WO2023131379A1 - Procédé de fabrication d'une couche photoactive dans un système de couches d'un composant électronique organique - Google Patents

Procédé de fabrication d'une couche photoactive dans un système de couches d'un composant électronique organique Download PDF

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Publication number
WO2023131379A1
WO2023131379A1 PCT/DE2023/100002 DE2023100002W WO2023131379A1 WO 2023131379 A1 WO2023131379 A1 WO 2023131379A1 DE 2023100002 W DE2023100002 W DE 2023100002W WO 2023131379 A1 WO2023131379 A1 WO 2023131379A1
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layer
photoactive layer
photoactive
acceptor
donor
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PCT/DE2023/100002
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German (de)
English (en)
Inventor
Martin PFEIFFER-JACOB
Marieta Levichkova
Ivan Ramirez
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Heliatek Gmbh
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Publication of WO2023131379A1 publication Critical patent/WO2023131379A1/fr

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    • 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
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • 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
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing

Definitions

  • the invention relates to a method for producing at least one photoactive layer of a layer system of an organic electronic component, wherein during the application of the at least one photoactive layer, energy is introduced into the at least one photoactive layer to be formed by means of at least one pulse or a series of pulses of radiation, and an organic electronic component produced by such a method.
  • Organic electronic components with photoactive layers based on small molecules or polymeric compounds are increasingly being used in many areas of the electronics industry.
  • Organic semiconductors are used, for example, in electronic components such as organic field effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic photovoltaic elements (OPVs) and photodetectors.
  • OFETs organic field effect transistors
  • OLEDs organic light-emitting diodes
  • OCVs organic photovoltaic elements
  • solar cells have photoactive layers made of amorphous silicon (a-Si) or GIGS (Cu(In,Ga)(S,Se) 2 ).
  • solar cells with organic photoactive layers are also known.
  • the organic photoactive layers can be made up of polymers or small molecules. While polymers are characterized by the fact that they cannot be vaporized and can therefore only be processed from solutions, small molecules can be vaporized.
  • the light in organic solar cells does not directly generate free charge carriers; instead, excitons, i.e. electrically neutral excitation states (bonded electron-hole pairs), form first. Only in a second step are these excitons separated into free charge carriers, which then contribute to the electric current flow.
  • excitons i.e. electrically neutral excitation states (bonded electron-hole pairs)
  • Organic photovoltaic elements in particular organic solar cells, usually consist of a series of thin layers with at least one photoactive layer between two electrodes, which are preferably vacuum-deposited or processed from a solution.
  • the photoactive layer can consist of two adjacent layers, a planar heterojunction (PHJ), or as a mixed layer, a bulk heterojunction (BHJ), to form donor-acceptor heterojunctions (heterojunctions) within a cell.
  • the electrical contact can be made by metal layers, transparent conductive oxides (TCOs) and/or transparent conductive polymers (PEDOT-PSS, PANI).
  • TCOs transparent conductive oxides
  • PEDOT-PSS transparent conductive polymers
  • the basic structure of organic electronic components is disclosed, for example, in WO2004083958A2, WO2006092134A1, WO2010139804A1 or WO2011138021A2.
  • OCV organic photovoltaic elements
  • BHJ bulk heterojunctions
  • the organic photovoltaic elements can be produced, for example, by evaporating the materials, by printing, or by processing from liquids.
  • the basic structure of organic photovoltaic elements is disclosed, for example, in WO 2004 083 958 or WO 2011 138 021.
  • the vapor deposition of the photoactive layers in a vacuum is particularly advantageous in the production of multilayer photovoltaic elements, in particular tandem or triple cells.
  • Organic single or tandem cells are known from the prior art.
  • DE102004014046A1 discloses organic photovoltaic elements consisting of organic layers of one or more stacked pi, ni and/or pin diodes.
  • the efficiency ( Power Conversion Efficiency, PCE ) of organic electronic components, in particular organic solar cells, is determined among other things by the nanomorphology of photoactive layers with absorber materials of such components, in particular the donor-acceptor system. Improved nanophase separation leads to an increase in efficiency in electronic components, in particular by increasing the fill factor FF and/or the current density.
  • an elevated temperature of the substrate on which this photoactive layer is applied is necessary. This temperature is even higher at high deposition rates required for rapid fabrication. However, such high temperatures are disadvantageous for many substrates, since they are damaged or have other mechanical properties, for example due to expansion during production. The optimum temperature for depositing the photoactive layer can often only be achieved if the substrate is damaged.
  • the morphology can be influenced by the substrate temperature during the application of the photoactive layer. Increasing the temperature of the substrate can to some extent offset the effect by increasing the deposition rate. In commercial production, however, the maximum temperatures of the substrate are limited, in particular due to the process and the nature of the substrate.
  • DE102011007544A1 discloses the treatment of already coated substrates by means of flash lamp irradiation.
  • DE102015100885A1 discloses a method and a device for treating an already coated substrate, energy being introduced into the coating by means of radiation from a flash lamp, while the area of the substrate to be irradiated is exposed to an inert liquid or flowing gaseous medium, at least on the coated side of the substrate.
  • Flash lamp annealing (FLA) and pulsed laser annealing (PLA) for thermally increasing film growth in atomic layer deposition (ALD) processes when applying thin layers to a substrate are known from the prior art. These processes are used to finish layers after they have been applied, particularly inorganic layers. In this case, materials for forming the layer are evaporated from a chamber in a vacuum and deposited on the substrate.
  • the layer is formed in particular by the deposition of individual monolayers, as a result of which particularly thin, uniform layers are obtained.
  • the substrates are heated.
  • the temperatures for depositing the materials in the atomic layer deposition process are often low and therefore the energy required to form optimal layers is also less than is necessary, so that there is often no optimal morphology or structure. Structure of the layer is obtained.
  • the formation of the layer can be improved by introducing additional energy after the layer has been applied.
  • annealing is used after the layer has been applied, the substrate with the applied layer being heated.
