WO2018193822A1 - Dispositif électronique et son procédé de production - Google Patents

Dispositif électronique et son procédé de production Download PDF

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Publication number
WO2018193822A1
WO2018193822A1 PCT/JP2018/014088 JP2018014088W WO2018193822A1 WO 2018193822 A1 WO2018193822 A1 WO 2018193822A1 JP 2018014088 W JP2018014088 W JP 2018014088W WO 2018193822 A1 WO2018193822 A1 WO 2018193822A1
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Prior art keywords
electrode
layer
substrate
forming
extraction
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PCT/JP2018/014088
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English (en)
Japanese (ja)
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有章 志田
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コニカミノルタ株式会社
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/06—Electrode terminals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode

Definitions

  • the present invention relates to an electronic device and a method for manufacturing the electronic device.
  • Organic electroluminescence panels (hereinafter, referred to as “organic EL panels”) are attracting attention for their advantages such as less viewing angle dependency, higher contrast ratios, and thinner films compared to liquid crystal display devices. R & D is being conducted in various places.
  • organic electroluminescence elements such as organic EL panels (hereinafter referred to as “organic EL elements”) are used for large-sized televisions due to their high visibility in addition to portable displays and portable rear displays.
  • the product development in the flat panel display field has been spurred, such as the use of the product is expected, and a part of the launch plan is reported.
  • organic EL elements are self-luminous light sources and surface-emitting light sources, they are in the limelight as next-generation lighting and are being developed in various places as organic EL lighting.
  • the organic EL illumination can freely change the emission color and the emission color intensity by forming RGB emission materials between the electrodes and finely adjusting the RGB emission output.
  • the white color required for illumination can be freely formed from a light bulb color such as 2000K or 3000K to a daylight white color such as 5000K or 6000K.
  • organic EL lighting is also likely to achieve luminous efficiency equivalent to or exceeding that of LEDs and fluorescent lamps by using phosphorescent materials, and development as thinning lighting is expected.
  • an ITO film is often used for the anode electrode (anode), but it is necessary to form the ITO film by a high temperature process.
  • anode electrode anode
  • the development of organic EL elements using flexible substrates has attracted attention.
  • a flexible substrate is inferior in heat resistance, it is necessary to form electrodes by a low-temperature process.
  • a decrease in luminance or a decrease in luminance uniformity may occur due to the high electric resistance of the electrode film.
  • Patent Document 1 discloses a transparent electrode having a low-resistance conductive layer mainly composed of silver and an organic EL element using the transparent electrode.
  • Patent Document 2 discloses a zinc oxide transparent electrode excellent in conductivity and an organic EL element using the same.
  • the extraction electrode for connecting to an external drive circuit is installed in the anode electrode (anode) and the cathode electrode (cathode) of the organic EL element.
  • the anode electrode and its extraction electrode, and the cathode electrode and its extraction electrode are electrically connected within the organic EL element.
  • the extraction electrodes of the anode electrode and the cathode electrode are connected to a driving circuit such as an IC by wiring using, for example, FPC or Ag paste.
  • the present invention has been made in view of the above problems. That is, the subject of this invention is providing the electronic device which suppressed that the function expression area shrunk with time, and its manufacturing method.
  • the present inventors have made various studies in order to solve the above problems. As a result, it has been found that the intrusion of moisture through the extraction electrode can be blocked by electrically connecting the electrode of the electronic device and the extraction electrode through a connection member without directly connecting them, and the above problem can be solved.
  • the invention has been reached.
  • the present invention has the following configuration. (1) An electronic device having a first electrode, at least one functional layer, a second electrode, a first electrode extraction electrode, and a second electrode extraction electrode on a substrate, wherein the first electrode, The functional layer and the second electrode are stacked in this order on the substrate, and the first electrode and the take-out electrode of the first electrode are disposed on the substrate with a gap therebetween, The electronic device in which the first electrode and the take-out electrode of the first electrode are electrically connected via a first connection member disposed between the first electrode and the extraction electrode of the first electrode.
  • the second electrode and the extraction electrode of the second electrode are arranged on the substrate with a space therebetween, and the extraction electrode of the second electrode and the second electrode is between them.
  • An electronic device comprising: a step of forming a take-out electrode; a step of forming a take-out electrode of the second electrode; and a step of forming a first connecting member for connecting the first electrode and the take-out electrode of the first electrode.
  • a step of forming a second electrode on the functional layer after performing a step of forming at least one functional layer on the first electrode and a step of forming an extraction electrode of the first electrode The method of manufacturing an electronic device according to (9), wherein the step of forming the first connecting member and the first connecting member are performed at the same time or one of them.
  • the present invention can provide an electronic device in which the functional expression area is prevented from shrinking over time.
  • an organic EL element used as organic EL lighting will be described as a representative example of an electronic device.
  • FIG. 1 is a schematic plan view of a conventional organic EL element.
  • FIG. 3 is a schematic cross-sectional view of a conventional organic EL element.
  • FIG. 3 is a schematic cross-sectional view taken along line III-III in FIG.
  • the organic EL element 1 includes a first electrode 3, at least one functional layer 4, a second electrode 5, a first electrode extraction electrode 6, a second electrode extraction electrode 7, and a sealing layer 8 on a substrate 2.
