WO2015166562A1 - Organic electroluminescent element and method for manufacturing same - Google Patents

Organic electroluminescent element and method for manufacturing same Download PDF

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Publication number
WO2015166562A1
WO2015166562A1 PCT/JP2014/062008 JP2014062008W WO2015166562A1 WO 2015166562 A1 WO2015166562 A1 WO 2015166562A1 JP 2014062008 W JP2014062008 W JP 2014062008W WO 2015166562 A1 WO2015166562 A1 WO 2015166562A1
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layer
organic electroluminescence
light emitting
electroluminescence device
organic
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PCT/JP2014/062008
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French (fr)
Japanese (ja)
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勇進 夫
貴之 千葉
城戸　淳二
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国立大学法人山形大学
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Priority to PCT/JP2014/062008 priority Critical patent/WO2015166562A1/en
Priority to JP2016515805A priority patent/JP6579471B2/en
Publication of WO2015166562A1 publication Critical patent/WO2015166562A1/en

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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
    • H05B33/10—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

Definitions

  • the present invention relates to a multi-photon emission organic electroluminescence element (hereinafter abbreviated as an organic EL element) that can be produced by a coating method and a method for producing the same.
  • an organic EL element multi-photon emission organic electroluminescence element
  • a multiphoton emission organic EL device in which a plurality of light emitting units are connected in series via a charge generation layer (intermediate layer) reduces the amount of current per unit when compared with a normal organic EL device with the same luminance.
  • the durability of the element can be improved.
  • each unit when the current value is constant, each unit can obtain the respective luminance, so that it is an effective means in terms of efficiency.
  • Patent Document 1 includes a charge generation layer (V 2 O 5 ) and an electron injection layer (Li). It is described that the intermediate layer is formed by vacuum deposition, and each light emitting unit is formed by a coating method.
  • Patent Document 2 describes that dipentaerythritol hexaacrylate is used as a thermal crosslinking material, and the light emitting layer, the charge generation layer, and the electron injection layer are insolubilized by heating and baking at 200 ° C. .
  • Patent Document 3 a photocrosslinkable group is introduced into a charge generation material or an electron injection layer, and is heated and fired at 120 ° C. under irradiation of a low-pressure mercury lamp (15 mW / cm 2 ) to form a multi-layered structure by a coating method. It is described to do.
  • Patent Document 1 needs to repeat a plurality of different film forming processes, so that it is difficult to produce a continuous element, which causes an increase in cost.
  • the coating film is formed on the electron-injecting metal material that is unstable with respect to moisture and oxygen, there is a concern about deterioration of element characteristics.
  • the present invention has been made to solve the above technical problem, and in a multi-photon emission organic EL element, by simplifying the coating lamination of the intermediate layer including the charge generation layer, all the constituent layers can be made efficient.
  • Another object of the present invention is to provide an organic EL element that can be easily formed by a coating method at low cost and without deteriorating element characteristics, and a method for producing the same.
  • the organic EL device is a multi-photon emission organic EL device in which a plurality of light emitting units each having at least one light emitting layer are stacked via an intermediate layer between a pair of electrodes, and the intermediate layer includes: It consists of a coating layer of a charge generation layer on the cathode side and an electron injection layer on the anode side, and has an inverted structure.
  • the inverted structure has a structure in which a cathode, a plurality of light emitting units stacked via an intermediate layer, and an anode are stacked in this order on a substrate.
  • the charge generation layer preferably contains one or more conductive polymers. According to such a charge generation layer, coating can be formed, and the film can be formed without requiring high-temperature heating at the time of film formation.
  • the conductive polymer is any one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and is preferably a doped n-type or p-type semiconductor. According to such a conductive polymer, a charge generation layer having excellent hole injection characteristics can be formed by coating film formation.
  • the electron injection layer preferably contains one or more metal oxide fine particles or polar polymers. According to such an electron injection layer, the intermediate layer has an effect of improving the film forming property of the adjacent upper layer and preventing penetration of the solvent into the adjacent lower layer.
  • metal oxide fine particles it is composed of any one of zinc oxide, titanium oxide, zirconium oxide and oxide, and in the case of a polar polymer, it is preferably a polyethyleneimine derivative.
  • the light emitting unit may be any one that emits fluorescence or phosphorescence. Since the electron injection layer exhibits good electron injection characteristics from the charge generation layer, any light emitting material can be suitably applied.
  • At least one of the cathode and the anode is transparent as a light extraction surface.
  • the cathode and the anode are preferably made of any one of metal, metal oxide, and conductive polymer.
  • metal it is one of aluminum, silver, and gold.
  • metal oxide indium-tin oxide (ITO), indium-zinc oxide (IZO), zinc oxide, aluminum addition One of zinc oxide (AZO) and gallium-doped zinc oxide (GZO), and in the case of a conductive polymer, one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative;
  • the n-type or p-type semiconductor is used.
  • the method for producing an organic EL device according to the present invention is a method for producing the above-mentioned organic EL device, wherein the intermediate layer is coated and laminated using a solvent, and then dried at 130 ° C. or less to form a film. It is characterized by comprising the step of: Since the intermediate layer can be formed by a low-temperature treatment at 130 ° C. or lower, a multiphoton emission organic EL element can be efficiently manufactured at a low cost by a coating method.
  • the intermediate layer including the charge generation layer in the multi-photon emission organic EL element can be easily applied and laminated, all the constituent layers can be formed by the application method. Therefore, by applying the intermediate layer in the present invention, it becomes possible to produce a multi-photon emission organic EL element that requires multi-layer stacking efficiently and at low cost, and further increase the efficiency of the element. Be expected.
  • 6 is a graph showing luminance-voltage characteristics of the elements of Example 2-1 and Comparative Examples 2-1 and 2-2. 6 is a graph showing external quantum efficiency-current density characteristics of the devices of Example 2-1 and Comparative Examples 2-1 and 2-2. 6 is a graph showing luminance-voltage characteristics of the elements of Example 3-1 and Comparative Examples 3-1 and 3-2. 6 is a graph showing external quantum efficiency-current density characteristics of the devices of Example 3-1 and Comparative Examples 3-1 and 3-2. 6 is a graph showing EL spectrum characteristics of the elements of Example 4-1 and Comparative Examples 4-1 and 4-2. 6 is a graph showing the external quantum efficiency-current density characteristics of the devices of Example 4-1 and Comparative Examples 4-1 and 4-2.
  • the organic EL device is a multi-photon emission organic EL device in which a plurality of light emitting units each having at least one light emitting layer are stacked via an intermediate layer between a pair of electrodes.
  • the intermediate layer is formed of a coating layer of a charge generation layer on the cathode side and an electron injection layer on the anode side, and has an inverted structure.
  • the inverted structure has a structure in which a plurality of light emitting units stacked on a substrate in the order of a cathode, an intermediate layer, and an anode are stacked in this order.
  • FIG. 1 shows an example of the layer structure of an inverted multi-photon emission organic EL element.
  • FIG. 2 shows an example of a layer structure of a multi-photon emission organic EL element having a standard structure.
  • the ITO transparent electrode on the glass substrate 11 is used as the anode 12, and the first light emitting unit 13, the charge generation layer 15, the electron injection layer 14, and the second light emitting unit are formed thereon. 16 is laminated, and an aluminum reflective electrode is formed thereon as a cathode 17.
  • the inverted structure element uses an ITO transparent electrode as the cathode 2 on the glass substrate 1, and the first light emitting unit 3, the charge generation layer 4, and the electron injection thereon.
  • the layer 5 and the second light emitting unit 6 are laminated, and an aluminum reflective electrode is formed thereon as the anode 7.
  • the intermediate layer including the charge generation layer can be formed by coating with a solvent that does not redissolve the lower layer (first light emitting unit), and the intermediate layer It is required to be insoluble in the solvent used for coating the upper layer (second light emitting unit). Further, in order to stably manufacture the device, the intermediate layer improves the film formability of the upper layer (second light emitting unit), and the solvent to the lower layer (first light emitting unit) of the intermediate layer. It is desirable to prevent penetration.
  • the multi-photon emission organic EL element has an inverted structure as described above, and a charge generation layer is formed on the light emitting unit by coating, and the influence of oxygen and moisture in the atmosphere is applied thereon.
  • An easily injectable electron injection layer can be continuously applied and formed, and an intermediate layer composed of a charge generation layer and an electron injection layer can be applied and laminated.
  • the charge generation layer preferably contains one or more conductive polymers.
  • the conductive polymer constituting the charge generation layer that can be coated and formed on the light emitting unit is any one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and is doped n-type or p-type.
  • a semiconductor is preferable.
  • PEDOT water-soluble poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate
  • PEDOT PSS
  • PEDOT: PSS has good hole injection characteristics, and when used in the charge generation layer, good hole injection characteristics to the first light emitting unit can be obtained.
  • PEDOT: PSS is an aqueous dispersion and it is difficult to form a coating on an organic film having a hydrophobic surface.
  • PEDOT: PSS exhibits strong acidity (pH 1 to 2), it is difficult to stack an electron injection layer made of a material inferior in acid resistance thereon. In this case, neutralize with an aqueous solution of sodium hydroxide (pH 6-8), and spin coat neutral PEDOT: PSS onto the acidic PEDOT: PSS film, thereby stacking an electron injection layer with insufficient acid resistance. It becomes possible.
  • the electron injection layer applied and laminated on the charge generation layer preferably contains one or more metal oxide fine particles or polar polymers.
  • metal oxide microparticles what consists of zinc oxide, a titanium oxide, a zirconium oxide, and an oxide oxide is used suitably. Since such metal oxide fine particles are insoluble in alcohol, toluene, xylene, tetrahydrofuran, chloroform and chlorobenzene, which are organic solvents generally used for coating film formation, adjacent organic films are coated and laminated using an organic solvent. can do.
  • the polar polymer for example, a polyethyleneimine derivative as shown in the following (Chemical Formula 1) is preferably used.
  • Polar polymers such as polyethyleneimine derivatives are water-soluble and are insoluble in toluene, xylene, tetrahydrofuran, chloroform and chlorobenzene, which are organic solvents generally used for coating film formation. Adjacent organic films can be applied and laminated using an organic solvent.
  • the electron injection layer in the intermediate layer is particularly preferably composed of zinc oxide fine particles / polyethyleneimine derivative.
  • the electron injection layer is particularly preferably composed of zinc oxide fine particles / polyethyleneimine derivative.
  • the intermediate layer composed of the charge generation layer and the electron injection layer as described above has an effect of suppressing the permeation of the solvent used during coating formation of the second light emitting unit to the first light emitting unit, This facilitates formation of a multiphoton structure having a plurality of light emitting units.
  • PEDOT PSS
  • zinc oxide fine particles zinc oxide fine particles
  • polyethyleneimine derivatives and the like can be dried at a relatively low temperature of 100 to 120 ° C. during film formation.
  • a flexible substrate made of resin or the like can be used as the element substrate.
  • the organic EL element according to the present invention may be capable of extracting light from either the cathode or the anode, and it is preferable that at least one of the cathode and the anode is transparent.
  • the constituent material of the cathode and the anode is preferably one of metal, metal oxide, and conductive polymer.
  • the metal include aluminum, silver, and gold
  • examples of the metal oxide include ITO, IZO, zinc oxide, AZO, and GZO.
  • the conductive polymer may be any one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and includes a doped n-type or p-type semiconductor.
  • the intermediate layer is coated and laminated using a solvent and then dried at 130 ° C. or less to form a film.
  • the heat treatment temperature can be relatively low. Thereby, the thermal adverse effect on the organic material is suppressed, and the multi-photon emission organic EL element can be efficiently manufactured at a low cost by the coating method. Further, it can also be applied to element fabrication using a flexible substrate, which is difficult to apply to the high-temperature heat treatment process.
