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
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
  • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/30—Devices specially adapted for multicolour light emission
  • H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
• • 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
  • 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

Definitions

• the invention relates to a method for the production of pixels illuminated on a substrate, which radiate when passing electric current, the pixels each comprising: an electron transport layer ETL, a hole transport layer HTL, a hole blocking layer HBL or electron blocking layer EBL and a light emitting layer EML-R, EML-G, EML-B or other color combinations.
• OLED layers consist of organic molecules that shine when passing current. Structured layers are first deposited on the substrate, among other things, in order to supply power to the red-glowing, green-shining or blue-shining or luminous pixels in other colors so that they light up.
• Such electron transport layers, hole transport layers or hole / electron blocking layers are deposited in the prior art by various methods.
• the most widely used at the time of application, technologically used method is a high vacuum method in which a source material is evaporated in a process chamber. The free path of the vapor molecules is greater than the expansion of the vacuum chamber, so that the vapor molecules arrive essentially in a straight-line path from the source to the substrate. For structuring a mask is used. For the production of the light-emitting layer is also a
• Layer systems of a pixel arrangement are also known from US 2016/0079316 AI, US 6,903,378 B2 or US 9,385,348 B2. The content of these documents is fully incorporated in the disclosure of this application. Moreover, it is known to print layers at atmospheric pressure on the substrate, wherein plungers or pressure jets are used. The starting materials are dissolved in solvents, the solvent then having to evaporate. These starting materials may be polymers, small molecules with masses ⁇ 1000 g / mol or particles with sphere-equivalent diameters ⁇ 10 ⁇ m.
• the high vacuum process requires long Abpump réelle, which increases the cycle time.
• the use of a solvent requires drying of the deposited films.
• the quality of the layers, especially the light-emitting layers, suffers when the solvent does not completely evaporate.
• the high vacuum process also has the disadvantage that the substantially straight-line movement of the molecules in the process chamber lead to shadowing effects in the deposition using a mask.
• US 2016/0164046 Al describes a method in which a layer sequence for OLED displays is to be deposited in successively arranged process chambers. In the individual process chambers processes are carried out either under vacuum conditions or under reduced pressures.
• US 6,337,102 B2 describes the deposition of organic layers using a carrier gas at pressures in the range between 0.001 Torr and 100 Torr.
• the invention has for its object to provide an efficient method for producing a pixel array, which provides layers of high quality, especially for electroluminescent application.
• the process should work with the highest possible pressures to avoid long pump-down times.
• the layers in particular the organic charge transport layers, be manufactured in gas atmospheres with a total pressure of at least 0.001 mbar, preferably of at least 0.01 mbar or 0.1 mbar to a maximum of 10 mbar. All layers are thus manufactured in a gas atmosphere in which the free path of the molecules is at most 10%, preferably in the range from 1% to 0.01% characteristic length of the process chamber, wherein the characteristic length may be the distance between a gas inlet member and a substrate.
• the use of masks is required.
• the invention therefore proposes to print the light-emitting layer onto the substrate or onto already deposited layers, it being possible to use printing punches or pressure jets in the printing process.
• light-emitting particles are dissolved in a solvent and this liquid is printed on the substrate.
• the particulates can be quantum dots (CANdots®), in particular CdSe-
• the application of the light-emitting layer takes place in a process similar to the high-pressure or gravure printing process.
• the application can be done pixel by pixel or line by line. However, the application can also take place with a process similar to inkjet printing with a liquid jet.
• a PVD or CVD process in particular an OVPD process, is preferably used.
• the PVD or CVD process is preferably carried out in a process chamber in which the total pressure is in the range of 0.01 mbar and 10 mbar, preferably 0.1 mbar to 1 mbar.
• the process chamber has a substrate holder on which the substrate is placed and cooled.
• a gas inlet member is arranged, which has nozzle-like arranged gas outlet nozzles.
• the structuring of these layers can be done with the aid of a mask.
• the substrate holder can be cooled and the gas inlet member heated. It is therefore preferred that the process chamber of this PVD or CVD reactor is also used to dry the previously deposited light-emitting layer. In this case, the substrate previously printed with the light-emitting layer is brought into the process chamber and placed on the substrate holder. The substrate holder does not have to be cooled for this process step. The gas inlet member is heated.
• the resulting heat leads to the evaporation of the solvent in which the light-emitting particles, in particular quantum dots, are dissolved.
• the total pressure can even be lowered further, for example to pressures of 0.01 mbar or 0.001 mbar.
• the method is preferably carried out in a system of interlinked process chambers, wherein only one layer is deposited in each process chamber. Depending on requirements, however, it is also possible for one or more layers to be deposited in the same process chamber and in particular consecutively. It may be provided a central transfer chamber, which is purged with a high purity gas. With this transfer chamber a plurality of process chambers is connected, each having a closable portal through which the substrate can be brought into the process chamber.
