Classifications

• • 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
  • H10K71/10—Deposition of organic active material
  • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
  • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/80—Constructional details
  • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/14—Carrier transporting layers
  • H10K50/15—Hole transporting layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/14—Carrier transporting layers
  • H10K50/16—Electron transporting layers
  • H10K50/165—Electron transporting layers comprising dopants
• • 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]
  • H10K50/17—Carrier injection layers
  • H10K50/171—Electron injection layers
• • 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
  • H10K85/10—Organic polymers or oligomers
  • H10K85/151—Copolymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention preferably relates to an optoelectronic component having a cathode and an anode and a layer system between the cathode and the anode, comprising a plurality of electroactive layers, wherein the component may be replaced by a cathode
• the invention relates to the field of optoelectronic components.
• OLEDs Organic light-emitting diodes
• an OLED usually consist of a sandwich structure, wherein there are usually several layers of organic semiconducting materials between two electrodes.
• an OLED comprises one or more emitter layers (EL), in which or in which electromagnetic radiation, preferably in the visible range, through a
• the electrons and electron holes are each provided by a cathode or anode, wherein preferably so-called injection layers facilitate the process by lowering the injection barrier.
• OLEDs therefore usually have electron or
• OLEDs usually have hole transport layer (HTL) or electron transport layer (ETL), which control the direction of diffusion of the electrons and holes
• the layers can comprise partially organic, partly also inorganic, semiconducting materials.
• hybrid LEDs which may include organic and inorganic semiconductor layers, are also considered organic
• OLEDs Light-emitting diodes
• OLEDs Due to their flexibility, OLEDs can be used excellently, for example, for screens, electronic paper or interior lighting.
• OLEDs organic semiconducting materials for light generation
• Solar cells or hybrid solar cells also by a thin layer structure, which significantly increases the potential applications compared to classical inorganic solar cells.
• the structure of organic solar cells or hybrid solar cells has similarities with OLEDs or hybrid LEDs. To the linguistic
• Simplification hybrid solar cells made of organic-inorganic layers are also subsumed under the term organic solar cells. Instead of an emitter layer, however, there are one or more absorber layers as the photoactive layer. In the absorber layer electron-hole pairs are generated due to incident electromagnetic radiation. In contrast to inorganic solar cells, the formation of so-called excitons, which are present as bound electron-hole pairs, usually first occurs in the case of the organic emitter layer. These are then separated into free charge carriers.
• the further layers include electron and hole transport layers as well as electron extraction and hole extraction layers. These consist of organic materials or of organic and inorganic materials whose
• electrochemical potentials are shifted as donor and acceptor layers such that they generate an internal field in the solar cell, which separates the excitons and discharges the free charge carriers to the electrodes.
• the incidence of the electromagnetic radiation in the absorber layer thus provides electrons at the cathode and electron holes at the anode for generating a voltage or a current.
• the particular advantage of organic solar cells is, in particular, the very high optical absorption coefficient of organic semiconductors, as a result of which, even with thin absorption layers in the range of less than 100 nm
• organic solar cells Due to the thin layer structure, organic solar cells can be produced inexpensively and can be applied over a wide area to buildings as a film coating or integrated into paper products such as packaging
• the materials of the semiconductor layers are constructed from so-called pi systems or ⁇ systems.
• the pi systems of the organic molecules and / or polymers used have delocalized, i. free electrons, which allow charge or current flow in the materials.
• the conductivity in organic semiconductors is essentially determined by the number of delocalized electrons (pi-electrons) present. Furthermore, the pi-electrons are delocalized only on the pi orbitals, which have a special geometric shape and thus an anisotropic (not in all
• organic semiconductors In order to improve the electrical conductivity and performance of organic semiconductors, it is known to dope organic semiconductors with other organic materials.
• foreign molecules are introduced into the organic semiconductor layers in order to influence electrical properties and in particular the charge carrier density in a targeted manner.
• organic molecules can be introduced which have different electron affinities or ionization potentials in order to reduce or oxidize the molecules of the organic semiconductor.
• the mass fractions of the dopants are significantly higher.
• concentration of the dopants in the per thousand or per cent range are not unusual. In the so-called p-doping be
• Electron acceptors doped, whereas in the so-called n-type doping
• Electron donors are doped.
• Optoelectronic component various methods have been developed. These include in particular evaporation processes in a vacuum or wet-chemical deposition processes.
• the molecules are removed by evaporation, i. by sublimation under vacuum conditions.
• the methods are therefore also referred to as vacuum deposition.
• the evaporation processes in vacuum allow the production of particularly defined layers, whereby a doping of organic semiconductors is possible.
• a disadvantage of the process is the high process costs.
• complex systems are required for vacuum deposition.
• the methods are characterized by a high loss of material, since the deposition is usually nonspecific and deposited not only on the substrate, but also on other parts of the evaporation plants.
• spin-coating process for example spin coating
• dip-coating process eg dt.
• a substrate is dipped in a coating solution.
• a liquid film remains on the substrate, so that the layers can be applied one after the other.
• printing methods such as e.g. Ink-Jet, Slot-Die, Blade-Coating are characterized by a particularly high flexibility and low production costs.
• doped organic semiconductors can also be applied in spin-coating or dip-coating processes, this is not possible on an industrial scale in current printing processes.
• the doping of the organic semiconductors produces aggregates in the solution which prevent effective printing or at least make it much more difficult. This leads to blockages in the printheads. Although these can be reduced via filter processes, this filtering of the aggregates leads to a cancellation of the desired doping. For this reason, no suitable printing processes currently exist in industry in order to reliably and inexpensively produce organic optoelectronic components by printing p- or n-doped organic materials.
