WO2022107798A1 - 有機エレクトロルミネッセンス素子、発光組成物の設計方法およびプログラム - Google Patents

有機エレクトロルミネッセンス素子、発光組成物の設計方法およびプログラム Download PDF

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WO2022107798A1
WO2022107798A1 PCT/JP2021/042205 JP2021042205W WO2022107798A1 WO 2022107798 A1 WO2022107798 A1 WO 2022107798A1 JP 2021042205 W JP2021042205 W JP 2021042205W WO 2022107798 A1 WO2022107798 A1 WO 2022107798A1
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organic compound
group
organic
compound
light emitting
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French (fr)
Japanese (ja)
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イティン リ
正樹 田中
展耀 陳
陽一 ▲土▼屋
一 中野谷
千波矢 安達
雄 稲田
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Kyulux Inc
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Kyulux Inc
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Priority to US18/252,740 priority Critical patent/US20240023437A1/en
Priority to KR1020237016481A priority patent/KR20230109633A/ko
Priority to CN202180076547.8A priority patent/CN116458278A/zh
Priority to JP2022563793A priority patent/JP7840571B2/ja
Publication of WO2022107798A1 publication Critical patent/WO2022107798A1/ja
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Definitions

  • the present invention relates to an organic electroluminescence device having a characteristic in a light emitting layer, a method for designing a light emitting composition, and a program.
  • organic electroluminescence elements organic electroluminescence elements
  • various measures have been taken to improve the luminous efficiency by newly developing and combining electron transport materials, hole transport materials, light emitting materials and the like constituting organic electroluminescence devices.
  • research on organic electroluminescence devices using delayed fluorescent materials can be seen.
  • the delayed fluorescence material is a material that emits fluorescence when returning from the excited singlet state to the ground state after an intersystem crossing from the excited triplet state to the excited singlet state occurs in the excited state. Fluorescence by such a pathway is called delayed fluorescence because it is observed later than the fluorescence from the excited singlet state directly generated from the ground state (normal fluorescence).
  • the probability of occurrence of the excited singlet state and the excited triplet state is statistically 25%: 75%, so that the excited singlet state directly generated is used. There is a limit to the improvement of light emission efficiency only by the fluorescence of.
  • the delayed fluorescent material not only the excited singlet state but also the excited triplet state can be used for fluorescence emission by the path via the above-mentioned inverse intersystem crossing, so that the emission is higher than that of the ordinary fluorescent material. Efficiency will be obtained.
  • Patent Document 1 describes adding a delayed fluorescent material having a minimum excitation singlet energy lower than that of the host material and higher than that of the light emitting material to the light emitting layer containing the light emitting material and the host material. By adding such a delayed fluorescent material, the lowest excited singlet energy of the delayed fluorescent material is transferred to the light emitting material, and the luminous efficiency of the light emitting material can be improved.
  • the organic electroluminescence device in which the delayed fluorescent material is added to the light emitting layer tends to have a short device life, and there is room for improvement in terms of practicality. Therefore, it is required to provide an organic electroluminescence device having an improved device life.
  • the present inventors have selected and combined the compounds used for the light emitting layer of the organic electroluminescence element so as to satisfy specific conditions. We have found that the device life can be improved.
  • the present invention has been proposed based on these findings, and specifically has the following configurations.
  • An organic electroluminescence device having an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode.
  • the light emitting layer contains a first organic compound, a second organic compound and a third organic compound.
  • the second organic compound is a delayed fluorescent material.
  • the maximum component of light emission from the element is light emission from the third organic compound.
  • E HOMO (2) represents the energy of HOMO of the second organic compound.
  • E HOMO (3) represents the energy of HOMO of the third organic compound.
  • [2] The organic electroluminescence element according to [1], wherein the minimum excited triplet energy of the third organic compound is larger than 1.90 eV.
  • [3] The organic electroluminescence element according to [1] or [2], wherein the maximum emission wavelength of the element is in the range of 380 to 780 nm.
  • a substituted or unsubstituted benzofuran ring or a substituted or unsubstituted benzothiophene is attached to at least one of the two benzene rings constituting the at least one carbazole-9-yl group present in the second organic compound.
  • the organic electro according to [10] or [11], wherein the five-membered ring constituting the ring, the substituted or unsubstituted indole ring, the substituted or unsubstituted inden ring, or the substituted or unsubstituted cylineden ring is condensed.
  • Luminescence element wherein the five-membered ring constituting the ring, the substituted or unsubstituted indole ring, the substituted or unsubstituted inden ring, or the substituted or unsubstituted cylineden ring is condensed.
  • [13] The organic electroluminescence according to any one of [1] to [12], wherein the light emitting layer contains a carbon atom, a hydrogen atom, a nitrogen atom, a boron atom, and an oxygen atom and does not contain any other element. element.
  • [14] [Step 1] Evaluate the emission lifetime of a composition containing the first organic compound, the second organic compound which is a delayed fluorescent material, and the third organic compound and satisfying the above formulas (a) and (b). death, [Step 2] A composition in which at least one of the first organic compound, the second organic compound which is a delayed fluorescent material, and the third organic compound is replaced within the range satisfying the above formula (a) and the above formula (b). Evaluate the emission lifetime of an object at least once. [Step 3] Select the combination of compounds having the best evaluated emission lifetime. A method for designing a luminescent composition, which comprises each step. [15] A program that implements the method according to [14].
  • the organic electroluminescence device of the present invention has an improved device life. According to the method for designing a light emitting composition of the present invention, it is possible to provide a light emitting composition capable of realizing a light emitting device having a long device life.
  • the hydrogen atom is indicated as H or the indication is omitted.
  • the indication of the atom bonded to the ring skeleton constituent carbon atom of the benzene ring is omitted, it is assumed that H is bonded to the ring skeleton constituent carbon atom at the place where the indication is omitted.
  • substituted means an atom or atomic group other than a hydrogen atom and a deuterium atom.
  • the expressions "substituted or unsubstituted” and “may be substituted” mean that the hydrogen atom may be substituted with a deuterium atom or a substituent.
  • the organic electroluminescence device of the present invention has an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode.
  • the light emitting layer contains a first organic compound, a second organic compound and a third organic compound, the second organic compound is a delayed fluorescent material, and the maximum component of light emission from the organic electroluminescence element is from the third organic compound. It is the light emission of.
  • the first organic compound, the second organic compound and the third organic compound satisfy the following (a) and the following formula (b).
  • ES1 (1) represents the lowest excited single-term energy of the first organic compound
  • ES1 (2) represents the lowest excited single-term energy of the second organic compound
  • ES1 (3) represents the first 3 Represents the lowest excited single term energy of an organic compound.
  • eV is adopted as a unit.
  • the minimum excitation single-term energy can be obtained by preparing a thin film of the compound to be measured or a toluene solution (concentration 10-5 mol / L) and measuring the fluorescence spectrum at room temperature (300 K) (details are in the second organic). Refer to the measurement method of the lowest excited single term energy in the description column of the compound).
  • ES1 ( 1 ) -ES1 (2) can be, for example, in the range of 0.20 eV or more, in the range of 0.40 eV or more, in the range of 0.60 eV or more, and also in the range of 0.60 eV or more. It can be within the range of 1.50 eV or less, within the range of 1.20 eV or less, or within the range of 0.80 eV or less.
  • ES1 (2) -ES1 (3) can be, for example, in the range of 0.05 eV or more, in the range of 0.10 eV or more, in the range of 0.15 eV or more, and also in the range of 0.15 eV or more. It can be within the range of 0.50 eV or less, within the range of 0.30 eV or less, or within the range of 0.20 eV or less.
  • ES1 ( 1 ) -ES1 (3) can be, for example, in the range of 0.25 eV or more, in the range of 0.45 eV or more, in the range of 0.65 eV or more, and also in the range of 0.65 eV or more. It can be within the range of 2.00 eV or less, within the range of 1.70 eV or less, or within the range of 1.30 eV or less.
  • E HOMO (2) in the formula (b) represents the energy of HOMO of the second organic compound
  • E HOMO (3) represents the energy of HOMO of the third organic compound.
  • HOMO is an abbreviation for Highest Occupied Molecular Orbital, and can be obtained by atmospheric photoelectron spectroscopy (AC-3 manufactured by RIKEN Keiki Co., Ltd.). Since the present invention satisfies the relationship of the formula (b), the energy of HOMO of the second organic compound contained in the light emitting layer is less than or equal to the energy of HOMO of the third organic compound.
  • the energy difference of HOMO [E HOMO (3) -E HOMO (2)] is larger than 0 eV and less than 0.65 eV.
  • the lower limit is preferably 0.05 eV or more.
  • the upper limit value is preferably 0.60 eV or less, more preferably 0.50 eV or less, and may be 0.40 eV or less or 0.30 eV or less. Further, for example, it may be selected from the range of 0.40 eV or more, the range of 0.30 eV or more, or the range of 0.20 eV or less.
  • [E HOMO (3) -E HOMO (2)] is selected from a range greater than 0.30 eV and less than 0.60 eV.
  • [E HOMO (3) -E HOMO (2)] is selected from the range of 0.05 eV or more and 0.30 eV or less.
  • [E HOMO (3) -E HOMO (2)] may be selected from the range of 0.01 eV or more and less than 0.20 eV.
  • it may be selected from a range of 0.01 eV or more and less than 0.10 eV, a range of 0.01 eV or more and 0.05 eV or less, or a range of 0.10 eV or more and less than 0.20 eV. You may choose from.
  • a compound having a HOMO energy in the range of ⁇ 5.20 to ⁇ 5.90 eV or a compound in the range of ⁇ 5.30 to ⁇ 5.80 eV may be adopted as the second organic compound.
  • a compound having a HOMO energy in the range of ⁇ 5.60 to ⁇ 5.90 eV or a compound having an energy in the range of ⁇ 5.20 to ⁇ 5.40 eV may be selected.
  • Conc (1) When the contents of the first organic compound, the second organic compound, and the third organic compound in the light emitting layer of the organic electroluminescence element of the present invention are Conc (1), Conc (2), and Conc (3), respectively, the following formula is used. It is preferable to satisfy the relationship (d). Conc (1)> Conc (2)> Conc (3) Equation (d) Conc (1) is preferably 30% by weight or more, can be in the range of 50% by weight or more, can be in the range of 60% by weight or more, and can be in the range of 99% by weight or less. , 85% by weight or less, or 70% by weight or less.
  • Conc (2) is preferably 5% by weight or more, and can be in the range of 15% by weight or more, in the range of 20% by weight or more, in the range of 30% by weight or more, and also. , 45% by weight or less, 40% by weight or less, and 35% by weight or less. It may be in the range of 25% by weight or less, or may be in the range of 20% by weight or less.
  • Conc (3) is preferably 5% by weight or less, and more preferably 3% by weight or less. Conc (3) can be in the range of 0.01% by weight or more, 0.1% by weight or more, 0.3% by weight or more, and 2% by weight. It can be within the following range or within the range of 1% by weight or less.
  • Conc (1) / Conc (3) can be in the range of 10 or more, in the range of 50 or more, in the range of 90 or more, in the range of 10,000 or less, or in the range of 1000 or less. It can be within the range of, within the range of 200 or less, or within the range of 100 or less.
  • Conc (2) / Conc (3) can be in the range of 5 or more, in the range of 10 or more, in the range of 20 or more, in the range of 30 or more, and in the range of 500 or less. It can be within the range of, within the range of 300 or less, within the range of 100 or less, or within the range of 40 or less.
  • the light emitting layer of the organic electroluminescence device of the present invention preferably does not contain a metal element other than boron.
  • the light emitting layer can be composed only of a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom and a boron atom.
  • the light emitting layer can be composed only of a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom and a boron atom.
  • the first organic compound used for the light emitting layer of the organic electroluminescence element of the present invention is selected from the compounds having the lowest excitation single term energy larger than those of the second organic compound and the third organic compound.
  • the first organic compound preferably has a function as a host material responsible for transporting carriers. Further, the first organic compound preferably has a function of confining the energy of the third organic compound in the compound. As a result, the third organic compound efficiently converts the energy generated by the recombination of holes and electrons in the molecule and the energy received from the first organic compound and the second organic compound into light emission. Can be done.
