WO2008131750A2 - Composant luminescent et son procédé de réalisation - Google Patents

Composant luminescent et son procédé de réalisation Download PDF

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Publication number
WO2008131750A2
WO2008131750A2 PCT/DE2008/000732 DE2008000732W WO2008131750A2 WO 2008131750 A2 WO2008131750 A2 WO 2008131750A2 DE 2008000732 W DE2008000732 W DE 2008000732W WO 2008131750 A2 WO2008131750 A2 WO 2008131750A2
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Prior art keywords
light
emission layer
eml
layer
component according
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PCT/DE2008/000732
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German (de)
English (en)
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WO2008131750A3 (fr
Inventor
Sebastian Reineke
Gregor Schwartz
Karl Leo
Karsten Walzer
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Novaled Ag
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Priority claimed from DE102007020644A external-priority patent/DE102007020644A1/de
Priority claimed from DE102007033209A external-priority patent/DE102007033209A1/de
Application filed by Novaled Ag filed Critical Novaled Ag
Priority to DE112008001738.7T priority Critical patent/DE112008001738B4/de
Priority to US12/598,080 priority patent/US8546816B2/en
Publication of WO2008131750A2 publication Critical patent/WO2008131750A2/fr
Publication of WO2008131750A3 publication Critical patent/WO2008131750A3/fr

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    • 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
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • 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
    • 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
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/27—Combination of fluorescent and phosphorescent emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the invention relates to technologies in the field of organic light emitting device, in particular organic light emitting diode.
  • Organic light-emitting diodes or organic light-emitting diodes are now generally recognized as having the potential, in the field of lighting technology, to offer an alternative to conventional light sources such as incandescent lamps or fluorescent tubes. Meanwhile, the achieved performance efficiencies (see, for example, D'Andrade et al., Adv., Mater., 16 (2004) 1585) are significantly higher than those of incandescent bulbs. Recent reports suggest that the efficiencies of fluorescent tubes can be surpassed. For highest power efficiencies, phosphorescent emitters are currently used because they are designed to convert 100% of the charged carriers into light, i. 100% quantum efficiency can be achieved.
  • Document EP 1 705 727 A1 describes a concept of how, in spite of the intrinsically limited 25% quantum efficiency of direct light emission of a fluorescent blue emitter, the overall efficiency of a white light OLED can be brought to 100% by using a fluorescent blue emitter with a triplet energy , which is higher than the triplet energy of at least one phosphorescent emitter used.
  • a fluorescent blue emitter with a triplet energy which is higher than the triplet energy of at least one phosphorescent emitter used.
  • OLEDs organic light-emitting diodes
  • functions of a hole transport layer and an electron and exciton block layer or a hole and exciton block layer and an electron transport layer may each be combined into one emission layer structure.
  • the preparation of the individual organic layers can take place by means of thermal evaporation, molecular beam epitaxy, spin-on from solutions and by deposition from the gas phase. Conventional methods, such as the evaporation of organic materials, allow only structuring in one dimension.
  • the standard emission layer structure may consist of a mixed evaporation of a host or matrix material and the phosphorescent emitter dye, usually at concentrations between 1mol% and 20mol%.
  • a light-emitting device with organic layers and emission of triplet-exciton states with increased efficiency is described in the document DE 102 24 021 B4, wherein the device has a layer order with a hole-injecting contact - the anode, one or more hole-injecting and hole-transporting Layers, a system of stacked layers in the light emitting zone, one or more electron injecting and electron transporting layers and an electron injecting contact - a cathode - wherein the light emitting zone consists of a series of heterojunctions which form interfaces between the stacked layers, in the system stacked layers alternately a layer of a material with hole-transporting or bipolar transport properties and a layer of another material with electron-transporting or bipolar transport properties angegan are arranged and wherein at least one of the materials is mixed with a triplet emitter dopant.
  • Phosphorescent light-emitting components are known, in particular also in the embodiment as OLEDs.
  • the external quantum efficiency decreases significantly at high brightnesses.
  • the main reason for the decline in efficiency is the nature of phosphorescent emitter molecules, which, unlike conventional fluorescent dyes, emit from the electronic triplet state.
  • the quantum-mechanically forbidden transition with total spin one becomes accessible to light emission through the use of heavy metals such as platinum or iridium as the central atom.
  • the excited states, called excitons have a mean lifetime that is orders of magnitude longer, even for modern phosphorescent emitter molecules, than for fluorescent dyes. For this reason, the triplet excitons are much more susceptible to all conceivable quenching mechanisms that cause the extinction of such excited State without the state can be the emission. Consequently, the quantum efficiency at high excitation densities or brightnesses decreases significantly.
  • the charge carriers namely electrons and holes
  • the excited states also referred to as excitons
  • this is the limit for internal conversion efficiency, i. 25%.
  • both excitation states, singlet and triplet are redirected to the triplet state (ISC) or formed so that the molecules are potential materials for internal 100% quantum efficiency in OLEDs.
  • a disadvantage of the molecules is the long lifetime of the excited state compared to fluorescent dyes. Even for state-of-the-art phosphorescent molecules, the lifetime is several orders of magnitude higher, in the order of a few microseconds, cf. for this purpose, the emission from the singlet state with lifetimes of a few nanoseconds (Kawamura et al., J. Journ. Appl. Phys. 43 (2004) 7729).
  • phosphorescent dyes diluted in a host material are mixed in order to avoid so-called aggregate quenching (see Kawamura et al., Phys. Rev. Lett. 2006) 017404).
  • the host material has a higher triplet energy than or at least as high triplet energy as the emitter dye to exclude the energy transfer of the emitter triplet excitons on the host molecules as a possible loss channel.
  • the emission layers require relatively high concentrations of the emitter dye ( ⁇ 5-10 mol%) because the energy transfer from the host material to the emitter molecule is slower and shorter-range.
  • the energy transfer is a Dexter process (see Dexter, Journ. Chem. Phys. 21 (1953) 836). This in turn is detrimental to the absolute efficiency, since it can already come to the aforementioned aggregate quenching at the concentrations. At concentration, exciton diffusion directly on the emitter molecules is readily possible.
  • Organic components with a mixed system of host material and phosphorescent emitter dye further contain blocker or block layers adjacent to the emission zone, since even with the long lifetime, the average diffusion length of the excitons increases, which are intended to confine both charge carriers and triplet excitons into the emission zone. To achieve the latter, the layers must have a much higher triplet energy than that of the emitter dye (T ⁇ iocker »temitter / ⁇ 0.4eV) (see Goushi et al., Journ. Appl. Phys., 95 (2004) 7798).
  • the long lifetime makes the excited triplet states very susceptible to all quenching mechanisms, which are triplet-triplet annihilation (TTA), triplet-carrier quenching, and field-induced dissociation of the excitons into free charge carriers, especially at high excitation densities (see Reineke et al., Phys Rev. B 75 (2007) 125328).
  • TTA triplet-triplet annihilation
  • the triplet-triplet annihilation is the dominant process.
  • the process can in principle be done by two different mechanisms: (a) by diffusion of the triplet excitons until two excited states are close enough to annihilate, and (b) by long-range interaction, based on the Förster energy transfer model.
  • the extinction step can also take place by the so-called Dexter energy transfer.
  • the extinction happens in one step.
  • the process is determined only by the so-called Försterradius the emitting molecule, which defines the maximum distance between two excited states, in the erasure still takes place (see Staroske et al., Phys. Rev. Lett 98 (2007) 197402).
  • the latter process in contrast to the diffusion-based mechanism, does not depend on the concentration of the emitter molecules, the Förster-based mechanism being an intrinsic limit for the triplet-triplet quenching TTA in the OLEDs, since it is determined solely by the optical properties of the materials used becomes. In other words, the diffusion-based extinguishing mechanism is always intrinsically accompanied by the ranger-based extinction.
  • Phosphorescent OLEDs whose emission zone has a quantum well structure are described in Cheng et al, Jpn. J. Appl. Phys. 42 (2003) L376.
  • the known triplet emitter 2,3,7,8,12,13,17,18-octaethyl-21H23 H-porphin platinum (II) PtOEP
  • the quantum well structure has an increase in external quantum efficiency by a factor of about two.