  • the sealing material 9 is included.
  • the first electrode 3, the functional layer 4 and the second electrode 5 are stacked on the substrate 2 in this order.
  • the functional layer 4 is not shown because it substantially overlaps with the second electrode 5.
  • the sealing layer 8 is not shown because it substantially overlaps with the sealing material 9.
  • the first electrode 3 and the second electrode 5 are a pair of electrodes for applying a charge to the at least one functional layer 4 and sending an electric signal. Which of the first electrode 3 and the second electrode 5 is an anode electrode (anode) or a cathode electrode (cathode) can be selected as appropriate, and either may be an anode electrode (anode). In the following description, it is assumed that the first electrode 3 as the lower electrode is an anode electrode and the second electrode 5 as the upper electrode is a cathode electrode.
  • the first electrode 3 and the second electrode 5 are connected to the first electrode extraction electrode 6 and the second electrode extraction electrode 7 for connection to an external drive circuit.
  • the first electrode extraction electrode 6 and the second electrode extraction electrode 7 are both exposed to the outside of the sealing layer 8.
  • “the extraction electrode of the first electrode” is simply referred to as “first extraction electrode”.
  • “extraction electrode of the second electrode” is simply described as “second extraction electrode”.
  • the first extraction electrode 6 and the first electrode 3 are in direct physical contact with each other in structure and are also electrically connected. Further, the second extraction electrode 7 and the second electrode 5 are physically in direct contact with each other in structure and are also electrically connected.
  • the first electrode 3 and the first extraction electrode 6 are directly connected in the conventional organic EL element 1, the first extraction electrode 6 and the sealing layer exposed to the outside are exposed. It has been confirmed that moisture penetrates into the organic EL element 1 through the interface with 8 or the interface between the first extraction electrode 6 and the substrate 2. Further, when the second electrode 5 and the second extraction electrode 7 are directly connected, the interface between the second extraction electrode 7 and the sealing layer 8 exposed to the outside, or between the second extraction electrode 7 and the substrate 2. It was confirmed that moisture penetrates into the organic EL element 1 through the interface.
  • invaded into the inside of the organic EL element 1 deteriorates the 1st electrode 3, the functional layer 4, and the 2nd electrode 5 which consist of a metal thin film, and shrinks (decreases) the function expression areas, such as light emission. It was found to cause the phenomenon.
  • FIG. 5 and 6 are schematic diagrams for explaining that the light emitting area shrinks with time.
  • the hatched area represents the light emitting area.
  • FIG. 5 shows the light emitting region of the organic EL element before the light emitting area shrinks over time
  • FIG. 6 shows the light emitting region of the organic EL element after the light emitting area shrinks over time. It can be seen that at the position indicated by 20 in FIG. 6, the light emitting region is reduced at a position inside from the outer end of the organic EL element.
  • the present inventors have studied various solutions for the problem that the functional expression area shrinks with time.
  • the first electrode 3 and the first extraction electrode 6 are not directly connected, but are electrically connected via the connection member, thereby blocking moisture intrusion through the first extraction electrode 6, I found out that it can be resolved.
  • the second electrode 5 and the second extraction electrode 7 are not directly connected, but are electrically connected via another connection member, thereby blocking moisture intrusion through the second extraction electrode 7.
  • the present inventors have found that the above problems can be solved.
  • FIG. 2 is a schematic plan view of the organic EL element 1 of the present embodiment.
  • FIG. 4 is a schematic cross-sectional view of the organic EL element 1 of the present embodiment. 4 is a schematic cross-sectional view taken along line IV-IV in FIG.
  • the organic EL element 1 includes a first electrode 3, at least one functional layer 4, a second electrode 5, a first extraction electrode 6, a second extraction electrode 7, a sealing layer 8, and a sealing material on a substrate 2. 9, a first connecting member 10 and a second connecting member 11 are provided.
  • the first electrode 3, the functional layer 4 and the second electrode 5 are stacked on the substrate 2 in this order.
  • the functional layer 4 is not shown because it substantially overlaps the second electrode 5.
  • the sealing layer 8 is not shown because it substantially overlaps with the sealing material 9.
  • the first electrode 3 and the first extraction electrode 6 are disposed on the substrate 2 with a gap. For this reason, the first electrode 3 and the first extraction electrode 6 are not directly and electrically connected to each other.
  • the 1st electrode 3 and the 1st extraction electrode 6 are electrically connected through the 1st connection member 10 which is an electroconductive raw material installed between both.
  • the first connection member 10 is a connection wiring that bridges the first electrode 3 and the first extraction electrode 6.
  • the first connecting member 10 is in direct contact with the substrate 2 between the first electrode 3 and the first extraction electrode 6.
  • first connection member 10 Since the first connection member 10 is installed between the first electrode 3 and the first extraction electrode 6, moisture entering from the outside through the interface passage around the first extraction electrode 6 is first The passage is blocked by the presence of the connecting member 10. In addition, it is difficult for moisture to go around the first connecting member 10. Therefore, the moisture is prevented from reaching the first electrode 3.
  • the first connecting member 10 is between the first electrode 3 and the first extraction electrode 6 and is in direct contact with the substrate 2. Therefore, by using a material having better adhesion to the substrate 2 than the first extraction electrode 6 as a material of the first connection member 10, moisture can be further prevented from entering at the interface between the first connection member 10 and the substrate 2. It becomes possible to prevent further.
