WO2012111595A1 - Dispositif organique à électroluminescence et procédé de fabrication de celui-ci - Google Patents

Dispositif organique à électroluminescence et procédé de fabrication de celui-ci Download PDF

Info

Publication number
WO2012111595A1
WO2012111595A1 PCT/JP2012/053237 JP2012053237W WO2012111595A1 WO 2012111595 A1 WO2012111595 A1 WO 2012111595A1 JP 2012053237 W JP2012053237 W JP 2012053237W WO 2012111595 A1 WO2012111595 A1 WO 2012111595A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic
layer
substrate
electrode
electroluminescence device
Prior art date
Application number
PCT/JP2012/053237
Other languages
English (en)
Japanese (ja)
Inventor
寛幸 齊藤
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2012111595A1 publication Critical patent/WO2012111595A1/fr

Links

Images

Classifications

    • 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
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

Definitions

  • the present invention relates to a method for manufacturing an organic electroluminescence device.
  • the organic electroluminescence device includes an anode, a cathode, and a light emitting layer disposed between the anode and the cathode, and holes and electrons injected from the anode and the cathode are combined in the light emitting layer. It emits light.
  • Examples of the method for forming an organic layer such as a light emitting layer included in the organic electroluminescence element include a dry film forming method and a coating method.
  • the film forming process can be simplified and the area of the substrate can be easily increased.
  • a solution containing an organic compound contained in an organic layer can be applied onto a substrate to form a coating film, and then the formed coating film can be dried to form an organic layer.
  • a solution containing a red light emitting material, a solution containing a green light emitting material, and a solution containing a blue light emitting material are formed on a substrate. It is necessary to paint separately.
  • a method of separately painting there is a method of partitioning between pixels with a partition and making the surface of the partition liquid repellent.
  • a method for manufacturing an organic electroluminescence device including a step of making a partition wall surface liquid-repellent for example, a method including a step of successively performing oxygen gas plasma treatment and fluorocarbon gas plasma treatment on the partition wall surface has been proposed. (Patent Document 1).
  • the organic electroluminescence device manufactured by the above method has a long life and a method capable of manufacturing an organic electroluminescence device having a long life has been desired.
  • An object of the present invention is to provide a method capable of producing an organic electroluminescence device having a long lifetime and an organic electroluminescence device having a long lifetime.
  • the present invention shows that, before forming the organic layer, the region for constituting the pixel such as the partition wall is washed with an organic solvent, thereby extending the life. It was found and completed.
  • the manufacturing method of the organic electroluminescence device is: A substrate, a first electrode provided on the substrate, a partition provided on the first electrode and defining a plurality of pixels, and formed on the first electrode surrounded by the partition
  • a method for producing an organic electroluminescent device having an organic layer comprising: An electrode forming step of forming a first electrode on the substrate; A partition formation step of forming the partition on the first electrode; A plasma treatment step of irradiating the partition with plasma of a fluorine compound; and A cleaning step of cleaning the partition and the first electrode surrounded by the partition with an organic solvent after the plasma treatment step; An organic layer forming step of forming an organic layer by applying an ink containing an organic compound on the first electrode surrounded by the partition after the cleaning step; including.
  • the organic layer includes all layers composed of organic substances such as a hole or electron injection layer, a hole or electron transport layer, and a light emitting layer.
  • the organic solvent is vibrated ultrasonically in the cleaning step.
  • the organic solvent used in the washing step is a halide.
  • the halide is a fluorine compound.
  • the organic solvent used in the cleaning step is alcohol.
  • the temperature of the organic solvent is in the range of 25 to 200 ° C. in the washing step.
  • the ink is applied by a printing method.
  • the ink is applied by an ink jet method or a nozzle printing method.
  • the organic compound is a polymer compound.
  • the organic compound is an organic light emitting material.
  • the organic compound is a hole transport organic substance.
  • a substrate a first electrode provided on the substrate, a partition wall provided on the first electrode and defining a plurality of pixels, and the first electrode surrounded by the partition wall
  • An organic electroluminescence device comprising an organic layer formed on an electrode, wherein the organic layer is any one of a charge injection layer, a charge transport layer and a light emitting layer, and on the surface of the organic layer,
  • An organic electroluminescent device is provided in which the amount of fluorine compound defined by the ratio of the ionic strength of fluorine to the ionic strength of carbon measured by time-of-flight secondary ion mass spectrometry is 25 or less.
  • the manufacturing method of the organic electroluminescence device according to the present invention configured as described above includes a cleaning step of cleaning the partition and the first electrode surrounded by the partition with an organic solvent after the plasma treatment step, and the cleaning step Thereafter, an organic layer forming step of forming an organic layer by applying an ink containing an organic compound on the first electrode surrounded by the partition wall can reduce the fluorine compound adhering to the pixel. Therefore, an organic electroluminescence device having a long lifetime can be manufactured.
  • the organic electroluminescence device has a carbon ion measured by time-of-flight secondary ion mass spectrometry on the surface of an organic layer that is one of a charge injection layer, a charge transport layer, and a light emitting layer.
  • a carbon ion measured by time-of-flight secondary ion mass spectrometry on the surface of an organic layer that is one of a charge injection layer, a charge transport layer, and a light emitting layer.
  • the present invention relates to a method for manufacturing an organic electroluminescence device, and the organic electroluminescence device manufactured by the manufacturing method includes a plurality of organic electroluminescence elements formed in regions partitioned by partition walls 8 on a substrate. It has pixels.
  • the cross-sectional view of FIG. 1 shows an example of the organic electroluminescence element 1 constituting one pixel in the organic electroluminescence device.
  • FIG. 1 shows an organic electroluminescence element having a simple configuration provided with a first electrode 3, a light emitting layer 6, and a second electrode 7 on a substrate 2, but the organic electroluminescence element It may have a functional layer such as a charge injection layer and / or a charge transport layer.
  • first electrode 3 and the second electrode 7 is an anode, and the other is a cathode. Furthermore, one of the first electrode 3 and the second electrode 7 is a transparent electrode, and light is emitted through the transparent electrode. Moreover, each organic electroluminescent element is comprised so that light, such as red, green, blue, etc., may be light-emitted, for example, and it arranges suitably according to the objective.
  • the manufacturing method of the organic electroluminescence device according to the embodiment will be described by taking the organic electroluminescence element 1 shown in FIG. 1 as an example. Details of components of the organic electroluminescence element 1 will be described later.
  • the 1st process of the method of this embodiment is a process of forming the 1st electrode 3 on a substrate.
  • a transparent or translucent electrode is used in the case of an organic EL element configured to extract light from the light emitting layer through the anode.
  • a transparent electrode or translucent electrode a thin film of metal oxide, metal sulfide, metal or the like having high electrical conductivity can be used, and one having high light transmittance is preferable.
  • a thin film made of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (Indium Zinc Oxide: abbreviation IZO), gold, platinum, silver, copper, or the like is used.
  • ITO Indium Zinc Oxide
  • a thin film made of IZO or tin oxide is more preferable.
  • Examples of the method for producing the first electrode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. From the viewpoint of film formability and process simplicity, it is preferable to form the film by sputtering.