  • the quantum well structure shows a greater decrease in the quantum efficiency at high brightnesses, so that the structures given at current densities of about 200mA / cm 2 ultimately have almost identical efficiency values. The effect is explained by the saturation of the emitter molecules.
  • the spatial separation of different areas of mixed systems of host material and emitter dye has another advantage in itself.
  • the separation largely decouples any energy transfer, also and especially at low excitation densities, between the centers.
  • Typical phosphorescent emitters have Förster radii of less than 2nm, allowing Förster-based energy transfer between neighboring molecules
  • Emission layer structures have been described in which all emitter dyes are incorporated in a host or matrix material having different concentrations (D'Andrade, Adv. Mat. 16 (2004) 624).
  • the presented emission layer structure reaches about 16 lm / W at 100 cd / m 2 and 11.1 ml / W at 1000 cd / m 2 . This corresponds to an efficiency reduction to 69% of the value at 100 cd / m 2.
  • the invention has for its object to provide an improved light-emitting device with high efficiency, even at high luminance and a method for manufacturing.
  • the invention encompasses the idea of a light-emitting component, in particular an organic light-emitting diode, having an electrode and a counterelectrode and an organic region arranged between the electrode and the counterelectrode with an organic light-emitting region which comprises at least one emission layer and which during application an electrical voltage is applied to the electrode and the counter electrode emitting light in several color ranges in the visible spectral range, optionally up to white light, the emission layer at least one predominantly in the blue or blue-green spectral light emitting fluorescent emitter and at least one predominantly in the non-blue spectral light emitting phosphorescent emitter, in the emission layer for the at least one fluorescent emitter a triplet energy for an energy level of a triplet state size r is equal to or approximately equal to (within 0, IeV) a triplet energy for an energy level of a triplet state of the at least one phosphorescent emitter, and the organic light emitting region comprises at least 5% of the generated light in the visible
  • a light-emitting organic component according to this embodiment has a very small drop in quantum efficiency with increasing current.
  • the invention thus has compared to the prior art, in particular over the Document EP 1 705 727 A1, has the advantage that a highly efficient and at the same time long-lasting light-emitting component for light emission in several color ranges in the visible spectral range up to white light is created even at high luminances, as are necessary in lighting technology.
  • Another important advantage of the invention is the simpler manufacture of the device, since less layers are to be applied by mixing the emitter.
  • a concentration of the phosphorescent emitter in the emission layer also promotes the transfer of singlet excitons from the fluorescent emitter. This is, to some degree, an undesirable effect, as it can no longer produce fluorescent light from the singlet excitons.
  • a concentration of the phosphorescent emitter of about 0.25 weight percent in the fluorescent emitter in the emission layer of the device leads to a balanced emission of fluorescent and phosphorescent light. This is a technically well controllable concentration (see, for example, Shao et al., Appl. Phys. Lett. 86, 073510 (2005)).
  • the actual concentration to be set of the phosphorescent emitter can also be chosen to be larger or smaller, depending on the emitters used and the desired color impression of the emitted light.
  • the proportion of fluorescent light is adjusted via the concentration ratio of fluorescent and phosphorescent material in the emission layer.
  • the fluorescent light can then be measured by recording an electroluminescence spectrum and determining the intensity component of the emitter which fluoresces in the blue spectral region.
  • the emission layer consists of a solid layer of the at least one fluorescent emitter used as the matrix material, in which the at least one phosphorescent emitter is embedded.
  • the invention also stands out in particular from the state of the art for multicolor-emitting polymer OLEDs, where the emission layer generally consists of a polymer with good charge carrier conduction properties, to which several types of emitter molecules are admixed (see, for example, Shih et al., Appl. Phys Lett., 88, 251110 (2006)), since here no matrix exclusively responsible for the charge carrier transport is used, but this function is taken over by the fluorescent emitter.
  • the emission layer consists of an organic material into which the at least one fluorescent emitter with a concentration between 0.1 and 50 mol% and the at least one phosphorescent emitter are embedded.
  • An advantageous embodiment of the invention provides that the organic light emitting region is at least 10% proportion of the generated light in the visible spectral range as fluorescent light of singlet states of the at least one fluorescent emitter in the emission layer is made.
  • a development of the invention provides that the organic light-emitting region is at least 15% proportion of the generated light in the visible spectral range as fluorescent light of singlet states of the at least one fluorescent emitter in the emission layer formed.
  • the organic light emitting area is at least 20% proportion of the generated light in the visible spectral range as fluorescent light of singlet states of the at least one fluorescent emitter in the emission layer made.
  • a further development of the invention can provide that the organic light-emitting region forms at least 25% of the generated light in the visible spectral range as fluorescent light of singlet states of the at least one fluorescent emitter in the emission layer.
  • the smaller a component is in the blue spectral range, that is to say for the components described here the fluorescent light component, the lower the color temperature of the electroluminescence spectrum.
  • the invention only allows high quantum efficiencies (close to 100% internal).
  • an electroluminescence spectrum with a 25% proportion of fluorescent light in the blue spectral range corresponds to the spectrum with the highest color temperature and at the same time the highest possible quantum efficiency when using highly efficient emitters with luminescence efficiencies close to 100%. If the fluorescence component is more than 25%, the color temperature becomes higher, but the quantum efficiency decreases.
  • the organic light-emitting region comprises a further emission layer with at least one phosphorescent emitter which emits light predominantly in the non-blue spectral range.
  • the emission layer and the further emission layer are formed adjoining one another.
  • An advantageous embodiment of the invention provides that the emission layer and the further emission layer are formed so as to transport holes, and that a distance between one of the surfaces of the emission layer facing the cathode and a surface of the cathode facing the emission layer is smaller than a distance between one of the cathodes facing surface of the further emission layer and the further emission layer facing surface of the cathode.
  • a development of the invention provides that the emission layer and the further emission layer are formed transporting electrons and that a distance between one of the counter electrode facing the anode surface of the Emission layer and one of the emission layer facing surface of the anode is smaller than a distance between an anode surface facing the further emission layer and the further emission layer facing surface of the anode.
  • the emission layer is formed transporting electrons and the further emission layer is formed holes transporting and that a distance between one of the electrode formed as a cathode surface facing the emission layer and the emission layer facing surface of the cathode smaller than is a distance between a surface of the further emission layer facing the cathode and a surface of the cathode facing the further emission layer.
  • a development of the invention can provide that the emission layer is formed transporting holes and the further emission layer is formed transporting electrons and that a distance between one of the counter electrode formed as an anode facing surface of the emission layer and one of the emission layer facing
  • a preferred embodiment of the invention provides that a hole block layer is arranged between the emission layer and the cathode, wherein the hole block layer is transporting electrons and an organic material of the hole block layer has a HOMO level which is at least about 0.3 eV lower than a HOMO. Level of the fluorescent emitter in the emission layer. It has been shown that an energy barrier of less than 0.3 eV is not sufficient to effectively block holes.
  • an electron block layer is arranged between the emission layer and the anode, wherein the electron block layer is hole transporting and an organic material of the electron block layer has a LUMO level which is at least about 0.3 eV is higher than a LUMO level of the fluorescent emitter in the emission layer. It has been shown that an energy barrier of less than 0.3 eV is usually insufficient to effectively block electrons.
  • An advantageous embodiment of the invention provides that a minimum energy of singlet excitons and triplet excitons in the hole block layer or in the electron block layer is greater than a minimum energy of singlet excitons and triplet excitons in the emission layer.
  • a development of the invention provides that the emission layer and / or the further emission layer are formed in multiple layers.
  • the emission layer has a thickness between about 10 nm and about 100 nm. Layers with a thickness of at least about 10 nm are still technically manageable. Layers with a thickness of more than 100 nm lead to an excessive voltage drop.
  • a development of the invention can provide that the organic light-emitting region is formed emitting white light, wherein the at least one phosphorescent emitter in the emission layer and / or in the further emission layer emitter emitting in the red, orange, yellow or green spectral emitter is.
  • a preferred embodiment of the invention provides that a respective doped organic layer is formed between the organic light emitting region and the electrode and / or between the organic light emitting region and the counter electrode.
