WO2018181573A1 - 有機エレクトロルミネッセンス素子用電極、有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス表示装置、及び有機エレクトロルミネッセンス素子用電極の製造方法 - Google Patents

有機エレクトロルミネッセンス素子用電極、有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス表示装置、及び有機エレクトロルミネッセンス素子用電極の製造方法 Download PDF

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WO2018181573A1
WO2018181573A1 PCT/JP2018/012968 JP2018012968W WO2018181573A1 WO 2018181573 A1 WO2018181573 A1 WO 2018181573A1 JP 2018012968 W JP2018012968 W JP 2018012968W WO 2018181573 A1 WO2018181573 A1 WO 2018181573A1
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layer
electrode
work function
organic
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PCT/JP2018/012968
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French (fr)
Japanese (ja)
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孝洋 伊東
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ジオマテック株式会社
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Priority to KR1020197027375A priority Critical patent/KR102489364B1/ko
Priority to CN201880020886.2A priority patent/CN110463349B/zh
Publication of WO2018181573A1 publication Critical patent/WO2018181573A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • 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
    • 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
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H05B33/24—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers of metallic reflective layers
    • 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
    • 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
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Definitions

  • the present invention relates to an electrode for an organic electroluminescence element, an organic electroluminescence element, an organic electroluminescence display device, and a method for producing an electrode for an organic electroluminescence element.
  • organic electroluminescence elements (hereinafter referred to as organic EL elements) have been used in various fields, and in particular, are used in applications such as display devices for smartphones, display devices such as flat-screen televisions, and lighting equipment.
  • Organic EL panels used in display devices and lighting devices using organic EL elements are roughly classified into two types, a top emission type and a bottom emission type, depending on the light extraction direction.
  • a TFT Thin Film Transistor
  • the top emission type takes out light from the opposite side of the substrate, that is, the opposite side to the TFT circuit.
  • the bottom emission type takes out light from the substrate side, that is, from a region other than the TFT circuit.
  • the top emission type organic EL element is suitable for high luminance and high definition because it can secure a high aperture ratio without being restricted by light blocking objects such as TFT and wiring, as compared with the bottom emission type organic EL element. .
  • TFT and wiring light blocking objects
  • Patent Document 1 relates to a technique for preventing mirroring of an EL light emitting device without using a circularly polarizing film, and describes an EL light emitting element provided with an anode or a cathode made of an oxide conductive film and a light shielding film. ing.
  • Patent Document 2 relates to an organic EL display element using molybdenum or chromium oxide as an antireflection layer.
  • molybdenum or chromium oxide is used as an antireflection layer.
  • Patent Document 3 relates to an organic light emitting device that suppresses reflection of ambient light from a cathode, and describes that an n-type semiconductor such as zinc oxide or calcium hexaboride is used as a reflection suppressing layer.
  • an n-type semiconductor such as zinc oxide or calcium hexaboride is used as a reflection suppressing layer.
  • Patent Document 4 relates to an EL color filter constituting an EL display device, and describes that a light-absorbing oxide such as molybdenum oxide is used as a material for an antireflection layer of the EL color filter. .
  • Patent Documents 1 to 4 a light-shielding film and an antireflection layer are provided to prevent external reflection in the organic EL element.
  • An electrode configuration with adjustable function has not been realized.
  • an electrode configuration that can be etched in a batch and that can adjust the work function while having a low visible light region reflectivity and good conductivity has not been realized.
  • the present invention has been made in view of the above problems, and an object of the present invention is to reduce external reflectance by reducing the reflectance in the visible light region and to arbitrarily adjust the work function. Another object of the present invention is to provide an organic EL element electrode applicable to both an anode and a cathode of an organic EL element, and a method for producing an organic EL element electrode. Another object of the present invention is to provide an organic EL element electrode and an organic EL element electrode that can be collectively etched, having a low visible light region reflectance, good conductivity, and a work function that can be adjusted. It is to provide a manufacturing method.
  • the problem is that a conductive layer mainly composed of a metal or an alloy and a black having a reflectance of 40% or less in a visible light region provided on the conductive layer.
  • a work function adjusting layer made of a transparent conductive oxide having a predetermined work function provided on the blackened layer, the reflectance in the visible light region is 10% or less, and the sheet resistance Is 1 ⁇ / sq or less.
