WO2016143508A1 - Élément électroluminescent organique et matériau d'élément électroluminescent organique - Google Patents

Élément électroluminescent organique et matériau d'élément électroluminescent organique Download PDF

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WO2016143508A1
WO2016143508A1 PCT/JP2016/055258 JP2016055258W WO2016143508A1 WO 2016143508 A1 WO2016143508 A1 WO 2016143508A1 JP 2016055258 W JP2016055258 W JP 2016055258W WO 2016143508 A1 WO2016143508 A1 WO 2016143508A1
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group
substituent
organic
compound
general formula
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麻由香 蟇目
昇 関根
優太 中村
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コニカミノルタ株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

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  • the present invention relates to an organic electroluminescence element and an organic electroluminescence element material. More specifically, the present invention relates to an organic electroluminescence element that achieves both performance and stability such as luminous efficiency.
  • organic electroluminescence element (hereinafter also referred to as “organic EL element”) is an all-film thin film type composed of an organic thin film layer (single layer portion or multilayer portion) containing an organic light-emitting substance between an anode and a cathode. It is a solid element.
  • organic EL element When a voltage is applied to the organic EL element, electrons are injected from the cathode into the organic thin film layer and holes are injected from the anode, and these are recombined in the light emitting layer (organic light emitting substance-containing layer) to generate excitons.
  • the organic EL element is a light-emitting element using light emission (fluorescence / phosphorescence) from these excitons, and is a technology expected as a next-generation flat display and illumination.
  • the phosphorescence emission method is a method having a very high potential.
  • a method for controlling the position of the emission center is significantly different from that using fluorescence emission. In order to capture the efficiency and lifetime of the device, it is important how recombination can be performed inside the light emitting layer to stabilize light emission.
  • a multilayer stacked device including 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, etc. adjacent to the light emitting layer, or a phosphor layer on the light emitting layer.
  • An element using a mixed layer containing a light-emitting compound and a host compound has been developed.
  • high carrier transportability and thermally and electrically stable materials are demanded.
  • T 1 triplet excitation energy level
  • T 1 energy high excited triplet energy
  • a material having a T 1 energy higher than that of the phosphorescent dopant. is required.
  • carbazole derivatives represented by CBP and mCP are well known as host compounds of phosphorescent dopants.
  • a compound used with a blue phosphorescent dopant a compound in which a plurality of carbazole skeletons are bonded to a dibenzofuran skeleton is known. However, these compounds have not reached a sufficiently high T 1 energy level.
  • the present invention has been made in view of the above-described problems and situations, and its solution is a high luminous efficiency, a low driving voltage and a long life, a small increase in voltage during driving, and further stability over time.
  • An organic electroluminescence device and an organic electroluminescence device material are provided.
  • the present inventor has a high luminous efficiency because the organic layer contains a compound having a structure represented by the following general formula (1) in the process of examining the cause of the problem.
  • the present inventors have found that an organic electroluminescence device having a low driving voltage and a long lifetime, having a small voltage increase during driving, and having excellent stability over time can be provided.
  • the above-mentioned problem according to the present invention is solved by the following means.
  • An organic electroluminescence device having an organic layer including a light emitting layer between at least a pair of an anode and a cathode, The organic layer contains a compound having a structure represented by the following general formula (1).
  • B represents a condensed aromatic heterocycle different from benzimidazole.
  • a compound having a structure represented by General Formula (1) is a branched alkyl group or cycloalkyl group having 3 or more carbon atoms.
  • the HOMO level of B is ⁇ 5.87 eV or less
  • the LUMO level of B is ⁇ 0.24 eV or less
  • the HOMO level of the substituent A 1 and the other substituent A 2 is ⁇ 5.87 eV or less, 2.
  • the organic electroluminescence device according to any one of items 1 to 3, wherein B is a condensed aromatic heterocyclic group represented by the following general formula (2).
  • B is a condensed aromatic heterocyclic group represented by the following general formula (2).
  • X represents O or S.
  • Y 21 to Y 28 each independently represents CH or N, and may have the substituent A 1 or the other substituent A 2.
  • * represents a binding site in the compound having the structure represented by the general formula (1).
  • B is a condensed aromatic heterocyclic group represented by the following general formula (3).
  • Y 31 to Y 33 and Y 35 to Y 37 each independently represent O, S, N, or CH.
  • Y 34 or Y 38 represents CH or N.
  • Y 31 to Y 38 may each independently have the substituent A 1 or the other substituent A 2 .
  • Said B is condensed aromatic heterocyclic group represented by following General formula (4), The organic electroluminescent element as described in any one of Claim 1 to 3 characterized by the above-mentioned.
  • Y 41 to Y 44 each independently represents CH or N.
  • Y 45 to Y 48 each independently represents O, S, N, or CH, and hydrogen represents N.
  • each of Y 41 to Y 48 may independently have the substituent A 1 or the other substituent A 2 , and * represents general (Represents a binding site in a compound having the structure represented by formula (1).)
  • Electroluminescence element (In the general formula (5), Y 51 to Y 54 each independently represents CH or N. Y 55 to Y 57 each independently represent O, S, N or CH, and hydrogen represents N. In addition, each of Y 51 to Y 57 may independently have the substituent A 1 or the other substituent A 2 , and * represents a general (Represents a binding site in a compound having the structure represented by formula (1).)
  • Said B is condensed aromatic heterocycle represented by following General formula (6), The organic electroluminescent element as described in any one of Claim 1 to 3 characterized by the above-mentioned.
  • Y 61 to Y 66 each independently represents O, S, N or CH, and in the case of representing N, they each have a hydrogen atom, a lone pair or a substituent.
  • Y 67 and Y 68 each independently represent CH.
  • Y 61 to Y 66 may each independently have the substituent A 1 or the other substituent A 2.
  • * is represented by the general formula (1). Represents a binding site in a compound having a structure.
  • substituents A 1 is an organic electroluminescent device according to any one of the first term to the eighth term, which is a substituent containing a silyl group having a substituent.
  • An organic electroluminescence device material comprising a compound having a structure represented by the following general formula (1).
  • B represents a condensed aromatic heterocycle different from benzimidazole.
  • a compound having a structure represented by General Formula (1) is a branched alkyl group or cycloalkyl group having 3 or more carbon atoms.
  • the HOMO level of B is ⁇ 5.87 eV or less
  • the LUMO level of B is ⁇ 0.24 eV or less
  • the HOMO level of the substituent A 1 and the other substituent A 2 is ⁇ 5.87 eV or less
  • an organic electroluminescence element and an organic electroluminescence element material having high luminous efficiency, low driving voltage and long life, small voltage increase during driving, and excellent stability over time. Can do.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • the present inventors introduce a site having a greater steric hindrance to a compound in which a condensed aromatic heterocyclic ring is substituted with benzimidazole, and apply it to an organic EL device in combination with a blue phosphorescent dopant. It was found that the interaction between the compounds can be suppressed and the aggregation can be suppressed even in the film state without degrading the performance of the film. Therefore, by using a compound having the structure represented by the general formula (1) in the organic layer, high emission luminance, low driving voltage, suppression of voltage increase during driving, and longer emission lifetime can be achieved at the same time. As a result, the present invention has been achieved. Furthermore, it has been found that an organic EL device produced using the compound of the present invention can be improved in terms of stability over time.
