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WO2014050417A1 - Élément électroluminescent organique, dispositif d'éclairage et écran - Google Patents

Élément électroluminescent organique, dispositif d'éclairage et écran Download PDF

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WO2014050417A1
WO2014050417A1 PCT/JP2013/073067 JP2013073067W WO2014050417A1 WO 2014050417 A1 WO2014050417 A1 WO 2014050417A1 JP 2013073067 W JP2013073067 W JP 2013073067W WO 2014050417 A1 WO2014050417 A1 WO 2014050417A1
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川邉　里美
大津　信也
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Konica Minolta Inc
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Definitions

  • the present invention relates to an organic electroluminescence element, an illumination device provided with the organic electroluminescence device, and a display device.
  • An organic electroluminescence element (hereinafter also referred to as an organic EL element) has a configuration in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and a positive electrode injected from the anode by applying an electric field.
  • This is a light emitting device that uses the emission of light (fluorescence / phosphorescence) when excitons are generated by recombining electrons injected from holes and cathodes in the light emitting layer to generate excitons. is there.
  • An organic EL element is an all-solid-state element composed of an organic material film with a thickness of only a submicron between electrodes, and can emit light at a voltage of several volts to several tens of volts. It is expected to be used for next-generation flat display and lighting.
  • Non-Patent Document 1 As for the development of organic EL elements for practical use, Princeton University has reported organic EL elements that use phosphorescence emission from excited triplets (see, for example, Non-Patent Document 1). Research on materials that exhibit phosphorescence has become active (see, for example, Patent Document 1 and Non-Patent Document 2). In addition, organic EL elements that utilize phosphorescence emission can in principle achieve light emission efficiency that is approximately four times that of organic EL elements that utilize fluorescence emission. Research and development of device layer configurations and electrodes are performed all over the world. For example, many compounds have been studied focusing on heavy metal complexes such as iridium complexes (see Non-Patent Document 3, for example).
  • the phosphorescence emission method is a method having a very high potential.
  • an organic EL device using phosphorescence emission is greatly different from an organic EL device using fluorescence emission, and controls the position of the emission center.
  • the method particularly how to recombine within the light emitting layer to stabilize the light emission, is an important technical issue in grasping the efficiency and lifetime of the device. Therefore, in recent years, a multi-layered element having a hole transport layer located on the anode side of the light emitting layer and an electron transport layer located on the cathode side of the light emitting layer in a form adjacent to the light emitting layer is well known. (For example, refer to Patent Document 2).
  • a mixed layer using a host compound and a phosphorescent compound as a dopant is often used for the light emitting layer.
  • organic EL elements are required to have high light emission efficiency and long light emission lifetime. Therefore, materials having high carrier transportability and thermally and electrically stable materials are required. Is required.
  • a short-wavelength blue light-emitting dopant that exhibits an emission maximum wavelength of 470 nm, more preferably 460 nm or less, is required. Indispensable.
  • fluorescent light-emitting dopants having anthracene, chrysene or the like in the skeleton are well known, but as described above, they are disadvantageous compared to phosphorescent light-emitting dopants in terms of light emission efficiency.
  • FIrpic is a material well known as a short wavelength phosphorescent blue light emitting dopant.
  • FIrpic is realized by using two fluorine atoms in the main ligand, phenylpyridine, and using picolinic acid as a sub-ligand, but with two fluorine atoms with high electronegativity. Due to the substitution, iridium as a central metal is easily oxidized, and the HOMO is very deep at about ⁇ 5.9 eV in a calculated value.
  • the HOMO is very deep, it is very difficult to select the material used for the anode side adjacent layer of the light emitting layer, and the hole injecting property is easily affected by slight impurity mixing or film quality change. It is also disadvantageous in terms of production aptitude.
  • a light emitting dopant having a shallow HOMO for example, less than ⁇ 4.50 eV, is used, the LUMO becomes relatively shallow and the compound becomes unstable. In addition, it is easily affected by external factors such as oxygen, and there is a problem in terms of stability of device performance.
  • the light emission maximum wavelength of the light emitting dopant having a phenylpyridine ligand substituted with a fluorine atom and an isopropyl group used in Examples in Patent Document 3 is a light emission maximum wavelength exceeding 470 nm as investigated by the present inventors. The results show that the wavelength is not long and satisfactory for use in high color temperature lighting applications and displays with a wide color gamut. Further, the above document does not describe any relationship between the luminescent dopant and the HOMO of the material used for the adjacent layer.
  • the present invention has been made in view of the above problems, and has high luminous efficiency, low driving voltage, long life, and good chromaticity, an organic electroluminescence element having good chromaticity, and an illumination device and a display device using the element It is an issue to provide.
  • an organic electroluminescence device having a plurality of organic layers including at least one light emitting layer sandwiched between an anode and a cathode and an adjacent layer adjacent to the anode side of the light emitting layer, at least one of the light emitting layers is formed in a solution.