  • the organic electroluminescence element electrode is composed of three layers including the conductive layer, the blackening layer, and the work function adjusting layer. In this way, it has a low visible light region reflectivity and sufficient conductivity, and can be used as both an anode and a cathode, but has a small number of layers of three layers. Therefore, the electrode can be easily manufactured and the electrode can be made thin.
  • the conductive layer is preferably a metal or alloy containing as a main component one or more metals selected from the group including Al, Cu, Ag, Mo, and Cr.
  • the conductive layer can be laminated by a simple process such as sputtering, and a low sheet resistance can be realized.
  • the blackening layer is preferably made of a lower oxide, a lower nitride, or a lower oxynitride containing Mo or Zn as a main component.
  • a conductive substance having a high absorbance in the visible light region as the blackening layer, a low visible light region reflectance and good conductivity can be realized.
  • the work function adjusting layer is made of a transparent conductive oxide based on In 2 O 3 or ZnO, and selected from the group containing Ga, Ce, Zn, Sn, Si, W, and Ti in In 2 O 3. It is preferable that it is made of a transparent conductive oxide to which one or more of these are added, or a transparent conductive oxide to which one or more selected from the group containing Al or Ga in ZnO is added.
  • a transparent conductive oxide various metals can be doped, and by using a transparent conductive oxide that can adjust the work function according to the amount of dopant added, it can be used as an anode or a cathode.
  • an electrode having a low reflectance in the visible light region can be provided.
  • the work function adjusting layer has a work function of 4.6 eV or less and is used as a cathode of an organic electroluminescence element, or has a work function of 4.7 eV or more and is used as an anode of an organic electroluminescence element. It is preferable.
  • the work function of the work function adjusting layer is adjusted according to the kind and amount of dopant added to the transparent conductive oxide as a base, it can be used as both an anode and a cathode of an organic EL element. Is possible.
  • the organic electroluminescent element provided with the electrode for organic electroluminescent elements of this invention and the organic electroluminescent display apparatus provided with the said organic electroluminescent element and not provided with the polarizing plate.
  • the organic electroluminescence element electrode of the present invention has a reduced reflectance in the visible light region, and therefore, when used as an electrode of an organic EL element and an organic EL display device, external reflection can be suppressed. Therefore, an organic EL display device without a polarizing plate can be provided.
  • the conductive material is mainly composed of one or more metals selected from the group including Al, Cu, Ag, Mo, and Cr on the base material.
  • a conductive layer laminating step of laminating layers, and a reflectance in a visible light region composed of a lower oxide, a lower nitride, or a lower oxynitride mainly composed of Mo or Zn on the conductive layer is 40% or less
  • a blackening layer laminating step of laminating the blackening layer, and a work function adjustment layer having a predetermined work function made of a transparent conductive oxide based on In 2 O 3 or ZnO is laminated on the blackening layer.
  • the problem is solved by performing a work function adjusting layer stacking step and an etching step of collectively etching the conductive layer, the blackening layer, and the work function adjusting layer.
  • the conductive layer, blackening layer, and work function adjustment layer are formed of appropriate materials, so that the wet etching using a phosphorous nitrate acetic acid-based etching solution (phosphoric acid, nitric acid, acetic acid mixed solution) is performed collectively. Therefore, the electrode can be easily manufactured.
  • the blackening layer and work function adjustment layer are provided on the conductive layer, external reflection can be suppressed by reducing the reflectance in the visible light region, the sheet resistance is low, and the work function can be adjusted arbitrarily.
  • a possible electrode for an organic EL device can be provided.
  • a conductive layer mainly composed of a metal or an alloy, and a blackened layer having a visible light region reflectance of 40% or less provided on the conductive layer.
  • a work function adjusting layer made of a transparent conductive oxide having a predetermined work function provided on the blackening layer, the reflectance in the visible light region is 10% or less, and the sheet resistance is 1 ⁇ . / Sq or less.
  • the electrode for an organic EL device of the present invention is a lower oxide, lower nitride, or lower oxynitride whose blackening layer is mainly composed of Mo or Zn having high electrical conductivity and high absorbance in the visible light region. Therefore, the reflectance can be lowered while the sheet resistance value is low. Moreover, since the transparent conductive oxide which has a suitable work function is used as a work function adjustment layer, it is possible to use an electrode for both an anode and a cathode. Furthermore, the reflectance in the visible light region can be lowered to 10% or less by combining the blackening layer and the work function adjusting layer. Therefore, a flexible organic EL panel without a polarizing plate can be formed.
