WO2012096241A1 - 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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Definitions
- the present invention relates to an organic electroluminescence element, a lighting device, 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 2V 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.
- An object of the present invention is to provide an organic electroluminescence device that retains a high hole injection property as compared with a conventional organic EL device.
- An organic electroluminescence element in which an organic compound layer is sandwiched between an anode and a cathode, wherein the organic compound layer includes at least a light emitting layer and a charge generation layer, (1) having the charge generation layer composed of at least one layer between the anode and the light emitting layer; (2) containing an organometallic complex in at least one of the charge generation layers; An organic electroluminescence device characterized by that.
- P and Q represent a carbon atom or a nitrogen atom
- A1 represents an atomic group forming an aromatic hydrocarbon ring or an aromatic heterocycle with PC
- A2 represents an aromatic hydrocarbon 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 represents P1
- P2 represents an atomic group forming a bidentate ligand
- r represents an integer of 1 to 3
- s represents an integer of 0 to 2
- r + s is 2 or 3.
- M1 represents an element period (Represents group 8-10 metal elements in the table.) 5. 5. The organic electroluminescence according to any one of 2 to 4, wherein the charge generation layer includes a layer containing the electron extracting material and a layer containing the organometallic complex adjacent thereto. element.
- the absolute value of the difference between the LUMO value of the electron withdrawing material and the adjacent organometallic complex HOMO value is 0.0 eV or more and 1.0 eV or less, according to any one of 2 to 5 above Organic electroluminescence device.
- R and S represent a carbon atom or a nitrogen atom
- A3 represents an atomic group which forms an aromatic hydrocarbon ring or an aromatic heterocycle with R—C.
- A4 represents an aromatic hydrocarbon with S—N.
- P3-L2-P4 represents a bidentate ligand
- P3 and P4 each independently represent a carbon atom, a nitrogen atom or an oxygen atom
- L2 represents P3
- P4 represents an atomic group forming a bidentate ligand
- r represents an integer of 1 to 3
- s represents an integer of 0 to 2
- r + s is 2 or 3.
- M2 represents an element period (Represents group 8-10 metal elements in the table.) 8).
- the absolute value of the difference between the HOMO value of the organometallic complex constituting the charge generation layer and the HOMO value of the organometallic complex contained in the light emitting layer is 0.0 eV or more and 1.0 eV or less, 8.
- the organic electroluminescence device according to any one of 1 to 7.
- An illumination device comprising the organic electroluminescence element according to any one of 1 to 11 above.
- a display device comprising the organic electroluminescence element according to any one of 1 to 11 above.
- the organic EL element material of the present invention was able to provide an organic electroluminescence element in which a voltage increase during driving was suppressed as compared with a conventional organic EL element.
- FIG. 4 is a schematic diagram of a display unit A.
- FIG. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is a schematic diagram of an illuminating device. The schematic block diagram of an organic electroluminescent full color display apparatus is shown.
- HOMO and LUMO mean the values of the highest occupied molecular orbital (HOMO) energy level and the lowest empty orbital (LUMO) energy level, and these are molecular orbital calculations made by GaU88ian, USA. Is a value calculated using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a key word Is defined as a value obtained by rounding off the second decimal place of a 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.
- Gaussian 98 Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.
- a key word Is defined as a value obtained by rounding off the second decimal place of a value (eV unit converted value) calculated by performing
- the organic EL device of the present invention preferably has a plurality of organic compound layers as a constituent layer, and examples of the organic compound layer include a hole transport layer, a light emitting layer, and a hole blocking layer in the above-described layer configuration.
- the organic compound layer according to the present invention an organic compound contained in a constituent layer of the organic EL element, such as a hole injection layer or an electron injection layer, is included. Defined.
- 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 organic compound layer includes a layer containing “organic EL element material that can be used for a constituent layer of an organic EL element” or the like.
- the blue light emitting layer preferably has an emission maximum wavelength of 430 to 480 nm
- the green light emitting layer has an emission maximum wavelength of 510 to 550 nm
- the red light emitting layer has an emission maximum wavelength of 600 to 640 nm.
- a monochromatic light emitting layer in the range is preferable, 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 electron extraction layer according to the present invention which is a layer containing an electron extraction material is a layer having a function of extracting electrons from an adjacent layer, and the electron extraction material constituting this layer is a compound having a high electron affinity, in other words, a deep layer.
- a compound having a LUMO value For example, a generally well-known electron acceptor (acceptor molecule) is preferably used, and its LUMO value is ⁇ 6.0 to ⁇ 3.0 eV, more preferably ⁇ 5.0 to ⁇ 4.0 eV. It is.
- the LUMO value is ⁇ 6.0 or more, it becomes a stable compound, so that it is not difficult to use regularly and the effects of the present invention can be exhibited.
- it exceeds -3.0 it functions as a material constituting the charge generation layer without any problem.
- charge transfer is performed. Since the relationship between the energy levels between adjacent layers, in particular the relationship with the light emitting layer, is important, it is preferably ⁇ 3.0 or less.
