WO2013027711A1 - 有機エレクトロルミネッセンス素子、照明装置及び表示装置 - Google Patents
有機エレクトロルミネッセンス素子、照明装置及び表示装置 Download PDFInfo
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- H—ELECTRICITY
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
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- 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
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- H10K2102/301—Details of OLEDs
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- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
Definitions
- the present invention relates to an organic electroluminescence element, an illumination device using the same, and a display device.
- An organic electroluminescence element (hereinafter also referred to as an organic EL element) is an all-solid-state element composed of an organic material film having a thickness of only about 0.1 ⁇ m between electrodes and emits light of 2 to Since it can be achieved at a relatively low voltage of about 20 V, it is a technology expected as a next-generation flat display and illumination.
- the organic EL device using phosphorescence emission is greatly different from the organic EL device using fluorescence emission, and the method for controlling the position of the emission center, particularly the emission layer, is particularly different.
- An important technical issue in capturing the efficiency and lifetime of the device is how to recombine inside to stably emit light.
- the present invention has been made in view of the above-described problems and situations, and its problems are high charge injection / transport performance, high external extraction quantum efficiency, little change in drive voltage over time when driven at constant voltage, and It is to provide a long-life organic electroluminescence element, a lighting device and a display device.
- an organic electroluminescence device having a plurality of organic compound layers including a hole transport layer, a light emitting layer and an electron transport layer sandwiched between an anode and a cathode, (1) The hole transport layer and the electron transport layer are adjacent to the light emitting layer, (2) Among the hole transport materials constituting the hole transport layer, the glass transition point (Tg) of the hole transport material having the highest composition ratio is Tg (HT), and among the host materials constituting the light emitting layer When the glass transition point (Tg) of the host material having the highest composition ratio is Tg (EM), Tg (HT)> Tg (EM).
- the glass transition point (Tg) of the electron transport material having the highest composition ratio is Tg (ET), and the most composed of the host materials composing the light emitting layer.
- Tg (EM) glass transition point of the host material having a high ratio
- EM glass transition point of the host material having a high ratio
- EM organic electroluminescence device
- P and Q represent a carbon atom or a nitrogen atom
- A1 represents an atomic group which forms an aromatic hydrocarbon ring or an aromatic heterocycle with PC
- A2 represents an aromatic heterocycle together with QN.
- P1-L1-P2 represents a bidentate ligand
- P1 and P2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom
- L1 together with P1 and P2 is a bidentate
- r represents an integer of 1 to 3
- s represents an integer of 0 to 2
- r + s is 2 or 3.
- M1 is a group 8 to 10 in the periodic table Represents a metal element.
- An illuminating device comprising the organic electroluminescence element according to any one of 1 to 6 above.
- a display device comprising the organic electroluminescence element as described in any one of 1 to 6 above.
- an organic electroluminescence element a lighting device, and a display device that have a high external extraction quantum efficiency, a small change in driving voltage with time when driven at a constant voltage, and a long lifetime.
- Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram of display part A Schematic diagram of pixels
- Schematic diagram of passive matrix type full color display device Schematic of lighting device
- Schematic diagram of lighting device Schematic configuration diagram of organic EL full-color display device
- Organic compound layer (also referred to as organic layer) >> The organic compound layer according to the present invention will be described.
- the organic EL element of the present invention preferably has a plurality of organic compound layers as a constituent layer.
- the organic compound layer examples include a hole transport layer, a light emitting layer, and an electron transport layer in the above-described layer configuration.
- a layer containing an organic compound constituting another constituent layer of the organic EL element such as a hole injection layer and an electron injection layer is also defined as the organic compound layer according to the present invention.
- an organic compound is used for the anode buffer layer, the cathode buffer layer, etc.
- the anode buffer layer, the cathode buffer layer, etc. each form an organic compound layer.
- the blue light emitting layer preferably has a light emission maximum wavelength in the range of 430 to 480 nm, and the green light emitting layer has a light emission maximum wavelength.
- the red light emitting layer is preferably a monochromatic light emitting layer having an emission maximum wavelength in the range of 600 to 640 nm, and a display device using these is preferable.
- a white light emitting layer may be formed by laminating at least three of these light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers.
- the organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these.
- the light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
- the total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 ⁇ m, more preferably in the range of 2 to 200 nm, and particularly preferably in the range of 10 to 20 nm.
- a light-emitting dopant or a host material is formed by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink-jet method. it can.
- the light emitting layer of the organic EL device of the present invention contains a host material (also referred to as a host compound) and a phosphorescent organometallic complex compound as a light emitting material (also referred to as a light emitting dopant). Moreover, you may mix and use the hole transport material and electron transport material which are mentioned later.
- the host material refers to a phosphorescent quantum yield of phosphorescence emission at a room temperature (25 ° C.) having a mass ratio of 20% or more in the compound contained in the light emitting layer. Is defined as a compound of less than 0.1.
- the phosphorescence quantum yield is preferably less than 0.01.
- a known host compound may be used in combination, or a plurality of types may be used in combination.
- a plurality of types of host compounds it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient.
- the hole transport layer and the electron transport layer are adjacent to the light emitting layer, respectively.
- the glass transition point of the hole transport material having the highest composition ratio is Tg (HT), and among the host materials similarly constituting the light emitting layer, When the glass transition point of the host material having the highest composition ratio is Tg (EM), Tg (HT)> Tg (EM), and (3)
- the glass transition point of the electron transport material having the highest composition ratio is Tg (ET), and, similarly, the most composed of the host materials constituting the light emitting layer.
- the glass transition point of the host material having the highest composition ratio is 70 ° C. or higher and 130 ° C. or lower.
- the material with the highest composition ratio in the hole transport layer, the electron transport layer, the light emitting layer, etc. determines the Tg (glass transition point) of each layer
- the material with the highest composition ratio in each of the layers will be described below.
- the Tg of the hole transport layer, the Tg of the light emitting layer, and the Tg of the electron transport layer are described.
- the hole transport layer and the electron transport layer are adjacent to the light emitting layer containing the phosphorescent organometallic complex compound, respectively, and more than the Tg (HT) of the hole transport layer and the Tg (ET) of the electron transport layer,
- Tg (EM) of the light emitting layer containing the phosphorescent organometallic complex compound is small, the charge injection / transport performance is high, the light emission efficiency is improved, the drive voltage change with time is small, and the life is long.
- the hole transport layer and the electron transport layer are layers adjacent to the light emitting layer.
- the light emitting layer has the highest component ratio among the materials constituting the light emitting layer.
- the glass transition point of the host material is 70 ° C. or higher and 130 ° C. or lower, the glass transition point of the light emitting layer is not increased so much that the glass transition point of the hole transport layer or the electron transport layer is that of the light emitting layer. It is preferable for designing larger.
- the hole transport layer and the electron transport layer preferably contain a polymer material so that the Tg is higher than that of the light emitting layer.
- the hole transport material and the electron transport material are polymers. It is preferable.