  • Flash lamp annealing FLA
  • FLA Flash lamp annealing
  • a substrate with the layer deposited thereon is exposed to a flash of light. The light is absorbed by the layer, rapidly heating the layer for a short period of time.
  • FLA flash lamp annealing
  • precursor molecules are applied from which the actual material for the film layer is then formed by the energy input by means of a flash of light.
  • Layers of a layer system are treated after they have been deposited on a substrate, in particular after they have been completely deposited.
  • Flash lamp annealing (FLA) and pulsed laser annealing (PLA) deposition are known for short-term thermal treatment of layers, in particular on solid supports, such as wafers. Both processes have already been used for the thermal treatment of thin Substrates, for example layer systems on films, are used, with short pulses of radiation entering energy into parts of the layer system and/or the substrate for heating.
  • the disadvantage of the prior art is that in the case of a subsequent treatment of the layer by heating, for example with an FLA or a PLA, after the application of larger parts of the layer or the entire layer, too high an energy input is necessary in order to change the morphology to change .
  • To change the morphology by heating the substrate, in particular a film before, during or after the application of parts of the layer or the entire layer, an optimal temperature of the substrate cannot be reached, since the substrate is damaged or damaged if the temperature is too high is deformed.
  • These types of treatment of a photoactive layer are therefore not suitable for all substrates, especially not for foils.
  • the fill factors FF of the photoactive layers obtained in this way are also disadvantageous.
  • these types of treatment can lead to reactions between the applied materials, with materials in the adjacent layers or with the surrounding gas phase. In the extreme case, undesired intermediate layers can arise, which also have a negative effect on the efficiency of such layer systems.
  • the invention is therefore based on the object of providing a method for producing at least one photoactive layer of a layer system of an organic electronic component, as well as an organic electronic component with a photoactive layer of a layer system produced in this way, in which case the aforementioned disadvantages do not occur, and in which in particular one photoactive layer of the layer system is provided with improved absorption.
  • the intensity of the absorption of the photoactive layer is increased. It is a particular object of the present invention to improve the morphology of photoactive layers during production at high deposition rates, without the temperature of the substrate having to be significantly increased.
  • the object is solved by the subject matter of the independent claims. Advantageous refinements result from the dependent claims.
  • the object is achieved in particular by a method for producing at least one photoactive layer of a layer system of an organic electronic component, having a base electrode, a cover electrode, and the layer system arranged between the base electrode and the cover electrode, the layer system having the at least one photoactive layer provided .
  • the method comprises the following steps: a) providing a substrate with at least one base electrode; b) Application of the at least one photoactive layer of the layer system to the substrate by means of simultaneous and/or sequential deposition of at least one donor and/or at least one acceptor by thermal evaporation, wherein during the application of the at least one photoactive layer energy by means of at least one pulse or a series pulses of radiation are introduced into the at least one photoactive layer to be formed; and c ) obtaining the at least one photoactive layer of the layer system on the substrate .
  • finished molecules ie no precursor molecules
  • the substrate in particular the already complete at least one donor and/or the already complete at least one acceptor are deposited on the substrate.
  • no precursor molecules are deposited, which are converted into the finished donor and/or finished acceptor only after the deposition by means of the energy input, but the finished donor and/or acceptor are already deposited, with their morphology and/or their structure be finalized by means of the energy input.
  • the at least one donor and/or the at least one acceptor is/are already complete absorber materials and not a precursor molecule or several precursor molecules.
  • a precursor molecule is understood to mean, in particular, a molecule which, by at least one reaction step with another molecule or by splitting off a molecule during or after application to form the at least one photoactive layer, forms the finished absorber, in particular a donor and/or an acceptor , forms .
  • the at least one donor and/or the at least one acceptor are processed in vacuo, ie applied to a layer of the layer system by evaporation in vacuo.
  • the at least one donor and the at least one acceptor of the at least one photoactive layer can be evaporated in vacuo, preferably processed in vacuo.
  • the at least one photoactive layer during growth of the at least one photoactive layer, energy is introduced into the at least one photoactive layer by means of at least one pulse of radiation in order to form the at least one photoactive layer.
  • a structural change in the coating preferably in the morphology of the coating, is produced in particular by means of the energy input during the application of the photoactive layer, in particular during the growth of the photoactive layer.
  • a photoactive layer with an improved morphology of at least one donor and/or at least one acceptor is preferably obtained, the photoactive layer having improved absorption.
  • the improved absorption of the photoactive layer leads to better efficiency of an organic electronic component based thereon, in particular due to an improved fill factor.
  • An improved morphology means in particular a specific and/or uniform crystal structure, a specific proportion of nanocrystallinity, a specific degree of phase separation, in particular with domains with a size of 3 nm to 20 nm, a specific orientation of the molecules, in particular with a maximum absorption, good charge carrier mobility vertical to the substrate, and/or a low roughness of the surface.
  • the improved morphology allows in particular a preferred orientation to increase an absorption maximum and a charge carrier mobility vertical to the substrate.
  • a substrate is understood to mean, in particular, a carrier material with a base electrode arranged thereon.
  • the substrate can also have further layers, in particular layers of the layer system, preferably a transport layer or a further photoactive layer.
  • the substrate preferably also contains a further layer of the layer system arranged between the substrate and the at least one photoactive layer to be applied.
  • photoactive means in particular a conversion of light energy into electrical energy.
  • absorber materials in photoactive layers have a large absorption coefficient, at least for a specific wavelength range.
  • Photoactive is preferably understood to mean that absorber materials, in particular at least one donor and/or at least one acceptor, change their charge state and/or their polarization state when exposed to light.
  • a photoactive layer is understood to mean in particular a layer of an electronic component which makes a contribution to the absorption of radiation and/or to the emission of radiation, in particular the photoactive layer absorbs radiation.
  • the photoactive layer with the donor/acceptor system can be designed as a bulk heterojunction (BHJ) or as a planar heterojunction (PHJ).