- electron withdrawing materials that can be suitably used in the present invention include polyfluorinated compounds, polycyano-substituted products, condensed electron aromatic ring-substituted condensed aromatic rings or condensed heteroaromatic rings, or patents. Examples thereof include, but are not limited to, compounds described in Japanese Patent No. 4315874, Japanese Patent Laid-Open No. 2006-135144, and Japanese Patent Laid-Open No. 2006-135145.
- the charge generation layer refers to a layer formed of at least one layer and having a function of injecting holes in the cathode direction and electrons in the anode direction when a voltage is applied.
- the charge generation layer is composed of at least two layers.
- the layer structure of the charge generation layer of the present invention will be described.
- the p-type or n-type layer shown in the following (1) to (11) can be used as the charge generation layer of the present invention by singly or arbitrarily combining a plurality of layers.
- the n-type layer is a transport layer in which majority carriers are electrons, and preferably has a conductivity higher than that of a semiconductor.
- the p-type layer is a transport layer in which majority carriers are holes, and preferably has conductivity higher than that of a semiconductor. Examples of the p-type layer and the n-type layer are shown below, but are not limited thereto.
- Electron transporting material layer (2) Electron extraction layer (organic acceptor material / inorganic acceptor material) (3) Mixed layer of electron transport material and alkali (earth) metal salt (or alkali (earth) metal precursor) (4) n-type semiconductor layer (organic material, inorganic material) (5) n-type conductive polymer layer (6) single hole injection / transport material layer (7) multiple types of hole injection / transport material mixed layer (8) organometallic complex layer (9) hole Mixed layer of transportable material and metal oxide (10) p-type semiconductor layer (organic material, inorganic material) (11) p-type conductive polymer layer
- the charge generation layer is composed of at least two layers, and one layer is (8). Further, the combination of the two layers is preferably composed of (8) and (9) or (8) and (2), more preferably (8) and (2).
- the position of charge generation may be in the charge generation layer, or may be at or near the interface between the charge generation layer and another adjacent layer.
- the charge generation layer is a single layer, the charge generation of electrons and holes (holes) may be performed in the charge generation layer or at the interface between the adjacent layer and the charge generation layer.
- the charge generation layer comprises two or more layers, and more preferably includes one or both of a p-type semiconductor layer and an n-type semiconductor layer.
- the layer interface of the charge generation layer composed of two or more layers may have an interface (heterointerface, homointerface), or a multidimensional interface such as a bulk heterostructure, island shape, or phase separation. May be formed.
- each of the two layers is preferably 1 nm or more and 100 nm or less, and more preferably 10 nm or more and 50 nm or less.
- the light transmittance of the charge generation layer of the present invention is desirably high for the light emitted from the light emitting layer.
- the transmittance at a wavelength of 550 nm is desirably 50% or more, and more preferably 80% or more.
- each layer constituting the charge generation layer of the present invention includes the above-mentioned organic compounds (organic acceptors, organic donors), organometallic complex compounds, aromatic hydrocarbon compounds, and derivatives thereof, heteroaromatic hydrocarbons.
- organic compounds organic acceptors, organic donors
- organometallic complex compounds aromatic hydrocarbon compounds, and derivatives thereof, heteroaromatic hydrocarbons.
- 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 compound which will be described later, 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 may contain a light emitting host compound and at least one kind of light emitting dopant (phosphorescent dopant (also referred to as phosphorescent dopant) or fluorescent dopant). preferable. Moreover, you may mix and use the hole transport material and electron transport material which are mentioned later.
- the host compound in the present invention is 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.
- the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
- a compound having a 0-0 band having a shorter wavelength than the phosphorescence 0-0 band of the luminescent dopant is preferable, and the 0-0 band of phosphorescence is characterized by having a wavelength of 460 nm or less.
- the 0-0 band of phosphorescence is preferably 450 nm or less, more preferably 440 nm or less, and even more preferably 430 nm or less.
- a method for measuring the 0-0 band of phosphorescence in the present invention will be described.
- a method for measuring a phosphorescence spectrum will be described.
- the above-described measuring method has no problem because the solvent effect of the phosphorescence wavelength is negligible.
- the 0-0 band is obtained.
- the emission maximum wavelength that appears on the shortest wavelength side in the phosphorescence spectrum chart obtained by the above-described measurement method is defined as the 0-0 band. Since the phosphorescence spectrum usually has a low intensity, when it is enlarged, it may be difficult to distinguish between noise and peak.
- the emission spectrum immediately after the excitation light irradiation (for convenience, this is referred to as a steady light spectrum) is expanded and superimposed on the emission spectrum 100 ms after the excitation light irradiation (for convenience, this is referred to as a phosphorescence spectrum),
- the peak wavelength derived from the phosphorescence spectrum can be determined by reading from the stationary light spectrum portion.
- by smoothing the phosphorescence spectrum noise and peaks can be separated and the peak wavelength can be read.
- a smoothing method of Savitzky & Golay can be applied.
- a well-known host compound may be used together, and may be used in combination of multiple types.
- a host compound By using 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. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.
- a conventionally known host compound that may be used in combination is preferably a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature).
- Luminescent dopant The light emitting dopant according to the present invention will be described.
- a fluorescent dopant also referred to as a fluorescent compound
- a phosphorescent dopant also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like
- the light emitting dopant used in the light emitting layer or the light emitting unit of the organic EL device of the present invention (sometimes simply referred to as a light emitting material) is as described above. It is preferable to contain a phosphorescent dopant simultaneously with the host compound.