  • Schematic diagram showing the relationship between the HOMO level and the LUMO level of each part of the compound according to the present invention Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram of display section A in FIG. Schematic diagram of pixels Schematic diagram of passive matrix type full color display device Schematic of lighting device Schematic diagram of lighting device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device
  • the organic electroluminescent element of the present invention is an organic electroluminescent element having an organic layer including a light emitting layer between at least a pair of an anode and a cathode, wherein the organic layer is represented by the general formula (1). It contains the compound which has this. This feature is a technical feature common to the claimed invention.
  • the HOMO level of B (hereinafter also referred to as HOMO energy level) is ⁇ 5.87 eV or less
  • the LUMO level of B (Hereinafter also referred to as the LUMO energy level) is ⁇ 0.24 eV or less
  • the HOMO levels of the substituent A 1 and the other substituent A 2 are ⁇ 5.87 eV or less
  • the substitution It is preferable that the LUMO levels of the group A 1 and the other substituent A 2 satisfy the formula (I). This is because a high T 1 energy level can be maintained even when the film is formed.
  • the substituent A 1 or the other substituent A 2 is a substituent selected from a group selected from the substituent group or a combination thereof. It is preferable.
  • B is a condensed aromatic heterocyclic group represented by the general formula (2) from the viewpoint of manifesting the effects of the present invention.
  • B is a condensed aromatic heterocyclic group represented by the following general formula (3) from the viewpoint of manifesting the effects of the present invention.
  • B is a condensed aromatic heterocyclic group represented by the following general formula (4) from the viewpoint of manifesting the effects of the present invention.
  • the B is preferably a condensed aromatic heterocyclic group different from benzimidazole represented by the following general formula (5). .
  • B is a condensed aromatic heterocycle represented by the following general formula (6) from the viewpoint of manifesting the effects of the present invention.
  • the substituent A 1 is a substituent including a silyl group having a substituent, from the viewpoint of manifesting the effect of the present invention. This is because it becomes possible to suppress the aggregation of the compound.
  • the light emitting layer contains a compound having a structure represented by the general formula (1) from the viewpoint of manifesting the effects of the present invention.
  • the light emitting layer contains an Ir complex as a phosphorescent dopant from the viewpoint of manifesting the effects of the present invention.
  • the light emitting layer contains two or more host compounds including a compound having a structure represented by the general formula (1). Is preferred.
  • the organic layer is produced by a wet process from the viewpoint of manifesting the effects of the present invention.
  • the organic electroluminescence device material of the present invention is characterized by containing a compound having a structure represented by the general formula (1).
  • the HOMO level of B is ⁇ 5.87 eV or less, and the LUMO level of B is ⁇ 0.24 eV or less.
  • the HOMO level of the substituent A 1 and the other substituent A 2 is ⁇ 5.87 eV or less, and the LUMO level of the substituent A 1 and the other substituent A 2 is It is preferable to satisfy I).
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit and an upper limit.
  • the light emitting layer according to the present invention is composed of a single layer or a plurality of layers, and when there are a plurality of light emitting layers, a non-light emitting intermediate layer may be provided between the light emitting layers.
  • a hole blocking layer also referred to as a hole blocking layer
  • an electron injection layer also referred to as a cathode buffer layer
  • An electron blocking layer also referred to as an electron barrier layer
  • a hole injection layer also referred to as an anode buffer layer
  • the electron transport layer used in the present invention is a layer 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. Moreover, you may be comprised by multiple layers.
  • the hole transport layer used in the present invention is a layer 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. Moreover, you may be comprised by multiple layers. In the above-described typical element configuration, a layer excluding the anode and the cathode is referred to as an “organic layer”.
  • the organic EL element of the present invention may be a so-called tandem element in which a plurality of light emitting units including at least one light emitting layer are stacked.
  • a tandem structure for example, the following configurations can be given.
  • the first light emitting unit The second light emitting unit and the third light emitting unit may all be the same or different. Further, the two light emitting units may be the same, and the remaining one may be different.
  • the third light emitting unit may not be provided, and on the other hand, a light emitting unit or an intermediate layer may be further provided between the third light emitting unit and the electrode.
  • a plurality of light emitting units may be laminated directly or via an intermediate layer, and the intermediate layer is generally an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, an intermediate layer.
  • Known materials and structures can be used as long as they are also called insulating layers and have a function of supplying electrons to the anode-side adjacent layer and holes to the cathode-side adjacent layer.
  • Examples of materials used for the intermediate layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiOx, VOx, CuI, InN, GaN, and CuAlO 2.
  • Preferred examples of the structure within the light emitting unit include those obtained by removing the anode and the cathode from the structures (1) to (7) mentioned in the above representative element structures, but the present invention is not limited to these.
  • Specific examples of the tandem organic EL element include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734. Specification, U.S. Pat. No. 6,337,492, International Publication No.
  • the organic layer according to the present invention contains a compound having a structure represented by the following general formula (1). Moreover, it is preferable that the compound which has a structure represented by following General formula (1) is contained in organic electroluminescent element material.
  • B represents a condensed aromatic heterocyclic ring different from benzimidazole.
  • the compound having the structure represented by the general formula (1) includes a branched alkyl group having 3 or more carbon atoms, a cycloalkyl group, an aromatic hydrocarbon ring group having 6 or more carbon atoms having a substituent at the ortho position, and an ortho position.
  • a group selected from the group consisting of a 6-membered or more aromatic heterocyclic group having a substituent, an amino group having a substituent, a silyl group having a substituent, a phosphoryl group having a substituent, and a thiophosphoryl group having a substituent It may have at least one substituent A 1 containing at least one and may further have other substituents A 2 .
  • the above 6-membered ring aromatic heterocyclic group, the amino group, the silyl group, a substituent wherein the phosphoryl group and the thiophosphoryl group has is be used as the other substituents A 2 shown below It can be selected from possible substituents.
  • the branched alkyl group and the cycloalkyl group may have a substituent can be used as other substituents A 2 shown below. Further, the substituent A 1 may be further substituted with another substituent A 2 .
  • the horizontal line which penetrates structural formula from B represents the bond substituted at any position among the structures represented by the general formula (1). The same applies to the following general formulas (2) to (6).
  • the other substituent A 2 is 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).
  • 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.
  • cycloalkyl group eg, cyclopentyl group, cyclohexyl group, etc.
  • alkenyl group eg, vinyl group, allyl group, etc.
  • alkynyl group eg, propargyl group, etc.
  • aromatic hydrocarbon group aryl
  • Non-aromatic heterocyclic group eg, epoxy ring, aziridine ring
  • the compound represented by the general formula (1) has a structure in which B, which is a condensed aromatic heterocyclic ring, is substituted on the benzimidazole skeleton. Is inhibited and aggregation of compounds can be suppressed. Moreover, since B is a condensed aromatic heterocyclic ring, a high T 1 energy level can be maintained. Furthermore, since the substituent A 1 is a group containing a substituent having high steric hindrance, aggregation at the time of film formation can also be suppressed. In addition, since solubility can be improved, the suitability for production by a wet process can be improved.
