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WO2018159663A1 - Matériaux luminescents, élément luminescent organique, et composés - Google Patents

Matériaux luminescents, élément luminescent organique, et composés Download PDF

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WO2018159663A1
WO2018159663A1 PCT/JP2018/007464 JP2018007464W WO2018159663A1 WO 2018159663 A1 WO2018159663 A1 WO 2018159663A1 JP 2018007464 W JP2018007464 W JP 2018007464W WO 2018159663 A1 WO2018159663 A1 WO 2018159663A1
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group
compound
general formula
material according
luminescent material
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PCT/JP2018/007464
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Japanese (ja)
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啓太 辻
陽一 ▲土▼屋
安達　千波矢
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国立大学法人九州大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a light emitting material and an organic light emitting device using the light emitting material.
  • the present invention also relates to compounds used for these light emitting materials and organic light emitting devices.
  • Thermally activated delayed fluorescent material is the transition from excited triplet state to excited singlet state due to the absorption of thermal energy when transitioning to excited triplet state. It is a compound that emits fluorescence when returning to the back.
  • the fluorescence due to such a route is called delayed fluorescence because it is observed later than the fluorescence from the excited singlet state (normal fluorescence) directly generated without passing through the reverse intersystem crossing.
  • delayed fluorescence because it is observed later than the fluorescence from the excited singlet state (normal fluorescence) directly generated without passing through the reverse intersystem crossing.
  • the generation probability of an excited singlet state and an excited triplet state is 25%: 75%, there is a limit to the improvement of the light emission efficiency only with the fluorescence generated directly from the excited singlet state. is there.
  • the excited triplet state energy generated with a probability of 75% can also be effectively used for fluorescence emission, so that higher luminous efficiency can be expected.
  • a conventional typical thermally activated delayed fluorescent material includes a structure (DA structure) in which a donor site (D) exhibiting electron donor properties and an acceptor site (A) exhibiting electron acceptor properties are bonded.
  • DA structure a structure in which a donor site (D) exhibiting electron donor properties and an acceptor site (A) exhibiting electron acceptor properties are bonded.
  • Known for example, Non-Patent Documents 1 to 4.
  • groups have been known as groups exhibiting electron donor properties and electron acceptor properties, and new groups have been developed. Then, by selecting a donor site (D) from a group exhibiting electron donor properties, selecting an acceptor site (A) from a group exhibiting electron acceptor properties, and designing a molecule that combines them, Various attempts have been made to develop compounds having good luminescent properties.
  • a light emitting material comprising a compound that satisfies any of the following conditions (A) to (C).
  • B A compound having a structure in which a donor group having a Hammett ⁇ p value of ⁇ 0.5 or more and less than 0 and an acceptor group having a Hammett ⁇ p value of more than 0 and 0.5 or less are linked.
  • C A compound having a structure in which two different donor groups are bonded to each other.
  • [3] luminescent material according to the minimum difference Delta] E ST excited singlet energy level E S1 and the lowest excited triplet energy level E T1 compound is less than 0.4 eV, [1] or [2].
  • R 1 to R 8 each independently represents a hydrogen atom or a substituent
  • R 9 represents a substituent.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 4 and R 9 , R 5 and R 9 are respectively They may be bonded to each other to form a cyclic structure.
  • Z represents an electron withdrawing group.
  • the general formula (1) satisfies the above (A) or (B).
  • the light emitting material according to [6], wherein Z in the general formula (1) is> C ⁇ O.
  • 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 18 and R 19 , R 19 and R 20 , R 20 And R 11 may be bonded to each other to form a cyclic structure.
  • n represents an integer of 1 to 4.
  • the general formula (2) satisfies the above (C).
  • [21] The luminescent material according to [20], wherein n is 2.
  • D represents an optionally substituted dibenzofuran-4,6-diyl group or an optionally substituted dibenzothiophene-4,6-diyl group.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all the hydrogen atoms in the molecule may be 1 H, or a part or all of the hydrogen atoms are 2 H. (Deuterium D) may be used.