- 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.
- a compound having a phosphorescence quantum yield of less than 0.01 at 25 ° C. is defined as a non-phosphorescent compound.
- 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 compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device.
- the phosphorescent 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), an osmium compound, or a platinum compound. (Platinum complex compounds) and rare earth complexes, with iridium compounds (Ir complexes) being most preferred among them.
- the phosphorescent dopant contained in the light emitting layer is preferably represented by the general formula (2), which is preferably contained in at least one layer of the charge generation layer. It is the same organometallic complex as the organometallic complex represented by (1).
- Organic metal complex represented by the general formula (1) As the organometallic complex according to the present invention, the compound represented by the general formula (1) is preferably used.
- the aromatic hydrocarbon ring formed 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 formed 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.
- aromatic hydrocarbon ring or aromatic heterocycle formed by A1 may have an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group).
- cycloalkyl group eg cyclopentyl group, cyclohexyl group etc.
- alkenyl group eg vinyl Group, allyl group, etc.
- alkynyl group eg, ethynyl group, propargyl group, etc.
- aromatic hydrocarbon group aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group Fluorenyl group, phenanthryl 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 hydrocarbon ring and aromatic heterocycle formed by A2 are respectively synonymous with the aromatic hydrocarbon ring and aromatic heterocycle formed by A1 in the general formula (1). is there.
- 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 transition metal element belonging to Group 8 to 10 in the periodic table of elements (also simply referred to as a transition metal), among which iridium and platinum are preferable, and iridium is particularly preferable.
- the light emitting layer contains a phosphorescent material represented by the general formula (2).
- R and S represent a carbon atom or a nitrogen atom
- A3 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with R—C.
- A4 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with S—N.
- P3-L2-P4 represents a bidentate ligand
- P3 and P4 each independently represent a carbon atom, a nitrogen atom or an oxygen atom.
- L2 represents an atomic group forming a bidentate ligand together with P3 and P4.
- r represents an integer of 1 to 3
- s represents an integer of 0 to 2
- r + s is 2 or 3.
- M2 represents a group 8-10 metal element in the periodic table.
- the aromatic hydrocarbon ring formed by A3 has the same meaning as the aromatic hydrocarbon ring formed by A1 in the general formula (1).
- the aromatic heterocycle formed by A3 has the same meaning as the aromatic heterocycle formed by A1 in the general formula (1).
- Examples of the substituent that the aromatic hydrocarbon ring or aromatic heterocyclic ring formed by A3 may have include the aromatic hydrocarbon ring or aromatic formed by A1 in General Formula (1). It is synonymous with the substituent which the group heterocyclic ring may have.
- the aromatic hydrocarbon ring and aromatic heterocycle formed by A4 have the same meanings as the aromatic hydrocarbon ring and aromatic heterocycle formed by A1 in general formula (1), respectively. is there.
- the bidentate ligand represented by P3-L2-P4 has the same meaning as the bidentate ligand represented by P1-L1-P2 in the general formula (1). is there.
- M2 is a transition metal element of group 8 to 10 in the periodic table (simply referred to as a transition metal).
- a transition metal iridium and platinum are preferable, and iridium is particularly preferable.
- organometallic complex represented by the general formula (1) or the general formula (2) 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.
- organometallic complex represented by the general formula (1) contained in the charge generation layer includes non-phosphorescent organometallic complexes that are not phosphorescent, and examples thereof include the following: Things.
- 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.
- 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.
- cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
- Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc.
- the buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 10 nm, depending 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 hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
- 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.
- a method of calculating from molecular orbital calculation (2)
- 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 transporting layer according to the present invention is preferably 3 to 100 nm, more preferably 5 to 30 nm.
- the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
- 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
- No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.
- NPD 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
- JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the
- polymer materials in which these materials are introduced into polymer chains or these materials are used as polymer main chains can also be used.
- inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
- JP-A-11-251067 J. Org. Huang et. al. A so-called p-type hole transport material as 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 thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
- the 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, JP-A-2001-102175, J. Pat. 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 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 cathode side with respect to the light emitting layer is injected from the cathode.
- any material can be selected and used 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.
- thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material.
- quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the 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 also 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 about 5 nm to 5 ⁇ m, preferably 5 nm 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.
- 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
- the anode may be formed by forming a thin film of these electrode materials 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 required (about 100 ⁇ m), 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 depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm 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 (Al 2 O 3 ) Mixtures, 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 in the range of 10 nm to 5 ⁇ m, preferably 50 nm to 200 nm.
- the emission luminance is advantageously improved.
- a transparent or semi-transparent cathode can be produced by producing a conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a film thickness of 1 nm to 20 nm. By applying this, 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. May be 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, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (
- 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 further, 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 that has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen.
- silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
- the method for forming the barrier film is not particularly limited.
- the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and 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 efficiency at room temperature of light emission of the organic EL element 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 any material that has 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.
- a polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a 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), and light emission from the 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.
- Bragg diffraction such as first-order diffraction and second-order diffraction.
- light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode). 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 interlayer or 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 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 element of the present invention can be processed on a light extraction side of a substrate, for example, by providing a microlens array-like structure, or combined with a so-called condensing sheet, for example in a specific direction, for example, with respect to the element light emitting surface.