• organic electronics such as e.g. organic light-emitting diodes, transistors and solar cells
• organic light-emitting diodes e.g. organic light-emitting diodes, transistors and solar cells
• Hole transport layer, hole injection layer, electron transport layer, etc. fulfill special task in the component to increase the electrical efficiency and performance of the component.
• tuning the electrical properties of several injection and transport layers can be achieved, for example, that OLEDs with the same voltage and the same power consumption develop a greater luminosity.
• Typical temperatures for cross-linking are 150-250 ° C, whereas normal drying of the wet layer is at 100-140 ° C.
• the cross-linking process is more likely to damage the organic materials (decomposition temperatures of the organic materials are between 140-250 ° C) and narrowed in use to only a few highly stable organic materials.
• processing in air is also no longer possible because the organic materials under their intrinsic decomposition temperatures begin to oxidize with oxygen.
• the printed ink i. the organic material, which is dissolved in a solvent, energetically activated after printing with strong UV radiation or very high temperatures of above 150 ° C.
• a chemical process is set in motion, which leads to a
• Typical temperatures for cross-linking are 150-250 ° C, whereas normal drying of the wet layer is at 100-140 ° C. As a result, the cross-linking process tends to damage the organic materials.
• the decomposition temperatures of the commonly used organic materials are between 140-250 ° C. For this reason, cross-linking methods limit the use to only a few, highly stable organic materials. Furthermore, processing in air is not possible because the organic materials begin to oxidize with oxygen below their intrinsic decomposition temperatures.
• An alternative to this was the use of orthogonal solvents.
• the inks for printing the organic semiconductor layers are prepared so that the solvent of a subsequent layer can not dissolve the lower layer. That is, the material of the lower layer should be insoluble in the solvent of the subsequent layer. Especially with thin layer structures of more than 3 layers, however, this condition quickly leads to difficulties in the practical implementation.
• the object of the invention was to provide an optoelectronic device and a
• an optoelectronic device and a method for producing the same should be provided in which a cost-effective, reliable and simple way doping of printed organic materials is achieved to simultaneously high electrical
• the invention should preferably allow the provision of a printed, optoelectronic component with a multilayer thin-film structure, in which undesired decoupling processes can be avoided in a simple and effective manner.
• the invention relates to an optoelectronic component having a cathode and an anode and a layer system between the cathode and the anode comprising a plurality of electroactive layers and at least one optically active layer, wherein at least two layers between the cathode and anode are produced by a method which comprises the following steps:
• step e wherein the second carrier means is selected such that by the method step e), the first layer is at least partially dissolved, so that between the first and second layer, an inductively doped mixed layer is generated in which the first and second semiconductor material are mixed. It may also be preferred that the process be modified in the following manner: after step b), step b) bis), provides a substrate.
• step c) is preferably carried out to step c ') to produce a first layer by applying the first ink to the substrate by means of a printing method.
• the optoelectronic component according to the invention is preferably characterized in that this electrode (ie an anode or cathode), an optically active layer and electrically active layers (ie, for example
• the functionality of the optoelectronic component is preferably characterized by the optically active layer, which can serve in particular for the generation of light or power.
• the electrically active layers preferably denote those layers which ensure the electrical functionality of the component and are arranged between the optically active layer and the electrodes.
• charge carrier injection or extraction layers for example, charge carrier injection or extraction layers and
• Charge carrier transport layers electrically active layers.
• charge carriers are preferably electrons or electron holes.
• the term hole or electron hole is used here preferably synonymously.
• the person skilled in the art knows how to arrange the electrically active layers in order to achieve the desired function of the optoelectronic component as a function of the optically active layer.
• the terms optoelectronic component or component or else thin-film component or thin-film component are preferably used synonymously.
• the terms used herein to describe the optoelectronic device, such as electrode, anode, cathode, optically active layer, charge carrier extraction or injection layer, and charge carrier transport layer, are to be understood by those skilled in the art in this context. Further definitions can also be found below in this document.
• the semiconductor material is preferably organic
• organic semiconductor material preferably refers to organic based materials that are semiconductive due to the nature of a pi-electron system.
• Semiconductor materials are preferably used synonymously.
• the terms related here, such as semiconductors and pi-electron systems, are preferably to be understood by those skilled in the art as interpreted in the specialist literature, for example in Low Molecular Weight Organic Semiconductors by Thorsten U. Kampen.
• the optoelectronic component according to the invention is preferably characterized
• the electrically active and / or optically active layers can be applied by means of a printing process.
• printing process is intended to cover all processes for the duplication of physical or
• printing ink or ink is preferably understood to mean a composition which is liquid at room temperature and comprises or consists of a semiconductor material and a carrier.
• the carrier is preferably a solvent or solvent mixture in which the semiconductor material to be printed is dissolved, so that the
• Layers can be applied to the optoelectronic component with common printing methods.
• offset printing for example, offset printing, screen printing, flexographic printing or, in particular, ink jet printing methods and / or slot die coating methods are suitable as printing methods.
• ink jet printing methods for example, ink jet printing methods and / or slot die coating methods are suitable as printing methods.
• slot die coating methods are suitable as printing methods.
• the printing process are characterized in particular by a high suitability for mass production.
• the method is particularly cost-effective.
• Carrier concentration is increased similar to inorganic doping.
• a charge transfer from the donor to the acceptor in the energetic ground state takes place without additional excitation if both materials are mixed together.