  • the conductive layer, the blackening layer, and the work function adjusting layer are selected from materials that can be etched at once, it is easy to manufacture an electrode.
  • an organic EL element electrode according to an embodiment of the present invention, a method for manufacturing the organic EL element electrode, an organic EL element including the organic EL element electrode, and an organic EL display device using the organic EL element explain.
  • the organic EL element electrode 20 of the present embodiment includes a conductive layer 1, a blackened layer 2 formed on the conductive layer 1, and a work formed on the blackened layer 2.
  • the function adjustment layer 3 is laminated.
  • each layer which comprises the electrode 20 for organic EL elements is explained in full detail.
  • the conductive layer 1 is a metal mainly composed of one or more selected from the group including Al, Cu, Ag, and Mo, or a group including APC (silver, palladium, copper alloy), AlNd, AlSi, AlCu, and AlSiCu.
  • the main component means a case where the conductive layer contains 50% by weight or more by weight.
  • a metal which comprises the conductive layer 1 what is necessary is just a metal which has sufficient electroconductivity and is used for the organic EL element.
  • Al, Cu, Ag, Mo and the like can be mentioned, but are not limited thereto.
  • the alloy constituting the conductive layer 1 may be any alloy that has sufficient conductivity and is used for an organic EL element.
  • the thickness of the conductive layer 1 is preferably 10 nm or more and 1000 nm or less, more preferably 20 nm or more and 800 nm or less, more preferably 30 nm or more and 700 nm or less, still more preferably 40 nm or more and 600 nm or less, and further preferably 50 nm or more and 500 nm or less. There should be. If the thickness of the conductive layer 1 becomes too thin, the conductivity will decrease. On the other hand, if the conductive layer 1 is too thick, the thickness of the organic EL element increases, and the etching processability and manufacturability are reduced.
  • the blackening layer 2 is a layer having Mo or Zn as a main component and made of a lower oxide, a lower nitride, or a lower oxynitride and having a reflectance in the visible light region of 40% or less.
  • the main component means a case where Mo or Zn contained in the blackened layer contains 50 atomic% or more in terms of the atomic ratio of metal atoms.
  • the lower oxide, lower nitride, or lower oxynitride constituting the blackening layer 2 may be any material that can sufficiently absorb light in the visible light region and has sufficient conductivity. Examples thereof include, but are not limited to, lower oxides, lower nitrides, and lower oxynitrides mainly composed of Mo or Zn.
  • a dopant metal may be added to a metal other than Mo or Zn as a main component.
  • the dopant metal is preferably a transition metal, such as Nb, W, Al, Ni, Cu, Cr, Ti, Ag, Ga, Zn, In, or Ta, but is not limited thereto.
  • the content of the dopant metal with respect to the lower oxide, lower nitride, or lower oxynitride containing Mo or Zn as the main component is preferably 20 atomic% or less.
  • the content ratio of the dopant metal Nb, Ta, etc.
  • good conductivity and light absorption in the visible light region can be realized.
  • the reflectance of the visible light region of the blackening layer 2 is preferably 50% or less, more preferably 40% or less.
  • the lower limit of the wavelength of electromagnetic waves corresponding to visible light is about 360 to 400 nm, and the upper limit is about 760 to 830 nm.
  • the visible light region is a wavelength of 400 nm to 700 nm. Say the area.
  • the thickness of the blackening layer 2 is preferably 5 nm or more and 200 nm or less, more preferably 10 nm or more and 150 nm or less, more preferably 20 nm or more and 100 nm or less, still more preferably 30 nm or more and 75 nm or less, and further preferably 40 nm or more and 60 nm or less. It is good to be. If the thickness of the blackening layer 2 becomes too thin, the absorption of light in the visible light region becomes insufficient or the film formation becomes difficult. On the other hand, if the blackening layer 2 is too thick, etching processability and manufacturability deteriorate.
  • the work function adjusting layer 3 is a layer made of a transparent conductive oxide having a predetermined work function.
