WO2016181772A1 - Composé pi-conjugué, matériau pour élément à électroluminescence organique, film mince électroluminescent, élément à électroluminescence organique, dispositif d'affichage et dispositif d'éclairage - Google Patents

Composé pi-conjugué, matériau pour élément à électroluminescence organique, film mince électroluminescent, élément à électroluminescence organique, dispositif d'affichage et dispositif d'éclairage Download PDF

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WO2016181772A1
WO2016181772A1 PCT/JP2016/062426 JP2016062426W WO2016181772A1 WO 2016181772 A1 WO2016181772 A1 WO 2016181772A1 JP 2016062426 W JP2016062426 W JP 2016062426W WO 2016181772 A1 WO2016181772 A1 WO 2016181772A1
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electron
organic
compound
light
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Japanese (ja)
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康生 宮田
威人 並川
貴之 飯島
隆太郎 菅原
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • 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

Definitions

  • the present invention relates to a ⁇ -conjugated compound, an organic electroluminescence element material, a light-emitting thin film, an organic electroluminescence element, and a display device and an illumination device provided with the organic electroluminescence element. More specifically, the present invention relates to a ⁇ -conjugated compound having improved luminous efficiency.
  • organic electroluminescence element also referred to as “organic electroluminescence element” or “organic EL element”
  • organic electroluminescence Electro Luminescence: hereinafter abbreviated as “EL”
  • EL Electro Luminescence
  • TTA triplet-triplet annihilation
  • TTF Triplet-Triplet Fusion
  • thermoally activated delayed fluorescence also referred to as “thermally excited delayed fluorescence”: Thermally Activated Delayed Fluorescence (hereinafter abbreviated as “TADF” where appropriate)
  • TADF Thermally Activated Delayed Fluorescence
  • the energy of singlet excitons can be transferred to the luminescent compound by fluorescence resonance energy transfer (Fluorescence resonance energy transfer: hereinafter abbreviated as “FRET” as appropriate), and light can be emitted by the energy transferred by the luminescent compound. It becomes. Therefore, theoretically, it becomes possible to cause the luminescent compound to emit light using 100% exciton energy, and high luminous efficiency is exhibited.
  • FRET fluorescence resonance energy transfer
  • 1 and 2 are schematic diagrams showing energy diagrams of a compound that expresses a TADF phenomenon (TADF compound) and a general fluorescent compound.
  • TADF compound TADF compound
  • 2CzPN having the structure shown in FIG. 1 HOMO is localized at the 1st and 2nd carbazolyl groups on the benzene ring, and LUMO is localized at the 4th and 5th cyano groups. Therefore, it is possible to separate the HOMO and LUMO of 2CzPN, ⁇ E ST express TADF phenomenon extremely small.
  • 2CzXy FIG.
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is to provide a new ⁇ -conjugated compound that can increase the light emission efficiency without increasing the light emission wavelength.
  • Another object of the present invention is to provide an organic electroluminescent element material containing the ⁇ -conjugated compound, a light-emitting thin film, and a display device and an illumination device provided with the organic electroluminescent element.
  • the present inventor contains a ⁇ -conjugated compound having an electron-donating part at the para-position of the nitrogen-containing aromatic six-membered ring that is an electron-withdrawing part.
  • the present inventors have conceived a new organic electroluminescence device characterized by the above, and found that the light emission efficiency can be improved, thereby reaching the present invention. That is, the said subject which concerns on this invention is solved by the following means.
  • the first of the present invention relates to a ⁇ -conjugated compound.
  • D 1 and D 2 are each independently selected from the group consisting of an aryl group substituted with an electron donating group, an optionally substituted electron donating heterocyclic group, and an optionally substituted amino group.
  • each Z independently represents a hydrogen atom, a deuterium atom, or a substituent.
  • the substituent is the electron donating group D or an alkyl group, or a fluorine atom, a cyano group, an alkyl group substituted with a fluorine atom, an optionally substituted carbonyl group, A sulfonyl group which may be substituted, a phosphine oxide group which may be substituted, a boryl group which may be substituted, an aryl group which may be substituted with an electron-withdrawing group, and an electron-withdrawing complex which may be substituted
  • the ⁇ -conjugated compound according to [1] which is an electron-withdrawing group A selected from the group consisting of a cyclic group.
  • the second aspect of the present invention relates to an organic electroluminescent element material and an organic electroluminescent element using the ⁇ -conjugated compound of the present invention.
  • An organic electroluminescence device material comprising the ⁇ -conjugated compound according to any one of [1] to [6].
  • a light-emitting thin film comprising the ⁇ -conjugated compound according to any one of [1] to [6].
  • the light emitting layer includes the ⁇ -conjugated compound, at least one of a fluorescent light emitting compound and a phosphorescent light emitting compound, and a host material.
  • the third aspect of the present invention relates to a display device and a lighting device using the organic electroluminescence element of the present invention.
  • a display device comprising the organic electroluminescence element according to any one of [9] to [11].
  • An illumination device comprising the organic electroluminescence element according to any one of [9] to [11].
  • the above-described means of the present invention can provide a new ⁇ -conjugated compound that achieves improved luminous efficiency.
  • the ⁇ -conjugated compound can provide an organic electroluminescent element material, a light-emitting thin film containing the organic electroluminescent element material, and a display device and a lighting device including the organic electroluminescent element.
  • an organic electroluminescence device comprising a ⁇ -conjugated compound having an electron donating moiety at the para-position of a nitrogen-containing aromatic six-membered ring, which is an electron-withdrawing moiety, has high luminous efficiency. It was.
  • the electron donating part is disposed away via the electron withdrawing part at the substitution position where the resonance structure can be obtained, It is presumed that the charge separation state can be stabilized with a wide ⁇ conjugate plane.
  • Schematic showing energy diagram of TADF compound Schematic diagram showing the energy diagram of a general fluorescent compound
  • Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram of an active matrix display device
  • Schematic showing the pixel circuit Schematic diagram of a passive matrix display device
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • ⁇ -conjugated compound of the present invention is a compound having a structure represented by the following general formula (1).
  • D 1 and D 2 existing in the para position are electron donating groups D.
  • M 1 to M 4 each independently represents a nitrogen atom or —CZ, and at least one of M 1 to M 4 is a nitrogen atom.