• aggregates form, which also as
• Charge transfer complexes represent a new material formed from the two original materials, which forms the actual doping.
• Optoelectronic components which can be produced by printing processes, no doped layers of organic semiconductor materials can be applied, as otherwise due to printing in the printing of the organic materials in the inks From aggregate formations, for example, can come to blockages on pressure nozzles.
• a printed component which comprises layers doped by a printing process of organic
• the second carrier agent is preferably chosen such that, after application to a lower or first layer, it is at least partially dissolved, that is to say that the detached part of the layer applied in a solid state of matter is preferred. is advantageously again substantially liquefied and brought into a state that a mixture of this part with the second carrier means is possible.
• the carrier means is preferably to be selected such that this one
• an inductively doped mixed layer is produced at the interface between the two layers.
• a partial dissolution of the organic or inorganic molecules of the first or lower layer takes place in the applied second layer.
• the mixing layer produced in this way the first and second semiconductor material are thus mixed in the boundary region of the two layers.
• a doped semiconductor layer is reacted. According to the inductive effect in the organic In this way, chemicals acquire the electrical charges in the mixed layer
• the inductive effect is caused in particular by different electronegativity of atoms or functional groups of a carbon compound. This leads to a charge asymmetry, which changes the electron density in the molecules.
• a negative inductive effect (-I effect)
• the electrons move to the atom or molecule with a higher electronegativity, while the positive inductive effect electrons are pulled away from atoms or molecules with low electron negativity.
• the displacement of the charge carriers advantageously leads to a provision of a higher mobility of the
• the inductively doped mixed layer thus preferably denotes a mixed layer resulting from the dissolution, in which the electrical conductivity is increased by doping on the basis of the inductive effect.
• the process of dissolving to form an inductively doped mixed layer is advantageous since the number of printing steps can be reduced. Instead of three printing steps, as in the case of a separate printing of the inductive mixed layer, only two printing steps are needed.
• the optoelectronic component according to the invention is thus characterized by a particularly good electrical performance, which can be produced by a cost-effective and reliable printing method. It is achieved an increase in performance of the component. Furthermore, the method can save time, material and work steps, and simplify manufacturing.
• the layers to be printed using the ink comprising organic and / or inorganic semiconductor materials may be both electroactive layers, ie injection or extraction layers or
• the first and second layer can each be a first and a second electroactive layer, the advantageous inductively doped mixed layer being produced between these electroactive layers.
• the first layer may, for example, also be an electroactive layer, while the second layer is an optically active layer, so that an inductively doped mixed layer is formed between these layers.
• the optoelectronic component according to the invention is preferably characterized by the presence of at least two layers of organic and / or
• Inorganic semiconductor material with inductive mixed layer in the border region characterized.
• Other layers of the optoelectronic device may, but need not, be printed from organic semiconductor materials.
• another electron transport layer include inorganic doped semiconductor materials, e.g. Aluminum-zinc oxide.
• inorganic doped semiconductor materials e.g. Aluminum-zinc oxide.
• the thickness of the mixed layer is between 1 nm and 20 nm, preferably between 1 nm and 10 nm. On the one hand, it is particularly preferred that the thickness of the mixed layer is between 1 nm and 20 nm. This thickness leads to particularly advantageous electrical properties and has proven to be surprisingly easy to implement at the same time in the aforementioned method. It is particularly preferred that the thickness of the mixed layers is between 1 nm and 10 nm. Such a thickness of
• the thickness of the mixed layer preferably corresponds to the extent in the boundary region between the first and second layer in which the first and second semiconductor material are present.
• the lower boundary of the mixed layer thus corresponds to the upper region of the first layer, which was not dissolved.
• the upper boundary of the mixed layer corresponds to the lower region of the second layer, in which no molecules of the first semiconductor material, and thus no doping longer exists.
• the thickness of the mixed layer can be adjusted in particular by the solubility of the first semiconductor material and the contact time before drying. Drying is preferably understood to mean an effect of heat induced to convert a material of an at least partially liquid state of aggregation into a solid state
• the thickness of the mixed layer it can be utilized that, in the case of inductive doping, a shift of the optical absorption edge in
• a UV-Vis-spectrometer can be used as a measuring instrument for this purpose.
• a UV-Vis spectrometer can preferably spectroscopy by using UV and
• UV light is preferably understood light in a wavelength range of less than 10 nm to 380 nm. Visible light is understood to mean, in particular, light from 380 nm to 700 nm.
• An ink is first made up of a plurality of solvents and a solid dissolved therein, i. a semiconductor material.
• a solvent A which can dissolve the lower layer
• a solvent B which can not dissolve the lower layer.
• An empirical method which works with the aforementioned proportions has been distinguished by a particular effectiveness. It was Surprisingly, by such a test method, a suitable vehicle could already be found within a test iteration.
• Evaluation is also the absorption of the pure materials, i. the lower layer and the solid which has been printed.
• the preferred layer thicknesses for the mixed layer are particularly advantageous in combination with a layer thickness of the first or second layer between 5 nm and 50 nm. In this range, the inductively doped mixed layer optimally supports the electrical conductivity between the layers, without the specific one
• the second carrier comprises at least one solvent which completely dissolves the first semiconductor material to a concentration of at least 1 g / l.
• Semiconductor material in the second carrier is thus at least 1 g / l (grams per liter).
• the specification corresponds to the common definition of the quantitative solubility by a mass concentration.