  • a generated pulse of radiation is understood to mean in particular the irradiation by means of a pulse from a radiation source during the application of the at least one photoactive layer.
  • Radiation has a wavelength spectrum that is not or only weakly is absorbed by the at least one photoactive layer, but which is absorbed by the substrate.
  • the substrate is heated to a greater extent for a short time by the energy input by means of the pulse or the series of pulses in comparison to the at least one photoactive layer.
  • the pulsed radiation has a wavelength spectrum which at least partially corresponds to an absorption range of the at least one photoactive layer, preferably selected such that the pulsed radiation is more strongly absorbed by the at least one photoactive layer than by other layers in the layer system and/or the substrate.
  • the at least one photoactive layer is irradiated over its entire extent with pulsed, focused radiation during application, so that each position of the photoactive layer is at least largely exposed to the same energy input, with the expansion of the pulsed, focused radiation preferably between 10 ⁇ m 2 and 10 mm 2 .
  • the focused radiation is preferably in the form of a circular, oval or line-shaped beam, with a step width of a raster process being selected such that each position is subjected to a pulse between 1 and 20 times.
  • a roll-to-roll method is understood to mean, in particular, the production of flexible electronic components that are printed onto a web, in particular a substrate, made from flexible plastic or metal foils. The substrate, which is on a roll, is unrolled, processed and finally rolled up again.
  • a roll-to-roll method is understood in particular to mean a continuous method in which individual components are processed one after the other, electronic components or semi-finished products of electronic components preferably being produced in more than one method step in a continuous method become .
  • the roll-to-roll method is characterized by a continuous substrate, in particular made of a plastic film, for example PET or PEN. Materials to form electronic components are applied to this substrate, in particular by vapor deposition, printing, coating, sputtering or plasma deposition.
  • the film has, for example, a layer thickness of 50 nm to 300 nm, preferably 100 nm to 200 nm.
  • the method according to the invention for producing at least one layer of a layer system of an electronic component has advantages compared to the prior art.
  • the morphology of a photoactive layer, in particular of the donor-acceptor system, is advantageously improved, in particular in the case of high-rate deposition in a vacuum.
  • the at least one photoactive layer is only irradiated for a short time and is thus heated only briefly and on a restricted layer plane, so that the substrate and the at least one donor and/or the at least one acceptor of the photoactive layer are not damaged.
  • the morphology of the at least one donor and/or the at least one acceptor reacts much more sensitively to an energy input during brief heating during the application of a photoactive layer to the substrate during the growth of the photoactive layer compared to a corresponding energy input after the photoactive layer has been applied is .
  • a short period of heating is advantageously sufficient to obtain sufficiently high temperatures of the surface of the substrate and already applied photoactive layer, which are required for an improved morphology of the at least one donor and/or the at least one acceptor. It is believed that the mobility within a monolayer or a small number of monolayers is higher compared to a large number of layers assembled together.
  • the energy input can therefore be reduced to an energy that increases the mobility of the molecules of a layer that is just being applied, without stressing other layers or the substrate.
  • the at least one photoactive layer in particular the at least one donor and/or the at least one acceptor, can be applied by applying monolayers with simultaneous optimization of the morphology up to the desired layer thickness of the at least one photoactive layer.
  • the heating phase is of short duration, the applied layer being heated but the heat not diffusing into the substrate or only partially diffusing.
  • the efficiency (Power Conversion Efficiency—PCE) of photovoltaic elements is increased.
  • a reduction in the filling factor and/or the no-load voltage, as occurs in the transition from production at a lower speed, ie lower deposition rate, to production at a higher speed, such as in commercial production, is reduced.
  • the method can advantageously be carried out in a roll-to-roll process for producing an electronic component.
  • the method for producing the coating is simple, flexible and inexpensive, and can be integrated into a roll-to-roll process.
  • the method enables increased deposition rates that would typically require increased substrate temperature for optimal growth conditions of the layer, damaging substrates or leading to compressive stress.
  • the growth of organic layers responds better to a temperature input during the growth than to a temperature input after the growth of the entire layer, it is assumed that the mobility of molecules, especially organic molecules, is too restricted after the layer is fully deposited, to sufficiently improve the morphology through the arrangement of the molecules.
  • the at least one pulse or the series of pulses of radiation is generated by means of flash lamp annealing (flash lamp annealing - FLA) or pulsed laser annealing (pulsed laser annealing - PLA) and/or the pulse duration at FLA is 10 ps to 200 ms, preferably 10 ps to 100 ms, preferably 10 ps to 10 ms, preferably 10 ps to 1 ms, preferably 100 ps to 10 ms, preferably 1 ms to 10 ms, or preferably 10 ms to 20 ms, or for PLA is 1 ns to 1 ps, preferably 1 ns to 100 ns, or preferably 5 ns to 50 ns.
  • Flash lamp annealing is a thermal treatment process in which surfaces are heated by one or more high-energy flashes from a flash lamp for a short period of time, preferably for a period of a few microseconds to milliseconds.
  • FLA Flash lamp annealing
  • Pulsed laser annealing is a modification of flash lamp annealing, in which the energy input for thermal surface treatment takes place via pulsed irradiation with high-energy laser light.
  • the duration of the individual pulses is preferably in the range of a few nanoseconds.
  • the at least one photoactive layer is applied in step b) by means of a deposition method, preferably the deposition method is an atomic layer deposition method (ALD), a flash-enhanced atomic layer deposition method (FEALD), a plasma-enhanced atomic layer deposition method (PEALD), a plasma-free atomic layer deposition process (PLALD), a chemical vapor deposition process (CVD), a plasma-enhanced vapor phase deposition process (PECVD), a plasma-free vapor phase deposition process (PLCVD), or a hollow cathode process, the at least one photoactive layer preferably being deposited by evaporation in a vacuum or under Protective gas is applied.