  • Al and glass form an interface with excellent adhesion, so that it is excellent in blocking moisture and the light emitting region is shrunk. Can be effectively delayed.
  • the second electrode 5 and the second extraction electrode 7 are disposed on the substrate 2 with a gap therebetween. For this reason, the second electrode 5 and the second extraction electrode 7 are not directly and electrically connected to each other.
  • the 2nd electrode 5 and the 2nd extraction electrode 7 are electrically connected via the 2nd connection member 11 which is an electroconductive material installed between both.
  • the second connection member 11 is a connection wiring that bridges the second electrode 5 and the second extraction electrode 7.
  • the second connecting member 11 is in direct contact with the substrate 2 between the second electrode 5 and the second extraction electrode 7.
  • the second connecting member 11 Since the second connecting member 11 is installed between the second electrode 5 and the second extraction electrode 7, moisture entering from the outside through the interface passage around the second extraction electrode 7 is second The passage is blocked by the presence of the connecting member 11. In addition, it is difficult for moisture to go around the second connection member 11. Therefore, the moisture is prevented from reaching the second electrode 5.
  • the second connection member 11 is between the second electrode 5 and the second extraction electrode 7 and is in direct contact with the substrate 2. Therefore, by using a material having better adhesion to the substrate 2 than the second electrode 5 as the material of the second connection member 11, moisture can be further infiltrated at the interface between the second connection member 11 and the substrate 2. It becomes possible to stop. For example, when glass is used as the substrate 2 and Al is used as the first connection member 10, it is effective as described above.
  • the time for delaying the occurrence of shrinking is such that the interval between the first electrode 3 and the first extraction electrode 6 and the interval between the second electrode 5 and the second extraction electrode 7 are increased, and the first connection member existing between the electrodes. 10 and the second connecting member 11 can be lengthened by increasing the distance between the portions in contact with the substrate 2.
  • Shrink resistance can be controlled by changing this distance according to the required quality of the organic EL element 1.
  • substrate 2 As the substrate 2, an inorganic glass plate, a Si substrate, an organic resin film, or the like can be used, and a transparent material is preferable.
  • the glass plate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • a preferred substrate 2 is a resin film that can give flexibility to the organic EL panel.
  • Examples of the resin of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC ), Cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PES polyethersulfone
  • PES polyetherimide
  • polyetherketone polyphenylene sulfide
  • PC polycarbonate
  • TAC Cellulose triacetate
  • CAP cellulose acetate propionate
  • the substrate 2 preferably has a barrier layer formed on at least one surface thereof.
  • the material for forming the barrier layer may be any material that has a function of suppressing intrusion of moisture, oxygen, or the like that degrades the organic EL element, and includes an inorganic substance, an organic substance, or a hybrid of these.
  • an inorganic material such as polysilazane, SiO 2 , Si 3 N 4 , Al 2 O 3 , TiO 2 , SiOxCy, or SiOxNy is used.
  • the barrier layer preferably has a laminated structure.
  • the laminated structure can be formed, for example, by alternately laminating inorganic layers and organic layers a plurality of times.
  • a method for forming the barrier layer for example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD (Chemical Vapor Deposition) method, laser CVD method, thermal CVD method, coating method and the like.
  • Examples of the flexible substrate having a barrier layer include a high barrier base material in which a barrier layer such as a layer containing polysilazane is formed on a polyethylene terephthalate (PET) film.
  • a barrier layer such as a layer containing polysilazane is formed on a polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • the surface of the substrate 2 may be subjected to a surface treatment such as imparting easy adhesion to ensure the wettability and adhesion of the coating solution.
  • a surface treatment such as imparting easy adhesion to ensure the wettability and adhesion of the coating solution.
  • the surface treatment include surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • an easy-adhesive layer is formed by applying polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, epoxy copolymer, etc. Also good.
  • the thickness of the substrate 2 is not particularly limited, but is preferably 10 to 200 ⁇ m. When the thickness of the substrate is within this range, the substrate is excellent in mechanical strength and flexible. A more preferable upper limit of the thickness of the substrate is 150 ⁇ m, and a more preferable lower limit is 20 ⁇ m.
  • the material of the first electrode 3 is not particularly limited as long as it is an inorganic metal material having low resistance.
  • the material used for the first electrode 3 include metals such as Al, Ag, Au, Ti, Mo, Ni, and W, or alloys thereof, ITO, IZO, IWZO, AZO, BZO, and SnO 2 .
  • metal oxides or laminates thereof examples include metal oxides or laminates thereof.
  • Ag, ITO, and IZO are preferable, and Ag is more preferably used.
  • the first electrode 3 can be formed using the above-mentioned material by a method such as a vapor deposition method or a sputtering method.
  • the first electrode 3 is formed by patterning an electrode material film into a desired shape. In the case where emitted light is extracted from the first electrode 3 side, it is desirable that the transmittance be greater than 10%.
  • the sheet resistance as the first electrode 3 is several hundred ⁇ / sq. The following is preferred.
  • the thickness of the first electrode 3 is usually in the range of 10 nm to 1 ⁇ m, preferably 10 to 300 nm, although it depends on the material.