• the solubility preferably indicates up to which
• the material can be dissolved in the solvent. That to which it mixes under a homogeneous distribution in the solvent without precipitating. Said limit allows a particularly reliable formation of an inductively doped mixed layer, in particular the preferred thickness of 1 nm to 20 nm, preferably 1 nm to 10 nm. By this preferred embodiment, errors in the production of the mixed layer can be eliminated.
• the solubility can be predicted on the basis of theoretical models.
• Hansen solubility parameters may be suitable for this (Hansen, Charles M. "The Three Dimensional Solubility Parameter.” Danish Technical: Copenhagen: 14 (1967)).
• the solubility is determined experimentally.
• a suitable experimental method for determining quantitative solubility is the following method which involves dissolving 10 milligrams of the solid in 10 milliliters of the solvent of interest. The amount of solid is added to the vessel with the solvent.
• a Teflon-coated magnetic stir bar is added and the vessel is gas tight locked. Subsequently, the vessel is placed on a heating plate with controllable magnetic field, a heating temperature of 25 ° C is set and the magnetic field is switched on, so that the stirring bar stirs the mixture.
• Solubility be determined particularly reliable.
• Quantitative solubilities of at least 1 g / l are in particular of the
• the second carrier comprises at least one aprotic polar solvent.
• a molecule of a solvent does not have an atomic group which is present in an organic compound and from which hydrogen atoms can be split off as protons, the solvent is termed aprotic.
• Polarity refers preferably to the formation of separate, resulting from charge shifting in atomic groups
• Optoelectronic component characterized in that the printing method is a slot die coating, a gravure printing, a screen printing, Doctor Blade printing, spraying and / or ink jet printing method.
• the slot nozzle coating is preferably a coating technique known to those skilled in the art, which is used to apply thin layers of liquid to web-like substrates.
• a gravure printing method is advantageously a printing technique in which elements to be imaged are present as recesses in a printing form.
• the ink is typically only in the wells and the substrate to be printed is pressed against the printing plate.
• Screen printing preferably refers to a printing process in which the printing ink is printed through a fine-meshed fabric onto the substrate or material to be printed.
• Doctor Blade printing a so-called doctor blade is preferably used to strip off excess printing ink from the printing cylinder.
• a printed image is produced by targeted firing or deflecting small droplets of ink.
• the layers can be applied very precisely and evenly. This results in mixed layers with a particularly reliable homogeneous mixture and doping. The so produced
• Optoelectronic device is characterized by excellent quality, robustness and performance.
• the drying following the application of the second electroactive layer preferably concludes the dissolution process and determines the layer thickness of the mixed layer.
• various methods are suitable, which are preferably by heating the device to accelerated evaporation of the
• Carrier or solvent lead for example, hot air dryers are suitable. However, it may also be preferred to allow the layer to dry at room temperature. At a lower temperature during drying, drying will usually take longer.
• the drying takes place in step f), i. following the application of the second layer by means of an infrared lamp, preferably at a temperature between 60 ° C and 200 ° C, more preferably between 80 ° C and 150 ° C for a drying time between 1 s and 60 s, preferably between 5 s and 30 s. Due to the preferred temperature range between 60 ° C and 200 ° C and the preferred drying time between 1 s and 60 s, a suitable layer system can be produced in a particularly reliable manner. In the mentioned temperature range and a preferred
• Drying time between 5 s and 30 s will increase the robustness of the coating system elevated. It is particularly preferred when drying a temperature range between 80 ° C and 150 ° C for a drying time between 1 s and 60 s
• a preparation comprising a drying in the temperature range between 80 ° C and 150 ° C for a drying time between 5 s and 30 s results in a simplification of the process and has particularly robust components result.
• an infrared lamp in particular at the abovementioned temperatures and time periods, represents a particularly effective, but at the same time gentle drying.
• the carrier is vaporized quickly and efficiently, the electrical or optical properties of the layers and the mixed layer formed are obtained.
• such a drying process can be very easily automated and streamlined.
• a waiting time between 0 and 60 s, preferably between 3 s and 40 s, is maintained.
• the waiting time preferably corresponds to the time which is provided at least for the dissolution and the formation of the mixed layer.
• the thickness of the mixed layer can be influenced by this parameter.
• the process of solubilization already starts during printing and does not end immediately with the onset of the drying step. For this reason, it may also be preferred not to comply with a waiting time, but with a waiting time of 3 s to 40 s, produces particularly reliable mixed layers. Also waiting times between 0 and 60 seconds have advantages, so
• the optoelectronic component is characterized in that the second carrier comprises a mixture of at least two different solvents, wherein a first solvent completely dissolves the first semiconductor material to a concentration of at least 1 g / l and a second solvent dissolves the first Dissolves semiconductor material to a concentration of at most 0.1 g / l completely.
• the second carrier in which the second semiconductor material is dissolved, thus comprises a combination of solvents of different solubility.
• the first semiconductor material is an organic material
• Polyphenylenevinylene copolymer e.g. MEH-PPV, Super Yellow or MDMO-PPV can be used as a strong solvent solvent butyl-lactate.
• the butyl lactate completely dissolves the polyphenylene vinylene copolymer of the lower first layer to a concentration of at least 1 g / l.
• isopropanol solves polyphenylene vinylene copolymers only below 0.1 grams / liter. Isopropanol is thus suitable as a weakly dissolving solvent in this case.
• a combination of butyl lactate and isopropanol can be used as carrier for the second organic semiconductor material, wherein the ratio of the
• the first (lower) layer is, for example, poly (vinylidene chloride-co-acrylonitrile)
• a carrier with a combination of the solvents ortho-dichloro-benzene and mesitylene in the ratio 80:20 is almost completely orthogonal. That dissolves the solvent combination of ortho-dichlorobenzene and mesitylene
• a strong solvent can be added to the carrier.