  • the first organic compound is preferably an organic compound having a hole transporting ability and an electron transporting ability, preventing a long wavelength of light emission, and having a high glass transition temperature. Further, in a preferred embodiment of the present invention, the first organic compound is selected from compounds that do not emit delayed fluorescence.
  • the light emission from the first organic compound is preferably less than 1%, more preferably less than 0.1%, for example, less than 0.01%, detection limit of the light emission from the organic electroluminescence element of the present invention. It may be as follows.
  • the first organic compound preferably does not contain a metal atom.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom and a sulfur atom can be selected.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom and an oxygen atom can be selected.
  • a compound composed of a carbon atom, a hydrogen atom and a nitrogen atom can be selected. The following are preferable compounds that can be used as the first organic compound.
  • the second organic compound used for the light emitting layer of the organic electroluminescence element of the present invention is smaller than the first organic compound, has a lower minimum excitation single term energy than the third organic compound, and is the third organic. It is a delayed fluorescent material having a lower HOMO energy than a compound.
  • the "delayed fluorescent material" in the present invention means that in the excited state, an intersystem crossing from the excited triplet state to the excited singlet state occurs, and when the excited singlet state returns to the ground state, fluorescence (delayed fluorescence) occurs. It is an organic compound that emits radiation.
  • the emission lifetime when the emission lifetime is measured by a fluorescence lifetime measurement system (such as a streak camera system manufactured by Hamamatsu Photonics), a material in which fluorescence with a emission lifetime of 100 ns (nanoseconds) or more is observed is referred to as a delayed fluorescence material.
  • the second organic compound is a material capable of emitting delayed fluorescence, it is not essential to emit delayed fluorescence derived from the second organic compound when used in the organic electroluminescence device of the present invention.
  • the light emission from the second organic compound is preferably less than 10% of the light emission from the organic electroluminescence element of the present invention, for example, less than 1%, less than 0.1%, less than 0.01%, below the detection limit. There may be.
  • the second organic compound receives energy from the first organic compound in the excited singlet state and transitions to the excited singlet state. Further, the second organic compound may receive energy from the first organic compound in the excited triplet state and transition to the excited triplet state. Since the difference between the excited singlet energy and the excited triplet energy ( ⁇ EST ) is small in the second organic compound, the second organic compound in the excited triplet state crosses the second organic compound in the excited singlet state between the inverse intersystem crossings. Cheap. The second organic compound in the excited singlet state generated by these paths applies energy to the third organic compound to make the third organic compound transition to the excited singlet state.
  • the difference ⁇ EST between the lowest excited single term energy and the lowest excited triplet energy of 77K is preferably 0.3 eV or less, more preferably 0.25 eV or less, and 0.2 eV or less. It is more preferably 0.15 eV or less, further preferably 0.1 eV or less, even more preferably 0.07 eV or less, and further preferably 0.05 eV or less. It is more preferably 0.03 eV or less, and particularly preferably 0.01 eV or less.
  • the second organic compound functions as a thermally activated delayed fluorescent material because it is easy to cross the excited singlet state to the excited triplet state by absorption of thermal energy. Thermally activated delayed fluorescent material absorbs the heat generated by the device, crosses the excited triplet state from the excited triplet state to the excited singlet relatively easily, and efficiently contributes the excited triplet energy to emission. Can be done.
  • the lowest excited singlet energy ( ES1 ) and the lowest excited triplet energy ( ET1 ) of the compound in the present invention are values obtained by the following procedure.
  • ⁇ EST is a value obtained by calculating ES1 - ET1 .
  • Minimum excitation singlet energy ( ES1 ) A thin film of the compound to be measured or a toluene solution (concentration 10-5 mol / L) is prepared and used as a sample. The fluorescence spectrum of this sample is measured at room temperature (300K). In the fluorescence spectrum, the vertical axis is light emission and the horizontal axis is wavelength.
  • the maximum point having a peak intensity of 10% or less of the maximum peak intensity of the spectrum is not included in the above-mentioned maximum value on the shortest wavelength side, and the value of the gradient closest to the maximum value on the shortest wavelength side is the maximum.
  • the tangent line drawn at the point where the value is taken is taken as the tangent line to the rising edge of the phosphorescent spectrum on the short wavelength side.
  • the second organic compound does not contain a metal atom.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom and a sulfur atom can be selected.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom and an oxygen atom can be selected.
  • a compound composed of a carbon atom, a hydrogen atom and a nitrogen atom can be selected.
  • a compound having a structure in which one or two cyano groups and at least one donor group are bonded to a benzene ring can be mentioned.
  • the donor group for example, a substituted or unsubstituted carbazole-9-yl group can be preferably exemplified.
  • a compound in which three or more substituted or unsubstituted carbazole-9-yl groups are bonded to the benzene ring, or at least one of two benzene rings constituting the carbazole-9-yl group is substituted or absent.
  • Examples thereof include a substituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted inden ring, and a compound in which each 5-membered ring portion of a substituted or unsubstituted sirainden ring is condensed. can do.
  • X 1 to X 5 represent N or CR.
  • R represents a hydrogen atom, a deuterium atom or a substituent.
  • X 1 to X 5 represent CR, they may be the same or different from each other.
  • at least one of X 1 to X 5 is CD (where D represents a donor group).
  • Z represents an acceptor group.
  • a particularly preferable compound is a compound represented by the following general formula (2).
  • X 1 to X 5 represent N or CR.
  • R represents a hydrogen atom, a deuterium atom or a substituent.
  • X 1 to X 5 may be the same or different from each other.
  • at least one of X 1 to X 5 is CD (where D represents a donor group).
  • none of X1 to X5 is C-CN. That is, it is a compound having a structure in which one or two cyano groups and at least one donor group are bonded to a benzene ring.
  • only X 2 represents C-CN and X 1 , X 3 to X 5 are not C-CN.
  • X 3 represents C-CN
  • X 1 , X 2 , X 4 , and X 5 are not C-CN. That is, it is a compound having a structure in which at least one donor group is bonded to the benzene ring of terephthalonitrile.
  • the acceptor group represented by Z in the general formula (1) is a group having a property of donating an electron to the ring to which Z is bonded. Can be done.
  • the donor group represented by D in the general formula (1) and the general formula (2) is a group having a property of attracting an electron to the ring to which D is bonded, for example, a group having a negative ⁇ p value of Hammett. You can choose from.
  • the acceptor group may be referred to as A.
  • the “hammet ⁇ p value” is L. P. Proposed by Hammett, it quantifies the effect of substituents on the reaction rate or equilibrium of para-substituted benzene derivatives.
  • Hammet's ⁇ p value and the numerical value of each substituent in the present invention, refer to the description of ⁇ p value in Hansch, C.et.al., Chem.Rev., 91,165-195 (1991).
  • the acceptor group a cyano group and an acceptor group preferable as A in the general formulas (12) to (14) described later can be referred to.
  • a preferred donor group as D in the general formulas (12) to (14) described later can be referred to.
  • X 1 to X 5 represent N or CR, but at least one is CD.
  • the number of N among X 1 to X 5 is 0 to 4, for example, X 1 and X 3 and X 5 , X 1 and X 3 , X 1 and X 4 , X 2 and X 3 , and X 1 .
  • X 5 , X 2 and X 4 , only X 1 , only X 2 , and only X 3 are N.
  • the number of CDs is 1 to 5, preferably 2 to 5.
  • At least one of X 1 to X 5 may be CA.
  • A represents an acceptor group.
  • the number of CAs is preferably 0 to 2, and more preferably 0 or 1.
  • Preferred examples of A in CA include a heterocyclic aromatic group having a cyano group and an unsaturated nitrogen atom.
  • X 1 to X 5 may be CD or CA independently.
  • the two Rs may be coupled to each other to form a cyclic structure.
  • the cyclic structure formed by bonding with each other may be an aromatic ring or an alicyclic ring, may contain a hetero atom, and the cyclic structure may be a fused ring having two or more rings.
  • the hetero atom referred to here is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • Examples of the cyclic structure formed include a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an imidazoline ring, an oxazole ring, an isooxazole ring, a thiazole ring, and an iso.
  • Examples thereof include thiazole ring, cyclohexadiene ring, cyclohexene ring, cyclopentaene ring, cycloheptatriene ring, cycloheptadiene ring, cycloheptaene ring, furan ring, thiophene ring, naphthylidine ring, quinoxalin ring, quinoline ring and the like. ..
  • a ring in which a large number of rings are condensed such as a phenanthrene ring or a triphenylene ring, may be formed.
  • the donor group D in the general formula (1) and the general formula (2) is preferably a group represented by the following general formula (3), for example.
  • R 11 and R 12 are independently substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group, respectively.
  • R 11 and R 12 may be coupled to each other to form an annular structure.
  • L represents a single bond, substituted or unsubstituted arylene group, or substituted or unsubstituted heteroarylene group.
  • the substituent that can be introduced into the arylene group or heteroarylene group of L may be a group represented by the general formula (1) or the general formula (2), or may be a group represented by the general formula (1) to (6) described later.
  • the groups represented by these (1) to (6) may be introduced up to the maximum number of substituents that can be introduced into L. Further, when a plurality of groups represented by the general formulas (1) to (6) are introduced, the substituents thereof may be the same or different from each other.
  • * Represents the bond position to the carbon atom (C) constituting the ring skeleton of the ring in the general formula (1) or the general formula (2).
  • the "alkyl group” may be linear, branched or cyclic. Further, two or more of the linear portion, the annular portion and the branched portion may be mixed. The number of carbon atoms of the alkyl group can be, for example, 1 or more, 2 or more, and 4 or more.
  • the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, and 4 or less.
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group and isohexyl group.
  • 2-Ethylhexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decanyl group, isodecanyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group can be mentioned.
  • the alkyl group as a substituent may be further substituted with an aryl group.
  • the "alkenyl group" may be linear, branched or cyclic. Further, two or more of the linear portion, the annular portion and the branched portion may be mixed.
  • the carbon number of the alkenyl group can be, for example, 2 or more and 4 or more. Further, the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, and 4 or less.
  • Specific examples of the alkenyl group include ethenyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, n-pentenyl group, isopentenyl group, n-hexenyl group, isohexenyl group and 2-ethylhexenyl group. Can be mentioned.
  • the alkenyl group as a substituent may be further substituted with a substituent.
  • the "aryl group” and the “heteroaryl group” may be a monocyclic ring or a condensed ring in which two or more rings are condensed.
  • the number of fused rings is preferably 2 to 6, and can be selected from, for example, 2 to 4.
  • the ring include a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a quinoline ring, a pyrazine ring, a quinoxaline ring, and a naphthylidine ring.
  • aryl group or heteroaryl group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthrasenyl group, a 2-anthrasenyl group, a 9-anthrasenyl group, a 2-pyridyl group, a 3-pyridyl group, and 4 -Pyridyl groups can be mentioned.
  • the "arylene group” and “heteroaryl group” can be read as the valences in the description of the aryl group and the heteroaryl group from 1 to 2.
  • Substituent means a monovalent group that can be substituted with a hydrogen atom, and is not a concept including those that condense.
  • substituent and the preferable range the description of the substituent of the general formula (7) described later and the preferable range can be referred to.
  • the compound represented by the general formula (3) is preferably a compound represented by any of the following general formulas (4) to (6).
  • General formula (4) General formula (5)
  • R 51 to R 60 , R 61 to R 68 , and R 71 to R 78 each independently represent a hydrogen atom, a deuterium atom, or a substituent.
  • R 51 to R 60 , R 61 to R 68 , and R 71 to R 78 are groups represented by any of the above general formulas (4) to (6) independently.
  • the number of substituents in the general formulas (4) to (6) is not particularly limited.
  • the substituents may be the same or different.
  • the substituent is preferably any one of R 52 to R 59 in the case of the general formula (4), and the general formula (5). If this is the case, it is preferably any of R 62 to R 67 , and if it is the general formula (6), it is preferably any of R 72 to R 77 .
  • X is a divalent oxygen atom having a chain length of 1 atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted carbon atom, a substituted or unsubstituted silicon atom, and a carbonyl.
