WO2012128078A1 - 有機エレクトロルミネッセンス素子及び照明器具 - Google Patents
有機エレクトロルミネッセンス素子及び照明器具 Download PDFInfo
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- WO2012128078A1 WO2012128078A1 PCT/JP2012/056115 JP2012056115W WO2012128078A1 WO 2012128078 A1 WO2012128078 A1 WO 2012128078A1 JP 2012056115 W JP2012056115 W JP 2012056115W WO 2012128078 A1 WO2012128078 A1 WO 2012128078A1
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- Prior art keywords
- light emitting
- emitting layer
- emission
- organic electroluminescence
- color
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Images
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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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
-
- 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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
-
- 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
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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
- H10K50/84—Passivation; Containers; Encapsulations
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- 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
- H10K2102/301—Details of OLEDs
- H10K2102/351—Thickness
Definitions
- the present invention relates to an organic electroluminescence element and a lighting fixture including the organic electroluminescence element.
- Organic electroluminescence devices can be used as flat panel displays, backlights for liquid crystal display devices, light sources for illumination, etc. due to their ability to emit surface light with high voltage and low voltage. It attracts attention as a generation light source.
- the light-emitting layer includes a hole-transporting light-emitting layer whose base material is a hole-transporting material to which the first fluorescent material is added, and an electron-transporting property to which the second fluorescent material is added. It is composed of an electron transporting light emitting layer having a material as a base material, and the hole transporting light emitting layer and the electron transporting light emitting layer are allowed to emit light at the same time so that the light emission colors from these light emitting layers are recognized as mixed colors.
- the hole-transporting light-emitting layer and the electron-transporting light-emitting layer so that the emission spectrum of the emission color emitted from the hole-transporting light-emitting layer and the emission spectrum of the emission color emitted from the electron-transporting light-emitting layer are substantially the same.
- Both the first fluorescent material and the second fluorescent material of the layer are made of two or more types of fluorescent materials, and the two or more types of fluorescent materials have different fluorescence peak wavelengths in the solid state.
- the organic electroluminescence element described in Patent Document 1 is configured from the viewpoint of preventing a change in chromaticity of a light emission color with a change in an applied current amount and a lapse of a light emission time.
- the present inventors when designing the organic electroluminescence element, the present inventors have made lighting that makes humans feel comfortable even when the luminance changes when the emission luminance of the organic electroluminescence element is adjusted according to the situation in which the element is used. A new study focusing on the matter that has not been sufficiently studied in the past was realized. Development of an organic electroluminescence element focusing on such a viewpoint has not been made yet.
- an organic electroluminescence element In developing such an organic electroluminescence element, a method of individually designing the light emission luminance and the color temperature of the organic electroluminescence element can be considered according to the application using the organic electroluminescence.
- a wide variety of organic electroluminescence elements are required depending on the application. For this reason, an increase in member cost, an increase in development burden, an increase in process tact associated with switching of product types, and the like occur, resulting in a problem that the cost cannot be reduced.
- an optimum element must be selected from a wide variety of products in accordance with the use environment, which is a heavy burden.
- the present invention has been made in view of the above reasons, and includes an organic electroluminescence element capable of realizing illumination that can be comfortably felt by humans even if the light emission luminance is changed according to the use environment, and the organic electroluminescence element. It aims at providing a lighting fixture.
- the organic electroluminescent device according to the present invention, light emission luminance in the front direction at 100 cd / m 2 or more 6000 cd / m 2 or less of the range, wherein the color temperature of the emission color increases as the luminance becomes higher.
- organic electroluminescent device it is that the difference between the maximum value and the minimum value of the emission color of the color temperature in the range emission luminance of 100 cd / m 2 or more 5000 cd / m 2 or less in the front direction is above 500K preferable.
- the color temperature of the emission color is in the white range defined by JIS Z9112, when the emission luminance in the front direction is in the range of 500 cd / m 2 to 3000 cd / m 2 .
- the locus drawn by the change in emission color accompanying the increase in emission luminance intersects the black body locus on the XY chromaticity diagram according to the CIE 1931 XYZ color system.
- the organic electroluminescence device is Comprising a first electrode, a first light emitting unit, an intermediate layer, a second light emitting unit, and a second electrode, these are stacked in the order described above,
- the first light emitting unit comprises a blue light emitting layer that emits blue light and a first green light emitting layer that emits green light.
- the second light emitting unit includes a red light emitting layer emitting red light and a second green light emitting layer emitting phosphorescent green light,
- the thickness ratio of the red light emitting layer based on the thickness of the second green light emitting layer is preferably 2 to 30%.
- the thickness of the second green light emitting layer is preferably in the range of 10 nm to 40 nm.
- the lighting fixture according to the present invention includes the organic electroluminescence element.
- the present invention it is possible to realize lighting that allows a human to feel comfortable even if the light emission luminance is changed according to the usage environment.