  • the second step of the manufacturing method of the present embodiment is a step of forming the partition wall 8 on the first electrode 3.
  • the partition wall 8 may have a single layer structure or a multilayer structure, and may be disposed between pixels. Moreover, the partition wall 8 may be patterned.
  • a material insoluble or hardly soluble in a solvent used for forming an organic layer such as a light emitting layer is preferable.
  • the material include inorganic materials, thermosetting resins, and thermoplastic resins.
  • the inorganic material include silicon oxide, silicon nitride, and silicon oxynitride.
  • the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, and polyimide.
  • thermoplastic resin examples include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, ABS resin, and acrylic resin.
  • polyimide and acrylic resin are preferable from the viewpoint of heat resistance, mechanical properties, and chemical properties.
  • a fluorine compound such as polytetrafluoroethylene is preferable.
  • Examples of the method for forming the partition walls 8 include a vapor deposition method and a coating method. From the viewpoint of ease of manufacturing the partition walls, a coating method is preferable.
  • a coating method is preferable.
  • a solution is prepared by dissolving the partition wall material in a solvent, the solution is applied onto the first electrode 3, and the applied solution is dried to form a film.
  • the partition wall 8 may be formed by applying a solution containing the partition wall material to a predetermined region on the first electrode and drying the solution. Alternatively, the partition wall 8 may be formed by coating the entire first electrode and drying to form a film, followed by patterning by exposure and development.
  • the atmosphere for forming the partition walls 8 by a coating method may be an air atmosphere or an atmosphere made of an inert gas. Drying may be performed at room temperature or by heating, and may be performed under normal pressure or under reduced pressure.
  • the third step of the method of the present invention is a step of irradiating the partition 8 with plasma of a fluorine compound.
  • liquid repellency is imparted to the partition wall.
  • fluorine compound CF 4 (tetrafluoromethane), CH 2 F 2 (difluoromethane), and CHF 3 (trifluoromethane) are preferable. From the viewpoint of improving the liquid repellency of the partition wall, it is preferable to irradiate oxygen plasma.
  • the third step may be performed in an air atmosphere or an atmosphere made of an inert gas, and may be performed under normal pressure or under reduced pressure.
  • the plasma power may be any power that can provide sufficient liquid repellency to the partition wall surface.
  • the plasma power is preferably 1 to 100 W, more preferably 5 to 80 W, and even more preferably 10 to 50 W, although it varies depending on the partition material.
  • the plasma treatment time may be a time that can impart sufficient liquid repellency to the partition wall surface.
  • the plasma treatment time is preferably 1 to 300 seconds, more preferably 5 to 180 seconds, and even more preferably 10 to 120 seconds, although it varies depending on the partition material.
  • the fourth step of the method of the present invention is a step of washing the partition wall 8 and the first electrode 3 surrounded by the partition wall with an organic solvent. Conventionally, after the plasma treatment before forming the organic layer, cleaning has not been carried out as it would reduce liquid repellency.
  • the present inventors have found that the cause of the decrease in the lifetime is the fluorine compound adhering to the partition 8 after the second step (partition forming step). It was found that a part of the film was peeled off and deposited on the first electrode 3. That is, when the organic layer is formed in a state where the amount of the fluorine compound deposited on the first electrode 3 is large, the life characteristics of the organic electroluminescence device are deteriorated. The same applies to a fluorine compound that is attached to the partition wall 8 and formed by an incomplete reaction that is easily detached.
  • the type of fluorine compound to be deposited depends on the material of the partition wall used and the gas to be plasma-treated, and the fluorine compound is in a state where the partition wall material is fluorinated (CF3- (CF2) nX). Presumed to be attached to the surface.
  • the amount of fluorine compound adhering to the upper part of the electrode and / or the organic layer in the pixel surrounded by the partition walls is analyzed using a time-of-flight secondary ion analyzer TOF-SIMSV (manufactured by ION-TOF). It can be carried out by irradiation.
  • the amount of fluorine compound defined by the ratio of the ionic strength of fluorine to the ionic strength of carbon measured by time-of-flight secondary ion analysis is preferably reduced to 50 or less, more preferably 25 or less, and further preferably 15 or less.
  • the fluorine compound deposited on the first electrode 3 or the fluoride compound formed by an incomplete reaction attached to the partition wall 8 is Although it is removed, it was found that the surface layer containing a fluorinated compound that imparts liquid repellency to the partition walls 8 was not removed, and liquid repellency was not reduced.
  • Organic solvents used for washing include halogen solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene, anisole, tetralin and phenylcyclohexane, acetone and methyl ethyl ketone. Examples thereof include ketone solvents, and ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate. A mixture of these solvents may also be used.
  • halogen solvents such as chloroform, methylene chloride and dichloroethane
  • ether solvents such as tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, xylene, anisole, tetralin and phenylcyclohexane
  • acetone and methyl ethyl ketone examples thereof
  • the cleaning method includes boiling cleaning, ultrasonic cleaning, steam cleaning, immersion cleaning, spray cleaning, electrolytic cleaning, and the like. From the viewpoint of ease of operation, ultrasonic cleaning is preferred.
  • the washing temperature may be any time that can maintain sufficient liquid repellency on the partition wall surface. Although it varies depending on the material of the partition wall, it is preferably 25 to 300 ° C, more preferably 25 to 250 ° C, and further preferably 25 to 200 ° C.
  • the cleaning time may be a time that can maintain sufficient liquid repellency on the partition wall surface. Although it depends on the material of the partition wall, it is preferably 1 second to 30 minutes, more preferably 10 seconds to 15 minutes, and even more preferably 30 seconds to 10 minutes.
  • the cleaning atmosphere may be an air atmosphere or an atmosphere made of an inert gas.
  • the washing may be performed at room temperature or by heating, and may be performed at normal pressure or under reduced pressure.
  • the fifth step of the method of the present invention is a step of forming an organic layer on the first electrode 3 surrounded by the partition walls 8 by a coating method.
  • the organic layer is the light emitting layer 6.
  • the light emitting layer 6 is formed by depositing a solution (ink) containing a light emitting organic compound on the first electrode 3.
  • the light-emitting organic compound is preferably a polymer compound.
  • a solution is prepared by dissolving a light-emitting organic compound in a solvent, the obtained solution is applied on the first electrode 3, and the applied solution is dried to form a thin film.
  • the applied solution may be dried at room temperature or heated, and may be performed at normal pressure or under reduced pressure.
  • the atmosphere for forming the light emitting layer may be an air atmosphere or an atmosphere made of an inert gas. Moreover, the atmosphere which flowed the inert gas in air
  • concentration of the inert gas may be sufficient.
  • the inert gas include helium gas, argon gas, nitrogen gas, and a mixed gas of these gases. Among these, nitrogen gas is preferable from the viewpoint of ease of device fabrication.
  • Solvents used in the coating method include chlorine solvents such as chloroform, methylene chloride, dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene, anisole, tetralin, phenylcyclohexane, acetone, methyl ethyl ketone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, and the like, and a mixture of these solvents may be used.
  • the solvents from the viewpoint of affinity with the fluorine compound, a halide is preferable, and a fluorine compound is more preferable. Alcohol is preferable from the viewpoint of wettability of the substrate surface to the ink.
  • Application methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating and