- both the hole transport layer and the electron transport layer are composed of a polymer.
- the polymer is a compound having a weight average molecular weight of 10,000 or more. Details of the measurement of the weight average molecular weight are shown below.
- the molecular weight (weight average molecular weight (Mw)) of the polymer according to the present invention can be measured using GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a column solvent.
- GPC measurement conditions are measured by stabilizing the column at 40 ° C., flowing THF (tetrahydrofuran) at a flow rate of 1 ml / min, and injecting about 100 ⁇ L of a sample having a concentration of 1 mg / ml.
- the column it is preferable to use a combination of commercially available polystyrene gel columns.
- Shodex GPC KF-801, 802, 803, 804, 805, 806, 807, etc. manufactured by Showa Denko KK
- a refractive index detector (RI detector) or a UV detector is preferably used.
- the molecular weight distribution of the sample is calculated using a calibration curve created using monodisperse polystyrene standard particles. About 10 points are preferably used as polystyrene for preparing a calibration curve.
- the glass transition point can be measured using a differential scanning calorimeter “DSC-7” (manufactured by PerkinElmer) and a thermal analyzer controller “TAC7 / DX” (manufactured by PerkinElmer).
- DSC-7 differential scanning calorimeter
- TAC7 / DX thermal analyzer controller
- DSC-7 differential scanning calorimeter
- the reference used an empty aluminum pan.
- the measurement conditions were a measurement temperature of 0 to 200 ° C., a temperature increase rate of 10 ° C./min, a temperature decrease rate of 10 ° C./min, and heat-cool-heat temperature control. Analysis was performed based on the data in Heat.
- the glass transition point is the extension of the baseline before the rise of the first endothermic peak and the first peak to the peak apex. A tangent line showing the maximum inclination is drawn between them, and the intersection is shown as the glass transition point.
- Luminescent dopant The light emitting dopant used together with the host material in the light emitting layer of the present invention will be described.
- a phosphorescent dopant also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like
- a phosphorescent organometallic complex compound is used as the phosphorescent dopant.
- the light-emitting layer and light-emitting unit of the organic EL device of the present invention contain the host compound and, at the same time, contain a phosphorescent organometallic complex compound as a light-emitting dopant (sometimes simply referred to as a light-emitting material). Is done.
- the phosphorescent dough will be described.
- the phosphorescent compound according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.) and has a phosphorescence quantum yield.
- the phosphorescence quantum yield is preferably 0.1 or more, although it is defined as a compound of 0.01 or more at 25 ° C.
- the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence emitting compound according to the present invention achieves the above phosphorescence quantum yield (0.01 or more) in any solvent. It only has to be done.
- phosphorescent compounds There are two types of emission of phosphorescent compounds in principle. One is the recombination of carriers on the host compound to which carriers are transported, generating an excited state of the host compound, and this energy is phosphorescently emitted. Energy transfer type to obtain light emission from the phosphorescent compound by transferring to the phosphorescent compound, the other is that the phosphorescent compound becomes a carrier trap, carrier recombination occurs on the phosphorescent compound, Examples include a carrier trap type in which light emission from a phosphorescent compound can be obtained.
- the phosphorescent organometallic complex compound used in the present invention as the phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device.
- the phosphorescent organometallic complex compound according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table, more preferably an iridium compound (Ir complex) or a platinum compound ( Platinum complex compounds), and most preferred among these are iridium compounds (Ir complexes).
- Phosphorescent Organometallic Complex Compound Represented by General Formula (1) As the phosphorescent organometallic complex compound according to the present invention, a compound represented by the general formula (1) is preferably used.
- the aromatic hydrocarbon ring represented by A1 includes a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, Examples include a pyranthrene ring and anthraanthrene ring. These rings may further have a substituent described later.
- examples of the aromatic heterocycle represented by A1 include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a benzimidazole.
- Examples of the substituent that the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A1 may have an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group) Pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, allyl group, etc.) Alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc.), for example, phenyl group,
- substituents may be further substituted with the above substituents.
- a plurality of these substituents may be bonded to each other to form a ring.
- the aromatic heterocycle represented by A2 has the same meaning as the aromatic heterocycle represented by A1 in the general formula (1).
- examples of the bidentate ligand represented by P1-L1-P2 include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone And picolinic acid.
- M1 is a group 8-10 transition metal element (also referred to simply as a transition metal) in the periodic table of elements. Among them, iridium and platinum are preferable, and iridium is particularly preferable.
- phosphorescent organometallic complex compound represented by the general formula (1) used as the phosphorescent dopant are shown below, but the present invention is not limited thereto. These compounds are described, for example, in Inorg. Chem. 40, 1704 to 1711, and the like.
- the light emitting layer according to the present invention may use a fluorescent dopant together with the phosphorescent organometallic complex compound.
- Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes Examples thereof include dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
- the hole transport layer and the electron transport layer used as the constituent layers of the organic EL device of the present invention will be described, and in addition, the injection layer, the blocking layer, and the like will be described.
- Injection layer electron injection layer, hole injection layer >> The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. May be.
- An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.
- Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
- anode buffer layer hole injection layer
- copper phthalocyanine is used.
- examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
- the details of the cathode buffer layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like.
- the buffer layer is preferably a very thin film, and the film thickness is preferably in the range of 0.1 to 10 nm, although it depends on the material.
- ⁇ Blocking layer hole blocking layer, electron blocking layer>
- the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.
- the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
- the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary.
- the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers.
- 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
- the ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.
- Gaussian 98 Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.
- the ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
- the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
- a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
- the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
- the structure of the hole transport layer described later can be used as an electron blocking layer as necessary.
- the film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
- the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
- the hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
- triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
- Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
- the above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
- aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
- polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain.
- JP-A-11-251067 J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.
- the hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. However, in the present invention, it is preferably produced by a coating method (wet process).
- the film thickness of the hole transport layer is not particularly limited, but is usually in the range of 5 nm to 5 ⁇ m, preferably in the range of 5 to 200 nm.
- This hole transport layer may have a single layer structure composed of one or more of the above materials.
- a hole transport layer having a high p property doped with impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, and JP-A-2001-102175. Appl. Phys. 95, 5773 (2004), and the like.
- a hole transport layer having such a high p property because a device with lower power consumption can be produced.
- the hole transport layer preferably contains an acceptor material.
- An acceptor material includes an n-type semiconductor material.
- n-type semiconductor materials include Au, Pt, W, Ir, POCl 3 , AsF 6 , Cl, Br, I, inorganic materials such as vanadium oxide (V 2 O 5 ), molybdenum oxide (MoO 2 ), and TCNQ.
- Preferred examples include cyano groups and fluorine-containing compounds such as (7,7,8,8-tetracyanoquinodimethane) and F4-TCNQ (tetrafluorotetracyanoquinodimethane).
- TBPAH tris (4-bromophenyl) aluminum hexachloroantimonate
- fullerene octaazaporphyrin
- p-type semiconductor perfluoro compounds perfluoropentacene, perfluorophthalocyanine, etc.