  • the compound of the present invention must have at least one nitrogen atom in the aromatic six-membered ring, but the number of nitrogen atoms is not particularly limited and is any one of 1 to 4.
  • Z is a hydrogen atom, a deuterium atom, or a substituent, preferably an electron donating group D, an alkyl group, or an electron withdrawing group A.
  • the electron donating group D represented by Z in D 1 and D 2 or —C—Z is an “aryl group which may be substituted with an electron donating group” or “an electron donating group which may be substituted”.
  • the “aryl group” of the “aryl group optionally substituted with an electron donating group” represented by D is preferably an aryl group having 6 to 24 carbon atoms.
  • a benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, anthracene ring, biphenylene ring, chrysene ring, pyrene ring, triphenylene ring, chrysene ring, fluoranthene ring, perylene ring, biphenyl ring and terphenyl ring are mentioned.
  • the “electron-donating heterocyclic group” of the “optionally substituted electron-donating heterocyclic group” represented by D is preferably a heterocyclic ring having 4 to 24 carbon atoms.
  • heterocycles include pyrrole ring, indole ring, carbazole ring, azacarbazole ring, diazacarbazole ring, indoloindole ring, 9,10-dihydroacridine ring, 5,10-dihydrophenazacillin ring 10,11-dihydrodibenzazepine ring, phenoxazine ring, phenothiazine ring, dibenzothiophene ring, benzofurylindole ring, benzothienoindole ring, indolocarbazole ring, benzofurylcarbazole ring, benzothienocarbazole ring, benzothienobenzothiophene A ring, a benzo
  • carbazole ring More preferred are carbazole ring, indoloindole ring, 9,10-dihydroacridine ring, phenoxazine ring, phenothiazine ring, dibenzothiophene ring, benzofurylindole ring, and benzocarbazole ring.
  • the above electron donating heterocycles may be combined by linking two or more of the same or different rings.
  • the “electron-donating group” of the “aryl group substituted with an electron-donating group” represented by D includes an alkyl group, an alkoxy group, an optionally substituted amino group, and an optionally substituted electron donor. Sex heterocycles and the like. Preferably, the heterocyclic group of the alkyl group and the electron-donating group which may be substituted is mentioned.
  • alkyl group of the “electron-donating group” in the “aryl group substituted with an electron-donating group” represented by D may be linear, branched, or cyclic. 20 linear, branched, or cyclic alkyl groups, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl, neopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, n-octyl, 2-hexyloctyl, n-nonyl, n-decyl, n-undecyl Group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group,
  • the “alkoxy group” of the “electron-donating group” of the “aryl group substituted with an electron-donating group” represented by D may be linear, branched, or cyclic. 20 linear, branched, or cyclic alkyl groups are mentioned, specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n -Pentyloxy group, neopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyl Oxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetrade
  • the substituent of the “optionally substituted amino group” of the “electron-donating group” of the “aryl group substituted with an electron-donating group” represented by D is an alkyl group or an alkyl group.
  • An aryl ring which may be used is mentioned. Examples of the alkyl group and aryl group include the same ones as described above, and the same ones are preferable.
  • Examples of the substituent of the “optionally substituted electron-donating heterocyclic group” represented by D include an alkyl group, an alkoxy group, an aryl ring which may be substituted with an alkyl group, and an optionally substituted group.
  • An amino group etc. are mentioned, Specifically, the same thing as the above-mentioned is mentioned, The same thing is preferable.
  • Examples of the “electron-donating heterocyclic group that may be substituted” of the “electron-donating group” of the “aryl group substituted with an electron-donating group” represented by D include the same groups as described above. Similar ones are preferred.
  • Examples of the substituent of the “optionally substituted amino group” represented by D include the same as described above, and the same is preferable.
  • Examples of the “alkyl group” represented by Z in —CZ include the same as those described above, and the same is preferable.
  • the electron-withdrawing group A represented by Z in —C—Z represents a “fluorine atom”, “cyano group”, “alkyl group substituted with a fluorine atom”, “optionally substituted carbonyl group”, “ “Optionally substituted sulfonyl group”, “optionally substituted phosphine oxide group”, “optionally substituted boryl group”, “optionally substituted aryl group (preferably an electron-withdrawing group) An optionally substituted aryl group), "or an” optionally withdrawing heterocyclic group ".
  • Examples of the “alkyl group” of the “alkyl group substituted with a fluorine atom” represented by A include the same ones as described above, and the same ones are preferable.
  • Examples of the “aryl group” of the “optionally substituted aryl group” represented by A include the same as those described above, and the same is preferable.
  • heterocyclic group of the “optionally withdrawing heterocyclic group which may be substituted” represented by A
  • a heterocyclic group having 3 to 24 carbon atoms is preferable.
  • heterocyclic groups include dibenzothiophene oxide ring, dibenzothiophene dioxide ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, quinoxaline Ring, phthalazine ring, pteridine ring, phenanthridine ring, phenanthroline ring, dibenzofuran ring, dibenzosilole ring, dibenzoborol ring, dibenzophosphole oxide ring, azadibenzofuran ring, diazadibenzofuran ring and the like.
  • the above heterocyclic group may be a combination of two or more rings that are the same or different.
  • Examples of the substituent of the “electron-withdrawing heterocyclic group which may be substituted” represented by A include a deuterium atom, a fluorine atom, a cyano group, an alkyl group which may be substituted with a fluorine atom, a fluorine atom An aryl ring which may be substituted with an alkyl group which may be substituted with, or an aryl ring which may be substituted with a fluorine atom. Specific examples of the alkyl group and the aryl ring include the same ones as described above, and the same ones are preferable.
  • Examples of the substituent of the “aryl group optionally substituted with an electron-withdrawing group” represented by A include a deuterium atom, a fluorine atom, a cyano group, an alkyl group optionally substituted with a fluorine atom, and a substituted group.
  • the substituent that the aryl group may have is preferably an electron-withdrawing group, and includes a fluorine atom, a cyano group, an alkyl group substituted with a fluorine atom, an optionally substituted carbonyl group, and a substituted group.
  • An alkyl group that is substituted or an electron-withdrawing heterocyclic group that may be substituted is more preferable.