- a condensing sheet for example in a specific direction, for example, with respect to the element light emitting surface.
- 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 10 ⁇ m 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 with a triangle 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 desired electrode material for example, a thin film made of an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably 10 nm to 200 nm.
- a method for forming each of these layers there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above.
- film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable from the viewpoint that holes are not easily generated.
- 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 nm to 200 nm.
- a desired organic EL element can be obtained.
- a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, 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.
- An alternating voltage may be applied.
- the alternating current waveform to be applied may be arbitrary.
- 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, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.
- 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 2V to 40V 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 L 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. 7 shows a schematic configuration diagram of an organic EL full-color display device.
- 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.
- the lighting device of the present invention will be described.
- the illuminating device of this 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 a photosensor, 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 three primary colors of blue, green, and red, or two using the 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 the lighting device, and the organic EL element 201 of the present invention is covered with a glass cover 202 (in addition, the sealing operation with the glass cover is to bring the organic EL element 201 into contact with the atmosphere. And a glove box under a nitrogen 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 glass substrate with a transparent electrode.
- the glass cover 202 is filled with nitrogen gas 208 and a water catching agent 209 is provided.
- FIG. 7 is a schematic diagram showing an example of a manufacturing process of a full color display device by an ink jet method.
- a non-photosensitive polyimide partition wall 103 was formed by photolithography on a glass substrate 101 on which an ITO electrode 102 was formed.
- the partition wall was discharged and injected using an inkjet head (manufactured by Epson Corporation; MJ800C).
- a first hole transport layer 104 having a thickness of 20 nm was formed on the ITO electrode 102.
- a light emitting unit 105 including a second hole transport layer having a thickness of 20 nm, a light emitting layer having a thickness of 40 nm, and an electron transport layer having a thickness of 30 nm was sequentially stacked.
- a cathode buffer layer / cathode 106 was formed by a vacuum deposition method, and an organic EL element was produced.
- an organic EL element formed by forming each light emitting layer using an ink jet method exhibits blue, green, and red light emission by applying a voltage to each electrode, and serves as a full color display device. I found that it was available.
- the light emitting unit 105 in the figure includes a light emitting unit 105R in which a red light emitting material is contained in a light emitting layer constituting the light emitting unit, a light emitting unit 105G in which a green light emitting material is contained, and a light emitting material in which a blue light emitting material is contained. This is distinguished from the unit 105B.
- Example 1 ⁇ Method for Manufacturing Organic EL Element 1-1> A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
- the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
- each material described later is packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode is formed in a vacuum vapor deposition apparatus, and the degree of vacuum becomes 1 ⁇ 10 ⁇ 4 Pa or less.
- the films were sequentially formed as follows.
- a charge generation layer consisting of two layers was formed.
- dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT) was deposited at a deposition rate of 0.1 nm / 20 nm was vapor-deposited at a rate of 2 seconds
- an organometallic complex D-4 was vapor-deposited at a rate of 0.01 nm / sec.
- OC-9 was deposited at a deposition rate of 0.1 nm / second
- D-1 was deposited at a deposition rate of 0.01 nm / second
- a 40 nm light-emitting layer, OC-10 was deposited at a deposition rate of 0.1 nm / second.
- Vapor deposition was performed at a rate of 2 seconds, and a 30 nm electron transport layer was provided.
- 1.0 nm of sodium fluoride was vapor-deposited as an electron injection layer, and 110 nm of aluminum was vapor-deposited as a cathode, and the organic EL element 1-1 was manufactured.
- a transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
- the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
- each material described later is packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode is formed in a vacuum vapor deposition apparatus, and the degree of vacuum becomes 1 ⁇ 10 ⁇ 4 Pa or less.
- the films were sequentially formed as follows.
- a charge generation layer consisting of two layers was formed.
- HAT is deposited at a deposition rate of 0.1 nm / second to 20 nm
- N, N′-di (1-naphthyl) -N, N '-Diphenylbenzidine ( ⁇ -NPD) was deposited to a thickness of 20 nm at a deposition rate of 0.1 nm / second.
- OC-9 was deposited at a deposition rate of 0.1 nm / second
- D-1 was deposited at a deposition rate of 0.01 nm / second
- a 40 nm light-emitting layer, OC-10 was deposited at a deposition rate of 0.1 nm / second.
- Vapor deposition was performed at a rate of 2 seconds, and a 30 nm electron transport layer was provided.
- 1.0 nm of sodium fluoride was vapor-deposited as an electron injection layer, and 110 nm of aluminum was vapor-deposited as a cathode, and the organic EL element 1-2 was manufactured.
- a transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
- the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
- each material described later is packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode is formed in a vacuum vapor deposition apparatus, and the degree of vacuum becomes 1 ⁇ 10 ⁇ 4 Pa or less.
- the films were sequentially formed as follows.
- CuPc copper phthalocyanine
- an organometallic complex D-4 was deposited on the first hole transport layer at a deposition rate of 0.01 nm / second to a thickness of 10 nm to form a second hole transport layer.