  • the luminescent material of the present invention is characterized by comprising a compound that satisfies any of the following conditions (A) to (C).
  • B A compound having a structure in which a donor group having a Hammett ⁇ p value of ⁇ 0.5 or more and less than 0 and an acceptor group having a Hammett ⁇ p value of more than 0 and 0.5 or less are linked.
  • C A compound having a structure in which two different donor groups are bonded to each other.
  • the “acceptor group” means a group whose Hammett ⁇ p + value is positive (greater than 0). Further, in the present application, the “donor group” means a group having a Hammett ⁇ p + value that is negative (less than 0).
  • the “Hammett ⁇ p + value” in the present invention is L. P. Proposed by Hammett, it quantifies the effect of substituents on the reaction rate or equilibrium of para-substituted benzene derivatives. Specifically, the following formula is established between the substituent in the para-substituted benzene derivative and the reaction rate constant or equilibrium constant: This is a constant ( ⁇ p ) peculiar to the substituent in.
  • k is a rate constant of a benzene derivative having no substituent
  • k 0 is a rate constant of a benzene derivative substituted with a substituent
  • K is an equilibrium constant of a benzene derivative having no substituent
  • K 0 is a substituent.
  • the equilibrium constant of the benzene derivative substituted with ⁇ , ⁇ represents the reaction constant determined by the type and conditions of the reaction.
  • the compound satisfying the above (A) has a structure in which two different acceptor groups are bonded to each other.
  • the two acceptor groups present in the compound satisfying (A) preferably have different acceptor strengths. That is, it is preferable to have a structure in which a relatively strong acceptor group and a relatively weak acceptor group are linked.
  • a relatively strong acceptor group for example, an optionally substituted triazine ring group can be exemplified.
  • examples of the relatively weak acceptor group include an optionally substituted acridone ring group.
  • the relatively strong acceptor group present in the compound satisfying the above (A) and the relatively weak acceptor group preferably have a ⁇ p value difference of 0.1 or more, and preferably 0.2 or more.
  • a range of 0.3 or more, a range of 0.5 or more, or a range of 0.7 or more may be selected.
  • a range of 1.5 or less and a range of 1.0 or less may be selected. May be.
  • ⁇ p of the relatively weak acceptor group may be selected, for example, from a range of more than 0 to 0.5 or less, may be selected from a range of more than 0 to 0.3 or less, or more than 0 to 0.15 or less You may select from the range.
  • Each of the two acceptor groups constituting the compound satisfying (A) may contain one or more small substituents.
  • the small substituent that may be contained in each acceptor group may not necessarily be a group that exhibits acceptor properties.
  • the acceptor group may contain a small donor group.
  • a donor group examples include an alkyl group, an alkoxy group, and an aryl group.
  • the alkyl group that can be a small substituent may be linear, branched, or cyclic, but is preferably linear or branched. Further, the number of carbon atoms of the alkyl group may be selected, for example, within the range of 1 to 10, selected from the range of 1 to 6, selected from the range of 1 to 4, or 1 to You may select from the range of 3.
  • the alkoxy group that can be a small substituent may be linear, branched, or cyclic, but is preferably linear or branched.
  • the number of carbon atoms of the alkoxy group may be selected, for example, from the range of 1 to 10, may be selected from the range of 1 to 6, may be selected from the range of 1 to 4, You may select from the range of 3.
  • the aryl group that can be a small substituent may be a single ring or a condensed ring, and the number of carbon atoms may be selected from the range of, for example, 6 to 40, or selected from the range of 6 to 14. It may also be selected from the range of 6-10. It is also preferable that the compound satisfying (A) does not contain any donor group in the molecule.