  • the transparent conductive oxide constituting the work function adjusting layer 3 may be a transparent conductive oxide that has sufficient conductivity and can adjust the work function by adding various metals. Examples of such transparent conductive oxides include In 2 O 3 , ZnO, Ga 2 O 3 , SnO 2 , TiO 2 , CdO, and composite oxides thereof, but are not limited thereto. Absent. In the present embodiment, it is preferable to use a transparent conductive oxide based on In 2 O 3 or ZnO as a material constituting the work function adjusting layer 3.
  • a transparent conductive oxide can be used.
  • IGO gallium-doped indium oxide
  • IZO indium zinc oxide
  • Zn Zinc oxide
  • ITO embedded with Sn
  • ITO indium tin oxide
  • ICO indium cerium oxide
  • IWZO tungsten-zinc doped indium oxide
  • the content of the metal element added to In 2 O 3 is not more than 50 wt% by weight. If the content exceeds this range, the resistance becomes high, such being undesirable.
  • other elements in the transparent conductive oxide based on In 2 O 3 have the performance of the electrode for the organic EL element of the present embodiment. It may be included as long as it is not damaged.
  • the transparent conductive oxide based on ZnO a transparent conductive oxide in which one or more metal elements selected from the group containing Al or Ga are added to the main component ZnO can be used.
  • Al added AZO aluminum doped zinc oxide
  • Ga added GZO gallium doped zinc oxide
  • Al and Ga added GAZO Gallium / aluminum-doped zinc oxide
  • the content rate of the metal element added to ZnO is 10 weight% or less by weight ratio. If the content exceeds this range, the resistance becomes high, such being undesirable.
  • the transparent conductive oxide based on ZnO may contain other elements in addition to Al or Ga as long as the performance of the electrode for an organic EL element of the present embodiment is not impaired.
  • the transparent conductive oxide may be selected so that the work function of the work function adjusting layer 3 is 4.6 eV or less.
  • the transparent conductive oxide may be selected so that the work function of the work function adjusting layer is 4.7 eV or more.
  • various metals are added to the work function adjusting layer 3 so that the work function is adjusted to a predetermined work function.
  • the addition of the various metals is based on crystals of In 2 O 3 or ZnO serving as a base. causess sex decline. Accordingly, the crystallinity of the work function adjusting layer 3 is lowered by the addition of the metal, and it becomes amorphous so that it can be etched using a predetermined etching solution.
  • the thickness of the work function adjusting layer 3 is preferably 5 nm or more and 150 nm or less, more preferably 10 nm or more and 100 nm or less, more preferably 20 nm or more and 80 nm or less, still more preferably 30 nm or more and 60 nm or less, and further preferably 40 nm or more and 50 nm. It may be the following. If the thickness of the work function adjusting layer 3 becomes too thin, absorption of light in the visible light region becomes insufficient, the work function is not stable, and film formation becomes difficult. On the other hand, if the work function adjusting layer 3 is too thick, etching processability and manufacturability are lowered.
  • the organic EL element electrode 20 has a low reflectivity in the visible light region that can be used for a polarizing plate-less organic EL display device and sufficient conductivity by adopting the above-described configuration. It is characterized by.
  • the reflectance of the visible light region (400 nm to 700 nm) of the electrode 20 for the organic EL element is 10% or less.
  • the sheet resistance of the organic EL element electrode 20 is 1 ⁇ / sq or less, more preferably 0.75 ⁇ / sq or less, still more preferably 0.5 ⁇ / sq or less, and particularly preferably 0.25 ⁇ / sq or less.
  • the work function of the organic EL element electrode 20 is determined by the work function of the work function adjusting layer 3. When the organic EL element electrode 20 is used as a cathode, the work function is 4.6 eV or less, while the organic EL element electrode is used. When 20 is used as the anode, it is 4.7 eV or more.
  • the organic EL element electrode 20 is composed of a small number of three layers including the conductive layer 1, the blackening layer 2, and the work function adjusting layer 3, but has a low visible light region reflectance, It has an advantage that it can be used as both an anode and a cathode of an organic EL element by appropriately selecting a material having sufficient conductivity and used for the work function adjusting layer.
  • the thickness of the organic EL element electrode 20 is preferably 20 nm or more and 1500 nm or less, more preferably 100 nm or more and 1000 nm or less, more preferably 200 nm or more and 800 nm or less, still more preferably 300 nm or more and 600 nm or less, and further preferably 350 nm or more. It is good that it is 500 nm or less. If the organic EL element electrode 20 is too thick, etching processability and manufacturability deteriorate.