- the organic electroluminescent element 1 includes a first light emitting unit 11, a second light emitting unit 12, and an intermediate layer 13 interposed between the first light emitting unit 11 and the second light emitting unit 12. It is an element.
- this organic electroluminescence element 1 a substrate 14, a first electrode 15, a first light emitting unit 11, an intermediate layer 13, a second light emitting unit 12, and a second electrode 16 are laminated in this order. It has a structure.
- the substrate 14 is preferably light transmissive.
- the substrate 14 may be colorless and transparent, or may be slightly colored.
- the substrate 14 may be ground glass.
- Examples of the material of the substrate 14 include transparent glass such as soda lime glass and alkali-free glass; plastic such as polyester resin, polyolefin resin, polyamide resin, epoxy resin, and fluorine resin.
- the shape of the substrate 14 may be a film shape or a plate shape.
- the substrate 14 has a light diffusion effect.
- a substrate 14 has a structure including a mother phase and particles, powders, bubbles, etc. having different refractive indexes from the mother phase dispersed in the mother phase; For example, a structure in which a light-scattering film or a microlens film is laminated on the surface of the substrate in order to improve light diffusibility.
- the substrate 14 may not have light transmittance.
- the material of the substrate 14 is not particularly limited as long as the light emission characteristics, life characteristics, etc. of the element are not impaired.
- the substrate 14 is preferably formed from a material having high thermal conductivity such as an aluminum metal foil.
- the first electrode 15 functions as an anode.
- the anode in the organic electroluminescence element 1 is an electrode for injecting holes into the light emitting layer 2.
- the first electrode 15 is preferably formed from a material such as a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function.
- the electrode 15 is preferably formed from a material having a work function of 4 eV or more. That is, the work function of the first electrode 15 is preferably 4 eV or more.
- a metal oxide such as ITO (indium-tin oxide), SnO 2 , ZnO, IZO (indium-zinc oxide), or the like is used. .
- the first electrode 15 can be formed using these materials by an appropriate method such as a vacuum deposition method, a sputtering method, or an application method.
- the light transmittance of the first electrode 15 is preferably 70% or more, and more preferably 90% or more.
- the sheet resistance of the first electrode 15 is preferably several hundred ⁇ / ⁇ or less, and particularly preferably 100 ⁇ / ⁇ or less.
- the thickness of the first electrode 15 is appropriately set so that characteristics such as the light transmittance and sheet resistance of the first electrode 15 have a desired level. Although the preferred thickness of the first electrode 15 varies depending on the material constituting the first electrode 15, the thickness of the first electrode 15 is set to 500 nm or less, preferably in the range of 10 to 300 nm.
- the material for forming the hole injection layer include conductive polymers such as PEDOT / PSS and polyaniline; conductive polymers doped with any acceptor; carbon nanotubes, CuPc (copper phthalocyanine), MTDATA [4 , 4 ', 4 "-Tris (3-methyl-phenylphenylamino) tri-phenylamine], TiOPC (titanyl phthalocyanine), amorphous carbon, and other materials having both conductivity and light transmittance.
- conductive polymers such as PEDOT / PSS and polyaniline
- conductive polymers doped with any acceptor carbon nanotubes
- CuPc copper phthalocyanine
- MTDATA [4 , 4 ', 4 "-Tris (3-methyl-phenylphenylamino) tri-phenylamine]
- TiOPC titanyl phthalocyanine
- amorphous carbon and other materials having both conductivity and light transmittance.
- the hole injection layer is formed by forming a film by a method such as a coating method or a printing method.
- the hole injection layer is formed by, for example, a vacuum deposition method.
- the second electrode 16 functions as a cathode.
- the cathode in the organic electroluminescence element 1 is an electrode for injecting electrons into the light emitting layer 2.
- the second electrode 16 is preferably formed from a material such as a metal, an alloy, an electrically conductive compound, or a mixture thereof having a small work function.
- the second electrode 16 is preferably formed of a material having a work function of 5 eV or less. That is, the work function of the second electrode 16 is preferably 5 eV or less.
- Examples of the material for forming the second electrode 16 include Al, Ag, and MgAg.
- the second electrode 16 can also be formed from an Al / Al 2 O 3 mixture or the like.
- the second electrode 16 When organic electroluminescence light is transmitted through the second electrode 16, the second electrode 16 is composed of a plurality of layers, and a part of the layer is made of a transparent conductive material typified by ITO, IZO or the like. It is also preferred that it be formed.
- the second electrode 16 can be formed using these materials by an appropriate method such as a vacuum deposition method or a sputtering method.
- the light transmittance of the second electrode 16 is preferably 10% or less.
- the light transmittance of the second electrode 16 is preferably 70% or more.
- the thickness of the second electrode 16 is appropriately set so that characteristics such as light transmittance and sheet resistance of the second electrode 16 become a desired level.