  • the layer structure other than the intermediate layer of the organic EL element according to the present invention as described above can be a known structure of the multiphoton emission organic EL element.
  • an electron injection layer may be provided between the cathode / first light emitting unit, and a hole injection layer may be provided between the second light emitting unit / anode.
  • a known laminated structure including a hole transport layer, an electron transport layer, a hole transport light-emitting layer, an electron transport light-emitting layer, and the like may be used. Note that the number of light emitting units including the light emitting layer is not limited to two and may be any number as long as it is plural.
  • the constituent materials of the layers other than the intermediate layer are not particularly limited, and can be appropriately selected from known materials, and may be either low molecular or high molecular. Further, the film thickness of each constituent layer of the organic EL element is appropriately determined according to the situation in consideration of the adaptability between the layers and the required total layer thickness, but usually 0.5 nm to 5 ⁇ m. It is preferable to be within the range.
  • each constituent layer other than the intermediate layer may be a dry process such as a vapor deposition method or a sputtering method, but the present invention has an advantage in that all layers can be formed by a coating method.
  • Wet such as spin coating method, ink jet method, casting method, dip coating method, bar coating method, blade coating method, roll coating method, gravure coating method, flexographic printing method, spray coating method, method using nanoparticle dispersion liquid, etc.
  • the process can be suitably applied. This makes it possible to produce a multiphoton emission organic EL element by a simple and efficient coating method.
  • Example 1-1 Production of coating type multi-photon emission organic EL element A photosensitive resist was coated on a glass substrate with ITO, and mask exposure, development and etching were performed to form a stripe pattern. This patterned glass substrate with ITO was washed with a neutral detergent, then ultrasonically washed with ultrapure water, boiled with 2-propanol, and then subjected to UV ozone treatment for 20 minutes. On the glass substrate with ITO, each layer was formed by a spin coat method in a glove box under the following conditions, and was sequentially laminated.
  • Electron injection layer 1 (film thickness: 10 nm): Spin-coated with a 2-ethoxyethanol dispersion of ZnO fine particles having a particle diameter of 10 nm, and then dried at 100 ° C. for 5 minutes.
  • Electron injection layer 2 (film thickness: 10 nm): A 2-ethoxyethanol solution of polyethyleneimine ethoxylated (PEIE) (Sigma Aldrich Japan) was spin-coated and then dried at 100 ° C. for 5 minutes.
  • PEIE polyethyleneimine ethoxylated
  • Light-emitting layer 1 (film thickness 80 nm): poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -o- (benzo [2,1,3] thiadiazole-4,8- A p-xylene solution of diyl)] (F8BT) (manufactured by Sumitomo Chemical Co., Ltd.) was spin-coated and then dried at 130 ° C. for 10 minutes.
  • Charge generation layer 1 (film thickness 40 nm): PEDOT: PSS (Clevious TM CH8000 manufactured by Heraeus Co., Ltd.) was diluted with methanol and isopropanol at a volume ratio of 1: 1: 4, and this dispersion mixture was spin-coated. And dried at 120 ° C. for 10 minutes.
  • Charge generation layer 2 (film thickness: 10 nm): PEDOT: PSS was mixed with an aqueous sodium hydroxide solution to adjust the pH to 7, then diluted with isopropanol at a volume ratio of 1: 4, and this dispersion mixture was spin coated. Then, it dried for 10 minutes at 120 degreeC.
  • Electron injection layer 3 (film thickness 10 nm): formed in the same manner as the electron injection layer 1.
  • Electron injection layer 4 (film thickness 10 nm): formed in the same manner as the electron injection layer 2.
  • Light-emitting layer 2 (film thickness 80 nm): formed in the same manner as the light-emitting layer 1.
  • Hole injection layer 1 (film thickness 40 nm): PEDOT: PSS was diluted with methanol and isopropanol at a volume ratio of 1: 1: 4, and this dispersion mixture was spin-coated and then dried at 120 ° C. for 10 minutes. did.
  • aluminum was vacuum-deposited to form a cathode having a film thickness of 100 nm, and a coating type multiphoton emission organic EL device having two light emitting units was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / F8BT / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / F8BT / PEDOT: PSS / Al.
  • Example 1-1 Fabrication of Element with First Light-Emitting Unit Only In Example 1-1, the electron injection layers 3 and 4, the light-emitting layer 2, and the hole injection layer 1 were not provided. In the same manner, an organic EL element having one light emitting unit (only the light emitting layer 1) was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / F8BT / PEDOT: PSS / n-PEDOT: PSS / Al.
  • Example 1-1 Fabrication of element having only second light emitting unit
  • the charge generation layer 2, the electron injection layers 3 and 4, the light emitting layer 1 and the hole injection layer 1 were not provided.
  • an organic EL element having only one light emitting unit (only the light emitting layer 2) was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / F8BT / PEDOT: PSS / Al.
  • FIG. 3 shows luminance-voltage characteristics.
  • the vertical axis represents luminance (cd / m 2 ) and the horizontal axis represents drive voltage (V).
  • FIG. 4 shows the external quantum efficiency-current density characteristics.
  • the vertical axis represents external quantum efficiency (%), and the horizontal axis represents current density (mA / cm 2 ).
  • Table 1 shows the drive voltage and external quantum efficiency at a luminance of 1000 cd / m 2 .
  • Example 1-1 the driving voltage and the external quantum efficiency of Example 1-1 were almost the total values of Comparative Example 1-1 and Comparative Example 1-2, and multiphoton emission characteristics were observed.
  • Example 1-2 Production of a coating type multi-photon emission organic EL device in which light emitting units having different emission colors are laminated
  • a polyfluorene blue fluorescent polymer A p-xylene solution manufactured by Sumitomo Chemical Co., Ltd.
  • a coating type multiphoton emission organic EL device was produced in the same manner as in Example 1-1.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / blue fluorescent polymer / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / F8BT / PEDOT: PSS / Al.
  • Example 1-3 Fabrication of organic EL element having only first light emitting unit
  • the electron injection layers 3 and 4, the light emitting layer 2, and the hole injection layer 1 were not provided.
  • an organic EL device having one light emitting unit (only the light emitting layer 1) was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / blue fluorescent polymer / PEDOT: PSS / n-PEDOT: PSS / Al.
  • Example 1-2 The evaluation results of the device characteristics of Example 1-2 and Comparative Examples 1-3 and 1-2 are shown below.
  • FIG. 5 shows the EL spectral characteristics.
  • the vertical axis represents EL relative intensity (au), and the horizontal axis represents wavelength (nm).
  • the blue light emission of the first light emitting unit and the yellow light emission of the second light emitting unit were obtained.
  • FIG. 6 shows the external quantum efficiency-current density characteristics.
  • Table 2 shows driving voltage and external quantum efficiency at a luminance of 1000 cd / m 2 .
  • Example 1-2 From the above evaluation results, the driving voltage and the external quantum efficiency of Example 1-2 were almost the total values of Comparative Example 1-3 and Comparative Example 1-2, and multiphoton emission characteristics were observed.
  • Example 2-1 Fabrication of coating type multiphoton emission organic EL device using hole transport layer
  • the light emitting layers 4 and 5 were formed in place of the light emitting layers 1 and 2, and the light emission was performed.
  • a coating type multiphoton emission organic EL device was produced in the same manner as in Example 1-1 except that the hole transport layer 1 was laminated on the layer 3 and the hole transport layer 2 was laminated on the light emitting layer 4.
  • the light emitting layers 4 and 5 and the hole transport layer 1 were formed as follows.
  • Light-emitting layer 4 (film thickness: 70 nm): A p-xylene solution of polyfluorene-based green fluorescent polymer SGP2 (manufactured by Sumitomo Chemical Co., Ltd.) was spin-coated and then dried at 130 ° C. for 10 minutes.
  • Hole transport layer 1 (film thickness: 10 nm): 1,4-dioxane solution of tetraphenylbenzidine-containing poly (arylene ether sulfone) (TPDPES) was spin-coated and then dried at 120 ° C. for 10 minutes.
  • Light emitting layer 5 (film thickness 70 nm): formed in the same manner as the light emitting layer 4.
  • -Hole transport layer 2 (film thickness 10 nm): formed in the same manner as the hole transport layer 1.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / Al.
  • Example 2-1 Production of organic EL element only with first light emitting unit
  • the electron injection layers 3 and 4, the light emitting layer 5, the hole transport layer 2 and the hole injection layer 1 were not provided. Except for the above, an organic EL device having one light emitting unit (only the light emitting layer 4) was produced in the same manner as in Example 2-1.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / n-PEDOT: PSS / Al.
  • Example 2-2 Production of Organic EL Device with Second Light-Emitting Unit Only In Example 2-1, charge generation layer 2, electron injection layers 3 and 4, light-emitting layer 4, hole transport layer 1 and hole injection layer 1 Otherwise, an organic EL device having one light emitting unit (only the light emitting layer 5) was produced in the same manner as in Example 2-1.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / Al.
  • Example 2-1 and Comparative Examples 2-1 and 2-2 The evaluation results of the device characteristics of Example 2-1 and Comparative Examples 2-1 and 2-2 are shown below.
  • FIG. 7 shows luminance-voltage characteristics.
  • FIG. 8 shows the external quantum efficiency-current density characteristics.
  • Table 3 shows the driving voltage and external quantum efficiency at times luminance 1000 cd / m 2 and 5000 cd / m 2 o'clock.
  • Example 2-1 the driving voltage and external quantum efficiency of Example 2-1 were almost the total values of Comparative Example 2-1 and Comparative Example 2-2, and multiphoton emission characteristics were observed.
  • Example 3-1 Production of coating type multiphoton emission organic EL element having phosphorescent light emitting layer
  • the light emitting layers 6 and 7 were formed in place of the light emitting layers 1 and 2, and the others were In the same manner as in Example 1-1, a coating type multiphoton emission organic EL element was produced.
  • the light emitting layers 6 and 7 were formed as follows.
  • Light emitting layer 6 (film thickness 70 nm): poly-N-vinylcarbazole (PVK), 10 wt% 4,4 ′, 4 ′′ -tris (carbazol-9-yl) triphenylamine (TCTA), 10 wt% 2 , 6-Bis [3- (carbazol-9-yl) phenyl] pyridine (26DCzppy), 10 wt% of tris (2-phenylpyridinato) iridium (III) (Ir (ppy) 3 ) in tetrahydrofuran And then dried at 130 ° C. for 10 minutes.
  • Light emitting layer 7 (film thickness 70 nm): formed in the same manner as the light emitting layer 6.
  • the outline of the layer structure of this element is as follows: glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (Ppy) 3 / PEDOT: PSS / Al.
  • Example 3-1 Fabrication of organic EL element having only first light emitting unit
  • the electron injection layers 3 and 4 the light emitting layer 7 and the hole injection layer 1 were not provided.
  • an organic EL device having one light emitting unit (only the light emitting layer 6) was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 / PEDOT: PSS / n-PEDOT: PSS / Al.
  • Example 3-2 Production of Organic EL Device with Second Light-Emitting Unit Only
  • the electron injection layers 3 and 4 the light-emitting layer 6, and the hole injection layer 1 were not provided.
  • an organic EL device having one light emitting unit (only the light emitting layer 7) was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 / PEDOT: PSS / Al.
  • Example 3-1 and Comparative Examples 3-1 and 3-2 The evaluation results of the device characteristics of Example 3-1 and Comparative Examples 3-1 and 3-2 are shown below.
  • FIG. 9 shows luminance-voltage characteristics.
  • FIG. 10 shows the external quantum efficiency-current density characteristics.
  • Table 4 shows the driving voltage and external quantum efficiency at times luminance 1000 cd / m 2 and 5000 cd / m 2 o'clock.