- OC-9 was deposited on the second hole transport layer at a deposition rate of 0.1 nm / second and D-1 was deposited at a deposition rate of 0.01 nm / second to obtain a 40 nm light emitting layer
- OC -10 was deposited at a deposition rate of 0.1 nm / second to provide a 30 nm electron transport layer.
- 1.0 nm of sodium fluoride was vapor-deposited as an electron injection layer, and 110 nm of aluminum was vapor-deposited as a cathode, and the organic EL element 1-3 was manufactured.
- a transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
- the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
- each material described later is packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode is formed in a vacuum vapor deposition apparatus, and the degree of vacuum becomes 1 ⁇ 10 ⁇ 4 Pa or less.
- the films were sequentially formed as follows.
- CuPc copper phthalocyanine
- ⁇ -NPD deposited on the first hole transporting layer at a deposition rate of 0.1 nm / second to 20 nm to form a second hole transporting layer.
- OC-9 was deposited on the second hole transport layer at a deposition rate of 0.1 nm / second and D-1 was deposited at a deposition rate of 0.01 nm / second to obtain a 40 nm light emitting layer
- OC -10 was deposited at a deposition rate of 0.1 nm / second to provide a 30 nm electron transport layer.
- 1.0 nm of sodium fluoride was vapor-deposited as an electron injection layer, and aluminum 110nm was vapor-deposited as a cathode, and the organic EL element 1-4 was manufactured.
- ⁇ Drive voltage> The voltage at the start of light emission was measured at 23 ° C. in a dry nitrogen gas atmosphere. Note that the voltage value at the start of light emission was measured when the luminance was 50 cd / m 2 or more.
- a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing was used.
- ⁇ 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 of the organic EL elements 1-1 to 1-4 are shown in Table 1 as a result of relative evaluation when the organic EL element 1-4 is set to 100.
- the device of the present invention (organic EL device 1-1) can achieve a lower driving voltage than the conventional hole injection material. It was. This is because the injection barrier between the anode and the light-emitting layer is concentrated at only one point of the injection barrier between the organometallic complex layer and the light-emitting layer by generating charges at a position adjacent to the light-emitting layer. As a result, the deterioration of the device due to the barrier can be suppressed, and the lifetime can be extended.
- organometallic complex is used as the hole transport material (organic EL element 1-3)
- the triarylamine material is not used at the position adjacent to the light emitting layer, the electron resistance is increased. Since there is no charge generation capability with copper phthalocyanine, the injection barrier between the anode and the light emitting layer is relatively increased compared to the present invention. Therefore, the effect on the drive voltage change is relatively poor, and the usefulness of the present invention is clear.
- Example 2 Comparison of electronic drawing materials ⁇ Method for producing organic EL element 2-5>
- a transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
- the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
- each material described later is packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode is formed in a vacuum vapor deposition apparatus, and the degree of vacuum becomes 1 ⁇ 10 ⁇ 4 Pa or less.
- the films were sequentially formed as follows.
- a charge generation layer consisting of two layers was formed.
- HAT was deposited at a deposition rate of 0.1 nm / second to 20 nm
- an organometallic complex D-1 was deposited at a deposition rate of 0.01 nm / second.
- OC-13 was deposited at a deposition rate of 0.1 nm / second and D-1 was deposited at a deposition rate of 0.02 nm / second, and an 80 nm light emitting layer, OC-103, was deposited at a deposition rate of 0.1 nm / second.
- Vapor deposition was performed at a rate of 2 seconds, and a 30 nm electron transport layer was provided. Subsequently, 1.0 nm of sodium fluoride was vapor-deposited as an electron injection layer, and 110 nm of aluminum was vapor-deposited as a cathode, and the organic EL element 2-5 was manufactured.
- Organic EL elements 2-1 to 2-4 were produced in exactly the same manner except that the HAT used in the organic EL element 2-5 was changed to the electron extraction layer material shown in Table 2. Further, as a material constituting the charge generation layer, an organic EL element 2-6 in which the electron extraction layer material used in the organic EL element 2-5 is replaced with molybdenum oxide which is a non-electron extraction layer material, and a charge generation layer are provided. An organic EL device 2-7 was manufactured. The evaluation of the organic EL elements 2-1 to 2-7 was performed by relative evaluation with the organic EL element 2-7 as 100. The results are shown in Table 2.
- Example 3 (comparison of relationship with HOMO level of complex) ⁇ Method for Manufacturing Organic EL Element 3-1> A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
- the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
- each material described later is packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode is formed in a vacuum vapor deposition apparatus, and the degree of vacuum becomes 1 ⁇ 10 ⁇ 4 Pa or less.
- the films were sequentially formed as follows.
- a charge generation layer consisting of two layers was formed.
- HAT was deposited at a deposition rate of 0.1 nm / second to 20 nm
- an organometallic complex D-15 was deposited at a deposition rate of 0.01 nm / second.
- OC-9 was deposited at a deposition rate of 0.1 nm / second and D-2 was deposited at a deposition rate of 0.01 nm / second, and a light-emitting layer of 80 nm and OC-103 were deposited at a deposition rate of 0.1 nm / second.