- the preferred thickness of the second electrode 16 varies depending on the material constituting the second electrode 16, but the thickness of the second electrode 16 is set to 500 nm or less, preferably in the range of 20 to 300 nm.
- an electron injection layer on the second electrode 16.
- the material for forming the electron injection layer include alkali metals, alkali metal halides, alkali metal oxides, alkali metal carbonates, alkaline earth metals, and alloys containing these metals. Specific examples thereof include sodium, sodium-potassium alloy, lithium, lithium fluoride, Li 2 O, Li 2 CO 3 , magnesium, MgO, magnesium-indium mixture, aluminum-lithium alloy, Al / LiF mixture, and the like. It is done.
- the electron injection layer can also be formed from an organic material layer doped with an alkali metal such as lithium, sodium, cesium, or calcium, or an alkaline earth metal.
- the first light emitting unit 11 includes the light emitting layer 2.
- the first light emitting unit 11 may further include a hole transport layer 3, an electron transport layer 4, and the like as necessary.
- the second light emitting unit 12 also includes the light emitting layer 2.
- the second light emitting unit 12 may further include a hole transport layer 3, an electron transport layer 4, and the like as necessary.
- Each light emitting unit has a laminated structure of, for example, hole transport layer 3 / one or more light emitting layers 2 / electron transport layer 4.
- the first light emitting unit 11 includes a blue light emitting layer 21 and a green light emitting layer 22 (first green light emitting layer 22) that emits fluorescent light as the light emitting layer 2.
- the blue light emitting layer 21 is the light emitting layer 2 that emits blue light
- the first green light emitting layer 22 is the light emitting layer 2 that emits green light.
- the second light emitting unit 12 includes, as the light emitting layer 2, a red light emitting layer 23 and a green light emitting layer 24 (second green light emitting layer 24) that emits phosphorescence.
- the red light emitting layer 23 is the light emitting layer 2 that emits red light
- the second green light emitting layer 24 is the light emitting layer 2 that emits green light.
- Each light emitting layer 2 can be formed of an organic material (host material) doped with a light emitting organic substance (dopant).
- any of an electron transporting material, a hole transporting material, and a material having both electron transporting property and hole transporting property can be used.
- an electron transporting material and a hole transporting material may be used in combination.
- a concentration gradient of the host material may be formed in the light emitting layer 2.
- the light emitting layer 2 is formed so that the closer to the first electrode 15 in the light emitting layer 2, the higher the concentration of the hole transporting material, and the closer to the second electrode 16, the higher the concentration of the electron transporting material. May be.
- the electron transporting material and hole transporting material used as the host material are not particularly limited.
- the hole transporting material can be appropriately selected from materials that can constitute the hole transport layer 3 described later.
- the electron transporting material can be appropriately selected from materials that can form the electron transporting layer 4 described later.
- Examples of the host material constituting the first green light emitting layer 22 include Alq 3 (tris (8-oxoquinoline) aluminum (III)), ADN, BDAF, and the like.
- the fluorescent luminescent dopant in the first green light emitting layer 22 C545T (coumarin C545T; 10-2- (benzothiazolyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl -1H, 5H, 11H- (1) benzopyropyrano (6,7, -8-ij) quinolidin-11-one)), DMQA, coumarin6, rubrene and the like.
- the concentration of the dopant in the first green light emitting layer 22 is preferably in the range of 1 to 20% by mass.
- Examples of the host material constituting the second green light emitting layer 24 include CBP, CzTT, TCTA, mCP, and CDBP.
- Examples of phosphorescent dopants in the second green light emitting layer 24 include Ir (ppy) 3 (factory (2-phenylpyridine) iridium), Ir (ppy) 2 (acac), Ir (mppy) 3 and the like. Can be mentioned.
- the dopant concentration in the second green light emitting layer 24 is preferably in the range of 1 to 40% by mass.
- Examples of the host material constituting the red light emitting layer 23 include CBP (4,4′-N, N′-dicarbazole biphenyl), CzTT, TCTA, mCP, CDBP, and the like.
- Examples of the dopant in the red light emitting layer 23 include Btp 2 Ir (acac) (bis- (3- (2- (2-pyridyl) benzothienyl) mono-acetylacetonate) iridium (III))), Bt 2 Ir ( acac), PtOEP, and the like.
- the dopant concentration in the red light emitting layer 23 is preferably in the range of 1 to 40% by mass.
- Examples of the host material constituting the blue light emitting layer 21 include TBADN (2-t-butyl-9,10-di (2-naphthyl) anthracene), ADN, BDAF, and the like.
- Examples of the dopant in the blue light emitting layer 21 include TBP (1-tert-butyl-perylene), BCzVBi, perylene and the like.
- NPD charge transfer assisting dopants
- TPD N, N′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl
- TPD N, N′-bis (3-methylphenyl)-(1,1 ′ -Biphenyl) -4,4'-diamine
- Spiro-TAD Spiro-TAD and the like
- the dopant concentration in the blue light emitting layer 21 is preferably in the range of 1 to 30% by mass.
