fluorine to increase the volatility of the complex.
  • a hydrocarbon group is preferably an alkyl, alkenyl, alkynyl, aryl or heteroaryl group, in particular an alkyl, aryl or heteroaryl group.
  • alkyl or alk each independently independently denotes a Ci - C 2 o, in particular a Ci - C 6 hydrocarbon group.
  • aryl preferably denotes an aromatic system having 5 to 20 carbon atoms, in particular 6 to 10 carbon atoms, it being possible for C atoms to be replaced by heteroatoms (for example N, S, O).
  • all substituents R 2 , R 3 , R 4 , R 6 and R 7 are hydrogen or halogen, ie sterically less demanding substituents.
  • the emitter layer comprises complexes of the formula (I) and / or of the formula (II) in a concentration of greater than 1% by weight, based on the total weight of the emitter layer, in particular greater than 2% by weight, more preferably greater 5 wt .-% and up to 10 wt .-%, in particular up to 8 wt .-% to.
  • emitter layers which comprise almost completely or completely complexes of the formula (I) or / and of the formula (II) and in particular> 80% by weight and most preferably> 90% by weight, in particular> 95% by weight, more preferably> 99% by weight.
  • the emitter layer is complete, ie 100% of complexes of the formula (I) or / and of the formula (II).
  • 100% of the complexes in the emitter layer no concentration fluctuations occur during production or they only have a slight effect in highly concentrated systems.
  • high luminance can be achieved at high current densities and a high efficiency, ie a high quantum efficiency, can be achieved.
  • the present invention provides i.a. the following advantages:
  • the complexes used according to the invention as emitters can be tuned in a simple manner by the choice of suitable matrix materials and, in particular, by the selection of electron-withdrawing or -shifting substituents in the wavelength range.
  • Neodymium (III) tetrakis (pyrazolyl) borate Neodymium (III) tetrakis (pyrazolyl) borate.
  • the device comprises at least one anode, one cathode and one Emitter layer.
  • one or both of the electrodes used as the cathode or anode is made transparent, so that the light can be emitted by this electrode.
  • a transparent Elektrodenmateria! Indium tin oxide (! TO) used.
  • a transparent anode is used.
  • the other electrode may also be formed of a transparent material, but may also be formed of another material with suitable electron work function, if light is to be emitted only by one of the two electrodes.
  • the second electrode, in particular the cathode consists of a metal with low electron work function and good electrical conductivity, for example of aluminum, or silver, or a Mg / Ag or a Ca / Ag alloy.
  • an emitter layer is arranged between the two electrodes. This may be in direct contact with the anode and the cathode, or in indirect contact, where indirect contact means that further layers are included between the cathode or anode and the emitter layer so that the emitter layer and the anode and / or cathode do not touch each other , but are electrically connected to each other via further intermediate layers.
  • a voltage for example a voltage of 3 to 20 V, in particular of 5 to 10 V
  • negatively charged electrons emerge from the cathode, for example a conductive metal layer, for example from an aluminum cathode, and migrate in the direction of the positive anode.
  • the organometallic complexes of the formulas (I) and (II) are present as emitter molecules.
  • the migrating charge carriers ie a negatively charged electron and a positively charged hole, recombine, leading to neutral but energetically excited states of the emitter molecules.
  • the excited states of the emitter molecules then give off their energy as light emission.
  • the light-emitting devices according to the invention can be produced by vacuum deposition.
  • a construction via wet-chemical application is possible, for example via spin coating processes, inkjet printing or screen printing processes.
  • the structure of OLED devices is described in detail, for example, in US 2005/0260449 A1 and in WO 2005/098988 A1.
  • the emitter layer performs functions of the hole or electron conduction layer (suitable materials are explained on pages 9/10).
  • the emitter layer preferably consists of an organic matrix material with a singlet S 0 - triplet TV energy gap sufficiently large for the respective emission color (depending on the selected Ln central ion), eg of UGH, PVK derivatives (polyvinylcarbazole), CBP (4,4'-bis ( 9-carbazolyl) biphenyl) or other matrix materials.
  • the emitter complex is doped, for example preferably with 1 to 10 weight percent.
  • the emitter layer can also be realized without a matrix in that the corresponding complex is applied as a 100% material.
  • the light-emitting device according to the invention also has a CsF intermediate layer between the cathode and the emitter layer or an electron conductor layer.
  • This layer has in particular a thickness of 0.5 nm to 2 nm, preferably of about 1 nm.
  • This intermediate layer mainly causes a reduction of the electron work function.
  • the light-emitting device is applied to a substrate, for example on a glass substrate.