  • the HOMO level of B is ⁇ 5.87 eV or less
  • the LUMO level of B is ⁇ 0.24 eV or less
  • the HOMO levels of the substituent A 1 and the other substituents A 2 Preferably, the position is ⁇ 5.87 eV or less
  • the LUMO levels of the substituent A 1 and the other substituent A 2 satisfy the following formula (I).
  • the HOMO level and LUMO level of the substituent refer to the HOMO level and LUMO level of the “substituent-derived compound”.
  • Substituent-derived compound refers to a compound formed by bonding a hydrogen atom to the substituent.
  • B which is a group according to the present invention
  • BH is a substituent-derived compound.
  • a 1 -H and A 2 -H are the substituent-derived compounds, respectively.
  • the HOMO level and the LUMO level of the B, the substituent A 1 and the other substituent A 2 are defined.
  • the benzimidazole skeleton and the portion of the substituent may have some coplanarity when the film is formed.
  • the HOMO site and the LUMO site are preferably localized in different sites. That is, in the benzimidazole skeleton in the general formula (1), the HOMO site of the compound having the structure represented by the general formula (1) is localized, and the LUMO site is localized in B in the general formula (1). It is preferable to be present.
  • the substituent A 1 and the other substituent A 2 do not affect the HOMO site and the LUMO site in order to maintain the high T 1 energy level of the compound having the structure represented by the general formula (1).
  • a level is preferable. That is, by setting the HOMO level and the LUMO level of B, the substituent A 1 , and the other substituent A 2 in the general formula (1) within a specified range, a high T 1 energy can be obtained even when a film is formed. It becomes possible to hold the level.
  • the values of the HOMO level and the LUMO level of the compound represented by the general formula (1) are Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, software for molecular orbital calculation manufactured by Gaussian, USA). , Et al, Gaussian, Inc., Pittsburgh PA, 2002.) and calculated by structural optimization using B3LYP / 6-31G * as a keyword (eV unit) (Converted value). This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
  • the HOMO level and LUMO level of each group were determined by substituting the benzimidazole ring or the group represented by B in the general formula (1) with a hydrogen atom.
  • the following values are calculated by calculating the HOMO level and LUMO level of the substituent-derived compound in which B is replaced with a hydrogen atom.
  • the benzimidazole ring is replaced with a hydrogen atom, and the calculation is performed as BH.
  • the substituent A 1 is also calculated as A 1 -H
  • the other substituent A 2 is also calculated as A 2 -H.
  • the relationship between the HOMO level and the LUMO level of the benzimidazole skeleton, B, and the substituent A 1 or other substituent A 2 in the present invention is shown in FIG.
  • the HOMO level and the LUMO level of the benzimidazole skeleton are represented as “I-HOMO” and “I-LUMO”, respectively.
  • the HOMO level and the LUMO level of the condensed aromatic ring represented by B are represented as “B-HOMO” and “B-LUMO”, respectively.
  • substituent A 1 or other substituents A 2 as the HOMO level and LUMO level of the substituent A 1 or other substituents A 2, respectively, "A 1, A 2 -HOMO” and "A 1 , A 2 -LUMO ”.
  • the HOMO level and LUMO level of B are preferably smaller than the calculated HOMO level and LUMO level of the benzimidazole skeleton.
  • the function of the present invention is sufficiently achieved if the HOMO level is localized in the benzimidazole and the LUMO level is localized in the B.
  • B has a HOMO level of ⁇ 5.87 eV or less and a LUMO level of ⁇ 0.24 eV. It is preferable that
  • the LUMO level is larger than the LUMO site B, and the HOMO level is the HOMO site. It is preferably smaller than the benzimidazole skeleton.
  • the LUMO level can sufficiently perform the function of the present invention if the LUMO is localized in the condensed aromatic heterocycle represented by B. The same applies to the HOMO level.
  • the function required in the present invention is sufficiently achieved.
  • the substituent A 1 and the other substituent A 2 have a HOMO level of ⁇ 5.87 eV or less.
  • the LUMO level preferably satisfies the following formula. Formula (I): [LUMO Level of Substituent A 1 and Other Substituent A 2 ]> [LUMO Level of B] ⁇ 0.2 eV
  • substituent A 1 or the other substituents A 2 is preferably a substituent formed from a base or a combination thereof selected from the following substituent group.
  • Substituent group Alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, non-aromatic heterocyclic group, an aromatic heterocyclic group, a cyano group, a silyl group, also phosphoryl group
  • substituents A 1 is of Of the substituents, a substituent containing a silyl group having a substituent is particularly preferable.
  • B is a condensed aromatic heterocyclic group represented by the following general formula (2).
  • X represents O or S.
  • Y 21 to Y 28 each independently represent CH or N, and may have the substituent A 1 or the other substituent A 2 .
  • * represents a binding site in the compound having the structure represented by the general formula (1).
  • B is a condensed aromatic heterocyclic group represented by the following general formula (3).
  • Y 31 to Y 33 and Y 35 to Y 37 each independently represent O, S, N, or CH. .
  • Y 34 or Y 38 represents CH or N.
  • Y 31 to Y 38 may each independently have the substituent A 1 or the other substituent A 2 .
  • B is a condensed aromatic heterocyclic group represented by the following general formula (4).
  • Y 41 to Y 44 each independently represent CH or N.
  • Y 45 to Y 48 each independently represents O, S, N, or CH, and in the case of representing N, each has a hydrogen atom, an unshared electron pair, or a substituent.
  • Y 41 to Y 48 may each independently have the substituent A 1 or the other substituent A 2 .
  • the B is preferably a condensed aromatic heterocyclic group different from benzimidazole represented by the following general formula (5).
  • Y 51 to Y 54 each independently represent CH or N.
  • Y 55 to Y 57 each independently represent O, S, N, or CH.
  • N 55 represents Y, it has a hydrogen atom, a lone pair, or a substituent.
  • Y 51 to Y 57 may each independently have the substituent A 1 or the other substituent A 2 .
  • the B is preferably a condensed aromatic heterocycle represented by the following general formula (6).
  • Y 61 to Y 66 each independently represent O, S, N, or CH.
  • N 61 represents Y, it has a hydrogen atom, an unshared electron pair, or a substituent.
  • Y 67 and Y 68 each independently represent CH or N.
  • Y 61 to Y 66 may each independently have the substituent A 1 or the other substituent A 2 .
  • the organic layer according to the present invention has a light emitting layer.
  • the light emitting layer according to the present invention is a layer that provides a field in which electrons and holes injected from an electrode or an adjacent layer are recombined to emit light via excitons, and the light emitting portion is a layer of the light emitting layer. Even within, it may be the interface between the light emitting layer and the adjacent layer.
  • the structure of the light emitting layer according to the present invention is not particularly limited as long as it satisfies the requirements defined in the present invention.