  • the compound satisfying the above (B) has a structure in which a donor group having a Hammett ⁇ p value of ⁇ 0.5 or more and less than 0 and an acceptor group having a Hammett ⁇ p value of more than 0 and 0.5 or less are linked.
  • a donor group include a carbazolyl group, and an N-carbazolyl group can be preferably exemplified.
  • an acridone ring group can be mentioned as such an acceptor group.
  • the ⁇ p value of the donor group may be selected from a range of ⁇ 0.1 or less, may be selected from a range of ⁇ 0.2 or less, and may be selected from a range of ⁇ 0.4 or more.
  • the ⁇ p value of the acceptor group may be selected, for example, from a range of 0.1 or more, may be selected from a range of 0.2 or more, or may be selected from a range of 0.4 or less, You may select from the range below 0.3.
  • the donor group having a Hammett's ⁇ p value of ⁇ 0.5 or more and less than 0 may contain a small acceptor group as long as the entire donor group exhibits a ⁇ p value of ⁇ 0.5 or more and less than 0. . Examples of such an acceptor group include a halogen atom (for example, a fluorine atom).
  • the acceptor group having a Hammett ⁇ p value of more than 0 and 0.5 or less may contain a small donor group as long as the entire acceptor group exhibits a ⁇ p value of more than 0 and less than 0.5. .
  • a donor group the corresponding description in (A) above can be referred to.
  • the compound satisfying the above (C) has a structure in which two different donor groups are bonded to each other.
  • the two donor groups present in the compound satisfying (C) preferably have different donor properties. That is, it is preferable to have a structure in which a relatively strong donor group and a relatively weak donor group are linked.
  • a relatively strong donor group for example, an optionally substituted triazine ring group can be exemplified.
  • the relatively weak donor group include a dibenzofuran ring group which may be substituted and a dibenzothiophene ring group which may be substituted.
  • the relatively strong donor group present in the compound satisfying the above (C) and the relatively weak donor group preferably have a ⁇ p value difference of 0.1 or more, and preferably 0.2 or more.
  • a range of 0.3 or more, a range of 0.5 or more, or a range of 0.7 or more may be selected.
  • a range of 1.5 or less or 1.0 or less may be selected. May be.
  • ⁇ p of the relatively weak donor group may be selected from a range of ⁇ 0.5 or more and less than 0, may be selected from a range of ⁇ 0.3 or more and less than 0, or ⁇ 0.15 You may select from the range below 0.
  • Each of the two donor groups constituting the compound satisfying (C) may each contain one or more small substituents.
  • the small substituent that may be contained in each donor group may not necessarily be a group that exhibits donor properties.
  • a small acceptor group may be included in the donor group.
  • an acceptor group include a halogen atom (for example, a fluorine atom). It is also preferred that the compound satisfying (C) does not contain any acceptor group in the molecule.
  • the light-emitting material of the present invention satisfies any of the conditions (A) to (C), and the difference between the lowest excited singlet energy level E S1 and the lowest excited triplet energy level E T1 of the compound ( ⁇ E ST ). Is particularly preferably small.
  • Delta] E ST may be selected within the range of, for example, 0.6eV or less, preferably less 0.4 eV, more preferably less 0.3 eV, and more preferably less 0.2 eV. If particular structures of compounds, approximate values of Delta] E ST is can be determined by calculation. For example, it can be calculated using a calculation method by Gaussian et al.
  • ⁇ E ST here is obtained by calculating the difference between the lowest excited singlet energy level (E S1 ) and the lowest excited triplet energy level (E T1 ) from the emission ends of the fluorescence and phosphorescence spectra. . Specifically, by implementing the following method can be determined easily Delta] E ST.
  • E S1 Lowest excited singlet energy level
  • a toluene solution (concentration: 1 ⁇ 10 ⁇ 5 M) containing a measurement target compound or a PMMA film (compound concentration: 0.1 mol%, thickness 100 nm) containing a measurement target compound formed on a silicon substrate is used as a measurement sample. Prepared and measured the fluorescence spectrum of this sample at room temperature (300K).