  • the respective doped organic layer can be a layer doped with an acceptor material or n-doped with a donor material.
  • An advantageous embodiment of the invention provides that the at least one fluorescent emitter in the emission layer, a metal-organic compound or a Complex compound with a metal with an atomic number is less than 40. This ensures that there is no strong spin-orbit coupling for the material.
  • the at least one fluorescent emitter in the emission layer comprises an electron-withdrawing substituent from one of the following classes: halogens such as fluorine, chlorine, bromine or iodine; CN; halogenated or cyano-substituted alkanes or alkenes, in particular trifluoromethyl, pentafluoroethyl,
  • halogens such as fluorine, chlorine, bromine or iodine
  • CN halogenated or cyano-substituted alkanes or alkenes, in particular trifluoromethyl, pentafluoroethyl
  • the at least one fluorescent emitter in the emission layer comprises an electron-donating substituent of one of the following classes: alkyl radicals such as methyl, ethyl, tert-butyl, isopropyl; alkoxy; Aryl radicals with or without substituents on the aryl, in particular tolyl and mesithyl; and amino groups, in particular NH 2, dialkylamine, diarylamine and diarlyamine having substituents on the aryl.
  • the fluorescent at least one emitter in the emission layer comprises a functional group having an electron acceptor property from one of the following classes: oxadiazole, triazole, benzothiadiazoles, benzimidazoles and N-aryl-benzimidazoles, bipyridine, cyanovinyl , Quinolines, triarylboryl, silol units, in particular derivative groups of silacyclopentadiene, cyclooctatetraene, quinoid structures and ketones, including quinolines, thiophene derivatives, pyrazolines, pentaaryl-cyclopentadiene, benzothiadiazoles, oligo-para-phenyl with electron-withdrawing substituents and fluorene and spiro Bifluorene with electron-withdrawing substituents.
  • oxadiazole triazole
  • benzothiadiazoles benzimidazoles and N-aryl-benzimidazoles
  • bipyridine cyano
  • the fluorescent at least one emitter in the emission layer comprises a functional group having an electron donor property from one of the following classes: triarylamines, oligo-para-phenyl or oligo-meta-phenyl, carbazoles, Fluorene or spiro-bifluorenes, phenylene-vinylene units, naphthalene, anthracene, perylene, pyrene and thiophene.
  • the electrode is formed as an optically reflective electrode
  • a charge carrier transport layer having a layer thickness d1 is arranged between the emission zone and the optically reflecting electrode
  • layer thickness dl ( ⁇ bi au / 4) -ET, where ET is the penetration depth of electromagnetic waves into the optically reflecting electrode and ⁇ b i au is a wavelength in the blue spectral range from 380nm to 500nm.
  • with ⁇ Thode Ka arctan (2n o k m / (n o -n 2 m 2 m 2 -k)).
  • U 0 is the real part and k 0 is the imaginary part of the complex refractive index of the organic layers, n m is the real part and k m is the imaginary part of the complex refractive index of the material of which the cathode is made.
  • n integer n is greater than or equal to zero, dOB2 is one
  • Support substrate m is a natural number greater than or equal to 1 and dAnode a layer thickness of the anode.
  • the carrier substrate used is preferably glass.
  • a development of the invention provides that in the emission layer, a space region having a first concentration of the at least one phosphorescent emitter and a further space region with a second, different from the first concentration concentration of the at least one phosphorescent emitter are formed.
  • a space area is formed, which is free of an admixture of the at least one phosphorescent emitter.
  • the invention provides an organic light-emitting component, in particular a phosphorescent organic light-emitting diode, having an anode and a cathode and an arrangement of organic layers therebetween, which comprises a hole transport layer, an emission layer and an electron transport layer, the emission layer having a sub-structuring with zones, which zones comprising at least one host material and zones comprising a mixing system with at least one phosphorescent emitter dye, wherein the zones consisting of the mixing system are spatially separated from each other by the zones consisting of the at least one host material.
  • a phosphorescent organic device may also be referred to as a phosphorescent organic device.
  • the triplet energies (Twin) of the at least one host material is greater than the triplet energy (T Em m er ) of the at least one phosphorescent emitter dye (Twm>
  • the mixing system may be formed by the at least one host material or by using one or more host materials different therefrom. Also, at least one additional host material may be added to the at least one host material. In contrast to the mixing system which contains one or more phosphorescent emitter dyes, the zones consisting of the at least one host material are free of emitter dyes and consist of one or more host materials. Host material (“matrix material", “host material”) is generally the material that is used to transfer excitons from it to the emitter dye, a kind of donor material.
  • the emission layer can have layer-like zones of the mixed system of host material and emitter dye by a given sub-structuring, the sub-structuring consisting of sequential sequence of layer-like zones in the form of a vertical structuring of zones of pure host material and mixed system zones Host material and phosphorescent emitter light emitting emitter is formed.
  • the emission layer may, on the other hand, have layered zones of the mixed system of host material and emitter dye by a given sub-patterning, the sub-patterning being formed by sequential sequence of layered zones in the form of a lateral structuring of zones of pure host material and mixed system zones of host material and phosphorescent emitter dye emitting light ,
  • the emission layer can also consist of a vertical structuring and a lateral structuring of layer-like zones.
  • the zones of the mixing systems and / or the host materials may be formed as spherical or cubic bodies or as bodies of predetermined geometry. Both host material and emitter dye of different emission layers may be different.
  • the hole transport layers can be combined in one layer and / or the electron transport layers can be combined in one layer.
  • the zones of pure host material may be replaced by zones of another host material, the triplet energy of which is greater than the triplet energy of the emitter dye employed.
  • the zones pure host material may be replaced by a plurality of materials by zones of a combination of materials, and their triplet energy TEmit Tic o m b greater than the triplet energy te r of the emitter dye with T ⁇ O mb> Temmer are for all materials.
  • different zones of pure host material may be replaced in any sequential order of zones of multiple materials.
  • Different zones of the mixing system may contain different phosphorescent emitter dyes.
  • the zones of a mixing system may contain a plurality of different host materials and / or a plurality of different emitter dyes.
  • the vertical patterning may be performed during a mixed vaporization of host material and emitter dye by an array of mechanically movable apertures in front of the emitter dye source which periodically interrupt the evaporation of the emitter dye.
  • the lateral structuring can be generated during the mixed vaporization of host material and emitter dye by periodically introducing a shadow mask directly in front of the substrate.
  • a shadow mask is in its resolution by the Production limited (for example, laser beam cutting diffraction limit), so that centers produced in this way have an extension in the micrometer range.
  • the effective openings of the mask can be drastically reduced.
  • the displacement in both directions is preferably smaller than the diameter of the openings in the shadow mask. Since a combination of vertical and lateral structuring is possible, a sub-structuring in all directions can be achieved.
  • the diffusion on the grating of the emitter dyes is effectively prevented.
  • the diffusion is suppressed by the substructure of the emission layer, which restricts the excitons in their diffusion.
  • the substructures are not needed to efficiently trap charges to increase, for example, recombination efficiency and thus absolute electroluminescent efficiency (Cheng et al., Jpn. J. Appl. Phys. 42 (2003) L376). Instead, it is attempted to confine the emitter dyes in zones spatially surrounded by a material whose triplet energy, similar to that of conventional blocking layers, is high relative to the triplet energy of the emitter dye.
  • the effective concentration of the emitter dyes in these zones is not reduced in order to allow efficient energy transfer of the Wirtsexzitonen on the emitter. It is exploited that the process of diffusion is a random process without preferential direction, and further that each diffusion step to an adjacent molecule is not affected by the previous step. By the introduction of energetic barriers that prevent diffusion of the excited state in this direction, so the effective probability of diffusion in favor of the radiative recombination of excitons, ie Emission of light, reduced. Neighboring excitonic sub-layer structures are located further apart than the average Dexter-type interaction range, ie, at least about 1 to about 2 nm.
  • this structure may be prepared from a combination of pure, conventional host material and a mixed system of host material and emitter dye.
  • the emission layer is patterned such that there are defined separated exciton sub-structures of the mixing system in an environment of the pure host material within the emission layer.