• the process chambers in which the electron transport layer, the hole transport layer and / or the hole / electron blocking layer are deposited are preferably PVD or CVD reactors, in particular OVPD reactors, as are known in principle from the prior art. They have a substrate holder for placing the substrate and a gas inlet member for introducing the gaseous starting materials, which either condense on the substrate or react on the substrate to form a layer. Masks can be used to pattern the layer. The substrate holder and the gas inlet member are tempered, either heated or cooled, depending on the process carried out in the PVD or CVD reactor.
• the process chambers in which the light-emitting layers are deposited have a printing device with either plungers or pressure-jet devices, here the printing process can be carried out as a wet-chemical process at atmospheric pressure.
• the total pressure in these process chambers usually ranges between 100 mbar and 1050 mbar.
• the printing process can also be carried out in a range between 200 mbar and atmospheric pressure. However, the minimum total pressure during printing can also be higher, for example 400 mbar, 500 mbar, 600 mbar, 700 mbar or 800 mbar.
• the method according to the invention for producing pixels applied to a substrate may comprise at least one electron transport layer ETL, a hole transport layer HTL, a hole blocking layer HBL or an electron blocking layer EBL.
• a method according to the invention is further characterized in that it comprises at least one electron transport layer ETL, a hole transport layer HTL. It may further comprise a hole blocking layer HBL or an electron blocking layer EBL.
• the relevant coating steps can each be carried out in a chamber in which only one layer is deposited in a series production. However, it is also provided that several different layers are deposited in a process chamber, in particular successively. It can be a cluster facility. However, the individual process chambers can also be arranged in an in-line arrangement and be spaced from each other with a transfer chamber.
• the invention thus relates to a method for producing electroluminescent quantum dot layers with organic transport layers for transporting the electrons or the holes, in which the pressure difference between the deposited organic films and the quantum dot printed with liquid process Films no more than four orders of magnitude gene (0.1 mbar - 1000 mbar). However, it is also envisaged that the pressure difference is not more than six orders of magnitude (0.001 - 1000 mbar). Typically, however, the pressure difference is only three orders of magnitude (1-1000 mbar).
• the invention relates to a method for the production of electroluminescent quantum dot layers with organic transport layers, in which after the liquid process in which the quantum dot film is deposited, the process chamber in which a subsequent coating step is carried out under vacuum conditions , Is heated to selectively evaporate the solvent with which the quantum dot film has been deposited.
• a carrier gas into the PVD or CVD chamber
• the solvent which may preferably be an organic solvent
• the evaporation of the solvent which is used in printing the light-emitting layers can be carried out in the same process chamber in which a PVD or CVD process is subsequently carried out.
• the trained in particular as a shower head gas inlet member is heated to up to 200 ° C or higher up to 500 ° C.
• the substrate holder can optionally not be cooled in this case.
• an attraction force between substrate and substrate holder may be modified such that the substrate temperature is higher than it is in the subsequent deposition.
• the substrate holder may for this purpose have an "electrostatic chuck” (ESC) or a magnetic device for attracting the substrate or a mask.
• ESC electrostatic chuck
• the ESC can act directly or indirectly on the substrate.
• BSC BackSide Cooling Gas
• the coupling of the substrate to the substrate holder can also be modified in such a way that, for example, the gas composition in a gap between the substrate and the substrate holder is selectively changed in order to temporarily change the substrate temperature.
• the Substrate holder to a temperature of about in the range of 100 ° C to - 50 ° C, typically cooled from about 20 ° C, so that a gas entering through the gas inlet member, which is conveyed with an inert gas can condense on the substrate.
• a gas entering through the gas inlet member which is conveyed with an inert gas can condense on the substrate.
• the drying time is about 60 seconds.
• all process steps in which a layer is deposited, ie the CVD or PVD deposition processes is carried out in a gas phase environment in which the mean free path is smaller than a characteristic length of the process chamber.
• the total pressures are preferably above 0.01 mbar or 0.1 mbar.
• the total pressures can also be in a range between 0.1 mbar to 10 mbar. Only for other process steps, for example. Drying steps, the total pressure in the process chamber can be set to lower values.
• an HIL layer hole injection layer
• EIL layer electron injection layer
• cathode layers for electrically contacting the structures described with the control electronics.
• the inventive method combines the known from the prior art ago printing a light-emitting layer and the deposition of blocking / transport layers in the OVPD process while pressure stamp can be used in the printing process can OVPD method, a mask arrangement can be used for structuring.
• the minimum pressure in both process sections is preferably at least 0.01 mbar, but may also be only 0.1 mbar.
• the total pressure at which the printing takes place is greater than the total pressure in the OVPD method, wherein the quotient of the two pressures is at least 10, preferably min. at least 100 is. It may also be provided that the minimum pressure during printing is at least 900 mbar.
• Fig. 1 shows schematically the section through an OVPD reactor
• Fig. 2c schematically shows a method of printing a light-emitting layer
• FIG. 3a shows an arrangement consisting of a plurality of OVPD reactors or pressure devices
• 3b shows a second embodiment of an arrangement consisting of several reactors
• FIG. 4 shows a first embodiment of a layer system 22
• FIG. 5 shows a second embodiment of a layer system 22
• FIG. 6 shows a third exemplary embodiment of a layer system 22.