- Each light emitting layer 2 can be formed by an appropriate method such as a dry process such as vacuum deposition or transfer, or a wet process such as spin coating, spray coating, die coating, or gravure printing.
- the material constituting the hole transport layer 3 is appropriately selected from the group of compounds having hole transport properties.
- the hole transporting material is preferably a compound which has an electron donating property and is stable even when radically cationized by electron donation.
- Examples of the hole transporting material include polyaniline, 4,4′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), N, N′-bis (3-methylphenyl)- (1,1′-biphenyl) -4,4′-diamine (TPD), 2-TNATA, 4,4 ′, 4 ′′ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine ( MTDATA), 4,4′-N, N′-dicarbazole biphenyl (CBP), spiro-NPD, spiro-TPD, spiro-TAD, TNB, and the like, including triarylamine compounds and carbazole
- the material for forming the electron transport layer 4 has the ability to transport electrons, receives electrons injected from the second electrode 16 and has an excellent electron injection effect on the light emitting layer 2. It is preferable to be a compound that exhibits, further inhibits the movement of holes to the electron transport layer 4 and has an excellent thin film forming ability.
- the electron transporting material include Alq3, oxadiazole derivatives, starburst oxadiazole, triazole derivatives, phenylquinoxaline derivatives, silole derivatives, and the like.
- the electron transporting material include fluorene, bathophenanthroline, bathocuproine, anthraquinodimethane, diphenoquinone, oxazole, oxadiazole, triazole, imidazole, anthraquinodimethane, 4,4′-N, N′-dicarbazole.
- Biphenyl (CBP) and the like, compounds thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives and the like can be mentioned.
- the metal complex compound examples include tris (8-hydroxyquinolinato) aluminum, tri (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis ( 10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) (o-cresolate) gallium, bis (2-methyl-8-quinolinato) ) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) -4-phenylphenolate and the like, but are not limited thereto.
- oxazole, thiazole, oxadiazole, thiadiazole, triazole derivatives and the like are preferable.
- 2,5-bis (1-phenyl) -1,3,4-oxazole, 2 5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ′′ -biphenyl) 1,3,4-oxadiazole, 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5 -Phenylthiadiazolyl)] benzene, 2,5-bis (1-naphthyl) -1,3,4-triazole, 3- (4-biphenylyl) -4-phenyl-5- (4-t-butyl
- the thickness of the electron transport layer 4 is not particularly limited, but is formed, for example, in the range of 10 to 300 nm
- the electron transport layer 4 can be formed by an appropriate method such as an evaporation method.
- the intermediate layer 13 functions to electrically connect two light emitting units in series.
- the intermediate layer 13 preferably has high transparency and high thermal and electrical stability.
- the intermediate layer 13 can be formed from, for example, a layer forming an equipotential surface, a charge generation layer, or the like.
- Examples of the material for forming the equipotential surface or the charge generation layer include metal thin films such as Ag, Au, and Al; metal oxides such as vanadium oxide, molybdenum oxide, rhenium oxide, and tungsten oxide; ITO, IZO, AZO, Transparent conductive film such as GZO, ATO, SnO 2 ; laminated body of so-called n-type semiconductor and p-type semiconductor; laminated body of metal thin film or transparent conductive film and one or both of n-type semiconductor and p-type semiconductor A mixture of an n-type semiconductor and a p-type semiconductor; a mixture of one or both of an n-type semiconductor and a p-type semiconductor and a metal, and the like.
- metal thin films such as Ag, Au, and Al
- metal oxides such as vanadium oxide, molybdenum oxide, rhenium oxide, and tungsten oxide
- ITO, IZO, AZO Transparent conductive film such as GZO, A
- the n-type semiconductor and the p-type semiconductor are not particularly limited and those selected as necessary are used.
- the n-type semiconductor and the p-type semiconductor may be either an inorganic material or an organic material.
- An n-type semiconductor or a p-type semiconductor is a mixture of an organic material and a metal; a combination of an organic material and a metal oxide; a combination of an organic material and an organic acceptor / donor material or an inorganic acceptor / donor material, etc. Also good.
- the intermediate layer 13 can also be formed from BCP: Li, ITO, NPD: MoO 3 , Liq: Al, or the like.
- BCP represents 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
- the intermediate layer 13 may have a two-layer structure in which a first layer made of BCP: Li is arranged on the anode side and a second layer made of ITO is arranged on the cathode side. It is also preferred that the intermediate layer 13 has a layer structure such as Alq3 / Li 2 O / HAT- CN6, Alq3 / Li 2 O, Alq3 / Li 2 O / Alq3 / HAT-CN6.
- the color temperature of the emission color increases as the luminance becomes higher.
- the front direction is a direction in which light coincides with the stacking direction of a plurality of layers constituting the organic electroluminescence element 1 and light is emitted.