  • ALD atomic layer deposition method
  • FFAD flash-enhanced atomic layer deposition method
  • PEALD plasma-enhanced atomic layer deposition method
  • PLAD plasma-free atomic layer deposition process
  • CVD chemical vapor deposition process
  • PECVD plasma
  • a time interval between the individual pulses is 1 ms to 500 ms, preferably 10 ms to 500 ms, preferably 10 ms to 100 ms, preferably 20 ms to 50 ms, 1 ps to 100 ms, preferably 10 ps to 100 ms, preferably 100 ps to 10 ms, preferably 1 ns to 1 ps, preferably 1 ns to 100 ns, or preferably 5 ns to 50 ns.
  • This can in particular the previously applied part of the photoactive layer, a layer of the layer system arranged under the photoactive layer, and/or the substrate cool down.
  • the pulse or the series of pulses is generated continuously or discontinuously during the application of the at least one photoactive layer and/or periodically during the application of the at least one photoactive layer; the pulse or the series is preferred of pulses with a repetition frequency of 0.001 to 1000 Hz, preferably 0.01 to 100 Hz, preferably 0.1 to 10 Hz, or preferably 0.1 to 1 Hz.
  • the pulse or the series of pulses is generated in each case after depositing a monolayer of the at least one donor and/or the at least one acceptor, preferably after depositing two monolayers, or preferably after depositing three monolayers , or the pulse or the series of pulses is generated in each case after deposition of a specific layer thickness of the at least one photoactive layer during the deposition of the at least one photoactive layer, preferably a layer thickness of 0.01 nm to 2 nm, preferably 0.1 nm to 1 nm, or preferably from 0.01 nm to 0.1 nm.
  • a monolayer is understood to mean in particular a layer with a layer thickness of less than 5 nm, preferably less than 4 nm, preferably less than 3 nm, preferably of less than 2 nm, preferably less than 1 nm, or preferably less than 0.5 nm, or preferably a layer with a layer of molecules.
  • the pulse or series of pulses is generated during the deposition of a single monolayer and not after the deposition of each individual monolayer.
  • the at least one photoactive layer has a layer thickness of 5 nm to 200 nm, preferably 5 nm to 100 nm, preferably 5 nm to 50 nm, preferably 10 nm to 200 nm, preferably of 10 nm to 100 nm, preferably from 10 nm to 50 nm, preferably from 20 nm to 100 nm, or preferably from 20 nm to 50 nm.
  • the at least one donor and the at least one acceptor of the at least one photoactive layer are deposited together, with the at least one donor and the at least one acceptor forming a donor-acceptor system, preferably a bulk heterojunction .
  • the at least one donor and the at least one acceptor are deposited in a homogeneously distributed manner.
  • the at least one photoactive layer is formed from organic materials, preferably from small organic molecules or polymeric organic molecules, particularly preferably from small organic molecules.
  • the photoactive layer of the layer system comprises small molecules which can be evaporated in a vacuum.
  • the layers of the layer system are applied by evaporating small organic molecules.
  • small molecules are understood as meaning non-polymeric organic molecules with monodisperse molar masses between 100 and 2000 g/mol, which are present in the solid phase under standard pressure (air pressure of the atmosphere surrounding us) and at room temperature.
  • the small molecules are photoactive.
  • a development of the invention provides that the at least one donor and the at least one acceptor are small molecules with a molecular weight of ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol, and/or the at least one donor is an ADA oligomer and/or a BODIPY, and the at least one acceptor is an ADA oligomer and/or a fullerene.
  • a BODIPY compound is understood to mean, in particular, a compound of the general formula C9H7BN2F2, i.e.
  • An ADA oligomer is in particular a conjugated acceptor-donor-acceptor oligomer (AD-A'-oligomer) with an acceptor unit (A) and another Acceptor unit (A'), each of which is bound to a donor unit (D).
  • AD-A'-oligomer conjugated acceptor-donor-acceptor oligomer
  • the temperature of the substrate during the application of the at least one photoactive layer of the layer system is 0 to 120° C., preferably 0 to 100° C., preferably 0 to 80° C., preferably 0 to 60° C. preferably 0 to 40°C, preferably 10 to 100°C, preferably 10 to 80°C, preferably 10 to 60°C, preferably 10 to 40°C, preferably 20 to 80°C, preferably 20 to 60°C, preferably 20 to 40°C, preferably 30 to 80°C, or preferably 30 to 60°C.
  • the temperature of the substrate is adjusted by means of a heating roller, a heating band or by irradiation, preferably VIS and/or IR radiation.
  • the at least one photoactive layer is applied to the substrate at a temperature of from 0 to 100° C., preferably from 0 to 80° C., preferably from 0 to 60° C., preferably from 0 to 40° C. preferably from 10 to 100°C, preferably from 10 to 80°C, preferably from 10 to 60°C, preferably from 10 to 40°C, preferably from 20 to 80°C, preferably from 20 to 60°C, preferably from 20 to 40°C, preferably from 30 to 80°C, or preferably from 30 to 60°C.
  • a deposition rate of the at least one photoactive layer is 0.001 nm/s to 2 nm/s, preferably 0.01 nm/s to 0.2 nm/s, preferably 0.1 nm/s to 2nm/s.
  • the pulse or the series of pulses for radiating in the energy is generated by means of a radiation source, in particular a flash lamp, preferably a xenon flash lamp.
  • the at least one photoactive layer is exposed to at least largely the same energy input over its entire extent during application, and/or the energy density of the pulse is 0.1 mJ/cm 2 to 200 J/cm 2 , preferably 1 mJ/cm 2 to 200 J/cm 2 , 0.1 mJ/cm 2 to 50 J/cm 2 , preferably 1 J/cm 2 to 50 J/cm 2 , 10 mJ/cm 2 to 100 J/ cm2 , preferably 1 J/cm 2 to 200 J/cm 2 , preferably 10 J/cm 2 to 200 J/cm 2 , preferably 10 J/cm 2 to 100 J/cm 2 , preferably 10 J/cm 2 to 80 J/cm 2 , preferably 10 mJ/cm 2 to 1 J/cm 2 , or preferably 0 . 1 mJ/cm 2 to 10 J/cm 2 .