  • E S1 [eV] 1239.85 / ⁇ edge (2)
  • E T1 Lowest excited triplet energy level
  • a tangent line was drawn with respect to the rising edge of the phosphorescence spectrum on the short wavelength side, and a wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis was obtained.
  • a value obtained by converting this wavelength value into an energy value by the following conversion formula was defined as ET1 .
  • Conversion formula: E T1 [eV] 1239.85 / ⁇ edge
  • the tangent to the short wavelength rising edge of the phosphorescence spectrum was drawn as follows. When moving on the spectrum curve from the short wavelength side of the phosphorescence spectrum to the maximum value on the shortest wavelength side of the maximum value of the spectrum, the tangent at each point on the curve toward the long wavelength side was considered.
  • the slope of this tangent line increases as the curve rises (that is, as the vertical axis increases).
  • the tangent drawn at the point where the value of the slope takes the maximum value was taken as the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.
  • the maximum point having a peak intensity of 10% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above, and the slope value closest to the maximum value on the shortest wavelength side is the maximum value.
  • the tangent drawn at the point taken was taken as the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.
  • a sample is a toluene solution, it measures with a phosphorescence measuring apparatus at 77 [K].
  • a molecule having a smaller Delta] E ST design Is possible. Since such a compound can be a molecule having a larger band gap than the conventional thermally activated delayed fluorescent material, various blue light emitting materials can be developed according to the present invention.
  • the conventional thermally activated delayed fluorescent material has a structure in which a donor group and an acceptor group are bonded, and a group that stabilizes a radical cation is selected as an electron donor group, and a radical is selected as an acceptor group. A group that stabilizes the anion is selected.
  • the lifetime of the delayed fluorescent component is relatively long, on the order of microseconds to milliseconds. This means that the lifetime as a T 1 exciton is long.
  • the exciton energy of the luminescent molecule moves to the oxygen molecule by the Dexter mechanism, and the excitons on the luminescent molecule disappear. For this reason, T 1 excitons capable of intersystem crossing to S 1 are decreased, and the emission quantum yield of the TADF molecule is decreased in the presence of oxygen.
  • the ability to stabilize one of the radical anion or the radical cation is deficient.
  • the path from 1 to the ground state through the reverse intersystem crossing is promoted, and the lifetime of the T 1 exciton is shortened so that it is less susceptible to the quenching by oxygen.
  • Z represents an electron withdrawing group.
  • electron withdrawing group means a group having a stronger property of attracting electrons than a methylene group.
  • As an electron-withdrawing group that can be preferably used as Z,>C ⁇ O,> C ⁇ C (CN) 2 ,> BR 10 ,> SO 2 ,> C (CF 3 ) 2 ,> P ( O) R 11 and S can be mentioned, but the electron-withdrawing group that can be employed in the present invention is not limited to these examples.
  • R 10 and R 11 represent a substituent.
  • R 10 and R 11 can take are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and more preferably those having 1 to 10 carbon atoms.
  • An unsubstituted aryl group Since the structural portion excluding R 9 in the general formula (1) has an electron-withdrawing group corresponding to Z together with a nitrogen atom connecting two benzene rings, it has both a donor property and an acceptor property. It has a characteristic structural part.
  • R 1 to R 8 each independently represents a hydrogen atom or a substituent.
  • R 9 represents a substituent.
  • substituents that R 1 to R 9 can take include, for example, a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, An alkyl-substituted amino group having 1 to 20 carbon atoms, an aryl-substituted amino group having 12 to 40 carbon atoms, an acyl group having 2 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, Substituted or unsubstituted carbazolyl group having 12 to 40 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms
  • substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted dialkylamino group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, and 12 to 40 carbon atoms A substituted or unsubstituted carbazolyl group; More preferred substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 4 and R 9 , R 5 and R 9 are respectively They may be bonded to each other to form a cyclic structure.