  • the description of the substituents in the above general formulas (1) and (2) can be referred to.
  • L 12 to L 14 represent a single-bonded, substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
  • L 12 to L 14 are preferably single-bonded, substituted or unsubstituted arylene groups.
  • the substituent of the arylene group or the heteroarylene group referred to here may be a group represented by the general formulas (1) to (6).
  • the groups represented by the general formulas (1) to (6) may be introduced up to the maximum number of substituents that can be introduced into L 11 to L 14 . Further, when a plurality of groups represented by the general formulas (1) to (6) are introduced, the substituents thereof may be the same or different from each other.
  • * Represents the bond position to the carbon atom (C) constituting the ring skeleton of the ring in the general formula (1) or the general formula (2).
  • a substituted or unsubstituted benzofuran ring a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted indene ring, and a substituted or unsubstituted sirainden ring are preferable.
  • It is a structure condensed with at least one of the benzene rings of the general formulas (4) to (6). More preferably, it is a group represented by the following general formulas (5a) to (5f) condensed with the general formula (5).
  • L 11 and L 21 to L 26 represent a single bond or a divalent linking group.
  • L 11 and L 21 to L 26 the above description and preferred range of L 2 can be referred to.
  • R 41 to R 110 each independently represent a hydrogen atom or a substituent.
  • R 94 , R 94 and R 95 , R 95 and R 96 , R 96 and R 97 , R 97 and R 98 , R 99 and R 100 , R 101 and R 102 , R 102 and R 103 , R 103 and R 104 , R 104 and R 105 , R 105 and R 106 , R 107 and R 108 , R 108 and R 109 , and R 109 and R 110 may be coupled to each other to form an annular structure.
  • the cyclic structure formed by bonding with each other may be an aromatic ring or an alicyclic ring, may contain a hetero atom, and the cyclic structure may be a fused ring having two or more rings. ..
  • the hetero atom referred to here is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • Examples of the cyclic structure formed include a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an imidazoline ring, an oxazole ring, an isooxazole ring, a thiazole ring, and an iso.
  • Examples thereof include thiazole ring, cyclohexadiene ring, cyclohexene ring, cyclopentaene ring, cycloheptatriene ring, cycloheptadiene ring, cycloheptaene ring, furan ring, thiophene ring, naphthylidine ring, quinoxalin ring, quinoline ring and the like. ..
  • a ring in which a large number of rings are condensed such as a phenanthrene ring or a triphenylene ring, may be formed.
  • the number of rings contained in the group represented by the general formula (6) may be selected from the range of 3 to 5, or may be selected from the range of 5 to 7.
  • the number of rings contained in the group represented by the general formulas (5a) to (5f) may be selected from the range of 5 to 7, or may be 5.
  • the substituents that R 41 to R 110 can take include the above-mentioned group of the substituent group B, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms or an unsubstituted substituent having 1 to 10 carbon atoms. It is an aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group.
  • R 41 to R 110 are hydrogen atoms or unsubstituted alkyl groups having 1 to 10 carbon atoms. In a preferred embodiment of the present invention, R 41 to R 110 are hydrogen atoms or unsubstituted aryl groups having 6 to 10 carbon atoms. In a preferred embodiment of the present invention, R 41 to R 110 are all hydrogen atoms.
  • the carbon atoms (ring skeleton constituent carbon atoms) to which R 41 to R 110 in the general formulas (5a) to (5f) are bonded may be independently substituted with nitrogen atoms. That is, CR 41 to CR 110 in the general formulas (5a) to (5f) may be independently substituted with N, respectively.
  • the number substituted with nitrogen atoms is preferably 0 to 4 among the groups represented by the general formulas (5a) to (5f), and more preferably 1 to 2. In one aspect of the invention, the number substituted with nitrogen atoms is zero. When two or more are substituted with nitrogen atoms, the number of nitrogen atoms substituted in one ring is preferably one.
  • X 1 to X 6 represent an oxygen atom, a sulfur atom or NR. In one aspect of the invention, X 1 to X 6 are oxygen atoms. In one aspect of the invention, X 1 to X 6 are sulfur atoms. In one aspect of the present invention, X1 to X6 are NR.
  • R represents a hydrogen atom or a substituent, and is preferably a substituent.
  • substituent a substituent selected from the above-mentioned Substituent Group A can be exemplified.
  • an unsubstituted phenyl group or a phenyl group substituted with one group selected from the group consisting of an alkyl group or an aryl group or a group in which two or more are combined can be preferably adopted.
  • * represents a bonding position.
  • a compound represented by the following general formula (7) and emitting delayed fluorescence can be particularly preferably used as a delayed fluorescent material.
  • the compound represented by the general formula (7) can be adopted as the second organic compound.
  • R 1 to R 5 represent a cyano group
  • at least one of R 1 to R 5 represents a substituted amino group
  • the remaining R 1 to R 5 represent hydrogen atoms.
  • the substituted amino group referred to here is preferably a substituted or unsubstituted diarylamino group, and the two aryl groups constituting the substituted or unsubstituted diarylamino group may be linked to each other.
  • the linkage may be a single bond (in which case a carbazol ring is formed), -O-, -S-, -N (R 6 )-, -C (R 7 ) (R 8 ). )-, -Si (R 9 ) (R 10 )-may be made of a linking group.
  • R 6 to R 10 represent a hydrogen atom, a deuterium atom or a substituent, and R 7 and R 8 and R 9 and R 10 may be connected to each other to form a cyclic structure.
  • the substituted amino group may be any of R 1 to R 5 , for example, R 1 and R 2 , R 1 and R 3 , R 1 and R 4 , R 1 and R 5 , R 2 and R 3 , R 2 .
  • R 3 and R 4 and R 5 can be substituted amino groups and the like.
  • the cyano group may also be any of R 1 to R 5 , for example R 1 , R 2 , R 3 , R 1 and R 2 , R 1 and R 3 , R 1 and R 4 , R 1 and R 5 , R 2 and R 3 , R 2 and R 4 , R 1 and R 2 and R 3 , R 1 and R 2 and R 4 , R 1 and R 2 and R 5 , R 1 and R 3 and R 4 , R 1 And R 3 and R 5 , R 2 and R 3 and R 4 can be cyano groups and the like.
  • R 1 to R 5 which are neither a cyano group nor a substituted amino group represent a hydrogen atom, a dehydrogen atom or a substituent.
  • substituent examples include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (for example, 1 to 40 carbon atoms), and an alkoxy group (for example, 1 to 40 carbon atoms).
  • Alkylthio group for example, 1 to 40 carbon atoms
  • aryl group for example, 6 to 30 carbon atoms
  • aryloxy group for example, 6 to 30 carbon atoms
  • arylthio group for example, 6 to 30 carbon atoms
  • heteroaryl group for example, 6 to 30 carbon atoms.
  • a ring skeleton constituent atom number 5 to 30 For example, a ring skeleton constituent atom number 5 to 30), a heteroaryloxy group (for example, a ring skeleton constituent atom number 5 to 30), a heteroarylthio group (for example, a ring skeleton constituent atom number 5 to 30), an acyl group (for example, a ring skeleton constituent atom number 1).
  • alkenyl group for example, 1 to 40 carbon atoms
  • alkynyl group for example, 1 to 40 carbon atoms
  • alkoxycarbonyl group for example, 1 to 40 carbon atoms
  • aryloxycarbonyl group for example, 1 to 40 carbon atoms
  • Heteroaryloxycarbonyl groups eg, 1-40 carbon atoms
  • silyl groups eg, trialkylsilyl groups with 1-40 carbon atoms
  • nitro groups the groups listed here are further one or more groups listed here.
  • a group of substituents A consisting of substituted groups can be mentioned.
  • the substituent of the above-mentioned substituent group A can be mentioned, and further, a cyano group and a substituted amino group can also be mentioned.
  • paragraphs 0008 to 0048 of WO2013 / 154064 and paragraphs 0009 to WO2015 / 080183 which are referred to herein as a part of the present specification.
  • paragraphs 0006 to 0019 of WO2015 / 129715, paragraphs 0013 to 0025 of JP2017-119663, and paragraphs 0013 to 0026 of JP2017-119664 can be referred to.
  • a compound represented by the following general formula (8) and emitting delayed fluorescence can also be particularly preferably used as the delayed fluorescent material of the present invention.
  • the compound represented by the general formula (8) can be adopted as the second organic compound.
  • Y 1 , Y 2 and Y 3 either represent a nitrogen atom and the remaining one represents a methine group, or all of Y 1 , Y 2 and Y 3 represent a nitrogen atom.
  • Z 1 and Z 2 independently represent a hydrogen atom, a deuterium atom or a substituent, respectively.
  • R 11 to R 18 independently represent a hydrogen atom, a deuterium atom or a substituent, and at least one of R 11 to R 18 is a substituted or unsubstituted arylamino group or a substituted or unsubstituted carbazolyl group. Is preferable.
  • the benzene ring constituting the arylamino group and the benzene ring constituting the carbazolyl group may be combined with R 11 to R 18 to form a single bond or a linking group, respectively.
  • the compound represented by the general formula (8) contains at least two carbazole structures in the molecule.
  • the substituents that Z 1 and Z 2 can take include the above-mentioned substituents of the substituent group A.
  • Specific examples of the substituents that can be taken from R 11 to R 18 , the above-mentioned arylamino group and carbazolyl group include the above-mentioned substituent, cyano group, substituted arylamino group and substituted alkylamino group of the substituent group A.
  • Y 1 , Y 2 and Y 3 either represent a nitrogen atom and the remaining one represents a methine group, or all of Y 1 , Y 2 and Y 3 represent a nitrogen atom.
  • Z 2 represents a hydrogen atom, a deuterium atom or a substituent.
  • R 11 to R 18 and R 21 to R 28 independently represent a hydrogen atom, a deuterium atom or a substituent, respectively. At least one of R 11 to R 18 and / or at least one of R 21 to R 28 preferably represent a substituted or unsubstituted arylamino group or a substituted or unsubstituted carbazolyl group.
  • the benzene ring constituting the arylamino group and the benzene ring constituting the carbazolyl group may be combined with R 11 to R 18 or R 21 to R 28 to form a single bond or a linking group, respectively.
  • substituents that Z 2 can take include the above-mentioned substituents of the substituent group A.
  • substituents that can be taken from R 11 to R 18 , R 21 to R 28 , the above arylamino group and the carbazolyl group are used.
  • Substituted alkylamino groups can be mentioned.
  • R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 25 and R 26 , R 26 and R 27 , and R 27 and R 28 may be coupled to each other to form an annular structure.
  • the compounds described in Let, 98,083302 (2011) can be referred to.
  • R 91 to R 96 each independently represent a hydrogen atom, a deuterium atom, a donor group, or an acceptor group, and at least one of them is the donor group, and at least two of them. One is the acceptor group.
  • the substitution position of at least two acceptor groups is not particularly limited, but it is preferable to include two acceptor groups having a meta-position relationship with each other.
  • R 91 is a donor group
  • a structure in which at least R 92 and R 94 are acceptor groups and a structure in which at least R 92 and R 96 are acceptor groups can be preferably exemplified.
  • the acceptor groups present in the molecule may be all the same or different from each other, but it is possible to select, for example, structures that are all the same.
  • the number of acceptor groups is preferably 2 to 3, and for example, 2 can be selected.
  • two or more donor sex groups may be present, and in that case, the donor sex groups may be the same or different from each other.
  • the number of donor groups is preferably 1 to 3, and may be, for example, only one or two.
  • the description and preferred range of the donor group and the acceptor group the description and preferred range of D and Z in the general formula (1) can be referred to.
  • the donor group is preferably represented by the general formula (3)
  • the acceptor group is preferably represented by the cyano group or the following general formula (11).
  • Y 4 to Y 6 represent a nitrogen atom or a methine group, but at least one represents a nitrogen atom, and preferably all represent a nitrogen atom.
  • Each of R 101 to R 110 independently represents a hydrogen atom, a deuterium atom, or a substituent, but at least one is preferably an alkyl group.
  • L 15 represents a single bond or a linking group, and the description and preferred range of L in the above general formula (3) can be referred to.