- naphthalenetetracarboxylic anhydride naphthalenetetra
- polymer compounds containing an aromatic carboxylic acid anhydride such as carboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, or an imidized product thereof as a skeleton.
- Fullerene-containing polymer compounds include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Examples thereof include a polymer compound having a skeleton.
- a polymer compound (derivative) having fullerene C60 as a skeleton is preferable.
- fullerene-containing polymers are roughly classified into polymers in which fullerene is pendant from a polymer main chain and polymers in which fullerene is contained in the polymer main chain. Fullerene is contained in the polymer main chain. Are preferred.
- the hole transport material contained in the hole transport layer may be selected from a light emitting layer or a material having a Tg higher than the Tg of the host compound used in the light emitting layer. It is a preferable form to have a Tg higher than that of the light emitting layer.
- the electron transport material described later is also preferably a polymer, and both the hole transport material and the electron transport material are more preferably a polymer.
- the hole transport material preferably used in the present invention is exemplified below, but is not limited thereto.
- the electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
- the electron transport layer can be provided as a single layer or a plurality of layers.
- an electron transport material also serving as a hole blocking material used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode.
- Any material may be used as long as it has a function of transferring electrons to the light-emitting layer, and any material can be selected from conventionally known compounds.
- Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
- a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can be used.
- metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.
- metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
- the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
- the electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
- the film thickness of the electron transport layer is not particularly limited, but is usually in the range of 5 nm to 5 ⁇ m, preferably in the range of 5 to 200 nm.
- the electron transport layer may have a single layer structure composed of one or more of the above materials.
- an electron transport layer having a high n property doped with impurities examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
- an electron transport layer having such a high n property because an element with lower power consumption can be produced.
- the electron transport layer preferably contains a donor material.
- An example of the donor material is a p-type semiconductor material.
- Examples of p-type semiconductor materials include inorganic materials such as alkali metals, alkaline earth metals, rare earth elements, Al, Ag, Cu, and In, organic and inorganic alkali metal salts, alkaline earth metal salts, and aniline, phenylenediamine, Examples include arylamines such as N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine, various condensed polycyclic aromatic compounds, and conjugated compounds.
- condensed polycyclic aromatic compound for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, sarkham anthracene, bisanthene, zestrene, heptazelene, Examples thereof include compounds such as pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and derivatives and precursors thereof.
- conjugated compound examples include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.
- thiophene hexamer ⁇ -seccithiophene ⁇ , ⁇ -dihexyl- ⁇ -sexualthiophene, ⁇ , ⁇ -dihexyl- ⁇ -kinkethiophene, ⁇ , ⁇ -bis (3- An oligomer such as butoxypropyl) - ⁇ -sexithiophene can be preferably used.
- polymer p-type semiconductor examples include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like.
- JP-A 2006-36755 and other substituted-unsubstituted alternating copolymer polythiophenes JP-A 2007-51289, JP-A 2005-76030, J. Org. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc.
- porphyrin copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex, etc.
- Organic molecular complexes such as C60, C70, C76, C78, and C84, carbon nanotubes such as SWNT, dyes such as merocyanine dyes and hemicyanine dyes, and ⁇ -conjugated polymers such as polysilane and polygerman Organic / inorganic hybrid materials described in 2000-260999 can also be used.
- conjugated materials at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, metal phthalocyanines, and metal porphyrins is preferable. Further, pentacenes are more preferable.
- pentacenes examples include substituents described in International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, JP-A-2004-107216, etc.
- Examples thereof include substituted acenes described in No. 14.4986 and the like and derivatives thereof.
- Such compounds include those described in J. Org. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. Acene-based compounds substituted with trialkylsilylethynyl groups described in US Pat. No. 9,2706, etc., pentacene precursors described in US Patent Application Publication No. 2003/136964, etc., and Japanese Patent Application Laid-Open No. 2007-224019 Examples include precursor type compounds (precursors) such as porphyrin precursors.
- the electron transport material having the highest component ratio among the electron transport materials constituting the electron transport layer according to the present invention has a Tg higher than the Tg of the host material having the highest component ratio among the host materials constituting the light emitting layer. Choose what you have.
- the electron transport material that is preferably used is exemplified below, but is not limited thereto.
- the electron transport material contained in the electron transport layer is preferably a polymer in order to have a higher Tg than the light emitting layer.
- both the hole transport material and the electron transport material are polymers.
- anode As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
- Electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
- an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film
- these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 ⁇ m or more)
- a pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
- wet film-forming methods such as a printing system and a coating system, can also be used.
- the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
- the film thickness is usually selected within the range of 10 to 1000 nm, preferably within the range of 10 to 200 nm.
- cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
- electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture. , Indium, lithium / aluminum mixtures, rare earth metals and the like.
- a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
- the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
- the sheet resistance as a cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected within the range of 10 nm to 5 ⁇ m, preferably within the range of 50 to 200 nm.
- the film thickness is usually selected within the range of 10 nm to 5 ⁇ m, preferably within the range of 50 to 200 nm.
- a transparent or translucent cathode can be manufactured by forming the above metal on the cathode with a film thickness in the range of 1 to 20 nm and then forming the conductive transparent material mentioned in the description of the anode thereon.
- an element in which both the anode and the cathode are transmissive can be manufactured.
- the support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. Or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent.
- the transparent support substrate that can be used include glass, quartz, and a transparent resin film.
- a particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
- polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate (PC), norbornene resin, polymethylpentene, polyether Ketone, polyimide, polyethersulfone (PES), polyphenylene sulfide, police Cycloolefins such as phons, polyether imides, polyether ketone imides, polyamides, fluororesins, nylon, polymethyl methacrylate, acrylics or polyarylates, Arton (trade name, manufactured by JSR) or
- the surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
- Relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / (m 2 ⁇ 24 h) or less, and oxygen measured by a method according to JIS K 7126-1987.
- a high barrier film having a permeability of 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ MPa) or less and a water vapor permeability of 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
- the material for forming the barrier film may be any material as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
- silicon dioxide, silicon nitride, or the like can be used.
- the method for forming the barrier film is not particularly limited.
- vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
- the opaque support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
- the external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.
- the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
- a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
- the ⁇ max of light emission of the organic EL element is preferably 480 nm or less.
- ⁇ Sealing> As a sealing means used for this invention, the method of adhere
- the sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.
- Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
- the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
- the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
- the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
- a polymer film and a metal film can be preferably used because the element can be thinned.
- the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ MPa) or less, and conforms to JIS K 7129-1992.
- the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by the method is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
- sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
- the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
- heat- and chemical-curing types such as epoxy type can be mentioned.
- hot-melt type polyamide, polyester, and polyolefin can be mentioned.
- a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
- an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
- a desiccant may be dispersed in the adhesive.
- coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
- the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
- the material for forming the film may be a material having a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
- silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
- the method for forming these films is not particularly limited.
- vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, plasma CVD method, laser CVD method, thermal CVD method, coating method, or the like can be used.
- an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
- an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil
- a vacuum is also possible.
- a hygroscopic compound can also be enclosed inside.
- hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
- metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
- sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate.
- metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
- perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
- anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
- a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film.
- the sealing is performed by the sealing film, the mechanical strength is not necessarily high. Therefore, it is preferable to provide such a protective film and a protective plate.
- a material that can be used for this the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
- the organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said.
- a method of improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate and preventing total reflection at the transparent substrate and the air interface (US Pat. No. 4,774,435), A method for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394), light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No.
- these methods can be used in combination with the organic EL device of the present invention.
- a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
- the low refractive index layer examples include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
- the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.
- the method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.
- This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction.
- Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.
- the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.
- the refractive index distribution a two-dimensional distribution
- the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
- the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
- the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of light in the medium.
- the arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.
- the organic EL device of the present invention can be processed to provide, for example, a microlens array-like structure on the light extraction side of the substrate, or combined with a so-called condensing sheet, for example, in a specific direction, for example, the device light emitting surface.
- luminance in a specific direction can be raised by condensing in a front direction.
- quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
- One side is preferably within a range of 10 to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
- the condensing sheet it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device.
- a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
- BEF brightness enhancement film
- the shape of the prism sheet for example, the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
- a light diffusion plate / film may be used in combination with the light collecting sheet.
- a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
- a thin film made of a desired electrode material for example, an anode material, is formed on a suitable substrate so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 10 to 200 nm, thereby producing an anode.
- an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, which is an organic EL element material
- a method for forming each of these layers there are a vapor deposition method, a wet method (coating method, wet process), etc., but a wet method is preferable.
- wet methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, etc., and a precise thin film can be formed.
- a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, and a spray coating method is preferable. Different film forming methods may be applied for each layer.
- the total number of layers (the constituent layers of the organic EL element) existing between the anode and the cathode 50% or more of the total number of layers is preferably formed by a coating method.
- the hole injection layer / hole transport layer When the total number of layers of light emitting layer / electron transport layer / electron injection layer is 5, it is preferable that at least three layers are formed by a coating method.
- examples of the liquid medium for dissolving or dispersing various organic EL materials used for coating include ketones such as methyl ethyl ketone and cyclohexanone, and fatty acid esters such as ethyl acetate.
- ketones such as methyl ethyl ketone and cyclohexanone
- fatty acid esters such as ethyl acetate.
- Halogenated hydrocarbons such as dichlorobenzene, aromatic hydrocarbons such as toluene, xylene, mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO be able to.
- dispersion method it can disperse
- a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm.
- a desired organic EL element can be obtained.
- the production of the organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
- the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
- lighting devices home lighting, interior lighting
- clock and liquid crystal backlights billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light
- the light source of a sensor etc. are mentioned, It is not limited to this, It can use effectively for the use as a backlight of a liquid crystal display device, and an illumination light source especially.
- patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary.
- the electrode In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.
- the light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.
- the display device of the present invention comprises the organic EL element of the present invention.
- the display device of the present invention may be single color or multicolor, but here, the multicolor display device will be described.
- a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.
- the method is not limited, but is preferably a vapor deposition method, an inkjet method, a spin coating method, or a printing method.
- the configuration of the organic EL element included in the display device is selected from the above-described configuration examples of the organic EL element as necessary.
- the manufacturing method of an organic EL element is as having shown in the one aspect
- a DC voltage When a DC voltage is applied to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
- the alternating current waveform to be applied may be arbitrary.
- the multicolor display device can be used as a display device, a display, and various light sources.
- a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
- Display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
- Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc.
- the present invention is not limited to these examples.
- FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
- the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
- the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal.
- the image information is sequentially emitted to scan the image and display the image information on the display unit A.
- FIG. 2 is a schematic diagram of the display unit A.
- the display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 on the substrate.
- the main members of the display unit A will be described below.
- the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
- the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not) When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.
- a full color display can be achieved by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
- FIG. 3 is a schematic diagram of a pixel.
- the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
- a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
- an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6.
- a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5
- the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.
- the capacitor 13 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on.
- the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
- the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
- the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
- the light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels. It is carried out.
- Such a light emitting method is called an active matrix method.
- the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good.
- the potential of the capacitor 13 may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
- the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
- FIG. 4 is a schematic view of a passive matrix display device.
- a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
- the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.
- FIG. 7 is a schematic configuration diagram of an organic EL full-color display device.
- a partition wall 103 is formed between the ITO transparent electrodes on the glass substrate.
- a hole injection layer composition is injected between the ITO electrode partition walls, and a hole injection layer 104 is produced by a drying process.
- a blue light emitting layer composition, a green light emitting layer composition, and a red color are formed on the hole injection layer, respectively.
- the light emitting layer composition is injected to form each light emitting layer 105B, light emitting layer 105G, and light emitting layer 105R.
- the cathode 106 is vacuum-deposited so as to cover the light emitting layers 105B, 105G, and 105R, and an organic EL element is manufactured.
- the lighting device of the present invention has the said organic EL element.
- the organic EL element of the present invention may be used as an organic EL element having a resonator structure.
- the purpose of use of the organic EL element having such a resonator structure is as follows.
- the light source of a machine, the light source of an optical communication processing machine, the light source of an optical sensor, etc. are mentioned, However It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.
- the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).
- the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
- the organic EL material of the present invention can be applied as an illumination device to an organic EL element that emits substantially white light.
- a plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing.
- the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
- a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.
- an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved.
- the elements themselves are luminescent white.
- luminescent material used for a light emitting layer For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.
- CF color filter
- the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 ⁇ m is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material.
- LC0629B is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and an illumination device as shown in FIGS. Can be formed.
- FIG. 5 shows a schematic view of a lighting device, and the organic EL element of the present invention is covered with a glass cover 202 (note that the sealing operation with the glass cover is performed without bringing the organic EL element into contact with the atmosphere. This was performed in a glove box under an atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more).
- FIG. 6 shows a cross-sectional view of the lighting device.
- 205 denotes a cathode
- 206 denotes an organic EL layer
- 207 denotes a transparent electrode
- 201 denotes a glass substrate.
- the glass cover 202 is filled with nitrogen gas 208 and a water catching agent 209 is provided.
- Example 1 Production of organic EL element >> (Preparation of organic EL device 1-1) Patterning was performed on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate as a positive electrode on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed, and then this ITO transparent electrode was provided.
- the transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
- the substrate provided with the first hole transport layer is fixed to a substrate holder of a commercially available vacuum deposition apparatus, each organic EL material described later is set on a resistance heating boat made of molybdenum or tantalum, and the vacuum chamber is set to 4 ⁇ .
- the pressure was reduced to 10 ⁇ 4 Pa.
- the heating boat containing HT-1 (hole transport material) was energized and heated, and deposited at a deposition rate of 0.1 nm / second to provide a 20 nm second hole transport layer.