  • At least one of R 1 to R 9 is a donor group or an acceptor group.
  • the condition (A) or (B) is selected.
  • a donor group as R 1 of the compound represented by the general formula (1).
  • a substituted or unsubstituted heteroaryl group or a substituted or unsubstituted aryl group can be preferably employed, and a substituted or unsubstituted heteroaryl group can be more preferably employed.
  • the substituted or unsubstituted heteroaryl group include a substituted or unsubstituted carbazolyl group.
  • R 9 is preferably a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and more preferably a substituted or unsubstituted aryl group.
  • an acceptor group as R 9 of the compound represented by the general formula (1).
  • the acceptor group include a substituted or unsubstituted triazinyl group. Of these, a diaryltriazinyl group can be preferably employed.
  • the basic skeleton of the general formula (1) exhibits characteristics useful as a light emitting material both when it is substituted with a donor group and when it is substituted with an acceptor group.
  • the method for synthesizing the compound represented by the general formula (1) is not particularly limited.
  • it can be synthesized by R 9 in the general formula (1) reacting a compound represented by the compound R 9-X is a hydrogen atom.
  • X is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom.
  • the compound represented by the general formula (1) can also be synthesized by combining other known synthesis reactions.
  • Compound represented by formula (2) The compound having the structure represented by the general formula (2) preferably used for the light emitting material of the present invention will be described.
  • D represents the dibenzofuran ring group which may be substituted, or the dibenzothiophene ring group which may be substituted.
  • R 11 to R 20 each independently represents a hydrogen atom or a substituent.
  • 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 18 and R 19 , R 19 and R 20 , R 20 And R 11 may be bonded to each other to form a cyclic structure.
  • n represents an integer of 1 to 4.
  • the dibenzofuran ring or dibenzothiophene ring constituting D may be substituted with a donor group, may be substituted with an acceptor group, or may be unsubstituted.
  • the substitution mode of the dibenzofuran ring or dibenzothiophene ring is not limited as long as D can be a donor group as a whole.
  • the substituent which R 11 to R 20 can take may be a donor group or an acceptor group. As long as the structural part excluding D exhibits donor properties as a whole, the type of these substituents is not limited.
  • R 19 and R 20 in the general formula (2) may be the same or different, but are preferably the same.
  • R 19 and R 20 are preferably an alkyl group, for example, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
  • N in the general formula (2) is an integer of 1 to 4, and is preferably 1 or 2.
  • D in the general formula (2) may be bonded at any position of the dibenzofuran ring or the dibenzothiophene ring.
  • n When n is 2, it is preferably bonded to any one of the 1 to 4 positions of the dibenzofuran ring or the dibenzothiophene ring and any one of the 6 to 9 positions.
  • a mode of bonding at the 2-position and the 8-position, a mode of bonding at the 3-position and the 7-position, and a mode of bonding at the 4-position and the 6-position can be exemplified. Among them, it is particularly preferable to bond at the 4-position and the 6-position (see Compound 9).
  • a method for synthesizing the compound represented by the general formula (2) is not particularly limited. For example, it can be synthesized by reacting a compound represented by DX with a compound in which D in the general formula (2) is a hydrogen atom.
  • X is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom.
  • the compound represented by the general formula (1) can also be synthesized by combining other known synthesis reactions.
  • the compound represented by the general formula (1) or the general formula (2) can emit delayed fluorescence. Therefore, the present invention includes an invention of a delayed phosphor having a structure represented by the general formula (1) or the general formula (2).
  • the molecular weight of the compound represented by the general formula (1) or the general formula (2) is used by, for example, forming an organic layer containing the compound represented by the general formula (1) or the general formula (2) by vapor deposition. When it is intended to do, it is preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less, and even more preferably 800 or less.
  • the lower limit of the molecular weight is the smallest molecular weight that the general formula (1) or the general formula (2) can take.