  • a development of the invention may provide that the zones are formed in a layer structure, wherein the layer structure comprises a sequential sequence of layer-like zones in the form of a vertical structuring of the zones consisting of the mixing system and the zones consisting of the at least one host material.
  • a preferred embodiment of the invention provides that the zones are formed in a layer structure, the layer structure comprising a sequential sequence of layer-like zones in the form of a lateral structuring of the zones consisting of the mixing system and the zones consisting of the at least one host material.
  • At least a portion of the zones are formed as a spherical or cubic body.
  • An advantageous embodiment of the invention provides that adjacent boundary surfaces of the zones consisting of the mixing system are at least at a distance in the nanometer range from each other, wherein the distance corresponds to a thickness of the zones consisting of the at least one host material.
  • the distance is preferably at least two nanometers.
  • a development of the invention provides that the hole transport layer is p-doped and / or the electron transport layer is n-doped. Provided is an electrical doping.
  • the zones consisting of the at least one host material are replaced by zones of another host material, wherein its triplet energy (Twi rt i) greater than the triplet energy (T em m er ) of the at least one phosphorescent emitter dye with Twirt9i> TEmmer.
  • a development of the invention can provide that zones consisting of the at least one host material are replaced by zones of a material combination of several materials, their triplet energies (T ⁇ Omb ) being greater than the triplet energies (T Em m er ) of the at least one phosphorescent emitter dye are with T ⁇ O mb> temm e r for all materials.
  • a preferred development of the invention provides that zones consisting of the at least one host material are formed in sequential order with zones of several materials.
  • various phosphorescent emitter dyes are included in the mixing systems.
  • the different emitter dyes differ by their respective emission spectrum.
  • a mixing system is preferably formed from one or more host materials and one or more emitter dyes incorporated therein.
  • a development of the invention provides that additional emission layers are formed with a fluorescence emission from singlet states.
  • Emission layers are considered to be areas composed of one or more fluorescent
  • the concentration of the at least one phosphorescent emitter dye in the at least one host material is between 0.1 mol% and 50 mol%. 0.1 mol% ensures efficient transfer of the excitons from the host or matrix material to the emitter dye, and greater than 50 mol% significantly reduces the efficiency of aggregation emission.
  • a development of the invention may provide that a distance between the zones consisting of the at least one host material is between about 2 nm and about 20 nm. At a distance of about 2nm distance, the individual zones are sufficiently separated so that short-range energy transfer processes do not prevent the desired effect of localization. A distance of more than about 20nm leads to high voltages in the device. In addition, the transfer of host material to emitter dye becomes inefficient or no longer takes place.
  • a preferred embodiment of the invention provides that the zones consisting of the mixing system have a spatial extent of about 0.5 nm to about 100 nm. Smaller 0.5nm leads to a molecular size, which is technically hardly practicable.
  • the organic layers consist of small molecules vapor-deposited in a vacuum or partly of polymers.
  • the emission layer has a further sub-structuring, in which a mixed color light up to the white light-emitting combination of different emitter dyes, which have different basic emission spectra, is provided in different zones of a mixed area.
  • a mixed color light up to the white light-emitting combination of different emitter dyes which have different basic emission spectra, is provided in different zones of a mixed area.
  • it is phosphorescent emitter dyes, but also fluorescent emitter dyes can be provided.
  • a further development of the invention provides that the triplet energies T W i rt of host materials are less than or equal to the triplet energies Te m m er of the emitter dyes.
  • an emission layer structure with at least one emission layer with a substructuring is formed.
  • the at least one emission layer comprises a combination of different emitter materials with different base emission spectra in different zones of a mixing area, so that color-matched light or white light can be emitted.
  • the different layers (zones) with different emission dyes, which in each case represent a mixed area, can also form an array of multiple emission layers.
  • the further sub-structuring of the emission layer is superimposed with the zone structuring described above.
  • both white light can be achieved by the emission of different zones with different emission spectrum and the reduction of the diffusion-based triplet triplet deletion. From the combinatorial possibility of arranging different emitter dyes spatially in the emission layer structure results in a simplified, modular variability in color matching to achieve light of a given spectrum, in particular white light.
  • the component for emitting white light with at least one emission layer may additionally contain fluorescent emission layers, which in turn may be either pure layers of the emitter dye and / or a mixed system of host material and emitter dye.
  • the light extraction efficiency of the device may be for the blue spectral range, the range between 400nm and 500nm in wavelength, and this optimization can be done by adjusting the layer thicknesses of the transport layers.
  • Such components are realized by means of a manufacturing method using different emitter dyes with different emission colors in a proposed emission layer structure for a coordinated color emission or a white light emission.
  • an organic component in particular a phosphorescent organic light-emitting diode, in which an anode and a cathode and between them an arrangement of organic layers are formed which comprises a hole transport layer, an emission layer and an electron transport layer, wherein the emission layer is provided with a sub-layer.
  • Structuring is formed with zones which zones comprises at least one host material and zones consisting of a mixed system of at least one phosphorescent emitter dye and the at least one host material, wherein the zones consisting of the mixing system spatially separated by the zones consisting of the at least one host material be formed.
  • the method of manufacture may be extended or adapted accordingly in connection with the advantageous embodiments of the component.
  • Fig. 1 is a schematic representation of a layer arrangement of an organic light-emitting component
  • Fig. 2 is a schematic representation of a layer arrangement of a further organic
  • 3 is a schematic representation of a layer arrangement of another organic light-emitting component
  • 4 shows a graph for the quantum efficiency as a function of the brightness of a reference light-emitting diode according to the prior art and an organic light-emitting diode according to the invention
  • 6 is a graphical representation of an electric field distribution of the light emission of an organic light-emitting component having a plurality of emission layers with different emission wavelengths
  • FIG. 7 is a graph showing a field distribution of light emission of two organic light emitting devices having different ones.
  • Cathode material (aluminum and silver),
  • FIG. 8 shows a graphic representation of an electric field distribution of light with a wavelength of 470 nm in an organic light-emitting component with layer thicknesses z and d optimized for this wavelength, which define distances of the emission zone from the cathode and an anode / glass substrate interface.
  • FIG. 10 shows a graph for the quantum efficiency as a function of the brightness of a reference light-emitting diode according to the prior art and a further organic light-emitting diode according to the invention
  • FIG. 11 shows a schematic representation of a layer sequence for a known OLED according to the prior art (I Ia ), an inventive OLED (I Ib) and an inventive OLED in a work function (eV) layer thickness diagram (Hc),
  • FIG. 12 is a schematic representation of an emission layer in vertical layer sequence B A (12a), B C (12b), B C + D (12c) and B C D (12d), where A is a pure
  • FIG. 13 is a schematic representation of an emission layer with A and B-components for a realization of a substructuring in all spatial directions in a perspective view (13a) and a side view (13b),
  • FIG. 14 shows a photoluminescence spectrum of one 20 nm mixed-system layer TCTA: Ir (ppy) 3 , wherein the broken-line quadratic curve for the reference emission layer is 9.6 mol% and the dashed-circle curve for the sub-layer structure emission layer is 11, FIG.
  • Fig. 15 shows a plurality of photoluminescence decay curves for samples from the preliminary investigation according to FIG. 14, the dashed square curve for the reference emission layer being 9.6 mol% and the dashed curve for the sub-layer structure emission layer
  • Fig. 16 is a current density-voltage characteristic of an OLED, wherein the dashed square curve for the reference emission layer is 9.6 mol% and the dashed-line curve is 11.4 mol% with the reference structure having larger TTA amounts for the sub-layer structure emission layer with 11, 4mol% apply and wherein for the sub-layer OLED a small additional barrier is to be noted
  • Fig. 17 Electroluminescence spectra of devices according to FIGS.
  • FIG. 19 shows several organic materials which can be used in the components
  • FIG. 20 shows further organic materials which can be used in the components
  • FIG. 21 shows schematic representations of emission layer structures for an emission layer structure with the relative triplet energies of all used Materials using F ⁇ r (pic), Ir (ppy) 3 and Ir (MDQ) 2 (acac) (21a), a
  • FIG. 22 shows basic emission spectra of usable emitter dyes (here: F ⁇ r (pic), Ir (ppy) 3 and Ir (MDQ) 2 (acac)) in an emission layer structure, FIG.