- the luminance and color temperature of the light source when a person visually recognizes the light source correlates with the feelings of pleasure and discomfort of the person.
- the color temperature is high, and when the luminance is low. Is preferred to have a low color temperature (see Kruithor, A. A 1941 Tubular luminescence Lamps general illumination, 30 Medical Welfare Research No.2 2006). Since the organic electroluminescence device 1 according to this embodiment has the luminance-color temperature characteristics as described above, the color temperature is high when the emission luminance is high, and the color temperature is low when the emission luminance is low. For this reason, even if a use environment changes, comfortable illumination is attained. In addition, since the color temperature changes according to the environmental temperature, such luminance-color temperature characteristics can be realized with only one type of element, so that comfortable illumination can be realized at low cost.
- the organic electroluminescent element 1 is preferably capable of emitting light at light emission luminance in the range of 100cd / m 2 ⁇ 5000cd / m 2 (the front direction of the light emission luminance).
- one kind of organic electroluminescence element is applied to a wide range of uses from a stand illumination for illuminating the hand to an indoor ceiling lamp. For this reason, cost reduction becomes possible.
- the difference between the maximum value and the minimum value of the emission color of the color temperature is above 500K. That is, the color temperature when light emission luminance in the front direction is 100 cd / m 2, the difference between the color temperature when light emission luminance in the front direction is 5000 cd / m 2 is preferably at least 500K. In this case, even if the luminance changes, humans do not feel uncomfortable, and it is possible to realize a difference in workability and the like particularly in a low color temperature region. This is because a human can perceive a difference in color temperature of 500K or more.
- the upper limit of the difference between the color temperatures is not particularly limited, but it is not preferable that the color appearance of the irradiated object is too different due to the difference in luminance.
- the color temperature of the emission color is also preferably in the white range defined by JIS Z 9112. In this case, the color temperature can be changed while maintaining the white range. In this case, the color of the irradiated object can be shown naturally.
- the locus drawn by the change in emission color accompanying the increase in emission luminance intersects the black body locus.
- the difference in the color to be visually recognized becomes clearer, and the workability is improved.
- Such an organic electroluminescence device 1 according to the present embodiment is realized as follows.
- the light emission luminance of the organic electroluminescence element 1 can be adjusted mainly by the light emission intensity of the light emitting layer 2 that emits light in the green region with sensitive sensitivity.
- the color temperature of the emission color of the organic electroluminescence element 1 can be adjusted by the emission intensity of the light emitting layer 2 emitting blue light and the light emitting layer 2 emitting red light.
- the light emission intensity of the light emitting layer 2 that emits light in the blue region and the light emitting layer 2 that emits light in the red region is the film thickness of each light emitting layer 2, the doping concentration, the transport layer existing around each light emitting layer 2, etc. It can be adjusted depending on the configuration, the configuration of the intermediate layer 13, and the like.
- Color temperature is defined by the spectrum when an object that originally has heat emits black body radiation.
- the color temperature of the light source is determined mainly by where in the black body radiation line the spectrum when emitting white light mainly for lighting applications corresponds (see JIS Z8725: 1999). That is, if the shape of the emission spectrum of the organic electroluminescence element 1 is determined, the color temperature can be obtained by calculation taking into account the intensity of the visibility curve at each wavelength.
- a high color temperature means that the relative intensity of components from the green region to the red region decreases when considering the balance when the white spectrum is decomposed into components of the red region, the green region, and the blue region. At the same time, it means that the relative intensity of the component from the blue region to the green region increases.
- the light emission luminance of the organic electroluminescence element 1 is almost proportional to the amount of current to be applied. Therefore, the emission characteristic that the color temperature of the emission color increases as the emission luminance increases is that the relative intensity of the component ranging from the green region to the red region of the white emission spectrum decreases as the energization amount of the organic electroluminescence element 1 increases. As a result, the relative intensity of the component from the blue region to the green region increases.
- the organic electroluminescence element 1 includes a light emitting layer 2 that emits red light, a light emitting layer 2 that emits green light, and a light emitting layer 2 that emits blue light. For this reason, as the energization amount decreases, the relative value of the emission intensity of the emission layer 2 that emits green light and the emission layer 2 that emits red light increases relative to the relative value of the emission intensity of the emission layer 2 that emits blue light. As the energization amount increases, the relative value of the emission intensity of the light emitting layer 2 that emits blue light and that of the light emitting layer 2 that emits green light may increase with respect to the relative value of the emission intensity of the light emitting layer 2 that emits red light. .
- the intensity and the emission intensity of the light emitting layer 2 that emits blue light vary depending on the state of carrier balance in the organic electroluminescence element 1.
- the amount of current is defined as the total charge of electrons and holes.
- One of the conditions for the relative value of the emission intensity of each light-emitting layer 2 to be the highest is that the balance between electrons and holes in each light-emitting layer 2 is close to 1: 1.