  • Optionally substituted carbonyl group "optionally substituted sulfonyl group”, “optionally substituted phosphine oxide group”, “optionally substituted boryl group” represented by A
  • substituents include a deuterium atom, a fluorine atom, a cyano group, an alkyl group that may be substituted with a fluorine atom, an aryl ring that may be substituted, and an electron-withdrawing heterocyclic ring that may be substituted. It is done. Specific examples include the same ones as described above, and the same ones are preferable.
  • the ⁇ -conjugated compound of the present invention is preferably represented by any one of the following general formulas (2) to (21).
  • D 1 to D 6 each independently represents an electron donating group D.
  • Examples of the electron donating group D include those similar to D 1 to D 2 in the general formula (1), and the same is preferable.
  • Z 1 to Z 4 each independently represents a hydrogen atom, a deuterium atom, an alkyl group, or the electron-withdrawing group A.
  • the electron-withdrawing group A is an electron-withdrawing group A that can be used as Z in the general formula (1), that is, a fluorine atom, a cyano group, an alkyl group substituted with a fluorine atom, an optionally substituted carbonyl group, A sulfonyl group that may be substituted, a phosphine oxide group that may be substituted, a boryl group that may be substituted, an aryl group that may be substituted with an electron-withdrawing group, or an electron that may be substituted It is an attractive heterocyclic group.
  • an “alkyl group” represented by Z 1 to Z 4 “an alkyl group substituted with a fluorine atom”, “an optionally substituted carbonyl group”, “substituted”
  • Examples of the “optionally substituted sulfonyl group”, “optionally substituted phosphine oxide group”, and “optionally substituted boryl group” include those described above, and the same are preferable.
  • examples of the “aryl group” of the “aryl group optionally substituted with an electron-withdrawing group” represented by Z 1 to Z 4 include the same as those described above. Similar ones are preferred.
  • the “electron-withdrawing heterocyclic group” of the “optionally substituted electron-withdrawing heterocyclic group” represented by Z 1 to Z 4 is as described above. The same thing is mentioned, The same thing is preferable.
  • examples of the substituent of the “optionally withdrawing heterocyclic group which may be substituted” represented by Z 1 to Z 4 include a deuterium atom, a fluorine atom, and a cyano group.
  • the “electron withdrawing group” of the “aryl ring optionally substituted with an electron withdrawing group” represented by Z 1 to Z 4 includes a fluorine atom, a cyano group , An alkyl group substituted with a fluorine atom, an optionally substituted carbonyl group, an optionally substituted sulfonyl group, an optionally substituted phosphine oxide group, an optionally substituted boryl group, a substituted Represents an electron-withdrawing heterocyclic ring, and preferably includes a fluorine atom, a cyano group, an alkyl group which may be substituted with a fluorine atom, or an optionally substituted electron-withdrawing heterocyclic ring.
  • the “electron withdrawing group” of the “aryl group optionally substituted with an electron withdrawing group” represented by A 1 to A 4 is substituted with a fluorine atom.
  • Examples of the “optionally withdrawing electron-withdrawing heterocyclic group” include the same groups as described above, and the same groups are preferable.
  • the absolute value ( ⁇ E ST ) of the energy difference between the lowest excited singlet level and the lowest excited triplet level of the ⁇ -conjugated compound is It is preferable that it is 0.50 eV or less, and it is preferable to contain in the said organic electroluminescent element, the said element material, or the said luminescent thin film.
  • ⁇ -conjugated compounds according to the present invention are shown below. However, these compounds may further have a substituent or may have a structural isomer, and are limited to this description. Not.
  • the absolute value of Delta] E ST of these compounds are for the following material 0.50EV, may exhibit TADF properties.
  • the present invention is not limited to use in a light emitting layer, and may be used for the above-described hole injection layer, hole transport layer, electron blocking layer, hole blocking layer, electron transport layer, electron injection layer, intermediate layer, and the like. .
  • the ⁇ -conjugated compound having the structure represented by the general formula (1) can be used as an organic electroluminescence (EL) element material containing the ⁇ -conjugated compound.
  • EL organic electroluminescence
  • Organic EL emission methods There are two types of organic EL emission methods: “phosphorescence emission” that emits light when returning from the triplet excited state to the ground state, and “fluorescence emission” that emits light when returning from the singlet excited state to the ground state. is there.
  • TTA triplet-triplet annihilation
  • the rate constant is usually small. That is, since the transition is difficult to occur, the exciton lifetime is increased from millisecond to second order, and it is difficult to obtain desired light emission.
  • a rare metal such as iridium, palladium, or platinum, which is a rare metal.
  • the price of the metal itself is a major industrial issue.
  • a general fluorescent compound is not necessarily a heavy metal complex like a phosphorescent compound, and is a so-called organic compound composed of a combination of general elements such as carbon, oxygen, nitrogen and hydrogen.
  • other non-metallic elements such as phosphorus, sulfur, and silicon can be used, and complexes of typical metals such as aluminum and zinc can be used.
  • TTA triplet-triplet annihilation
  • Thermal activated delayed fluorescence (TADF) compound is a method that can solve the problems of TTA.
  • Fluorescent compounds have the advantage of infinite molecular design as described above. That is, among the molecularly designed compounds, there are compounds in which the energy level difference between the triplet excited state and the singlet excited state is extremely close.
  • HOMO is distributed in electron donating sites and LUMO is distributed in electron withdrawing sites in the electron orbit of the molecule.
  • LUMO is distributed in electron withdrawing sites in the electron orbit of the molecule.
  • Rigidity described here means that there are few sites that can move freely in the molecule, for example, by suppressing free rotation in the bond between the rings in the molecule or by introducing a condensed ring with a large ⁇ conjugate plane. means.
  • TADF compounds have various problems in terms of their light emission mechanism and molecular structure. The following describes some of the problems generally associated with TADF compounds.
  • stabilization is achieved by bringing the donor part of one molecule and the acceptor part of the other molecule close to each other.
  • a stabilization state is not limited to the formation between two molecules, but can also be formed between a plurality of molecules such as three or five molecules.
  • various stabilization states with a wide distribution are obtained.
  • the shape of the absorption spectrum and emission spectrum becomes broad.
  • various existence states can be taken depending on the direction and angle of interaction between the two molecules.
  • the shape of the emission spectrum becomes broad.
  • the broad emission spectrum causes two major problems.