  • Example 3-1 the driving voltage and the external quantum efficiency of Example 3-1 are almost the total values of Comparative Example 3-1 and Comparative Example 3-2, and the multiphoton emission characteristics are also obtained in the element using the phosphorescent material. was recognized.
  • Example 4-1 Production of a coating type multiphoton emission organic EL device having phosphorescent light emitting layers having different emission colors
  • the light emitting layers 8 and 9 were formed in place of the light emitting layers 1 and 2.
  • a coating type multiphoton emission organic EL device was produced in the same manner as in Example 1-1.
  • the light emitting layers 8 and 9 were formed as follows.
  • Light-emitting layer 8 (film thickness 70 nm): PVK, 10 wt% TCTA, 10 wt% 26 DCzppy, 10 wt% Ir (ppy) 3 ), 1 wt% tris (2-phenylisoquinoline) iridium (III) (Ir (phq) 3 ) After spin coating with a tetrahydrofuran solution, the solution was dried at 130 ° C. for 10 minutes.
  • Light-emitting layer 9 (film thickness 70 nm): PVK, 10 wt% TCTA, 10 wt% 26 DCzppy), 10 wt% of tris (2- (2,4-difluorophenyl) pyridine) iridium (III) (Ir (Fppy) 3 ) After spin-coating the tetrahydrofuran solution, it was dried at 130 ° C. for 10 minutes.
  • the outline of the layer structure of this element is as follows: glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 : Ir (phq) 3 / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / PVK : TCTA: 26DCzppy: Ir (Fppy) 3 / PEDOT: PSS / Al.
  • Example 4-1 Production of Organic EL Element with First Light-Emitting Unit Only
  • the electron injection layers 3 and 4, the light-emitting layer 9, and the hole injection layer 1 were not provided.
  • an organic EL device having one light emitting unit (only the light emitting layer 8) was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 : Ir (phq) 3 / PEDOT: PSS / n-PEDOT: PSS / Al.
  • Example 4-2 Production of Organic EL Device with Second Light-Emitting Unit Only
  • the electron injection layers 3 and 4 the light-emitting layer 8, and the hole injection layer 1 were not provided.
  • an organic EL device having one light emitting unit (only the light emitting layer 9) was produced.
  • the outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (Fppy) 3 / PEDOT: PSS / Al.
  • Example 4-1 and Comparative Examples 4-1 and 4-2 The evaluation results of the device characteristics of Example 4-1 and Comparative Examples 4-1 and 4-2 are shown below.
  • FIG. 11 shows the EL spectral characteristics.
  • FIG. 12 shows the external quantum efficiency-current density characteristics.
  • Table 5 shows the driving voltage and external quantum efficiency at times luminance 1000 cd / m 2 and 5000 cd / m 2 o'clock.
  • Example 4-1 the driving voltage and the external quantum efficiency of Example 4-1 are almost the total values of Comparative Example 4-1 and Comparative Example 4-2, and even in an element using phosphorescent materials having different emission colors. Multi-photon emission characteristics were observed.

Abstract

Provided is an organic EL element with which the applying and layering of intermediary layers that include a charge-generating layer in a multiphoton-emitting organic electroluminescent element are simplified, making it possible to efficiently and inexpensively form all constituting layers without degrading the properties of the element, and making it possible to form the element using a coating technique. Also provided is a method for manufacturing an organic EL element. A multiphoton-emitting organic electroluminescent element in which a plurality of light-emitting units that have at least one light-emitting layer are layered between a pair of electrodes with an intermediary layer therebetween, wherein the intermediary layer is configured by applying and layering the electric charge-generating layer near a negative electrode and an electron-injecting layer near a positive electrode, and an inverted-structure configuration is obtained.

Description

有機エレクトロルミネッセンス素子及びその製造方法Organic electroluminescence device and method for manufacturing the same
　本発明は、塗布法により作製することができるマルチフォトンエミッション有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子と略称する）及びその製造方法に関する。 The present invention relates to a multi-photon emission organic electroluminescence element (hereinafter abbreviated as an organic EL element) that can be produced by a coating method and a method for producing the same.
　複数の発光ユニットを電荷発生層（中間層）を介して直列に接続したマルチフォトンエミッション有機ＥＬ素子は、同一輝度で通常の有機ＥＬ素子と比較した場合、各ユニット当たりの電流量を低減させることで、素子の耐久性を向上させることができる。また、電流値を一定とした場合、各ユニットからそれぞれの輝度が得られるため、効率面においても有効な手段である。 A multiphoton emission organic EL device in which a plurality of light emitting units are connected in series via a charge generation layer (intermediate layer) reduces the amount of current per unit when compared with a normal organic EL device with the same luminance. Thus, the durability of the element can be improved. In addition, when the current value is constant, each unit can obtain the respective luminance, so that it is an effective means in terms of efficiency.
　しかしながら、有機材料の多段積層化や、電荷発生層として金属酸化物又は金属の使用が必要となるため、塗布法を用いた素子作製が困難であり、各構成層の積層工程には、一般に、真空蒸着法が用いられている。 However, since multi-layered organic materials and the use of a metal oxide or metal as a charge generation layer are required, it is difficult to produce an element using a coating method. A vacuum deposition method is used.
　近年、蒸着法と塗布法を組み合わせたマルチフォトンエミッション有機ＥＬ素子の製造方法も提案されており、例えば、特許文献１に、電荷発生層（Ｖ2Ｏ5）と電子注入層（Ｌｉ）からなる中間層を真空蒸着にて成膜し、各発光ユニットを塗布法にて成膜することが記載されている。 In recent years, a method for producing a multi-photon emission organic EL element in which a vapor deposition method and a coating method are combined has been proposed. For example, Patent Document 1 includes a charge generation layer (V 2 O 5 ) and an electron injection layer (Li). It is described that the intermediate layer is formed by vacuum deposition, and each light emitting unit is formed by a coating method.
　一方、発光ユニット及び中間層のいずれも塗布成膜した素子も開示されている。例えば、特許文献２には、ジペンタエリシリトールヘキサアクリレートを熱架橋材料として用い、発光層、電荷発生層及び電子注入層を２００℃にて加熱焼成することで不溶化することが記載されている。また、特許文献３には、電荷発生材料や電子注入層に光架橋性基を導入し、低圧水銀灯（１５ｍＷ／ｃｍ2）照射下、１２０℃にて加熱焼成することで塗布法による多段積層化を行うことが記載されている。 On the other hand, an element in which both the light emitting unit and the intermediate layer are coated is disclosed. For example, Patent Document 2 describes that dipentaerythritol hexaacrylate is used as a thermal crosslinking material, and the light emitting layer, the charge generation layer, and the electron injection layer are insolubilized by heating and baking at 200 ° C. . In Patent Document 3, a photocrosslinkable group is introduced into a charge generation material or an electron injection layer, and is heated and fired at 120 ° C. under irradiation of a low-pressure mercury lamp (15 mW / cm 2 ) to form a multi-layered structure by a coating method. It is described to do.
特開２０１０－１９２４７４号公報JP 2010-192474 A 特開２００９－１５２０１５号公報JP 2009-152015 A 特開２０１１－８６４４２号公報JP 2011-86442 A
　しかしながら、上記特許文献１に記載されたような方法は、複数の異なる成膜プロセスを繰り返す必要があるため、連続的な素子作製が困難であり、高コスト化の要因となる。また、水分や酸素に対して不安定である電子注入金属材料に対して塗布成膜を行うため、素子特性の低下が懸念される。 However, the method as described in the above-mentioned Patent Document 1 needs to repeat a plurality of different film forming processes, so that it is difficult to produce a continuous element, which causes an increase in cost. In addition, since the coating film is formed on the electron-injecting metal material that is unstable with respect to moisture and oxygen, there is a concern about deterioration of element characteristics.
　また、上記特許文献２に記載されているような方法では、塗布法のみで各構成層を作製することが可能となるが、発光層への架橋材料の添加は、発光効率の低下や素子の高電圧化を引き起こす要因となる。また、加熱温度が２００℃と高温であり、使用する材料や基板が耐熱性のあるものに限定される等の課題を有している。
　さらに、上記特許文献３に記載されているような方法では、架橋反応による輸送特性及び注入特性の低下が、素子特性に悪影響を及ぼすおそれがある。 In addition, in the method as described in Patent Document 2, it is possible to produce each constituent layer only by a coating method. However, addition of a crosslinking material to the light-emitting layer reduces the light emission efficiency or reduces the element. It becomes a factor causing high voltage. In addition, the heating temperature is as high as 200 ° C., and there is a problem that the material and the substrate to be used are limited to those having heat resistance.
Furthermore, in the method as described in Patent Document 3, a decrease in transport characteristics and injection characteristics due to a crosslinking reaction may adversely affect device characteristics.
　このように、従来の方法では、素子作製の簡略化と高効率化を両立することは困難であった。また、架橋性材料を使用せずに、電荷発生層及び電子注入層を塗布法にて成膜し、リン光材料を適用したという先行技術は報告されていない。 Thus, with the conventional method, it has been difficult to achieve both simplification of device fabrication and high efficiency. In addition, no prior art has been reported in which a charge generation layer and an electron injection layer are formed by a coating method without using a crosslinkable material and a phosphorescent material is applied.
　したがって、マルチフォトンエミッション有機ＥＬ素子を、塗布法で簡便に、かつ、素子特性を低下させることなく形成するための中間層の好適な材料や層構成を見出すことが求められている。 Therefore, it is required to find a suitable material and layer structure of an intermediate layer for forming a multi-photon emission organic EL element easily by a coating method without deteriorating element characteristics.
　本発明は、上記技術課題を解決するためになされたものであり、マルチフォトンエミッション有機ＥＬ素子において、電荷発生層を含む中間層の塗布積層を簡略化することにより、すべての構成層を効率的に低コストで、かつ、素子特性を低下させることなく、塗布法で簡便に形成することができる有機ＥＬ素子及びその製造方法を提供することを目的とするものである。 The present invention has been made to solve the above technical problem, and in a multi-photon emission organic EL element, by simplifying the coating lamination of the intermediate layer including the charge generation layer, all the constituent layers can be made efficient. Another object of the present invention is to provide an organic EL element that can be easily formed by a coating method at low cost and without deteriorating element characteristics, and a method for producing the same.
　本発明に係る有機ＥＬ素子は、１対の電極間に、少なくとも１つの発光層を有する発光ユニットが中間層を介して複数積層されたマルチフォトンエミッション有機ＥＬ素子であって、前記中間層が、陰極側の電荷発生層と、陽極側の電子注入層との塗布積層からなり、インバーテッド構造を有することを特徴とする。
　前記インバーテッド構造は、具体的には、基板上に、陰極、中間層を介して複数積層された発光ユニット、陽極の順に積層された構成からなる。
　このようなインバーテッド構造とすることにより、マルチフォトンエミッション有機ＥＬ素子の積層構造を塗布法により簡便に構成することが可能となる。 The organic EL device according to the present invention is a multi-photon emission organic EL device in which a plurality of light emitting units each having at least one light emitting layer are stacked via an intermediate layer between a pair of electrodes, and the intermediate layer includes: It consists of a coating layer of a charge generation layer on the cathode side and an electron injection layer on the anode side, and has an inverted structure.
Specifically, the inverted structure has a structure in which a cathode, a plurality of light emitting units stacked via an intermediate layer, and an anode are stacked in this order on a substrate.
By adopting such an inverted structure, it is possible to easily construct a laminated structure of multi-photon emission organic EL elements by a coating method.