- Vapor deposition was performed at a rate of 2 seconds, and a 30 nm electron transport layer was provided. Subsequently, 1.0 nm of sodium fluoride was deposited as an electron injection layer and 110 nm of aluminum was deposited as a cathode, thereby manufacturing an organic EL element 3-1.
- Organic EL elements 3-1 to 3-8 were produced in exactly the same manner except that the organometallic complex D-15 used in the organic EL element 3-1 was changed to the organometallic complex shown in Table 3.
- the organic EL elements 3-1 to 3-8 were evaluated by relative evaluation with the organic EL element 3-8 as 100. The results are shown in Table 3.
- the difference between the LUMO level of the adjacent electron extraction layer forming the charge generation layer and the HOMO level of the organometallic complex layer has a significant effect on the degree of increase in driving voltage. I understood. In particular, in order to make the most of the effects of the present invention, it is clear that this becomes remarkable when the absolute value of the difference is 1.0 eV or less, and more preferably 0.5 eV or less.
- an organic EL element 3-7 in which the organometallic complex material used in the organic EL element 3-1 was changed to a non-phosphorescent organometallic complex ND-1 an organic EL element 3-7 was produced. A trend was observed.
- Organic EL devices 3-9 to 3-11 were produced in exactly the same manner except that the electron extraction layer and the organometallic complex material used in the organic EL device 3-1 were replaced with the materials shown in Table 4. Even when the LUMO level was changed, the same tendency as before was observed. This also indicates that the difference between the LUMO level of the adjacent electron extraction layer forming the charge generation layer and the HOMO level of the organometallic complex layer is an important factor of the present invention.
- Example 4 ⁇ Method for Manufacturing Organic EL Element 4-1> A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
- the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
- each material described later is packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode is formed in a vacuum vapor deposition apparatus, and the degree of vacuum becomes 1 ⁇ 10 ⁇ 4 Pa or less.
- the films were sequentially formed as follows.
- a charge generation layer consisting of two layers was formed.
- HAT was deposited at a deposition rate of 0.1 nm / second to 20 nm
- an organometallic complex D-4 was deposited at a deposition rate of 0.01 nm / second.
- Vapor deposition was performed at a rate of 10 nm.
- OC-16 was vapor-deposited at a deposition rate of 0.1 nm / sec and D-16 was vapor-deposited at a vapor deposition rate of 0.01 nm / sec, and an 80 nm light-emitting layer, OC-10 was vapor-deposited at a rate of 0.1 nm / sec.
- Vapor deposition was performed at a rate of 2 seconds, and a 30 nm electron transport layer was provided. Subsequently, 1.0 nm of sodium fluoride was vapor-deposited as an electron injection layer, and 110 nm of aluminum was vapor-deposited as a cathode, and the organic EL element 4-1 was manufactured.
- Organic EL elements 4-1 to 4-4 were produced in exactly the same manner except that the organometallic complex D-4 used in the organic EL element 4-1 was changed to the organometallic complex shown in Table 5.
- the evaluation of the organic EL elements 4-1 to 4-4 was performed by relative evaluation with the organic EL element 4-4 set to 100. The results are shown in Table 5.
- organic EL elements 4-5 to 4-12 were produced in exactly the same manner except that the organometallic complex D-4 used in the organic EL element 4-1 was changed to the electron extraction layer material and the light emitting dopant material shown in Table 6. did.
- the evaluation of the organic EL elements 4-5 to 4-12 was performed by relative evaluation with the organic EL element 4-12 as 100. The results are shown in Table 6.
- results in Table 6 also have the same tendency as the results of the organic EL elements 4-1 to 4-4 described above.
- Example 5 Provide of full-color display device> (Blue light emitting organic EL device) The organic EL element 4-11 produced in Example 4 was used.
- the green light emitting organic EL element 4 was prepared in the same manner as in the production of the organic EL element 4-5 prepared in Example 4, except that D-1 used as the light emitting dopant was changed to D-15. -5G was produced.
- red light emitting organic EL element 4-5R was produced in the same manner as in the production of the organic EL element 4-5 produced in Example 4, except that D-1 was changed to D-21.
- the red, green, and blue light-emitting organic EL elements are juxtaposed on the same substrate to produce an active matrix type full-color display device having the form shown in FIG. 1, and FIG. 2 shows the produced display device. Only the schematic diagram of the display part A is shown.
- a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of juxtaposed pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.)
- the scanning lines 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 lattice shape and are connected to the pixels 3 at the orthogonal positions ( Details are not shown).
- the plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data.
- a full color display device was produced by juxtaposing the red, green, and blue pixels appropriately.
- Example 6 Preparation of white light emitting lighting device ⁇
- the white light emitting organic EL element 4-11W was produced in the same manner except that D-1 was changed to D-1, D-15, and D-21. did.
- the obtained organic EL element 4-11W 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.