  • the compound which has a structure represented by General formula (1) based on this invention should just be contained in the organic layer, and it is preferable to contain in a light emitting layer.
  • the total thickness of the light emitting layer is not particularly limited, but it is possible to prevent the homogeneity of the layer to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color against the driving current. Therefore, it is preferably adjusted to a range of 2 nm to 5 ⁇ m, more preferably adjusted to a range of 2 to 500 nm, and further preferably adjusted to a range of 5 to 200 nm.
  • the thickness of each light emitting layer is preferably adjusted to a range of 2 nm to 1 ⁇ m, more preferably adjusted to a range of 2 to 200 nm, and further preferably adjusted to a range of 3 to 150 nm.
  • the light emitting layer according to the present invention preferably contains a light emitting dopant (a light emitting dopant compound, a dopant compound, also simply referred to as a dopant) and a host compound (a matrix material, a light emitting host compound, also simply referred to as a host).
  • a light emitting dopant a light emitting dopant compound, a dopant compound, also simply referred to as a dopant
  • a host compound a matrix material, a light emitting host compound, also simply referred to as a host
  • a compound having a structure represented by the general formula (1) is preferably used as a host compound.
  • the said light emitting layer contains 2 or more types of host compounds containing the compound which has a structure represented by the said General formula (1).
  • the host compound used in the present invention is a compound mainly responsible for charge injection and transport in the light emitting layer, and its own light emission is not substantially observed in the organic EL device.
  • it is a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.1 at room temperature (25 ° C.), more preferably a compound having a phosphorescence quantum yield of less than 0.01.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • the excited state energy of a host compound is higher than the excited state energy of the light emission dopant contained in the same layer.
  • a host compound may be used independently or may be used in combination of multiple types. 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.
  • the compound conventionally used with an organic EL element can be used. It may be a low molecular compound or a high molecular compound having a repeating unit, or a compound having a reactive group such as a vinyl group or an epoxy group.
  • a known host compound while having a hole transporting ability or an electron transporting ability, the emission of light is prevented from being increased in wavelength.
  • Tg is preferably 90 ° C. or higher, more preferably 120 ° C. or higher.
  • the glass transition temperature (Tg) is a value determined by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).
  • 2007/063796 International Publication No. 2007/063754, International Publication No. 2004/107822, WO 2005/030900, WO 2006/114966, WO 2009/086028, WO 2009/003898, WO 2012/023947, JP 2008- No. 074939, JP-A-2007-254297, European Patent No. 2034538, and the like.
  • a fluorescent luminescent dopant also referred to as a fluorescent dopant or a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent dopant or a phosphorescent compound
  • at least one light emitting layer contains a phosphorescent dopant.
  • concentration of the luminescent dopant in the luminescent layer can be arbitrarily determined based on the specific dopant used and the requirements of the device, and is contained at a uniform concentration in the thickness direction of the luminescent layer. It may also have an arbitrary concentration distribution.
  • the light emission dopant used for this invention may be used in combination of multiple types, and may combine and use the combination of the dopants from which a structure differs, and the fluorescence emission dopant and a phosphorescence emission dopant. Thereby, arbitrary luminescent colors can be obtained.
  • the light emission color of the organic EL device of the present invention and the compound used in the present invention is shown in FIG. 5.16 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 the luminance meter CS-1000 (manufactured by Konica Minolta Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • the light emitting layer of one layer or a plurality of layers contains a plurality of light emitting dopants having different emission colors and emits white light.
  • the combination of the light-emitting dopants that exhibit white and examples include blue and orange, and a combination of blue, green, and red.
  • the white color in the organic EL device of the present invention is not particularly limited, and may be white near orange or white near blue, but when the 2 ° viewing angle front luminance is measured by the method described above.
  • the phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed, and specifically, phosphorous dopant at room temperature (25 ° C.). It is a compound that emits light, and is defined as a compound having a phosphorescence quantum yield of 0.01 or more at 25 ° C., but a preferable phosphorescence quantum yield is 0.1 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 dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
  • phosphorescent dopants There are two types of light emission of phosphorescent dopants in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant. It is an energy transfer type to obtain light emission from the phosphorescent dopant. The other is a carrier trap type in which a phosphorescent dopant serves as a carrier trap, and carrier recombination occurs on the phosphorescent dopant to emit light from the phosphorescent dopant. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound. As a phosphorescence dopant which can be used in this invention, it can select from the well-known thing used for the light emitting layer of an organic EL element suitably, and can use it.
  • a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode among metal-carbon bond, metal-nitrogen bond, metal-oxygen bond and metal-sulfur bond is preferable.
  • fluorescent dopant used in the present invention
  • fluorescent dopant is a compound that can emit light from an excited singlet, and is not particularly limited as long as light emission from the excited singlet is observed.
  • fluorescent dopant used in the present invention include anthracene derivatives, pyrene derivatives, chrysene derivatives, fluoranthene derivatives, perylene derivatives, fluorene derivatives, arylacetylene derivatives, styrylarylene derivatives, styrylamine derivatives, arylamine derivatives, boron complexes, coumarins.
  • pyran derivatives cyanine derivatives, croconium derivatives, squalium derivatives, oxobenzanthracene derivatives, fluorescein derivatives, rhodamine derivatives, pyrylium derivatives, perylene derivatives, polythiophene derivatives, rare earth complex compounds, and the like.
  • luminescent dopant using delayed fluorescence include, for example, compounds described in International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like. Is not limited to these.
  • the electron transport layer is made of a material having a function of transporting electrons, and may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • the total thickness of the electron transport layer used in the present invention is not particularly limited, but is usually in the range of 2 nm to 5 ⁇ m, more preferably 2 to 500 nm, and further preferably 5 to 200 nm.
  • the organic EL element when the light generated in the light emitting layer is extracted from the electrode, the light extracted directly from the light emitting layer interferes with the light extracted after being reflected by the electrode from which the light is extracted and the electrode located at the counter electrode. It is known to wake up. When light is reflected by the cathode, this interference effect can be efficiently utilized by appropriately adjusting the thickness of the electron transport layer between several nanometers and several micrometers.
  • the electron mobility of the electron transport layer is 1 ⁇ 10 ⁇ 5 cm 2 / Vs or more, particularly when the layer thickness is large. Is preferred.
  • the material used for the electron transport layer (hereinafter referred to as an electron transport material) may have any of an electron injecting property, a transporting property, and a hole blocking property. Any one can be selected and used.
  • nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, Triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzthiazole derivatives, etc.), dibenzofuran derivatives, And dibenzothiophene derivatives, silole derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene, etc.)
  • a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand 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), etc.
  • a metal complex in which the central metal is replaced with In, Mg, 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 transport 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.
  • 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.
  • the electron transport layer may be doped with a doping material as a guest material to form an electron transport layer having a high n property (electron rich).
  • the doping material include n-type dopants such as metal complexes and metal compounds such as metal halides.
  • Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004) and the like.
  • More preferable electron transport materials in the present invention include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.