　前記有機ＥＬ素子においては、電荷発生層が導電性高分子を１層又は複数層含有していることが好ましい。
　このような電荷発生層によれば、塗布成膜が可能となり、かつ、成膜時に高温加熱を要することなく成膜することができる。 In the organic EL element, the charge generation layer preferably contains one or more conductive polymers.
According to such a charge generation layer, coating can be formed, and the film can be formed without requiring high-temperature heating at the time of film formation.
　前記導電性高分子としては、ポリチオフェン誘導体、ポリアニリン誘導体及びポリアリールアミン誘導体のうちのいずれかであり、ドープされたｎ型又はｐ型半導体であることが好ましい。
　このような導電性高分子によれば、塗布成膜によりホール注入特性に優れた電荷発生層を構成し得る。 The conductive polymer is any one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and is preferably a doped n-type or p-type semiconductor.
According to such a conductive polymer, a charge generation layer having excellent hole injection characteristics can be formed by coating film formation.
　また、前記電子注入層が、金属酸化物微粒子又は極性高分子を１層又は複数層含有していることが好ましい。
　このような電子注入層によれば、前記中間層が、隣接する上層の成膜性を向上させ、かつ、隣接する下層への溶媒の浸透を防止する効果を奏するものとなる。 The electron injection layer preferably contains one or more metal oxide fine particles or polar polymers.
According to such an electron injection layer, the intermediate layer has an effect of improving the film forming property of the adjacent upper layer and preventing penetration of the solvent into the adjacent lower layer.
　金属酸化物微粒子の場合は、酸化亜鉛、酸化チタン、酸化ジルコニウム及び酸化ズズのうちのいずれかからなり、また、極性高分子の場合は、ポリエチレンイミン誘導体であることが好ましい。 In the case of metal oxide fine particles, it is composed of any one of zinc oxide, titanium oxide, zirconium oxide and oxide, and in the case of a polar polymer, it is preferably a polyethyleneimine derivative.
　また、前記発光ユニットは、蛍光又はリン光発光するもののいずれでもよい。
　前記電子注入層が、電荷発生層からの良好な電子注入特性を発揮するため、いずれの発光材料でも好適に適用し得る。 The light emitting unit may be any one that emits fluorescence or phosphorescence.
Since the electron injection layer exhibits good electron injection characteristics from the charge generation layer, any light emitting material can be suitably applied.
　さらに、光取り出し面として、前記陰極及び前記陽極の少なくともいずれか一方が透明であることが好ましい。 Furthermore, it is preferable that at least one of the cathode and the anode is transparent as a light extraction surface.
　前記陰極及び前記陽極は、金属、金属酸化物及び導電性高分子のうちのいずれかからなることが好ましい。
　金属の場合は、アルミニウム、銀及び金のうちのいずれかであり、また、金属酸化物の場合は、インジウム－錫酸化物（ＩＴＯ）、インジウム－亜鉛酸化物（ＩＺＯ）、酸化亜鉛、アルミニウム添加酸化亜鉛（ＡＺＯ）及びガリウム添加酸化亜鉛（ＧＺＯ）のうちのいずれかであり、また、導電性高分子の場合は、ポリチオフェン誘導体、ポリアニリン誘導体及びポリアリールアミン誘導体のうちのいずれかであり、ドープされたｎ型又はｐ型半導体であることが好ましい。 The cathode and the anode are preferably made of any one of metal, metal oxide, and conductive polymer.
In the case of metal, it is one of aluminum, silver, and gold. In the case of metal oxide, indium-tin oxide (ITO), indium-zinc oxide (IZO), zinc oxide, aluminum addition One of zinc oxide (AZO) and gallium-doped zinc oxide (GZO), and in the case of a conductive polymer, one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative; Preferably, the n-type or p-type semiconductor is used.
　また、本発明に係る有機ＥＬ素子の製造方法は、上記の有機ＥＬ素子を製造する方法であって、前記中間層を、溶媒を用いて塗布積層した後、１３０℃以下で乾燥させて成膜する工程を備えていることを特徴とする。
　前記中間層は、１３０℃以下の低温処理で成膜することができるため、マルチフォトンエミッション有機ＥＬ素子を塗布法で効率的に低コストで製造することが可能となる。 The method for producing an organic EL device according to the present invention is a method for producing the above-mentioned organic EL device, wherein the intermediate layer is coated and laminated using a solvent, and then dried at 130 ° C. or less to form a film. It is characterized by comprising the step of:
Since the intermediate layer can be formed by a low-temperature treatment at 130 ° C. or lower, a multiphoton emission organic EL element can be efficiently manufactured at a low cost by a coating method.
　本発明によれば、マルチフォトンエミッション有機ＥＬ素子における電荷発生層を含む中間層を簡便に塗布積層することができるため、すべての構成層を塗布法により形成することが可能となる。
　したがって、本発明における中間層を適用することにより、多段積層が必要なマルチフォトンエミッション有機ＥＬ素子を、塗布法で効率的に低コストで製造することが可能となり、さらに、素子の高効率化も期待される。 According to the present invention, since the intermediate layer including the charge generation layer in the multi-photon emission organic EL element can be easily applied and laminated, all the constituent layers can be formed by the application method.
Therefore, by applying the intermediate layer in the present invention, it becomes possible to produce a multi-photon emission organic EL element that requires multi-layer stacking efficiently and at low cost, and further increase the efficiency of the element. Be expected.
インバーテット構造のマルチフォトンエミッション有機ＥＬ素子の層構造を模式的に示した概略断面図である。It is the schematic sectional drawing which showed typically the layer structure of the multiphoton emission organic EL element of an inverted structure. 標準構造のマルチフォトンエミッション有機ＥＬ素子の層構造を模式的に示した概略断面図である。It is the schematic sectional drawing which showed typically the layer structure of the multiphoton emission organic EL element of a standard structure. 実施例１－１及び比較例１－１，１－２の素子の輝度－電圧特性を示したグラフである。6 is a graph showing luminance-voltage characteristics of the elements of Example 1-1 and Comparative Examples 1-1 and 1-2. 実施例１－１及び比較例１－１，１－２の素子の外部量子効率－電流密度特性を示したグラフである。6 is a graph showing external quantum efficiency-current density characteristics of the devices of Example 1-1 and Comparative Examples 1-1 and 1-2. 実施例１－２及び比較例１－３，１－２の素子のＥＬスペクトル特性を示したグラフである。6 is a graph showing EL spectral characteristics of the elements of Example 1-2 and Comparative Examples 1-3 and 1-2. 実施例１－２及び比較例１－３，１－２の素子の外部量子効率－電流密度特性を示したグラフである。4 is a graph showing external quantum efficiency-current density characteristics of the devices of Example 1-2 and Comparative Examples 1-3 and 1-2. 実施例２－１及び比較例２－１，２－２の素子の輝度－電圧特性を示したグラフである。6 is a graph showing luminance-voltage characteristics of the elements of Example 2-1 and Comparative Examples 2-1 and 2-2. 実施例２－１及び比較例２－１，２－２の素子の外部量子効率－電流密度特性を示したグラフである。6 is a graph showing external quantum efficiency-current density characteristics of the devices of Example 2-1 and Comparative Examples 2-1 and 2-2. 実施例３－１及び比較例３－１，３－２の素子の輝度－電圧特性を示したグラフである。6 is a graph showing luminance-voltage characteristics of the elements of Example 3-1 and Comparative Examples 3-1 and 3-2. 実施例３－１及び比較例３－１，３－２の素子の外部量子効率－電流密度特性を示したグラフである。6 is a graph showing external quantum efficiency-current density characteristics of the devices of Example 3-1 and Comparative Examples 3-1 and 3-2. 実施例４－１及び比較例４－１，４－２の素子のＥＬスペクトル特性を示したグラフである。6 is a graph showing EL spectrum characteristics of the elements of Example 4-1 and Comparative Examples 4-1 and 4-2. 実施例４－１及び比較例４－１，４－２の素子の外部量子効率－電流密度特性を示したグラフである。6 is a graph showing the external quantum efficiency-current density characteristics of the devices of Example 4-1 and Comparative Examples 4-1 and 4-2.
　以下、本発明について、図面を参照して、より詳細に説明する。
　本発明に係る有機ＥＬ素子は、１対の電極間に、少なくとも１つの発光層を有する発光ユニットが中間層を介して複数積層されたマルチフォトンエミッション有機ＥＬ素子である。そして、前記中間層が、陰極側の電荷発生層と、陽極側の電子注入層との塗布積層からなり、インバーテッド構造を有していることを特徴としている。前記インバーテッド構造は、具体的には、基板上に、陰極、中間層を介して複数積層された発光ユニット、陽極の順に積層された構成である。 Hereinafter, the present invention will be described in more detail with reference to the drawings.
The organic EL device according to the present invention is a multi-photon emission organic EL device in which a plurality of light emitting units each having at least one light emitting layer are stacked via an intermediate layer between a pair of electrodes. The intermediate layer is formed of a coating layer of a charge generation layer on the cathode side and an electron injection layer on the anode side, and has an inverted structure. Specifically, the inverted structure has a structure in which a plurality of light emitting units stacked on a substrate in the order of a cathode, an intermediate layer, and an anode are stacked in this order.
　図１に、インバーテッド構造のマルチフォトンエミッション有機ＥＬ素子の層構成の一例を示す。また、図２に、標準構造のマルチフォトンエミッション有機ＥＬ素子の層構成の一例を示す。
　図２に示すような標準構造の素子においては、ガラス基板１１上のＩＴＯ透明電極を陽極１２とし、その上に、第一発光ユニット１３、電荷発生層１５、電子注入層１４、第二発光ユニット１６が積層され、その上に、陰極１７としてアルミニウム反射電極が形成されている。
　これに対して、インバーテッド構造の素子は、図１に示すように、ガラス基板１上の陰極２にＩＴＯ透明電極を用い、その上に、第一発光ユニット３、電荷発生層４、電子注入層５、第二発光ユニット６が積層され、その上に、陽極７としてアルミニウム反射電極が形成されている。 FIG. 1 shows an example of the layer structure of an inverted multi-photon emission organic EL element. FIG. 2 shows an example of a layer structure of a multi-photon emission organic EL element having a standard structure.
In the element having a standard structure as shown in FIG. 2, the ITO transparent electrode on the glass substrate 11 is used as the anode 12, and the first light emitting unit 13, the charge generation layer 15, the electron injection layer 14, and the second light emitting unit are formed thereon. 16 is laminated, and an aluminum reflective electrode is formed thereon as a cathode 17.
On the other hand, as shown in FIG. 1, the inverted structure element uses an ITO transparent electrode as the cathode 2 on the glass substrate 1, and the first light emitting unit 3, the charge generation layer 4, and the electron injection thereon. The layer 5 and the second light emitting unit 6 are laminated, and an aluminum reflective electrode is formed thereon as the anode 7.
　マルチフォトンエミッション有機ＥＬ素子を塗布法により作製する場合、電荷発生層を含む中間層が、その下層（第一発光ユニット）を再溶解しない溶媒で塗布成膜可能であり、かつ、該中間層の上層（第二発光ユニット）の塗布に用いられる溶媒に不溶であることが求められる。さらに、安定的に素子を作製するためには、前記中間層がその上層（第二発光ユニット）の成膜性を向上させ、かつ、該中間層の下層（第一発光ユニット）への溶媒の浸透が防止されることが望ましい。 When producing a multi-photon emission organic EL device by a coating method, the intermediate layer including the charge generation layer can be formed by coating with a solvent that does not redissolve the lower layer (first light emitting unit), and the intermediate layer It is required to be insoluble in the solvent used for coating the upper layer (second light emitting unit). Further, in order to stably manufacture the device, the intermediate layer improves the film formability of the upper layer (second light emitting unit), and the solvent to the lower layer (first light emitting unit) of the intermediate layer. It is desirable to prevent penetration.