  • an OLED structure for a sublimable emitter according to the invention in addition to an anode, emitter layer and cathode, also comprises at least one, in particular more and more preferably all of the layers mentioned below and shown in FIG.
  • the entire structure is preferably located on a carrier material, in which case in particular glass or any other solid or flexible transparent material can be used.
  • the anode is arranged on the carrier material, for example an indium tin oxide anode (ITO).
  • ITO indium tin oxide anode
  • a hole transport layer (HTL, Hole Transport Layer) is arranged on the anode and between the emitter layer and the anode, for example, ⁇ -NPD (N, N'-diphenyl-N, N l -bis (1-methyl) -1,1-biphenyl l 4,4'-diamine).
  • the thickness of the hole transport layer is preferably 10 to 100 nm, in particular 30 to 50 nm.
  • Further layers can be arranged between the anode and the hole transport layer, which improve the hole injection, for example a copper phthalocyanine (CuPc) layer.
  • This layer is preferably 5 to 50, in particular 8 to 15 nm thick.
  • an electron blocking layer is applied to the hole transport layer and between the hole transport and emitter layers, which ensures that the electron transport to the anode is prevented, since such a current would only cause ohmic losses.
  • the thickness of this electron blocking layer is preferably 10 to 100 nm, in particular 20 to 40 nm. This additional layer can be dispensed with in particular if the HTL layer is intrinsically already a poor electron conductor.
  • the next layer is the emitter layer which contains or consists of the emitter material according to the invention.
  • the emitter materials are preferably applied by sublimation.
  • the layer thickness is preferably between 40 nm and 200 nm, in particular between 70 nm and 100 nm.
  • the emitter material according to the invention can also be co-evaporated together with other materials, in particular with matrix materials.
  • matrix materials for emitting green or red emitter materials according to the invention are common matrix materials such as CBP (4,4'-bis (N-carbazolyl) biphenyl).
  • CBP 4,4'-bis (N-carbazolyl) biphenyl.
  • a hole-blocking layer is preferably applied, which reduces ohmic losses, which can be caused by hole currents to the cathode.
  • This hole-blocking layer is preferably 10 to 50 nm, in particular 15 to 25 nm thick.
  • a suitable material for this is, for example, BCP (4,7-diphenyl-2,9-dimethyl-phenanthroline, also called bathocuproine).
  • An ETL layer of electron transport layer (ETL) is preferably applied to the hole-blocking layer and between this layer and the cathode.
  • this layer consists of aufdampfbarem Alq 3 with a thickness of 10 to 100 nm, in particular from 30 to 50 nm.
  • an intermediate layer for example, CsF or LiF.
  • This interlayer reduces the electron injection barrier and protects the ETL layer. This shift is in progress! evaporated.
  • the intermediate layer is preferably very thin, in particular 0.5 to 2 nm, more preferably 0.8 to 1.0 nm thick.
  • a conductive cathode layer is evaporated, in particular with a thickness of 50 to 500 nm, more preferably 100 to 250 nm.
  • the cathode layer is preferably made of Al, Mg / Ag (in particular in the ratio 10: 1) or other metals. Voltages between 3 and 15 V are preferably applied to the described OLED structure for a sublimable emitter according to the invention.
  • the OLED device can also be manufactured partially wet-chemically, for example according to the following structure: glass substrate, transparent ITO
  • a suitable matrix eg 40 nm
  • evaporated Alq 3 eg 40 nm
  • evaporated metal cathode Al or Ag e.g., 0.8 nm
  • evaporated metal cathode Al or Ag e.g., 0.8 nm
  • Mg / Ag e.g. 200 nm
  • An OLED structure for a soluble emitter according to the invention particularly preferably has the structure described below and illustrated in FIG. 3, but comprises at least one, more preferably at least two, and most preferably all of the layers mentioned below.
  • the device is preferably applied to a carrier material, in particular to glass or another solid or flexible transparent material.
  • An anode is applied to the carrier material, for example an indium tin oxide anode.
  • the layer thickness of the anode is preferably 10 nm to 100 nm, in particular 30 to 50 nm.
  • An HTL layer (hole transport layer) of a hole conductor material is applied to the anode and between the anode and emitter layer, in particular from a hole conductor material which is water-soluble.
  • a hole conductor material is for example PEDOT / PSS
  • the layer thickness of the HTL layer is preferably 10 to 100 nm, in particular 40 to 60 nm.
  • the emitter layer (EML) is applied, which contains a soluble emitter according to the invention.
  • the material can be dissolved in a solvent, for example in acetone, dichloromethane or acetonitrile. As a result, a dissolution of the underlying PEDOT / PSS layer can be avoided.
  • the emitter material of the invention may be used for complexes of formula (I) and formula (II) in low concentration, e.g.
  • a layer of electron transport material is preferably applied, in particular with a
  • Layer thickness 10 to 80 nm, more preferably from 30 to 50 nm.