  • Specific preferred examples of the compound used for the electron transport layer of the organic EL device of the present invention are shown below, but the present invention is not limited thereto.
  • the electron transport material may be used alone or in combination of two or more.
  • the hole blocking layer is a layer having the function of an electron transport layer in a broad sense, and is preferably made of a material having a function of transporting electrons and a small ability to transport holes. By blocking the holes, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the electron carrying layer mentioned above can be used as a hole-blocking layer used for this invention as needed.
  • the hole blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the cathode side of the light emitting layer.
  • the layer thickness of the hole blocking layer used in the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • the material used for the hole blocking layer the material used for the above-described electron transport layer is preferably used, and the material used as the above-described host compound is also preferably used for the hole blocking layer.
  • the electron injection layer (also referred to as “cathode buffer layer”) used in the present invention is a layer provided between the cathode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. 2 and Chapter 2 “Electrode Materials” (pages 123 to 166) of the 2nd volume of “The Forefront of Industrialization” (published by NTT Corporation on November 30, 1998).
  • the electron injection layer may be provided as necessary, and may be present between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.
  • the electron injection layer is preferably a very thin film, and the layer thickness is preferably in the range of 0.1 to 5 nm depending on the material. Moreover, the nonuniform film
  • JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like Specific examples of materials preferably used for the electron injection layer are as follows. , Metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkaline earth metal compounds typified by magnesium fluoride, calcium fluoride, etc., oxidation Examples thereof include metal oxides typified by aluminum, metal complexes typified by lithium 8-hydroxyquinolate (Liq), and the like. Further, the above-described electron transport material can also be used. Moreover, the material used for said electron injection layer may be used independently, and may be used in combination of multiple types.
  • the hole transport layer is made of a material having a function of transporting holes and may have a function of transmitting holes injected from the anode to the light emitting layer.
  • the total thickness of the hole transport layer used in the present invention is not particularly limited, but is usually in the range of 5 nm to 5 ⁇ m, more preferably 2 to 500 nm, and further preferably 5 to 200 nm.
  • the material used for the hole transporting layer (hereinafter also referred to as a hole transporting material) may have any of a hole injecting property, a transporting property, and an electron barrier property. Any one can be selected and used.
  • porphyrin derivatives for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives , Indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, and polyvinyl carbazole, polymer materials or oligomers with aromatic amines introduced into the main chain or side chain, polysilane, conductive And polymer (for example, PEDOT / PSS, aniline copolymer, polyaniline, polythiophene, etc.).
  • PEDOT / PSS aniline copolymer, poly
  • Examples of the triarylamine derivative include a benzidine type typified by ⁇ -NPD, a starburst type typified by MTDATA, and a compound having fluorene or anthracene in the triarylamine linking core part.
  • hexaazatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as hole transport materials.
  • a hole transport layer having a high p property doped with impurities can also 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.
  • JP-A-11-251067 J. Org. Huang et. al.
  • a so-called p-type hole transport material or an inorganic compound such as p-type-Si or p-type-SiC, as described in the literature (Appl. Phys. Lett., 80 (2002), p. 139) is used. You can also.
  • ortho-metalated organometallic complexes having Ir or Pt as the central metal as typified by Ir (ppy) 3 are also preferably used.
  • the above-mentioned materials can be used as the hole transport material, a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organometallic complex, or an aromatic amine is introduced into the main chain or side chain.
  • the polymer materials or oligomers used are preferably used.
  • Specific examples of known preferred hole transport materials used in the organic EL device of the present invention include the compounds described in the following documents in addition to the documents listed above, but the present invention is not limited thereto. Not. For example, Appl. Phys. Lett. 69, 2160 (1996); Lumin. , 72-74,985 (1997), Appl. Phys. Lett. 78, 673 (2001), Appl.
  • the electron blocking layer is a layer having a function of a hole transport layer in a broad sense, and is preferably made of a material having a function of transporting holes and a small ability to transport electrons, while transporting holes. By blocking electrons, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned above can be used as an electron blocking layer used for this invention as needed.
  • the electron blocking layer provided in the organic EL device of the present invention is preferably provided adjacent to the anode side of the light emitting layer.
  • the thickness of the electron blocking layer used in the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • the material used for the electron blocking layer the material used for the above-described hole transport layer is preferably used, and the material used as the above-described host compound is also preferably used for the electron blocking layer.
  • the hole injection layer (also referred to as “anode buffer layer”) used in the present invention is a layer provided between the anode and the light emitting layer in order to lower the driving voltage or improve the light emission luminance. It is described in detail in the second chapter, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Elements and the Forefront of Industrialization (issued by NTT Corporation on November 30, 1998)”.
  • the hole injection layer may be provided as necessary, and may be present between the anode and the light emitting layer or between the anode and the hole transport layer as described above.
  • the details of the hole injection layer are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc.
  • Examples of materials used for the hole injection layer include: Examples thereof include materials used for the above-described hole transport layer.
  • phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives, metal oxides typified by vanadium oxide, amorphous carbon as described in JP-T-2003-519432 and JP-A-2006-135145, etc.
  • the materials used for the hole injection layer described above may be used alone or in combination of two or more.
  • the organic layer in the present invention described above may further contain other additives.
  • the additive content include halogen elements such as bromine, iodine and chlorine, halogenated compounds, alkali metals such as Pd, Ca and Na, alkaline earth metals, transition metal compounds, complexes, and salts.
  • the content of the additive content can be arbitrarily determined, but it is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 50 ppm or less with respect to the total mass% of the contained layer. is there. However, it is not within this range depending on the purpose of improving the transportability of electrons and holes or the purpose of favoring the exciton energy transfer.
  • a method for forming an organic layer (hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) according to the present invention will be described.
  • the method for forming the organic layer according to the present invention is not particularly limited, and a conventionally known method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used. Is more preferable.
  • the wet method include spin coating method, casting method, ink jet method, printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, and LB method (Langmuir-Blodgett method).
  • 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.
  • liquid medium for dissolving or dispersing the organic EL material of the present invention examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, mesitylene, Aromatic hydrocarbons such as 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
  • vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within a range of 50 nm / second, a substrate temperature of ⁇ 50 to 300 ° C., and a layer thickness of 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the organic layer according to the present invention is preferably formed 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 formation methods. In that case, it is preferable to perform the work in a dry inert gas atmosphere.
  • anode As the anode in the organic EL element, a material having a work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • a conductive transparent material such as a metal such as Au, 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.
  • a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not required (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.
  • a wet film formation method such as a printing method or a coating method can also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • cathode As the 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. 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, aluminum, 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, from the point of durability against electron injection and oxidation, 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 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or translucent cathode can be produced by producing a conductive transparent material mentioned in the description of the anode on the cathode after producing the above metal with a thickness of 1 to 20 nm.
  • the support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. Or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. 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.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, Arton (trade name, manufactured by JSR) or Appel (
  • an inorganic film, an organic film, or a hybrid film of both may be formed on the surface of the resin film.
  • a relative humidity (90 ⁇ 2)%) of 0.01 g / (m 2 ⁇ 24 h) or less is preferable.
  • oxygen measured by a method according to JIS K 7126-1987 A high gas barrier film having a permeability of 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
  • the material for forming the gas barrier film may be any material that has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, and the like can be used.
  • the method for forming the gas 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, and ceramic substrates.
  • the external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, and more preferably 5% or more.
  • external extraction quantum efficiency (%) number of photons emitted to the outside of the organic EL element / number of electrons flowed 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.
  • Examples of the sealing means used for sealing the organic EL element of the present invention include a method of bonding a sealing member, an electrode, and a support substrate with an adhesive.
  • a sealing member it should just be arrange
  • transparency and electrical insulation are not particularly limited. Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • polymer plate examples include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • metal plate examples 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 organic EL 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 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and a method according to JIS K 7129-1992.
  • the measured water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)%) is preferably that of 1 ⁇ 10 -3 g / (m 2 / 24h) or less.
  • 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.
  • 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 adhesive-hardened from room temperature to 80 degreeC 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.
  • a laminated structure of these inorganic layers and layers made of organic materials it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials.
  • the method of forming these films There are no particular limitations on the method of forming these films. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination 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.
  • a vacuum can also be used.
  • 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 outside the sealing film or the sealing film on the side facing the support substrate with the organic layer interposed therebetween.
  • 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, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • An organic electroluminescent element emits light inside a layer having a refractive index higher than that of air (with a refractive index of about 1.6 to 2.1), and about 15% to 20% of light generated in the light emitting layer. It is generally said that only light can be extracted. 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 element, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light undergoes total reflection between the light, the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the side surface direction of the element.
  • a technique 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 transparent substrate and the air interface (for example, US Pat. No. 4,774,435), A method for improving efficiency by providing light condensing property (for example, Japanese Patent Laid-Open No. 63-134795), a method for forming a reflective surface on the side surface of an element (for example, Japanese Patent Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (for example, 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 low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally in the range of about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Furthermore, it is preferable that it is 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 exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface that causes total reflection or in any medium has a feature that the effect of improving the light extraction efficiency is high. 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 or second-order diffraction. The light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating into any layer or medium (in the transparent substrate or transparent electrode). , Trying to extract light out.
  • the introduced diffraction grating desirably 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. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL device of the present invention can be processed to provide, for example, a structure on a microlens array on the light extraction side of a support substrate (substrate), or combined with a so-called condensing sheet, for example, in a specific direction, such as device light emission. Condensing light in the front direction with respect to the surface can increase the luminance in a specific direction.
  • a support substrate substrate
  • condensing sheet for example, in a specific direction, such as device light emission.
  • Condensing light in the front direction with respect to the surface can increase the luminance in a specific direction.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate. One side is preferably within a range of 10 to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the condensing sheet for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used.
  • 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, a substrate may be formed with a ⁇ -shaped stripe having an apex angle of 90 degrees and a pitch of 50 ⁇ m, or the apex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • 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 as needed during film formation. 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 organic EL element of the present invention can be used for a display device.
  • the display device 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. However, 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.
  • 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.
  • 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.
  • 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 emitting 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.
  • FIG. 2 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, a wiring unit C that electrically connects the display unit A and the control unit B, and the like. .
  • the control unit B is electrically connected to the display unit A via the wiring unit C, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside. Sequentially emit light according to the image data signal, scan the image, and display the image information on the display unit A.
  • FIG. 3 is a schematic diagram of a display device using an active matrix method.
  • the display unit A includes a wiring unit C 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.
  • FIG. 3 shows a case where the light emitted from the pixel 3 (the emitted light L) 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 lattice shape and are connected to the pixels 3 at the orthogonal positions (details are shown in FIG. Not shown).
  • 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. 4 is a schematic diagram showing a pixel circuit.
  • 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.
  • 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 organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. 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. 5 is a schematic diagram of a passive matrix display device.
  • a plurality of scanning lines 5 and a plurality of 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 organic EL element of the present invention By using the organic EL element of the present invention, a display device with improved luminous efficiency was obtained.
  • 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 300 ⁇ m thick glass substrate is used as a sealing substrate, and an epoxy photocurable adhesive (LUX The track 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, sealed, and illuminated as shown in FIGS.
  • a device can be formed.
  • FIG. 1 One Embodiment of Lighting Device of the present invention that includes the organic EL element of the present invention.
  • FIG. 6 shows a schematic diagram of the lighting device, and the organic EL element 101 of the present invention is covered with a glass cover 102 (in the sealing operation with the glass cover, the organic EL element 101 is brought 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. 7 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.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • the organic EL device material of the present invention contains a compound having a structure represented by the general formula (1).
  • the HOMO level of B is ⁇ 5.87 eV or less
  • the LUMO level of B is ⁇ 0.24 eV or less
  • the substituent A 1 and the others It is preferable that the HOMO level of the substituent A 2 is ⁇ 5.87 eV or less
  • the LUMO levels of the substituent A 1 and the other substituent A 2 satisfy the formula (I).
  • Example 1 ⁇ Production of Organic EL Element 1-1 >> After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as an anode on a 100 nm ITO (indium tin oxide) film, this ITO transparent electrode was provided.
  • the transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of HT-1 is put into a molybdenum resistance heating boat, and 200 mg of HT-2 is put into another molybdenum resistance heating boat, and made of another molybdenum.
  • 200 mg of Comparative Compound 1 is put into a resistance heating boat, 200 mg of DP-1 is put into another resistance heating boat made of molybdenum, 200 mg of ET-1 is put into another resistance heating boat made of molybdenum, and another resistance heating boat made of molybdenum is added.
  • 200 mg of ET-2 was placed and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing HT-1, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / sec.
  • An injection layer was provided.
  • the heating boat containing HT-2 was heated by energization, and was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to provide a 30 nm hole transport layer.
  • the heating boat containing Comparative Compound 1 and DP-1 was heated by energization, and co-deposited on the hole transport layer at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively, to emit light of 40 nm.
  • a layer was provided.
  • the heating boat containing ET-1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm hole blocking layer. Further, the heating boat containing ET-2 was energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to provide an electron transport layer of 30 nm. Subsequently, lithium fluoride 0.5 nm was vapor-deposited as an electron injection layer (cathode buffer layer), and aluminum 110 nm was vapor-deposited to form a cathode, thereby producing an organic EL device 1-1.
  • Stability over time After storing an organic EL device at 60 ° C. and 70% RH for one month, the power efficiency before and after storage is obtained, and the respective power efficiency ratios are obtained according to the following formulas.
  • a scale. Stability over time (%) power efficiency after storage / power efficiency before storage x 100
  • the power efficiency was determined by measuring the front luminance and luminance angle dependency of each organic EL element using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Co., Ltd.) and using the value obtained at a front luminance of 1000 cd / m 2 . It was.
  • the above evaluation results are shown in Table 4.
  • the organic EL device using the compound having the structure represented by the general formula (1) according to the present invention is superior in luminous efficiency and luminous lifetime and low in comparison with the organic EL device of the comparative example. It was clear that it was a voltage, and it was found that the voltage rise during driving was also suppressed. It was also found that the stability over time was excellent.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus.