  • the compound represented by the general formula (1) or the general formula (2) may be formed by a coating method regardless of the molecular weight. If a coating method is used, a film can be formed even with a compound having a relatively large molecular weight.
  • the compound that emits delayed fluorescence and is capable of intramolecular proton transfer may be a polymer obtained by polymerizing a polymerizable monomer that emits delayed fluorescence and is capable of intramolecular proton transfer.
  • a polymer obtained by preliminarily allowing a polymerizable group to exist in the structure represented by the general formula (1) or (2) and polymerizing the polymerizable group is used for the organic light emitting device. It can be considered to be used as a material.
  • a monomer containing a polymerizable functional group in any of R 1 to R 9 in the general formula (1), R 11 to R 20 in the general formula (2), or D is prepared.
  • a polymer having a repeating unit is obtained by polymerizing the polymer alone or with other monomers, and the polymer is used as a material for the organic light-emitting device.
  • Examples of a polymer having a repeating unit containing a structure represented by the general formula (1) or (2) include a polymer containing a structure represented by the following general formula (11) or (12) Can do.
  • Q represents a group including a structure represented by General Formula (1) or General Formula (2)
  • L 1 and L 2 represent a linking group.
  • the linking group preferably has 0 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 2 to 10 carbon atoms. And preferably has a structure represented by - linking group -X 11 -L 11.
  • X 11 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • L 11 represents a linking group, and is preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted group A phenylene group is more preferable.
  • R 101 , R 102 , R 103 and R 104 each independently represent a substituent.
  • it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms.
  • An unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and a chlorine atom and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms and an unsubstituted alkoxy group having 1 to 3 carbon atoms.
  • the linking group represented by L 1 and L 2 is any one of R 1 to R 9 having the structure of the general formula (1) constituting Q, R 11 to R 20 having the structure of the general formula (2), and D Can be bound to either. Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.
  • the polymer having a repeating unit containing the formulas (13) to (16) is any one of R 1 to R 9 having the structure of the general formula (1), or R 11 to R 20 having the structure of the general formula (2). It can be synthesized by introducing a hydroxy group into any of D and D, reacting the following compound as a linker to introduce a polymerizable group, and polymerizing the polymerizable group.
  • the polymer containing the structure represented by the general formula (1) or the general formula (2) in the molecule is a polymer composed only of repeating units having the structure represented by the general formula (1) or the general formula (2). It may be a polymer containing a repeating unit having other structure.
  • the repeating unit having a structure represented by the general formula (1) or the general formula (2) contained in the polymer may be a single type or two or more types.
  • Examples of the repeating unit not having the structure represented by the general formula (1) or the general formula (2) include those derived from monomers used in ordinary copolymerization. Examples thereof include a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene and styrene.
  • Organic light emitting device In the organic light emitting device of the present invention, a compound that emits delayed fluorescence and is capable of intramolecular proton transfer is used.
  • a compound that emits delayed fluorescence and is capable of intramolecular proton transfer exhibits a sufficiently high quantum yield for practical use, and can be effectively used as a light-emitting material of an organic light-emitting device.
  • a compound that emits delayed fluorescence and is capable of intramolecular proton transfer can also be used as a host or assist dopant in an organic light-emitting device.
  • an organic light-emitting device using a compound that emits delayed fluorescence and is capable of intramolecular proton transfer as a light-emitting material has a feature of high luminous efficiency because this compound functions as a delayed fluorescent material.
  • the principle will be described below by taking an organic electroluminescence element as an example.
  • the organic electroluminescence element carriers are injected into the light emitting material from both positive and negative electrodes to generate an excited light emitting material and emit light.
  • 25% of the generated excitons are excited to the excited singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the use efficiency of energy is higher when phosphorescence, which is light emission from an excited triplet state, is used.
  • the excited triplet state has a long lifetime, energy saturation occurs due to saturation of the excited state and interaction with excitons in the excited triplet state, and in general, the quantum yield of phosphorescence is often not high.