  • at least one phosphorescent dopant having an emission maximum wavelength on the shortest wavelength side of 470 nm or less and a HOMO value of ⁇ 4.50 to ⁇ 5.50 eV is contained.
  • An organic electroluminescence device comprising a nonmetallic complex compound represented by the formula (1) and having a HOMO value of ⁇ 4.50 to ⁇ 5.10 eV.
  • R represents a substituent.
  • L represents a linking group or a simple bond.
  • Ar 1 and Ar 2 represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • Ar 1 and Ar 2 are indole ring, azaindole ring, carbazole ring, azacarbazole ring or a benzene ring having a condensed aromatic heterocyclic group as a substituent. Or the organic electroluminescent element of 2.
  • R 111 and R 112 represent a hydrogen atom, an alkyl group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and the compound represented by General Formula (11) further has a substituent. (You may have it.)
  • R 211 and R 212 represent an alkyl group, an aromatic hydrocarbon ring group, or an aromatic heterocyclic group.
  • Rings Z 1 to Z 3 represent an aromatic hydrocarbon ring. Or, it represents a residue that forms an aromatic heterocyclic ring, and may have a substituent.
  • R 311 and R 312 each represent a hydrogen atom, an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a diarylamino group, or an alkyl group.
  • 1 to A 8 each independently represent C—Rx or N, and the plurality of Rxs may be the same or different, and Rx each independently represents a hydrogen atom or a substituent.
  • M represents Ir, Pt, Rh, Ru, Ag or Cu
  • X 1 and X 2 represent a carbon atom or a nitrogen atom
  • ring Z 1 represents a 6-membered aromatic with C ⁇ C.
  • L ′ represents a monoanionic divalent ring coordinated to M
  • m ′ represents an integer of 0 to 2
  • n ′ is an integer of at least 1
  • m ′ + n ′ is 2 or 3.
  • the ring Z 2 is an organic electroluminescent device according to the 7, characterized in that a substituted or unsubstituted imidazole ring.
  • the ring Z 2 is an organic electroluminescent device according to the 7, characterized in that a substituted or unsubstituted triazole ring.
  • 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 present invention improves the hole injectability into the light emitting layer by defining the relationship between the HOMO of the light emitting dopant and the HOMO of the material containing the adjacent layer as in the present invention, and is further represented by the general formula (1).
  • a compound having a structure was used in the adjacent layer. Accordingly, it is possible to provide an organic electroluminescence element that achieves high luminous efficiency and long life, has a low driving voltage, and has good chromaticity, an illumination device using the element, and a display device.
  • FIG. 3 is a schematic diagram of a passive matrix type full-color display device according to a display unit A in FIG. 2. It is the schematic of an illuminating device. It is a schematic diagram of an illuminating device.
  • (A)-(e) is a schematic block diagram of an organic electroluminescent full color display apparatus.
  • the organic EL device of the present invention has a plurality of organic layers including at least one light emitting layer sandwiched between an anode and a cathode and an adjacent layer adjacent to the anode side of the light emitting layer. Then, at least one of the light emitting layers is provided with a phosphorescent light emitting dopant having an emission maximum wavelength on the shortest wavelength side of 470 nm or less and a HOMO value of ⁇ 4.50 to ⁇ 5.50 eV in the emission spectrum in the solution. At least one kind is contained, and the adjacent layer contains a nonmetallic complex compound represented by the general formula (1) and having a HOMO value of ⁇ 4.50 to ⁇ 5.10 eV.
  • the injection property of holes into the light emitting layer is improved by making the relationship between the HOMO of the light emitting dopant and the HOMO of the material contained in the adjacent layer as in the present invention.
  • the carrier injection balance into the light emitting layer was improved, and the recombination region was separated from the vicinity of the interface between the light emitting layer and the adjacent layer.
  • the compound represented by the general formula (1) has a condensed ring structure, molecules are more easily arranged than a triarylamine derivative typified by ⁇ -NPD generally used in a hole transport layer. As a result, the carrier mobility in the layer was improved and a low driving voltage was achieved.
  • a non-light emitting intermediate layer may be provided between the light emitting layers.
  • an organic layer including a light emitting layer excluding an anode and a cathode can be used as one light emitting unit, and a plurality of light emitting units can be stacked.
  • the plurality of stacked light emitting units may have a non-light emitting intermediate layer between the light emitting units, and the intermediate layer may further include a charge generation layer.
  • the organic EL element of the present invention is preferably a white light emitting layer, and is preferably an illumination device or a display device using these. That is, the organic EL element preferably emits white light.
  • Each layer which comprises the organic EL element of this invention is demonstrated.
  • 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 material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • a plurality of hole transport layers may be provided. For example, a hole transport layer close to the anode side is a first hole transport layer, and a hole transport layer adjacent to the light emitting layer side is a second hole transport layer. The transport layer.
  • the compound represented by the general formula (1) is contained in a layer adjacent to the light emitting layer.