  • L15 in the general formula ( 11) is a single bond. * Represents the bond position to the carbon atom (C) constituting the ring skeleton of the ring in the general formula (10).
  • the compound represented by the general formula (12) can be adopted as the second organic compound.
  • the compound represented by the general formula (12) includes the compound represented by the general formula (12a).
  • General formula (12) General formula (12a)
  • a particularly preferable compound is a compound represented by the following general formula (13) or a compound represented by the general formula (14).
  • General formula (13) General formula (14)
  • D represents a donor group
  • A represents an acceptor group
  • R represents a hydrogen atom, a deuterium atom or a substituent.
  • the substituent of R include an alkyl group and an aryl group which may be substituted with one group selected from the group consisting of an alkyl group and an aryl group or a group in which two or more are combined.
  • Specific examples of the donor property group preferable as D in the general formulas (12) to (14) are given below.
  • * represents a bond position
  • "D" represents a deuterium atom.
  • the hydrogen atom may be substituted with, for example, an alkyl group. Further, the substituted or unsubstituted benzene ring may be further condensed.
  • acceptor groups preferred as A in the general formulas (12) to (14) are given below.
  • * represents a bond position and "D" represents a deuterium atom.
  • R in the general formulas (12) to (14) are given below.
  • * represents a bond position and "D" represents a deuterium atom.
  • t-Bu represents a tertiary butyl group. Further, the display of CH 3 of the methyl group is omitted. Therefore, for example, T157 represents a structure in which two methyl groups are bonded to the central benzene ring.
  • WO2014 / 136860 WO2014 / 196585, WO2014 / 189122, WO2014 / 168101, WO2015 / 008580, WO2014 / 203840, WO2015 / 002213, WO2015 / 016200, WO2015 / 019725, WO2015 / 072470, WO2015 / 108049, WO2015 / 080182, WO2015 / 072537, WO2015 / 080183, JP2015-129240, WO2015 / 129714, Described in WO2015 / 129715, WO2015 / 133501, WO2015 / 136880, WO2015 / 137244, WO2015 / 137202, WO2015 / 137136, WO2015 / 146541, WO2015 / 159541. It is also possible to adopt a light emitting material that emits delayed fluorescence. It should be noted that the above publications described in this paragraph are cited here
  • the third organic compound used for the light emitting layer of the organic electroluminescence element of the present invention has the lowest excitation single term energy smaller than that of the first organic compound and the second organic compound, and is HOMO than that of the second organic compound. It is a fluorescent material with a large energy.
  • the organic electroluminescence device of the present invention emits fluorescence derived from a third organic compound. Emissions from the third organic compound usually include delayed fluorescence.
  • the maximum component of light emission from the organic electroluminescence element of the present invention is light emission from the third organic compound. That is, among the light emitted from the organic electroluminescence element of the present invention, the amount of light emitted from the third organic compound is the largest.
  • the third organic compound is the energy from the first organic compound in the excited singlet state, the second organic compound in the excited singlet state, and the second organic compound that crosses between the inverted triplets and becomes the excited singlet state. Is received and transitions to the excited singlet state. Further, in a preferred embodiment of the present invention, the third organic compound receives energy from the second organic compound in the excited singlet state and the second organic compound which crosses between the excited triplet states and becomes the excited singlet state.
  • the fluorescent material used as the third organic compound is not particularly limited as long as it can receive energy from the first organic compound or the second organic compound and emit light, and the emission can be fluorescent, delayed fluorescence, or phosphorescence. It does not matter which one is included. It is preferable that the emission contains fluorescence or delayed fluorescence, and more preferably, the maximum component of the emission from the third organic compound is fluorescence. In one aspect of the invention, the organic electroluminescence element does not emit phosphorescence, or the amount of phosphorescence emitted is 1% or less of the fluorescence.
  • the third organic compound preferably has a minimum excitation triplet energy of more than 1.90 eV, and may be, for example, larger than 2.45 eV, 2.48 eV or more, or 2.60 eV or more. You may use it.
  • the maximum emission wavelength of the third organic compound is preferably shorter than the maximum emission wavelength of the second organic compound.
  • the difference in wavelength may be 2 nm or more, 10 nm or more, 20 nm or more, 25 nm or more, for example, 50 nm or less, 30 nm or less, 10 nm or less, or 5 nm or less. May be.
  • the ionization energy of the third organic compound is larger than the ionization energy of the second organic compound.
  • the difference may be 0.2 eV or more, 0.4 eV or more, 0.7 eV or more, 1.0 eV or less, 0.8 eV or less, 0.5 eV or less. You may.
  • the third organic compound two or more kinds may be used as long as they satisfy the conditions of the present invention. For example, by using two or more kinds of tertiary organic compounds having different emission colors in combination, it becomes possible to emit a desired color. Further, one kind of the third organic compound may be used to emit a single color from the third organic compound.
  • the maximum emission wavelength of the compound that can be used as the third organic compound is not particularly limited. Therefore, the light emitting material having the maximum emission wavelength in the visible region (380 to 780 nm), the light emitting material having the maximum emission wavelength in the infrared region (780 nm to 1 mm), and the maximum emission wavelength in the ultraviolet region (for example, 280 to 380 nm).
  • a fluorescent material having a maximum emission wavelength in the visible region For example, a light emitting material having a maximum emission wavelength in the range of 380 to 570 nm in the region of 380 to 780 nm may be selected and used, or a light emitting material having a maximum emission wavelength in the range of 570 to 650 nm may be selected and used. A light emitting material having a maximum emission wavelength in the range of 650 to 700 nm may be selected and used, or a light emitting material having a maximum emission wavelength in the range of 700 to 780 nm may be selected and used.
  • the compounds are selected and combined so that there is an overlap between the emission wavelength region of the second organic compound and the absorption wavelength region of the third organic compound.
  • the edge on the short wavelength side of the emission spectrum of the second organic compound and the edge on the long wave side of the absorption spectrum of the third organic compound overlap.
  • the third organic compound preferably does not contain a metal atom other than a boron atom.
  • it may be a compound containing a boron atom but not a fluorine atom. Further, it may not contain any metal atom.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a heavy hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom and a boron atom can be selected.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a heavy hydrogen atom, a nitrogen atom, an oxygen atom and a boron atom can be selected.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a heavy hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom and a boron atom can be selected.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a heavy hydrogen atom, a nitrogen atom and a boron atom can be selected.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a heavy hydrogen atom, a nitrogen atom, an oxygen atom and a sulfur atom can be selected.
  • a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a heavy hydrogen atom, a nitrogen atom and an oxygen atom can be selected.
  • a compound consisting of a carbon atom and a hydrogen atom can be selected as the third organic compound.
  • Examples of the third organic compound include compounds having a multiple resonance effect of a boron atom and a nitrogen atom, and compounds containing a fused aromatic ring structure such as anthracene, pyrene, and perylene.
  • the compound represented by the following general formula (15) is used as the third organic compound.
  • Ar 1 to Ar 3 are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen atom in these rings may be substituted or the rings are condensed. May be.
  • the hydrogen atom is substituted, it is preferably substituted with one group selected from the group consisting of a deuterium atom, an aryl group, a heteroaryl group and an alkyl group, or a group in which two or more are combined.
  • the rings are condensed, it is preferable that a benzene ring or a complex aromatic ring (for example, a furan ring, a thiophene ring, a pyrrole ring, etc.) is condensed.
  • R a and R a' represent a substituent independently of each other, and are preferably one group selected from the group consisting of a heavy hydrogen atom, an aryl group, a heteroaryl group and an alkyl group, or a group in which two or more are combined.
  • Ra and Ar 1 , Ar 1 and Ar 2 , Ar 2 and Ra ', Ra'and Ar 3 , and Ar 3 and Ra may be coupled to each other to form a cyclic structure.
  • the compound represented by the general formula (15) preferably contains at least one carbazole structure.
  • one benzene ring constituting the carbazole structure may be a ring represented by Ar 1
  • one benzene ring constituting the carbazole structure may be a ring represented by Ar 2
  • One of the benzene rings constituting the above may be a ring represented by Ar 3 .
  • a carbazolyl group may be bonded to any one or more of Ar 1 to Ar 3 .
  • a substituted or unsubstituted carbazole-9-yl group may be attached to the ring represented by Ar 3 .
  • a condensed aromatic ring structure such as anthracene, pyrene, or perylene may be bonded to Ar 1 to Ar 3 .
  • the ring represented by Ar 1 to Ar 3 may be one ring constituting the condensed aromatic ring structure.
  • at least one of Ra and Ra' may be a group having a condensed aromatic ring structure.
  • a plurality of skeletons represented by the general formula (15) may be present in the compound.
  • the skeletons represented by the general formula (15) may have a structure in which they are bonded to each other via a single bond or a linking group.
  • the skeleton represented by the general formula (15) may be further added with a structure showing a multiple resonance effect in which benzene rings are linked by a boron atom, a nitrogen atom, an oxygen atom, and a sulfur atom.
  • a compound containing a BODIPY (4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene) structure is used as the third organic compound.
  • a compound represented by the following general formula (16) is used.
  • R 1 to R 7 are independently hydrogen atoms, deuterium atoms or substituents, respectively. At least one of R 1 to R 7 is preferably a group represented by the following general formula (17).
  • R 11 to R 15 independently represent a hydrogen atom, a deuterium atom or a substituent, and * represents a bond position.
  • the group represented by the general formula (17) may be one, two, or three of R 1 to R 7 of the general formula (16). Further, it may be at least four, and may be, for example, four or five.
  • one of R 1 to R 7 is a group represented by the general formula (17).
  • at least R 1 , R 3 , R 5 , and R 7 are groups represented by the general formula (17).
  • only R 1 , R 3 , R 4 , R 5 , and R 7 are the groups represented by the general formula (17).
  • R 1 , R 3 , R 4 , R 5 , R 7 are groups represented by the general formula (17), and R 2 and R 4 are hydrogen atoms, heavy hydrogen atoms, and none. It is a substituted alkyl group (for example, 1 to 10 carbon atoms) or an unsubstituted aryl group (for example, 6 to 14 carbon atoms).
  • all of R 1 to R 7 are groups represented by the general formula (17).
  • R 1 and R 7 are the same.
  • R 3 and R 5 are identical.
  • R 2 and R 6 are identical.
  • R 1 and R 7 are the same, R 3 and R 5 are the same, and R 1 and R 3 are different from each other.
  • R 1 , R 3 , R 5 , and R 7 are the same.
  • R 1 , R 4 and R 7 are the same and different from R 3 and R 5 .
  • R 3 and R 4 and R 5 are the same and different from R 1 and R 7 .
  • R 1 , R 3 , R 5 , and R 7 are all different from R 4 .
  • Examples of the substituents that can be adopted by R 11 to R 15 of the general formula (17) include selection from the above-mentioned substituent group a, selection from the above-mentioned substituent group b, and selection from the above-mentioned substituent group c. It can be selected from the above-mentioned substituent group d.
  • a substituted amino group is selected as the substituent, a di-substituted amino group is preferable, and the two substituents for the amino group are independently substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, or substituted, respectively.
  • the substituent that can be taken by the two aryl groups of the diarylamino group include, for example, selection from the above-mentioned substituent group a, selection from the above-mentioned substituent group b, selection from the above-mentioned substituent group c, and the above-mentioned substituent. It can be selected from the group d.
  • the two aryl groups of the diarylamino group may be bonded to each other via a single bond or a linking group, and the description of the linking group in R 33 and R 34 can be referred to here for the linking group.
  • a substituted or unsubstituted carbazole-9-yl group can be adopted.
  • the substituted or unsubstituted carbazole-9-yl group include a group in which L 11 of the above general formula (9) is a single bond.
  • R 13 of the general formula (17) is a substituent, and R 11 , R 12 , R 14 and R 15 are hydrogen atoms.
  • R 11 of the general formula (17) is a substituent
  • R 12 , R 13 , R 14 and R 15 are hydrogen atoms.
  • R 11 and R 13 of the general formula (17) are substituents
  • R 12 , R 14 and R 15 are hydrogen atoms.
  • R 1 to R 7 of the general formula (16) may contain a group (that is, a phenyl group) in which all of R 11 to R 15 of the general formula (17) are hydrogen atoms.