  • the first electrode 3 When a layer composed mainly of Ag is formed as the first electrode 3, another conductive layer containing Pd or the like, an organic functional layer such as a nitrogen compound or a sulfur compound, and the underlayer of the first electrode 3 are used. You may form as.
  • the base layer By forming the base layer, it is possible to improve the film formation of the layer composed mainly of Ag, to reduce the resistivity of the first electrode, and to improve the light transmittance of the first electrode 3.
  • the underlayer includes an organic compound containing a nitrogen atom, Pd, Mo, Zn, Ge, Nb or In, an alloy of these metals with another metal, an oxide or sulfide of these metals (for example, , ZnS).
  • the underlayer may contain only one kind or two or more kinds.
  • the underlayer preferably contains Pd or Mo.
  • the organic compound containing a nitrogen atom constituting the underlayer is not particularly limited as long as it is a compound containing a nitrogen atom in the molecule, but is preferably a compound having a heterocycle having a nitrogen atom as a heteroatom.
  • the heterocycle having a nitrogen atom as a hetero atom include aziridine, azirine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepan, azepine, imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, Examples include isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline
  • the amount of the metal contained in the underlayer is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more.
  • the base layer contains an organic compound containing a nitrogen atom or 20% by mass or more of the above metal, the affinity between the base layer and the conductive layer increases, and the adhesion between the base layer and the conductive layer tends to increase.
  • the metal that forms an alloy with Pd, Mo, Zn, Ge, Nb, or In is not particularly limited.
  • a Pt group other than Pd, Au, Co, Ni, Ti, Al, Cr, or the like can be used.
  • the underlayer is preferably a layer formed by vapor deposition or sputtering.
  • the vapor deposition method includes a vacuum vapor deposition method, an electron beam vapor deposition method, an ion plating method, an ion beam vapor deposition method and the like.
  • the deposition time is appropriately selected according to the desired thickness of the underlying layer and the formation speed.
  • the material of the second electrode 5 is not particularly limited as long as it is an inorganic metal material with low resistance.
  • the material used for the second electrode include metals such as Al, Ti, Ni, Cr, Ag, and Au, or alloys thereof, metal oxides such as ITO, IZO, IWZO, AZO, BZO, and SnO 2 . Or a laminate thereof.
  • Al and Ag are preferable, and Al is more preferably used.
  • the second electrode 5 can be formed by depositing the electrode material using a method such as vapor deposition or sputtering.
  • the second electrode 5 is formed by patterning an electrode material film into a desired shape. In the case where emitted light is extracted from the second electrode 5 side, it is desirable that the transmittance be greater than 10%.
  • the sheet resistance of the second electrode 5 is several tens of ohms / sq. The following is preferred.
  • the thickness of the second electrode 5 is usually in the range of 10 nm to 5 ⁇ m, preferably 50 to 300 nm.
  • the material used for the extraction electrodes 6 and 7 is not particularly limited as long as it is an inorganic metal material with low resistance.
  • materials used for the extraction electrodes 6 and 7 include metals such as Al, Ag, Au, Ti, Mo, Ni, W, and Nb, or alloys thereof, or ITO, IZO, IWZO, AZO, BZO, and SnO 2. And metal oxides such as these, or a laminate thereof.
  • Al and Al system material are used preferably.
  • a laminate having a three-layer structure such as Mo / Al / Mo is also used.
  • the method for forming the extraction electrodes 6 and 7 includes a sputtering method and a vapor deposition method, and is not particularly limited.
  • the material is appropriately selected according to the material used for the extraction electrodes 6 and 7 and the shape of the extraction electrode.
  • the extraction electrodes 6 and 7 are formed by patterning the conductive layer into a desired shape.
  • the electrical resistance of the extraction electrodes 6 and 7 is preferably 100 ⁇ or less, for example, the electrical resistance of the functional layer 4 to the light emitting layer.
  • the material of the extraction electrodes 6 and 7 is selected so that the resistance becomes low, and the shape is formed.
  • the thickness of the extraction electrodes 6 and 7 is usually in the range of 10 nm to 5 ⁇ m, preferably 50 to 300 nm.
  • connection members 10 and 11 is not particularly limited as long as it is an inorganic metal material with low resistance.
  • the material used for the first electrode 3 include metals such as Al, Ag, Au, Ti, Mo, Ni, and W, or alloys thereof, ITO, IZO, IWZO, AZO, BZO, and SnO 2 . Examples thereof include metal oxides or laminates thereof.
  • a material having better adhesion to the substrate 2 than the second electrode 5 as the material of the connection members 10 and 11.
  • Examples of such a material having excellent adhesion to the substrate 2 include Al.
  • the second electrode 5 and the first connecting member 10 are formed of the same material because both can be formed simultaneously. Examples of such the same material include Al.
  • the method for forming the connection members 10 and 11 includes a sputtering method and a vapor deposition method, and is not particularly limited.
  • the material is appropriately selected according to the material used for the connection members 10 and 11 and the shape of the extraction electrode.
  • the connection members 10 and 11 are formed by patterning the conductive layer into a desired shape.
  • the thickness of the connecting members 10 and 11 is usually in the range of 10 nm to 5 ⁇ m, preferably 50 to 300 nm.