  • One problem is that the color purity of the emitted color is lowered. This is not a big problem when applied to lighting applications, but when used for electronic displays, the color gamut is small and the color reproducibility of pure colors is low. It becomes difficult.
  • fluorescence 0-0 band the rising wavelength on the short wavelength side of the emission spectrum (referred to as “fluorescence 0-0 band”) is shortened, that is, the S 1 is increased (the lowest excited singlet energy level is increased). It is to do.
  • the compound used for the host compound needs to have a high S 1 level and a high T 1 level in order to prevent reverse energy transfer from the dopant.
  • a host compound consisting essentially of an organic compound takes a plurality of active and unstable chemical species such as a cation radical state, an anion radical state, and an excited state in an organic EL device.
  • active and unstable chemical species such as a cation radical state, an anion radical state, and an excited state in an organic EL device.
  • a transition that is deactivated from a triplet excited state to a ground state is a forbidden transition, and therefore the existence time (exciton lifetime) in the triplet excited state is from several hundred microseconds to millisecond. It is very long with second order. For this reason, even if the T 1 energy level of the host compound is higher than that of the fluorescent compound, the triplet excited state of the fluorescent compound from the triplet excited state to the host compound is determined from the length of the existence time. The probability of causing reverse energy transfer increases.
  • HOMO and LUMO are substantially separated in the molecule.
  • the distribution states of these HOMO and LUMO can be obtained from the electron density distribution when the structure is optimized by molecular orbital calculation.
  • structure optimization and calculation of electron density distribution by molecular orbital calculation of ⁇ -conjugated compounds in the present invention are performed using molecular orbital calculation software using B3LYP as a functional and 6-31G (d) as a basis function as a calculation method.
  • B3LYP molecular orbital calculation software
  • 6-31G (d) 6-31G
  • Gaussian 09 (Revision C.01, MJ Frisch, et al, Gaussian, Inc., 2010.) manufactured by Gaussian, USA was used as molecular orbital calculation software.
  • HOMO and LUMO are substantially separated means that the HOMO orbital distribution calculated by the above molecular calculation and the central part of the LUMO orbital distribution are separated, more preferably the HOMO orbital distribution and the LUMO orbital. This means that the distributions of do not overlap.
  • the time-dependent density functional method (Time-Dependent DFT) is used.
  • Delta] E ST is small, indicating that the HOMO and LUMO are more separated.
  • the lowest excited singlet energy level S 1 of the ⁇ -conjugated compound in the present invention is defined in the present invention as calculated in the same manner as in a normal method. That is, a sample to be measured is deposited on a quartz substrate to prepare a sample, and the absorption spectrum (vertical axis: absorbance, horizontal axis: wavelength) of this sample is measured at room temperature (300 K). A tangent line is drawn with respect to the rising edge of the absorption spectrum on the long wavelength side, and is calculated from a predetermined conversion formula based on the wavelength value at the intersection of the tangent line and the horizontal axis.
  • the molecules themselves of the ⁇ -conjugated compound used in the present invention have a relatively high aggregation property, an error due to aggregation may occur in the measurement of the thin film.
  • the lowest excited singlet energy level S 1 in the present invention is room temperature (25 ° C.
  • the peak value of the maximum emission wavelength in the solution state of the ⁇ -conjugated compound in (1) was used as an approximate value.
  • a solvent which does not affect the aggregation state of the ⁇ -conjugated compound that is, a solvent having a small influence of the solvent effect, for example, a nonpolar solvent such as cyclohexane or toluene can be used.
  • the lowest excited triplet energy level (T 1 ) of the ⁇ -conjugated compound used in the present invention was calculated from the photoluminescence (PL) characteristics of the solution or thin film.
  • PL photoluminescence
  • the transient PL characteristics are measured to separate the fluorescent component and the phosphorescent component, the absolute value of the energy difference can be determined the lowest excited triplet energy level of the lowest excited singlet energy level as Delta] E ST.
  • an absolute PL quantum yield measurement apparatus C9920-02 manufactured by Hamamatsu Photonics
  • the light emission lifetime was measured using a streak camera C4334 (manufactured by Hamamatsu Photonics) while exciting the sample with laser light.
  • Organic EL Element is an organic electroluminescence element having at least a light emitting layer between an anode and a cathode, and at least one layer of the light emitting layer is represented by the general formula (1). It contains a ⁇ -conjugated compound having
  • the light emitting layer used in 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.
  • the layer excluding the anode and the cathode is also referred to as “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.
  • first light emitting unit, the second light emitting unit, and the third light emitting unit may all be the same or different.
  • Two light emitting units may be the same, and the remaining one may be different.
  • 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.
  • a known material structure can be used as long as it is also called an insulating layer and has 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, CuAlO 2 , Conductive inorganic compound layers such as CuGaO 2 , SrCu 2 O 2 , LaB 6 , RuO 2 and Al, two-layer films such as Au / Bi 2 O 3 , SnO 2 / Ag / SnO 2 , ZnO / Ag / ZnO , Bi 2 O 3 / Au / Bi 2 O 3 , TiO 2 / TiN / TiO 2 , TiO 2 / ZrN / TiO 2 and other multilayer films, C 60 and other fullerenes, conductive organic layers such as oligothiophene, Examples include conductive organic compound layers such as metal phthalocyanines, metal-free phthalocyanines, metal porphyrins, metal-free
  • Preferred examples of the configuration within the light emitting unit include, for example, those obtained by removing the anode and the cathode from the configurations (1) to (7) mentioned in the above representative device configurations. It is not limited.
  • tandem organic EL element examples 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, US Pat. No. 6,337,492, International JP 2005/009087, JP 2006-228712, JP 2006-24791, JP 2006-49393, JP 2006-49394, JP 2006-49396, JP 2011. No. -96679, JP 2005-340187, JP 47114424, JP 34966681, JP 3884564, JP 4213169, JP 2010-192719, JP 2009-076929, JP Open 2008-078 No. 14, JP 2007-059848 A, JP 2003-272860 A, JP 2003-045676 A, International Publication No. 2005/094130, and the like.
  • the present invention is not limited to these.