  • the adjacent layer is a layer adjacent to the anode side of the light emitting layer, specifically, a hole transport layer.
  • the hole injection layer and the electron blocking layer are also included in the hole transport layer in a broad sense, when the hole injection layer and the electron blocking layer are adjacent to the anode side, these layers are included. May have a compound represented by the general formula (1).
  • the layer represented by the general formula (1) is included in the layer adjacent to the anode side of the light emitting layer among the plurality of hole transport layers. .
  • the hole transport layer close to the anode side is the first hole transport layer and the hole transport layer adjacent to the light emitting layer side is the second hole transport layer, It has a compound represented by Formula (1).
  • the compound represented by the general formula (1) is a nonmetallic complex compound and has a HOMO value of ⁇ 4.50 to ⁇ 5.10 eV.
  • Gaussian 03 As the value of HOMO in the present invention, Gaussian 03 (Gaussian 03, Revision D02, MJ Frisch, et al, Gaussian, Inc., Wallingford CT, 2004.), which is a molecular orbital calculation software manufactured by Gaussian, USA. This is the value obtained.
  • the compound represented by the general formula (1) of the present invention, the host compound, the hole transport material, and the electron transport material use B3LYP / 6-31G * as a keyword, and the phosphorescent dopant compound uses B3LYP / LanL2DZ.
  • the HOMO value is calculated by optimizing the structure of the target molecular structure (eV unit conversion value). It is known that the correlation between the calculated value obtained by this method and the experimental value is high as a background to the effectiveness of this calculated value.
  • the HOMO value of the compound represented by the general formula (1) of the present invention is ⁇ 4.50 to ⁇ 5.10 eV.
  • the reason for setting the HOMO value in the above range is that when the HOMO value is deeper than ⁇ 5.10 eV, hole injection into the light emitting layer is remarkably reduced, resulting in deterioration of efficiency and lifetime. On the other hand, if it is shallower than ⁇ 4.50 eV, the hole trapping property of the dopant in the light emitting layer is strong, so that holes are likely to accumulate at the light emitting layer / hole transporting layer interface, resulting in a decrease in efficiency and life.
  • the HOMO value is preferably ⁇ 4.70 to ⁇ 5.10 eV.
  • R represents a substituent.
  • substituents include a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, (t) butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group.
  • aryl group 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, indenyl group, pyrenyl group, biphenylyl group Etc.
  • heterocyclic groups eg, epoxy ring, aziridine ring
  • substituents may be further substituted with the above-mentioned substituents, or they may be condensed with each other to further form a ring.
  • an alkyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a heterocyclic group, and a cycloalkyl group are preferable.
  • L represents a linking group or a simple bond
  • examples of the linking group include an oxygen atom, a nitrogen atom, a sulfur atom, an amide group, an ester group, a carbonyl group, a sulfonyl group, an alkylene group (for example, a methylene group, an ethylene group, etc.)
  • examples include an arylene group (for example, a phenylene group), a heteroarylene group, or a group obtained by combining these.
  • an oxygen atom, an alkylene group, and an arylene group are preferable.
  • a mere bond is a bond that directly bonds the connecting substituents together.
  • Ar 1 and Ar 2 represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • the aromatic hydrocarbon ring include 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, Examples thereof include a p-terphenyl ring, an acenaphthene ring, a coronene ring, a fluorene ring, a fluoranthrene ring, a pentacene ring, a perylene ring, a pentaphen ring, a picene ring, a pyranthrene ring, and an anthraanthrene ring.
  • aromatic heterocycle for example, silole ring, furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, Pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, quinoline ring, quinoxaline ring, quinazoline ring, phthalazine ring, thienothiophene ring, carbazole ring, azacarbazole ring (carbon constituting carbazole ring) Any one or more of the carbon atoms constituting the dibenzosilole ring, dibenzofuran ring, dibenzothiophene ring, be
  • Ar 1 represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring
  • Ar 2 represents a non-condensed aromatic hydrocarbon ring having a substituent, a non-fused aromatic heterocyclic ring having a substituent, or a condensed aromatic
  • L represents a single bond
  • Ar 1 and Ar 2 each represent a 6-membered aromatic hydrocarbon ring or a 6-membered aromatic heterocycle.
  • Ar 1 and Ar 2 are an indole ring, an azaindole ring, a carbazole ring, an azacarbazole ring or a benzene ring having a condensed aromatic heterocyclic group as a substituent.
  • R 111 and R 112 represent a hydrogen atom, an alkyl group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and the compound represented by the general formula (11) further has a substituent. You may do it.
  • R 111 and R 112 are more preferably a phenyl group, dibenzofuran, dibenzothiophene or carbazole.
  • R 111, R 112 in formula (12) to (14) has the same meaning as R 111, R 112 in formula (11).
  • R 111 and R 112 are more preferably a phenyl group, dibenzofuran, dibenzothiophene, or carbazole.
  • R 211 and R 212 each represents an alkyl group, an aromatic hydrocarbon ring group, or an aromatic heterocyclic group.