  • 200 mg of HT-2 as a hole transport material is placed in a molybdenum resistance heating boat, and a comparative compound as a host compound in another molybdenum resistance heating boat.
  • 200 mg of 1 was put, 200 mg of ET-1 as an electron transport material was put into another molybdenum resistance heating boat, and 100 mg of DP-2 as a dopant compound was put into another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing HT-2, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec.
  • the second hole transport layer was provided. Further, the second hole transport layer was heated by energizing the heating boat containing Comparative Compound 1 as a host compound and DP-2 as a dopant compound, respectively, at a deposition rate of 0.1 nm / second and 0.006 nm / second, respectively.
  • a light-emitting layer having a layer thickness of 40 nm was provided by co-evaporation.
  • the heating boat containing ET-1 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 layer thickness of 30 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • lithium fluoride was vapor-deposited to form an electron injection layer having a thickness of 0.5 nm, and aluminum was further vapor-deposited to form a cathode having a thickness of 110 nm.
  • an organic EL element 2-1 was produced.
  • the organic EL device using the compound having the structure represented by the general formula (1) according to the present invention is superior in luminous efficiency and luminous lifetime and low in comparison with the organic EL device of the comparative example. It was clear that it was a voltage, and it was found that the voltage rise during driving was also suppressed. It was also found that the stability over time was excellent.
  • spin coating was performed using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Baytron P Al4083, Baytron P Al4083) to 70% with pure water. After forming a thin film by the method, it was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a layer thickness of 30 nm.
  • a hole transport material Poly N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl)) benzidine (manufactured by American Dye Source, ADS- A thin film was formed by spin coating using the chlorobenzene solution of No. 254). Heat drying at 150 ° C. for 1 hour to provide a second hole transport layer having a layer thickness of 40 nm.
  • a thin film was formed by spin coating using Comparative Compound 1 as a host compound and a butyl acetate solution of DP-3 as a dopant compound, and dried by heating at 120 ° C. for 1 hour.
  • a light emitting layer having a layer thickness of 30 nm was provided.
  • a 1-butanol solution of ET-3 as an electron transport material was used and a thin film was formed by spin coating to provide an electron transport layer having a layer thickness of 20 nm.
  • This substrate was attached to a vacuum deposition apparatus, and the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa.
  • lithium fluoride was vapor-deposited to form an electron injection layer having a thickness of 1.0 nm
  • aluminum was vapor-deposited to form a cathode having a thickness of 110 nm.
  • an organic EL element 3-1 was produced.
  • the organic EL device using the compound having the structure represented by the general formula (1) according to the present invention is superior in light emission efficiency and light emission lifetime and low in comparison with the organic EL device of the comparative example. It was clear that it was a voltage, and it was found that the voltage rise during driving was also suppressed. It was also found that the stability over time was excellent.
  • Example 4 After patterning on a substrate (NA45 manufactured by NH Techno Glass Co., Ltd.) with a 100 nm ITO film formed on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode, the transparent support substrate provided with this ITO transparent electrode was made of isopropyl alcohol. Ultrasonic cleaning, drying with dry nitrogen gas, and UV ozone cleaning were performed for 5 minutes.
  • Ultraviolet light was irradiated at 120 ° C. for 90 seconds to perform photopolymerization / crosslinking, and further vacuum dried at 60 ° C. for 1 hour to form a second hole transport layer having a layer thickness of about 20 nm.
  • a solution prepared by dissolving 100 mg of Comparative Compound 1 and 20 mg of DP-4, 0.5 mg of D-1, 0.2 mg of D-2 in 10 ml of butyl acetate was used at 600 rpm.
  • a thin film was formed by spin coating under the condition of 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the light emitting layer with a layer thickness of about 70 nm.
  • a thin film was formed on this light emitting layer by spin coating using a solution of 50 mg of ET-4 dissolved in 10 ml of hexafluoroisopropanol (HFIP) at 1500 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a layer thickness of about 20 nm. Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, 0.4 nm of potassium fluoride was deposited as an electron injection layer, and further, 110 nm of aluminum was deposited. Thus, a cathode was formed to produce an organic EL element 4-1.
  • HFIP hexafluoroisopropanol
  • organic EL elements 4-2 to 4-11 were produced in the same manner except that the comparative compound 1 was changed to the compounds shown in Table 2, Table 9-1 and Table 9-2. did. Tables 9-1 and 9-2 show the molecular calculation results of each compound other than the comparative compound.
  • the organic EL device using the compound having the structure represented by the general formula (1) according to the present invention is superior in light emission efficiency and light emission lifetime and low in comparison with the organic EL device of the comparative example. It was clear that it was a voltage, and it was found that the voltage rise during driving was also suppressed. It was also found that the stability over time was excellent.
  • Example 5 After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as an anode on a 100 nm ITO (indium tin oxide) film, this ITO transparent electrode was provided.
  • the transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of HT-6 is put into a resistance heating boat made of molybdenum, and 200 mg of HT-5 is put into another molybdenum resistance heating boat.
  • Comparative Compound 1 200 mg is put into a resistance heating boat, 200 mg of DP-5 is put into another resistance heating boat made of molybdenum, 200 mg of D-3 is put into another resistance heating boat made of molybdenum, and D is put into another resistance heating boat made of molybdenum. 200 mg of -4 was put, 200 mg of ET-5 was put into another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing HT-6, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second.
  • An injection layer was provided.
  • the heating boat containing HT-5 was energized and heated, and was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to provide a 20 nm hole transport layer.
  • the heating boat containing Comparative Compound 1, DP-5, D-3, and D-4 was energized and heated, and the deposition rates were 0.1 nm / second, 0.025 nm / second, 0.0007 nm / second, A light-emitting layer having a thickness of 60 nm was formed by co-evaporation on the hole transport layer at 0.0002 nm / second.
  • the heating boat containing ET-5 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 20 nm electron transport layer. Subsequently, 0.5 nm of potassium fluoride was vapor-deposited as an electron injection layer, and further, 110 nm of aluminum was vapor-deposited to form a cathode, thereby producing an organic EL element 5-1.
  • organic EL elements 5-2 to 5-14 were produced in the same manner except that the comparative compound 1 was changed to the compounds described in Table 2, Table 11-1, and Table 11-2. did. The molecular calculation results of each compound other than the comparative compound are shown in Table 11-1 and Table 11-2.
  • the organic EL device in which the dopant compound of the present invention and the host compound are used in combination is clearly superior in luminous efficiency and luminous lifetime and low voltage compared to the organic EL device of the comparative example. It was also found that the voltage rise during driving was suppressed. It was also found that the stability over time was excellent.
  • Example 6 A transparent substrate with an ITO (Indium Tin Oxide) film having a thickness of 120 nm formed on a glass substrate of 50 mm ⁇ 50 mm and a thickness of 0.7 mm, patterned, and then attached with this ITO transparent electrode After ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen gas and UV ozone cleaning for 5 minutes, this transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Each of the resistance heating boats in the vacuum deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication. The resistance heating boat used was made of a resistance heating material made of molybdenum or tungsten.