  • the light-emitting layer used in 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 the light-emitting layer. Even in the layer, it may be the interface between the light emitting layer and the adjacent layer. If the light emitting layer used for this invention satisfy
  • the total thickness of the light emitting layer is not particularly limited, but it prevents the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color against the drive current. From the viewpoint, 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.
  • each light emitting layer used in the present invention 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 in a range of 3 to 150 nm. Adjusted.
  • the light emitting layer used in the present invention may be a single layer or a plurality of layers.
  • the ⁇ -conjugated compound of the present application may be used alone or in combination with a host material, a fluorescent light emitting material, a phosphorescent light emitting material, etc. described later.
  • At least one layer of the light emitting layer contains a light emitting dopant (a light emitting compound, a light emitting dopant, also simply referred to as a dopant), and further contains a host compound (a matrix material, a light emitting host compound, also simply referred to as a host). preferable.
  • At least one layer of the light-emitting layer contains the ⁇ -conjugated compound of the present application and a host compound because luminous efficiency is improved. It is preferable that at least one layer of the light-emitting layer contains the ⁇ -conjugated compound of the present application and at least one of a fluorescent compound and a phosphorescent compound because luminous efficiency is improved. It is preferable that at least one layer of the light emitting layer contains the present ⁇ -conjugated compound, at least one of a fluorescent light emitting compound and a phosphorescent light emitting compound, and a host compound because the light emission efficiency is improved.
  • the luminescent dopant As the luminescent dopant, a fluorescent luminescent dopant (also referred to as a fluorescent luminescent compound or a fluorescent dopant) and a phosphorescent dopant (also referred to as a phosphorescent luminescent compound or a phosphorescent dopant) are used. Preferably used.
  • the light-emitting layer contains the ⁇ -conjugated compound according to the present invention as a fluorescent light-emitting compound or an assist dopant in a range of 0.1 to 50% by mass, particularly in a range of 1 to 30% by mass. It is preferable to contain within.
  • the light emitting layer preferably contains the light emitting compound in the range of 0.1 to 50% by mass, and particularly preferably in the range of 1 to 30% by mass.
  • the concentration of the light-emitting compound in the light-emitting layer can be arbitrarily determined based on the specific light-emitting compound used and the requirements of the device, and is uniform in the thickness direction of the light-emitting layer. It may be contained and may have any concentration distribution.
  • the luminescent compound used in the present invention may be used in combination of two or more kinds, a combination of fluorescent luminescent compounds having different structures, or a combination of a fluorescent luminescent compound and a phosphorescent luminescent compound. May be. Thereby, arbitrary luminescent colors can be obtained.
  • the absolute value ( ⁇ E ST ) of the difference between the lowest excited singlet energy level and the lowest excited triplet energy level is 0.50 eV or less, a ⁇ -conjugated compound according to the present invention, a luminescent compound, and a host compound.
  • the ⁇ -conjugated compound according to the present invention acts as an assist dopant.
  • the ⁇ -conjugated compound according to the present invention acts as a host compound.
  • the ⁇ -conjugated compound according to the present invention acts as a host compound / light-emitting compound.
  • the mechanism for producing the effect is the same in any case, and the triplet exciton generated on the ⁇ -conjugated compound according to the present invention is converted into a singlet exciton by reverse intersystem crossing (RISC). It is in.
  • RISC reverse intersystem crossing
  • the energy levels of S 1 and T 1 of the ⁇ -conjugated compound are S of the host compound. 1 and T 1 of the lower than the energy level, it is preferably higher than the energy level of the S 1 and T 1 of the light-emitting compound.
  • light emitting layer the energy level of the S 1 and T 1 of the case containing the two components of the light emitting compound and [pi conjugated compound according to the present invention, [pi-conjugated compounds, S 1 luminescent compound higher than the energy level of T 1 and is preferable.
  • FIG. 3 and FIG. 4 show schematic diagrams when the ⁇ -conjugated compound of the present invention acts as an assist dopant and a host compound, respectively.
  • 3 and 4 are examples, and the generation process of the triplet exciton generated on the ⁇ -conjugated compound according to the present invention is not limited to the electric field excitation, and the energy transfer from the light emitting layer or the peripheral layer interface. And electronic transfer.
  • a fluorescent compound is used as a light-emitting material, but the present invention is not limited to this, and a phosphorescent compound may be used, or a fluorescent compound and a phosphorescent compound may be used. Both of the functional compounds may be used.
  • the light-emitting layer contains a host compound in a mass ratio of 100% or more with respect to the ⁇ -conjugated compound, and the fluorescent compound and / or phosphorescent compound. Is preferably contained within a range of 0.1 to 50% by mass with respect to the ⁇ -conjugated compound.
  • the light emitting layer has a mass ratio of 0.1 to 50% of the fluorescent compound and / or phosphorescent compound with respect to the ⁇ -conjugated compound. It is preferable to contain.
  • the emission spectrum of the ⁇ -conjugated compound according to the present invention and the absorption spectrum of the luminescent compound preferably overlap.
  • 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. 3.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a luminance meter CS-1000 (manufactured by Konica Minolta Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • one or a plurality of light-emitting layers contain a plurality of light-emitting dopants having different emission colors and emit white light.
  • fluorescent luminescent dopant the ⁇ -conjugated compound of the present invention may be used, or a known fluorescent dopant or delayed fluorescence used in the light emitting layer of the organic EL device. You may use it, selecting suitably from sex dopant.
  • the phosphorescent dopant used in the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and a phosphorescence quantum yield. Is defined as a compound of 0.01 or more at 25 ° C., but a preferable phosphorescence quantum yield is 0.1 or more.
  • the phosphorescent 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 used in the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. Just do it.
  • the phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL element. Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents.
  • a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond is preferable.
  • 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.
  • the host compound preferably has a mass ratio in the layer of 20% or more among the compounds contained in the light emitting layer.
  • the host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the efficiency of the organic electroluminescence element can be improved.
  • the ⁇ -conjugated compound used in the present invention may be used as described above, but there is no particular limitation. From the viewpoint of reverse energy transfer, those having an excitation energy larger than the excitation singlet energy of the dopant are preferred, and those having an excitation triplet energy larger than the excitation triplet energy of the dopant are more preferred.
  • the host compound is responsible for carrier transport and exciton generation in the light emitting layer. Therefore, it can exist stably in all active species states such as cation radical state, anion radical state, and excited state, and does not cause chemical changes such as decomposition and addition reaction. It is preferable not to move at the angstrom level.