  • the overall extent is understood to mean, in particular, an extent over the entire width and the entire length of the photoactive layer on the substrate.
  • the energy of the pulse or the series of pulses is higher at the beginning of the growth of the at least one photoactive layer than in the further course of the layer growth. This leads to the formation of enlarged crystallization nuclei for further growth.
  • the object of the present invention is also achieved by an organic electronic component with a base electrode, a cover electrode and a layer system, the layer system being arranged between the base electrode and the cover electrode, and the layer system having at least one photoactive layer produced by a method according to the invention , is provided, in particular according to one of the exemplary embodiments described above.
  • the organic electronic component has in particular the advantages that have already been described in connection with the method for producing at least one photoactive layer of a layer system of an organic electronic component.
  • the organic electronic component is an organic photovoltaic element (OPV), an OLED (organic light emitting diode), an organic field effect transistor (OFET), or an organic photodetector.
  • OLED organic photovoltaic element
  • OLED organic light emitting diode
  • OFET organic field effect transistor
  • An organic electronic component is understood to mean, in particular, an organic photovoltaic element.
  • the organic photovoltaic element is preferably made up of a number of photovoltaic cells which can be connected in series or in parallel.
  • the multiple photovoltaic cells can work in different ways be arranged and/or connected in the organic electronic component.
  • An organic photovoltaic element is understood to mean in particular a photovoltaic element with at least one organic photoactive layer, in particular a polymeric organic photovoltaic element or an organic photovoltaic element based on small molecules.
  • the organic photoactive layer is in particular a photoactive layer in which excitons (electron-hole pairs) are formed by radiation of visible light, UV radiation and/or IR radiation.
  • the organic materials are printed, glued, coated, vapor-deposited or otherwise applied to the foils in the form of thin films or small volumes.
  • the layer system has at least one charge transport layer between the base electrode and the at least one photoactive layer and/or between the top electrode and the at least one photoactive layer, the charge transport layer being a hole transport layer (HTL) and/or an electron transport layer (ETL ) , the layer system preferably has at least a first charge transport layer and a second charge transport layer, the first charge transport layer being arranged between the base electrode and the at least one photoactive layer, and the second charge transport layer being arranged between the at least one photoactive layer and the cover electrode.
  • HTL hole transport layer
  • ETL electron transport layer
  • the organic electronic component is a flexible electronic component, preferably a flexible organic photovoltaic element.
  • a flexible organic electronic component is understood to mean, in particular, an electronic component which can be bent and/or stretched in a specific area.
  • the object of the present invention is also achieved by using a layer system with at least one photoactive layer produced by a method according to the invention in a Organic electronic component is provided, in particular according to one of the exemplary embodiments described above.
  • the use of the layer system results in particular in the advantages that have already been described in connection with the method for producing at least one photoactive layer of a layer system of an organic electronic component and the organic electronic component.
  • Fig. 1 shows a schematic illustration of an exemplary embodiment of a layer system of an organic electronic component in cross section
  • Fig. 2 shows a schematic representation of an exemplary embodiment of a method for producing at least one photoactive layer of a layer system of an organic electronic component in a flow diagram
  • Fig. 3 in one embodiment, an absorption spectrum of a photoactive layer 4 according to the invention with absorber 1 with an energy input through a series of pulses during the application of the photoactive layer 4 and of photoactive layers 4 not according to the invention with tempering of the substrate 1 at different temperatures after the application of the photoactive layer 4 ; and Fig. 4 in one embodiment an absorption spectrum of a non-inventive photoactive layer with absorber without energy input and an inventive photoactive layer with absorber with energy input during the application of the photoactive layer.
  • the exemplary embodiments relate in particular to an organic electronic component 10 produced in a roll-to-roll process.
  • the organic electronic component 10 is an organic photovoltaic element.
  • the connections absorberl and absorber! are each absorbers from the class of small molecules.
  • Fig. 1 shows a schematic representation of an exemplary embodiment of a layer system of an organic electronic component 10 in cross section.
  • a layer system 7 of such an organic electronic component 10 is shown in an exemplary embodiment in FIG. 1 .
  • the layer system 7 of the organic electronic component 10 is arranged on a substrate 1 .
  • the layer system 7 has a base electrode 2 , a cover electrode 6 and at least one photoactive layer 4 , the at least one photoactive layer 4 being arranged between the base electrode 2 and the cover electrode 6 .
  • the layer system 7 also has a first transport layer 3 and a second transport layer 5 .
  • the photoactive layer 4 was vapor-deposited in vacuo.
  • the layer system 7 is arranged on a transparent substrate 1 , for example made of a film, which is preferably designed to be flexible.
  • the base electrode 2 is made of a transparent indium tin oxide layer (ITO), but alternatively an electrode made of a metal, another conductive oxide, in particular ZnO: Al or a conductive oxide or polymer, such as PEDOT: PSS or PANI possible.
  • a charge transport layer 3 which is in the form of an electron transport layer (ETL), is arranged on the base electrode 2 .
  • the photoactive layer 4 is arranged on the charge carrier transport layer 3, with at least one donor, for example absorber 1 or absorber!
  • the donor-acceptor system is in the form of a bulk heterojunction (BHJ), but can alternatively also be in the form of a planar heterojunction (PHJ).
  • a further charge transport layer 5 is arranged on the photoactive layer 4 and is in the form of a hole transport layer (HTL), for example made of fullerene C60 or doped fullerene C60.
  • the top electrode 6 is formed of, for example, a metal such as Al or Au.
  • the layer system 7 of the organic electronic component 10 can be produced by evaporating the materials of the respective layer in a vacuum, with or without a carrier gas.
  • WO2011/161108A1 discloses a construction and a production of a common organic photovoltaic element.
  • a pin cell consists of a carrier/substrate with an adjoining mostly transparent base contact, p-layer(s), i-layer(s), n-layer(s) and a cover contact.