  • R 2 , R 4 , and R 6 may be phenyl groups.
  • R 8 and R 9 independently form a hydrogen atom, a heavy hydrogen atom, a halogen atom, an alkyl group (for example, 1 to 40 carbon atoms), an alkoxy group (for example, 1 to 40 carbon atoms), and an aryloxy. It is preferably one group selected from the group consisting of a group (for example, 6 to 30 carbon atoms) and a cyano group, or a group in which two or more are combined.
  • R8 and R9 are identical.
  • R 8 and R 9 are halogen atoms, particularly preferably fluorine atoms.
  • t-Bu represents a tertiary butyl group.
  • Examples of the derivative of the above-mentioned exemplified compound include a compound in which at least one hydrogen atom is substituted with a heavy hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, and a diarylamino group.
  • the compounds described in paragraphs 0220 to 0239 of WO2015 / 022774 and the compounds described in paragraphs 0196 to 0255 of WO2021 / 015177 can also be particularly preferably used as the third organic compound of the present invention.
  • alkyl group alkenyl group, aryl group, heteroaryl group, arylene group, and heteroarylene group in the present specification represent the following contents unless otherwise specified.
  • the "alkyl group” may be linear, branched or cyclic. Further, two or more of the linear portion, the annular portion and the branched portion may be mixed.
  • the number of carbon atoms of the alkyl group can be, for example, 1 or more, 2 or more, and 4 or more. Further, the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, and 4 or less.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group and isohexyl group.
  • the alkyl group as a substituent may be further substituted with an aryl group.
  • the description of the "alkyl group” here can also be referred to for the alkyl moiety of the "alkoxy group", “alkylthio group", "acyl group” and "alkoxycarbonyl group”.
  • the "alkenyl group” may be linear, branched or cyclic. Further, two or more of the linear portion, the annular portion and the branched portion may be mixed.
  • the carbon number of the alkenyl group can be, for example, 2 or more and 4 or more. Further, the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, and 4 or less.
  • alkenyl group examples include ethenyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, n-pentenyl group, isopentenyl group, n-hexenyl group, isohexenyl group and 2-ethylhexenyl group. Can be mentioned.
  • the alkenyl group as a substituent may be further substituted with a substituent.
  • the "aryl group” and the "heteroaryl group” may be a monocyclic ring or a condensed ring in which two or more rings are condensed.
  • the number of fused rings is preferably 2 to 6, and can be selected from, for example, 2 to 4.
  • the ring include a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a quinoline ring, a pyrazine ring, a quinoxaline ring, and a naphthylidine ring.
  • aryl group or heteroaryl group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthrasenyl group, a 2-anthrasenyl group, a 9-anthrasenyl group, a 2-pyridyl group, a 3-pyridyl group, and 4 -Pyridyl groups can be mentioned.
  • the "arylene group” and “heteroaryl group” can be read as the valences in the description of the aryl group and the heteroaryl group from 1 to 2.
  • aryl group here can also be referred to for the aryl portion of the "aryloxy group”, “arylthio group” and “aryloxycarbonyl group”.
  • heteroaryl group here can also be referred to for the heteroaryl portion of the “heteroaryloxy group”, “heteroarylthio group” and “heteroaryloxycarbonyl group”.
  • the light emitting layer of the organic electroluminescence element of the present invention comprises a light emitting composition containing a first organic compound satisfying the formulas (a) and (b), a second organic compound which is a delayed fluorescent material, and a third organic compound.
  • the light emitting layer does not contain, in addition to the first organic compound, the second organic compound, and the third organic compound, a compound that transfers electric charges or energy, or a metal element.
  • the light emitting layer may be composed of only the first organic compound, the second organic compound and the third organic compound.
  • the light emitting layer may be composed only of a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, a boron atom, an oxygen atom and a sulfur atom.
  • the light emitting layer can be composed only of a compound consisting of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, a boron atom and an oxygen atom.
  • the light emitting layer contains carbon atoms, hydrogen atoms, nitrogen atoms, boron atoms and oxygen atoms, and more preferably contains no other elements.
  • the light emitting layer may be formed by a wet step using a light emitting composition containing the first organic compound satisfying the formulas (a) and (b), the second organic compound which is a delayed fluorescent material, and the third organic compound. However, it may be formed by a dry process. In the wet step, a solution in which the light emitting composition is dissolved is applied to the surface, and a light emitting layer is formed after removing the solvent. Examples of the wet process include, but are not limited to, a spin coating method, a slit coating method, an inkjet method (spray method), a gravure printing method, an offset printing method, and a flexographic printing method.
  • an appropriate organic solvent capable of dissolving the luminescent composition is selected and used.
  • a substituent eg, an alkyl group
  • a vacuum vapor deposition method can be preferably adopted.
  • each compound constituting the light emitting layer may be co-deposited from an individual vapor deposition source, or may be co-deposited from a single vapor deposition source in which all the compounds are mixed.
  • a mixed powder in which powders of all the compounds are mixed may be used, a compression molded product obtained by compressing the mixed powder may be used, or each compound is heated and melted and mixed. Then a cooled mixture may be used.
  • the composition ratio of the plurality of compounds contained in the vapor deposition source is obtained by performing co-evaporation under the condition that the vapor deposition rates (weight reduction rates) of the plurality of compounds contained in a single vapor deposition source are the same or almost the same. It is possible to form a light emitting layer having a composition ratio corresponding to the above.
  • a light emitting layer having a desired composition ratio can be easily formed.
  • a temperature at which each compound to be co-deposited has the same weight loss rate can be specified, and that temperature can be adopted as the temperature at the time of co-depositing.
  • the molecular weights of each of the first organic compound, the second organic compound, and the third organic compound are preferably 1500 or less, more preferably 1200 or less, and 1000 or less. Is even more preferable, and 900 or less is even more preferable.
  • the lower limit of the molecular weight may be, for example, 200, 400, or 600.
  • An organic photoluminescence element (Layer structure of organic electroluminescence element) An organic photoluminescence element ( It is possible to provide an excellent organic electroluminescence element such as an organic PL element) or an organic electroluminescence element (organic EL element).
  • the thickness of the light emitting layer can be, for example, 1 to 15 nm, 2 to 10 nm, or 3 to 7 nm.
  • the organic photoluminescence device has a structure in which at least a light emitting layer is formed on a base material. Further, the organic electroluminescence device has at least an anode, a cathode, and a structure in which an organic layer is formed between the anode and the cathode.
  • the organic layer includes at least a light emitting layer, and may be composed of only a light emitting layer, or may have one or more organic layers in addition to the light emitting layer.
  • examples of such other organic layers include a hole transport layer, a hole injection layer, an electron barrier layer, a hole barrier layer, an electron injection layer, an electron transport layer, an exciton barrier layer, and the like.
  • the hole transport layer may be a hole injection transport layer having a hole injection function
  • the electron transport layer may be an electron injection transport layer having an electron injection function.
  • FIG. 1 shows a specific structural example of the organic electroluminescence element. In FIG.
  • the organic electroluminescence element of the present invention is a multi-wavelength emission type organic electroluminescence element
  • the shortest wavelength emission can include delayed fluorescence. It is also possible that the shortest wavelength emission does not include delayed fluorescence.
  • An organic electroluminescence element comprising a luminescent composition containing a first organic compound satisfying the formulas (a) and (b), a second organic compound which is a delayed fluorescent material, and a third organic compound is obtained by thermal or electronic means.
  • an organic electroluminescence device When excited, it can emit light in the ultraviolet region, the blue, green, yellow, orange, red region (eg 420-500 nm, 500-600 nm or 600-700 nm) of the visible spectrum or the near infrared region.
  • an organic electroluminescence device can emit light in the red or orange region (eg, 620-780 nm).
  • an organic electroluminescence device can emit light in the orange or yellow region (eg, 570-620 nm).
  • an organic electroluminescence device can emit light in the green region (eg, 490-575 nm).
  • an organic electroluminescence device can emit light in a blue region (for example, 400 to 490 nm).
  • an organic electroluminescence device can emit light in the ultraviolet spectral region (for example, 280 to 400 nm).
  • an organic electroluminescence device can emit light in the infrared spectral region (for example, 780 nm to 2 ⁇ m).
  • the maximum emission wavelength of the device is longer than 570 nm (eg, 570-780 nm).
  • the organic electroluminescence element of the invention is held by a substrate, the substrate is not particularly limited and is commonly used in organic electroluminescence devices, such as glass, clear plastics, quartz and silicon. Any material formed by the above may be used.
  • the anode of an organic electroluminescence device is manufactured from a metal, alloy, conductive compound or a combination thereof.
  • the metal, alloy or conductive compound has a high work function (4 eV or higher).
  • the metal is Au.
  • the conductive transparent material is selected from CuI, indium tin oxide (ITO), SnO 2 and ZnO.
  • an amorphous material capable of forming a transparent conductive film such as IDIXO (In 2 O 3 -ZnO), is used.
  • the anode is a thin film. In some embodiments, the thin film is made by vapor deposition or sputtering.
  • the film is patterned by a photolithography method.
  • the pattern may be formed using a mask having a shape suitable for vapor deposition or sputtering on the electrode material.
  • a wet film forming method such as a printing method or a coating method is used.
  • synchrotron radiation passes through the anode, the anode has a transmittance of greater than 10% and the anode has a sheet resistance of no more than a few hundred ohms per unit area.
  • the thickness of the anode is 10-1,000 nm. In some embodiments, the thickness of the anode is 10-200 nm. In some embodiments, the thickness of the anode will vary depending on the material used.
  • the cathode is made of an electrode material such as a metal with a low work function (4 eV or less) (referred to as an electron-injected metal), an alloy, a conductive compound or a combination thereof.
  • the electrode material is 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 ) Selected from mixtures, indium, lithium-aluminum mixtures and rare earth elements.
  • a mixture of the electron-injected metal and a second metal which is a stable metal with a higher work function than the electron-injected metal, is used.
  • the mixture is selected from a magnesium-silver mixture, a magnesium-aluminum mixture, a magnesium-indium mixture, an aluminum-aluminum oxide (Al 2 O 3 ) mixture, a lithium-aluminum mixture and aluminum.
  • the mixture improves electron injection properties and resistance to oxidation.
  • the cathode is manufactured by forming the electrode material as a thin film by vapor deposition or sputtering.
  • the cathode has a sheet resistance of tens of ohms or less per unit area. In some embodiments, the cathode has a thickness of 10 nm to 5 ⁇ m. In some embodiments, the thickness of the cathode is 50-200 nm. In some embodiments, any one of the anode and cathode of the organic electroluminescence element is transparent or translucent in order to transmit synchrotron radiation. In some embodiments, the transparent or translucent electroluminescent device improves the light radiance. In some embodiments, the cathode is formed of the conductive transparent material described above with respect to the anode to form a transparent or translucent cathode. In some embodiments, the device comprises an anode and a cathode, both of which are transparent or translucent.
  • the injection layer is the layer between the electrode and the organic layer. In some embodiments, the injection layer reduces the drive voltage and enhances the light radiance. In some embodiments, the injection layer comprises a hole injection layer and an electron injection layer. The injection layer can be arranged between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. In some embodiments, an injection layer is present. In some embodiments, there is no injection layer. The following are examples of preferable compounds that can be used as hole injection materials.
  • the barrier layer is a layer capable of preventing charges (electrons or holes) and / or excitons present in the light emitting layer from diffusing outside the light emitting layer.
  • the electron barrier layer resides between the light emitting layer and the hole transport layer, preventing electrons from passing through the light emitting layer to the hole transport layer.
  • the hole barrier layer exists between the light emitting layer and the electron transport layer to prevent holes from passing through the light emitting layer to the electron transport layer.
  • the barrier layer prevents excitons from diffusing outside the light emitting layer.
  • the electron barrier layer and the hole barrier layer constitute an exciton barrier layer.
  • the term "electron barrier layer" or "exciton barrier layer” includes both an electron barrier layer and a layer having both the functions of an exciton barrier layer.
  • Hole barrier layer functions as an electron transport layer. In some embodiments, the hole barrier layer prevents holes from reaching the electron transport layer during electron transport. In some embodiments, the hole barrier layer increases the probability of electron-hole recombination in the light emitting layer.