  • the existence time of the triplet excited state of the TADF compound is long, so that the T 1 energy level of the host compound itself is high, and the host compounds are associated with each other.
  • Molecules in which the host compound does not decrease in T 1 such as not forming a low T 1 state in the state, TADF compound and the host compound do not form an exciplex, or the host compound does not form an electromer due to an electric field. Appropriate design of the structure is required.
  • the host compound itself must have high electron hopping mobility, high hole hopping movement, and small structural change when it is in a triplet excited state. It is.
  • Preferred examples of host compounds that satisfy such requirements include those having a high T 1 energy level such as a carbazole skeleton, an azacarbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, or an azadibenzofuran skeleton.
  • the host compound has a hole transporting ability or an electron transporting ability, prevents the emission of light from becoming longer, and further stabilizes the organic electroluminescence device against heat generation during high temperature driving or during device driving. From the viewpoint of operating, it is preferable to have a high glass transition temperature (Tg). Tg is preferably 90 ° C. or higher, more preferably 120 ° C. or higher.
  • the glass transition point (Tg) is a value determined by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).
  • the host compound used in the present invention it is also preferable to use the ⁇ -conjugated compound according to the present invention as described above.
  • the ⁇ -conjugated compound according to the present invention has a high T 1 and can be suitably used for a light-emitting material having a short emission wavelength (that is, a high energy level of T 1 and S 1 ). It is.
  • 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 according to 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 total thickness of the electron transport layer between several nanometers and several micrometers.
  • the electron mobility of the electron transport layer is preferably 10 ⁇ 5 cm 2 / Vs or more.
  • the material used for the electron transport layer may be any of electron injecting or transporting properties and hole blocking properties, and can be selected from conventionally known compounds. 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, Dibenzothiophene derivatives, silole derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene derivatives, etc.) It is.
  • 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 transporting material.
  • the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials as a polymer main chain can 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 known electron transport materials in the present invention include aromatic heterocyclic compounds containing at least one nitrogen atom and compounds containing a phosphorus atom.
  • aromatic heterocyclic compounds containing at least one nitrogen atom include aromatic heterocyclic compounds containing at least one nitrogen atom and compounds containing a phosphorus atom.
  • the electron transport material may be used alone or in combination of two or more.
  • the hole blocking layer is a layer having a function of an electron transport layer in a broad sense, and is preferably made of a material having a function of transporting electrons while having a small ability to transport holes, and transporting electrons while transporting holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the structure of the electron transport layer described above can be used as a hole blocking layer according to the present invention, if necessary.
  • 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 according to 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 As 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”) according to 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. It is described in detail in Chapter 2 “Electrode Materials” (pages 123 to 166) of the second edition of “The Forefront of Industrialization (issued 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 layer (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 8-hydroxyquinolinate lithium (Liq), and the like. Further, the above-described electron transport material can also be used.
  • the materials used for the electron injection layer may be used alone or in combination of two or more.
  • 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 according to 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.
  • a material used for the hole transport layer (hereinafter referred to as a hole transport material), any material that has either a hole injection property or a transport property or an electron barrier property may be used. 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
  • Triarylamine derivatives include benzidine type typified by ⁇ -NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), starburst type typified by MTDATA, Examples include compounds having fluorene or anthracene in the triarylamine-linked core.
  • hexaazatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.
  • 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. It is also possible to use so-called p-type hole transport materials and inorganic compounds such as p-type-Si and p-type-SiC, as described in the literature (Applied Physics Letters 80 (2002), p. 139). Further, ortho-metalated organometallic complexes having Ir or Pt as the central metal represented 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.
  • the hole transport material may be used alone or in combination of two or more.
  • 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.
  • the above-described configuration of the hole transport layer can be used as an electron blocking layer according to the present invention, if necessary.
  • 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 layer thickness of the electron blocking layer according to the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
  • the material used for the electron blocking layer As the material used for the electron blocking layer, the material used for the above-described hole transport layer is preferably used, and the above-mentioned host compound is also preferably used for the electron blocking layer.
  • the hole injection layer (also referred to as “anode buffer layer”) according to the present invention is a layer provided between the anode and the light emitting layer for the purpose of lowering the driving voltage and improving the light emission luminance. It is described in detail in Volume 2, Chapter 2, “Electrode Materials” (pages 123 to 166) of “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, 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 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 can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, and further preferably 50 ppm or less with respect to the total mass% of the contained layer. .
  • the formation method of the organic layer according to the present invention is not particularly limited, and a conventionally known formation method such as a vacuum deposition method or a wet method (also referred to as a wet process) can be used.
  • wet method examples 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). From the viewpoint of obtaining a homogeneous thin film easily and high productivity, a method with high roll-to-roll method suitability such as a die coating method, a roll coating method, an ink jet method and a spray coating method is preferable.
  • liquid medium for dissolving or dispersing the organic EL material used in 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, Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • fatty acid esters such as ethyl acetate
  • halogenated hydrocarbons such as dichlorobenzene, toluene, xylene
  • Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene
  • a dispersion method it can be dispersed by a dispersion method such as ultrasonic wave, high shearing force dispersion or media dispersion.
  • 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 the range of 50 nm / second, substrate temperature ⁇ 50 to 300 ° C., layer (film) thickness 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the organic layer according to the present invention it is preferable to consistently produce from the hole injection layer to the cathode by one evacuation, but it may be taken out halfway and subjected to different film forming 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.
  • electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • the anode may be formed by depositing a thin film of these electrode materials by vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • a wet film forming method such as a printing method or a coating method can 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 within the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • cathode As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, 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 than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is improved, which is convenient.
  • 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 or a substrate) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic and the like, and is transparent or opaque. May be.
  • the support substrate is preferably transparent.
  • 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 polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by J
  • the surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
  • Relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / m 2 ⁇ 24 h or less, and further, oxygen permeability measured by a method according to JIS K 7126-1987.
  • it is preferably a high-barrier film having 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / m 2 ⁇ 24 h or less.