• acetophenone which can dissolve the poly (vinylidene chloride-co-acrylonitrile) at a concentration of significantly more than 1 g / l, is suitable for this purpose.
• acetophenone instead of o-dichlorobenzene, i. one
• Acetophenone based on the poly (vinylidene chloride-co-acrylonitrile) (PVDC-co-acrylate) PAN copolymer) a resolution of 1 -3 nm can be achieved, whereby an electrically advantageous doped mixed layer is achieved.
• aprotic polar solvents e.g. the
• Acetophenone not only for the exemplified PVDC-co-PAN copolymers, but for almost all organic semiconductor materials, which come into consideration for the electrically active or optically active layers.
• a carrier which contains a weak solvent or solvent mixture which can be optimally adjusted by adding defined small amounts of aprotic polar solvent to form an inductively doped mixed layer.
• Another advantage of applying the second layer under a controlled dissolution of the first layer is that, in addition to the improvement of the electrical performance by a doped mixed layer, the combination of layers as well
• Shielding can be used before solving the following layers.
• the second material of the second layer can be chosen such that it is a few
• Magnitudes less soluble than the material of the underlying first layer or that the material of the second layer is soluble in a much smaller number of solvents This allows the printing of the following layer, ie, for example, another electrically or optically active layer using carriers from a larger selection of solvents.
• the second semiconductor material can therefore be chosen so that the second layer functions as a kind of electrically active sacrificial layer or interlayer, which effects a passivation against further solvents of the subsequent inks to be printed.
• Embodiment saves time, material, work stages and therefore costs.
• this is the optoelectronic
• Electron transport layer and an electron injection layer or - extraction layer is present.
• the invention preferably relates to two groups of optoelectronic components.
• the optically active layer is an emitter layer which serves to generate light.
• the optoelectronic component is preferably used as an organic light-emitting diode (OLED).
• the optically active layer is an absorber layer in which free charge carriers are generated by the absorption of electromagnetic radiation.
• the second group of optoelectronic components is thus preferably organic solar cells or photodetectors.
• the invention relates to an optoelectronic component for generating light, for example as a light-emitting diode.
• the optoelectronic component comprises a cathode and an anode and a layer system between the cathode and the anode comprising at least one preferably cathode-near electron injection layer, at least one electron transport layer, at least one optically active layer, which is an emitter layer, at least one hole transport layer, at least one Preferably near-anode hole injection layer and is characterized in that at least one inductively doped mixed layer between a hole transport layer and a hole injection layer is present and / or at least one inductively doped Mixed layer between an electron transport layer and a
• Electron injection layer is present.
• the cathode serves as an electron supplier in this preferred embodiment.
• the cathode preferably has a low surface resistance in order to allow the most uniform possible injection of the electrons across the surface of the OLED.
• the electron injection layer performs the function of matching the work function of the cathode and the following layer, the electron transport layer.
• the work function preferably corresponds to the energy that must be expended to at least dissolve an electron out of an uncharged solid.
• Electron-transporting layer reduces the voltage necessary to inject electrons from the cathode into the electron-transporting layer.
• the electron transport layer serves for the directed electron transport between the cathode and the optically active layer, ie the preferred embodiment of the emitter layer.
• the electron transport layer should preferably have a sufficient mobility or mobility of electrons (preferably from 10 -6 to 100 cm 2 / (V * sec).)
• Electron transport layer lie between the energy level of the emitter material and the work function of the cathode, that is, after work function bars, no additional energy is required to transport the electrons before recombining with the holes.
• the emitter layer preferably consists of semiconducting organic polymers or molecules which produce light in the visible range upon electrical excitation, ie preferably in a wavelength range of 400 to 700 nm.
• the electrons of the cathode recombine with the holes of the anode to form excitons.
• the proportion of singlet excitons outweighs so that it comes to an effective light generation.
• the hole transport layer is the counterpart to the electron transport layer and serves to transport (electron) holes from the anode to the emitter layer.
• the hole transport layer should therefore a sufficient mobility or mobility of electron holes, preferably from 10 "6 to 100 cm 2 / (V * sec), have.
• the energy level for the transport of electron holes that is, the Conduction band or HOMO (English, highest occupied molecular orbital) of the
• the hole injection layer like its counterpart on the cathode side (the electron injection layer), preferably consists of strongly dielectric polymers and is preferably an insulator.
• the hole injection layer serves to match the energy levels of the anode and the subsequent layer to the hole transport layer to ensure effective injection of electron holes.
• the anode is preferably the electron hole supplier and therefore preferably has a significantly higher work function than the cathode. Furthermore, it is preferred that the anode has a high surface conductivity for holes. In addition, it may be preferred that the anode material is transparent in order to allow the light to exit through the anode, preferably.
• the optically active layer is a
• Emitter layer and the electrically active layers at least one
• Electron injection layer at least one electron transport layer, at least one hole transport layer and at least one hole injection layer.
• inventive mixed layers By forming one or more inventive mixed layers between the transport layers and injection layers, a particularly high electrical conductivity of the active layers can be achieved.
• the OLEDs that can be produced in this way are characterized by a greatly increased luminosity in the case of equal voltage compared to OLEDs without doped mixed layers and thus by a greatly increased effectiveness.
• Production costs are also characterized by low operating costs and improved performance.
• an absorber layer is preferably used, which is capable of photon absorption, the energy of the incident electromagnetic To convert radiation into the generation of free charge carriers.