• FIG. 3a shows schematically an arrangement of seven process chambers 11 to 17, each having loading and unloading portals, not shown, through which a substrate from a transport conveyor, not shown. direction of the transfer chamber 10 in the individual process chambers 11 to 17 can be promoted.
• a deposition process for depositing a layer is carried out, for example in the process chamber 11 a hole transport layer HTL, in the process chamber 12 an electron blocking layer EBL, in the process chamber 13 a red light emitting layer EML-R, in the process chamber 14 a green light emitting layer EML-G, in the process chamber 15 a blue light emitting layer EML-B, in the process chamber a hole blocking layer HBL and in the process chamber 17 an electron layer ETL deposited.
• a substrate 4 In the process chambers 11, 12, 16 and 17, layers are deposited on a substrate 4 using an OVPD reactor, as shown schematically in FIG. 1, using a mask.
• the substrate 4 lies on a substrate holder 3 cooled by means of cooling elements 5.
• a gas inlet member 6 in the form of a shower head with a gas outlet surface 6, into which gas outlet openings 9 open, through which a vapor, in particular an organic starting material the process chamber 1 between gas inlet member 2 and substrate holder 3 can enter.
• the gas outlet plate whose underside forms the gas outlet surface 6, is heated by means of heating elements 8 to temperatures above 200 °, but also to higher temperatures.
• a supply line 7 is provided, through which an inert gas transports an organic vapor which condenses in the openings of the mask, not shown, on the substrate 4.
• the process chambers 11 - 17 are arranged around a transfer chamber.
• the process chambers 11, 12 and 13, 14, 15 and 16, 17 are arranged one behind the other in a line.
• the individual process chambers are separated from one another by transfer chambers 10.
• In the process chamber 11, 12, two or more mutually different layers can be deposited.
• In the process chamber 13, 14, 15, the light-emitting layers are deposited.
• In the process chamber 16, 17 also deposited two or more mutually different layers or only one layer.
• a printing process takes place in the process chambers 13, 14 and 15, in which the red-shining, green-shining or blue-shining layers are deposited.
• a printing device a jet printing device can be used with which dissolved in a solvent organic particles or inorganic particles but also on the substrate 4 or on the substrate 4 previously deposited layers is deposited.
• the steps 13, 14, 15 can also be carried out in one chamber or in one or more chambers.
• the steps 11, 12, 15, 16 can also be carried out in one or more chambers.
• Figures 3a and 3b show alternatives in this regard as examples.
• Figures 2a to 2c show schematically a printing process in which a plunger 18 is used, the raised zones 19 has.
• the raised zone 19 having the side of the plunger 18 has in the figure 2 upwards and is wetted with a liquid.
• This is a solvent 21 in which quantum dots 20 are contained.
• the liquid is distributed on the surface in such a way that approximately one monolayer of the quantum dots 20 is formed on the raised zones 19, as shown in FIG. 2b.
• FIG. 4 shows schematically typical layer sequences 22, as they can be applied to a substrate 4 in the apparatus shown in Figure 3.
• the reference numeral 23 denotes a single-layer or multi-layer anode.
• Reference numeral 24 denotes a single-layer or multi-layered cathode.
• the gas atmosphere is preferably more than 90% nitrogen, argon or another noble gas.
• the gas atmosphere may also have other compositions.
• a method which is characterized in that the electron transport layer ETL, the hole transport layer HTL, hole blocking layer HBL and / or the electron blocking layer EBL in a CVD or PVD process, in particular OVPD process, at a total pressure between 0, 1 mbar and 10 mbar is performed.
• All disclosed features are essential to the invention (individually, but also in combination with one another).
• the disclosure content of the associated / attached priority documents (copy of the prior application) is hereby also incorporated in full in the disclosure of the application, also for the purpose of defining features of these documents in claims of the present application. to take with you.
• the subclaims characterize, even without the features of a claimed claim, with their features independent inventive developments of the prior art, in particular in order to make divisional applications based on these claims.
• each claim may additionally have one or more of the features described in the preceding description, in particular with reference numerals and / or given in the reference numerals.
• the invention also relates to design forms in which individual features mentioned in the above description are not realized, in particular insofar as they are recognizably dispensable for the respective intended use or can be replaced by other technically equivalent means.

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• 2017
  • 2017-10-02 DE DE102017122886.1A patent/DE102017122886A1/de active Pending
• 2018
  • 2018-10-01 KR KR1020207012193A patent/KR102710721B1/ko active IP Right Grant
  • 2018-10-01 WO PCT/EP2018/076581 patent/WO2019068607A1/de active Application Filing
  • 2018-10-01 CN CN201880072379.3A patent/CN111316457B/zh active Active
  • 2018-10-02 TW TW107134822A patent/TW201924112A/zh unknown

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