  • FIG. 23 shows emission spectra of two OLEDs with emission layer structures according to FIG. 21a and FIG. 21b, the spectra of which is an additive composition from the basic emission spectra shown in FIG. 22, FIG.
  • FIG. 24 shows an emission spectrum of a third OLED according to FIG. 21 d with a third emission layer structure according to FIG. 21 c, which component of all
  • FIG. 25 shows the external quantum efficiency and the power efficiency of the third embodiment.
  • FIG. 26 shows usable organic materials for the emission layer structures of components: 1. Iridium bis (4,6, -difluorophenyl-pyridinato-N, C2)
  • FIG. 26 shows the emission layer structure according to FIG. 21c and FIG. -picolinate, abbreviated F ⁇ r (pic), 2.
  • FIG. 27 utilizes organic materials for the emission layer structures of FIG. 27
  • FIG. 28 usable organic material: 9,2,2'2 "(1, 3, 5-benzenetriyl) tris - (1-phenyl-1H-benzimidazole) (TPBi).
  • FIG. 1 shows a schematic representation of a layer arrangement of an organic light-emitting component.
  • anode 1 and cathode 2 there are formed two electrodes, anode 1 and cathode 2, between which an organic region having a hole transport layer 3 of an organic substance, optionally doped with an acceptor material, an electron block 7 of an organic substance, an organic light emitting region 4 having an emission layer EML 1, a hole block layer 6 of an organic substance and an electron transport layer 5 of an organic substance optionally doped with a donor material is arranged.
  • the emission layer EML 1 comprises a fluorescent emitter which emits light predominantly in the blue or blue-green spectral region and to which one or more phosphorescent emitters predominantly emitting in the non-blue spectral region are / are mixed.
  • the electron block layer 7 and / or the hole block layer 6 are omitted.
  • the OLED operates as follows: Holes are injected through the anode 1 into the hole transport layer 3, pass through the hole transport layer 3, and reach the light emitting organic region 4, optionally through the electron block layer 7. Electrons are injected into the electron transport layer 5 through the cathode 2 , migrate through the electron transport layer 5 and reach, if necessary, through the hole block layer 6, the light-emitting organic region 4. In the light-emitting organic region 4 holes and electrons meet and recombine on the blue or blue-green fluorescent emitter molecules to excited states, so-called Excitons formed in triplet and singlet states. The singlet excitons partially recombine with the emission of blue fluorescent light; in some cases an energy transfer occurs after the Förster transfer mechanism to the phosphorescent emitters. The triplet excitons on the fluorescent blue or cyan emitter are predominantly transferred to the non-blue phosphorescent emitters, where they recombine with the emission of phosphorescent light.
  • FIG. 2 shows a schematic representation of a layer arrangement of a further organic light-emitting component e.
  • a further organic light-emitting component e For the same features, the same reference numerals as in Fig. 1 are used in Fig. 2.
  • the light-emitting organic region 4 consists of two emission layers EML 1 and EML 2.
  • the additional emission layer EML 2 comprises one or more predominantly non-blue spectral emitting phosphorescent emitter (s).
  • EML 1 is mainly holes conductive
  • EML 2 is predominantly electron conductive. Therefore, the main recombination zone is located in the region of the interface between EML 1 and EML 2.
  • the term main recombination zone refers to a spatial area within the region of the organic layers between the anode and the cathode in which at least about 50% of the injected charge carriers recombine.
  • EML 1 is mainly electronically conductive
  • EML 2 is predominantly holes conductive. Therefore, the main recombination zone is located at the interface between EML 1 and EML 2.
  • ITO indium tin oxide
  • P-doped hole transport layer 60 nm N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine (MeO-TPD) doped with tetrafluoro-tetracyano-quinodimethanes (F4-TCNQ)
  • Red emission layer 20 nm N, N'-di (naphthalen-1-yl) -N, N'-diphenyl-benzidine ( ⁇ -NPD) doped with iridium (III) bis (2-methyldibenzo [f, h] quinoxaline) (acetylacetonate) (ADS 076RE) (5% by weight)
  • Green emission layer 10 nm l, 3,5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBi) doped with fac tris (2-phenylpyridine) iridium (Ir (ppy) 3) (4% by weight) 7)
  • Electron-side intermediate layer 10 nm bathophenanthroline (BPhen)
  • N-doped electron transport layer 30 nm BPhen doped with Cs
  • An exemplary embodiment of an inventive OLED provides the following layer structure: 1.1 Anode: indium tin oxide (ITO)
  • 1.2 P-doped hole transport layer 60 nm N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine (MeO-TPD) doped with tetrafiuoro-tetracyano-quinodimethane (F4-TCNQ)
  • N-doped electron transport layer 30 nm BPhen doped with Cs 1.8 cathode: 100 nm aluminum
  • This OLED is a white OLED in so-called pin design, which shows a brightness of over 1000 cd / m 2 at a voltage of 4.2 V.
  • the external quantum efficiency (see FIG. 4) is almost constant up to a brightness of about 1500 cd / m 2 , while it has already dropped by a factor of about 2 in the reference component.
  • the external quantum efficiency of the inventive OLED from a brightness of about 500 cd / m 2 is greater.
  • ITO Indium Tin Oxide
  • P-doped hole transport layer 60 nm N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine (MeO-TPD) doped with tetrafluoro-tetracyano-quinodimethanes ( F4-TCNQ)
  • Hole side intermediate layer 10 nm l, l-bis (4-methylphenyl) aminophenyl) cyclohexane (TAPC)
  • Blue and red emitting layer N, N'-di-1-naphthalenyl-N, N '-diphenyl-
  • Electron-side intermediate layer 10 nm TPBi
  • N-doped electron transport layer 30 nm bathophenanthroline (BPhen) doped with Cs 2.8 cathode: 100 nm aluminum
  • the device according to the further embodiment is a white light emitting organic device in so-called pin-execution, which at a voltage of 3.7 V shows a brightness of over 1000 cd / m 2 .
  • the external quantum efficiency (see FIG. 10) over the entire measured brightness range of about 10 cd / m 2 to about 10000 cd / m 2 is significantly greater.
  • the external quantum efficiency remains virtually constant up to a brightness of about 1500 cd / m 2 , in contrast to the reference OLED, which shows a strong efficiency drop, starting even at low magnitudes of 10 cd / m 2 .
  • an emission zone can be defined for the light-emitting organic devices with layer construction by means of a spatial distribution of the radiatively relaxing excitons, which depends on a charge carrier balance, exciton diffusion and the like.
  • the emission zone thus forms a partial area within the emission layer of the component in which the predominant portion of the light is formed. Assuming that the emission zone extends over a broad range of the emission layer, the emission zone and emission layer can be treated approximately equally.
  • a distance z between the cathode of the component and the emission zone then corresponds in the simplest case to the distance between the electrode and the center of the emission layer (see FIG. 6). This ensures at the same time that the wavelength range around ⁇ b i au also optimally coupled to the optical field.
  • with ⁇ Thode Ka arctan (2nok m / (NO2 -N 2 m - k m 2)), where n is 0, n mi k m ... optical constants of the organic material and the metal material of the cathode.
  • 550 nm about 64 nm results for Al and 55 nm for Ag (see FIG.
  • Microresonator effects occur in bottom emitting OLEDs primarily due to the refractive index difference between ITO and glass substrate. This is at fixed ITO Layer thickness given the cavity length by d cav + duo.
  • , (m 1,2, ).
  • the condition ensures that a field maximum occurs at the boundary between ITO and glass substrate. In other words: 3/4, 5/4, 7/4 ... times the wavelength fit between ITO and glass and Al (+ effective penetration depth).
  • the condition gives guideline values. Precise optimization is achieved by simulation using thin-film optics.
  • the proportion of fluorescent light to the light generated in the emission layer is determined by the concentration ratio of fluorescent and phosphorescent material in the
  • Fluorescence light can then be measured by an electroluminescence spectrum is recorded and the intensity of the fluorescence in the blue spectral emitter is determined.