  • Rings Z 1 to Z 3 represent a residue that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent.
  • the alkyl group, aromatic hydrocarbon ring group or aromatic heterocyclic group in general formulas (21) and (22) has the same meaning as described for R, Ar 1 and Ar 2 in general formula (1).
  • the substituents for the rings Z 1 to Z 3 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon ring group having 6 to 12 carbon atoms, or Represents an aromatic heterocyclic group having 3 to 11 carbon atoms.
  • the substituent of the ring Z 2 may form a condensed ring together with the ring to which the substituent is bonded.
  • rings Z 1 to Z 3 are aromatic hydrocarbon rings, more preferably benzene rings.
  • the rings Z 1 to Z 3 are all benzene rings.
  • R 211 and R 212 are preferably an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and more preferably a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring, or a quinoline ring.
  • R 311 and R 312 each represent a hydrogen atom, an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a diarylamino group, or an alkyl group.
  • R 311 and R 312 are preferably any of an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group, and any of an aromatic hydrocarbon ring group or an aromatic heterocyclic group More preferably.
  • a substituent containing an oxygen atom or a sulfur atom is preferable.
  • the aromatic hydrocarbon ring group or aromatic heterocyclic group in R 311 and R 312 has the same meaning as described for R, Ar 1 and Ar 2 in the general formula (1).
  • a dibenzofuryl group, a dibenzothienyl group, etc. are mentioned as the most preferable substituents.
  • a 1 to A 8 each independently represent C—Rx or N, and the plurality of Rx may be the same or different.
  • Rx each independently represents a hydrogen atom or a substituent. As a substituent, it is synonymous with the substituent quoted by R of General formula (1).
  • any one or more of A 1 , A 2 , A 4 is preferably C—Rx, and more preferably A 1 or A preferably any one or more of 2 is C-Rx, in particular a 1 may be mentioned as more preferred form to be a C-Rx.
  • Rx is an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, or a diarylamino group. It is preferably any one, and further preferably any one of an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group, and among them, an aromatic hydrocarbon ring group or an aromatic heterocyclic group. It is more preferably any of a cyclic group, and particularly preferably an aromatic heterocyclic group.
  • a substituent containing an oxygen atom or a sulfur atom is preferable because it has a high charge transporting ability and high durability against charges, and an aromatic heterocyclic group is preferable because of high thermal stability.
  • a dibenzofuryl group, a dibenzothienyl group, etc. are mentioned as the most preferable substituents.
  • the substituent represented by Rx is preferably further substituted, and the substituent is any of an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, and a diarylamino group. And more preferably an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon ring group, or an aromatic heterocyclic group, and among them, an aromatic hydrocarbon ring group or an aromatic heterocyclic ring Particularly preferred is any of the groups.
  • any one or more of the plurality of Rx, R 311 and R 312 in the general formula (31) is a pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group.
  • hole transport materials include 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, 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
  • 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.
  • 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.
  • cyclometalated complexes and orthometalated complexes such as copper phthalocyanine and tris (2-phenylpyridine) iridium complex can also be used as 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.
  • a hole transport layer having a high p property doped with impurities can be used.
  • 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.
  • 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. it can.
  • 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 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 with a single layer or a plurality of layers.
  • An electron transport material (including a hole blocking material and an electron injection material) used for the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer. Can be selected from any conventionally known compounds and used alone or in combination.
  • electron transport materials examples include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, And azacarbazole derivatives including carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, carboline derivatives, and the like.
  • the azacarbazole derivative refers to one in which one or more carbon atoms constituting the carbazole ring are replaced with a nitrogen atom.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material. It is also possible to use a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain.
  • 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 the terminal substituted with an alkyl group or a sulfonic acid group can also be used as the electron transport material.
  • inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.
  • the electron transport layer is made of an electron transport material such as a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, an ink jet method, a printing method, or a spraying method.
  • the film is preferably formed by thinning by a coating method, curtain coating method, LB method (Langmuir Brodgett method, etc.).
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5000 nm, preferably 5 nm to 200 nm.
  • This electron transport layer may have a single layer structure composed of one or more of the above materials.
  • you may dope and use n-type dopants, such as metal compounds, such as a metal complex and a metal halide.
  • Examples of conventionally known compounds (electron transport materials) that are preferably used for forming an electron transport layer include, for example, compounds of ET-1-ET-43 described in JP2012-164731A, but are not limited thereto. Not.
  • the light-emitting layer 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. It may be an interface with an 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 nm to 200 nm, and particularly preferably in the range of 5 nm to 100 nm.
  • a light emitting dopant or host compound described later is used, for example, a vacuum deposition method, a wet method (also referred to as a wet process, for example, a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method,
  • the film can be formed by an inkjet method, a printing method, a spray coating method, a curtain coating method, an LB method (including Langmuir-Blodgett method)) and the like.