  • the organic EL element electrode 20 of the present embodiment is a conductive material mainly composed of one or more metals selected from the group including Al, Cu, Ag, Mo, and Cr on a base material.
  • a conductive layer laminating step of laminating layers, and a reflectance in a visible light region composed of a lower oxide, a lower nitride, or a lower oxynitride mainly composed of Mo or Zn on the conductive layer is 40% or less
  • a blackening layer laminating step of laminating the blackening layer, and a work function adjustment layer having a predetermined work function made of a transparent conductive oxide based on In 2 O 3 or ZnO is laminated on the blackening layer.
  • a method for producing an electrode for an organic EL device comprising: a work function adjusting layer laminating step; and an etching step of collectively etching the laminated conductive layer, blackening layer, and work function adjusting layer. Manufactured by. Hereinafter, each step will be described in detail with reference to FIG.
  • the conductive layer 1 mainly composed of one or more metals selected from the group including Al, Cu, Ag, Mo, and Cr is laminated on the substrate 10.
  • the method for forming the conductive layer 1 on the substrate 10 can use a physical vapor deposition method such as a sputtering method, a vacuum vapor deposition method, or an ion plating method, but is not limited thereto.
  • a lower oxide, lower nitride, or lower acid containing Mo or Zn as a main component on the conductive layer 1 stacked on the substrate 10 in the conductive layer stacking step.
  • a blackening layer 2 made of nitride and having a visible light region reflectance of 40% or less is stacked.
  • the method for forming the blackening layer 2 on the conductive layer 1 can use a physical vapor deposition method such as a sputtering method, a vacuum vapor deposition method, or an ion plating method, but is not limited thereto.
  • step S3 a predetermined conductive layer made of a transparent conductive oxide based on In 2 O 3 or ZnO is formed on the blackening layer 2 laminated on the conductive layer 1 in the blackening layer laminating step.
  • a work function adjusting layer 3 having a work function is laminated.
  • the method of forming the work function adjusting layer 3 on the blackening layer 2 can use a physical vapor deposition method such as a sputtering method, a vacuum vapor deposition method, or an ion plating method, but is not limited thereto.
  • ITO and GZO are used as targets, and the oxygen flow rate is set to 5 sccm.
  • the formation method of the conductive layer 1, the blackening layer 2, and the work function adjusting layer 3 is, for example, a vacuum evaporation method and / or a sputtering method
  • the organic layer is continuously formed on the substrate 10 continuously by a dry process.
  • the EL element electrode 20 can be formed.
  • the conductive layer 1, the blackening layer 2, and the work function adjusting layer 3 laminated on the base material 10 are etched together.
  • a photoresist is applied by photolithography on the conductive layer 1, the blackening layer 2, and the work function adjustment layer 3 laminated on the base material 10, and exposure and development are performed to transfer a mask pattern to the resist.
  • portions other than those to be left as electrodes by etching are removed. Thereafter, when the resist is removed, the remaining portion is obtained as the organic EL element electrode 20.
  • etching method wet etching using an etchant, or dry etching such as reactive gas etching, reactive ion etching, reactive ion beam etching, ion beam etching, and reactive laser beam etching can be used.
  • dry etching such as reactive gas etching, reactive ion etching, reactive ion beam etching, ion beam etching, and reactive laser beam etching.
  • a phosphorous nitrate acetic acid-based etching solution phosphoric acid, nitric acid, acetic acid mixed solution
  • a top emission type organic EL element 100 including the organic EL element electrode 20 of the present embodiment as an anode (anode) includes a base material 10, an organic EL element electrode 20, and hole transport.
  • the layer 30, the organic light emitting layer 40, the electron transport layer 50, and the transparent electrode 60 are formed in this order and the light emission L is taken out from the opposite side of the substrate 10.
  • the electrode 20 for an organic EL element of the present embodiment has an advantage that it is not necessary to use a polarizing plate because the reflectance in the visible light region is 10% or less and external light reflection is suppressed. Below, each component of the organic EL element 100 is demonstrated in detail.
  • the base material 10 constituting the organic EL element 100 of the present invention may be any material that does not change when the electrode and the organic layer are formed.