• the electrically active layers preferably ensure that within the optoelectronic
• Component is generated an internal electric field which separates the excitons and subtracts the free charge carriers to the corresponding electrodes.
• the electrons are extracted, while at the anode the holes are extracted.
• the potential difference provided thereby serves to generate electrical voltage or, under load, electrical current.
• the layer structure is preferably as follows.
• the optoelectronic component comprises a cathode and an anode and a layer system between the cathode and the anode comprising at least one preferably near-cathode electron extraction layer, at least one
• Electron transport layer at least one optically active layer which is an absorber layer, at least one hole transport layer, at least one preferably anode near hole extraction layer and is characterized in that at least one inductively doped mixed layer between a hole transport layer and a hole extraction layer and / or at least one inductively doped
• Electron extraction layer is present.
• the electrically active layers are in turn such that the function of the
• the optically active layer is a
• Electron extraction layer the at least one electron transport layer, the at least one hole extraction layer and the at least one hole transport layer.
• Injection layers for particularly good electrically active layers.
• the inductive doping in the mixed layers significantly improves the electrical properties of the transport or injection layers.
• Solar cells or phototransistors are therefore characterized by a particularly good luminous efficacy or sensitivity and thus by a high degree of effectiveness.
• the producibility by a printing process furthermore allows a high degree of flexibility for the provision of more efficient effect Solar cells for a wide variety of applications. Also, the costs can be reduced compared to other methods.
• the optoelectronic component is characterized in that the first or second layer is a
• Hole injection layer or extraction layer whose organic semiconductor material is selected from a group comprising dielectric polymers, preferably polymers with functional groups selected from a group comprising -CN, -SCN, -F, -Cl, -I and / or -Br and more preferably polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC), poly (vinylidene chloride-co-acrylonitrile), polyacrylonitrile (PAN), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), hexaazatriphenylenehexacarbonitrile (HATCN),
• PVDF polyvinylidene fluoride
• PVDC polyvinylidene chloride
• PVDC poly (vinylidene chloride-co-acrylonitrile)
• PAN tetrafluoroethylene-hexafluoropropylene cop
• the first or second layer is a hole injection layer or extraction layer whose organic semiconductor material is selected from a group comprising dielectric polymers. These have superior electrical and mechanical properties, increasing reliability. These are preferably polymers with functional groups selected from a group
• Hole injection layer or extraction layer comprised polyvinylidene fluoride
• PVDF polyvinylidene chloride
• PVDC polyvinylidene chloride-co-acrylonitrile
• PAN Polyacrylonitrile
• FEP tetrafluoroethylene-hexafluoropropylene copolymer
• PCTFE Polychlorotrifluoroethylene
• HTCN hexaazatriphenylene hexacarbonitrile
• II copper
• hexafluoroacetylacetonate [Cu (tfac) 2]
• the aforementioned materials are particularly suitable for ensuring the electrical function of the injection or extraction layers for electron holes.
• the aforementioned polymers fulfill the preferred injection property, ie an increase in the work function for electrons at the contact surfaces to the injection layer and thus an effective hole injection.
• the optoelectronic component is characterized in that the first or second layer is a hole transport layer whose organic semiconductor material is selected from a group comprising a doped metal thiocyanate, preferably a doped copper thiocyanate and / or a doped metal oxide, preferably a doped zinc oxide , preferably doped with a metal thiocyanate, preferably selected from a group comprising
• Transition metal thiocyanates and / or preferably doped with a metal oxide preferably selected from a group comprising tungsten oxide, vanadium oxide, nickel oxide, copper oxide, molybdenum oxide and / or other transition metal oxides and / or preferably doped with a halogen, more preferably fluorine.
• first or second layer a
• Hole transport layer whose organic semiconductor material is selected from a group comprising a doped metal thiocyanate.
• Materials selected from this group are particularly easy to process.
• a doped copper thiocyanate and / or a doped metal oxide can preferably be included, which have particularly advantageous mechanical properties.
• the likewise preferably included doped zinc oxide improves the effectiveness of the component.
• the preferred doping with a metal thiocyanate improves the electrical properties.
• the preferred choice of metal thiocyanate from a group comprising sodium thiocyanate, potassium thiocyanate, silver thiocyanate, tungsten thiocyanate, vanadium thiocyanate,
• Molybdenum thiocyanate, copper thiocyanate and / or other transition metal thiocyanates provides an increase in performance of the component.
• the likewise preferred doping with a metal oxide eliminates errors in the production of the component.
• These are preferably selected from a group comprising tungsten oxide,
• Transition metal oxides can increase the maintenance of the component.
• the further preferred doping with a halogen may be the electrical
• the doping means the introduction of impurities, the dopants, in a layer, wherein the introduced amount in is usually lower compared to the carrier material. That is, it may be preferred that the mass fraction of the dopants is less than 10%, preferably less than 1%, of the total layer. However, it may also be preferred that the mass fraction of the dopants is up to 40% of the total layer. In the so-called p-type doping electron acceptors are doped, whereas in the so-called n-type doping electron donors are doped.
• electron acceptor or donor is preferably understood a particle (atom, molecule, ion) which is capable of accepting or donating electrons.
• hole transport layer it is preferable to select materials having strong acceptor properties and preferably a LUMO in the vicinity of the HOMO from the support of the
• Metal thiocyanate or metal oxides preferably of copper thiocyanate or zinc oxide.