- the heating boat containing OC-3 (host material) and PD-1 (phosphorescent dopant) is energized and heated, and the deposition rate is 0.1 nm / second and 0.006 nm / second, respectively.
- a 40 nm light emitting layer was provided by co-evaporation on the two-hole transport layer.
- ET-4 electron transport material
- ET-4 electron transport material
- the heating boat was energized and heated, and was deposited on the first electron transport layer at a deposition rate of 0.1 nm / second to provide a second electron transport layer having a thickness of 20 nm.
- lithium fluoride 0.5 nm was vapor-deposited as a cathode buffer layer, and aluminum 110 nm was vapor-deposited to form a cathode, thereby producing an organic EL device 1-1.
- the substrate temperature at the time of vapor deposition was room temperature.
- Film formation conditions for the second hole transport layer HT-19 After preparing a 0.5% dichlorobenzene solution of HT-19, this solution was formed into a film by spin coating at 1500 rpm for 30 seconds, and then dried at 200 ° C. for 1 hour to give a second hole having a thickness of 30 nm. A transport layer was provided. The weight average molecular weight of HT-19 measured by the following measurement method was 70,000.
- PVK polyvinylcarbazole
- PD-1 PD-1-phosphate-semiconductor-semiconductor
- 10 mg of polyvinylcarbazole (PVK) and 0.3 mg of PD-1 were dissolved in 3 ml of toluene. This solution was formed into a film by spin coating at 1000 rpm for 30 seconds and then dried at 120 ° C. for 1 hour to provide a light emitting layer having a thickness of 40 nm.
- the weight average molecular weight of PVK measured by the following measurement method was 120,000.
- Film formation conditions for the first electron transport layer ET-16 After preparing a 0.2% toluene: hexafluoroisopropanol (HFIP) (5:95) solution of ET-16, this solution was formed into a film by spin coating at 1500 rpm for 30 seconds, and then at 120 ° C. for 1 hour. It dried and provided the 1st electron carrying layer with a film thickness of 20 nm.
- the weight average molecular weight of ET-16 measured by the following measurement method was 28,000.
- GPC measurement conditions are measured by stabilizing the column at 40 ° C. and flowing THF (tetrahydrofuran).
- Tables 2 to 4 show the glass transition points of the constituent materials used in the examples.
- the glass transition point was measured using a differential scanning calorimeter “DSC-7” (Perkin Elmer) and a thermal analyzer controller “TAC7 / DX” (Perkin Elmer).
- the non-light-emitting surface of each organic EL device after production was covered with a glass case, a glass substrate having a thickness of 300 ⁇ m was used as a sealing substrate, and an epoxy was used as a sealing material around.
- a photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied, and this is stacked on the cathode and brought into intimate contact with the transparent support substrate.
- the glass substrate side is irradiated with UV light, cured, and sealed.
- the lighting device as shown in FIGS. 5 and 6 was formed and evaluated.
- Luminescent life When driving at a constant current of 2.5 mA / cm 2 in a dry nitrogen gas atmosphere at 23 ° C., the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured. was used as an index of life as half-life time ( ⁇ 0.5).
- a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing was used in the same manner. The results are shown as relative values when the organic EL element 1-1 is 100.
- the glass transition point (Tg) generally referred to so far is not necessarily high, and the relationship between Tg of three layers including two adjacent layers on both sides of the light emitting layer is important. It is clear that there is. This is because when the Tg relationship between the light emitting layer and the adjacent layer takes the relationship of the present invention, the carrier trapping capability in the light emitting layer is increased, the exciton confinement effect can be exhibited, and deterioration near an undesirable interface is suppressed. Therefore, it is considered that not only the external quantum efficiency is improved, but also a remarkable effect is exerted on the voltage change during constant current driving. Furthermore, as a result, a great improvement in the light emission lifetime was recognized.
- Example 2 Production of organic EL element >> (Preparation of organic EL elements 2-1 to 2-4) Organic EL devices 2-1 to 2-4 were produced in exactly the same manner except that the material of each layer in Example 1-1 was replaced with that in Table 6. The film forming conditions for the coating material are exactly the same as in Example 1.
- Example 2 it is clear that the relationship between the Tg of the three layers including the two adjacent layers on both sides of the light emitting layer is important. Furthermore, the results suggest that there is an optimum Tg of the host material. This is because the smaller the Tg or the larger the Tg difference between the two adjacent layers, the better, in order to make the best use of the carrier trapping capability, which is the aim of the present invention, but as has been said so far. From the standpoint of the contradiction, it is desirable that the Tg of the host material itself is desirably larger from the viewpoint of thermal and temporal thin film stability. From these points, the Tg of the host material more preferable in the present invention is 70 ° C. or higher and 130 ° C. or lower.
- Example 3 Provide of full-color display device> (Blue light emitting organic EL device) The organic EL element 2-3 produced in Example 2 was used.
- the produced organic EL element showed blue, green, and red light emission by applying a voltage to each electrode, and was found to be usable as a full-color display device.
- Example 4 Preparation of white light emitting lighting device ⁇ Similarly, the white light-emitting organic EL element 2-3W was changed except that PD-13 of the organic EL element 2-3 produced in Example 2 was changed to a ternary mixture of PD-1, PD-13, and PD-10. Was made. The obtained organic EL element 2-3W was covered with a glass case on the non-light emitting surface to obtain a lighting device.
- the illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.
- a full-color display device can be manufactured by arranging blue light-emitting organic EL elements, green light-emitting organic EL elements, and red light-emitting organic EL elements in a pattern.
- a white light-emitting organic EL element can be produced by combining phosphorescent light-emitting organometallic complex compounds having different emission colors, and the white light-emitting organic EL element is used as a backlight of a lighting device or a liquid crystal display device.