  • the coating method include a nozzle coating method, and a printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, an ink jet printing method, and a nozzle printing method. From the viewpoint of easy pattern formation and multi-color coating, a printing method is preferable, and an inkjet printing method and a nozzle printing method are more preferable.
  • the organic layer is preferably formed in an atmosphere having an oxygen concentration of 1000 ppm or less on a volume basis and / or a moisture concentration of 1000 ppm or less on a volume basis. More preferably, it is formed in an atmosphere having a reference of 10 ppm or less and / or a water concentration of 10 ppm or less by volume.
  • the organic electroluminescence device including a plurality of organic electroluminescence elements 1, after forming the first electrode 3 on the substrate 2, the second step is performed so that a plurality of pixel regions are formed, and then the first step is performed. It can be manufactured by carrying out the third to fifth steps.
  • the method for manufacturing the organic electroluminescence device having the organic electroluminescence element having the basic configuration shown in FIG. 1 has been described above.
  • the method of the present invention is applied to an organic electroluminescence device including a functional layer in addition to the light emitting layer.
  • the functional layer means a layer that does not usually participate in light emission and has a function of improving device characteristics such as charge injection or transport.
  • a hole injection layer, a hole transport layer, a positive layer, and the like are included.
  • This organic electroluminescent element 10 has a first electrode 3 on a substrate 2, a first functional layer 4 in a region surrounded by a partition wall 8 on the first electrode 3, A second functional layer 5 is provided on one functional layer 4, a light emitting layer 6 is provided on the second functional layer 5, and a second electrode 7 is provided on the light emitting layer 6.
  • the first functional layer 4 and the second functional layer 5 may each independently be an organic layer containing an organic compound or an inorganic layer made of an inorganic compound.
  • the inventors of the present invention shorten the lifetime of the organic electroluminescence device if the amount of the fluorine compound deposited under the organic layer formed first is large. I found out.
  • a part of the fluorine compound attached to the partition wall 8 is peeled off.
  • a fluorine compound is deposited on the first electrode 3.
  • a fluorine compound is deposited on the first functional layer 4 or the second functional layer 5.
  • the present invention when the present invention is applied to a method for manufacturing an organic electroluminescence device including a functional layer, for example, when the first functional layer 4 is an organic layer, the first functional layer 4 is formed on the first electrode 3.
  • the step of forming by a coating method corresponds to the fourth step of the present invention (that is, the organic layer forming step).
  • coating method is this invention. This corresponds to the fourth step.
  • coating method corresponds to the 4th process of this invention. That is, in the present invention, when the organic electroluminescence device includes a plurality of organic layers, the first organic layer is formed in the fourth step, and the third step (cleaning step) is at least the first organic layer. It may be performed before the fourth step in which the layer is formed.
  • the first electrode 3 is an anode
  • the second electrode 7 is a cathode
  • the first functional layer 4 is a hole injection layer
  • the second functional layer. 5 is a hole transport layer.
  • the hole injection layer made of an organic compound is formed as follows, for example.
  • the hole injection layer is formed by, for example, forming a first electrode 3 that is an anode on a substrate, and then forming a partition on the anode, a second step of irradiating the partition with plasma of a fluorine compound. After performing the step, the third step of washing the partition wall and the anode surrounded by the partition wall with an organic solvent, a thin film containing an organic compound having a hole injection function is formed on the anode surrounded by the partition wall 8 by a coating method. The thin film is formed by firing.
  • the organic compound constituting the hole injection layer may be a low molecular compound or a high molecular compound, but is preferably a high molecular compound from the viewpoint of coatability.
  • the solvent and the coating method for forming the thin film by the coating method include the solvent used for forming the light emitting layer 6 described above, the same solvent as the coating method, and the coating method.
  • the thin film can be formed in an atmosphere made of air or an inert gas.
  • the inert gas include helium gas, argon gas, nitrogen gas, and a mixed gas of these gases.
  • nitrogen gas is preferable from the viewpoint of ease of device fabrication.
  • the thin film can be formed under any of atmospheric pressure, reduced pressure, and high pressure. From the viewpoint of ease of production, it is preferable to form the thin film under atmospheric pressure.
  • the thin film in an atmosphere having an inert gas concentration of 99.5% or more.
  • the thin film is preferably formed in an atmosphere having an oxygen concentration of 1000 ppm or less on a volume basis and / or a moisture concentration of 1000 ppm or less on a volume basis, and the oxygen concentration is on a volume basis. More preferably, the thin film is formed in an atmosphere of 10 ppm or less and / or a moisture concentration of 10 ppm or less on a volume basis.
  • the firing is preferably performed by heating the thin film in a state where the oxygen concentration and moisture concentration in the atmosphere are each kept at 1000 ppm or less on a volume basis. By this heating, the solvent contained in the thin film is removed.
  • the heating is preferable to perform the heating at a temperature within the range of 50 ° C. to 250 ° C., and more preferably at the temperature within the range of 50 ° C. to 200 ° C. preferable.
  • the heating time is appropriately selected depending on the organic compound contained in the thin film, and is usually about 5 minutes to 2 hours.
  • the heating of the thin film is preferably performed in an atmosphere containing an inert gas and / or in an atmosphere containing a reducing gas from the viewpoint of extending the life of the organic electroluminescence device.
  • the inert gas include helium gas, argon gas, nitrogen gas, and a mixed gas of these gases.
  • nitrogen gas is preferable from the viewpoint of ease of device fabrication.
  • the reducing gas include carbon monoxide gas and hydrogen gas.
  • the thin film can be heated under atmospheric pressure, reduced pressure, or high pressure. From the viewpoint of ease of production, it is preferable to form the thin film in an atmosphere under atmospheric pressure or reduced pressure (10 Pa or less).
  • the heating of the thin film is preferably performed in a state in which the oxygen concentration and the moisture concentration in the atmosphere are kept at 600 ppm or less on a volume basis from the viewpoint of the light emission characteristics and life characteristics of the organic electroluminescence element. More preferably, the moisture concentration is kept at 300 ppm or less on a volume basis, more preferably, the oxygen concentration and the moisture concentration are kept at 100 ppm on a volume basis, respectively. It is particularly preferable that the reaction be carried out in a state where the volume is kept at 10 ppm or less.
  • the hole transport layer 5 contains an organic compound
  • the hole transport layer 5 can be formed by forming a thin film containing the organic compound on the hole injection layer 4 and heating.
  • Examples of the method for forming the hole transport layer 5 include the same method as the method for forming the hole injection layer 4.
  • the light-emitting layer 6 is an organic layer containing a light-emitting organic compound, and can be formed by the same method as the method for forming the light-emitting layer 6 in the organic electroluminescent element 1 except that the light-emitting layer 6 is formed on the second functional layer 5. it can.
  • the first step is performed so that a plurality of pixel regions are formed.
  • Each can be manufactured by forming the organic electroluminescence element 10.
  • the organic electroluminescent element manufactured by the method according to the present invention has at least a first electrode, a second electrode, and a light emitting layer disposed between the first electrode and the second electrode.
  • the first electrode for example, the anode
  • the second electrode for example, the cathode
  • the first and second functional layers are provided between the first electrode (for example, the anode) and the second electrode (for example, the cathode), for example, in order to improve device characteristics, the above-described light emitting layer.
  • another functional layer may be provided.