  • the following structure is formed: glass / ITO (90 nm) / MeO-TPD: F 4 -TCNQ (60 nm, 4 mol%) / ⁇ -NPD (10 nm) / 4P NPD: Ir (MDQ ) 2 (acac) (30 nm, 0.11 weight percent) / TPBi (10 nm) / BPhen: Cs (30 nm) / Al (100 nm).
  • the emission layer consists of a solid layer (matrix material) of the blue-fluorescent emitter 4P-NPD, to which 0.11 percent by weight of the red-phosphorescent emitter Ir (MDQ) 2 (acac) is admixed.
  • the electroluminescence spectrum has about 50% of its intensity in the blue. This corresponds to an approximately 50% proportion of fluorescent light in the total light emission.
  • Fig. 9 shows an electroluminescence spectrum for the above-described embodiment.
  • FIG. 10 shows a graph for the quantum efficiency as a function of the brightness of a reference light-emitting diode according to the prior art and a further organic light-emitting diode according to the invention.
  • 1 b shows a schematic illustration of a triplet state phosphorescent light emission device 1010, wherein the device 1010 comprises an injection hole anode 101, at least one hole injecting or hole transporting layer 102, 103 (hole transport layer), at least one emission layer 104, at least one electron injecting or electron transporting layer 105, 106 (electron transport layer) and an electron injection cathode 107, wherein the layers 102, 103, 104, 105, 106 are made of organic material.
  • the emission layer 1042 has a sub-structuring of zones 1014,
  • Twirt> TEmitter are.
  • Adjacent interfaces 1012, 1013 of the zones 1014, 1016, 1018, 1020, 1022 of the mixing system 108 are spaced apart by a predetermined distance a with a minimum amount in the nanometer range.
  • the minimum amount of the distance a may be two nanometers between the adjacent interfaces 1012, 1013 of the zones 1014, 1016, 1018, 1020, 1022 of the mixing system 108.
  • the host material 109 as well as the emitter dye 101 1 of different emission layers 1042, 1043, 1044, 1045, 1046 may each be different.
  • the emission layer 1042 has, by a given sub-patterning, layered zones 1014, 1016, 1018, 1020, 1022 of the mixed system 108 of host material 109 and emitter dye 101 1 and layered zones of the host material 109, the sub-patterning being by sequential succession of layered layers Zones in the form of a vertical structuring of zones 1015, 1017, 1019, 1021 pure host material of at least two nanometers thickness and mixing system zones 1014, 1016, 1018, 1020, 1022 formed of host material and phosphorescent light-emitting emitter dye.
  • FIG. 12 with respect to the vertical structuring, a plurality of schematic embodiments of the emission layers 1042, 1043, 1044, 1045 are shown in vertical layer sequence, wherein in FIG. 12a the emission layer 1042 with alternating layers B and A, in FIG. 12b the emission layer 1043 with alternating layers B and C, in Fig. 12c the emission layer 1044 with alternating layers B and C + D and in Fig. 12d the emission layer 1045 with alternating layers B, C and D are shown and where A is pure host material, B is a mixed system of host material 109 and Emitter dye 101 1, C is a material other than A, with the physical specifications that apply to A, D is another material other than A, with the physical specifications that apply to A.
  • the hole transport layer 102 may be p-doped and / or the electron transport layer 106 may be n-doped. However, the hole transport layers 102, 103 may also be combined in one layer and / or the electron transport layers 105, 106 may be combined in one layer.
  • the zones 1015, 1017, 1019, 1021 pure host material 109 can be replaced 191 (not shown) through zones of another host material, wherein the triplet energy Twi rt i 9 i is greater than the triplet energy TEmitter the inserted emitter dye with Twirti9i>
  • the zones 1015, 1017, 1019, 1021 of the pure host material 109 can be replaced by zones of a material combination of a plurality of materials, their triplet energies T ⁇ omb being greater than the triplet energies TEmmer of the emitter dye 1011 with T ⁇ O mb > TEmitter for all materials ,
  • Different zones 1015, 1017, 1019, 1021 of pure host material may be replaced in any sequential order of zones of multiple materials.
  • Different zones 1014, 1016, 1018, 1020, 1022 of the mixing system may contain various phosphorescent emitter dyes.
  • the zones of a mixing system may contain a plurality of different host materials and / or a plurality of different emitter dyes.
  • the device 1010 may include additional emission layers having fluorescence emission from singlet states, wherein the additional emission layers are pure zones or mixing systems.
  • the concentration of emitter dye in host material 109 may be between 0.1 mol% and 50 mol%.
  • the distance of zones of pure host material may be between 2nm and 20nm.
  • the zones of the mixed system of host material and emitter dye can have a spatial extent of 0.5 nm to 100 nm.
  • the zones 1023, 1024, 1025 of the mixing systems 108 and / or the zones 1091 of the host materials may be formed as layers or as spherical or cubic bodies or as bodies of other predetermined geometry.
  • the zones formed as layers can consist of vacuum-deposited small molecules or partially of polymers.
  • the emission layer 1042, 1043, 1044, 1045; 1046 by a targeted sub-structuring of zones 1014, 1016, 1018, 1020, 1022; 1023, 1024, 1025 of at least one mixing system 108 of at least one host material 109 and at least one emitter dye 1011 and zones 1015, 1017, 1019, 1021; 1091 of a host material 109, wherein the zones 1014, 1016, 1018, 1020, 1022 of the mixing system 108 are spatially defined by zones 1015, 1017, 1019, 1021; 1091 of the host material are positioned apart 109 whose triplet energy greater than that of the emitter Twm dye 1011 T emitter (Twin> T Em i tter), wherein the sub-structure by sequential sequence of zones in the form of a vertical structuring of layers 1015, 1017, 10
  • the vertical patterning may be performed during a mixed vaporization of host material 109 and emitter dye 1011 by an array of mechanically movable apertures in front of the emitter dye source which periodically interrupt the vaporization of emitter dye 1011.
  • the sub-patterning may also be achieved by means of a lateral structuring (not shown) during a mixed evaporation of host material 109 and emitter dye 1011 by periodically introducing shadow masks between substrate and evaporation sources.
  • a lateral structuring (not shown) during a mixed evaporation of host material 109 and emitter dye 1011 by periodically introducing shadow masks between substrate and evaporation sources.
  • a combination of vertical and lateral structuring is also possible, so that a sub-structuring in all spatial directions can be achieved.
  • the block layers 103, 105 are obligatory in order to avoid exciton quenching at the interfaces.
  • Conventional, electrically undoped OLEDs can have a reduced number of layers depending on the design.
  • the preparation of the individual organic layers can be done by thermal evaporation, molecular beam epitaxy, spin-on from solutions and by deposition from the gas phase.
  • the mixing system is generally subject to the following conditions: a) The triplet energy Twin of the host material 109, 191 should be greater than or equal to the triplet energy Te m m er of the emitter dye 1011, and b) The absorption spectrum of the emitter dye 1011 should be strongly with overlap the emission spectrum of the host material 109, 191, so that an efficient exciton energy transfer can take place.
  • the requirement that the triplet energy Tw of the host material 109, 191 be greater than the triplet energy T E of the emitter dye 1011 means to capture the triplet excitons efficiently on the emitter dye 1011, ie, to prevent their diffusion to host states.
  • the zones of the mixing system 108 should be as thin as possible to minimize diffusion in the individual zones.
  • the pure layers of the host material 109 should be as thin as possible to both inhibit fluorescence thereof and avoid side electrical effects such as higher operating voltages through thick additional intrinsic layers in the emission layer 1042.
  • the pure layers with the host material 109 must be at least so thick that dextransfer processes between the substructures 1042 is not possible (> 1-2nm).
  • the following materials are used in the OLED 10 corresponding to FIG. 1 lb, the chemical names of the materials being illustrated in FIGS. 19, 20:
  • ITO indium tin oxide
  • the sub-layer structure 1042 corresponds exactly to the structure explained below in the preliminary investigation.
  • photoluminescence investigations of the TCTA Ir (ppy) 3 emission layer (reference structure 1041 and sub-layer structure 1042) are carried out. In each case, 20 nm of emission layer are vapor-deposited on quartz glass substrates.