　本発明は、マルチフォトンエミッション有機ＥＬ素子を上記のようなインバーテッド構造とすることにより、発光ユニットの上に電荷発生層を塗布成膜し、その上に、大気中の酸素や水分の影響を受けやすい電子注入層を連続的に塗布成膜することが可能となり、電荷発生層及び電子注入層からなる中間層を塗布積層することを可能とするものである。 In the present invention, the multi-photon emission organic EL element has an inverted structure as described above, and a charge generation layer is formed on the light emitting unit by coating, and the influence of oxygen and moisture in the atmosphere is applied thereon. An easily injectable electron injection layer can be continuously applied and formed, and an intermediate layer composed of a charge generation layer and an electron injection layer can be applied and laminated.
　本発明に係る有機ＥＬ素子においては、電荷発生層が導電性高分子を１層又は複数層含有していることが好ましい。
　さらに、発光ユニット上に塗布成膜可能な電荷発生層を構成する導電性高分子としては、ポリチオフェン誘導体、ポリアニリン誘導体及びポリアリールアミン誘導体のうちのいずれかであり、ドープされたｎ型又はｐ型半導体であることが好ましい。 In the organic EL device according to the present invention, the charge generation layer preferably contains one or more conductive polymers.
Further, the conductive polymer constituting the charge generation layer that can be coated and formed on the light emitting unit is any one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and is doped n-type or p-type. A semiconductor is preferable.
　前記導電性高分子のうち、特に、水溶性であるポリ（３，４－エチレンジオキシチオフェン）－ポリスチレンスルホネート（ＰＥＤＯＴ：ＰＳＳ）が好適に用いられる。ＰＥＤＯＴ：ＰＳＳは、塗布成膜に一般に用いられる有機溶媒であるアルコール、トルエン、キシレン、テトラヒドロフラン、クロロホルム及びクロロベンゼンに不溶であることから、その上の有機膜を、有機溶媒を用いて塗布積層することができる。
　また、ＰＥＤＯＴ：ＰＳＳは、良好なホール注入特性を有するものであり、電荷発生層に用いた場合、第一発光ユニットへの良好なホール注入特性が得られる。
　なお、ＰＥＤＯＴ：ＰＳＳは、水分散液であり、表面が疎水性である有機膜上への塗布成膜が困難であるため、メタノールやイソプロパノール等のアルコール系溶媒で希釈することにより、有機膜上への濡れ性を改善し、良好な成膜性を得ることができる。さらに、熱や光架橋性材料を用いることなく、容易に多積層化させることが可能となる。
　また、ＰＥＤＯＴ：ＰＳＳは、強い酸性（ｐＨ１～２）を示すため、耐酸性に劣る材料かならなる電子注入層をその上に積層させることは困難である。この場合は、水酸化ナトリウム水溶液で中和（ｐＨ６～８）し、酸性のＰＥＤＯＴ：ＰＳＳ膜上に中性のＰＥＤＯＴ：ＰＳＳをスピンコートすることにより、耐酸性が十分でない電子注入層を積層させることが可能となる。 Among the conductive polymers, in particular, water-soluble poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT: PSS) is preferably used. PEDOT: PSS is insoluble in alcohols, toluene, xylene, tetrahydrofuran, chloroform, and chlorobenzene, which are organic solvents generally used for coating film formation. Can do.
PEDOT: PSS has good hole injection characteristics, and when used in the charge generation layer, good hole injection characteristics to the first light emitting unit can be obtained.
PEDOT: PSS is an aqueous dispersion and it is difficult to form a coating on an organic film having a hydrophobic surface. Therefore, by diluting with an alcohol solvent such as methanol or isopropanol, This improves the wettability of the film and provides good film formability. Furthermore, it is possible to easily make multiple layers without using heat or a photocrosslinkable material.
In addition, since PEDOT: PSS exhibits strong acidity (pH 1 to 2), it is difficult to stack an electron injection layer made of a material inferior in acid resistance thereon. In this case, neutralize with an aqueous solution of sodium hydroxide (pH 6-8), and spin coat neutral PEDOT: PSS onto the acidic PEDOT: PSS film, thereby stacking an electron injection layer with insufficient acid resistance. It becomes possible.
　前記電荷発生層に塗布積層される電子注入層は、金属酸化物微粒子又は極性高分子を１層又は複数層含有していることが好ましい。
　前記金属酸化物微粒子としては、酸化亜鉛、酸化チタン、酸化ジルコニウム及び酸化ズズからなるものが好適に用いられる。このような金属酸化物微粒子は、塗布成膜に一般に用いられる有機溶媒であるアルコール、トルエン、キシレン、テトラヒドロフラン、クロロホルム及びクロロベンゼンに不溶であることから、隣接する有機膜を有機溶媒を用いて塗布積層することができる。
　また、前記極性高分子としては、例えば、下記（化１）に示すようなポリエチレンイミン誘導体が好適に用いられる。ポリエチレンイミン誘導体等の極性高分子は、水溶性であり、塗布成膜に一般に用いられる有機溶媒であるトルエン、キシレン、テトラヒドロフラン、クロロホルム及びクロロベンゼンに不溶であることから、前記金属酸化物微粒子と同様に、隣接する有機膜を有機溶媒を用いて塗布積層することができる。 The electron injection layer applied and laminated on the charge generation layer preferably contains one or more metal oxide fine particles or polar polymers.
As said metal oxide microparticles | fine-particles, what consists of zinc oxide, a titanium oxide, a zirconium oxide, and an oxide oxide is used suitably. Since such metal oxide fine particles are insoluble in alcohol, toluene, xylene, tetrahydrofuran, chloroform and chlorobenzene, which are organic solvents generally used for coating film formation, adjacent organic films are coated and laminated using an organic solvent. can do.
As the polar polymer, for example, a polyethyleneimine derivative as shown in the following (Chemical Formula 1) is preferably used. Polar polymers such as polyethyleneimine derivatives are water-soluble and are insoluble in toluene, xylene, tetrahydrofuran, chloroform and chlorobenzene, which are organic solvents generally used for coating film formation. Adjacent organic films can be applied and laminated using an organic solvent.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　前記中間層における電子注入層は、特に、酸化亜鉛微粒子／ポリエチレンイミン誘導体から構成されることが好ましい。電子注入層をこのような複数層の構成とすることにより、電荷発生層から第二発光ユニットへの良好な電子注入特性が得られる。これは、極性高分子であるポリエチレンイミン誘導体が酸化亜鉛微粒子の仕事関数を低エネルギー側へと変化させ、電子の注入障壁がより緩和することによる。
　このように電子注入特性が向上することにより、発光ユニットは、蛍光材料による発光のみならず、リン光材料により発光するものにも好適に適用することができる。 The electron injection layer in the intermediate layer is particularly preferably composed of zinc oxide fine particles / polyethyleneimine derivative. By configuring the electron injection layer to have such a plurality of layers, good electron injection characteristics from the charge generation layer to the second light emitting unit can be obtained. This is because the polyethyleneimine derivative, which is a polar polymer, changes the work function of the zinc oxide fine particles to a lower energy side, thereby further relaxing the electron injection barrier.
Thus, by improving the electron injection characteristics, the light emitting unit can be suitably applied not only to the light emission by the fluorescent material but also to the light emission by the phosphorescent material.
　上記のような電荷発生層及び電子注入層により構成される中間層は、第二発光ユニットの塗布形成時に用いられる溶媒が第一発光ユニットにまで浸透することを抑制する効果を奏するものであり、これにより、複数の発光ユニットを有するマルチフォトン構造の形成が容易となる。 The intermediate layer composed of the charge generation layer and the electron injection layer as described above has an effect of suppressing the permeation of the solvent used during coating formation of the second light emitting unit to the first light emitting unit, This facilitates formation of a multiphoton structure having a plurality of light emitting units.
　また、前記中間層を構成する材料のうち、ＰＥＤＯＴ：ＰＳＳ、酸化亜鉛微粒子、ポリエチレンイミン誘導体等は、成膜時に１００～１２０℃と比較的低温で乾燥させることができるため、有機材料への熱的な悪影響が抑制され、素子基板として樹脂製等のフレキシブル基板の適用も可能となる。 Among the materials constituting the intermediate layer, PEDOT: PSS, zinc oxide fine particles, polyethyleneimine derivatives, and the like can be dried at a relatively low temperature of 100 to 120 ° C. during film formation. Thus, a flexible substrate made of resin or the like can be used as the element substrate.
　なお、本発明に係る有機ＥＬ素子は、陰極又は陽極のいずれから光を取り出すことができるものであってもよく、陰極及び陽極の少なくともいずれか一方が透明であることが好ましい。
　前記陰極及び前記陽極の構成材料は、金属、金属酸化物及び導電性高分子のうちのいずれかであることが好ましい。
　具体的には、金属としては、アルミニウム、銀又は金、また、金属酸化物としては、ＩＴＯ、ＩＺＯ、酸化亜鉛、ＡＺＯ又はＧＺＯが挙げられる。また、導電性高分子としては、ポリチオフェン誘導体、ポリアニリン誘導体及びポリアリールアミン誘導体のうちのいずれかであって、ドープされたｎ型又はｐ型半導体が挙げられる。 In addition, the organic EL element according to the present invention may be capable of extracting light from either the cathode or the anode, and it is preferable that at least one of the cathode and the anode is transparent.
The constituent material of the cathode and the anode is preferably one of metal, metal oxide, and conductive polymer.
Specifically, examples of the metal include aluminum, silver, and gold, and examples of the metal oxide include ITO, IZO, zinc oxide, AZO, and GZO. The conductive polymer may be any one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and includes a doped n-type or p-type semiconductor.
　また、上記のような本発明に係る有機ＥＬ素子の製造方法においては、前記中間層を、溶媒を用いて塗布積層した後、１３０℃以下で乾燥させて成膜する工程を経ることが好ましい。
　上述したように、前記電荷発生層及び電子注入層からなる中間層は、成膜時に１３０℃以下で乾燥させることができるため、熱処理温度は比較的低温で行うことができる。これにより、有機材料への熱的な悪影響が抑制され、かつ、マルチフォトンエミッション有機ＥＬ素子を塗布法で効率的に低コストで製造することが可能となる。また、高温熱処理工程には適用することが困難であるフレキシブル基板を用いた素子作製にも適用することができる。 Moreover, in the manufacturing method of the organic EL element according to the present invention as described above, it is preferable that the intermediate layer is coated and laminated using a solvent and then dried at 130 ° C. or less to form a film.
As described above, since the intermediate layer composed of the charge generation layer and the electron injection layer can be dried at 130 ° C. or lower during film formation, the heat treatment temperature can be relatively low. Thereby, the thermal adverse effect on the organic material is suppressed, and the multi-photon emission organic EL element can be efficiently manufactured at a low cost by the coating method. Further, it can also be applied to element fabrication using a flexible substrate, which is difficult to apply to the high-temperature heat treatment process.
　上記のような本発明に係る有機ＥＬ素子の中間層以外の層構造は、マルチフォトンエミッション有機ＥＬ素子の公知の構成とすることができる。例えば、陰極／第一発光ユニット間には、電子注入層を設けてもよく、また、第二発光ユニット／陽極間には、ホール注入層を設けてもよい。さらに、ホール輸送層、電子輸送層、ホール輸送発光層、電子輸送発光層等をも含む公知の積層構造であってもよい。
　なお、発光層を含む発光ユニットの数は、２つに限られず、複数であればいくつでもよい。 The layer structure other than the intermediate layer of the organic EL element according to the present invention as described above can be a known structure of the multiphoton emission organic EL element. For example, an electron injection layer may be provided between the cathode / first light emitting unit, and a hole injection layer may be provided between the second light emitting unit / anode. Furthermore, a known laminated structure including a hole transport layer, an electron transport layer, a hole transport light-emitting layer, an electron transport light-emitting layer, and the like may be used.