  • the functional layer includes a functional layer provided adjacent to the light emitting layer.
  • Examples of the functional layer provided between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer.
  • the functional layer in contact with the cathode is called an electron injection layer, and the functional layer excluding this electron injection layer is the electron transport layer.
  • the electron injection layer is a layer having a function of improving the electron injection efficiency from the cathode.
  • the electron transport layer is a layer having a function of improving electron injection from the cathode, the electron injection layer, or the electron transport layer closer to the cathode.
  • the hole blocking layer is a layer having a function of blocking hole transport. In the case where the electron injection layer and / or the electron transport layer have a function of blocking hole transport, these layers may also serve as the hole blocking layer.
  • the hole blocking layer has a function of blocking hole transport
  • the hole blocking layer has a function of blocking hole transport.
  • an element that allows only a hole current to flow For example, an element that does not include a hole blocking layer and that allows only a hole current to flow, and an element that includes a hole blocking layer inserted into the element are manufactured. It can be confirmed that the hole blocking layer has a function of blocking hole transport.
  • Examples of the functional layer provided between the anode and the light emitting layer include an electron blocking layer in addition to the hole injection layer and the hole transport layer described above.
  • the layer in contact with the anode is called a hole injection layer, and the layers other than the hole injection layer are positive.
  • a hole transport layer sometimes referred to as a hole transport layer.
  • the hole injection layer is a layer having a function of improving hole injection efficiency from the anode.
  • the hole transport layer is a layer having a function of improving hole injection from the anode, the hole injection layer, or the hole transport layer closer to the anode.
  • the electron block layer is a layer having a function of blocking electron transport. In the case where the hole injection layer and / or the hole transport layer has a function of blocking electron transport, these layers may also serve as an electron blocking layer.
  • the electron block layer has a function of blocking electron transport
  • an element that allows only electron current to flow for example, an element that does not include an electron blocking layer and that only allows an electron current to flow, and an element that includes an electron blocking layer inserted into the element are manufactured. It can be confirmed that it has a function of blocking electron transport.
  • Anode / hole injection layer / light emitting layer / cathode b) Anode / hole injection layer / light emitting layer / electron injection layer / cathode c) Anode / hole injection layer / light emitting layer / electron transport layer / cathode e) Anode / Hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode f) anode / hole transport layer / light emitting layer / cathode d) anode / hole transport layer / light emitting layer / electron injection layer / cathode e) Anode / hole transport layer / light emitting layer / electron transport layer / cathode f) Anode / hole transport layer / light emitting layer / electron transport layer / cathode f) Anode / hole transport layer / light emitting layer / electron transport layer / cathode f) Anode / hole
  • the organic electroluminescent element may have two or more light emitting layers.
  • the layer provided between the anode and the cathode is “repeating unit A”
  • an organic electroluminescence device having two light emitting layers is as shown in n) below.
  • the element structure shown can be mentioned.
  • the organic electroluminescence device having three or more light-emitting layers has the device configuration shown in the following o). Can be mentioned. o) Anode / (Repeating unit B) x / (Repeating unit A) / Cathode
  • the charge generation layer is a layer in which holes and electrons are generated by applying an electric field.
  • Examples of the charge generation layer include a thin film made of vanadium oxide, indium tin oxide (IndiumdiTin Oxide: abbreviation ITO), molybdenum oxide, and the like.
  • the organic electroluminescence element may be further covered with a sealing member such as a sealing film or a sealing plate for sealing.
  • a sealing member such as a sealing film or a sealing plate for sealing.
  • the layers arranged on the side from which the light is taken out with reference to the light emitting layer are made transparent.
  • the degree of transparency it is preferable that the visible light transmittance between the surface of the organic electroluminescence element on the light extraction side and the light emitting layer is 40% or more.
  • an organic electroluminescence element that is required to emit light in the ultraviolet region or infrared region one that exhibits a light transmittance of 40% or more in the region is preferable.
  • an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode in order to further improve the adhesion with the electrode or improve the charge injection property from the electrode.
  • a thin buffer layer may be inserted between each of the aforementioned layers in order to improve adhesion at the interface or prevent mixing.
  • the order of the layers to be laminated, the number of layers, and the thickness of each layer can be appropriately set in consideration of the light emission efficiency and the element lifetime.
  • a substrate that is not chemically changed in the process of manufacturing the organic electroluminescence element is suitably used.
  • a glass substrate, a plastic substrate, a silicon substrate, or a substrate obtained by stacking these substrates is used. From the viewpoint of rigidity, a glass substrate is preferable.
  • a commercially available material may be used as the material of the substrate, and the material may be manufactured by a known method.
  • a transparent or translucent electrode is used as the anode.
  • a metal oxide thin film, a metal sulfide thin film, a metal thin film, or the like having a high electrical conductivity is used, and one having a high light transmittance is preferably used.
  • a thin film of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (Indium Zinc Oxide: abbreviation IZO), gold, platinum, silver, and copper can be mentioned.
  • ITO, IZO A thin film of tin oxide is preferably used.
  • Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
  • a material that reflects light may be used for the anode, and the material is preferably a metal, metal oxide, or metal sulfide having a work function of 3.0 eV or more.
  • the thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 40 nm to 500 nm. .
  • oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanine compounds, amorphous carbon, Examples thereof include polyaniline and polythiophene derivatives.
  • the film thickness of the hole injection layer varies depending on the material used, and is set as appropriate so that the drive voltage and light emission efficiency are appropriate. If it is thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the hole injection layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • the hole transport material constituting the hole transport layer examples include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amine residues in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene. Derivatives, triphenyldiamine derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyarylamine and its derivatives, polypyrrole and its derivatives, poly (p-phenylene vinylene) and its derivatives, poly (2,5-thienylene vinylene) And a derivative thereof, a polyfluorene derivative, a polymer compound having an aromatic amine residue, and the like.
  • hole transport materials include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine residue in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly Preferred are arylamines and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, or poly (2,5-thienylene vinylene) and derivatives thereof, polyfluorene derivatives, and polymer compounds having an aromatic amine residue.
  • Polyvinylcarbazole and derivatives thereof, polyfluorene derivatives, and polymer compounds having an aromatic amine residue are preferable.
  • polystyrene examples thereof include polyvinyl chloride and polysiloxane.
  • the thickness of the hole transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • the light emitting layer is usually formed of an organic substance that mainly emits fluorescence and / or phosphorescence, or an organic substance and a dopant that assists the organic substance.
  • the dopant is added, for example, in order to improve the luminous efficiency or change the emission wavelength.