  • the light emitting unit corresponds to the functional layer 4. Therefore, in the following, the light emitting unit will be described as an example.
  • the light emitting unit is provided between the first electrode 3 and the second electrode 5 and includes at least one light emitting layer including an organic material having a light emitting property.
  • Typical element configurations of the light emitting unit include the following configurations, but are not limited thereto. (1) Hole injection transport layer / light emitting layer / electron injection transport layer (2) Hole injection transport layer / light emitting layer / hole blocking layer / electron injection transport layer (3) Hole injection transport layer / electron blocking layer / Light emitting layer / hole blocking layer / electron injecting and transporting layer (4) hole injecting layer / hole transporting layer / light emitting layer / electron transporting layer / electron injecting layer (5) hole injecting layer / hole transporting layer / light emitting layer / Hole blocking layer / electron transport layer / electron injection layer (6) hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / electron injection layer
  • the light emitting layer is formed of a single layer or multiple layers.
  • an intermediate connector layer may be provided between the light emitting layers.
  • the electron transport layer is a layer having a function of transporting electrons.
  • the electron transport layer includes an electron injection layer and a hole blocking layer in a broad sense. Further, the electron transport layer may be composed of a plurality of layers.
  • the hole transport layer is a layer having a function of transporting holes.
  • the hole transport layer includes a hole injection layer and an electron blocking layer in a broad sense.
  • the hole transport layer may be composed of a plurality of layers.
  • each layer constituting these light emitting units conventionally known materials and forming methods can be used.
  • the layer thickness of the individual layers included in each light emitting unit is not particularly limited.
  • the thickness of each layer is within the range of 5 to 200 nm from the viewpoint of the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color with respect to the drive current. It is preferable to adjust, and more preferably in the range of 10 to 100 nm or less.
  • the light emitting layer is a layer including a light emitting organic semiconductor thin film that provides a field in which electrons and holes injected from an electrode or an adjacent layer are recombined to emit light via excitons.
  • the light-emitting layer preferably contains a light-emitting dopant (a light-emitting dopant compound, a dopant compound, also simply referred to as a dopant) and a host compound (a matrix material, a light-emitting host compound, also simply referred to as a host).
  • the method for forming the light emitting layer is not particularly limited, and can be formed by a conventionally known method such as a vacuum deposition method or a wet method. It is preferable to form by a wet method from the manufacturing cost of an organic EL element.
  • a fluorescent luminescent dopant also referred to as a fluorescent dopant or a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent dopant or a phosphorescent compound
  • the concentration of the light-emitting dopant in the light-emitting layer can be arbitrarily determined based on the specific dopant used and the device requirements.
  • the concentration of the light emitting dopant may be contained at a uniform concentration in the thickness direction of the light emitting layer, or may have an arbitrary concentration distribution.
  • the light emitting layer may contain a plurality of kinds of light emitting dopants.
  • dopants having different structures may be used in combination, or a fluorescent light emitting dopant and a phosphorescent light emitting dopant may be used in combination. Thereby, arbitrary luminescent colors can be obtained.
  • sealing layer examples of the sealing member in the present embodiment include a sealing layer 8 and a sealing material 9 described below.
  • the sealing layer 8 has a barrier property, and is for isolating and sealing the inside of the organic EL element 1 on the substrate 2 from the outside.
  • a material constituting the sealing layer 8 there are an inorganic material and an organic material.
  • the inorganic material include SiN, SiC, SiOC, SiOCN, and DLC.
  • organic material include epoxy resin, acrylic resin, silicone resin, urea resin, melamine resin, phenol resin, resorcinol resin, unsaturated polyester resin, polyurethane resin, etc. Examples thereof include a curable resin and a photocurable resin.
  • the SiN film is a hard film, it is effective in preventing physical damage when the first electrode, the second electrode, the first extraction electrode, the second extraction electrode, and the like are thin.
  • the SiN film is also effective as a sealing film that prevents moisture from entering. Therefore, it is preferable to form so that the whole organic EL element 1 on the board
  • the SiN film is usually formed by a CVD method with a thickness of 200 nm to 10 ⁇ m, more preferably with a thickness of 500 nm to 2 ⁇ m.
  • the sealing material 9 has a barrier property, and is for isolating and sealing the inside of the organic EL element 1 on the substrate 2 from the outside. It is formed or installed on the sealing layer 8.
  • a flat sealing material is usually used. Since the flat sealing material 9 is made of the same material as the substrate 2, the sealing material 9 and the substrate 2 are not distinguished from each other and can be used for any purpose. Moreover, in order to adhere
  • Examples of the flat sealing material 9 include a resin film having a barrier layer. Since the specific description has already been made on the substrate 2, the description is omitted.
  • a specific example of the resin film having a barrier layer is an Al-deposited PET film having a thermosetting adhesive layer. An Al vapor-deposited PET film having a thermosetting adhesive layer can be placed on the sealing layer 8 and heat-cured to be brought into close contact with the sealing layer 8.
  • the organic EL element 1 of the present embodiment can be manufactured by a manufacturing method having the following steps.
  • (A) Step of forming first electrode on substrate (b) Step of forming at least one functional layer on first electrode (c) Step of forming second electrode on functional layer (d) Step of forming first extraction electrode (e) Step of forming second extraction electrode (f) Step of forming first connection member (g) Step of forming second connection member
  • steps will be described below. .