Note that the number of light emitting units including the light emitting layer is not limited to two and may be any number as long as it is plural.
　前記中間層以外の層の構成材料は、特に限定されるものではなく、公知のものから適宜選択して用いることができ、低分子系又は高分子系のいずれであってもよい。
　また、前記有機ＥＬ素子の各構成層の膜厚は、各層同士の適応性や求められる全体の層厚さ等を考慮して、適宜状況に応じて定められるが、通常、０．５ｎｍ～５μｍの範囲内であることが好ましい。 The constituent materials of the layers other than the intermediate layer are not particularly limited, and can be appropriately selected from known materials, and may be either low molecular or high molecular.
Further, the film thickness of each constituent layer of the organic EL element is appropriately determined according to the situation in consideration of the adaptability between the layers and the required total layer thickness, but usually 0.5 nm to 5 μm. It is preferable to be within the range.
　前記中間層以外の各構成層の形成方法は、蒸着法、スパッタリング法等のドライプロセスでもよいが、本発明は、特に、すべての層を塗布法により形成可能である点に利点を有しており、スピンコート法、インクジェット法、キャスティング法、ディップコート法、バーコート法、ブレードコート法、ロールコート法、グラビアコート法、フレキソ印刷法、スプレーコート法、ナノパーティクル分散液を用いる方法等のウェットプロセスを好適に適用することができる。
　これにより、簡便で効率的な塗布法によるマルチフォトンエミッション有機ＥＬ素子の作製が可能となる。 The formation method of each constituent layer other than the intermediate layer may be a dry process such as a vapor deposition method or a sputtering method, but the present invention has an advantage in that all layers can be formed by a coating method. Wet such as spin coating method, ink jet method, casting method, dip coating method, bar coating method, blade coating method, roll coating method, gravure coating method, flexographic printing method, spray coating method, method using nanoparticle dispersion liquid, etc. The process can be suitably applied.
This makes it possible to produce a multiphoton emission organic EL element by a simple and efficient coating method.
　以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.
［実施例１－１］塗布型マルチフォトンエミッション有機ＥＬ素子の作製
　ＩＴＯ付ガラス基板上に、感光性レジストを塗布し、マスク露光、現像、エッチングを行い、ストライプ状のパターンを形成した。このパターン形成したＩＴＯ付きガラス基板を中性洗剤で洗浄後、超純水で超音波洗浄し、２－プロパノールにて煮沸後、ＵＶオゾン処理を２０分間行った。
　このＩＴＯ付きガラス基板上に、以下に示す条件にて、グローブボックス内にてスピンコート法により各層を成膜し、順に積層させた。
・電子注入層１（膜厚１０ｎｍ）：粒径１０ｎｍのＺｎＯ微粒子の２－エトキシエタノール分散液をスピンコートした後、１００℃で５分間乾燥した。
・電子注入層２（膜厚１０ｎｍ）：ポリエチレンイミンエトキシレイティド（ＰＥＩＥ）（シグマアルドリッチジャパン社製）の２－エトキシエタノール溶液をスピンコートした後、１００℃にて５分間乾燥した。
・発光層１（膜厚８０ｎｍ）：ポリ［（９，９－ジ－ｎ－オクチルフルオレニル－２，７－ジイル）－ｏ－（ベンゾ［２，１，３］チアジアゾール－４，８－ジイル）］（Ｆ８ＢＴ）（住友化学株式会社製）のｐ－キシレン溶液をスピンコートした後、１３０℃で１０分間乾燥した。
・電荷発生層１（膜厚４０ｎｍ）：ＰＥＤＯＴ：ＰＳＳ（ヘレウス株式会社製CleviousTMＣＨ８０００）をメタノール及びイソプロパノールを用いて体積比１：１：４で希釈し、この分散混合液をスピンコートした後、１２０℃にて１０分間乾燥した。
・電荷発生層２（膜厚１０ｎｍ）：ＰＥＤＯＴ：ＰＳＳを水酸化ナトリウム水溶液と混合してｐＨ７に調整した後、イソプロパノールを用いて体積比１：４で希釈し、この分散混合液をスピンコートした後、１２０℃にて１０分間乾燥した。
・電子注入層３（膜厚１０ｎｍ）：電子注入層１と同様にして形成した。
・電子注入層４（膜厚１０ｎｍ）：電子注入層２と同様にして形成した。
・発光層２（膜厚８０ｎｍ）：発光層１と同様にして形成した。
・ホール注入層１（膜厚４０ｎｍ）：ＰＥＤＯＴ：ＰＳＳを、メタノール及びイソプロパノールを用いて体積比１：１：４で希釈し、この分散混合液をスピンコートした後、１２０℃にて１０分間乾燥した。
　この上に、アルミニウムを真空蒸着し、膜厚１００ｎｍの陰極を形成し、２つの発光ユニットを有する塗布型マルチフォトンエミッション有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／Ｆ８ＢＴ／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／ＺｎＯ／ＰＥＩＥ／Ｆ８ＢＴ／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Example 1-1] Production of coating type multi-photon emission organic EL element A photosensitive resist was coated on a glass substrate with ITO, and mask exposure, development and etching were performed to form a stripe pattern. This patterned glass substrate with ITO was washed with a neutral detergent, then ultrasonically washed with ultrapure water, boiled with 2-propanol, and then subjected to UV ozone treatment for 20 minutes.
On the glass substrate with ITO, each layer was formed by a spin coat method in a glove box under the following conditions, and was sequentially laminated.
Electron injection layer 1 (film thickness: 10 nm): Spin-coated with a 2-ethoxyethanol dispersion of ZnO fine particles having a particle diameter of 10 nm, and then dried at 100 ° C. for 5 minutes.
Electron injection layer 2 (film thickness: 10 nm): A 2-ethoxyethanol solution of polyethyleneimine ethoxylated (PEIE) (Sigma Aldrich Japan) was spin-coated and then dried at 100 ° C. for 5 minutes.
Light-emitting layer 1 (film thickness 80 nm): poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -o- (benzo [2,1,3] thiadiazole-4,8- A p-xylene solution of diyl)] (F8BT) (manufactured by Sumitomo Chemical Co., Ltd.) was spin-coated and then dried at 130 ° C. for 10 minutes.
Charge generation layer 1 (film thickness 40 nm): PEDOT: PSS (Clevious TM CH8000 manufactured by Heraeus Co., Ltd.) was diluted with methanol and isopropanol at a volume ratio of 1: 1: 4, and this dispersion mixture was spin-coated. And dried at 120 ° C. for 10 minutes.
Charge generation layer 2 (film thickness: 10 nm): PEDOT: PSS was mixed with an aqueous sodium hydroxide solution to adjust the pH to 7, then diluted with isopropanol at a volume ratio of 1: 4, and this dispersion mixture was spin coated. Then, it dried for 10 minutes at 120 degreeC.
Electron injection layer 3 (film thickness 10 nm): formed in the same manner as the electron injection layer 1.
Electron injection layer 4 (film thickness 10 nm): formed in the same manner as the electron injection layer 2.
Light-emitting layer 2 (film thickness 80 nm): formed in the same manner as the light-emitting layer 1.
Hole injection layer 1 (film thickness 40 nm): PEDOT: PSS was diluted with methanol and isopropanol at a volume ratio of 1: 1: 4, and this dispersion mixture was spin-coated and then dried at 120 ° C. for 10 minutes. did.
On top of this, aluminum was vacuum-deposited to form a cathode having a film thickness of 100 nm, and a coating type multiphoton emission organic EL device having two light emitting units was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / F8BT / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / F8BT / PEDOT: PSS / Al.
［比較例１－１］第一発光ユニットのみの素子の作製
　実施例１－１において、電子注入層３，４、発光層２及びホール注入層１を設けず、それ以外は実施例１－１と同様にして、発光ユニットが１つ（発光層１のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／Ｆ８ＢＴ／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 1-1] Fabrication of Element with First Light-Emitting Unit Only In Example 1-1, the electron injection layers 3 and 4, the light-emitting layer 2, and the hole injection layer 1 were not provided. In the same manner, an organic EL element having one light emitting unit (only the light emitting layer 1) was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / F8BT / PEDOT: PSS / n-PEDOT: PSS / Al.
［比較例１－２］第二発光ユニットのみの素子の作製
　実施例１－１において、電荷発生層２、電子注入層３，４、発光層１及びホール注入層１を設けず、それ以外は実施例１－１と同様にして、発光ユニットが１つ（発光層２のみ）のみの有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／Ｆ８ＢＴ／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 1-2] Fabrication of element having only second light emitting unit In Example 1-1, the charge generation layer 2, the electron injection layers 3 and 4, the light emitting layer 1 and the hole injection layer 1 were not provided. In the same manner as in Example 1-1, an organic EL element having only one light emitting unit (only the light emitting layer 2) was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / F8BT / PEDOT: PSS / Al.
　上記実施例１－１及び比較例１－１，１－２の素子特性の評価結果を下記に示す。
　図３に、輝度－電圧特性を示す。縦軸が輝度（ｃｄ／ｍ2）、横軸が駆動電圧（Ｖ）を表している。
　図４に、外部量子効率－電流密度特性を示す。縦軸が外部量子効率（％）、横軸が電流密度（ｍＡ／ｃｍ2）を表している。
　また、表１に、輝度１０００ｃｄ／ｍ2時における駆動電圧と外部量子効率を示す。 The evaluation results of the device characteristics of Example 1-1 and Comparative Examples 1-1 and 1-2 are shown below.
FIG. 3 shows luminance-voltage characteristics. The vertical axis represents luminance (cd / m 2 ) and the horizontal axis represents drive voltage (V).
FIG. 4 shows the external quantum efficiency-current density characteristics. The vertical axis represents external quantum efficiency (%), and the horizontal axis represents current density (mA / cm 2 ).
Table 1 shows the drive voltage and external quantum efficiency at a luminance of 1000 cd / m 2 .
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記評価結果から、実施例１－１の駆動電圧及び外部量子効率は、比較例１－１及び比較例１－２のほぼ合計値であり、マルチフォトンエミッション特性が認められた。 From the above evaluation results, the driving voltage and the external quantum efficiency of Example 1-1 were almost the total values of Comparative Example 1-1 and Comparative Example 1-2, and multiphoton emission characteristics were observed.
［実施例１－２］発光色の異なる発光ユニットを積層した塗布型マルチフォトンエミッション有機ＥＬ素子の作製
　実施例１－１において、発光層１で用いたＦ８ＢＴに代えて、ポリフルオレン系青色蛍光ポリマー（住友化学株式会社社製）のｐ－キシレン溶液をスピンコートした後、１３０℃にて１０分間乾燥し、第一発光ユニットとして膜厚７０ｎｍの発光層３を形成した。それ以外は実施例１－１と同様にして、塗布型マルチフォトンエミッション有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／青色蛍光ポリマー／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／ＺｎＯ／ＰＥＩＥ／Ｆ８ＢＴ／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Example 1-2] Production of a coating type multi-photon emission organic EL device in which light emitting units having different emission colors are laminated In place of F8BT used in the light emitting layer 1 in Example 1-1, a polyfluorene blue fluorescent polymer A p-xylene solution (manufactured by Sumitomo Chemical Co., Ltd.) was spin-coated and then dried at 130 ° C. for 10 minutes to form a light-emitting layer 3 having a thickness of 70 nm as a first light-emitting unit. Otherwise, a coating type multiphoton emission organic EL device was produced in the same manner as in Example 1-1.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / blue fluorescent polymer / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / F8BT / PEDOT: PSS / Al.