  • the organic substance may be a low molecular compound or a high molecular compound, and the light emitting layer preferably contains a high molecular compound having a polystyrene-equivalent number average molecular weight of 10 3 to 10 8 .
  • Examples of the light emitting material constituting the light emitting layer include a polymer material.
  • Polymer material examples include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and dye-based dopant materials and metal complex systems as exemplified below. The thing which polymerized dopant material etc. can be mentioned.
  • examples of materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives.
  • materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives.
  • polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives that are polymer materials are preferable.
  • examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like. Of these, polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferred.
  • examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives.
  • polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferable.
  • Dopant material examples include a pigment-based dopant material and a metal complex-based dopant material.
  • dye-based dopant materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophenes.
  • Ring compounds pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, coumarin derivatives, rubrene derivatives, squalium derivatives, porphyrin derivatives, tetracene derivatives, pyrazolones Derivatives, decacyclene, phenoxazone can be mentioned.
  • the metal complex dopant material examples include, for example, Al, Zn, Be or the like as the central metal, or rare earth metals such as Tb, Eu, or Dy, and oxadiazole, thiadiazole, phenylpyridine, phenyl as the ligand.
  • a metal complex having a benzimidazole, a quinoline structure, or the like can be given.
  • Specific examples thereof include metal complexes that emit light from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, A porphyrin zinc complex and a europium complex can be mentioned.
  • the thickness of the light emitting layer is usually about 2 nm to 200 nm.
  • Electrode transport material constituting the electron transport layer
  • known materials can be used, such as oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthra.
  • oxadiazole derivatives anthraquinodimethane and its derivatives
  • benzoquinone and its derivatives naphthoquinone and its derivatives
  • anthraquinone and its derivatives tetracyanoanthra.
  • oxadiazole derivatives as an electron transport material, oxadiazole derivatives, benzoquinone and derivatives thereof, anthraquinones and derivatives thereof, or metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene And 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline. preferable.
  • Examples of the method for forming the electron transport layer include a method in which a thin film containing an electron transport material is formed and then heated or dried.
  • a vacuum deposition method from a powder or a film formation from a solution or a molten state can be exemplified.
  • the electron transport material include film formation from a solution or a molten state.
  • the method for forming the electron transport layer from the solution include the same film formation method as the method for forming the hole injection layer from the above-described solution, and the same method as that for forming the hole injection layer described above. It is preferable to form a film in an atmosphere.
  • the film thickness of the electron transport layer varies depending on the material used, and is set appropriately so that the drive voltage and the light emission efficiency are appropriate, and at least a thickness that does not cause pinholes is required, and is too thick. In such a case, the driving voltage of the element increases, which is not preferable. Accordingly, the thickness of the electron transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • an optimum material is appropriately selected according to the type of the light emitting layer, and an alloy containing at least one of alkali metal, alkaline earth metal, alkali metal and alkaline earth metal, alkali Examples thereof include metal or alkaline earth metal oxides, halides, carbonates, and mixtures of these substances.
  • alkali metals, alkali metal oxides, halides, and carbonates include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, and oxide. Examples thereof include rubidium, rubidium fluoride, cesium oxide, cesium fluoride, and lithium carbonate.
  • Alkaline earth metals, alkaline earth metal oxides, halides, and carbonates include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, and fluoride. Examples thereof include barium, strontium oxide, strontium fluoride, and magnesium carbonate.
  • the electron injection layer may be composed of a laminate in which two or more layers are laminated, and examples of the laminate include a laminate (LiF / Ca) of lithium fluoride and calcium.
  • the electron injection layer is formed by vapor deposition, sputtering, printing, or the like.
  • the thickness of the electron injection layer is preferably about 1 nm to 1 ⁇ m.
  • a material for the cathode As a material for the cathode, a material having a small work function, easy electron injection into the light emitting layer, and high electrical conductivity is preferable. Moreover, in the organic electroluminescent element which takes out light from an anode side, in order to reflect the light from a light emitting layer to an anode side with a cathode, the material of a high visible light reflectance is preferable as a material of a cathode. As the cathode, an alkali metal, an alkaline earth metal, a transition metal, a group III-B metal, or the like can be used.
  • Cathode materials include metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc. , An alloy of two or more of the metals, one or more of the metals and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin Or graphite or a graphite intercalation compound.
  • metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc.
  • alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.
  • a transparent conductive electrode made of a conductive metal oxide, a conductive organic material, or the like can be used.
  • the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO, and IZO.
  • Specific examples of the conductive organic material include polyaniline and derivatives thereof, and polythiophene and derivatives thereof.
  • the cathode may be a laminate in which two or more layers are laminated.
  • the film thickness of the cathode is appropriately set in consideration of electric conductivity and durability, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
  • Examples of the method for producing the cathode include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.
  • the material for the insulating layer examples include metal fluorides, metal oxides, and organic insulating materials.
  • an organic electroluminescent element provided with an insulating layer having a thickness of 2 nm or less an organic electroluminescent element provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, or an insulating layer having a thickness of 2 nm or less adjacent to the anode.
  • the provided organic electroluminescent element can be mentioned.
  • the organic electroluminescence element described above can be suitably used for a curved or flat illumination device, for example, a planar light source used as a light source of a scanner, and a display device.
  • Examples of the display device including the organic electroluminescence element include an active matrix display device, a passive matrix display device, a segment display device, a dot matrix display device, and a liquid crystal display device.
  • the organic electroluminescence element is used as a light emitting element constituting each pixel in an active matrix display device and a passive matrix display device, and is used as a light emitting element constituting each segment in a segment display device. In a liquid crystal display device, it is used as a backlight.
  • the contact angle was measured using an automatic contact angle measuring device OCA30 (manufactured by Data Physics). 2 ⁇ l of solvent was dropped on the surface to be measured, and the contact angle was measured.
  • a glass substrate on which an ITO film having a thickness of 60 nm was formed by sputtering was irradiated with UV using a UV irradiation apparatus (MODEL208, manufactured by Technovision) to clean the substrate surface.
  • a UV irradiation apparatus MODEL208, manufactured by Technovision
  • a low-pressure mercury lamp (wavelength: 184.9 nm to 253.7 nm) was used as the light source, and the distance between the light source and the substrate was kept at 10 cm and irradiated for 5 minutes.
  • a resist material (OFPR-800C, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the ITO film by spin coating to form a film.
  • the spin coating method was performed under the condition of rotating at 1000 rpm for 7 seconds.
  • the formed resist material was baked by heating for 110 seconds on a hot plate heated to 110 ° C. to obtain a resist film.