  • substrate 2 is preferably removed from foreign matters and contaminants by wet cleaning.
  • a wet cleaning method for example, there is a method in which a substrate is immersed in a heated cleaning solution containing a neutral detergent, scrubbed with a brush, and subjected to ultrasonic cleaning, nitrogen blowing, and drying.
  • the cleaning method is not particularly limited, and a known method can be appropriately used.
  • the first electrode 3 is formed by using an electrode material such as a vacuum deposition method or a sputtering method.
  • the first electrode 3 is formed by patterning an electrode film into a desired shape.
  • the method for forming the pattern is not particularly limited, and a known method such as a photolithography method, a mask patterning method, or a laser ablation method can be used.
  • the underlayer can be formed by vapor deposition or sputtering. As described above, the underlayer is also patterned in a predetermined shape using a known method such as a photolithography method, a mask patterning method, or a laser ablation method. Usually, the pattern of the underlayer is almost the same as the pattern of the first electrode 3.
  • Step B Step of forming at least one functional layer on the first electrode A functional layer is formed on the first electrode formed in the above step.
  • a method for forming the functional layer an appropriate method is used depending on the configuration of the functional layer.
  • a gas phase method is used.
  • the vapor phase method include a vapor deposition method, a sputtering method, an ion plating method, a CVD method, and a molecular beam epitaxy method, and a vapor deposition method, a sputtering method, and a CVD method are common.
  • the pattern formation of the functional layer is usually performed by a known method such as a photolithography method, a mask patterning method, or a laser ablation method.
  • the process of forming a 2nd electrode on a functional layer The 2nd electrode 5 is formed on the functional layer formed at the said process.
  • the second electrode 5 is formed by using an electrode material such as a vacuum deposition method or a sputtering method.
  • the other description is the same as (a) the step of forming the first electrode on the substrate, and the description is omitted.
  • the first extraction electrode 6 is formed using a method such as sputtering or vapor deposition.
  • the extraction electrode 6 is formed by patterning a formed conductive film into a desired shape.
  • the method for forming the pattern is not particularly limited, and a known method such as a photolithography method, a mask patterning method, or a laser ablation method can be used.
  • Step of forming second extraction electrode The second extraction electrode 7 is formed using a method such as sputtering or vapor deposition.
  • the other description is the same as (d) the step of forming the take-out electrode of the first electrode, and the description is omitted.
  • the first connection member 10 is formed using a method such as a sputtering method or a vapor deposition method.
  • the first connection member 10 is formed by patterning the formed conductive film into a desired shape.
  • the method for forming the pattern is not particularly limited, and a known method such as a photolithography method, a mask patterning method, or a laser ablation method can be used.
  • Step of forming second connection member The second connection member 11 is formed using a method such as a sputtering method or a vapor deposition method.
  • the other description is the same as (f) the step of forming the first connecting member, and the description is omitted. This step is performed as necessary.
  • a step of forming a first electrode on the substrate (b) a step of forming at least one functional layer on the first electrode, (c) a second on the functional layer.
  • the process of forming an electrode is performed in this order.
  • the step (f) forming the first connection member is performed.
  • a step of forming a second connecting member is performed after the step of forming the second extraction electrode.
  • a step of forming at least one functional layer on the first electrode and (d) forming a first extraction electrode After performing the step, (c) the step of forming the second electrode on the functional layer and (f) the step of forming the first connecting member can be performed simultaneously or one of them. If (c) the step of forming the second electrode on the functional layer and (f) the step of forming the first connecting member can be performed simultaneously, the process can be simplified.
  • the order of each step is not particularly limited. The order can be changed as necessary. For example, either (a) the step of forming the first electrode on the substrate or (d) the step of forming the first extraction electrode may be performed first. Similarly, either (a) the step of forming the first electrode on the substrate and (e) the step of forming the second extraction electrode may be performed first. Further, the steps (a) to (g) can be performed in the following order: (d) step ⁇ (e) step ⁇ (a) step ⁇ (b) step ⁇ (c) step ⁇ (f) Process-> (g) process.
  • the organic EL element has been described as a representative example of the electronic device, but the same applies to other electronic devices.
  • Specific examples of other electronic devices include solar cells, organic transistors, and organic sensors.
  • Example 1 A transparent glass substrate containing no alkali was used as the substrate.
  • the surface of the substrate was cleaned by a wet cleaning method.
  • the conditions for wet cleaning are as follows.
  • the alkaline detergent was diluted to 5% and heated to 60 ° C.
  • the substrate was immersed in the detergent solution, and the foreign matter on the substrate surface was removed by scrub cleaning.
  • the substrate was subjected to ultrasonic (ultrasonic) cleaning, rinsed with pure water, blown with nitrogen, and dried by infrared rays. Further, UV irradiation was performed to remove organic substances on the substrate surface. Thereafter, the substrate was dried in an oven at about 90 ° C. to obtain a substrate for forming an organic EL panel.
  • a film of the first extraction electrode and the second extraction electrode was formed on the substrate by sputtering.
  • a material for the extraction electrode MoNb was used, and the film was formed to a thickness of 300 nm so that the electrical resistance to the light emitting layer was 100 ⁇ or less.