- the organic electroluminescence element 1 includes a first light emitting unit 11, a second light emitting unit 12, and an intermediate layer interposed between the first light emitting unit 11 and the second light emitting unit 12. 13 is a multi-unit element.
- a multi-unit type element as one method for realizing that the color temperature increases as the light emission luminance increases, the red region in the second light emitting unit 12 increases as the light emission luminance increases.
- An example is to design the device so that the carrier balance in the light emitting layer 23 is deteriorated and the carrier balance in the second green light emitting layer 24 adjacent to the red light emitting layer 23 is improved. That is, the device is designed so that the light emission intensity of the red light emitting layer 23 decreases when the light emission luminance increases and the carrier balance of the organic electroluminescence device 1 as a whole shifts in the hole rich direction.
- the second green light emitting layer 24 is disposed on the cathode side, the red light emitting layer 23 is disposed on the anode side, and the thickness of the second green light emitting layer 24 is set.
- the element is designed such that the thickness ratio of the red light emitting layer 23 as a reference is 2 to 30%.
- the carrier balance between holes and electrons is closer to the optimum in the second green light emitting layer 24 than in the red light emitting layer 23.
- the relative value of the light emission intensity of the red light emitting layer 23 decreases and the relative value of the light emission luminance of the second green light emitting layer 24 increases, so that the color temperature of the light emission color shifts to the high temperature side.
- FIG. 2 conceptually shows a mechanism assumed as a cause of a decrease in emission intensity in the green range.
- reference numeral 51 denotes a phosphorescent dopant (green dopant) in the second green light emitting layer 24, and reference numeral 52 denotes a dopant (red dopant) in the red light emitting layer 23.
- the reason why the energy transition from the second green light emitting layer 24 to the red light emitting layer 23 is presumed is as follows. Since the exciton in phosphorescence emission usually has a longer exciton lifetime than the fluorescent material due to the transition from the triplet, the second green region light emitting layer 24 containing the phosphorescent dopant to the red region light emitting layer. The energy transition to 23 appears prominently. The amount of energy that transitions from the second green light emitting layer 24 to the red light emitting layer 23 can be controlled by adjusting the exciton lifetime, exciton travel distance, dopant concentration, and the like.
- the second green color light emitting layer 24 As the thickness of the second green light emitting layer 24 increases, the exciton travel distance from the second green light emitting layer 24 to the red light emitting layer 23 also increases, and the amount of energy transition decreases. In addition, as the thickness of the red light emitting layer 23 decreases and the concentration of the dopant in the red light emitting layer 23 decreases, the energy hardly transitions from the green light emitting layer 22 to the red light emitting layer 23. Therefore, the second green color light emitting layer 24, the thickness of the red color light emitting layer 23, the concentration of the dopant in the red color light emitting layer 23, and the like are adjusted to increase the second green color when the light emission luminance increases. The transition of energy from the light emitting layer to the red light emitting layer 23 can be suppressed.
- the red light region based on the thickness of the second green light emitting layer 24 is used.
- the thickness ratio of the light emitting layer 23 is preferably in the range of 2 to 30%. In such a case, the thickness of the red light emitting layer 23 is sufficiently reduced, so that the exciton energy of the second green light emitting layer 24 does not easily shift to the red light emitting layer. In this case, the thickness of the second green light emitting layer is preferably in the range of 10 nm to 40 nm.
- a material having a higher rate of increase in hole mobility than the rate of increase in electron mobility at a high temperature may be used as the organic material constituting the organic electroluminescence element 1.
- the mobility of the transport layer is low, charges are accumulated in the organic layer other than the light emitting layer 2, thereby causing voltage division in the organic electroluminescent element 1 and reducing the partial pressure applied to the organic layer. As a result, the electric field strength in the organic layer is lowered, and the charge is difficult to move.
- the second light emitting unit 12 in order for the locus drawn by the change in emission color accompanying the increase in emission luminance to intersect the black body locus, the second light emitting unit 12 is used.
- the film thickness of the red light emitting layer 23 in FIG. Preferably, the ratio of the thickness of the red light emitting layer 23 based on the thickness of the second green light emitting layer 24 is in the range of 2% to 30%.
- the film thickness of the red light emitting layer 23 in the second light emitting unit 12 only needs to be smaller than the film thickness of the second green light emitting layer 24.
- the ratio of the red light emitting layer 23 based on the thickness of the second green light emitting layer 24 is preferably in the range of 2% to 30%, more preferably in the range of 3% to 10%.
- the lighting fixture 3 includes an organic electroluminescence element 1, a connection terminal that connects the organic electroluminescence element 1 and a power source, and a housing that holds the organic electroluminescence element 1.
- 3 to 5 show an example of a lighting fixture 3 including an organic electroluminescence element.
- the luminaire 3 includes a unit 31 including the organic electroluminescence element 1, a casing that holds the unit 31, a front panel 32 that emits light emitted from the unit 31, and a wiring unit that supplies power to the unit 31. 33.