• An organic p-type dopant may also be preferred, for example
• Tetrafluorotetracyanoquinodimethane or Hexaazatriphenylenehexacarbonitrile be. These are characterized by particular effectiveness. It is particularly preferred to use as support of the hole transport layer copper thiocyanate, nickel oxides, copper (I) oxide or zinc oxide with the o.g. suitable dopants. This combination has improved electrical properties.
• organic semiconductor material poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 '- (N- (4-sec-butylphenyl) diphenylamine)] (TFB ) and / or 4, 4 ', 4 "-tris [phenyl (m-tolyl) amino] triphenylamine (m-MTDATA), which are particularly reliable.
• the optoelectronic component is characterized in that the first or second layer is a
• Semiconductor material is selected from a group comprising dielectric polymers, preferably hydrophilic polymers and / or polyelectrolytes, more preferably polymers selected from a group comprising polyoxazolines, polymethacrylates, polyacrylamides, polyethylene oxides, polyacrylic acids, polyacrylates, polyvinylpyrolidone, polysaccharides, ethylene-vinyl alcohol copolymer ( EVOH), polyvinyl alcohol (PVOH) and co-polymers thereof, and very particularly preferably polyethyleneimine (PEI) or ethoxylated polyethylenimine (PEIE).
• dielectric polymers preferably hydrophilic polymers and / or polyelectrolytes
• a preferred embodiment of the invention is thus characterized in that the at least one electron injection layer or extraction layer comprises dielectric polymers. These are characterized by a particular robustness, whereby a durable component can be produced. It is particularly preferred to use hydrophilic polymers and / or polyelectrolytes. These can be processed very easily and thus mean a saving in time material and work steps and therefore in costs. Very particular preference is given to polymers selected from a group comprising polyoxazolines, polymethacrylates,
• Polyacrylamides polyethylene oxides, polyacrylic acids, polyacrylates, polyvinylpyrrolidone, polysaccharides, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVOH) and co-polymers of this group. These have proven to be particularly useful and are characterized by superior electrical properties.
• PEIE Polyethyleneimine
• the aforementioned materials are particularly suitable for ensuring the electrical function of the injection or extraction layers for electrons.
• the electrons as charge carriers can use the quantum effect of "tunneling" and either from the cathode into the electron transport layer (in the case of the
• Electron injection layer or jump from the electron transport layer to the cathode (in the case of the electron extraction layer).
• the aforementioned dielectric polymers preferably produce corresponding surface dipoles, thus reducing the injection barrier for electrons.
• the optoelectronic component is characterized in that the first or second layer is a
• Electron transport layer whose semiconductor material is selected from a group comprising a doped metal oxide preferably comprises a doped zinc oxide, wherein the doping is preferably carried out with aluminum, magnesium, alkali, alkaline earth, metallocenes and / or organic n-type dopants and the electron transport layer particularly preferably comprises an aluminum zinc oxide.
• a doped metal oxide is characterized in particular by an improvement in the quality of the component.
• a doped zinc oxide results in a particularly robust Component.
• the preferred doping with aluminum, magnesium, alkali, alkaline earth, metallocenes and / or organic n-dopants leads to improved electrical properties.
• An electron transport layer comprising an aluminum zinc oxide provides a particularly effective component. In a preferred embodiment of the invention, this is the optoelectronic
• Electron injection layers or extraction layers at least two
• Electron transport layers and / or at least two hole transport layers and at least two Lochinjemies slaughteren or -extratations lambda comprises, wherein the electron injection layers or -extratations slaughter and the
• Electron transport layers and / or the Lochinjetechnischs slaughteren or - extraction layers and the hole transport layers are arranged alternately, wherein between a transport layer and an injection or extraction layer in each case an inductively doped mixed layer is present. Due to the formation of inductively doped mixed layers between the
• the optoelectronic component is characterized in that a second inductively doped mixed layer is present between an electroactive layer and the optically active layer.
• the stated advantages with regard to the improvement of the electrical performance due to the provision of additional charge carriers by the inductively doped mixed layer can be increased by forming a further doped mixed layer between the optically active layer and adjacent electrically active layer.
• the carrier means of an emitter layer can be chosen such that it dissolves the underlying electrically active layer. Such a mixed layer contributes to the feeding of the charge carriers in the
• Emitter layer and thus increases the performance of the OLED.
• this is the optoelectronic
• photogenerating layer is selected from a group comprising super yellow (polyphenylene vinylene copolymer), poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxy) -1, 4- phenylenevinylenes (MDMO-PPV), poly [9,9-didecanofluoreno-alt- (bis-thienylenes) benzothiadiazoles] (PF10TBT), poly (9,9-di-n-octylfluorenyl-2,7, -diyl (PFO),
• the invention relates to a method comprising the following steps:
• the second carrier means is selected such that by the method step e), the first layer is at least partially dissolved, so that between the first and second layer, an inductively doped mixed layer is generated, in which the first and second semiconductor material is present mixed.
• the method is preferably suitable for producing an optoelectronic component having a cathode and an anode and a layer system between the cathode and the anode comprising a plurality of electroactive layers and at least one optically active layer.
• step b) bis provides a substrate.
• step c) to step c ') a first layer is formed by applying the first ink to the substrate by means of a printing process.
• the first and second layers are an electroactive or optically active layer.
• the method may preferably comprise further steps.
• a cathode may first be provided, e.g. through a
• a particularly maintenance-free component can be produced.
• a second layer e.g. a
• the method according to the invention is suitable for producing the optoelectronic component according to the invention.
• Embodiments which have been disclosed for the component which can be produced according to the invention likewise preferably find an advantageous application for the method according to the invention.
• the second carrier agent preferably comprises at least one solvent which completely dissolves the first semiconductor material to a concentration of at least 1 g / l.