  • the resist film was exposed using an exposure apparatus (manufactured by Dainippon Kaken). At the time of exposure, a mask that shields a part of the resist film was used, and the space between the mask and the substrate was adjusted to 200 ⁇ m. For the exposure, an ultrahigh pressure mercury lamp (DNK-2KW, manufactured by Dainippon Kaken) was used, and the resist film was irradiated with light until the integrated light amount reached 200 mJ.
  • DNK-2KW ultrahigh pressure mercury lamp
  • potassium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • pure water are mixed so that potassium hydroxide is 0.8% by weight.
  • the resist film was peeled from the substrate. Thereafter, the remaining resist film was baked by heating on a hot plate heated to 120 ° C. for 5 minutes, and the resist film was patterned.
  • ITO was patterned using an etching apparatus (manufactured by Micro Engineering).
  • a salt iron solution (produced by Hayashi Junyaku Kogyo Co., Ltd.), which is a liquid in which iron chloride and hydrochloric acid aqueous solution are mixed so that the weight ratio of iron chloride to hydrochloric acid aqueous solution is 2, is heated until the liquid temperature reaches 50 ° C.
  • the salt iron solution was poured over the substrate for 5 minutes, and then the substrate was rinsed with pure water for 30 seconds to pattern the ITO.
  • the substrate is immersed in 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 minute, and then the substrate is immersed in acetone for 1 minute. Peeled from the substrate.
  • 1-methyl-2-pyrrolidone manufactured by Wako Pure Chemical Industries, Ltd.
  • the substrate was rinsed with pure water, and then dried while rotating the substrate, thereby producing a substrate patterned with ITO.
  • the substrate surface was cleaned using an atmospheric pressure plasma apparatus (AP-T03, manufactured by Sekisui Chemical Co., Ltd.). Cleaning was performed under the conditions of flowing nitrogen (N 2 ) gas at 100 mL / min and argon (Ar) gas at 100 mL / min, applying voltage of 130 V, and the head speed of the atmospheric pressure plasma apparatus at 50 mm / min.
  • API-T03 atmospheric pressure plasma apparatus
  • a polyimide coating agent (Photo Nice (SL1904), manufactured by Toray) was applied on the ITO film by spin coating to form a thin film having a thickness of 1 ⁇ m.
  • the thin film was baked by heating at 120 ° C. for 5 minutes on a hot plate to obtain a polyimide film.
  • the polyimide film was exposed using an exposure apparatus (manufactured by Dainippon Kaken). At the time of exposure, a mask that shields a part of the polyimide film was used, and the space between the mask and the substrate was adjusted to 50 ⁇ m. For the exposure, an ultra-high pressure mercury lamp (DNK-2KW, manufactured by Dainippon Kaken) was used to irradiate the polyimide film with light until the integrated light amount reached 200 mJ.
  • DNK-2KW ultra-high pressure mercury lamp
  • the polyimide film was developed for 120 seconds using a developer (NPD-18, manufactured by Nagase Chemtex), washed with ultrapure water, and then dried while rotating the substrate on which the polyimide film was formed. It was.
  • NPD-18 manufactured by Nagase Chemtex
  • the substrate on which the polyimide film was formed in a clean oven (DT62, manufactured by Yamato Kagaku) was baked at 230 ° C. for 30 minutes and then cooled to room temperature (25 ° C.).
  • the film formation process, the baking process, and the cooling process were all performed in an air atmosphere.
  • a polyimide partition was formed on the ITO film by patterning the polyimide film.
  • a reactive ion etching apparatus / dry etching apparatus (RIE-200L, manufactured by SAMCO) is used to continuously perform O 2 plasma treatment and CF 4 plasma treatment.
  • RIE-200L reactive ion etching apparatus / dry etching apparatus
  • a substrate S1 was manufactured.
  • CF 4 plasma treatment a fluorine compound can be attached to the surface of the polyimide film, and liquid repellency can be imparted to the polyimide film.
  • the O 2 plasma treatment was performed under the conditions that the flow rate of oxygen gas was 40 Sccm, the output was 30 W, the pressure was 5 Pa, and the treatment time was 60 seconds.
  • the CF 4 plasma treatment was performed under the conditions that the flow rate of tetrafluoromethane was 10 Sccm, the output was 30 W, the pressure was 40 Pa, and the treatment time was 30 seconds.
  • a hole injection layer was formed as follows using the substrate S1 produced as described above, and the amount of the fluorine compound thereon was measured.
  • Example 1 The cleaning liquid (HFE7100: manufactured by 3M) was filled in a brown bottle, and the substrate S1 was immersed in the cleaning liquid (HFE7100).
  • the brown bottle was placed in an ultrasonic cleaner (BRANSON 2210, manufactured by Yamato Scientific Co., Ltd.) while being immersed, and ultrasonic cleaning was performed for 3 minutes.
  • the substrate S1 was taken out from the brown bottle, and the solution L1 was applied on the substrate S1 by an inkjet method.
  • the solution L1 was prepared by adding ultrapure water, glycerin, ethylene glycol, and 2 to a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (CLEVIOS (registered trademark) PVP CH8000, manufactured by Starck).
  • CLEVIOS registered trademark
  • PVP CH8000 polystyrene sulfonic acid
  • the film was dried under reduced pressure of 1 Pa to form a thin film having a thickness of 65 nm, and a hole injection layer was formed.
  • the analytical substrate of Example 1 was produced.
  • the amount of the fluorine compound on the hole injection layer was determined to be 6.4 by a time-of-flight secondary ion analyzer.
  • Example 2 In Example 2, after forming a thin film having a thickness of 65 nm as in Example 1, the substrate was further baked on a hot plate at 200 ° C. for 10 minutes to form a hole injection layer. Thus, the analysis substrate of Example 2 was produced in the same manner as in Example 1 except that the substrate was baked on a hot plate at 200 ° C. for 10 minutes. The thin film heating step was performed in an air atmosphere. In the analysis substrate of Example 1, the amount of the fluorine compound on the hole injection layer was 8.6.
  • Example 3 In Example 3, a brown bottle filled with 2-propanol (manufactured by Wako Pure Chemical Industries) was heated to 130 ° C., and the substrate S1 was immersed in heated 2-propanol for 3 minutes. The substrate S1 was taken out from the brown bottle, and the solution L1 was applied onto the substrate S1 by an inkjet method. Then, by drying under a reduced pressure of 1 Pa, a thin film having a thickness of 65 nm was formed, and a hole injection layer was formed. The amount of the fluorine compound on the hole injection layer in the analytical substrate thus prepared was 2.6.
  • 2-propanol manufactured by Wako Pure Chemical Industries
  • Example 4 In the same manner as in Example 3, after forming a thin film having a thickness of 65 nm, the substrate was further baked on a hot plate at 200 ° C. for 10 minutes to form a hole injection layer.
  • the analysis substrate of Example 4 was produced in the same manner as in Example 3 except that the substrate was baked on a hot plate at 200 ° C. for 10 minutes.
  • the thin film heating step was performed in an air atmosphere.
  • the amount of the fluorine compound on the hole injection layer was 10.3.
  • Example 5 The cleaning solution HFE7100 was filled in a brown bottle, and the substrate S1 was immersed in the cleaning solution HFE7100. With the soaked state, a brown bottle was placed in an ultrasonic cleaner and ultrasonic cleaning was performed for 3 minutes. The substrate S1 was taken out from the brown bottle, and then the substrate S1 was placed in a brown bottle filled with 2-propanol heated to 130 ° C., and the substrate S1 was immersed in heated 2-propanol for 3 minutes. The substrate S1 was taken out from the brown bottle, and the solution L1 was applied onto the substrate S1 by an inkjet method. The film was dried under reduced pressure of 1 Pa to form a thin film having a thickness of 65 nm, and a hole injection layer was formed. The amount of the fluorine compound on the hole injection layer of the analytical substrate thus produced was found to be 2.4 by a time-of-flight secondary ion analyzer.
  • Example 6 In the same manner as in Example 5, after a thin film having a thickness of 65 nm was formed, the substrate was further baked on a hot plate at 200 ° C. for 10 minutes. The amount of the fluorine compound on the hole injection layer in the analytical substrate produced in the same manner as in Example 5 except that the substrate was baked on a hot plate at 200 ° C. for 10 minutes was 3.9. The thin film heating step was performed in an air atmosphere.
  • Comparative Example 1 Without cleaning the substrate S1, the solution L1 was applied onto the substrate S1 by an inkjet method. By drying under a reduced pressure of 1 Pa and forming a thin film having a thickness of 65 nm, an analysis substrate of Comparative Example 1 in which a hole injection layer was formed was produced. It was 27.9 when the amount of fluorine compounds on the positive hole injection layer in the analysis board