  • glass, plastic, polymer film, silicon substrate, a laminate of these, and the like Can be used.
  • hole transport layer 30 Materials constituting the hole transport layer 30 include polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyl. Diamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thienylene vinylene) or derivative thereof Etc.
  • the method of forming the hole transport layer 30 is not particularly limited, but for low molecular hole transport materials, a method of forming a film from a mixed solution with a polymer binder may be used. Examples of the material include a method by film formation from a solution.
  • the film thickness of the hole transport layer 30 differs depending on the material, and may be selected so that the driving voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. is there. If the film thickness is too thick, the driving voltage of the organic EL element 100 becomes high. Therefore, the film thickness of the hole transport layer 30 is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm. It is good to be ⁇ 200 nm.
  • the organic light emitting layer 40 contains an organic substance (a low molecular compound and a high molecular compound) that emits fluorescence or phosphorescence. Further, a dopant material may be further included. Examples of the material for forming the organic light emitting layer 40 that can be used in the present embodiment include, but are not limited to, pigment materials, metal complex materials, and polymer materials. In addition, a dopant may be added to the organic light emitting layer 40 for the purpose of improving the light emission efficiency or changing the light emission wavelength.
  • a method for forming the organic light emitting layer 40 is not particularly limited, and a method of applying a solution containing a light emitting material on or above the substrate, a vacuum deposition method, a transfer method, or the like can be used.
  • the thickness of the organic light emitting layer 40 is usually 20 to 2000 mm.
  • Electrode transport layer As the material constituting the electron transport layer 50, known materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquino. Examples include dimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like. It is done.
  • the method for forming the electron transport layer 50 is not particularly limited, but for the low molecular electron transport material, a vacuum deposition method from powder or a method by film formation from a solution or a molten state can be mentioned.
  • the electron transport material include a method of forming a film from a solution or a molten state.
  • the film thickness of the electron transport layer 50 differs depending on the material and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. . If the film thickness is too thick, the driving voltage of the organic EL element 100 becomes high. Therefore, the film thickness of the electron transport layer 50 is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to It is good that it is 200 nm.
  • Transparent electrode Since the organic EL element 100 according to the present embodiment emits light through the transparent electrode 60, the transparent electrode 60 needs to use a transparent or translucent electrode.
  • the material constituting the transparent electrode 60 that is a cathode has a small work function and the electron transport layer 50 and the organic light emitting layer 40.
  • a material that can easily inject electrons into is preferable.
  • a conductive metal oxide or a conductive organic material can be used.
  • indium oxide, zinc oxide, tin oxide, and ITO or IZO which are composites thereof can be used as the conductive metal oxide, but are not limited thereto.
  • An organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof can be used as the conductive organic material, but is not limited thereto.
  • FIG. 3 shows a top emission type organic EL element 100 provided with the organic EL element electrode 20 of the present embodiment as an anode (anode).
  • the organic EL element electrode 20 of the present embodiment is a cathode (cathode).
  • an organic EL element 100 ′ using the organic EL element electrode 20 ′ as a cathode is shown in FIG.
  • the base material 10 the organic EL element electrode 20 ′, the electron transport layer 50, the organic light emitting layer 40, the hole transport layer 30, and the transparent electrode 60 ′ are sequentially stacked. Since the organic EL element electrode 20 ′ is used as a cathode, the positions of the electron transport layer 50 and the hole transport layer 30 are different.
  • the organic EL element electrode 20 ′ is used as a cathode, and the material constituting the transparent electrode 60 ′ that is an anode has a work function.
  • a material that can easily inject holes into the hole transport layer 30 and the organic light emitting layer 40 is preferable.
  • the transparent electrode or translucent electrode a metal oxide, metal sulfide or metal thin film having high electrical conductivity can be used.
  • the transparent electrode indium oxide, zinc oxide, tin oxide, and ITO or IZO, which are composites thereof, are preferable, but not limited thereto.
  • Organic light emitting device Since the organic EL elements 100 and 100 ′ of the present embodiment have low reflectance in the visible light region and reduced external reflection, it is possible to produce a polarizing plate-less organic EL display device that does not use a polarizing plate. Is possible.
  • the organic EL display device include, but are not limited to, a display of a portable terminal such as a smartphone or a tablet terminal, a display such as a thin TV. If a flexible material such as a plastic film is selected as the substrate 10, a flexible organic EL display device can be obtained.