  • a suitable material for the electron transport material layer is, for example, Alq 3 , which is aufdampfbar.
  • a thin intermediate layer is preferably applied which reduces the electron injection barrier and protects the ETL layer.
  • Layer preferably has a thickness between 0.5 and 2 nm, in particular between 0.5 and 1, 0 nm and preferably consists of
  • the cathode layer preferably consists of a metal, in particular of Al or Mg / Ag (in particular in the ratio 10: 1).
  • Voltages of 3 to 15 V are preferably applied to the device.
  • the invention further relates to the use of a compound of the formula (I) or (II), as defined herein, as emitter of a light-emitting device, in particular in an organic light-emitting device.
  • Another object of the invention are Ln complexes of the formula (I) or (II) as hereinbefore defined.
  • the emission color can be adjusted in particular by selecting the central atom.
  • Ce 3+ complexes of the formulas (I) or (II) have a blue emission, in particular an emission of ⁇ 520 nm, more preferably ⁇ 500 nm and of> 380 nm, in particular> 430 nm.
  • Complexes with Nd 3+ As central atom, in particular, have an emission in the infrared, in particular with a wavelength> 600 nm, more preferably> 700 nm and even more preferably> 780 nm and up to 1 mm, preferably up to 500 microns.
  • a further subject of the invention is therefore a hole blocking layer comprising a complex of the formula (I) or (II)
  • Ln Ce 3+ or Gd 3+
  • R 1 a pyrazolyl, triazolyl, heteroaryl, alkyl, aryl, alkoxy, phenolate,
  • Amine or amide group which may be substituted or unsubstituted, or
  • R 5 R 1 or H 1 and
  • R 2 , R 3 , R 4 , R 6 , R 7 H, is halogen or a hydrocarbon group which may contain heteroatoms and / or be substituted.
  • a further subject of the invention is therefore a matrix material for an emitter layer comprising at least one complex of the formula (I) or (II)
  • R 2 , R 3 , R 4 , R 6 , R 7 H, is halogen or a hydrocarbon group which may contain heteroatoms and / or be substituted.
  • Suitable emitter complexes can be doped into the matrix material.
  • the matrix material according to the invention is preferred for blue emitters.
  • any blue emitter can be doped.
  • Ce complex matrix materials emitters which have a somewhat lower emission energy than the Ce complex emission are advantageously doped.
  • the matrix materials according to the invention comprising Gd or Ce complexes can replace conventional matrix materials, for example the UGH matrix materials mentioned hereinbefore.
  • the matrix materials according to the invention ie layers which consist of Gd or Ce complexes of the formula (I) or (II), have a significantly higher long-term stability than the matrix materials known hitherto, in particular as previously known matrix materials for blue emitters.
  • matrix materials comprising Gd complexes have a significantly higher energy gap than most previously known blue emitter matrix materials.
  • a complex of the formula (I) or (II) comprising as the central atom Ce 3+ as an emitter and another complex of the formula (I) or (II) is used as the central atom Gd as matrix material according to the invention.
  • the invention therefore also relates to an emitter layer, in particular comprising a light-emitting device
  • Ln Gd 3+
  • R 1 a pyrazolyl, triazolyl, heteroaryl, alkyl, aryl, alkoxy, phenolate,
  • Amine or amide group which may be substituted or unsubstituted, or
  • R 5 R 1 or H
  • R 2 , R 3 , R 4 , R 6 , R 7 H, is halogen or a hydrocarbon group which may contain heteroatoms and / or be substituted, as well as
  • R 1 a pyrazolyl, triazolyl, heteroaryl, alkyl, aryl, alkoxy, phenolate,
  • Amine or amide group which may be substituted or unsubstituted, or
  • R 5 R 1 or H
  • R 2 , R 3 , R 4 , R 6 , R 7 H
  • the Ce complex is the emitter, while the Gd complex serves as the matrix material.
  • a preferred concentration for the Ce emitter complex is 1 to 10 wt .-%, based on the total weight of the emitter layer.
  • FIG. 1 shows an example of an OLED device that can be created by means of vacuum sublimation technology with complexes according to the invention.
  • FIG. 2 shows an example of a differentiated, highly efficient OLED device with sublimable emitter materials according to the invention.
  • FIG. 3 shows an example of an OLED device for emitters according to the invention which are to be applied wet-chemically.
  • the layer thickness specifications are given as example values.
  • Figure 4 shows the absorption and emission spectrum of Ce [B (pz) 4 ] 3 (blue emitter). The conditions were as follows: Excitation: 300 nm, solution in EtOH; Temperature: 300 K.
  • Figure 5 shows the absorption and emission spectrum of Eu [B (pz) 4 ] 3 (red emitter).
  • FIG. 6 shows the absorption and emission spectrum of Tb [B (pz) 4 ] 3 (green emitter).
  • the conditions were as follows: Excitation: 260 nm, solution in EtOH, 300K; Filter: 375.
  • Potassium tetrakis (pyrazolyl) borate is available from Acros, potassium hydro [tris (triazo! Y!) Borate, and potassium tetrakis (triazo! Y!) Borate is prepared from KBH 4 and triazole, derivatized borate ligands corresponding to formula (I) and formula (II) can be obtained by different synthetic strategies.