  • Comparative Example 2 In the same manner as in Comparative Example 1, after forming a thin film having a thickness of 65 nm, a substrate for analysis was prepared in the same manner as in Comparative Example 1 except that the substrate was baked on a hot plate at 200 ° C. for 10 minutes. The amount of the above fluorine compound was determined. The thin film heating step was performed in an air atmosphere. The amount of the fluorine compound on the hole injection layer was 159.
  • a glass substrate on which an ITO film having a thickness of 60 nm was formed by sputtering was irradiated with plasma using an atmospheric pressure plasma apparatus (AP-T03, manufactured by Sekisui Chemical Co., Ltd.) to clean the substrate surface. Cleaning was performed under the conditions of flowing nitrogen (N 2 ) gas at 100 mL / min and argon (Ar) gas at 100 mL / min, applying voltage of 130 V, and the head speed of the atmospheric pressure plasma apparatus at 50 mm / min.
  • N 2 nitrogen
  • Ar argon
  • a polyimide coating agent (Photo Nice (SL1904), manufactured by Toray) was applied on the ITO film by spin coating to form a thin film having a thickness of 1 ⁇ m.
  • the thin film was baked by heating at 120 ° C. for 5 minutes on a hot plate to obtain a polyimide film.
  • the polyimide film was developed for 120 seconds using a developer (NPD-18, manufactured by Nagase Chemtex), washed with ultrapure water, and then dried while rotating the substrate on which the polyimide film was formed. It was.
  • NPD-18 manufactured by Nagase Chemtex
  • the substrate on which the polyimide film was formed in a clean oven (DT62, manufactured by Yamato Kagaku) was baked by heating at 230 ° C. for 30 minutes, and then cooled to room temperature (25 ° C.).
  • DT62 manufactured by Yamato Kagaku
  • the film formation process, the baking process, and the cooling process were all performed in an air atmosphere.
  • a reactive ion etching apparatus / dry etching apparatus (RIE-200L, manufactured by SAMCO) is used to continuously perform O 2 plasma treatment and CF 4 plasma treatment.
  • RIE-200L reactive ion etching apparatus / dry etching apparatus
  • the substrate S2 was manufactured.
  • CF 4 plasma treatment a fluorine compound can be attached to the surface of the polyimide film, and liquid repellency can be imparted to the polyimide film.
  • the O 2 plasma treatment was performed under the conditions that the flow rate of oxygen gas was 40 Sccm, the output was 30 W, the pressure was 5 Pa, and the treatment time was 60 seconds.
  • the CF 4 plasma treatment was performed under the conditions that the flow rate of tetrafluoromethane was 10 Sccm, the output was 30 W, the pressure was 40 Pa, and the treatment time was 30 seconds.
  • Example 7 the cleaning liquid HFE7100 (manufactured by 3M) was filled in a brown bottle, and the substrate S2 was immersed in the cleaning liquid HFE7100.
  • the brown bottle was placed in an ultrasonic cleaner (BRANSON 2210, manufactured by Yamato Scientific Co., Ltd.) while being immersed, and ultrasonic cleaning was performed for 3 minutes.
  • the contact angle of the polyimide film on the substrate S2 after washing with respect to water was 105.5 °.
  • Example 8 FIG. In Example 8, a brown bottle filled with 2-propanol (manufactured by Wako Pure Chemical Industries) was heated to 130 ° C., and the substrate S2 was immersed in heated 2-propanol for 3 minutes. The contact angle of the polyimide film on the substrate S2 after washing with respect to water was 112.8 °.
  • Comparative Example 3 In Comparative Example 3, the contact angle of the polyimide film on the substrate S2 was measured without cleaning the substrate S2. The contact angle of the polyimide film of the substrate S2 with respect to water was 107.8 °.
  • Comparative Example 4 Further, as Comparative Example 4, a substrate S3 was manufactured by performing the same operation as that of the substrate S1 except that the CF 4 plasma treatment was not performed. And when the solution L1 was apply
  • Examples 9 to 11 and Comparative Example 5 an organic electroluminescence element was produced and evaluated.
  • the substrate S1 used in Examples 9 to 11 and Comparative Example 5 was manufactured in the same manner as the substrate S1 used in Examples 1 to 6, except that the thickness of ITO was 150 nm.
  • Comparative Example 5 An organic electroluminescence element of a comparative example having the following configuration was produced. “Glass substrate / ITO (150 nm) / hole injection layer: CLEVIOS (registered trademark) P VP CH8000 (65 nm) / hole transporting material (20 nm) / blue light emitting polymer material (65 nm) / Ba (5 nm) / Al (100nm) "
  • a hole transport material was dissolved in xylene to prepare a solution 2.
  • the concentration of the hole transport material in the solution 2 was 0.5% by weight.
  • the solution 2 was applied onto the hole injection layer by a spin coating method to form a thin film for a hole transport layer having a thickness of 20 nm.
  • the thin film was baked by heating at 180 ° C. for 1 hour to obtain a hole transport layer.
  • a blue light emitting polymer material was dissolved in xylene to prepare a solution 3.
  • the concentration of the blue light emitting polymer material in the solution 3 was 1.0% by weight.
  • the solution 3 was applied on the hole transport layer by a spin coating method to form a thin film for a light emitting layer having a film thickness of 65 nm.
  • the thin film was heated at 130 ° C. for 10 minutes in a hydrogen atmosphere in which the oxygen concentration and the water concentration were controlled to 10 ppm or less on a volume basis to obtain a light emitting layer.
  • the pressure in the thin film formation step and the heating step was 1 atm.
  • Example 9 An organic electroluminescent element of Example 9 having the following configuration was produced. “Glass substrate / ITO (150 nm) / hole injection layer: CLEVIOS® P VP CH8000 (65 nm) / hole transport material (20 nm) / blue light emitting polymer material (65 nm) / Ba (5 nm) / Al ( 100nm) "
  • a cleaning solution HFE7100 (manufactured by 3M), which is a fluorinated solvent, was filled in a brown bottle, and the substrate S1 was immersed in the cleaning solution HFE7100.
  • the brown bottle was placed in an ultrasonic cleaner (BRANSON 2210, manufactured by Yamato Scientific Co., Ltd.) while being immersed, and ultrasonic cleaning was performed for 3 minutes.
  • the substrate S1 was taken out from the brown bottle, and nitrogen was blown onto the solvent attached to the substrate S1 to remove the solvent. These cleaning steps were performed in an air atmosphere.
  • Example 10 An organic electroluminescence element of Example 10 having the following configuration was produced. “Glass substrate / ITO (150 nm) / hole injection layer: CLEVIOS® P VP CH8000 (65 nm) / hole transport material (20 nm) / blue light emitting polymer material (65 nm) / Ba (5 nm) / Al ( 100nm) "
  • Example 11 An organic electroluminescence device of Example 11 having the following configuration was produced. “Glass substrate / ITO (150 nm) / hole injection layer: CLEVIOS® P VP CH8000 (65 nm) / hole transport material (20 nm) / blue light emitting polymer material (65 nm) / Ba (5 nm) / Al ( 100nm) "
  • the cleaning liquid HFE7100 (manufactured by 3M) was filled in a brown bottle, and the substrate S1 was immersed in the cleaning liquid HFE7100.
  • the brown bottle was placed in the ultrasonic cleaner while being immersed, and after ultrasonic cleaning for 3 minutes, the substrate S1 was taken out from the brown bottle.
  • the brown bottle filled with 2-propanol (manufactured by Wako Pure Chemical Industries) was heated to 130 ° C., and the substrate S1 was immersed in the heated 2-propanol for 3 minutes.
  • the substrate S1 was taken out from the brown bottle, and nitrogen was blown onto the solvent attached to the substrate S1 to remove the solvent.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un dispositif organique à électroluminescence équipé d'un substrat, d'une première électrode formée sur le substrat, d'une paroi de séparation formée sur la première électrode et définissant une pluralité de pixels, et d'une couche organique formée sur la première électrode partitionnée par la paroi de séparation. La couche organique est une couche d'injection de charge électrique, une couche de transport de charge électrique ou une couche émettrice de lumière, et à la surface de la couche organique, la quantité de composé de fluor, qui est définie comme étant le rapport de la force ionique du fluor par la force ionique du carbone telle qu'elle est mesurée par spectrométrie de masse du temps de vol des ions secondaires, est réalisée de manière à ne pas être supérieure à 25, ce qui confère une longue durée de vie au dispositif organique à électroluminescence.
PCT/JP2012/053237 2011-02-14 2012-02-13 Dispositif organique à électroluminescence et procédé de fabrication de celui-ci WO2012111595A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011028302 2011-02-14
JP2011-028302 2011-02-14