  • the material used for the hole barrier layer may be the same material as described above for the electron transport layer. The following are examples of preferable compounds that can be used for the hole barrier layer.
  • the electron barrier layer transports holes.
  • the electron barrier layer blocks electrons from reaching the hole transport layer during hole transport.
  • the electron barrier layer increases the probability of electron-hole recombination in the light emitting layer.
  • the material used for the electron barrier layer may be the same material as described above for the hole transport layer. Specific examples of preferable compounds that can be used as an electron barrier material are given below.
  • Exciton barrier layer prevents excitons generated through the recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. In some embodiments, the exciton barrier layer allows for effective exciton confinement in the light emitting layer. In some embodiments, the light emission efficiency of the device is improved. In some embodiments, the exciton barrier layer is adjacent to the light emitting layers on either the anode side and the cathode side, and on either side of the anode side. In some embodiments, when the exciton barrier layer is present on the anode side, the layer may be present between the hole transport layer and the light emitting layer and adjacent to the light emitting layer.
  • the layer when the exciton barrier layer is present on the cathode side, the layer may be present between the light emitting layer and the cathode and adjacent to the light emitting layer.
  • a hole injection layer, an electron barrier layer or a similar layer resides between the anode and the exciton barrier layer adjacent to the light emitting layer on the anode side.
  • the hole injection layer, electron barrier layer, hole barrier layer or similar layer is present between the cathode and the exciton barrier layer adjacent to the light emitting layer on the cathode side.
  • the exciter barrier layer comprises an excited singlet energy and an excited triplet energy, at least one of which is higher than the excited singlet energy and the excited triplet energy of the light emitting material, respectively.
  • the hole transport layer contains a hole transport material.
  • the hole transport layer is a single layer. In some embodiments, the hole transport layer has multiple layers. In some embodiments, the hole transport material has one of the hole injection or transport properties and the electron barrier properties. In some embodiments, the hole transport material is an organic material. In some embodiments, the hole transport material is an inorganic material. Examples of known hole transport materials that can be used in the present invention are, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane inducers, pyrazoline derivatives, pyrazolones.
  • the hole transport material is selected from porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds.
  • the hole transport material is an aromatic tertiary amine compound. Specific examples of preferable compounds that can be used as hole transport materials are given below.
  • Electron transport layer contains an electron transport material.
  • the electron transport layer is a single layer.
  • the electron transport layer has multiple layers.
  • the electron transport material only needs to have the function of transporting the electrons injected from the cathode to the light emitting layer.
  • the electron transport material also functions as a hole barrier material.
  • electron transport layers examples include, but are not limited to, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidene methane derivatives, anthracinodimethanes, antron derivatives, and oxadi. Examples thereof include azole derivatives, azole derivatives, azine derivatives or combinations thereof, or polymers thereof.
  • the electron transport material is a thiadiazole inducer or a quinoxaline derivative.
  • the electron transport material is a polymeric material. Specific examples of preferable compounds that can be used as electron transport materials are given below.
  • preferable compounds as materials that can be added to each organic layer are given.
  • it may be added as a stabilizing material.
  • the light emitting layer is incorporated into the device.
  • devices include, but are not limited to, OLED bulbs, OLED lamps, television displays, computer monitors, mobile phones and tablets.
  • the electronic device comprises an OLED having an anode, a cathode, and at least one organic layer comprising a light emitting layer between the anode and the cathode.
  • the components described herein can be incorporated into a variety of photosensitive or photoactivating devices, such as OLEDs or optoelectronic devices.
  • the construct may be useful for facilitating charge transfer or energy transfer within the device and / or as a hole transport material.
  • Examples of the device include an organic light emitting diode (OLED), an organic integrated line (OIC), an organic field effect transistor (O-FET), an organic thin film (O-TFT), an organic light emitting transistor (O-LET), and an organic solar cell. (O-SC), organic optical detectors, organic photoreceivers, organic field-quench devices (O-FQD), light emitting fuel cells (LECs) or organic laser diodes (O-lasers).
  • OLED organic light emitting diode
  • OIC organic integrated line
  • O-FET organic field effect transistor
  • OFTFT organic thin film
  • O-LET organic light emitting transistor
  • O-SC organic solar cell.
  • O-SC organic solar cell.
  • organic optical detectors organic photoreceivers
  • O-FQD organic field-quench devices
  • LOCs light emitting fuel cells
  • O-lasers organic laser diodes
  • the electronic device comprises an OLED comprising an anode, a cathode, and at least one organic layer comprising a light emitting layer between the anode and the cathode.
  • the device comprises an OLED of different colors.
  • the device comprises an array containing a combination of OLEDs.
  • the combination of OLEDs is a combination of three colors (eg RGB).
  • the combination of OLEDs is a combination of colors that are neither red nor green nor blue (eg, orange and yellow-green).
  • the combination of OLEDs is a combination of two colors, four colors or more.
  • the device is A circuit board having a first surface with a mounting surface and a second surface opposite the mounting surface and defining at least one opening.
  • At least one OLED that has The housing for the circuit board and An OLED light comprising at least one connector located at the end of the housing, wherein the housing and the connector define a package suitable for mounting in a lighting fixture.
  • the OLED light has a plurality of OLEDs mounted on a circuit board such that light is emitted in multiple directions.
  • some light emitted in the first direction is polarized and emitted in the second direction.
  • a reflector is used to polarize the light emitted in the first direction.
  • the light emitting layer of the present invention can be used in a screen or display.
  • the compounds according to the invention are deposited onto a substrate using steps such as, but not limited to, vacuum evaporation, deposition, vapor deposition or chemical vapor deposition (CVD).
  • the substrate is a photoplate structure useful in two-sided etching that provides pixels with a unique aspect ratio.
  • the screen also referred to as a mask
  • the design of the corresponding artwork pattern allows the placement of very steep, narrow tie bars between pixels in the vertical direction, as well as large, wide-ranging bevel openings in the horizontal direction.
  • Pixel internal patterning makes it possible to construct 3D pixel openings with different aspect ratios in the horizontal and vertical directions.
  • imaged "stripe" or halftone circles in the pixel area protects the etching in the particular area until these particular patterns are undercut and removed from the substrate. At that time, all the pixel regions are processed at the same etching rate, but the depth varies depending on the halftone pattern.
  • By changing the size and spacing of the halftone patterns it is possible to etch with different protection rates within the pixel, allowing for the deep localized etching required to form steep vertical bevels. ..
  • the preferred material for the vapor deposition mask is Invar.
  • Invar is a metal alloy that is cold-rolled in the form of a long thin sheet at a steel mill. Invar cannot be electrodeposited onto the spin mandrel as a nickel mask.
  • a suitable and low-cost method for forming an opening region in a vapor deposition mask is a wet chemical etching method.
  • the screen or display pattern is a pixel matrix on a substrate.
  • the screen or display pattern is processed using lithography (eg, photolithography and e-beam lithography).
  • the screen or display pattern is processed using wet chemical etching.
  • the screen or display pattern is processed using plasma etching.
  • the OLED display is generally manufactured by forming a large mother panel and then cutting the mother panel in cell panel units. Normally, each cell panel on the mother panel forms a thin film transistor (TFT) having an active layer and a source / drain electrode on a base substrate, a flattening film is applied to the TFT, and a pixel electrode and a light emitting layer are applied. , The counter electrode and the encapsulating layer are formed in order over time, and are formed by cutting from the mother panel.
  • TFT thin film transistor
  • the OLED display is generally manufactured by forming a large mother panel and then cutting the mother panel in cell panel units.
  • each cell panel on the mother panel forms a thin film transistor (TFT) having an active layer and a source / drain electrode on a base substrate, a flattening film is applied to the TFT, and a pixel electrode and a light emitting layer are applied.
  • TFT thin film transistor
  • the counter electrode and the encapsulating layer are formed in order over time, and are formed by cutting from the mother panel.
  • a method of manufacturing an organic light emitting diode (OLED) display is provided, wherein the method is: The process of forming a barrier layer on the base base material of the mother panel, A step of forming a plurality of display units on a cell panel unit on the barrier layer, A step of forming an encapsulation layer on each of the display units of the cell panel, A step of applying an organic film to the interface portion between the cell panels is included.
  • the barrier layer is, for example, an inorganic film formed of SiNx, the ends of the barrier layer being coated with an organic film formed of polyimide or acrylic.
  • the organic film helps the mother panel to be softly cut in cell panel units.
  • the thin film transistor (TFT) layer comprises a light emitting layer, a gate electrode, and a source / drain electrode.
  • Each of the plurality of display units may have a thin film transistor (TFT) layer, a flattening film formed on the TFT layer, and a light emitting unit formed on the flattened film, and the interface portion may have a light emitting unit.
  • the applied organic film is formed of the same material as the flattening film, and is formed at the same time as the flattening film is formed.
  • the light emitting unit is coupled to the TFT layer by a passivation layer, a flattening film in between, and an encapsulating layer that coats and protects the light emitting unit.
  • the organic film is not coupled to either the display unit or the encapsulation layer.
  • each of the organic film and the flattening film may contain either polyimide or acrylic.
  • the barrier layer may be an inorganic film.
  • the base substrate may be made of polyimide.
  • the method further comprises a step of attaching a carrier substrate made of a glass material to the other surface of the base substrate before forming a barrier layer on one surface of the base substrate made of polyimide. It may include a step of separating the carrier substrate from the base substrate prior to cutting along the interface portion.
  • the OLED display is a flexible display.
  • the passivation layer is an organic film placed on the TFT layer for coating the TFT layer.
  • the flattening film is an organic film formed on the passivation layer.
  • the flattening film is made of polyimide or acrylic, similar to the organic film formed at the ends of the barrier layer. In some embodiments, the flattening film and the organic film are formed simultaneously during the manufacture of the OLED display. In some embodiments, the organic film may be formed at the edges of the barrier layer, whereby a portion of the organic film is in direct contact with the base substrate and the rest of the organic film is removed. , Surrounding the edge of the barrier layer and in contact with the barrier layer.
  • the light emitting layer has a pixel electrode, a counter electrode, and an organic light emitting layer disposed between the pixel electrode and the counter electrode.
  • the pixel electrode is connected to a source / drain electrode in the TFT layer.
  • an appropriate voltage is formed between the pixel electrode and the counter electrode so that the organic light emitting layer emits light, thereby the image. Is formed.
  • an image forming unit having a TFT layer and a light emitting unit will be referred to as a display unit.
  • the encapsulation layer that covers the display unit and prevents the penetration of external moisture may be formed in a thin film encapsulation structure in which organic films and inorganic films are alternately laminated.
  • the encapsulation layer has a thin film encapsulation structure in which a plurality of thin films are laminated.
  • the organic film applied to the interface section is spaced apart from each of the plurality of display units.
  • the organic film is formed in such a manner that some of the organic films are in direct contact with the base substrate and the rest of the organic film surrounds the edges of the barrier layer while in contact with the barrier layer. Will be done.
  • the OLED display is flexible and uses a flexible base substrate made of polyimide.
  • the base substrate is formed on a carrier substrate made of a glass material, which is then separated.
  • the barrier layer is formed on the surface of the base substrate opposite the carrier substrate.
  • the barrier layer is patterned according to the size of each cell panel. For example, a base substrate is formed on all surfaces of the mother panel, while a barrier layer is formed according to the size of each cell panel, thereby forming a groove in the interface portion between the barrier layers of the cell panel. Each cell panel can be cut along the groove.
  • the manufacturing method further comprises the step of cutting along an interface portion, where a groove is formed in the barrier layer, at least a portion of the organic film is formed in the groove, and the groove is formed. Does not penetrate the base substrate.
  • the TFT layer of each cell panel is formed and a passivation layer, which is an inorganic film, and a flattening film, which is an organic film, are placed on the TFT layer to cover the TFT layer.
  • a polyimide or acrylic flattening film is formed, for example, the groove of the interface portion is covered with an organic film made of polyimide or acrylic, for example. This prevents cracking by allowing the organic film to absorb the impact generated when each cell panel is cut along the groove at the interface section.