  • the first extraction electrode and the second extraction electrode were patterned by a photolithography method. Specifically, in order to form a pattern, a resist film was formed and an etching process was performed to form a first extraction electrode and a second extraction electrode having a predetermined shape.
  • a base layer having a predetermined shape was formed by vacuum vapor deposition using a mask. That is, as the underlayer, an organic compound containing nitrogen atoms containing 20% Mo was formed with a thickness of 15 nm.
  • a first electrode was formed as an Ag film having a thickness of 10 nm on the underlayer by a vacuum deposition method using the same mask as the underlayer.
  • film formation was performed using a mask having a predetermined shape so that the first extraction electrode and the first electrode were not in direct contact with each other.
  • a vapor deposition shadow (deposition film formed on the shadow portion of the mask) is formed, so that the vapor deposition shadow and the first extraction electrode do not contact each other.
  • the film was formed at a large distance.
  • the first extraction electrode can obtain a high pattern accuracy by a photolithography method, but a vapor deposition shadow is formed by a vacuum vapor deposition method using a mask.
  • the film formation tolerance is calculated based on the relationship between the relative position of the mask and the evaporation source and the evaporation beam, and the same tolerance + photolithography tolerance + alignment tolerance.
  • the first electrode was formed with a larger distance than the first electrode.
  • the tolerance of photolithography is ⁇ 3 ⁇ m
  • the tolerance of alignment is ⁇ 5 ⁇ m
  • the mask forming tolerance and the mask attaching tolerance in the deposition using the mask are 50 ⁇ m
  • the deposition tolerance due to the Ag film wrapping around the mask is used. 200 ⁇ m was assumed.
  • the first extraction electrode and the first electrode were formed with an interval (space) of 1000 ⁇ m. By providing such an interval, it was confirmed that the first extraction electrode and the first electrode were not electrically and physically connected.
  • a light emitting unit was formed on the first electrode by a vacuum deposition method.
  • the configuration of the light emitting unit is as follows.
  • a light emitting unit including a light emitting layer (hole transport / injection layer, light emitting layer, hole blocking layer, electron transport / injection layer) is placed on the first electrode as follows. Sequentially formed.
  • ⁇ Hole transport / injection layer> A hole transport / injection layer that serves both as a hole injection layer and a hole transport layer made of ⁇ -NPD, heated by energizing a heating boat containing ⁇ -NPD represented by the following structural formula as a hole transport injection material was formed on the first electrode. At this time, the deposition rate was 0.1 nm / second to 0.2 nm / second, and the film thickness was 20 nm.
  • the heating boat containing the host material H4 represented by the following structural formula and the heating boat containing the phosphorescent compound Ir-4 represented by the following structural formula were respectively energized independently, and the host material H4 and phosphorescent light emission were emitted.
  • the light emitting layer made of the active compound Ir-4 was formed on the hole transport / injection layer.
  • the thickness of the light emitting layer was 30 nm.
  • a heating boat containing BAlq represented by the following structural formula as a hole blocking material was energized and heated to form a hole blocking layer made of BAlq on the light emitting layer.
  • the deposition rate was 0.1 nm / second to 0.2 nm / second, and the thickness of the hole blocking layer was 10 nm.
  • a second electrode was formed on the light emitting unit.
  • the second electrode was formed as a 200 nm thick Al film by vacuum deposition using a mask.
  • a mask having not only an opening for forming the second electrode but also an opening for forming the first connection member was used as the mask. By using such a mask, the second electrode and the first connecting member could be formed simultaneously.
  • the mask forming the first connection member had an opening having a width of 1000 ⁇ m or more between the first extraction electrode and the first electrode. Further, the deposited film covers an area larger than the opening by the wraparound of the mask. Therefore, it was confirmed that the first connection member can form a structure in which the first electrode and the first extraction electrode are bridge-wired, and are electrically and physically connected.
  • the first connecting member is formed between the first extraction electrode and the first electrode, and is formed so as to be in contact with the substrate between the first extraction electrode and the first electrode.
  • thermosetting adhesive layer was attached onto the sealing layer and was thermoset.
  • the specific operation is as follows. In an N 2 environment of about 5 Pa, the Al-deposited PET film was attached with a low vacuum and pressed with a roller so that the thermosetting adhesive layer and the sealing layer (SiN film) were in close contact with each other. Thereafter, the thermosetting adhesive layer of the Al-deposited PET film was cured by a heat treatment at 110 ° C. for 30 minutes, and a sealing treatment with a sealing material was performed to obtain an organic EL element. In this embodiment, the step of forming the first connection member is performed, but the step of forming the second connection member is not performed.
  • Example 2 An organic EL device was obtained in the same manner as in Example 1 except for the following.
  • a barrier film having a surface containing the polysilazane described above was used as the substrate.
  • the barrier film was previously removed from foreign matters and contaminants by wet cleaning.
  • the conditions for wet cleaning are as follows. An aqueous solution containing 5% neutral detergent was prepared and heated to 60 ° C. The substrate was immersed in the detergent solution, and foreign matters on the substrate surface were removed by scrub cleaning with a brush. Next, the substrate was subjected to ultrasonic cleaning (ultrasonic), blown with nitrogen, and dried by infrared rays. Thereafter, the substrate was dried in an oven at about 90 ° C. to obtain a substrate for producing an organic EL element.