- the casing includes a front side casing 34 and a rear side casing 35.
- the front side housing 34 is formed in a frame shape
- the back side housing 35 is formed in a lid shape having a lower surface opening.
- the front housing 34 and the back housing 35 overlap each other and hold the unit 31.
- the front-side housing 34 has a groove for passing the wiring portion 33 such as a conductor lead wire or a connector in a peripheral portion in contact with the side wall of the back-side housing 35, and the lower surface opening has a light-transmitting property.
- a plate-like front panel 32 having the above is installed.
- the unit 31 includes the organic electroluminescence element 1, a power feeding unit 36 that feeds power to the organic electroluminescence element 1, and a front side case 37 and a back side element case 38 that hold the organic electroluminescence element 1 and the power feeding unit 36. .
- the positive electrode 39 connected to the first electrode 15 and the negative electrode 40 connected to the second electrode 16 are also formed on the substrate 14 of the organic electroluminescence element 1.
- a sealing substrate 44 that covers the organic electroluminescent element 1 is also provided on the substrate 14.
- the pair of power supply units 36 to which the wiring unit 33 is attached are in contact with the positive electrode 39 and the negative electrode 40, thereby supplying power to the organic electroluminescence element 1.
- the power feeding unit 36 includes a plurality of contact portions 41 that are in contact with the plus electrode 39 and the minus electrode 40, and the contact portions 41 are mechanically connected to the plus electrode 39 and the minus electrode 40 by the element cases 37 and 38. And electrically connected at multiple points.
- the contact portion 41 is formed in a dimple shape by bending the power feeding portion 36 made of a metal conductor such as plate-like copper or stainless steel, and the convex side of the dimple portion is a plus electrode 39 and a minus electrode. Touch 40.
- the power feeding portion 36 may be, for example, a wire-shaped metal conductor formed with a coil-shaped contact portion 41 other than a plate-shaped metal conductor formed with a dimple-shaped contact portion 41. Good.
- the element cases 37 and 38 are both formed in a lid shape.
- the front element case 37 has an opening 42 for emitting light to the case wall facing the substrate 14 of the organic electroluminescence element 1, and a groove 43 for holding the power feeding part 36 on the case side wall.
- the element cases 37 and 38 are made of a resin such as acrylic, and are overlapped so that the side walls are in contact with each other, thereby forming a rectangular parallelepiped box shape, and holding the organic electroluminescence element 1 and the power feeding unit 36.
- the first electrode 15 was formed by depositing ITO on the glass substrate 14 to a thickness of 130 nm. Furthermore, a 35 nm thick hole injection layer made of PEDOT / PSS was formed on the first electrode 15 by a wet method. Subsequently, a hole transport layer 3, a blue region light emitting layer 2 (fluorescent light emission), a first green region light emitting layer 22 (fluorescent light emission), and an electron transport layer 4 were sequentially formed to a thickness of 5 to 60 nm by vapor deposition. Next, an intermediate layer 13 having a layer structure of Alq 3 / Li 2 O / Alq 3 / HAT-CN 6 was laminated with a layer thickness of 15 nm.
- a hole transport layer 3 a red light emitting layer 23 (phosphorescent light emission), a second green light emitting layer 24 (phosphorescent light emission), and an electron transport layer 4 were sequentially formed with a thickness of 50 nm at the maximum.
- an electron injection layer made of a Li film and a second electrode 16 made of an Al film were sequentially formed.
- the thickness of the red light emitting layer 23 was 2 nm
- the thickness of the second green light emitting layer 24 was 40 nm.
- the peak wavelength of the emission spectrum of the dopant in the blue light emitting layer 21 is 450 nm
- the peak wavelength of the emission spectrum of the dopant in the second green light emitting layer 24 is 563 nm
- the peak wavelength of the emission spectrum of the dopant in the red light emitting layer 23 is 620 nm. Met.
- the spectrum, various color rendering properties, and emission color of the organic electroluminescence device 1 were measured using a spectral radiance meter (CS-2000), and the results were as follows.
- the peak intensity ratio of blue (450 nm): green (563 nm): red (623 nm) in the emission spectrum of the organic electroluminescence element 1 at an element temperature of 30 ° C. was 1: 1.5: 2.5.
- the spectrum, emission luminance, and emission color of the organic electroluminescence device 1 were measured using a spectral radiance meter (CS-2000), and the results were as follows.
- FIG. 6 shows the measurement result of the change in the color temperature of the emission color when the organic electroluminescence element 1 is caused to emit light with the emission luminance changed.
- the color temperature of the emitted color also increased as the emission luminance increased.
- FIG. 7 shows the result of plotting the change in the emission color accompanying the change in the emission luminance from 100 to 5000 cd / m 2 on the XY chromaticity diagram by the CIE 1931 XYZ color system. As a result, the locus drawn by the change in emission color intersected with the blackbody locus.