  • An nip cell consists of a carrier/substrate with an adjoining mostly transparent base contact, n-layer(s), i-layer(s), p-layer(s) and a top contact.
  • FIG. 2 shows a schematic representation of an exemplary embodiment of a method for producing at least one photoactive layer 4 of a layer system 7 of an organic electronic component 10 in a flow diagram. Elements that are the same and have the same function are provided with the same reference symbols, so that reference is made to the previous description.
  • the layer system 7 with the at least one photoactive layer 4 is shown in FIG. 1 built on .
  • the method for producing at least one photoactive layer 4 of a layer system 7 of an organic electronic component 10, having a base electrode 2, a cover electrode 6, and the layer system 7 arranged between the base electrode 2 and the cover electrode 6, the layer system 7 comprising the at least one photoactive 4th layer comprises the following steps: a) providing a substrate 1 with at least one base electrode 2; b ) Application of the at least one photoactive layer 4 of the layer system 7 to the substrate 1 by means of simultaneous and/or sequential deposition of at least one donor and/or at least one acceptor by thermal evaporation, with energy being released during the application of the at least one photoactive layer 4 by means of at least one Pulses or a series of pulses of radiation into which at least one photoactive layer 4 to be formed is introduced; and c ) obtaining the at least one photoactive layer 4 of the layer system 7 on the substrate 1 .
  • Step B) can be repeated before step C) in order to
  • the method is carried out in a roll-to-roll process, preferably a continuous roll-to-roll process.
  • the method enables the morphology of the photoactive layer 4 in the layer system 7 to be improved, in particular the donor-acceptor system of the photoactive layer 4 . In this way, in particular, an improved efficiency of organic electronic components 10, in particular of organic photovoltaic elements, with such a layer system 7 is obtained.
  • the photoactive layer 4 is periodically irradiated with a pulse in the form of a flash using a flash lamp while the at least one photoactive layer 4 is being applied by vaporizing at least one donor and/or at least one acceptor in a vacuum.
  • a short-term energy input is generated during the application of the at least one photoactive layer 4 .
  • the at least one pulse or the series of pulses of radiation is generated by means of flash lamp annealing (flash lamp annealing - FLA) or pulsed laser annealing (pulsed laser annealing - PLA), and/or the pulse duration is at FLA 10 ps to 200 ms, preferably 10 ps to 100 ms, preferably 10 ps to 10 ms, preferably 10 ps to 1 ms, preferably 100 ps to 10 ms, preferably 1 ms to 10 ms, or preferably 10 ms to 20 ms, or for PLA 1 ns to 1 ps, preferably 1 ns to 100 ns, or preferably 5 ns to 50 ns.
  • the at least one photoactive layer is applied in step b) by means of a deposition method, preferably the deposition method is an atomic layer deposition method (ALD), a flash-enhanced atomic layer deposition method (FEALD), a plasma-enhanced atomic layer deposition method (PEALD), a plasma-free one Atomic layer deposition process (PLLD), a chemical vapor deposition process (CVD), a plasma-enhanced vapor phase deposition process (PECVD), a plasma-free vapor phase deposition process (PLCVD), or a hollow cathode process, the at least one photoactive layer preferably being applied by evaporation in a vacuum or under protective gas becomes .
  • ALD atomic layer deposition method
  • FFAD flash-enhanced atomic layer deposition method
  • PEALD plasma-enhanced atomic layer deposition method
  • PLLD plasma-free one Atomic layer deposition process
  • CVD chemical vapor deposition process
  • PECVD plasma
  • the pulse or the series of pulses is generated continuously or discontinuously during the application of the at least one photoactive layer 4 and/or periodically during the application of the at least one photoactive layer 4, preferably the pulse or the series of Pulses are generated with a repetition frequency of 0.001 to 1000 Hz, preferably 0.01 to 100 Hz, preferably 0.1 to 10 Hz, or preferably 0.1 to 1 Hz.
  • the pulse or the series of pulses is generated after a monolayer of at least one donor and/or at least one acceptor has been deposited, preferably after two monolayers have been deposited, or preferably after three monolayers have been deposited.
  • the pulse is generated in each case after deposition of a specific layer thickness of the at least one photoactive layer 4 during the deposition of the at least one photoactive layer 4 from 0.01 nm to 2 nm, preferably from 0.1 nm to 1 nm , or preferably from 0.01 nm to 0.1 nm.
  • the at least one photoactive layer 4 has a layer thickness of 5 nm to 200 nm, preferably 5 nm to 100 nm, preferably 5 nm to 50 nm, preferably 10 nm to 100 nm, preferably 20 nm to 100 nm, or preferably from 20 nm to 50 nm.
  • the at least one donor and the at least one acceptor of the at least one photoactive layer 4 are deposited together, with the at least one donor and the at least one acceptor forming a donor-acceptor system, preferably a bulk heterojunction.
  • a temperature of the substrate 1 during the application of the at least one photoactive layer 4 of the layer system 7 is 0 to 100° C., preferably 20 to 80° C., preferably 20 to 60° C., preferably 30 to 80° C. or preferably 30 to 60°C.
  • a deposition rate of the at least one photoactive layer 4 is 0.001 nm/s to 2 nm/s, preferably 0.01 nm/s to 0.2 nm/s, preferably 0.1 nm/s to 2 nm/s.
  • the energy density of the pulse or a pulse of the series of pulses is 0.1 mJ/cm 2 to 200 J/cm 2 , 0.1 mJ/cm 2 to 50 J/cm 2 , preferably 10 mJ/cm cm 2 to 100 J/cm 2 , preferably 10 mJ/cm 2 to 1 J/cm 2 , or preferably 0.1 mJ/cm 2 to 10 J/cm 2 .
  • the at least one photoactive layer 4 is at least largely exposed to the same energy input over its entire extent.
  • the at least one donor and the at least one acceptor of the at least one photoactive layer 4 are deposited together, with the at least one donor and the at least one acceptor forming a donor-acceptor system, preferably a bulk heterojunction.