  • a light-emitting dopant phosphorescent light-emitting dopant (also referred to as phosphorescent dopant, phosphorescent light-emitting dopant, phosphorescent light-emitting dopant group) or fluorescent dopant) compound and host Compound.
  • phosphorescent light-emitting dopant also referred to as phosphorescent dopant, phosphorescent light-emitting dopant, phosphorescent light-emitting dopant group
  • fluorescent dopant a light-emitting dopant
  • Luminescent dopant compound A light-emitting dopant compound (also referred to as a light-emitting dopant or a light-emitting dopant compound) will be described.
  • a fluorescent dopant also referred to as a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent dopant compound, a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like
  • a phosphorescent light-emitting dopant compound 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 is defined as a compound having a phosphorescence quantum yield of 0.01 or more at 25 ° C. 1 or more.
  • the phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence emission dopant should just achieve the said phosphorescence quantum yield (0.01 or more) in any solvent. .
  • the energy transfer type in which light emission from the phosphorescent light-emitting dopant is obtained by transferring to the light dopant, and the other is that the phosphorescent dopant becomes a carrier trap, and carrier recombination occurs on the phosphorescent light-emitting dopant, and phosphorescence
  • the excited state energy of the phosphorescent light emitting dopant is lower than the excited state energy of the host compound.
  • the present inventors have found that at least one of the light emitting layers of the organic EL element is on the shortest wavelength side in the emission spectrum in the solution.
  • Inclusion of at least one phosphorescent light-emitting dopant having an emission maximum wavelength of 470 nm or less and a HOMO value of ⁇ 4.50 to ⁇ 5.50 eV improves the light emission efficiency, lifetime, and driving voltage of the organic EL device, It was clarified that the color gamut of the element can be improved.
  • At least one of the phosphorescent dopants used in the present invention has an emission maximum wavelength on the shortest wavelength side of 470 nm or less and a HOMO value of ⁇ 4 in the emission spectrum of the solution in the region of 400 to 700 nm.
  • the phosphorescent emission dopant used in the present invention has an emission maximum wavelength (peak wavelength) of emission at the shortest wavelength side of 470 nm or less.
  • peak wavelength peak wavelength
  • the emission maximum wavelength of the phosphorescent light emitting dopant is 470 nm or less.
  • the emission spectrum in the solution can be obtained from, for example, a fluorescence spectrum obtained by irradiating a solution obtained by dissolving a dopant in a nonpolar solvent with excitation light.
  • a dopant was dissolved in 2-methyltetrahydrofuran, and a fluorescence spectrum in the region of 400 to 700 nm was measured using Hitachi F-4500.
  • the HOMO value of the phosphorescent light-emitting dopant used in the present invention is ⁇ 4.50 to ⁇ 5.50 eV.
  • the value of HOMO in the phosphorescent light emitting dopant can be obtained by the calculation method described in the hole transport layer.
  • the reason why the HOMO value is in the above range is that when the HOMO value is deeper than ⁇ 5.50 eV, the hole injection property from the hole transport layer to the light emitting layer is remarkably reduced, resulting in deterioration of efficiency and lifetime. It becomes.
  • the HOMO value is shallower than ⁇ 4.50 eV
  • the LUMO of the dopant becomes shallow or the compound becomes unstable in order to make a blue phosphorescent light-emitting dopant whose emission maximum wavelength is 470 nm or less.
  • a preferred phosphorescent light-emitting dopant is a compound represented by the following general formula (41).
  • M represents Ir, Pt, Rh, Ru, Ag or Cu
  • X 1 and X 2 represent a carbon atom or a nitrogen atom
  • the ring Z 1 is a 6-membered aromatic together with C ⁇ C. hydrocarbon ring or an aromatic 5- or 6-membered heterocyclic ring
  • the ring Z 2 represents a heterocyclic 5-membered together with X 1 -X 2.
  • Examples of the 6-membered aromatic hydrocarbon ring of the ring Z 1 include a benzene ring.
  • Examples of the 5-membered or 6-membered aromatic heterocycle include furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, An imidazole ring, a pyrazole ring, a thiazole ring, etc. are mentioned.
  • Ring Z 1 and ring Z 2 may have a substituent, and those exemplified for R in formula (1) can be used.
  • L ′ is one or more of monoanionic bidentate ligands coordinated to M
  • m ′ represents an integer of 0 to 2
  • n ′ is an integer of at least 1
  • m ′ + N ′ is 2 or
  • ring Z 1 is a substituted or unsubstituted benzene ring or pyridine ring
  • ring Z 2 is a substituted or unsubstituted imidazole ring, substituted or unsubstituted pyrazole ring, or substituted or unsubstituted triazole ring. It is preferable that it represents.
  • Preferred as the compound represented by the general formula (41) are the compounds represented by the following general formulas (42), (43) and (44).
  • R 1 represents an electron-withdrawing group
  • R 2 represents an electron-donating group or F.