［比較例１－３］第一発光ユニットのみの有機ＥＬ素子の作製
　実施例１－２において、電子注入層３，４、発光層２及びホール注入層１を設けず、それ以外は実施例１－２と同様にして、発光ユニットが１つ（発光層１のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／青色蛍光ポリマー／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 1-3] Fabrication of organic EL element having only first light emitting unit In Example 1-2, the electron injection layers 3 and 4, the light emitting layer 2, and the hole injection layer 1 were not provided. In the same manner as -2, an organic EL device having one light emitting unit (only the light emitting layer 1) was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / blue fluorescent polymer / PEDOT: PSS / n-PEDOT: PSS / Al.
　上記実施例１－２及び比較例１－３，１－２の素子特性の評価結果を下記に示す。
　図５に、ＥＬスペクトル特性を示す。縦軸がＥＬ相対強度（ａ．ｕ．）、横軸が波長（ｎｍ）を表している。
　実施例１－２において、第一発光ユニットの青色発光と第二発光ユニットの黄色発光がそれぞれ得られることが認められた。 The evaluation results of the device characteristics of Example 1-2 and Comparative Examples 1-3 and 1-2 are shown below.
FIG. 5 shows the EL spectral characteristics. The vertical axis represents EL relative intensity (au), and the horizontal axis represents wavelength (nm).
In Example 1-2, it was confirmed that the blue light emission of the first light emitting unit and the yellow light emission of the second light emitting unit were obtained.
　図６に、外部量子効率－電流密度特性を示す。
　また、表２に、輝度１０００ｃｄ／ｍ2時における駆動電圧と外部量子効率を示す。 FIG. 6 shows the external quantum efficiency-current density characteristics.
Table 2 shows driving voltage and external quantum efficiency at a luminance of 1000 cd / m 2 .
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記評価結果から、実施例１－２の駆動電圧及び外部量子効率は、比較例１－３及び比較例１－２のほぼ合計値であり、マルチフォトンエミッション特性が認められた。 From the above evaluation results, the driving voltage and the external quantum efficiency of Example 1-2 were almost the total values of Comparative Example 1-3 and Comparative Example 1-2, and multiphoton emission characteristics were observed.
［実施例２－１］ホール輸送層を用いた塗布型マルチフォトンエミッション有機ＥＬ素子の作製
　実施例１－１において、発光層１，２に代えて発光層４，５を形成し、また、発光層３の上にホール輸送層１を、発光層４の上にホール輸送層２を積層させ、それ以外は実施例１－１と同様にして、塗布型マルチフォトンエミッション有機ＥＬ素子を作製した。
　発光層４，５及びホール輸送層１は、以下のようにして形成した。
・発光層４（膜厚７０ｎｍ）：ポリフルオレン系緑色蛍光ポリマーＳＧＰ２（住友化学株式会社製）のｐ－キシレン溶液をスピンコートした後、１３０℃にて１０分間乾燥した。
・ホール輸送層１（膜厚１０ｎｍ）：テトラフェニルベンジジン含有ポリ（アリーレンエーテルスルホン）（ＴＰＤＰＥＳ）の１，４－ジオキサン溶液をスピンコートした後、１２０℃にて１０分間乾燥した。
・発光層５（膜厚７０ｎｍ）：発光層４と同様にして形成した。
・ホール輸送層２（膜厚１０ｎｍ）：ホール輸送層１と同様にして形成した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＳＧＰ２／ＴＰＤＰＥＳ／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／ＺｎＯ／ＰＥＩＥ／ＳＧＰ２／ＴＰＤＰＥＳ／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Example 2-1] Fabrication of coating type multiphoton emission organic EL device using hole transport layer In Example 1-1, the light emitting layers 4 and 5 were formed in place of the light emitting layers 1 and 2, and the light emission was performed. A coating type multiphoton emission organic EL device was produced in the same manner as in Example 1-1 except that the hole transport layer 1 was laminated on the layer 3 and the hole transport layer 2 was laminated on the light emitting layer 4.
The light emitting layers 4 and 5 and the hole transport layer 1 were formed as follows.
Light-emitting layer 4 (film thickness: 70 nm): A p-xylene solution of polyfluorene-based green fluorescent polymer SGP2 (manufactured by Sumitomo Chemical Co., Ltd.) was spin-coated and then dried at 130 ° C. for 10 minutes.
Hole transport layer 1 (film thickness: 10 nm): 1,4-dioxane solution of tetraphenylbenzidine-containing poly (arylene ether sulfone) (TPDPES) was spin-coated and then dried at 120 ° C. for 10 minutes.
Light emitting layer 5 (film thickness 70 nm): formed in the same manner as the light emitting layer 4.
-Hole transport layer 2 (film thickness 10 nm): formed in the same manner as the hole transport layer 1.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / Al.
［比較例２－１］第一発光ユニットのみの有機ＥＬ素子の作製
　実施例２－１において、電子注入層３，４、発光層５、ホール輸送層２及びホール注入層１を設けず、それ以外は実施例２－１と同様にして、発光ユニットが１つ（発光層４のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＳＧＰ２／ＴＰＤＰＥＳ／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 2-1] Production of organic EL element only with first light emitting unit In Example 2-1, the electron injection layers 3 and 4, the light emitting layer 5, the hole transport layer 2 and the hole injection layer 1 were not provided. Except for the above, an organic EL device having one light emitting unit (only the light emitting layer 4) was produced in the same manner as in Example 2-1.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / n-PEDOT: PSS / Al.
［比較例２－２］第二発光ユニットのみの有機ＥＬ素子の作製
　実施例２－１において、電荷発生層２、電子注入層３，４、発光層４、ホール輸送層１及びホール注入層１を設けず、それ以外は実施例２－１と同様にして、発光ユニットが１つ（発光層５のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＳＧＰ２／ＴＰＤＰＥＳ／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 2-2] Production of Organic EL Device with Second Light-Emitting Unit Only In Example 2-1, charge generation layer 2, electron injection layers 3 and 4, light-emitting layer 4, hole transport layer 1 and hole injection layer 1 Otherwise, an organic EL device having one light emitting unit (only the light emitting layer 5) was produced in the same manner as in Example 2-1.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / SGP2 / TPDPES / PEDOT: PSS / Al.
　上記実施例２－１及び比較例２－１，２－２の素子特性の評価結果を下記に示す。
　図７に、輝度－電圧特性を示す。
　図８に、外部量子効率－電流密度特性を示す。
　また、表３に、輝度１０００ｃｄ／ｍ2時及び５０００ｃｄ／ｍ2時における駆動電圧と外部量子効率を示す。 The evaluation results of the device characteristics of Example 2-1 and Comparative Examples 2-1 and 2-2 are shown below.
FIG. 7 shows luminance-voltage characteristics.
FIG. 8 shows the external quantum efficiency-current density characteristics.
Further, Table 3 shows the driving voltage and external quantum efficiency at times luminance 1000 cd / m 2 and 5000 cd / m 2 o'clock.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記評価結果から、実施例２－１の駆動電圧及び外部量子効率は、比較例２－１及び比較例２－２のほぼ合計値であり、マルチフォトンエミッション特性が認められた。 From the above evaluation results, the driving voltage and external quantum efficiency of Example 2-1 were almost the total values of Comparative Example 2-1 and Comparative Example 2-2, and multiphoton emission characteristics were observed.
［実施例３－１］リン光発光層を有する塗布型マルチフォトンエミッション有機ＥＬ素子の作製
　実施例１－１において、発光層１，２に代えて発光層６，７を形成し、それ以外は実施例１－１と同様にして、塗布型マルチフォトンエミッション有機ＥＬ素子を作製した。
　発光層６，７は、以下のようにして形成した。
・発光層６（膜厚７０ｎｍ）：ポリ－Ｎ－ビニルカルバゾール（ＰＶＫ）、１０ｗｔ％の４，４’，４”－トリス（カルバゾール－９－イル）トリフェニルアミン（ＴＣＴＡ）、１０ｗｔ％の２，６－ビス［３－（カルバゾール－９－イル）フェニル］ピリジン（２６ＤＣｚｐｐｙ）、１０ｗｔ％のトリス（２－フェニルピリジナト）イリジウム（III）（Ｉｒ（ｐｐｙ）3）のテトラヒドロフラン溶液をスピンコートした後、１３０℃にて１０分間乾燥した。
・発光層７（膜厚７０ｎｍ）：発光層６と同様にして形成した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（ｐｐｙ）3／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（ｐｐｙ）3／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Example 3-1] Production of coating type multiphoton emission organic EL element having phosphorescent light emitting layer In Example 1-1, the light emitting layers 6 and 7 were formed in place of the light emitting layers 1 and 2, and the others were In the same manner as in Example 1-1, a coating type multiphoton emission organic EL element was produced.
The light emitting layers 6 and 7 were formed as follows.
Light emitting layer 6 (film thickness 70 nm): poly-N-vinylcarbazole (PVK), 10 wt% 4,4 ′, 4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 10 wt% 2 , 6-Bis [3- (carbazol-9-yl) phenyl] pyridine (26DCzppy), 10 wt% of tris (2-phenylpyridinato) iridium (III) (Ir (ppy) 3 ) in tetrahydrofuran And then dried at 130 ° C. for 10 minutes.
Light emitting layer 7 (film thickness 70 nm): formed in the same manner as the light emitting layer 6.
The outline of the layer structure of this element is as follows: glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (Ppy) 3 / PEDOT: PSS / Al.
［比較例３－１］第一発光ユニットのみの有機ＥＬ素子の作製
　実施例３－１において、電子注入層３，４、発光層７及びホール注入層１を設けず、それ以外は実施例３－１と同様にして、発光ユニットが１つ（発光層６のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（ｐｐｙ）3／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 3-1] Fabrication of organic EL element having only first light emitting unit In Example 3-1, the electron injection layers 3 and 4, the light emitting layer 7 and the hole injection layer 1 were not provided. In the same manner as in Example 1, an organic EL device having one light emitting unit (only the light emitting layer 6) was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 / PEDOT: PSS / n-PEDOT: PSS / Al.
［比較例３－２］第二発光ユニットのみの有機ＥＬ素子の作製
　実施例３－１において、電子注入層３，４、発光層６及びホール注入層１を設けず、それ以外は実施例３－１と同様にして、発光ユニットが１つ（発光層７のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（ｐｐｙ）3／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 3-2] Production of Organic EL Device with Second Light-Emitting Unit Only In Example 3-1, the electron injection layers 3 and 4, the light-emitting layer 6, and the hole injection layer 1 were not provided. In the same manner as in Example 1, an organic EL device having one light emitting unit (only the light emitting layer 7) was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 / PEDOT: PSS / Al.
　上記実施例３－１及び比較例３－１，３－２の素子特性の評価結果を下記に示す。
　図９に、輝度－電圧特性を示す。
　図１０に、外部量子効率－電流密度特性を示す。
　また、表４に、輝度１０００ｃｄ／ｍ2時及び５０００ｃｄ／ｍ2時における駆動電圧と外部量子効率を示す。 The evaluation results of the device characteristics of Example 3-1 and Comparative Examples 3-1 and 3-2 are shown below.
FIG. 9 shows luminance-voltage characteristics.
FIG. 10 shows the external quantum efficiency-current density characteristics.
Further, Table 4 shows the driving voltage and external quantum efficiency at times luminance 1000 cd / m 2 and 5000 cd / m 2 o'clock.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　上記評価結果から、実施例３－１の駆動電圧及び外部量子効率は、比較例３－１及び比較例３－２のほぼ合計値であり、リン光材料を用いた素子においてもマルチフォトンエミッション特性が認められた。 From the above evaluation results, the driving voltage and the external quantum efficiency of Example 3-1 are almost the total values of Comparative Example 3-1 and Comparative Example 3-2, and the multiphoton emission characteristics are also obtained in the element using the phosphorescent material. Was recognized.