  • the at least one donor and the at least one acceptor are small molecules with a molecular weight of ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol, and/or the at least one donor is an ADA oligomer and/or a BODIPY, and the at least one acceptor is an ADA oligomer and/or a fullerene.
  • the organic electronic component 10 has a base electrode 2 , a cover electrode 6 and a layer system 7 , the layer system 7 being arranged between the base electrode 2 and the cover electrode 6 .
  • the layer system 7 has at least one photoactive layer 4 produced using a method according to the invention.
  • the organic electronic component 10 is an organic photovoltaic element (OPV), an organic photodetector, an organic field effect transistor (OFET) or an OLED.
  • OOV organic photovoltaic element
  • OFET organic field effect transistor
  • Fig. 3 shows in one embodiment an absorption spectrum of a photoactive layer 4 according to the invention with absorber 1 with an energy input through a series of pulses during the application of the photoactive layer 4 and of photoactive layers 4 not according to the invention with tempering of the substrate 1 at different temperatures after the application of the photoactive Layer 4 .
  • Elements that are the same and have the same function are provided with the same reference symbols, so that reference is made to the previous description.
  • a PET film was used as the substrate 1 . absorber
  • the photoactive layer 4 with the absorber was deposited in a layer thickness of 10 nm on EHT022 in a layer thickness of 50 nm on a PET film.
  • EHT022 is a commercial HTL matrix material from Merck AG (Merck SHT-218).
  • the photoactive layer 4 (Abs) according to the invention was applied with an energy input during vapor deposition.
  • the energy was introduced into the photoactive layer by means of pulsed flash lamp annealing (pulsed lamp annealing - PLA).
  • the principle of flash lamp annealing is based on the pulsed ignition of a quartz glass tube filled with the inert gas xenon (Rovak Basic Line 3.0 for ex situ FLA).
  • the distance of the flash lamp from the substrate from the on the applied photoactive layer was 20 mm.
  • the pulse time was 2 in this exemplary embodiment. 1 ms with a pulse energy of 20 J/cm 2 .
  • the pulse time or however, the pulse energy can be adapted to the requirements of the layer to be applied.
  • the temperature of the substrate 1 of the photoactive layer 4 according to the invention was room temperature.
  • the absorption spectra (optical density over wavelength in nm) of the non-inventive photoactive layers 4 were measured for 10 nm thick vacuum-evaporated layers with the absorber 1 at different substrate temperatures.
  • the temperature of the substrate 1 of the non-inventive layers was room temperature (RT), 60 ° C, 80 ° C, 100 ° C, 120 ° C, 130 ° C, 140 ° C and 150 ° C and was using a heating roller or a heating band or by irradiation from the rear over a period of 2 minutes.
  • the photoactive layer according to the invention with the absorber has a greater optical density and thus better absorption compared to photoactive layers not according to the invention, which were deposited at different substrate temperatures but without energy input by means of a pulse during application.
  • the photoactive layer according to the invention with the at least partially crystalline state shows a changed absorption spectrum compared to the amorphous layer, with the optical density of the absorption being significantly increased.
  • FIG. 4 shows an absorption spectrum of a non-inventive photoactive layer 4 with absorber 1 without energy input and an inventive photoactive layer 4 with absorber 1 with energy input during the application of the photoactive layer 4 .
  • Elements that are the same and have the same function are provided with the same reference symbols, so that reference is made to the previous description.
  • a photoactive layer 4 with the absorber 1 was deposited in a layer thickness of 10 nm at room temperature on EHT022 in a layer thickness of 50 nm on a PET film.
  • the photoactive layer 4 was applied without an energy input during the vapor deposition (untreated) and in a further exemplary embodiment with energy input during the vapor deposition.
  • the energy was introduced into the photoactive layer by means of flash lamp annealing (FLA).
  • FLA flash lamp annealing
  • the distance of the flash lamp from the substrate from the applied photoactive layer was 20 mm.
  • the pulse time was 2.1 ms with a pulse energy of 20 J/cm 2 .
  • a single FLA pulse of 2.1 ms of 20 J/cm 2 converts an amorphous photoactive layer with the absorber, which was deposited at room temperature, into an at least partially crystalline state, compared to a photoactive layer not according to the invention , which was also applied at room temperature but without energy input during application and has a largely amorphous structure.
  • the photoactive layer according to the invention with the at least partially crystalline state shows a changed absorption spectrum compared to the amorphous layer, with the optical density of the absorption being significantly increased.
  • the absorption optical density corresponds to a photoactive layer deposited at a temperature of 90 °C.
  • a current-voltage characteristic of an organic electronic component 10 with a donor-acceptor system Absorber2: C60 in a photoactive layer 4 of a layer system 7 with and without energy input according to the invention was determined during the deposition of the photoactive layer 4 (not shown). Elements that are the same and have the same function are provided with the same reference symbols, so that reference is made to the previous description.
  • the organic Electronic component 10 is an organic photovoltaic element in this exemplary embodiment.
  • the BHJ cell has a layer of C60 as the electron transport layer (ETL) with a layer thickness of 15 nm on the ITO layer as the base electrode (150 nm).
  • the absorber was placed on this layer! applied together with C60 in a ratio of 2:3 in a layer thickness of 30 nm as a bulk heterojunction (BHJ).
  • An undoped hole conduction layer (HTL) 6 made of EHT022 (10 nm) and a doped hole conduction layer (HTL) 6 with NDP9-doped EHT022 (4.2% by weight, 45 nm) are applied to the photoactive layer.
  • This layer is followed by a further layer with NDP9 in a layer thickness of 1 nm, which is followed by a gold layer in a layer thickness of 50 nm.
  • ITO Indium Tin Oxide NDP9: commercial p-dopant from Novaled GmbH
  • EHT022 is a commercial HTL matrix material from Merck AG (Merck SHT-218 )
  • the photoactive layer 4 according to the invention was irradiated during application by means of flash lamp annealing.