Abstract
Description
(1)前記陽極と前記発光層の間に、少なくとも1層から成る前記電荷発生層を有し、
(2)前記電荷発生層の少なくとも1層に有機金属錯体を含有する、
ことを特徴とする有機エレクトロルミネッセンス素子。
5.前記電荷発生層が、前記電子引抜材料を含有する層とそれに隣接した前記有機金属錯体を含有する層で構成されることを特徴とする前記2~4のいずれか1項に記載の有機エレクトロルミネッセンス素子。
8.前記電荷発生層を構成する有機金属錯体のHOMO値と前記発光層に含有される有機金属錯体のHOMO値の差の絶対値が、0.0eV以上1.0eV以下であることを特徴とする前記1~7のいずれか1項に記載の有機エレクトロルミネッセンス素子。
本発明において、HOMO、LUMOの値とは、分子の最高被占軌道(HOMO)のエネルギーレベルと最低空軌道(LUMO)のエネルギーレベルの値を意味し、これらは米国GaU88ian社製の分子軌道計算用ソフトウェアである、Gaussian 98(Gaussian 98、Revision A.11.4,M.J.Frisch,et al,Gaussian,Inc.,Pittsburgh PA,2002.)を用いて計算した時の値であり、キイワードとしてB3LYP/6-31G*を用いて構造最適化を行うことにより算出した値(eV単位換算値)の小数点第2位を四捨五入した値と定義する。この計算値が有効な背景には、この手法で求めた計算値と実験値の相関が高いためである。
本発明の有機EL素子の構成層、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/電荷発生層/発光層/正孔阻止層/電子輸送層/陰極
(iii)陽極/電荷発生層/発光層/正孔阻止層/電子輸送層/陰極バッファー層/陰極
(iv)陽極/陽極バッファー層/電荷発生層/発光層/正孔阻止層/電子輸送層/陰極バッファー層/陰極
(v)陽極/電荷発生層1/発光層1/電子輸送層/電荷発生層2/発光層2/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、正孔阻止層、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素子の構成層に含有される有機化合物が含有されていれば、本発明に係る有機化合物層として定義される。
電子引抜材料を含有する層である本発明に係る電子引抜層は、隣接層から電子を引き抜く機能を有する層であり、この層を構成する電子引抜材料は、電子親和力の大きな化合物、言い換えると深いLUMO値を有する化合物を指す。例えば、一般的によく知られた電子受容体(アクセプタ分子)が好適に用いられ、そのLUMO値は、-6.0~-3.0eV、より好ましくは、-5.0~-4.0eVである。
〈電荷発生層の構成層〉
本発明において電荷発生層とは、少なくとも1層以上の層から形成され、電圧印加時、素子の陰極方向に正孔を、陽極方向に電子を注入する機能を有する層を指す。
(1)電子輸送性材料層
(2)電子引抜層(有機アクセプター材料・無機アクセプター材料)
(3)電子輸送性材料とアルカリ(土類)金属塩(若しくはアルカリ(土類)金属前駆体)の混合層
(4)n型半導体層(有機材料、無機材料)
(5)n型導電性ポリマー層
(6)単一の正孔注入・輸送性材料層
(7)複数種の正孔注入・輸送性材料混合層
(8)有機金属錯体層
(9)正孔輸送性材料と金属酸化物の混合層
(10)p型半導体層(有機材料、無機材料)
(11)p型導電性ポリマー層
本発明の効果を最大限得るためには、電荷発生層は少なくとも2層以上から構成され、かつ1層は、(8)である。更に、2層の組み合わせとしては(8)と(9)あるいは(8)と(2)から構成されることが好ましく、より好ましくは、(8)と(2)から構成されることが好ましい。
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化合物について説明する。ここで、本発明においてホスト化合物とは、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。また、発光層に含有される化合物の中で、その層中での質量比が20%以上であることが好ましい。
本発明に係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化合物(リン光発光性ドーパント)について説明する。
本発明に係る有機金属錯体としては、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で形成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良い置換基としては、置換基の例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)、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。
蛍光ドーパント(蛍光性化合物)としては、クマリン系色素、ピラン系色素、シアニン系色素、クロコニウム系色素、スクアリウム系色素、オキソベンツアントラセン系色素、フルオレセイン系色素、ローダミン系色素、ピリリウム系色素、ペリレン系色素、スチルベン系色素、ポリチオフェン系色素、又は希土類錯体系蛍光体等が挙げられる。
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。
(1)前述のとおり、分子軌道計算から算出する方法
(2)イオン化ポテンシャルは光電子分光法で直接測定する方法により求めることもできる。例えば、理研計器社製の低エネルギー電子分光装置「Model AC-1」を用いて、あるいは紫外光電子分光として知られている方法を好適に用いることができる。
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、広い意味で正孔注入層、電子阻止層も正孔輸送層に含まれる。正孔輸送層は単層又は複数層設けることができる。
電子輸送層とは電子を輸送する機能を有する材料からなり、広い意味で電子注入層、正孔阻止層も電子輸送層に含まれる。電子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。
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、あるいはいわゆる集光シートと組み合わせることにより、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。
本発明の有機EL素子の作製方法の一例として、陽極/正孔注入層/正孔輸送層/発光層/正孔阻止層/電子輸送層/電子注入層/陰極からなる有機EL素子の作製法を説明する。
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1-1の製造方法〉
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。次に、後述の各材料をモリブデン製又はタングステン製の蒸着用ボートに詰め、真空蒸着装置内に前述の透明電極を形成したガラス基板と共にセットし、真空度が1×10-4Pa以下となったところで、以下のように順次成膜を行った。