  • the groove of the interface portion between the barrier layers is covered with an organic film to absorb the impact that can be transmitted to the barrier layer without the organic film, so that each cell panel is softly cut and the barrier layer is used. It may be prevented from cracking.
  • the organic film and the flattening film covering the grooves of the interface portion are arranged at intervals from each other.
  • the organic film and the flattening film are interconnected as one layer, external moisture may infiltrate into the display unit through the flattening film and the portion where the organic film remains.
  • the organic film and the flattening film are spaced apart from each other so that the organic film is spaced apart from the display unit.
  • the display unit is formed by the formation of a light emitting unit and the encapsulation layer is placed on the display unit to cover the display unit.
  • the carrier base material that supports the base base material is separated from the base base material.
  • the carrier substrate is separated from the base substrate due to the difference in the coefficient of thermal expansion between the carrier substrate and the base substrate.
  • the mother panel is cut in cell panel units.
  • the mother panel is cut along the interface between the cell panels using a cutter.
  • the grooves in the interface section where the mother panel is cut are covered with an organic film so that the organic film absorbs the impact during cutting.
  • the barrier layer can be prevented from cracking during cutting. In some embodiments, the method reduces the defective rate of the product and stabilizes its quality. Another aspect is the barrier layer formed on the base substrate, the display unit formed on the barrier layer, the encapsulated layer formed on the display unit, and the organic coating on the edges of the barrier layer.
  • the present application also provides a method for designing a light emitting composition that can be used for a light emitting layer of an organic electroluminescence element.
  • the method for designing a luminescent composition of the present invention includes the following steps 1 to 3. [Step 1] The emission lifetime of a composition containing the first organic compound, the second organic compound which is a delayed fluorescent material, and the third organic compound and satisfying the formulas (a) and (b) is evaluated.
  • Step 2 A composition in which at least one of the first organic compound, the second organic compound which is a delayed fluorescent material, and the third organic compound is replaced within the range satisfying the formulas (a) and (b). Evaluate the emission lifetime at least once [Step 3] The combination of compounds having the best evaluated lifetime is selected.
  • the luminescence lifetime may be evaluated by actually causing the luminescent composition to emit light, or by calculation. Further, the luminescent composition may be actually made to emit light and evaluated by using a calculation method.
  • the evaluation is preferably performed from a comprehensive viewpoint using the high practicality as an index.
  • it is required to select and replace the first organic compound, the second organic compound and the third organic compound within the range satisfying the formulas (a) and (b).
  • the second organic compound needs to be selected from delayed fluorescent materials and substituted. Substitution of the compound in step 2 is preferably replaced with a compound that is likely to give a better evaluation.
  • Step 2 may be performed, for example, 10 times or more, 100 times or more, 1000 times or more, and 10000 times or more.
  • performance other than the light emission lifetime may also be measured and evaluated.
  • the light emitting composition designed by the design method of the present invention can be used as a light emitting layer of an organic electroluminescence element (particularly, the organic electroluminescence element of the present invention).
  • the method for designing a luminescent composition of the present invention can be stored and used as a program.
  • the program can be stored in a recording medium and can be transmitted and received by electronic means.
  • the features of the present invention will be described in more detail with reference to Test Examples, Examples and Synthesis Examples.
  • the materials, treatment contents, treatment procedures, etc. shown below can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the specific examples shown below.
  • the emission characteristics are evaluated by a source meter (Caseley: 2400 series), a semiconductor parameter analyzer (Agilent Technology: E5273A), an optical power meter measuring device (Newport: 1930C), and an optical spectroscope.
  • a cathode was formed by depositing aluminum (Al) to a thickness of 100 nm to obtain a device for measuring hole mobility. Further, a device for hole mobility measurement was produced by the same procedure, changing only the point that the third organic compound was not used. The hole mobility was measured using each device, and the result of calculating (hole mobility of the device using the third organic compound) / (hole mobility of the device not using the third organic compound) was calculated. The hole mobility ratio was RHM . As the device, H1 was used as the first organic compound, T1 was used as the second organic compound, and each compound shown in Table 1 was used as the third organic compound.
  • Table 1 shows the HOMO energy E HOMO (3), the LUMO energy E LUMO (3), the lowest excited single term energy ES1 (3), and the lowest excited triplet energy ET1 (3) of each third organic compound used. ), The difference ⁇ EST between the excited single-term energy and the excited triple-term energy is shown. Since the energy of the HOMO of T1 used as the second organic compound is -6.01 eV, the energy difference ⁇ E HOMO between the HOMO of the third organic compound and the HOMO of the second organic compound is calculated for each device using the third organic compound. Can be calculated.
  • FIG. 2 plots the relationship between the hole mobility ratio RHM and the energy difference ⁇ E HOMO between the HOMOs of the third organic compound and the second organic compound.
  • the results in FIG. 2 show that the hole mobility significantly decreases when the energy difference ⁇ E HOMO between the HOMOs of the third organic compound and the second organic compound becomes 0.65 eV or more. That is, it was confirmed that when ⁇ E HOMO was 0.65 eV or more, the hole mobility was lowered due to the generation of trap sites by the third organic compound.
  • Examples 1 and 2 Comparative Example 1
  • An organic electroluminescence element was prepared and evaluated. By laminating each of the following thin films at a vacuum degree of 5.0 ⁇ 10-5 Pa on a glass substrate on which an anode made of indium tin oxide (ITO) having a film thickness of 50 nm is formed by a vacuum vapor deposition method.
  • An organic electroluminescence element was manufactured. First, HAT-CN was formed on ITO to a thickness of 10 nm, and NPD was formed on it to a thickness of 30 nm. Next, Tris-PCz was formed to a thickness of 10 nm, and EB1 was formed on the Tris-PCz to a thickness of 5 nm.
  • the first organic compound, the second organic compound, and the third organic compound were co-deposited from different vapor deposition sources to form a layer having a thickness of 30 nm to form a light emitting layer.
  • SF3-TRZ was formed to a thickness of 10 nm, and then Liq and SF3-TRZ were co-deposited from different vapor deposition sources to form a layer having a thickness of 30 nm.
  • the contents of Liq and SF3-TRZ in this layer were 30% by weight and 70% by weight, respectively.
  • each organic electroluminescence element of Examples 1 and 2 and Comparative Example 1 was prepared. Further, each organic electroluminescence element corresponding to Examples 1 and 2 and Comparative Example 1 was produced in the same manner by changing only the point that the third organic compound was not used, and the element containing the third organic compound was prepared in the same manner. It was measured how many times the LT95 was multiplied by the element containing no third organic compound.
  • LT95 is the time required for the emission intensity to reach 95% of the start of emission.
  • the results are shown in Table 2 as relative values with the element of Comparative Example 1 as 1.
  • Table 2 also shows the results of measuring the minimum excited singlet energy ES1 , the maximum emission wavelength, and the ionization energy of each organic compound.
  • Example 3 an organic electroluminescence device using two types of delayed fluorescent materials as the second organic compound was produced.
  • compound H2 is 68.5% by weight as the first organic compound
  • compound T133 is 30% by weight and compound T33 is 1% by weight as the second organic compound
  • compound F4 is 0 as the third organic compound.
  • the point where the light emitting layer was co-deposited was changed so as to be .5% by weight, and the organic electroluminescence element was produced by the same procedure as in Example 1 except for the above.
  • Table 2 shows the results of the same measurements as in Example 1.
  • the data of the second organic compound was the data of the compound T133 having a large content.
  • the energy difference ⁇ E HOMO (that is, E HOMO (3) -E HOMO (2)] between the HOMOs of the third organic compound and the second organic compound is less than 0.65 eV.
  • each organic electroluminescence element of Example 2 is a stable element due to a long life
  • the organic electroluminescence element of Comparative Example 1 having ⁇ E HOMO of 0.65 eV may have a short life and lack stability. confirmed.
  • the change in voltage when each of the organic electroluminescence elements of Examples 1 and 2 and Comparative Example 1 was driven at 10 mA / cm 2 the voltage increase in Examples 1 and 2 was higher than that in Comparative Example 1. It was suppressed. Further, when Example 1 and Example 2 were compared, it was confirmed that the element of Example 1 was more suppressed in the voltage increase.
  • Example 4 an organic electroluminescence element having a different light emitting method was produced.
  • compound H1 was used as the first organic compound
  • compound T63 was used as the second organic compound
  • compound F was used as the third organic compound.
  • the energy of HOMO of compound F is higher than the energy of HOMO of compound T63.
  • Each thin film was laminated with a vacuum degree of 1 ⁇ 10 -6 Pa by a vacuum vapor deposition method on a glass substrate having a thickness of 2 mm on which an anode made of indium tin oxide (ITO) having a film thickness of 50 nm was formed.
  • ITO indium tin oxide
  • HAT-CN was formed on ITO to a thickness of 10 nm, and EB1 was formed on it to a thickness of 10 nm.
  • the first organic compound (69% by weight), the second organic compound (30% by weight), and the third organic compound (1% by weight) are co-deposited from different vapor deposition sources to form a light emitting layer having a thickness of 40 nm. did.
  • HB1 was formed to a thickness of 10 nm, and then SF3-TRZ and Liq (weight ratio 70:30) were formed to a thickness of 30 nm. Further, Liq was formed to a thickness of 2 nm, and then aluminum (Al) was deposited to a thickness of 100 nm to form a cathode. As a result, a bottom emission type organic electroluminescence element was produced.
  • a multilayer transparent anode of indium tin oxide (ITO) having a thickness of 10 nm and a silver-palladium-copper alloy (APC) having a thickness of 150 nm was formed on a glass substrate having a thickness of 2 mm.
  • the thin films were laminated by a vacuum deposition method at a vacuum degree of 1 ⁇ 10 -6 Pa.
  • HAT-CN was formed on ITO to a thickness of 10 nm
  • EB1 was formed on it to a thickness of 10 nm.
  • the first organic compound (69% by weight), the second organic compound (30% by weight), and the third organic compound (1% by weight) are co-deposited from different vapor deposition sources to form a light emitting layer having a thickness of 40 nm.
  • HB1 was formed to a thickness of 10 nm
  • SF3-TRZ Liq (weight ratio is the same as that of the bottom emission method) was formed to a thickness of 30 nm, and Liq was further formed to a thickness of 2 nm. ..
  • a cathode was formed by depositing Mg: Ag (weight ratio 1:10) to a thickness of 15 nm, and a cap layer was formed by further depositing NPD to a thickness of 105 nm. As a result, a top-emission organic electroluminescence element was produced.
  • the EQE of the top emission method was 1.15 times that of the bottom emission method, showing a high value of 27.6%.
  • the emission peak intensity of the top emission method was 2.98 times that of the bottom emission method.
  • the composition of the light emitting layer was changed to the first organic compound (Compound H1; 69.5% by weight), the second organic compound (Compound T63; 30% by weight), and the third organic compound (Compound F; 0.5% by weight). Then, in the same manner, a top emission type element and a bottom emission type element were manufactured and evaluated. As a result, the external quantum yield (EQE) and emission peak intensity of each of the produced organic electroluminescence devices showed higher values.
  • the EQE of the top emission method was 1.52 times that of the bottom emission method, showing a high value of 36.4%.
  • the emission peak intensity of the top emission method was 4.32 times that of the bottom emission method. From the above, it was confirmed that the organic electroluminescence element satisfying the conditions of the present invention realizes high luminous efficiency.
  • N-Butyllithium (1.15 mL, 1.8 mmol, 1.6 M hexane solution) was added to a dehydrated toluene solution (80 mL) in which Intermediate 1 (1.00 g, 1.5 mmol) was dissolved, and a nitrogen atmosphere at -30 ° C was added. The mixture was gradually added below, warmed to room temperature, and then stirred at 60 ° C. for 2 hours. Further, boron tribromide (0.18 mL, 1.8 mmol) was added at ⁇ 15 ° C., and the mixture was stirred at room temperature for 2 hours.
  • N, N-diisopropylethylamine (0.53 mL, 3.6 mmol) was added to this mixture at 0 ° C., the mixture was warmed to room temperature, and then stirred at 110 ° C. for 10 hours. After cooling this reaction mixture to room temperature, an aqueous solution of sodium acetate and ethyl acetate was added, and the precipitated precipitate was separated by filtration. The obtained crude product was dissolved in warm toluene, recrystallized, and further sublimated to obtain the desired compound 1 in a yield of 0.30 g and a yield of 34%.