  • ultrasonic cleaning ultrasonic
  • the barrier film was introduced into a vacuum apparatus, and in the same manner as in Example 1, using Mo as the first extraction electrode, a film having a thickness of 300 nm was formed by sputtering. Thereafter, a pattern was formed by a photolithography method. At that time, phosphoric acid was used for etching, and tetramethylammonium hydroxide (TMAH) was used for development.
  • TMAH tetramethylammonium hydroxide
  • Example 2 an underlayer and a first electrode (Ag film) were formed by vacuum deposition.
  • the distance between the first extraction electrode and the first electrode is set to 1.5 mm (1500 ⁇ m), and the physical contact between the electrodes is performed. I tried to avoid it.
  • Example 2 a light emitting unit was formed on the first electrode, and a second electrode was formed on the light emitting unit. Thereafter, an SiN film sealing layer having a thickness of 500 nm was formed on each layer by CVD, and further sealed in the same manner using an Al-deposited PET film to obtain an organic EL element.
  • the step of forming the first connection member is performed, but the step of forming the second connection member is not performed.
  • a light emitting unit was formed in the same manner as in Example 1, and an Al film was formed as a second electrode by vacuum deposition.
  • the second electrode was formed so that the second electrode of the Al film was in direct contact with the second extraction electrode.
  • the first electrode and the first take-out electrode are all covered with each other in a length of 3 mm so that the first electrode and the first take-out electrode are electrically connected to each other.
  • An Al film was formed.
  • the sealing layer and the sealing material were formed similarly to Example 1, and the organic EL element was obtained.
  • Example 1 The sealing performance of the organic EL elements of Example 1, Example 2 and Comparative Example 1 was evaluated by the following method.
  • the extraction electrode of the organic EL element was exposed and stored in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 1000 hours, and the state in which the light emitting area shrinks with time due to moisture entering from the outside was observed.
  • Table 1 shows the results after 1000 hours.
  • FIG. 7 is a diagram showing a situation in which the light emission area shrinks over time.
  • the horizontal axis represents storage time, and the vertical axis represents shrink width.
  • the light emitting area was not particularly shrunken after 1000 hours.
  • Comparative Example 1 since the intrusion of moisture from the outside, the light emitting area shrinks with time. After 1000 hours, it shrank 500 ⁇ m and was inferior in sealing performance.
  • Organic EL elements (electronic devices) 2 Substrate 3 First electrode 4 Functional layer 5 Second electrode 6 First extraction electrode 7 Second extraction electrode 8 Sealing layer 9 Sealing material

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Abstract

La présente invention concerne un dispositif électronique qui est supprimé lors du rétrécissement d'une zone de développement de fonction dans le temps. Un dispositif électronique (1) selon l'invention comprend, sur un substrat (2), une première électrode (3), au moins une couche fonctionnelle (4), une seconde électrode (5), une électrode d'extraction (6) pour la première électrode et une électrode d'extraction (7) pour la seconde électrode. La première électrode (3), la couche fonctionnelle (4) et la seconde électrode (5) sont stratifiées successivement sur le substrat (2) dans cet ordre ; la première électrode (3) et l'électrode d'extraction (6) pour la première électrode sont disposées sur le substrat (2) à une certaine distance l'une de l'autre ; et la première électrode (3) et l'électrode d'extraction (6) pour la première électrode sont électriquement connectées l'une à l'autre par l'intermédiaire d'un premier élément de connexion (10) qui est interposé entre la première électrode (3) et l'électrode d'extraction (6) pour la première électrode. L'invention concerne également un procédé de production de ce dispositif électronique (1).
PCT/JP2018/014088 2017-04-21 2018-04-02 Dispositif électronique et son procédé de production WO2018193822A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022048615A1 (fr) * 2020-09-04 2022-03-10 深圳市光羿科技有限公司 Dispositif électrochromique et dispositif électronique

Citations (4)

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Publication number Priority date Publication date Assignee Title
KR20020029810A (ko) * 2000-10-14 2002-04-20 김순택 유기 전계발광 디바이스 및 이의 제조 방법
JP2006012993A (ja) * 2004-06-23 2006-01-12 Dainippon Printing Co Ltd 有機デバイス
WO2008126263A1 (fr) * 2007-03-30 2008-10-23 Pioneer Corporation Dispositif à électroluminescence organique et son procédé de fabrication
WO2014178282A1 (fr) * 2013-05-01 2014-11-06 コニカミノルタ株式会社 Élément électroluminescent organique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020029810A (ko) * 2000-10-14 2002-04-20 김순택 유기 전계발광 디바이스 및 이의 제조 방법
JP2006012993A (ja) * 2004-06-23 2006-01-12 Dainippon Printing Co Ltd 有機デバイス
WO2008126263A1 (fr) * 2007-03-30 2008-10-23 Pioneer Corporation Dispositif à électroluminescence organique et son procédé de fabrication
WO2014178282A1 (fr) * 2013-05-01 2014-11-06 コニカミノルタ株式会社 Élément électroluminescent organique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022048615A1 (fr) * 2020-09-04 2022-03-10 深圳市光羿科技有限公司 Dispositif électrochromique et dispositif électronique

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