  • the reference structure 1041 is a mixed system layer of TCTA: Ir (ppy) 3 with a concentration of about 10 mol%.
  • FIG. 14 shows the photoluminescence (PL) spectra of both structure layers 1041, 1042. Both show strong emission of the Ir (ppy) 3 triplet state with a maximum at around 510nm.
  • PL photoluminescence
  • the two structural layers 1041, 1042 were time-resolved, i. excited with a short laser pulse and measured the decay behavior of the emission.
  • the corresponding decay curves are shown in FIG. A purely exponential decay occurs when the triplet triplet deletion TTA is negligible, i. the excited species only relax directly.
  • the curvature to be observed at the beginning of the decay is a measure of the bimolecular recombination, in this case the triplet triplet deletion TTA (compare Reineke et al., Phys. Rev. B 75 (2007) 125328).
  • the sub-layer structure 1042 has a significantly reduced contribution of the triplet triplet deletion TTA.
  • the effect is even more pronounced if the active volume, ie the volume in which Ir (ppy) 3 is located, is smaller by approximately 2/3 than in the reference structure 1041, ie the effective exciton density in the sub-layer structure 1042 is larger by a factor of three.
  • the energetic positions of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) or work function (WF) in the case of metals are shown in the following list (Reineke et al., Phys Rev. B 75 (2007) 125328 and Kundu et al., Adv. Funct. Mat. 13 (2003) 445):
  • FIG. 17 shows the electroluminescence (EL) spectra of both structure layers 1041, 1042.
  • TCTA host material
  • the slightly lower efficiency of the sub-layer structure 1042 is statistical in nature, and the photoluminescence measurement at the same excitation density as shown in Fig.
  • both OLEDs 101, 1010 achieve equal intensities.
  • the course of the external quantum efficiency of both OLEDs 101, 1010 shows that the sub-layer structure 1042 has a reduced efficiency drop at high current densities.
  • the efficiencies of both OLEDs 101, 1010 are approximately equal to 12% EQE.
  • the sub-layer structure 1042 is only mentioned and illustrated in this specific exemplary embodiment as representative of the other substructures 1043, 1044, 1045, 1046.
  • the model equation is based on the following rate equation, which describes the time evolution of the exciton density of excited emitter dyes:
  • the triplet lifetime ⁇ is determined to be 1.64 ⁇ s and recorded.
  • TTA rate constant krr and triplet carrier extinction rate constant kp values are taken and recorded that were measured on other comparable TCTA: Ir (ppy) 3 -based OLEDs 101 (Reineke et al., Phys. Rev. B 75 (2007 125328).
  • the thickness of the recombination zone was used for fitting. The result is the solid fit straight line from FIG. 18.
  • the sub-layer structure has a maximum of 8nm due to its composition Emission zone available because the excitons are trapped in the mixed layer parts. Furthermore, as mentioned in the above structure, NPB is used as an electron blocker which, due to its low triplet level with a maximum wavelength of about 540 nm, deletes the Ir (ppy) 3 localized at 510 nm, ie the excitons are applied to the non-radiative NPB triplet level (Goushi et al., Journ. Appl. Phys. 95 (2004) 7798). For the sub-layer OLED 1010, therefore, a significantly lower output efficiency at low brightnesses should be expected. It can be concluded that the recombination zone thickness of the sub-layer structure 1042 is smaller than the nominal 8 nm, thus comparable to the reference structure 1041.
  • a current density j c is defined as the current density at which the efficiency equals half the value of those at low magnitudes, in which extinguishing mechanisms are irrelevant, the model calculation can be used to make quantitative statements about the differences.
  • the current density j c can be almost doubled from 140mA / cm 2 to 270mA / cm 2 for the sub-structure 1042.
  • the invention describes a way to reduce the efficiency decrease by a targeted modification of the sub-structure of the emission zone, i. the layer in which the charge carriers are converted into light.
  • emission layer structures 2020, 2030, 2040 of components 2070 for phosphorescent light emission from triplet states are shown.
  • At least one emission layer 209, 2010 is present in an emission layer structure 2020, 2030 or 2040 for producing a matched colored light emission 2053, 2054 or white light emission 2055, at least one of the emission layers 209, 2010 being present or at least one
  • Emission layer 209, 2010 is present with a sub-structuring, in which the
  • Combination of different emitter materials, with different base emission spectra, is provided in different zones of the mixing area.
  • FIGS. 21a and 21b show a first emission layer structure 2020 and a second emission layer structure 2030, each with a composition for simple, modular color matching by the sub-structuring and FIG. 21 c shows a third emission layer structure 2040 and FIG. 21 c shows a component 2070 which is embodied concretely on the basis of the emitter layer structure 2040 and emits white light.
  • the following materials are used, the chemical names of which are given in FIGS. 26, 27, 28.
  • the various emission zones of the emission layer structures 2020, 2030, 2040 are shown in FIGS. 21a, 21b, 21c.
  • the schematically illustrated, associated layer structure of the complete OLED 2070, which is shown in FIG. 2 Id, is constructed as follows, wherein the reference numeral 2060 denotes transparent ITO (indium tin oxide) on a glass substrate (90 nm) as an anode,
  • a reflective aluminum layer (100 nm) as a cathode, wherein the respective layer thicknesses in nanometers - nm - are indicated represent.
  • the emission layer structures 2020, 2030 can be used for producing a coordinated color emission.
  • FIG. 21 schematically illustrates the emission layer structures 2020, 2030, 2040 for the associated components 2070-OLED. These are each a combination of two sequentially used host materials 207, 208, wherein the host material 207 is TCTA and the host material 208 TPBi, whose structural formula and structure are given in FIGS. 27 and 28.
  • the emitter dyes are each incorporated in the respective host material 207, 208 at about ten percent by weight.
  • the individual layers 201, 202, 203, 204, 205, 206 of the mixing zones are thick, the zones of pure host material 207, 208 have a thickness of 2 nm, so that in each case the entire emission layer structures 2020, 2030 are about 20 nm and the emission layer Structure 2040 are about 17nm thick, wherein the emission layer structures 2020, 2030, 2040 are composed of two single emission layers 209, 2010 each 10nm (or 7nm in the case of 2040), where the individual emission layers 209, 2010 are defined by the choice of host materials 207 and 208.
  • the triplet energy of the host material 208 TPBi is smaller than that of the emitter dye F ⁇ r (pic) in the mixed zone layer 204 in Fig. 21.
  • the nature of the blue dyes also requires host materials with ever higher triplet energies, which has the consequence the band gap of the transport levels (difference HOMO-LUMO) also gets bigger.
  • Such host materials often have the disadvantage that thus the injection of charge carriers in such a material is significantly heavier, which drives the operating voltage soaring.
  • a compromise is achieved by providing a worse energy conversion efficiency for the blue color due to the higher triplet energy of the blue dye compared to the host material for the emission layer structure, to keep the operating voltage low and thus ensure high power efficiencies.
  • Figure 22 shows three basic electroluminescence spectra 2050, 2051, 2052 of the emitter dyes as can be measured in monochrome emission layer structures.
  • the monochrome emission layer structures have the base colors whose additive combination reaches the tuned emission spectrum 2053, 2054, in particular the white light emission 2055.
  • FIG. 23 shows the composite electroluminescence spectra 2053, 2054 of the emission layer structures 2020, 2030 according to FIGS. 21a and 21b.
  • a composition of the base spectra 2050, 2051 and 2050, 2052 from FIG. 22 is present.
  • Noteworthy is the difference of the spectral distribution of the emission layer structures 2020, 2030 according to FIG. 21 a and FIG. 21 b, taking into account the similarity of both structures 2020, 2030.
  • FIG. 21b shows the electroluminescence spectrum 2055 of the emission layer structure 2040 of a schematically illustrated OLED 2070. All spectra 2050, 2051, 2052 of the base emitter dyes illustrated in FIG. 22 contribute to the spectrum 2055.
  • the CIE coordinates in the CIE color space are (0.42, 0.47), which are close to the white point (0.445.0.405).
  • the inventive method for producing a device 2070 for phosphorescent light emission from triplet states is performed with a proposed emission layer structure 2020, 2030 or 2040, wherein using different emitter dyes with different emission colors a coordinated color emission 2053, 2054 or a white light emission 2055 is realized.