  • the organic EL element electrode, the organic EL element, the organic EL display device, and the method for manufacturing the organic EL element electrode according to the present invention have been mainly described.
  • said embodiment is only an example for making an understanding of this invention easy, and does not limit this invention.
  • the present invention can be changed and improved without departing from the gist thereof, and the present invention includes the equivalents thereof.
  • Sputtering equipment Carousel type batch type sputtering equipment Target: Example 1 5 ′′ ⁇ 25 ′′, thickness 6 mm, Mo 90 atom%, Nb 10 atom% (Comparative Example 1) 5 “x 25", thickness 6 mm, Mo 90 atom%, Nb 10 atom% (Examples 2 to 6) 5 ” ⁇ 25”, thickness 6 mm, Mo 100 atomic% (Comparative example 2) 5 "x 25", thickness 6mm, Mo100 atomic%
  • Sputtering method DC magnetron sputtering Exhaust device: Turbo molecular pump Ultimate vacuum: 5 ⁇ 10 ⁇ 4 Pa Substrate temperature: 25 ° C. (room temperature) Sputtering power: 3kW Blackening layer thickness: 50 ⁇ 5 nm Ar flow rate: 250 sccm Oxygen flow rate: 50 sccm
  • Sputtering equipment Carousel type batch type sputtering equipment Target: (Example 1) 5 " ⁇ 25", thickness 6mm, In 2 O 3 60 wt%, Ga 2 O 3 40 wt% (Example 2) 5 “ ⁇ 25", thickness 6mm, In 2 O 3 60 wt%, Ga 2 O 3 40 wt% (Example 3) 5 " ⁇ 25", thickness 6mm, In 2 O 3 90 wt%, Sn 2 O 3 10 wt% (Example 4) 5 " ⁇ 25", thickness 6mm, In 2 O 3 90 wt%, ZnO10 wt% (Example 5) 5 " ⁇ 25", thickness 6mm, In 2 O 3 86.5 wt%, CeO 2 10 wt%, SnO 2 3.2% by weight, TiO 2 0.3% by weight (Example 6) 5 " ⁇ 25", thickness 6mm, In 2 O 3 96.5 wt%, WO 3 3.0 wt%, ZnO0.5 wt% Sputtering method: DC
  • FIGS. 5A and 5B The optical constants of the blackened layers of Reference Example 1 and Reference Example 2 were measured. The optical constant was measured using a spectroscopic ellipsometer (manufactured by JASCO Corporation, M-220). The results are shown in FIGS. 5A and 5B.
  • FIG. 5A is a graph showing the refractive index
  • FIG. 5B is a graph showing the extinction coefficient. Table 1 shows the refractive index n and extinction coefficient k at 550 nm.
  • Reference Test 3 Work function adjustment layer reflectivity measurement
  • the reflectivities of the work function adjusting layers of Reference Examples 4 to 8 were measured.
  • the reflectance was measured in a wavelength region from 350 nm to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
  • the results are shown in FIG.
  • the reflectance of the work function adjusting layer of Reference Examples 4 to 8 is larger than 10%, and it is found that the reflectance in the visible light region cannot be lowered to 10% or less simply by laminating the work function adjusting layer. It was.
  • Example 1 Measurement of reflectance of organic EL element electrode
  • Example 1 Comparative Examples
  • the reflectance of Comparative Example 2 indicated by the dotted line was 10% or more.
  • the reflectances of Examples 2 to 6 were as low as 10% or less in the entire visible light region of 400 nm to 700 nm. From these results, the reflectance in the visible light region cannot be lowered to 10% or less simply by laminating the blackened layer on the conductive layer, and the three layers comprising the conductive layer, the blackened layer, and the work function adjusting layer. It has been found that the reflectance in the visible light region can be reduced to 10% or less by using the configuration.
  • Example 2 Measurement of sheet resistance and work function of electrode for organic EL element
  • the sheet resistance of the electrodes of Example 1 and Comparative Example 1 was measured by a four-terminal method using a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., model name MCP-T610).
  • the work functions of the electrodes of Examples 1 to 6 and Comparative Examples 1 and 2 were calculated using an atmospheric photoelectron spectrometer (model name AC-2, manufactured by Riken Keiki Co., Ltd.). The results are shown in Table 3 below.