  • X 1 and X 2 represents a carbon atom or a nitrogen atom
  • the ring Z 2 represents a heterocyclic 5-membered together with X 1 -X 2.
  • the electron withdrawing group include a keto group such as a halogen atom, a cyano group, a nitro group, a phenyl group, and an acyl group
  • examples of the electron donating group include an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.
  • M, L ′, m ′, and n ′ are synonymous with the general formula (41).
  • R 3 , R 4 and R 5 each represent a hydrogen atom or a substituent, and R 4 and R 5 may form a ring.
  • Ring Z 1 represents a 6-membered aromatic hydrocarbon ring together with C ⁇ C, or a 5-membered or 6-membered aromatic heterocycle.
  • the substituents for R3, R4, and R5 represent the same groups as the substituents represented by R in the general formula (1).
  • X 1 to X 4 each represent —CR 6 or a nitrogen atom. When X 3 and X 4 are —CR 6 , they may form a ring.
  • Ring Z 3 represents a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle, and ring Z 4 represents a 5-membered heterocycle together with X 1 -X 2 .
  • R 6 represents a carbon atom or a nitrogen atom.
  • Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, rare earth complex phosphors, and the like, and compounds having a high fluorescence quantum yield such as laser dyes.
  • the light emitting dopant may be used in combination of a plurality of types of compounds, or may be a combination of phosphorescent dopants having different structures or a combination of a phosphorescent dopant and a fluorescent dopant.
  • Light emitting host compound also referred to as light emitting host or host compound
  • Specific examples of the known light-emitting host include compounds described in the following documents. JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No.
  • the injection layer is a layer provided between the electrode and the organic layer for reducing the driving voltage and improving the light emission luminance as required.
  • the organic EL element and its industrialization front line June 30, 1998 Chapter 2 “Electrode Materials” (pages 123 to 166) of Volume 2 of “TS Co., Ltd.”) is described 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.
  • Representative phthalocyanine buffer layer oxide buffer layer typified by vanadium oxide, amorphous carbon buffer layer, polymer buffer layer using conductive polymer such as polyaniline (emeraldine) or polythiophene, tris (2-phenylpyridine) )
  • Orthometalated complex layers represented by iridium complexes and the like.
  • the details of the cathode buffer layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
  • Metal buffer layer typified by, alkali metal compound buffer layer typified by lithium fluoride, sodium fluoride and potassium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, and aluminum oxide And an oxide buffer layer.
  • 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 5 ⁇ m, although it depends on the material.
  • the materials used for the anode buffer layer and the cathode buffer layer can be used in combination with other materials. For example, they can be mixed in the hole transport layer or the electron transport 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 (issued by NTT Corporation on November 30, 1998)” on page 237.
  • 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 above-mentioned electron carrying layer can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
  • the hole blocking layer contains carbazole derivatives, azacarbazole derivatives (where azacarbazole derivatives are those in which one or more carbon atoms constituting the carbazole ring are replaced by nitrogen atoms), pyridine derivatives, and the like. It is preferable to contain a nitrogen compound. Further, in the present invention, when a plurality of light emitting layers having different emission colors are provided, the light emitting layer having the shortest wavelength of the light emission maximum wavelength (shortest wave layer) is closest to the anode among all the light emitting layers. preferable. In such a case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the shortest wave layer.
  • the thickness of the hole blocking layer and electron blocking layer that can be used in the present invention is preferably 3 nm to 100 nm, and more preferably 3 nm to 30 nm.
  • an electrode material made of a metal, an alloy, an electrically conductive compound and 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.
  • 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 may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 ⁇ m or more)
  • a pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%
  • 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.
  • a material having a low work function (4 eV or less) metal referred to as an electron injecting metal
  • an alloy referred to as an electrically conductive compound and a mixture thereof as an electrode material
  • Specific examples of such 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 value 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 the 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 light emission luminance is improved, which is convenient.
  • a transparent or semi-transparent cathode can be produced by producing the 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.
  • a 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, there is no particular limitation on the type of glass, plastic, etc., and it is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably 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.
  • a desired electrode material for example, a thin film made of an anode material is formed on a suitable substrate so as to have a thickness of 1 ⁇ m or less, preferably 10 nm to 200 nm, and an anode is manufactured.
  • a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, which is a device material, is formed thereon.
  • the thin film can be formed by a vacuum deposition method, a wet method (also referred to as a wet process), or the like.
  • Wet methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, and LB, but precise thin films can be formed. From the viewpoint of high productivity, a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable. Different film formation methods may be applied for each layer.
  • liquid medium for dissolving or dispersing the organic EL material examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, Aromatic hydrocarbons such as xylene, mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO can be used.
  • a dispersion method it can disperse
  • a thin film made of a cathode material is formed thereon so as to have a thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a desired organic EL device can be obtained by providing a cathode.
  • the cathode, electron injection layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in this order in the reverse order.
  • the organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.
  • a sealing means used for this invention the method of adhere
  • a sealing member it should just be arrange
  • sandblasting, chemical etching, or the like is used.