  • Both a white light emission 2055 can be achieved by the emission of different zones with different emission spectrum 2050, 2051, 2052 as well as the reduction of the diffusion-based triplet triplet deletion.
  • the combinatorial spatial arrangement of different emitter dyes spatially in emission layer structure 2020, 2030, 2040 can provide modular variability in color matching to produce light of a given spectrum, particularly white light.
  • Fig. 25 shows the external quantum efficiency and the power efficiency of the emission layer structure 2030 of an OLED as a function of the brightness.
  • the emission layer structure 2040 achieves an external quantum efficiency (circular connection curve) of 12.5% and a power efficiency (black square connection curve) of 29.6 InVW, measured in the forward direction assuming a Lambertian radiation characteristic.
  • both the absolute value of the power efficiency at 1000 cd / m 2 is higher, ie by a factor of three, and the efficiency decrease at high brightnesses significantly reduced.

Abstract

La présente invention concerne un composant luminescent, en particulier une diode luminescente organique, comprenant une électrode et une contre-électrode ainsi qu'une zone organique comprise entre l'électrode et la contre-électrode et présentant une zone luminescente organique. L'invention a également pour objet un procédé de réalisation d'un tel composant.
PCT/DE2008/000732 2007-04-30 2008-04-30 Composant luminescent et son procédé de réalisation WO2008131750A2 (fr)

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DE112008001738.7T DE112008001738B4 (de) 2007-04-30 2008-04-30 Licht emittierendes Bauelement
US12/598,080 US8546816B2 (en) 2007-04-30 2008-04-30 Light-emitting component and method for the production thereof

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DE102007020644A DE102007020644A1 (de) 2007-04-30 2007-04-30 Lichtemittierendes Bauelement
DE102007020644.7 2007-04-30
DE102007033209A DE102007033209A1 (de) 2007-07-11 2007-07-11 Bauelement zur phosphoreszenten Lichtemisssion aus Triplett-Zuständen und Verfahren zur Herstellung solcher Bauelemente
DE102007033209.4 2007-07-11
DE102007061755A DE102007061755A1 (de) 2007-07-11 2007-12-14 Bauelement zur phosphoreszenten Lichtemission aus Triplett-Zuständen und Verfahren zur Herstellung solcher Bauelemente
DE102007061755.2 2007-12-14

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EP1993155A3 (fr) * 1998-03-13 2012-05-02 Cambridge Display Technology Limited Dispositifs électroluminescents
CN102115447B (zh) * 2009-12-30 2013-10-30 宁波大学 含有氟取代基的三芳胺衍生物及其制备方法
CN102115447A (zh) * 2009-12-30 2011-07-06 宁波大学 含有氟取代基的三芳胺衍生物及其制备方法
DE102011054774B4 (de) * 2010-10-26 2018-05-03 Lg Display Co., Ltd. Weisslicht emittierende organische vorrichtungen
US9159957B2 (en) 2010-10-26 2015-10-13 Lg Display Co., Ltd. White organic light emitting device
WO2012064987A1 (fr) * 2010-11-11 2012-05-18 Nitto Denko Corporation Élément émetteur composite hybride et dispositifs électroluminescents l'utilisant
TWI610477B (zh) * 2010-11-11 2018-01-01 日東電工股份有限公司 混成複合材料發光結構及使用其的發光元件
CN103229323A (zh) * 2010-11-11 2013-07-31 日东电工株式会社 混合复合材料发射结构及使用该发射结构的发光装置
US8604689B2 (en) 2010-11-11 2013-12-10 Nitto Denko Corporation Hybrid composite emissive construct and light-emitting devices using the same
JP2013546139A (ja) * 2010-11-11 2013-12-26 日東電工株式会社 ハイブリッドコンポジット発光性構成体およびこれを使用する発光デバイス
CN102281660A (zh) * 2010-12-23 2011-12-14 友达光电股份有限公司 白光电致发光元件
US20120161111A1 (en) * 2010-12-23 2012-06-28 Au Optronics Corporation White organic light electroluminescence device
DE102011056448B4 (de) * 2010-12-28 2017-08-31 Lg Display Co., Ltd. Organische, weißes Licht emittierende Vorrichtung und Anzeigevorrichtung, die diese verwendet
US8823019B2 (en) 2010-12-28 2014-09-02 Lg Display Co., Ltd. White organic light emitting device and display device using the same
US20120223296A1 (en) * 2011-03-01 2012-09-06 Sensient Imaging Technologies Gmbh Organic Semiconducting Materials and Organic Component
US9048435B2 (en) * 2011-03-01 2015-06-02 Novaled Ag Organic semiconducting materials and organic component
WO2013005029A1 (fr) 2011-07-04 2013-01-10 Cambridge Display Technology Limited Composition électroluminescente organique, dispositif et procédé associés
WO2013005031A1 (fr) 2011-07-04 2013-01-10 Cambridge Display Technology Limited Dispositif électroluminescent organique et procédé correspondant
US8735873B2 (en) 2011-07-11 2014-05-27 Lg Display Co., Ltd. Organic light emitting diode
DE102011054604B4 (de) * 2011-07-11 2017-09-21 Lg Display Co., Ltd. Organische Leuchtdiode
US9853220B2 (en) 2011-09-12 2017-12-26 Nitto Denko Corporation Efficient organic light-emitting diodes and fabrication of the same
US8829504B2 (en) 2011-09-20 2014-09-09 Lg Display Co., Ltd. White organic light emitting device
US9343684B2 (en) 2013-03-21 2016-05-17 Nitto Denko Corporation Substituted bisaryloxybiphenyl compounds for use in light-emitting devices
EP3916822A1 (fr) 2013-12-20 2021-12-01 UDC Ireland Limited Dispositifs oled hautement efficaces avec de très courts temps de détérioration
US11765967B2 (en) 2013-12-20 2023-09-19 Udc Ireland Limited Highly efficient OLED devices with very short decay times
US11075346B2 (en) 2013-12-20 2021-07-27 Udc Ireland Limited Highly efficient OLED devices with very short decay times
US10347851B2 (en) 2013-12-20 2019-07-09 Udc Ireland Limited Highly efficient OLED devices with very short decay times
CN105845830A (zh) * 2015-01-12 2016-08-10 上海和辉光电有限公司 有机发光器件结构
WO2016116570A1 (fr) * 2015-01-22 2016-07-28 Osram Oled Gmbh Composant luminescent, procédé de fabrication d'un composant luminescent et procédé pour faire fonctionner un composant luminescent
DE102015100913B4 (de) * 2015-01-22 2017-08-10 Osram Oled Gmbh Lichtemittierendes Bauelement, Verfahren zum Herstellen eines lichtemittierenden Bauelements und Verfahren zum Betreiben eines lichtemittierenden Bauelements
KR20170106303A (ko) * 2015-01-22 2017-09-20 오스람 오엘이디 게엠베하 발광 소자, 발광 소자의 제작 방법 및 발광 소자의 작동 방법
US10490761B2 (en) 2015-01-22 2019-11-26 Osram Oled Gmbh Light emitting component having a phosphorescent and fluorescent materials in an emitter layer
CN107431083A (zh) * 2015-01-22 2017-12-01 欧司朗Oled股份有限公司 发光器件、用于制造发光器件的方法和用于运行发光器件的方法
KR102399358B1 (ko) 2015-01-22 2022-05-18 오스람 오엘이디 게엠베하 발광 소자, 발광 소자의 제작 방법 및 발광 소자의 작동 방법
DE102015100913A1 (de) * 2015-01-22 2016-07-28 Osram Oled Gmbh Lichtemittierendes Bauelement, Verfahren zum Herstellen eines lichtemittierenden Bauelements und Verfahren zum Betreiben eines lichtemittierenden Bauelements
WO2016193243A1 (fr) 2015-06-03 2016-12-08 Udc Ireland Limited Dispositifs oled très efficaces à temps de déclin très courts
EP4060757A1 (fr) 2015-06-03 2022-09-21 UDC Ireland Limited Dispositifs delo hautement efficaces avec de très courts temps de déclin

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