  • N-Butyllithium (3.07 mL, 4.9 mmol, 1.6 M hexane solution) was added to a dehydrated toluene solution (50 mL) in which Intermediate 2 (2.00 g, 4.1 mmol) was dissolved, and a nitrogen atmosphere at -30 ° C was added. The mixture was gradually added below, warmed to room temperature, and then stirred at 60 ° C. for 2 hours. Further, boron tribromide (0.47 mL, 4.9 mmol) was added at ⁇ 15 ° C., and the mixture was stirred at room temperature for 1 hour.
  • N, N-diisopropylethylamine (1.43 mL, 8.2 mmol) was added to this mixture at 0 ° C., the mixture was warmed to room temperature, and then stirred at 110 ° C. for 8 hours. After cooling the reaction mixture to room temperature, an aqueous solution of sodium acetate and ethyl acetate was added, and the precipitated precipitate was filtered off. The obtained crude product was dissolved in warm toluene, recrystallized, and further sublimated to obtain the desired compound 2 in a yield of 0.49 g and a yield of 29%.
  • a toluene solution of compound 1 (concentration 10-5 mol / L) was prepared in a glove box with a nitrogen atmosphere. Further, a thin film (single film) of Compound 1 was formed on a quartz substrate by a vacuum vapor deposition method under the condition of a vacuum degree of 10-5 Torr or less to have a thickness of 50 nm to obtain an organic photoluminescence element. Separately, a thin film in which compound 1 and mCBP are deposited from different vapor deposition sources on a quartz substrate by a vacuum vapor deposition method under the condition of a vacuum degree of 10-5 Torr or less, and the concentration of compound 1 is 1% by weight.
  • A (mixed film) was formed to a thickness of 30 nm to obtain an organic photoluminescence element.
  • a toluene solution of compound 2, a single membrane of compound 2, and a mixed membrane of compound 2 and mCBP were prepared by the same production method as for each element of compound 1, except that compound 2 was used instead of compound 1.
  • a mixed film of Comparative Compound A and mCBP was prepared by the same preparation method as that of the mixed film of Compound 1 and mCBP except that Comparative Compound A was used instead of Compound 1.
  • kr is the rate constant of the radiation deactivation process
  • k nr is the rate constant of the non-radiation deactivation process
  • k ISC is the intersystem crossing from the excited singlet state to the excited triplet state.
  • the rate constant of the process, “k RISC” indicates the rate constant of the inverse intersystem crossing process from the excited triplet state to the excited singlet state. 340 nm excitation light was used to measure the emission characteristics.
  • ⁇ Evaluation of EL element> The results of the evaluation of the EL element are shown below.
  • the light absorption spectrum is measured using a spectrophotometer (Perkin Elmer Co., Ltd .: LAMBDA950-PKA), and the emission characteristics are evaluated using a fluorescence spectrophotometer (Nippon Spectral Co., Ltd .: FP-6500), absolute PL quantum yield.
  • the rate measurement system (Hamamatsu Photonics: C11347-01 Quantaurus-QY), fluorescence lifetime measurement device (Hamamatsu Photonics: C11367-03), and streak camera (Hamamatsu Photonics: C4334) were used.
  • the EL element characteristics were evaluated using a source meter (Keithley: 2400 series), an absolute EQE measurement system (Hamamatsu Photonics: C9920-12), and a luminance meter (Topcon: SR-3AR).
  • the HOMO and LUMO energies were measured with a voltammetry analyzer (ALS608D) using ferrocene as a standard substance and an N, N-dimethylformamide solution of TBAPF 6 as an electrolytic solution.
  • Table 5 summarizes the lowest excited singlet energy ES1, the HOMO energy E HOMO , and the LUMO energy E LUMO of the material used for the light emitting layer of the EL element.
  • Example 5 In this example, mCBP was used as the first organic compound, HDT-1 as the second organic compound, and compound 1 as the third organic compound to prepare an organic electroluminescence. Specifically, each thin film was laminated on a glass substrate having an anode made of indium tin oxide (ITO) having a film thickness of 100 nm by a vacuum vapor deposition method at a vacuum degree of 10-5 Torr or less. First, HAT-CN was formed on ITO to a thickness of 10 nm, and Tris-PCz was formed on it to a thickness of 30 nm. Subsequently, mCBP was formed to a thickness of 5 nm.
  • ITO indium tin oxide
  • mCBP, HDT-1 and compound 1 were co-deposited from different vapor deposition sources to form a layer having a thickness of 30 nm to form a light emitting layer.
  • the concentration of HDT-1 was 20% by weight, and the concentration of compound 1 was 1% by weight.
  • SF3-TRZ was formed to a thickness of 10 nm, and SF3-TRZ and Liq were co-deposited from different vapor deposition sources on the SF3-TRZ to form a layer having a thickness of 20 nm.
  • the concentration of Liq was set to 30% by weight.
  • Liq was formed to a thickness of 2 nm, and then aluminum (Al) was vapor-deposited to a thickness of 100 nm to form a cathode, which was used as an organic electroluminescence device (EL device 1).
  • an organic electroluminescence device (EL device 2) was manufactured by the same manufacturing method as that of the EL device 1 except that the concentration of the compound 1 in the light emitting layer was changed to 0.5% by weight.
  • Example 6 Similar to Example 5, an organic electroluminescence element (EL element 3) having a compound 2 concentration of 1% by weight in the light emitting layer and light emitting light are used, except that compound 2 is used as the third organic compound instead of compound 1.
  • Example 7 In the same manner as in Example 5, the organic electroluminescence element (EL element 5) having a compound 3 concentration of 1% by weight in the light emitting layer and light emission, except that compound 3 is used as the third organic compound instead of compound 1. An organic electroluminescence device (EL device 6) having a layer compound 3 concentration of 0.5% by weight was produced.
  • Table 6 shows the device characteristics of each EL element manufactured in Examples 5 to 7.
  • the turn- on voltage Von shows the voltage at 10 cd / m 2
  • the drive voltage V driving shows the voltage at 5 mA / cm 2 .
  • the maximum luminance L max , the external quantum efficiency EQE, and the emission maximum wavelength ⁇ EL were measured at 1000 cd / m 2 .
  • EQE / EQE max indicates the ratio of the external quantum efficiency to the maximum external quantum efficiency measured at 1000 cd / m 2
  • LT90 indicates the time until the brightness becomes 90% of the initial luminance (1000 cd / m 2 ).
  • the emission maximum wavelength ⁇ EL of each EL element is approximately one with the emission maximum wavelength ⁇ em observed in the mixed film of the light emitting material (compounds 1 to 3 which are the third organic compounds) and mCBP. I was doing it. From this, it was confirmed that the light emission observed by each EL element was derived from the light emitting material, and that the energy transfer from HDT-1 to each light emitting material was ensured. Further, when the device characteristics are compared between the elements having the same concentration of the light emitting material, the LT90 of the EL elements 1 and 3 has a larger value than that of the EL element 5, and the EL elements 2 and 4 have the same as the EL element 6. Compared with this, LT90 was a large value.
  • the EL element 2 showed an LT90 more than twice that of the EL element 6 using the compound 3 known as an excellent light emitting material.
  • the EL elements 1 to 4 have lower roll-off (larger EQE / EQE max ), higher maximum brightness L max , and turn-on voltage Von and turn-on voltage V on , respectively, as compared with EL elements 5 and 6 having the same concentration of light emitting material.
  • the driving voltage V driving showed a low value. In this way, the EL elements 1 to 4 have better performance than the EL elements 5 and 6, because in the EL elements 1 to 4, the HOMO level of the compounds 1 and 2 is the HOMO level of HDT-1.
  • FIG. 5 shows the results of measuring the transient attenuation curve of the emission intensity immediately after driving the EL elements 1 to 4 at 6 V, supplying a current with a reverse bias voltage of ⁇ 10 V, and turning off the current.
  • "0" corresponds to the time when the reverse bias current is turned off.
  • EL elements 1 to 6 are indicated as “EL1” to "EL6”.
  • the spike signal of the EL element 3 is larger than the spike signal of the EL element 4 in which the concentration of the light emitting material is halved, this spike signal is mainly derived from the carrier trapped by the light emitting material. It was understood that the emission intensity of the spike signal reflects the number of carrier traps in the emission material. Further, as shown in Table 6, since the EL element 4 has a lower roll-off, a higher maximum brightness L max , and a large LT90 than the EL element 3, the smaller the number of carrier traps in the light emitting material, the better. It was also confirmed that better device performance can be obtained. On the other hand, looking at FIG.
  • a spike signal is hardly recognized from the EL elements 1 and 2 in which the HOMO levels of the delayed fluorescent material (second organic compound) and the light emitting material (third organic compound) are almost the same, and the delay is observed.
  • the spike signal of the EL elements 3 and 4 whose HOMO level of the light emitting material is 0.17 eV shallower than that of the HOMO level of the fluorescent material is also the spike signal of the EL elements 5 and 6 whose HOMO level of the light emitting material is as large and shallow as 0.35 eV.
  • the intensity was clearly lower than that of the signal. That is, the magnitude of the spike signal changed depending on the positional relationship between the HOMO levels of the delayed fluorescent material and the light emitting material.
  • the spike signal was derived from the hole trapped in the HOMO of the light emitting material.
  • the HOMO level of the light emitting material is deeper than the HOMO level, based on the level shallower by 0.2 eV than the HOMO level of the delayed fluorescence material.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009084256A (ja) * 2007-10-03 2009-04-23 Canon Inc ビナフチル化合物及びこれを用いた有機発光素子
WO2014157619A1 (ja) * 2013-03-29 2014-10-02 国立大学法人九州大学 有機エレクトロルミネッセンス素子
JP5669163B1 (ja) * 2013-08-14 2015-02-12 国立大学法人九州大学 有機エレクトロルミネッセンス素子
JP2017168803A (ja) * 2015-07-23 2017-09-21 株式会社半導体エネルギー研究所 発光素子、表示装置、電子機器、及び照明装置
WO2020039930A1 (ja) * 2018-08-23 2020-02-27 国立大学法人九州大学 有機発光素子、組成物および膜
WO2020067143A1 (ja) * 2018-09-25 2020-04-02 国立大学法人京都大学 化合物、発光材料、遅延蛍光体、有機発光素子、酸素センサー、分子の設計方法およびプログラム

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3401972B1 (en) 2017-05-08 2019-03-27 cynora GmbH Blue light emitting electroluminescent device
US11696495B2 (en) 2018-08-06 2023-07-04 Lg Display Co., Ltd. Organic emitting compound, and organic light emitting diode and organic light emitting display device including the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009084256A (ja) * 2007-10-03 2009-04-23 Canon Inc ビナフチル化合物及びこれを用いた有機発光素子
WO2014157619A1 (ja) * 2013-03-29 2014-10-02 国立大学法人九州大学 有機エレクトロルミネッセンス素子
JP5669163B1 (ja) * 2013-08-14 2015-02-12 国立大学法人九州大学 有機エレクトロルミネッセンス素子
JP2017168803A (ja) * 2015-07-23 2017-09-21 株式会社半導体エネルギー研究所 発光素子、表示装置、電子機器、及び照明装置
WO2020039930A1 (ja) * 2018-08-23 2020-02-27 国立大学法人九州大学 有機発光素子、組成物および膜
WO2020067143A1 (ja) * 2018-09-25 2020-04-02 国立大学法人京都大学 化合物、発光材料、遅延蛍光体、有機発光素子、酸素センサー、分子の設計方法およびプログラム

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SAKURAI MANABU, KABE RYOTA, FUKI MASAAKI, LIN ZESEN, JINNAI KAZUYA, KOBORI YASUHIRO, ADACHI CHIHAYA, TACHIKAWA TAKASHI: "Organic photostimulated luminescence associated with persistent spin-correlated radical pairs", COMMUNICATIONS MATERIALS, vol. 2, no. 1, 1 December 2021 (2021-12-01), XP055931684, DOI: 10.1038/s43246-021-00178-3 *

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