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Abstract
Description
(1)前記正孔輸送層及び電子輸送層は発光層にそれぞれ隣接し、
(2)前記正孔輸送層を構成する正孔輸送材料のうち、最も構成比の高い正孔輸送材料のガラス転移点(Tg)をTg(HT)、前記発光層を構成するホスト材料のうち、最も構成比の高いホスト材料のガラス転移点(Tg)をTg(EM)とした場合、Tg(HT)>Tg(EM)であり、
(3)前記電子輸送層を構成する電子輸送材料のうち、最も構成比の高い電子輸送材料のガラス転移点(Tg)をTg(ET)、前記発光層を構成するホスト材料のうち、最も構成比の高いホスト材料のガラス転移点(Tg)をTg(EM)とした場合、Tg(ET)>Tg(EM)であり、
(4)前記発光層を構成する材料として、リン光発光性有機金属錯体化合物を含有する、ことを特徴とする有機エレクトロルミネッセンス素子。
7.白色に発光することを特徴とする前記1~6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。
本発明の有機EL素子の構成層及び有機化合物層等について説明する。本発明の有機EL素子の層構成の好ましい具体例を以下に示すが、本発明はこれらに限定されない。
(ii)陽極/正孔輸送層/発光層/電子輸送層/陰極バッファー層/陰極
(iii)陽極/陽極バッファー層/正孔輸送層/発光層/電子輸送層/陰極バッファー層/陰極
《有機化合物層(有機層ともいう。)》
本発明に係る有機化合物層について説明する。本発明の有機EL素子は、構成層として複数の有機化合物層を有することが好ましく、該有機化合物層としては、例えば、上記の層構成の中で、正孔輸送層、発光層、電子輸送層等が挙げられるが、その他、正孔注入層、電子注入層等、有機EL素子のその他の構成層を構成する有機化合物が含有される層についても本発明に係る有機化合物層として定義される。
本発明に係る発光層は、電極又は電子輸送層、正孔輸送層から注入されてくる電子及び正孔が再結合して発光する層であり、発光する部分は発光層の層内であっても発光層と隣接層との界面であってもよい。
本発明に用いられるホスト材料について説明する。ここで、本発明においてホスト材料とは、発光層に含有される化合物の内でその層中での質量比が20%以上であり、かつ室温(25℃)においてリン光発光のリン光量子収率が、0.1未満の化合物と定義される。好ましくはリン光量子収率が0.01未満である。
(1)正孔輸送層、及び電子輸送層は発光層にそれぞれ隣接し、
(2)前記正孔輸送層を構成する正孔輸送材料のうち、最も構成比の高い正孔輸送材料のガラス転移点をTg(HT)、同様に前記発光層を構成するホスト材料のうち、最も構成比の高いホスト材料のガラス転移点をTg(EM)とした場合、Tg(HT)>Tg(EM)、且つ、
(3)前記電子輸送層を構成する電子輸送材料のうち、最も構成比の高い電子輸送材料のガラス転移点をTg(ET)、前記同様に、発光層を構成するホスト材料のうち、最も構成比の高いホスト材料のガラス転移点(Tg)をTg(EM)とした場合、Tg(ET)>Tg(EM)である。
本発明に係る高分子の分子量(重量平均分子量(Mw))の測定は、THF(テトラヒドロフラン)をカラム溶媒として用いるGPC(ゲルパーミエーションクロマトグラフィー)を用いて分子量測定を行うことができる。
上記においてガラス転移点は、示差走査カロリーメーター「DSC-7」(パーキンエルマー社製)、熱分析装置コントローラー「TAC7/DX」(パーキンエルマー社製)を用いて測定することが出来る。
本発明の発光層においてホスト材料と共に用いられる発光ドーパントについて説明する。
本発明に係るリン光発光性有機金属錯体化合物としては、前記一般式(1)で表される化合物が好ましく用いられる。
上記のA1で表される芳香族炭化水素環又は芳香族複素環が有していてもよい置換基としては、アルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、tert-ブチル基、ペンチル基、ヘキシル基、オクチル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基等)、シクロアルキル基(例えば、シクロペンチル基、シクロヘキシル基等)、アルケニル基(例えば、ビニル基、アリル基等)、アルキニル基(例えば、エチニル基、プロパルギル基等)、芳香族炭化水素基(芳香族炭化水素環基、芳香族炭素環基、アリール基等ともいい、例えば、フェニル基、p-クロロフェニル基、メシチル基、トリル基、キシリル基、ナフチル基、アントリル基、アズレニル基、アセナフテニル基、フルオレニル基、フェナントリル基、インデニル基、ピレニル基、ビフェニリル基等)、芳香族複素環基(例えば、ピリジル基、ピリミジニル基、フリル基、ピロリル基、イミダゾリル基、ベンゾイミダゾリル基、ピラゾリル基、ピラジニル基、トリアゾリル基(例えば、1,2,4-トリアゾール-1-イル基、1,2,3-トリアゾール-1-イル基等)、オキサゾリル基、ベンゾオキサゾリル基、チアゾリル基、イソオキサゾリル基、イソチアゾリル基、フラザニル基、チエニル基、キノリル基、ベンゾフリル基、ジベンゾフリル基、ベンゾチエニル基、ジベンゾチエニル基、インドリル基、カルバゾリル基、カルボリニル基、ジアザカルバゾリル基(前記カルボリニル基のカルボリン環を構成する炭素原子の一つが窒素原子で置き換わったものを示す。)、キノキサリニル基、ピリダジニル基、トリアジニル基、キナゾリニル基、フタラジニル基等)、非芳香族複素環基(例えば、ピロリジル基、イミダゾリジル基、モルホリル基、オキサゾリジル基等)、アルコキシ基(例えば、メトキシ基、エトキシ基、プロピルオキシ基、ペンチルオキシ基、ヘキシルオキシ基、オクチルオキシ基、ドデシルオキシ基等)、シクロアルコキシ基(例えば、シクロペンチルオキシ基、シクロヘキシルオキシ基等)、アリールオキシ基(例えば、フェノキシ基、ナフチルオキシ基等)、アルキルチオ基(例えば、メチルチオ基、エチルチオ基、プロピルチオ基、ペンチルチオ基、ヘキシルチオ基、オクチルチオ基、ドデシルチオ基等)、シクロアルキルチオ基(例えば、シクロペンチルチオ基、シクロヘキシルチオ基等)、アリールチオ基(例えば、フェニルチオ基、ナフチルチオ基等)、アルコキシカルボニル基(例えば、メチルオキシカルボニル基、エチルオキシカルボニル基、ブチルオキシカルボニル基、オクチルオキシカルボニル基、ドデシルオキシカルボニル基等)、アリールオキシカルボニル基(例えば、フェニルオキシカルボニル基、ナフチルオキシカルボニル基等)、スルファモイル基(例えば、アミノスルホニル基、メチルアミノスルホニル基、ジメチルアミノスルホニル基、ブチルアミノスルホニル基、ヘキシルアミノスルホニル基、シクロヘキシルアミノスルホニル基、オクチルアミノスルホニル基、ドデシルアミノスルホニル基、フェニルアミノスルホニル基、ナフチルアミノスルホニル基、2-ピリジルアミノスルホニル基等)、アシル基(例えば、アセチル基、エチルカルボニル基、プロピルカルボニル基、ペンチルカルボニル基、シクロヘキシルカルボニル基、オクチルカルボニル基、2-エチルヘキシルカルボニル基、ドデシルカルボニル基、フェニルカルボニル基、ナフチルカルボニル基、ピリジルカルボニル基等)、アシルオキシ基(例えば、アセチルオキシ基、エチルカルボニルオキシ基、ブチルカルボニルオキシ基、オクチルカルボニルオキシ基、ドデシルカルボニルオキシ基、フェニルカルボニルオキシ基等)、アミド基(例えば、メチルカルボニルアミノ基、エチルカルボニルアミノ基、ジメチルカルボニルアミノ基、プロピルカルボニルアミノ基、ペンチルカルボニルアミノ基、シクロヘキシルカルボニルアミノ基、2-エチルヘキシルカルボニルアミノ基、オクチルカルボニルアミノ基、ドデシルカルボニルアミノ基、フェニルカルボニルアミノ基、ナフチルカルボニルアミノ基等)、カルバモイル基(例えば、アミノカルボニル基、メチルアミノカルボニル基、ジメチルアミノカルボニル基、プロピルアミノカルボニル基、ペンチルアミノカルボニル基、シクロヘキシルアミノカルボニル基、オクチルアミノカルボニル基、2-エチルヘキシルアミノカルボニル基、ドデシルアミノカルボニル基、フェニルアミノカルボニル基、ナフチルアミノカルボニル基、2-ピリジルアミノカルボニル基等)、ウレイド基(例えば、メチルウレイド基、エチルウレイド基、ペンチルウレイド基、シクロヘキシルウレイド基、オクチルウレイド基、ドデシルウレイド基、フェニルウレイド基ナフチルウレイド基、2-ピリジルアミノウレイド基等)、スルフィニル基(例えば、メチルスルフィニル基、エチルスルフィニル基、ブチルスルフィニル基、シクロヘキシルスルフィニル基、2-エチルヘキシルスルフィニル基、ドデシルスルフィニル基、フェニルスルフィニル基、ナフチルスルフィニル基、2-ピリジルスルフィニル基等)、アルキルスルホニル基(例えば、メチルスルホニル基、エチルスルホニル基、ブチルスルホニル基、シクロヘキシルスルホニル基、2-エチルヘキシルスルホニル基、ドデシルスルホニル基等)、アリールスルホニル基又はヘテロアリールスルホニル基(例えば、フェニルスルホニル基、ナフチルスルホニル基、2-ピリジルスルホニル基等)、アミノ基(例えば、アミノ基、エチルアミノ基、ジメチルアミノ基、ブチルアミノ基、シクロペンチルアミノ基、2-エチルヘキシルアミノ基、ドデシルアミノ基、アニリノ基、ナフチルアミノ基、2-ピリジルアミノ基等)、ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子等)、フッ化炭化水素基(例えば、フルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基、ペンタフルオロフェニル基等)、シアノ基、ニトロ基、ヒドロキシ基、メルカプト基、シリル基(例えば、トリメチルシリル基、トリイソプロピルシリル基、トリフェニルシリル基、フェニルジエチルシリル基等)、ホスホノ基等が挙げられる。
注入層は必要に応じて設け、電子注入層と正孔注入層があり、上記の如く陽極と発光層又は正孔輸送層の間、及び陰極と発光層又は電子輸送層との間に存在させてもよい。
阻止層は、上記の如く有機化合物薄膜の基本構成層の他に必要に応じて設けられるものである。例えば、特開平11-204258号公報、同11-204359号公報、及び「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の237頁等に記載されている正孔阻止(ホールブロック)層がある。
正孔輸送層とは正孔を輸送する機能を有する正孔輸送材料からなり、正孔輸送層は単層又は複数層設けることができる。
有機EL素子における陽極としては、仕事関数の大きい(4eV以上)金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。
一方、陰極としては仕事関数の小さい(4eV以下)金属(電子注入性金属と称する)、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム-カリウム合金、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、インジウム、リチウム/アルミニウム混合物、希土類金属等が挙げられる。
本発明の有機EL素子に用いることのできる支持基板(以下、基体、基板、基材、支持体等ともいう。)としては、ガラス、プラスチック等の種類には特に限定はなく、また透明であっても不透明であってもよい。支持基板側から光を取り出す場合には、支持基板は透明であることが好ましい。
本発明に用いられる封止手段としては、例えば、封止部材と電極、支持基板とを接着剤で接着する方法を挙げることができる。
有機層を挟み支持基板と対向する側の前記封止膜、あるいは前記封止用フィルムの外側に、素子の機械的強度を高めるために保護膜、あるいは保護板を設けてもよい。
有機EL素子は空気よりも屈折率の高い(屈折率が1.7~2.1程度)層の内部で発光し、発光層で発生した光のうち15%から20%程度の光しか取り出せないことが一般的に言われている。
このとき、回折格子の周期は媒質中の光の波長の約1/2~3倍の範囲内程度が好ましい。
本発明の有機EL素子は基板の光取り出し側に、例えば、マイクロレンズアレイ状の構造を設けるように加工したり、あるいは所謂集光シートと組み合わせたりすることにより、特定方向、例えば、素子発光面に対し正面方向に集光することにより、特定方向上の輝度を高めることができる。
有機EL素子の製造方法の一例として、陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/陰極からなる素子の製造方法について説明する。
本発明の有機EL素子は、表示デバイス、ディスプレイ、各種発光光源として用いることができる。発光光源として、例えば、照明装置(家庭用照明、車内照明)、時計や液晶用バックライト、看板広告、信号機、光記憶媒体の光源、電子写真複写機の光源、光通信処理機の光源、光センサーの光源等が挙げられるがこれに限定するものではないが、特に液晶表示装置のバックライト、照明用光源としての用途に有効に用いることができる。
本発明の表示装置について説明する。本発明の表示装置は、本発明の有機EL素子を具備したものである。
本発明の照明装置について説明する。本発明の照明装置は上記有機EL素子を有する。 本発明の有機EL素子に共振器構造を持たせた有機EL素子として用いてもよく、このような共振器構造を有した有機EL素子の使用目的としては、光記憶媒体の光源、電子写真複写機の光源、光通信処理機の光源、光センサーの光源等が挙げられるが、これらに限定されない。また、レーザ発振をさせることにより上記用途に使用してもよい。
本発明の有機EL素子を具備した、本発明の照明装置の一態様について説明する。
《有機EL素子の作製》
(有機EL素子1-1の作製)
陽極として100mm×100mm×1.1mmのガラス基板上にITO(インジウムチンオキシド)を100nm成膜した基板(NHテクノグラス社製NA-45)にパターニングを行った後、このITO透明電極を設けた透明支持基板をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、UVオゾン洗浄を5分間行った。この透明支持基板上に、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、Bayer社製、Baytron P Al 4083)を純水で70%に希釈した溶液を3000rpm、30秒でスピンコート法により成膜した後、200℃にて1時間乾燥し、膜厚30nmの第1正孔輸送層を設けた。
有機EL素子1-1で使用した各層を構成する材料を表1のものに変更した以外は全く同様にして、真空蒸着成膜を行い、有機EL素子1-2~1-8を作製した。ただし、高分子材料であるHT-19(正孔輸送材料)、ポリビニルカルバゾール(PVK)及びET-16(電子輸送材料)を用いた成膜は、塗布で行なった。塗布成膜条件については、以下の通りである。
HT-19の0.5%ジクロロベンゼン溶液を調整した後、この溶液を1500rpm、30秒でスピンコート法により成膜した後、200℃にて1時間乾燥し、膜厚30nmの第2正孔輸送層を設けた。なお、下記測定方法で測定したHT-19の重量平均分子量は70,000であった。
10mgのポリビニルカルバゾール(PVK)と0.3mgのPD-1を3mlのトルエンに溶解した。この溶液を1000rpm、30秒でスピンコート法により成膜した後、120℃にて1時間乾燥し、膜厚40nmの発光層を設けた。なお、下記測定方法で測定したPVKの重量平均分子量は120,000であった。