  • the material for forming the barrier film may be any material that has a function of suppressing the 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 barrier film is not particularly limited.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the external extraction quantum efficiency at room temperature (25 ° C.) of light emission of the organic EL device of the present invention is preferably 1% or more, and more preferably 5% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • 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.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the 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 or less, and measured by a method according to JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2%) is preferably 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
  • the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
  • the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • 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 EL element emits light inside a layer having a refractive index higher than that of air (within a refractive index of about 1.6 to 2.1), and is about 15% to 20% of light generated in the light emitting layer. It is generally said that it can only be taken out. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side surface of the device.
  • 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.
  • the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
  • the low refractive index layer examples include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally 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 diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any layer or in the medium (in the transparent substrate or 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 is front-facing to a specific direction, for example, the light emitting surface of the device by combining a so-called condensing sheet, for example, by providing a structure on the microlens array on the light extraction side of the support substrate (substrate). By condensing in the direction, the luminance in a specific direction can be increased.
  • a quadrangular pyramid having a side of 30 ⁇ m and an apex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably within a range of 10 to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the condensing sheet it is possible to use, for example, an LED backlight of a liquid crystal display device that has been put into practical use.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • the shape of the prism sheet for example, the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the organic EL element of the present invention can be used as an electronic device such as a display device, a display, and various light emitting devices.
  • Examples of light emitting devices include lighting devices (home lighting, interior lighting), clocks and backlights for liquid crystals, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary.
  • patterning only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned.
  • a conventionally known method is used. Can do.
  • the display device including the organic EL element of the present invention may be either 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 or printing.
  • the method is not limited, but a vapor deposition method, an ink jet method, a spin coating method, and a printing method are preferable.
  • the configuration of the organic EL element included in the display device is selected from the above-described configuration examples of the organic EL element as necessary.
  • the manufacturing method of an organic EL element is as having shown in the one aspect
  • a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, or 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.
  • Examples of the display device or display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in a car.
  • the display device or display may be used as a display device for reproducing still images and moving images
  • the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light-emitting devices include household lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, optical storage media light sources, electrophotographic copying machine light sources, optical communication processor light sources, optical sensor light sources, etc.
  • the present invention is not limited to these.
  • FIG. 5 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. 6 is a schematic diagram of a display device using an active matrix method.
  • the display unit A has 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. 6 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated Not)
  • the pixel 3 When the scanning signal is applied from the scanning line 5, the pixel 3 receives the image data signal from the data line 6 and emits light according to the received image data.
  • a full color display can be achieved by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 7 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 When the scanning signal moves to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, since the capacitor 13 holds the charged potential of the image data signal even if 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 When the scanning signal is next applied by sequential scanning, 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.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 8 is a schematic diagram of a passive matrix display device.
  • a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
  • the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.
  • a display device with improved luminous efficiency was obtained by using the organic EL element of the present invention.
  • the organic EL element of the present invention can also be used for a lighting device.
  • the organic EL element of the present invention may be used as an organic EL element having a resonator structure.
  • Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.
  • the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a display device (display).
  • the drive method when used as a display device for moving image reproduction may be either a passive matrix method or an active matrix method.
  • the ⁇ -conjugated compound used in the present invention can be applied to a lighting device including an organic EL element that emits substantially white light.
  • white light emission can be obtained by simultaneously emitting a plurality of light emission colors and mixing the colors.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of three primary colors of red, green, and blue, or two of the complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
  • the organic EL device forming method of the present invention may be simply arranged by providing a mask only when forming a light emitting layer, a hole transporting layer, an electron transporting layer, etc. Since the other layers are common, patterning of a mask or the like is unnecessary, and for example, an electrode film can be formed on one surface by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is improved.
  • 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 FIG. 9 and FIG. A device can be formed.
  • LUX epoxy photocurable adhesive
  • FIG. 9 shows a schematic diagram of a lighting device, and the organic EL element (organic EL element 101 in the lighting device) of the present invention is covered with a glass cover 102 (note that the sealing operation with the glass cover is performed by lighting. This was performed in a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) without bringing the organic EL element 101 in the apparatus into contact with the air.
  • a nitrogen atmosphere in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more
  • FIG. 10 is a cross-sectional view of the lighting device, 105 is a cathode, 106 is an organic layer, and 107 is 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.
  • an illumination device with improved luminous efficiency can be obtained.
  • the light-emitting thin film according to the present invention contains the above-described ⁇ -conjugated compound according to the present invention, and can be produced in the same manner as the method for forming the organic layer.
  • the light-emitting thin film and the present invention can be produced in the same manner as the organic layer forming method.
  • the method for forming the light-emitting thin film of the present invention is not particularly limited, and conventionally known methods such as a vacuum deposition method and a wet method (also referred to as a wet process) can be used.
  • wet method examples 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). From the viewpoint of obtaining a homogeneous thin film easily and high productivity, a method with high roll-to-roll method suitability such as a die coating method, a roll coating method, an ink jet method and a spray coating method is preferable.
  • liquid medium for dissolving or dispersing the light emitting material used in 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, and 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 be dispersed by a dispersion method such as ultrasonic wave, high shearing force dispersion or media dispersion.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is in the range of 10 ⁇ 6 to 10 ⁇ 2 Pa.
  • the deposition rate is within the range of 0.01 to 50 nm / second
  • the substrate temperature is within the range of ⁇ 50 to 300 ° C.
  • the layer thickness is within the range of 0.1 to 5 ⁇ m, and preferably within the range of 5 to 200 nm. desirable.
  • the spin coat method when adopted for film formation, it is preferable to perform the spin coater within a range of 100 to 1000 rpm and within a range of 10 to 120 seconds in a dry inert gas atmosphere.
  • Example 1 (Preparation of organic EL device 1-1) A transparent substrate with an ITO (Indium Tin Oxide) film having a thickness of 150 nm formed on a glass substrate of 50 mm ⁇ 50 mm and a thickness of 0.7 mm, patterned, and this ITO transparent electrode was attached 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 vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • ITO Indium Tin Oxide
  • the deposition crucible containing HI-1 (1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile) is energized and heated to deposit Vapor deposition was performed on the ITO transparent electrode at a speed of 0.1 nm / second to form a hole injection transport layer having a layer thickness of 10 nm.
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • the hole transport layer was formed.
  • the host compound mCP (1,3-bis (N-carbazolyl) benzene) and the comparative compound 1 were co-deposited at a deposition rate of 0.1 nm / second so as to be 94% and 6% by volume, respectively, and the layer thickness was 30 nm.