  • 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. .
  • 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 mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • the same glass plate, polymer plate / film, metal plate / film, and the like 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. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.
  • a method for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (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.
  • by combining these means it is possible to obtain an element having higher luminance or durability.
  • the organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface.
  • a specific direction for example, the device light emitting surface.
  • the luminance in a specific direction can be increased.
  • the microlens array 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 is smaller than this, the effect of diffraction is generated and colored.
  • Other details of the “sheet” and the like can be the same as those described in publicly known documents such as Japanese Patent Application Laid-Open No. 2012-164731 and Japanese Patent Application Laid-Open No. 2012-156299.
  • the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • lighting devices home lighting, interior lighting
  • clock and liquid crystal backlights billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light
  • the light source of a sensor etc. are mentioned, It is not limited to this, It can use effectively for the use as a backlight of a liquid crystal display device, and an illumination light source especially.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation.
  • 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.
  • 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 of CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • the display device of the present invention will be described.
  • the display device of the present invention includes the organic EL element of the present invention.
  • the display device of the present invention may be single color or multicolor, the multicolor display device will be described here.
  • 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.
  • the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.
  • the configuration of the organic EL element provided 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 to the one aspect
  • the multicolor display device can be used as a display device, a display, and various light emission sources. In display devices and displays, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile.
  • it may be used as a display device for reproducing still images and moving images
  • 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 includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate.
  • the main members of the display unit A will be described below.
  • the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning 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 grid pattern and are connected to the pixels 3 at orthogonal positions (details are shown in the figure). 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. Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 3 is a schematic diagram of a pixel.
  • the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6.
  • a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5
  • the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.
  • the capacitor 13 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on.
  • the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels. It is carried out.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good.
  • the potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.
  • FIG. 4 is a schematic view of a passive matrix display device according to the display unit A of FIG.
  • 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 scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.
  • the pixel 3 has no active element, and the manufacturing cost can be reduced.
  • the lighting device of the present invention includes the organic EL element of the present invention.
  • 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 driving 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.
  • a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.
  • the organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device.
  • a plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc.
  • the thing containing the light emission maximum wavelength may be used.
  • the combination of luminescent materials for obtaining multiple luminescent colors is a combination of multiple phosphorescent or fluorescent materials that emit light, fluorescent materials or phosphorescent materials, and light from the luminescent materials. Any combination with a dye material that emits light as light may be used, but in the white organic EL device according to the present invention, it is only necessary to mix and mix a plurality of light emitting dopants.
  • 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. According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, 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
  • FIG. 1 One Embodiment of Lighting Device of the Present Invention.
  • 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 an epoxy-based photocurable adhesive
  • FIG. 5 shows a schematic diagram of a lighting device, and the organic EL element 101 of the present invention is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is to bring the organic EL element 101 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 is a cross-sectional view of the lighting device.
  • reference numeral 105 denotes a cathode
  • 106 denotes an organic EL layer
  • 107 denotes a glass substrate with a transparent electrode (anode).
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • PEDOT / PSS polystyrene sulfonate
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while a hole-transporting material 2 and a host compound 11-12 (same as compound (1) described in WO2011 / 122132) are mounted on a molybdenum resistance heating boat.
  • a hole-transporting material 2 and a host compound 11-12 (same as compound (1) described in WO2011 / 122132) are mounted on a molybdenum resistance heating boat.
  • the pressure in the vacuum chamber was reduced to 4 ⁇ 10 ⁇ 4 Pa, and the heating boat containing 11-12 was heated by heating, and the film thickness was formed on the first hole transport layer at a deposition rate of 0.1 nm / second.
  • a 20 nm second hole transport layer was provided.
  • the second hole transport is carried out by energizing and heating the heating boat containing 11-12 as a host compound and compound (BD) as a dopant compound, respectively, at a deposition rate of 0.1 nm / second and 0.025 nm / second, respectively.
  • a light-emitting layer having a thickness of 30 nm was provided by co-evaporation on the layer.
  • the heating boat containing ET-8 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide an electron transport layer having a thickness of 30 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • Organic EL element 1-15 was produced in the same manner as in the production of organic EL element 1-4, except that the host of the light emitting layer was changed to host compound (H-1).
  • the organic EL elements 1-4 and 1-7 to 1-15 of the present invention are higher than the organic EL elements 1-1 to 1-3, 1-5, and 1-6 of the comparative example, respectively. It can be seen that the light emitting efficiency and long life are exhibited, the driving voltage is low, and the characteristics as an element are improved. Moreover, it turns out that element characteristics are improved by making the HOMO level of the light-emitting dopant and the adjacent layer-containing material into the relationship of the present invention.
  • the obtained organic EL elements 2-1 to 2-12 were subjected to the same method as in Example 1, (1) external extraction quantum efficiency (also simply referred to as efficiency), (2) half-life, and (3) driving.