ET-16の0.2%トルエン:ヘキサフルオロイソプロパノール(HFIP)(5:95)溶液を調整した後、この溶液を1500rpm、30秒でスピンコート法により成膜した後、120℃にて1時間乾燥し、膜厚20nmの第1電子輸送層を設けた。なお、下記測定方法で測定したET-16の重量平均分子量は28,000であった。
測定試料を1mgに対してTHF(脱気処理を行ったものを用いる)を1mL加え、室温下にてマグネチックスターラーを用いて撹拌を行い、充分に溶解させる。ついで、ポアサイズ0.45~0.50μmのメンブランフィルターで処理した後に、GPC(ゲルパーミエーションクロマトグラフ)装置に注入する。
装置:東ソー高速GPC装置 HLC-8220GPC
カラム:TOSOH TSKgel Super HM-M
検出器:RI及び/またはUV
溶出液流速:0.6ml/分
試料濃度:0.1質量%
試料量:100mL
検量線:標準ポリスチレンにて作製:標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=1000000~500迄の13サンプルを用いて検量線(校正曲線ともいう)を作成、分子量の算出に使用した。13サンプルは、ほぼ等間隔にする。
作製した有機EL素子について、23℃、乾燥窒素ガス雰囲気下で2.5mA/cm2定電流を印加した時の外部取り出し量子効率(%)を測定した。なお、測定には分光放射輝度計CS-1000(コニカミノルタセンシング製)を用いた。外部取り出し量子効率は、有機EL素子1-1を100とした時の相対値で示す。
温度23℃、乾燥窒素ガス雰囲気下での2.5mA/cm2定電流駆動時の電圧を測定した。後述の発光寿命測定条件下で、初期輝度時の電圧値(DV0)とし、初期輝度から30%低下した時の電圧値(DV70)、初期輝度から50%低下(半減)した時の電圧値(DV50)とした時、(DV70)-(DV0)をΔ1、(DV50)-(DV0)をΔ2として経時的な駆動電圧変化の指標とした。Δ1、Δ2は、有機EL素子1-1を100とした時の相対値で示す。
23℃、乾燥窒素ガス雰囲気下で2.5mA/cm2の一定電流で駆動したときに、輝度が発光開始直後の輝度(初期輝度)の半分に低下するのに要した時間を測定し、これを半減寿命時間(τ0.5)として寿命の指標とした。なお、測定には同様に分光放射輝度計CS-1000(コニカミノルタセンシング製)を用いた。結果を、有機EL素子1-1を100とした時の相対値で示す。
《有機EL素子の作製》
(有機EL素子2-1~2-4の作製)
実施例1-1の各層材料を表6のもとに置き換えた以外は全く同様にして、有機EL素子2-1~2-4を作製した。尚、塗布材料の成膜条件は実施例1と全く同様である。
《フルカラー表示装置の作製》
(青色発光有機EL素子)
実施例2で作製した有機EL素子2-3を用いた。
実施例1で作製した有機EL素子1-8を用いた。
実施例1で作製した有機EL素子1-8において、発光層に用いたPD-1をPD-10に変更した以外は全く同様にして作製した有機EL素子1-8Rを製造して、これを用いた。
《白色発光照明装置の作製》
実施例2で作製した有機EL素子2-3のPD-13をPD-1、PD-13、PD-10の三者混合体に変更した以外は同様して、白色発光有機EL素子2-3Wを作製した。得られた有機EL素子2-3Wを、非発光面をガラスケースで覆い、照明装置とした。照明装置は、発光効率が高く発光寿命の長い白色光を発する薄型の照明装置として使用することができた。
3 画素
5 走査線
6 データ線
7 電源ライン
10 有機EL素子
11 スイッチングトランジスタ
12 駆動トランジスタ
13 コンデンサ
A 表示部
B 制御部
101 ガラス基板
102 ITO透明電極
103 隔壁
104 正孔注入層
105B、105G、105R 発光層
106 陰極
201 ガラス基板
207 透明電極付きガラス基板
206 有機EL層
205 陰極
202 ガラスカバー
208 窒素ガス
209 捕水剤
L 光
Claims (9)
- 陽極と陰極との間に挟持された正孔輸送層、発光層及び電子輸送層を含む複数の有機化合物層を有する有機エレクトロルミネッセンス素子において、
(1)前記正孔輸送層及び電子輸送層は発光層にそれぞれ隣接し、
(2)前記正孔輸送層を構成する正孔輸送材料のうち、最も構成比の高い正孔輸送材料のガラス転移点(Tg)をTg(HT)、前記発光層を構成するホスト材料のうち、最も構成比の高いホスト材料のガラス転移点(Tg)をTg(EM)とした場合、Tg(HT)>Tg(EM)であり、
(3)前記電子輸送層を構成する電子輸送材料のうち、最も構成比の高い電子輸送材料のガラス転移点(Tg)をTg(ET)、前記発光層を構成するホスト材料のうち、最も構成比の高いホスト材料のガラス転移点(Tg)をTg(EM)とした場合、Tg(ET)>Tg(EM)であり、
(4)前記発光層を構成する材料として、リン光発光性有機金属錯体化合物を含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。 - 前記発光層に含有されるホスト材料のガラス転移点Tgが、70℃以上、130℃以下であることを特徴とする請求項1に記載の有機エレクトロルミネッセンス素子。
- 前記正孔輸送層に含有される正孔輸送材料は、高分子であ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。
- 前記電子輸送層に含有される電子輸送材料は、高分子であることを特徴とする請求項1~3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。
- 前記正孔輸送層に含有される正孔輸送材料及び前記電子輸送層に含有される電子輸送材料が、共に高分子であ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。
- 前記リン光発光性有機金属錯体化合物の少なくとも1種が、下記一般式(1)で表される化合物であることを特徴とする請求項1~5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。
- 白色に発光することを特徴とする請求項1~6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。
- 請求項1~6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ことを特徴とする照明装置。
- 請求項1~6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ことを特徴とする表示装置。
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CN104681741A (zh) * | 2013-11-26 | 2015-06-03 | 剑桥显示技术有限公司 | 有机发光器件和方法 |
JP2016012551A (ja) * | 2014-06-04 | 2016-01-21 | 住友化学株式会社 | 発光素子 |
JP2016225575A (ja) * | 2015-06-03 | 2016-12-28 | セイコーエプソン株式会社 | 発光素子、発光装置、認証装置および電子機器 |
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KR20220047458A (ko) * | 2020-10-08 | 2022-04-18 | 삼성디스플레이 주식회사 | 헤테로고리 화합물, 이를 포함한 발광 소자 및 상기 발광 소자를 포함한 전자 장치 |
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