  • ITO Indium Tin Oxide
  • the deposition crucible containing compound HT-1 was energized and heated, and deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second. A hole injection layer was formed.
  • Compound HT-2 was deposited in the same manner to form a hole transport layer having a layer thickness of 30 nm. Subsequently, Comparative Compound 1 and DP-6 were co-deposited at a deposition rate of 0.1 nm / second so that the volume percentage was 90% and 10%, respectively, to form a light emitting layer having a layer thickness of 30 nm. Next, ET-1 was deposited at a deposition rate of 0.1 nm / second to form a first electron transport layer having a layer thickness of 10 nm, and further, ET-2 was deposited at a deposition rate of 0.1 nm / second, A second electron transport layer having a layer thickness of 45 nm was formed.
  • the organic EL device using the dopant compound of the present invention and the host compound in combination is superior in luminous efficiency and luminous lifetime and has a low voltage compared to the organic EL device of the comparative example. It was also found that the voltage rise during driving was suppressed. It was also found that the stability over time was excellent.
  • FIG. 8 shows a schematic configuration diagram of an organic EL full-color display device.
  • a substrate NH45 manufactured by NH Techno Glass
  • ITO transparent electrode 202 formed as an anode on a glass substrate 201
  • FIG. 8A A non-photosensitive polyimide partition wall 203 (width 20 ⁇ m, thickness 2.0 ⁇ m) was formed between the ITO transparent electrodes 202 by photolithography (see FIG. 8B).
  • a hole injection layer composition having the following composition is ejected and injected on the ITO electrode 202 between the partition walls 203 using an inkjet head (manufactured by Epson Corporation; MJ800C), irradiated with ultraviolet light for 200 seconds, and 60 ° C.
  • a hole injection layer 204 having a layer thickness of 40 nm was provided by a drying process for 10 minutes (see FIG. 8C).
  • 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. Then, the light emitting layers 205B, 205G, and 205R for each color were provided (see FIG. 8D).
  • 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) having a thickness of 20 nm, and further lithium fluoride is deposited to form a layer having a thickness of 0.6 nm.
  • An electron injection layer (not shown) was provided, Al was vapor-deposited, and a cathode 206 having a thickness of 130 nm was provided to produce an organic EL device (see FIG. 8E). 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.
  • Example 8 ⁇ Preparation of organic EL element 8-1 >> After patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ⁇ 100 mm ⁇ 1.1 mm glass substrate was formed as an anode on a 100 nm ITO (indium tin oxide) film, this ITO transparent electrode was provided.
  • the transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of HT-1 is put into a molybdenum resistance heating boat, and 200 mg of HT-2 is put into another molybdenum resistance heating boat, and made of another molybdenum.
  • 200 mg of Comparative Compound 4 is put in a resistance heating boat, 200 mg of DP-6 is put in another resistance heating boat made of molybdenum, 200 mg of ET-1 is put in another resistance heating boat made of molybdenum, and another resistance heating boat made of molybdenum is added.
  • 200 mg of ET-2 was placed and attached to a vacuum deposition apparatus.
  • the vacuum chamber was then depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing HT-1, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / sec.
  • An injection layer was provided.
  • the heating boat containing HT-2 was heated by energization, and was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to provide a 30 nm hole transport layer.
  • the heating boat containing the comparative compound 4 and DP-6 was heated by energization, and co-evaporated on the hole transport layer at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively, to emit light of 40 nm.
  • a layer was provided.
  • the heating boat containing ET-1 was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm hole blocking layer. Further, the heating boat containing ET-2 was energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to provide an electron transport layer of 30 nm. Subsequently, lithium fluoride 0.5 nm was vapor-deposited as an electron injection layer (cathode buffer layer), and aluminum 110 nm was vapor-deposited to form a cathode, thereby producing an organic EL device 1-1.
  • an organic EL element 8-2 was produced in the same manner except that a light emitting layer was provided by the following procedure.
  • 200 mg of Exemplified Compound H2-1 was placed in a molybdenum resistance heating boat.
  • the heating boat containing Comparative Compound 4, Example Compound H2-1 and DP-6 was energized and heated, and the deposition rates were 0.1 nm / second, 0.010 nm / second, and 0.010 nm / second, respectively.
  • a 40 nm light emitting layer was provided by co-evaporation on the hole transport layer.
  • Organic EL devices 8-3 to 8-9 were prepared in the same manner as in the production of the organic EL device 8-2 except that the exemplified compound H2-1 was changed to the compounds shown in Table 15.
  • the organic EL device in which the compound having the structure represented by the general formula (1) according to the present invention is used in combination in the light emitting layer has a light emission efficiency and a light emission lifetime as compared with the organic EL device of the comparative example. It was clear that the voltage was excellent and low, and the increase in voltage during driving was suppressed. It was also found that the stability over time was excellent.
  • An apparatus can be provided. Moreover, it turned out that there exists an outstanding effect also about the organic EL element manufactured by the wet process. Furthermore, the organic EL element which has the said effect can be manufactured also by using together with another host compound for a light emitting layer.
  • the organic electroluminescence device of the present invention is a display device, display, home lighting, interior lighting, clock or liquid crystal backlight, signboard advertisement, traffic light, light source of optical storage medium, electrophotographic copying, which includes an organic EL device. It can be suitably used as a wide light source such as a light source of a machine, a light source of an optical communication processor, a light source of an optical sensor, and a general household appliance requiring a display device.

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Abstract

La présente invention concerne un élément électroluminescent organique qui présente un rendement lumineux élevé, une faible tension de commande, une longue durée de vie et une excellente stabilité à long terme, et qui ne présente pas d'augmentation de tension lorsqu'il est commandé. L'élément électroluminescent organique selon la présente invention comprend une couche organique contenant une couche électroluminescente au moins entre une paire d'électrodes, constituée d'une électrode positive et d'une électrode négative. Cet élément électroluminescent organique est caractérisé en ce que la couche organique contient un composé dont la structure est représentée par la formule générale (1).
PCT/JP2016/055258 2015-03-06 2016-02-23 Élément électroluminescent organique et matériau d'élément électroluminescent organique WO2016143508A1 (fr)

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WO2020180127A1 (fr) * 2019-03-07 2020-09-10 두산솔루스 주식회사 Composé organique et dispositif électroluminescent organique le comprenant
CN114315845A (zh) * 2020-09-28 2022-04-12 江苏绿人半导体有限公司 一种有机化合物及在有机电致发光器件中的应用
US11352328B2 (en) 2016-07-12 2022-06-07 Arisan Therapeutics Inc. Heterocyclic compounds for the treatment of arenavirus
US11700768B2 (en) 2017-04-27 2023-07-11 Lg Chem, Ltd. Compound and organic light emitting device comprising the same
KR20230129409A (ko) 2021-01-06 2023-09-08 미쯔비시 케미컬 주식회사 유기 전계 발광 소자용 조성물, 유기 전계 발광 소자,표시 장치 및 조명 장치

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