  • the light emitting layer was formed.
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • lithium fluoride with a film thickness of 0.5 nm
  • 100 nm of aluminum was vapor-deposited to form a cathode.
  • the non-light-emitting surface side of the above element was covered with a can-shaped glass case in an atmosphere of high purity nitrogen gas having a purity of 99.999% or more, and an electrode lead-out wiring was installed to prepare an organic EL element 1-1.
  • Organic EL devices 1-2 to 1-16 were produced in the same manner as the organic EL device 1-1 except that the light emitting compound was changed from the comparative compound 1 as shown in Table 1.
  • the organic EL elements 1-4 to 1-16 containing the light emitting material of the present invention as the light emitting material exhibit higher emission luminance than the organic EL elements 1-1, 1-2, and 1-3 containing the comparative compound.
  • Particularly Delta] E ST the following compounds 0.50EV, compared with comparative compounds 3 Delta] E ST exceeds 0.50EV, it can be seen that a high luminous efficiency.
  • Example 2 (Preparation of organic EL element 2-1) Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • polystyrene sulfonate PEDOT / PSS, Bayer, Baytron P Al 4083
  • PEDOT / PSS polystyrene sulfonate
  • a thin film was formed by spin coating under conditions of 30 seconds, and then dried at 200 ° C. for 1 hour to provide a hole injection layer having a layer thickness of 20 nm.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, and each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with a constituent material of each layer in an amount optimal for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • ⁇ -NPD was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to form a hole transport layer having a layer thickness of 40 nm.
  • CDBP as the host material
  • 2,5,8,11-tetra-t-butylperylene as the light-emitting material were simultaneously used at a deposition rate of 0.1 nm / second so as to be 97% and 3% by volume, respectively.
  • Evaporation was performed to form a light emitting layer with a layer thickness of 30 nm.
  • TPBi (1,3,5-tris (N-phenylbenzimidazol-2-yl)
  • TPBi 1,3,5-tris (N-phenylbenzimidazol-2-yl)
  • 100 nm of aluminum was vapor-deposited to form a cathode.
  • the non-light-emitting surface side of the above element was covered with a can-shaped glass case in an atmosphere of high purity nitrogen gas having a purity of 99.999% or more, and an electrode lead-out wiring was installed to produce an organic EL element 2-1.
  • organic EL element 2-2 (Preparation of organic EL element 2-2) Using CDBP as the host compound, 2,5,8,11-tetra-t-butylperylene as the luminescent compound, and comparative compound 1 as the third component, the respective proportions were 82%, 3%, and 15% by volume.
  • An organic EL device 2-2 was manufactured in the same manner as the organic EL device 2-1, except that the light emitting layer was formed.
  • organic EL elements 2-3 to 2-8 were produced in the same manner as the organic EL element 2-2 except that the third component was changed.
  • Organic EL elements 2-5 to 2-8 containing the light-emitting material of the present invention as the third component include organic EL elements 2-1 not containing the third component, and organic EL elements 2-2, 2 containing a comparative compound. It can be seen that the emission luminance is higher than -3 and 2-4. Particularly Delta] E ST the following compounds 0.50EV, compared with comparative compounds 3 Delta] E ST exceeds 0.50EV, it can be seen that a high luminous efficiency.
  • Example 3 Preparation of organic EL element 3-1
  • a transparent substrate with an ITO (Indium Tin Oxide) film formed at a thickness of 150 nm as a positive electrode 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
  • this transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.
  • Each of the resistance heating boats for vapor deposition in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an optimum amount for device fabrication.
  • the resistance heating boat was made of molybdenum or tungsten.
  • the resistance heating boat containing HI-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.
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • a resistance heating boat containing Comparative Compound 1 as a host material and GD-1 as a light emitting material is energized and heated.
  • On the hole transport layer at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively.
  • a light emitting layer having a layer thickness of 40 nm was formed by co-evaporation.
  • HB-1 was deposited at a deposition rate of 0.1 nm / second to form a first electron transport layer having a layer thickness of 5 nm.
  • ET-1 was deposited at a deposition rate of 0.1 nm / second to form a second electron transport layer having a layer thickness of 45 nm.
  • lithium fluoride was vapor-deposited to a thickness of 0.5 nm, and then 100 nm of aluminum was vapor-deposited to form a cathode, thereby producing an organic EL element 3-1.
  • Organic EL elements 3-2 to 3-9 were produced in the same manner as the organic EL element 3-1, except that the host material was changed as shown in Table 3.
  • Organic EL devices 3-4 to 3-9 containing the light emitting material of the present invention as a host material exhibit higher emission luminance than organic EL devices 3-1, 3-2 and 3-3 containing a comparative compound.
  • Particularly Delta] E ST the following compounds 0.50EV, compared with comparative compounds 3 Delta] E ST exceeds 0.50EV, it can be seen that a high luminous efficiency.
  • the present invention it is possible to provide a luminescent material capable of improving luminous efficiency without increasing the emission wavelength.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Non-Portable Lighting Devices Or Systems Thereof (AREA)
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Abstract

La présente invention concerne un composé pi-conjugué qui augmente l'efficacité d'émission de lumière sans augmenter la longueur d'onde d'émission de lumière. Ce composé pi-conjugué est un composé ayant une structure indiquée par la formule générale (1). (Dans la formule générale (1) : D1 et D2 représentent chacun indépendamment un groupe donneur d'électrons D choisi dans le groupe constitué d'un groupe aryle substitué par un groupe donneur d'électrons, un groupe hétérocyclique donneur d'électrons pouvant être substitué, et un groupe amino pouvant être substitué; M1-M4 représentent chacun indépendamment un atome d'azote ou -C-Z; au moins l'un parmi M1-M4 est un atome d'azote; et si l'un de M1-M4 est -C-Z, chaque Z indique indépendamment un atome d'hydrogène, un atome de deutérium, ou un groupe pouvant être substitué.)
PCT/JP2016/062426 2015-05-08 2016-04-19 Composé pi-conjugué, matériau pour élément à électroluminescence organique, film mince électroluminescent, élément à électroluminescence organique, dispositif d'affichage et dispositif d'éclairage WO2016181772A1 (fr)

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