  • the substrate 1 was heated to 60 ° C to apply the photoactive layer 4 and the donor / acceptor system of absorber! and C60 applied at a deposition rate of 0.01 nm/s as bulk heterojunction (BHJ).
  • BHJ bulk heterojunction
  • pulses with a pulse duration of 340 ps and a pulse energy of 10 J/cm 2 were radiated onto the substrate 1 from a xenon flash lamp.
  • the pulse was carried out every 30 s, which corresponds to a layer thickness growth of 0.3 nm between two pulses.
  • the pulses were radiated onto the substrate 1 from the back, ie from the side of the layer system 7 opposite the photoactive layer 4 to be applied.
  • the flash lamp was arranged at a distance of 10 cm from the substrate 1 .
  • the non-inventive photoactive layer 4 was treated by flash lamp annealing after the complete application of the photoactive layer 4 .
  • the substrate 1 was heated to 60 ° C to apply the photoactive layer 4 and the donor / acceptor system of absorber! and C60 applied at a deposition rate of 0.01 nm/s as bulk heterojunction (BHJ).
  • BHJ bulk heterojunction
  • the illuminant irradiates the sample in such a way that the gold layer is turned away from the light.
  • the filling factor FF is 60.0%, the no-load voltage Uoc is 0.7 V and the short-circuit current Jsc is 12.0 mA/cm 2 .
  • the efficiency ( PCE ) is 5.0 .
  • the filling factor FF is 66.0%, the no-load voltage Uoc is 0.7 V and the short-circuit current Jsc is 12.2 mA/cm 2 .
  • the efficiency ( PCE ) is 5.6 .
  • a photoactive layer 4 with the absorber! with an energy input according to the invention by means of a pulse or a series of pulses during the growth of the photoactive layer 4 leads to an advantageous organic photovoltaic element compared to an energy input by means of a post-treatment by radiation when the photoactive layer is completely deposited.
  • the production of the photoactive layer 4 according to the invention shows that an increase in the efficiency (power conversion efficiency, PCE) is obtained.
  • the efficiency (PCE) of organic electronic components, in particular organic photovoltaic elements is determined, among other things, by the morphology of photoactive layers of the absorber materials, in particular the morphology of the donor-acceptor system. In this context, improved nanophase separation in particular leads to an increase in the efficiency of organic photovoltaic elements.

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Abstract

L'invention concerne un procédé de fabrication d'au moins une couche photoactive d'un système de couches d'un composant électronique organique, selon lequel, lorsque la ou les couches photoactives sont appliquées, de l'énergie est introduite dans la ou les couches photoactives à former au moyen d'au moins une impulsion ou d'une série d'impulsions de rayonnement. L'invention concerne également un composant électronique organique comprenant au moins une couche photoactive produite selon un tel procédé.
PCT/DE2023/100002 2022-01-04 2023-01-04 Procédé de fabrication d'une couche photoactive dans un système de couches d'un composant électronique organique WO2023131379A1 (fr)

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Citations (9)

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Publication number Priority date Publication date Assignee Title
US20020155632A1 (en) * 2001-02-21 2002-10-24 Shunpei Yamazaki Method and apparatus for film deposition
DE102004014046A1 (de) 2003-03-19 2004-09-30 Technische Universität Dresden Photoaktives Bauelement mit organischen Schichten
WO2006092134A1 (fr) 2005-03-04 2006-09-08 Heliatek Gmbh Composant photoactif organique
US20070190235A1 (en) * 2006-02-10 2007-08-16 Semiconductor Energy Laboratory Co., Ltd. Film forming apparatus, film forming method, and manufacturing method of light emitting element
WO2010139804A1 (fr) 2009-06-05 2010-12-09 Heliatek Gmbh Composant photoactif à deux couches mixtes organiques ou plus
WO2011138021A2 (fr) 2010-05-04 2011-11-10 Heliatek Gmbh Composant photoactif à couches organiques
WO2011161108A1 (fr) 2010-06-21 2011-12-29 Heliatek Gmbh Composant photoactif comportant plusieurs systèmes de couches de transport
DE102011007544A1 (de) 2011-04-15 2012-10-18 Von Ardenne Anlagentechnik Gmbh Verfahren und Vorrichtung zur thermischen Behandlung von Substraten
DE102015100885A1 (de) 2015-01-22 2016-07-28 Von Ardenne Gmbh Verfahren und Vorrichtung zur Behandlung eines beschichteten Substrats

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020155632A1 (en) * 2001-02-21 2002-10-24 Shunpei Yamazaki Method and apparatus for film deposition
DE102004014046A1 (de) 2003-03-19 2004-09-30 Technische Universität Dresden Photoaktives Bauelement mit organischen Schichten
WO2004083958A2 (fr) 2003-03-19 2004-09-30 Technische Universität Dresden Composant photo-actif presentant des couches organiques
WO2006092134A1 (fr) 2005-03-04 2006-09-08 Heliatek Gmbh Composant photoactif organique
US20070190235A1 (en) * 2006-02-10 2007-08-16 Semiconductor Energy Laboratory Co., Ltd. Film forming apparatus, film forming method, and manufacturing method of light emitting element
WO2010139804A1 (fr) 2009-06-05 2010-12-09 Heliatek Gmbh Composant photoactif à deux couches mixtes organiques ou plus
WO2011138021A2 (fr) 2010-05-04 2011-11-10 Heliatek Gmbh Composant photoactif à couches organiques
WO2011161108A1 (fr) 2010-06-21 2011-12-29 Heliatek Gmbh Composant photoactif comportant plusieurs systèmes de couches de transport
DE102011007544A1 (de) 2011-04-15 2012-10-18 Von Ardenne Anlagentechnik Gmbh Verfahren und Vorrichtung zur thermischen Behandlung von Substraten
DE102015100885A1 (de) 2015-01-22 2016-07-28 Von Ardenne Gmbh Verfahren und Vorrichtung zur Behandlung eines beschichteten Substrats

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