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Abstract

L'invention concerne des dispositifs luminescents et en particulier des dispositifs électroluminescents organiques (ODEL). En particulier, l'invention concerne l'utilisation de complexes lanthanides luminescents, utilisés en tant qu'émetteur dans lesdits dispositifs.
EP07818927A 2006-10-11 2007-10-11 Émetteur contenant des lanthanides utilisé dans des applications pour des diodes électroluminescentes organiques (odel) Withdrawn EP2100339A1 (fr)

Applications Claiming Priority (2)

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DE102006048202A DE102006048202A1 (de) 2006-10-11 2006-10-11 Lanthanoid-Emitter für OLED-Anwendungen
PCT/EP2007/008856 WO2008043562A1 (fr) 2006-10-11 2007-10-11 Émetteur contenant des lanthanides utilisé dans des applications pour des diodes électroluminescentes organiques (odel)

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EP2100339A1 true EP2100339A1 (fr) 2009-09-16

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US (1) US20100117521A1 (fr)
EP (1) EP2100339A1 (fr)
JP (1) JP5661282B2 (fr)
DE (1) DE102006048202A1 (fr)
WO (1) WO2008043562A1 (fr)

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GB0423506D0 (en) * 2004-10-22 2004-11-24 Univ Belfast Light emitting complex salts
JP5677026B2 (ja) * 2009-10-28 2015-02-25 住友化学株式会社 多座配位子金属錯体
TWI566449B (zh) 2011-11-30 2017-01-11 Novaled Gmbh 有機電子裝置及其用途
DE102011089687A1 (de) 2011-12-22 2013-06-27 Hartmut Yersin Singulett-Harvesting mit speziellen organischen Molekülen ohne Metallzentren für opto-elektronische Vorrichtungen
CN102867921B (zh) * 2012-09-13 2015-11-25 深圳市华星光电技术有限公司 有机显示装置
CN103247666A (zh) * 2013-04-25 2013-08-14 深圳市华星光电技术有限公司 一种红外oled显示装置及其制造方法
RU2663671C2 (ru) * 2017-01-11 2018-08-08 Сиа Эволед Пиразолкарбоксилаты лантанидов, проявляющие люминесцентные свойства в видимом диапазоне
DE102020103268B8 (de) * 2020-02-10 2023-04-20 Sichuan Knowledge Express Institute For Innovative Technologies Co., Ltd. Ce(III)-Komplexe, Zusammensetzung aufweisend Ce(III)-Komplexe, optoelektronische Vorrichtung, Verfahren zu deren Herstellung, Verfahren zum Dublett-Harvesting und Verfahren für Hyperfluoreszenz mit sehr kurzer Abklingzeit

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US20100117521A1 (en) 2010-05-13
DE102006048202A1 (de) 2008-04-17
JP5661282B2 (ja) 2015-01-28
JP2010506411A (ja) 2010-02-25
WO2008043562A1 (fr) 2008-04-17

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