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。次に、後述の各材料をモリブデン製又はタングステン製の蒸着用ボートに詰め、真空蒸着装置内に前述の透明電極を形成したガラス基板と共にセットし、真空度が1×10-4Pa以下となったところで、以下のように順次成膜を行った。
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。次に、後述の各材料をモリブデン製又はタングステン製の蒸着用ボートに詰め、真空蒸着装置内に前述の透明電極を形成したガラス基板と共にセットし、真空度が1×10-4Pa以下となったところで、以下のように順次成膜を行った。
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。次に、後述の各材料をモリブデン製又はタングステン製の蒸着用ボートに詰め、真空蒸着装置内に前述の透明電極を形成したガラス基板と共にセットし、真空度が1×10-4Pa以下となったところで、以下のように順次成膜を行った。
得られた有機EL素子1-1~1-4を評価するに際しては、作製後の各有機EL素子の非発光面をガラスケースで覆い、厚み300μmのガラス基板を封止用基板として用いて、周囲にシール材として、エポキシ系光硬化型接着剤(東亞合成製ラックストラックLC0629B)を適用し、これを上記陰極上に重ねて前記透明支持基板と密着させ、ガラス基板側からUV光を照射して、硬化させて、封止して、図5、図6に示すような照明装置を作製して評価した。
23℃、乾燥窒素ガス雰囲気下で発光開始の電圧を測定した。なお、発光開始の電圧は、輝度50cd/m2以上となったときの電圧値を測定した。輝度の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。
23℃、乾燥窒素ガス雰囲気下で25mA/cm2定電流を印加した時、初期の駆動電圧V0、100時間駆動後の駆動電圧をV100とし、V100-V0を駆動電圧の上昇度として評価した。
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。
〈有機EL素子2-5の製造方法〉
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。
〈有機EL素子3-1の製造方法〉
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。次に、後述の各材料をモリブデン製又はタングステン製の蒸着用ボートに詰め、真空蒸着装置内に前述の透明電極を形成したガラス基板と共にセットし、真空度が1×10-4Pa以下となったところで、以下のように順次成膜を行った。
〈有機EL素子4-1の製造方法〉
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。次に、後述の各材料をモリブデン製又はタングステン製の蒸着用ボートに詰め、真空蒸着装置内に前述の透明電極を形成したガラス基板と共にセットし、真空度が1×10-4Pa以下となったところで、以下のように順次成膜を行った。
《フルカラー表示装置の作製》
(青色発光有機EL素子)
実施例4で作製した有機EL素子4-11を用いた。
緑色発光有機EL素子として、実施例4で作製した有機EL素子4-5の作製において、発光ドーパントに用いたD-1をD-15に変更した以外は同様にして、緑色発光有機EL素子4-5Gを作製した。
実施例4で作製した有機EL素子4-5の作製において、D-1をD-21に変更した以外は同様にして、赤色発光有機EL素子4-5Rを作製した。
《白色発光照明装置の作製》
実施例4で作製した有機EL素子4-11の作製において、D-1をD-1、D-15、D-21に変更した以外は同様して、白色発光有機EL素子4-11Wを作製した。得られた有機EL素子4-11W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
201 有機EL素子
202 ガラスカバー
205 陰極
206 有機EL層
207 透明電極付きガラス基板
208 窒素ガス
209 捕水剤
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
Claims (13)
- 陽極と陰極の間に、有機化合物層が挟持されてなる有機エレクトロルミネッセンス素子であって、前記有機化合物層は、少なくとも発光層と電荷発生層とを含むものであり、
(1)前記陽極と前記発光層の間に、少なくとも1層から成る電荷発生層を有し、
(2)前記電荷発生層の少なくとも1層に有機金属錯体を含有する、
ことを特徴とする有機エレクトロルミネッセンス素子。 - 前記電荷発生層の少なくとも1層に電子引抜材料を含有す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。
- 前記電子引抜材料のLUMO値が、-6.0~-3.0eVであることを特徴とする請求項2に記載の有機エレクトロルミネッセンス素子。
- 前記有機金属錯体が、一般式(1)で表されることを特徴とする請求項1~3のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記電荷発生層が、前記電子引抜材料を含有する層とそれに隣接した前記有機金属錯体を含有する層で構成されることを特徴とする請求項2~4のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記電子引抜材料のLUMO値と隣接する有機金属錯体HOMO値の差の絶対値が、0.0eV以上1.0eV以下であることを特徴とする請求項2~5のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記発光層に、一般式(2)で表されるリン光発光性材料を含有することを特徴とする請求項1~6のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記電荷発生層を構成する有機金属錯体のHOMO値と前記発光層に含有される有機金属錯体のHOMO値の差の絶対値が、0.0eV以上1.0eV以下であることを特徴とする請求項1~7のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記電荷発生層を構成する有機金属錯体と前記発光層に含有される有機金属錯体が、同一であることを特徴とする請求項1~8のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記電荷発生層を構成する有機金属錯体が、非リン光発光性であることを特徴とする請求項1~8のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 白色に発光することを特徴とする請求項1~10のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 請求項1~11のいずれか1項に記載の有機エレクトロルミネッセンス素子を備えたことを特徴とする照明装置。
- 請求項1~11のいずれか1項に記載の有機エレクトロルミネッセンス素子を備えたことを特徴とする表示装置。
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