Publications (1)

Publication Number Publication Date
WO2012111595A1 true WO2012111595A1 (fr) 2012-08-23

Family

ID=46672514

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/053237 WO2012111595A1 (fr) 2011-02-14 2012-02-13 Dispositif organique à électroluminescence et procédé de fabrication de celui-ci

Country Status (3)

Country Link
JP (1) JP2012186157A (fr)
TW (1) TW201244222A (fr)
WO (1) WO2012111595A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9444050B2 (en) 2013-01-17 2016-09-13 Kateeva, Inc. High resolution organic light-emitting diode devices, displays, and related method
US9614191B2 (en) 2013-01-17 2017-04-04 Kateeva, Inc. High resolution organic light-emitting diode devices, displays, and related methods
WO2015005165A1 (fr) * 2013-07-09 2015-01-15 コニカミノルタ株式会社 Film barrière contre les gaz, procédé de fabrication d'élément électroluminescent organique, et élément électroluminescent organique
CN103996697B (zh) 2014-05-16 2016-06-15 京东方科技集团股份有限公司 一种像素单元及其制作方法、显示装置
KR102401987B1 (ko) * 2014-08-01 2022-05-25 올싸거널 인코포레이티드 유기 전자 장치의 포토리소그래피 패터닝
JP2020031070A (ja) * 2019-12-02 2020-02-27 パイオニア株式会社 発光装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281184A (ja) * 2003-03-14 2004-10-07 Sharp Corp パターニングされた薄膜を有する基板、およびその製造方法ならびに有機ｅｌ素子およびその製造方法
JP2007053334A (ja) * 2005-07-20 2007-03-01 Seiko Epson Corp 膜パターンの形成方法、デバイス、電気光学装置、電子機器、及びアクティブマトリクス基板の製造方法
JP2009076290A (ja) * 2007-09-20 2009-04-09 Sekisui Chem Co Ltd 表面処理方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281184A (ja) * 2003-03-14 2004-10-07 Sharp Corp パターニングされた薄膜を有する基板、およびその製造方法ならびに有機ｅｌ素子およびその製造方法
JP2007053334A (ja) * 2005-07-20 2007-03-01 Seiko Epson Corp 膜パターンの形成方法、デバイス、電気光学装置、電子機器、及びアクティブマトリクス基板の製造方法
JP2009076290A (ja) * 2007-09-20 2009-04-09 Sekisui Chem Co Ltd 表面処理方法

Also Published As

Publication number Publication date
JP2012186157A (ja) 2012-09-27
TW201244222A (en) 2012-11-01

Similar Documents

Publication Publication Date Title
JP5417732B2 (ja) 親液撥液パターンの形成方法および有機エレクトロルミネッセンス素子の製造方法
US8278126B2 (en) Method for manufacturing organic electroluminescence device
JP4852008B2 (ja) 有機エレクトロルミネッセンス素子の製造方法
WO2009122876A1 (fr) Élément électroluminescent organique et procédé de fabrication associé
KR101690806B1 (ko) 유기 전계 발광 소자용 잉크젯 잉크 및 유기 전계 발광 소자의 제조 방법
KR20120043012A (ko) 유기 전계발광 소자
KR20100053534A (ko) 유기 전계발광 장치의 제조 방법
WO2012111595A1 (fr) Dispositif organique à électroluminescence et procédé de fabrication de celui-ci
JP2009238694A (ja) 有機エレクトロルミネッセンス素子およびその製造方法
WO2010024136A1 (fr) Élément électroluminescent organique et son procédé de fabrication
WO2011096509A1 (fr) Élément organique électroluminescent, son procédé de production, et dispositif pour la production d'un tel élément
JP3923038B2 (ja) 有機ｅｌ発光表示装置及びその製造方法
JP2010147180A (ja) 有機エレクトロルミネッセンス素子の製造方法
JP2010129345A (ja) 有機エレクトロルミネッセンス素子の製造方法
JP2010080308A (ja) 有機エレクトロルミネッセンス素子
JP5036680B2 (ja) 有機エレクトロルミネッセンス素子の製造方法
JP2012028338A (ja) 有機エレクトロルミネッセンス素子およびその製造方法
JP5314395B2 (ja) 有機エレクトロルミネッセンス素子の製造方法
JP2010087346A (ja) 有機エレクトロルミネッセンス素子、およびその製造方法
JP2009044102A (ja) 有機エレクトロルミネッセンス素子及び製造方法
JP5184938B2 (ja) 有機エレクトロルミネッセンス素子及びその製造方法
WO2013024885A1 (fr) Procédé de fabrication d'un élément d'électroluminescence organique
JP2010238509A (ja) 有機エレクトロルミネッセンス素子の製造方法
JP6945983B2 (ja) 有機ｅｌデバイス、表示素子及び有機ｅｌデバイスの製造方法
JP2010027539A (ja) 有機エレクトロルミネッセンス素子およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12747037

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12747037

Country of ref document: EP

Kind code of ref document: A1