  • the voltage was evaluated and expressed as a relative value where the organic EL element 2-1 was 100.
  • the organic EL elements 2-5 and 2-8 to 2-12 of the present invention are higher than the organic EL elements 2-1 to 2-4, 2-6, and 2-7 of the comparative examples, respectively. It can be seen that the light emitting efficiency and long life are exhibited, the driving voltage is low, and the characteristics as an element are improved. Moreover, it turns out that element characteristics are improving by making the HOMO level of the material contained in a light emitting dopant and an adjacent layer into the relationship of this invention.
  • Organic EL element 3-16 was produced in the same manner as in the production of the organic EL element 3-5, except that the host of the light emitting layer was changed to the host compound (H-1).
  • the obtained organic EL devices 3-1 to 3-16 were subjected to the same method as in Example 1, (1) external extraction quantum efficiency (also simply referred to as efficiency), (2) half-life, and (3) driving. The voltage was evaluated and expressed as a relative value where the organic EL element 3-1 was 100.
  • the organic EL elements 3-5 and 3-8 to 3-16 of the present invention are higher than the organic EL elements 3-1 to 3-4, 3-6, and 3-7 of the comparative example, respectively. It can be seen that the luminous efficiency and long life are exhibited, and the driving voltage is low and the characteristics as an element are improved. Moreover, it turns out that element characteristics are improved by making the HOMO level of the light-emitting dopant and the adjacent layer-containing material into the relationship of the present invention.
  • the organic EL device 4 was prepared in the same manner as described above except that the dopant compound of the light emitting layer and the compound of the second hole transport layer were changed to the compounds shown in Table 4. 1 to 4-19 were produced.
  • the obtained organic EL elements 4-1 to 4-19 were subjected to the same method as in Example 1, (1) external extraction quantum efficiency (also simply referred to as efficiency), (2) half-life, and (3) driving.
  • the voltage was evaluated and expressed as a relative value where the organic EL element 4-1 was 100.
  • the organic EL elements 4-12 to 4-19 of the present invention show higher luminous efficiency and longer life than the organic EL elements 4-1 to 4-11 of the comparative examples, respectively, and the driving voltage is low. It can be seen that the characteristics as an element are improved. Moreover, it turns out that element characteristics are improved by making the HOMO level of the light-emitting dopant and the adjacent layer-containing material into the relationship of the present invention.
  • Preparation of white light-emitting organic EL element 5-1 A transparent substrate provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) as an anode on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, while 200 mg of ⁇ -NPD is placed in a molybdenum resistance heating boat as a hole transport material and 11 mg as a hole transport material 2 is placed in a molybdenum resistance heating boat.
  • each of the heating boats containing ⁇ -NPD was separately energized and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec.
  • a first hole transport layer was provided.
  • the heating boat containing 11-12 was energized and heated, and a second hole transport layer having a film thickness of 5 nm was provided on the first hole transport layer at a deposition rate of 0.05 nm / second.
  • the heating boat containing the host compound (H-1) as the host compound and DP-1 and D-10 as the dopant compounds was energized and heated, and the respective deposition rates were 100: 5: 0.6.
  • a light emitting layer having a thickness of 30 nm was provided.
  • the heating boat containing ET-8 was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide an electron transport layer having a thickness of 30 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • FIG. 7 shows a schematic configuration diagram of an organic EL full-color display device.
  • a hole injection layer composition having the following composition is ejected and injected on the ITO transparent electrode 202 between the partition walls 203 using an inkjet head (manufactured by Epson Corporation; MJ800C), irradiated with ultraviolet light for 200 seconds, 60 A 40-nm-thick hole injection layer 204 was provided by a drying process at 10 ° C. for 10 minutes (see FIG. 7C).
  • a blue light-emitting layer composition, a green light-emitting layer composition, and a red light-emitting layer composition having the following compositions are similarly ejected and injected onto the hole injection layer 204 using an inkjet head, and dried at 60 ° C. for 10 minutes.
  • light emitting layers 205B, 205G, and 205R for each color were provided (see FIG. 7D).
  • an electron transport material is deposited so as to cover each of the light emitting layers 205B, 205G, and 205R to provide an electron transport layer (not shown) with a thickness of 20 nm, and further lithium fluoride is deposited to have a thickness of 0.6 nm.
  • a cathode buffer layer (not shown) was provided, Al was deposited, and a cathode 206 having a thickness of 130 nm was provided to produce an organic EL device (see FIG. 7E). It was found that the produced organic EL elements each emitted blue, green, and red light when a voltage was applied to the electrodes, and could be used as a full-color display device.
  • Host compound (H-1) 0.7 parts by mass Host DP-1 0.04 parts by mass
  • Host compound (H-1) 0.7 parts by mass D-10 0.04 parts by mass Cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 50 parts by mass

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CN113939923A (zh) * 2019-10-08 2022-01-14 Lt素材株式会社 有机发光装置、用于制造其的方法和用于有机发光装置的有机材料层的组合物
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