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Abstract
Description
第一の電極、第一の発光ユニット、中間層、第二の発光ユニット、及び第二の電極を備え、これらが前記の順番に積層しており、
前記第一の発光ユニットが、青色光を発する青色域発光層と緑色光を蛍光発光する第一の緑色域発光層とを備え、
前記第二の発光ユニットが、赤色光を発する赤色域発光層と緑色光を燐光発光する第二の緑色域発光層とを備え、
前記第二の緑色域発光層の厚みを基準とした前記赤色域発光層の厚みの割合が2~30%であることが、好ましい。
リウム、ビス(2-メチル-8-キノリナート)(1-ナフトラート)アルミニウム、ビス(2-メチル-8-キノリナート)-4-フェニルフェノラート等が挙げられるが、これらに限定されない。含窒素五員環誘導体としては、オキサゾール、チアゾール、オキサジアゾール、チアジアゾール、トリアゾール誘導体などが好ましく、具体的には、2,5-ビス(1-フェニル)-1,3,4-オキサゾール、2,5-ビス(1-フェニル)-1,3,4-チアゾール、2,5-ビス(1-フェニル)-1,3,4-オキサジアゾール、2-(4’-tert-ブチルフェニル)-5-(4”-ビフェニル)1,3,4-オキサジアゾール、2,5-ビス(1-ナフチル)-1,3,4-オキサジアゾール、1,4-ビス[2-(5-フェニルチアジアゾリル)]ベンゼン、2,5-ビス(1-ナフチル)-1,3,4-トリアゾール、3-(4-ビフェニルイル)-4-フェニル-5-(4-t-ブチルフェニル)-1,2,4-トリアゾール等が挙げられるが、これらに限定されない。電子輸送性材料として、ポリマー有機エレクトロルミネッセンス素子1に使用されるポリマー材料も挙げられる。このポリマー材料として、ポリパラフェニレン及びその誘導体、フルオレン及びその誘導体等が挙げられる。電子輸送層4の厚みに特に制限はないが、例えば、10~300nmの範囲に形成される。電子輸送層4は蒸着法などの適宜の方法で形成され得る。
3 照明器具
Claims (7)
- 複数の層が積層して構成される有機エレクトロルミネッセンス素子であって、
100cd/m2以上6000cd/m2以下の範囲内で、複数の前記層の積層方向と一致する方向の発光輝度が高くなるに従って、発光色の色温度が高くなる特性を有する有機エレクトロルミネッセンス素子。 - 複数の前記層の積層方向と一致する方向の発光輝度が100cd/m2以上5000cd/m2以下の範囲内である場合の、発光色の色温度の最大値と最小値との差が、500K以上である特性を有する請求項1に記載の有機エレクトロルミネッセンス素子。
- 複数の前記層の積層方向と一致する方向の発光輝度が500cd/m2以上3000cd/m2以下の範囲である場合に、発光色の色温度が、JIS Z9112で規定する白色範囲内にある特性を有する請求項1又は2に記載の有機エレクトロルミネッセンス素子。
- CIE 1931 XYZ表色系によるXY色度図上で、発光輝度の上昇に伴う発光色の変化が描く軌跡が、黒体軌跡と交差する特性を有する請求項1乃至3のいずれか一項に記載の有機エレクトロルミネッセンス素子。
- 第一の電極、第一の発光ユニット、中間層、第二の発光ユニット、及び第二の電極を備え、これらが前記の順番に積層しており、
前記第一の発光ユニットが、青色光を発する青色域発光層と緑色光を蛍光発光する第一の緑色域発光層とを備え、
前記第二の発光ユニットが、赤色光を発する赤色域発光層と緑色光を燐光発光する第二の緑色域発光層とを備え、
前記第二の緑色域発光層の厚みを基準とした前記赤色域発光層の厚みの割合が2~30%である請求項1乃至4のいずれか一項に記載の有機エレクトロルミネッセンス素子。 - 前記第二の緑色域発光層の厚みが10nm~40nmの範囲である請求項5に記載の有機エレクトロルミネッセンス素子。
- 請求項1乃至6のいずれか一項に記載の有機エレクトロルミネッセンス素子を備える照明器具。
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- 2012-03-09 CN CN201280015006.5A patent/CN103443951B/zh active Active
- 2012-03-09 WO PCT/JP2012/056115 patent/WO2012128078A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
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DE112012001413B4 (de) | 2018-03-08 |
DE112012001413T5 (de) | 2014-01-30 |
JP2012204532A (ja) | 2012-10-22 |
CN103443951B (zh) | 2015-12-23 |
US20140014933A1 (en) | 2014-01-16 |
JP5699282B2 (ja) | 2015-04-08 |
CN103443951A (zh) | 2013-12-11 |
TW201244206A (en) | 2012-11-01 |
US8987721B2 (en) | 2015-03-24 |
TWI478411B (zh) | 2015-03-21 |
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