• a preferred embodiment of the method according to the invention also comprises a provision of such a solvent for the second carrier.
• the optoelectronic component according to the invention and its production in the described method are thus not limited in their embodiments to the above preferred embodiments. Rather, a variety of
• FIG. 1 Schematic diagram of a preferred embodiment of
• FIG. 2 Schematic diagram of a preferred embodiment of
• FIG. 4 Schematic illustration of the inductive doping according to FIG.
• the illustrated optoelectronic component 1 is an organic light-emitting diode (OLED).
• OLED organic light-emitting diode
• the layer structure is composed as follows. A cathode 3 serves to provide electrons while the anode 5
• Electron holes deliver as soon as a voltage is applied to these.
• Signs + and - preferably indicate the voltage direction.
• the electron injection layer 7 and the hole injection layer 9 preferably allow efficient quantum mechanical tunneling of the charge carriers.
• the electron transport layer 1 1 and the hole transport layer 13 are characterized by a high mobility for the charge carriers and ensure a targeted transport to the optically active layer 15, which is a light-generating or emitter layer. In the optically active layer 15 recombine the optically active layer 15 .
• the inductive doped mixed layer 2 results from a successive protrusion of the hole injection layer 9 and the hole transport layer 13 by means of a printing process with a suitable choice of the carrier means of the printing inks.
• the support means of the printing ink for the second applied hole transport layer 13 is selected such that it is the material of the above
• lower hole injection layer 9 can dissolve.
• a mixed layer 2 in which the material of the hole injection layer 9 is doped in the hole transport layer 13, is produced on the basis of the inductive effect.
• the resulting doped mixed layer 2 is characterized by a high density and
• the inductive mixing layer 2 can preferably be produced by the following method steps:
• the organic semiconductor material PAN-co-PVDC is dissolved in a first carrier before.
• a suitable composition is 1 mg / mL PAN-co-PVDC dissolved in 20% vol. Acetophenones and 80% vol. Ethyl-L-Lactate.
• a suitable composition is 3 mg / mL Cu (I) SCN dissolved in 60% vol.
• a final layer thickness of 5 nm for the hole injection layer 9, 3 nm for the inductively doped mixed layer 2 and 17 nm for the hole transport layer 13 is achieved.
• Electron transport layer 1 1, the electron injection layer 7 and the cathode 3 are also preferably carried out by a printing method, preferably by a
• FIG. 2 shows a schematic illustration of a further preferred embodiment of an optoelectronic component 1 with two inductively doped mixed layers 2.
• the illustrated optoelectronic component is shown in FIG Component 1 to an organic light emitting diode (OLED).
• OLED organic light emitting diode
• the illustrated OLED is distinguished by the fact that an inductively doped mixed layer 2 is present both between a hole transport layer 13 and a hole injection layer 9 and between the hole injection layer 9 and the optically active layer 15.
• the inductively doped mixed layers result from a successive rise of the layers 13, 9 and 15 by means of a printing process with a suitable choice of the carrier means of the printing inks.
• the carrier of the printing ink for the second hole injection layer 9 to be applied is chosen such that it can dissolve the material of the lower hole transport layer 13 applied in front of it.
• the dissolving results in a mixed layer 2 based on the inductive effect, in which the material of the hole transport layer 13 is doped together with the material of the hole injection layer 9.
• the ink carrier for applying the optically active layer 15 is selected such that it can in turn dissolve the hole injection layer 9.
• a doped mixed layer 2 is formed between the optically active layer 15 and the hole injection layer 9.
• the resulting two mixed layers 2 increase the electrical performance of the optoelectronic component 1 particularly strong and lead to a high luminosity at low power consumption.
• the following example represents a particularly preferred layer structure for an optoelectronic component 1 according to FIG. 2:
• the two inductive mixed layers 2 are preferably by the following
• the organic semiconductor material m-MTDATA is dissolved in a first carrier means before.
• a suitable composition is 4 mg / mL m-MTDATA dissolved in 90% vol. ortho-dichlorobenzene and 10% vol. Mesitylene.
• the organic semiconductor material PAN-co-PVDC is present dissolved in a second carrier.
• a suitable composition is 3 mg / mL PAN-co-PVDC dissolved in 80% vol. Ethyl L-lactate and 20% vol. Acetophenones.
• the PAN-co-PVDC of the hole injection layer 9 is dissolved in steps 8) and 9), so that in the boundary region between the two
• an inductively doped mixed layer 2 of PFO and PAN-co-PVDC is formed.
• Electron transport layer 1 1 and cathode 3 are also preferably carried out by a printing process, preferably by an ink jet printing process, to a
• Optoelectronic component 1 according to FIG. 2 to obtain.
• FIG. 3 shows a schematic illustration of the formation of charge transfer complexes in known dopants of organic semiconductor materials. This results in the formation of new intermolecular orbitals by hybridization between organic materials, e.g. Molecular Electrical Doping; Phys. Rev. Lett., 108, 035502 (2012), Mendez et al., Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling; Chemie 52; 7751-7755; (2013))
• FIG. 3 illustrates, hybridization between semiconductor and dopant takes place in known dopings of organic materials. This results in a charge carrier transition, whereby the charge transfer complexes are formed. The charge transfer complexes form a new chemical compound.
• FIG. 4 shows a schematic illustration of the principle of inductive doping. An inductive effect causes a shift
• FIG. 3A shows the intramolecular shift of the electron density in 1-fluoropropane (intraactive inductive effect).
• Fig. 3B shows the resulting shift of

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