［実施例４－１］発光色の異なるリン光発光層を有する塗布型マルチフォトンエミッション有機ＥＬ素子の作製
　実施例１－１において、発光層１，２に代えて発光層８，９を形成し、それ以外は実施例１－１と同様にして、塗布型マルチフォトンエミッション有機ＥＬ素子を作製した。
　発光層８，９は、以下のようにして形成した。
・発光層８（膜厚７０ｎｍ）：ＰＶＫ、１０ｗｔ％ＴＣＴＡ、１０ｗｔ％２６ＤＣｚｐｐｙ、１０ｗｔ％Ｉｒ（ｐｐｙ）3）、１ｗｔ％のトリス（２－フェニルイソキノリン）イリジウム（III）（Ｉｒ（ｐｈｑ）3）のテトラヒドロフラン溶液をスピンコートした後、１３０℃にて１０分間乾燥した。
・発光層９（膜厚７０ｎｍ）：ＰＶＫ、１０ｗｔ％ＴＣＴＡ、１０ｗｔ％２６ＤＣｚｐｐｙ）、１０ｗｔ％のトリス（２－（２，４－ジフルオロフェニル）ピリジン）イリジウム（III）（Ｉｒ（Ｆｐｐｙ）3）のテトラヒドロフラン溶液をスピンコートした後、１３０℃にて１０分間乾燥した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（ｐｐｙ）3：Ｉｒ（ｐｈｑ）3／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（Ｆｐｐｙ）3／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Example 4-1] Production of a coating type multiphoton emission organic EL device having phosphorescent light emitting layers having different emission colors In Example 1-1, the light emitting layers 8 and 9 were formed in place of the light emitting layers 1 and 2. Other than that, a coating type multiphoton emission organic EL device was produced in the same manner as in Example 1-1.
The light emitting layers 8 and 9 were formed as follows.
Light-emitting layer 8 (film thickness 70 nm): PVK, 10 wt% TCTA, 10 wt% 26 DCzppy, 10 wt% Ir (ppy) 3 ), 1 wt% tris (2-phenylisoquinoline) iridium (III) (Ir (phq) 3 ) After spin coating with a tetrahydrofuran solution, the solution was dried at 130 ° C. for 10 minutes.
Light-emitting layer 9 (film thickness 70 nm): PVK, 10 wt% TCTA, 10 wt% 26 DCzppy), 10 wt% of tris (2- (2,4-difluorophenyl) pyridine) iridium (III) (Ir (Fppy) 3 ) After spin-coating the tetrahydrofuran solution, it was dried at 130 ° C. for 10 minutes.
The outline of the layer structure of this element is as follows: glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 : Ir (phq) 3 / PEDOT: PSS / n-PEDOT: PSS / ZnO / PEIE / PVK : TCTA: 26DCzppy: Ir (Fppy) 3 / PEDOT: PSS / Al.
［比較例４－１］第一発光ユニットのみの有機ＥＬ素子の作製
　実施例４－１において、電子注入層３，４、発光層９及びホール注入層１を設けず、それ以外は実施例４－１と同様にして、発光ユニットが１つ（発光層８のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（ｐｐｙ）3：Ｉｒ（ｐｈｑ）3／ＰＥＤＯＴ：ＰＳＳ／ｎ－ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 4-1] Production of Organic EL Element with First Light-Emitting Unit Only In Example 4-1, the electron injection layers 3 and 4, the light-emitting layer 9, and the hole injection layer 1 were not provided. In the same manner as in Example 1, an organic EL device having one light emitting unit (only the light emitting layer 8) was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (ppy) 3 : Ir (phq) 3 / PEDOT: PSS / n-PEDOT: PSS / Al.
［比較例４－２］第二発光ユニットのみの有機ＥＬ素子の作製
　実施例４－１において、電子注入層３，４、発光層８及びホール注入層１を設けず、それ以外は実施例４－１と同様にして、発光ユニットが１つ（発光層９のみ）の有機ＥＬ素子を作製した。
　この素子の層構成の概略は、ガラス／ＩＴＯ／ＺｎＯ／ＰＥＩＥ／ＰＶＫ：ＴＣＴＡ：２６ＤＣｚｐｐｙ：Ｉｒ（Ｆｐｐｙ）3／ＰＥＤＯＴ：ＰＳＳ／Ａｌである。 [Comparative Example 4-2] Production of Organic EL Device with Second Light-Emitting Unit Only In Example 4-1, the electron injection layers 3 and 4, the light-emitting layer 8, and the hole injection layer 1 were not provided. In the same manner as in Example 1, an organic EL device having one light emitting unit (only the light emitting layer 9) was produced.
The outline of the layer structure of this element is glass / ITO / ZnO / PEIE / PVK: TCTA: 26DCzppy: Ir (Fppy) 3 / PEDOT: PSS / Al.
　上記実施例４－１及び比較例４－１，４－２の素子特性の評価結果を下記に示す。
　図１１に、ＥＬスペクトル特性を示す。
　図１２に、外部量子効率－電流密度特性を示す。
　また、表５に、輝度１０００ｃｄ／ｍ2時及び５０００ｃｄ／ｍ2時における駆動電圧と外部量子効率を示す。 The evaluation results of the device characteristics of Example 4-1 and Comparative Examples 4-1 and 4-2 are shown below.
FIG. 11 shows the EL spectral characteristics.
FIG. 12 shows the external quantum efficiency-current density characteristics.
Further, Table 5 shows the driving voltage and external quantum efficiency at times luminance 1000 cd / m 2 and 5000 cd / m 2 o'clock.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　上記評価結果から、実施例４－１の駆動電圧及び外部量子効率は、比較例４－１及び比較例４－２のほぼ合計値であり、発光色の異なるリン光材料を用いた素子においてもマルチフォトンエミッション特性が認められた。 From the above evaluation results, the driving voltage and the external quantum efficiency of Example 4-1 are almost the total values of Comparative Example 4-1 and Comparative Example 4-2, and even in an element using phosphorescent materials having different emission colors. Multi-photon emission characteristics were observed.
１，１１　ガラス基板
２　　　　陰極（ＩＴＯ）
３，１３　第一発光ユニット
４，１５　電荷発生層
５，１４　電子注入層
６，１６　第二発光ユニット
７　　　　陰極（Ａｌ）
１２　　　陽極（ＩＴＯ）
１７　　　陰極（Ａｌ） 1,11 Glass substrate 2 Cathode (ITO)
3, 13 First light emitting unit 4, 15 Charge generation layer 5, 14 Electron injection layer 6, 16 Second light emitting unit 7 Cathode (Al)
12 Anode (ITO)
17 Cathode (Al)

Claims (14)

  1. 　１対の電極間に、少なくとも１つの発光層を有する発光ユニットが中間層を介して複数積層されたマルチフォトンエミッション有機エレクトロルミネッセンス素子であって、前記中間層が、陰極側の電荷発生層と、陽極側の電子注入層との塗布積層からなり、インバーテッド構造を有することを特徴とする有機エレクトロルミネッセンス素子。 A multi-photon emission organic electroluminescence device in which a plurality of light emitting units each having at least one light emitting layer are laminated via an intermediate layer between a pair of electrodes, the intermediate layer including a charge generation layer on a cathode side; An organic electroluminescence element comprising an inverted structure with an application layer on an anode side electron injection layer.
  2. 　前記インバーテッド構造は、基板上に、陰極、中間層を介して複数積層された発光ユニット、陽極の順に積層された構成からなることを特徴とする請求項１記載の有機エレクトロルミネッセンス素子。 2. The organic electroluminescence device according to claim 1, wherein the inverted structure has a structure in which a plurality of light emitting units stacked on a substrate via a cathode, an intermediate layer, and an anode are stacked in this order.
  3. 　前記電荷発生層が、導電性高分子を１層又は複数層含有していることを特徴とする請求項１又は２に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 1 or 2, wherein the charge generation layer contains one or more conductive polymers.
  4. 　前記導電性高分子が、ポリチオフェン誘導体、ポリアニリン誘導体及びポリアリールアミン誘導体のうちのいずれかであり、ドープされたｎ型又はｐ型半導体であることを特徴とする請求項３記載の有機エレクトロルミネッセンス素子。 4. The organic electroluminescence device according to claim 3, wherein the conductive polymer is one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and is a doped n-type or p-type semiconductor. .
  5. 　前記電子注入層が、金属酸化物微粒子又は極性高分子を１層又は複数層含有していることを特徴とする請求項１～４のうちのいずれか１項に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to any one of claims 1 to 4, wherein the electron injection layer contains one or more metal oxide fine particles or polar polymers.
  6. 　前記金属酸化物微粒子が、酸化亜鉛、酸化チタン、酸化ジルコニウム及び酸化ズズのうちのいずれかからなることを特徴とする請求項５記載の有機エレクトロルミネッセンス素子。 6. The organic electroluminescence device according to claim 5, wherein the metal oxide fine particles are made of any one of zinc oxide, titanium oxide, zirconium oxide and oxide oxide.
  7. 　前記極性高分子が、ポリエチレンイミン誘導体であることを特徴とする請求項５記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 5, wherein the polar polymer is a polyethyleneimine derivative.
  8. 　前記発光ユニットが、蛍光又はリン光発光するものであることを特徴とする請求項１～７のうちのいずれか１項に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to any one of claims 1 to 7, wherein the light emitting unit emits fluorescence or phosphorescence.
  9. 　前記陰極及び前記陽極の少なくともいずれか一方が透明であることを特徴とする請求項１～８のうちのいずれか１項に記載の有機エレクトロルミネッセンス素子。 9. The organic electroluminescence device according to claim 1, wherein at least one of the cathode and the anode is transparent.
  10. 　前記陰極及び前記陽極が、金属、金属酸化物及び導電性高分子のうちのいずれかからなることを特徴とする請求項９記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 9, wherein the cathode and the anode are made of any one of a metal, a metal oxide, and a conductive polymer.
  11. 　前記金属が、アルミニウム、銀及び金のうちのいずれかであることを特徴とする請求項１０記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence element according to claim 10, wherein the metal is any one of aluminum, silver, and gold.
  12. 　前記金属酸化物が、インジウム－錫酸化物（ＩＴＯ）、インジウム－亜鉛酸化物（ＩＺＯ）、酸化亜鉛、アルミニウム添加酸化亜鉛（ＡＺＯ）及びガリウム添加酸化亜鉛（ＧＺＯ）のうちのいずれかであることを特徴とする請求項１０記載の有機エレクトロルミネッセンス素子。 The metal oxide is any one of indium-tin oxide (ITO), indium-zinc oxide (IZO), zinc oxide, aluminum-added zinc oxide (AZO), and gallium-added zinc oxide (GZO). The organic electroluminescent element according to claim 10.
  13. 　前記導電性高分子が、ポリチオフェン誘導体、ポリアニリン誘導体及びポリアリールアミン誘導体のうちのいずれかであり、ドープされたｎ型又はｐ型半導体であることを特徴とする請求項１０記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 10, wherein the conductive polymer is any one of a polythiophene derivative, a polyaniline derivative, and a polyarylamine derivative, and is a doped n-type or p-type semiconductor. .
  14. 　請求項１～１３のうちのいずれか１項に記載された有機エレクトロルミネッセンス素子を製造する方法であって、
    　前記中間層を、溶媒を用いて塗布積層した後、１３０℃以下で乾燥させて成膜する工程を備えていることを特徴とする有機エレクトロルミネッセンス素子の製造方法。     A method for producing an organic electroluminescence device according to any one of claims 1 to 13,
    A method for producing an organic electroluminescence device, comprising: forming a film by coating the intermediate layer using a solvent and then drying it at 130 ° C. or less.
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