  • the sheet resistance value of the electrode of Example 1 was a sufficiently small value of 0.11 ⁇ / sq and can be used as an electrode for an organic EL element.
  • the electrode of Example 1 shows the same value as the value of the sheet resistance of Comparative Example 1 having no work function adjustment layer, and the work function adjustment layer does not affect the sheet resistance value in the visible light region. It was found that the reflectance can be reduced to 10% or less.
  • the work function of the work function adjusting layer can be set to an arbitrary value depending on the type of dopant added to the transparent conductive oxide serving as a base, it can be used as an anode or a cathode of an organic EL element. I found out that
  • Example 2 Etching evaluation was performed on the electrode of Example 2.
  • the conductive film of Example 2 was coated with a photoresist (OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd.), and a pattern was baked onto the photoresist by irradiating with ultraviolet rays using a patterned mask original.
  • TMAH tetramethylammonium hydroxide
  • the uncured photoresist is removed to develop the pattern of the original plate, and an unnecessary portion of the conductive film from which the photoresist has been removed is etched into the etching solution. It was removed by etching using (phosphoric acid, nitric acid, acetic acid mixed solution).
  • Example 2 Thereafter, the photoresist remaining on the conductive film was peeled and washed to obtain an etching sample of Example 2. Thereafter, SEM cross-sectional analysis (S-4300 manufactured by Hitachi High-Tech Fielding) was performed on the etching sample of Example 2. The SEM cross-sectional photograph of the etching sample of Example 2 is shown in FIG. As shown in FIG. 10, the etched surface was observed as a clear boundary, and it was found that good etching was performed.
  • S-4300 manufactured by Hitachi High-Tech Fielding
  • Example 7 Al—Nd / nitride Mo—Nb / IGO conductive film
  • an Al—Nd alloy layer film thickness: 330 nm
  • a Mo—Nb alloy nitride layer film thickness: 40 nm
  • an IGO layer film thickness: 30 nm
  • a membrane was obtained.
  • An Al—Nd alloy layer having a thickness of 330 nm was formed on a glass substrate by DC magnetron sputtering.
  • the target, film thickness, sputtering power and introduced gas were changed as follows, and an IGO layer was formed on the nitride layer of the Mo—Nb alloy.
  • the conductive film of Example 7 was obtained.
  • the reflectivity of the conductive film of Example 7 indicated by a solid line shows a low value of 10% or less in the entire visible light region of 400 nm to 700 nm.
  • the sheet resistance value of the conductive film of Example 7 was a sufficiently small value of 0.16 ⁇ / sq, indicating that it can be used as a conductive film.
  • the organic EL element electrode has been described as a specific example of the electrode of the present invention.
  • the electrode of the present invention has a low resistance and a low reflectance of about 10% or less in the visible light region. Therefore, the use is not limited to the electrode for organic EL elements, but can also be used as an electrode for electronic equipment and an electrode for optical equipment.
  • the touch panel refers to a touch sensor integrated display device that is integrally provided with a touch sensor and a display device.
  • a touch panel on the viewing side of a display device such as a liquid crystal device, a touch sensor substrate using a pattern formed of a transparent conductive film on a transparent substrate as a detection electrode is bonded, or on a display device substrate.
  • a touch sensor integrated pattern display device by forming a touch sensor electrode pattern.
  • the electrode In an electronic device in which a substrate with an electrode is arranged on the front surface of a display element such as a touch panel, it is necessary that the visibility of display is not hindered. Therefore, the electrode has shielding, scattering, stray light, reflection, and the like. It needs to be as small as possible. According to the electrode of the present invention, since the reflectance in the visible light region is 10% or less, even when used for an electrode of a capacitive touch panel input device, glare is suppressed and the contrast ratio of the display is reduced. While the decrease is suppressed and the sheet resistance is as small as 1 ⁇ / sq or less, the power consumption of an electronic device such as a capacitive input device can be reduced.

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PCT/JP2018/012968 2017-03-29 2018-03-28 有機エレクトロルミネッセンス素子用電極、有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス表示装置、及び有機エレクトロルミネッセンス素子用電極の製造方法 WO2018181573A1 (ja)

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CN111244114B (zh) 2020-02-10 2023-10-17 Tcl华星光电技术有限公司 显示面板
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