  • delayed fluorescent materials after energy transition to an excited triplet state due to intersystem crossing, etc., are then crossed back to an excited singlet state due to triplet-triplet annihilation or absorption of thermal energy, and emit fluorescence.
  • a thermally activated delayed fluorescent material by absorption of thermal energy is particularly useful.
  • excitons in the excited singlet state emit fluorescence as usual.
  • excitons in the excited triplet state absorb the heat of the outside air and the heat generated by the device, and cross the terms into the excited singlet to emit fluorescence.
  • the light is emitted from the excited singlet, the light is emitted at the same wavelength as the fluorescence, but the light lifetime (luminescence lifetime) generated by the reverse intersystem crossing from the excited triplet state to the excited singlet state is normal. Since the fluorescence becomes longer than the fluorescence and phosphorescence, it is observed as fluorescence delayed from these. This can be defined as delayed fluorescence. If such a heat-activated exciton transfer mechanism is used, the ratio of the compound in an excited singlet state, which normally generated only 25%, is increased to 25% or more by absorbing thermal energy after carrier injection. It can be raised.
  • the heat of the device will sufficiently cause intersystem crossing from the excited triplet state to the excited singlet state and emit delayed fluorescence. Efficiency can be improved dramatically.
  • organic photoluminescence element has a structure in which at least a light emitting layer is formed on a substrate.
  • organic electroluminescence element has a structure in which at least an anode, a cathode, and an organic layer are formed between the anode and the cathode.
  • the organic layer includes at least a light emitting layer, and may consist of only the 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 blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer.
  • 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 A specific example of the structure of an organic electroluminescence element is shown in FIG. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, and 7 is a cathode. Below, each member and each layer of an organic electroluminescent element are demonstrated. In addition, description of a board
  • the organic electroluminescence device of the present invention is preferably supported on a substrate.
  • the substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements.
  • a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.
  • the light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and the light emitting material may be used alone for the light emitting layer.
  • the light emitting material Preferably including a luminescent material and a host material.
  • the luminescent material one or more selected from a group of compounds that emit delayed fluorescence and are capable of intramolecular proton transfer can be used.
  • a host material in addition to the light emitting material in the light emitting layer.
  • the host material an organic compound in which at least one of excited singlet energy and excited triplet energy has a value higher than that of the light-emitting material can be used.
  • singlet excitons and triplet excitons generated in the light emitting material can be confined in the molecule of the light emitting material, and the light emission efficiency can be sufficiently extracted.
  • high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention.
  • light emission is generated from a light-emitting material (compound that emits delayed fluorescence and is capable of intramolecular proton transfer) contained in the light-emitting layer.
  • This emission includes both fluorescence and delayed fluorescence.
  • light emission from the host material may be partly or partly emitted.
  • the amount of a compound that is a light emitting material, that is, a compound that emits delayed fluorescence and capable of intramolecular proton transfer is preferably 0.1% by weight or more.
  • the host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.
  • the injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission.
  • the injection layer can be provided as necessary.
  • the blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer.
  • the electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer.
  • a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer.
  • the blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer.
  • the term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense.
  • the hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer.
  • the material for the hole blocking layer the material for the electron transport layer described later can be used as necessary.
  • the electron blocking layer has a function of transporting holes in a broad sense.
  • the electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .
  • the exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved.
  • the exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
  • the layer when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer.
  • a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided.
  • an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided.
  • the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  • the electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide oxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • a compound that emits delayed fluorescence and capable of intramolecular proton transfer may be used for a light emitting layer, but also for a layer other than the light emitting layer.
  • the compound that emits delayed fluorescence contained in each layer and is capable of intramolecular proton transfer may be the same or different depending on whether it is used for the light-emitting layer or a layer other than the light-emitting layer.
  • the above injection layer, blocking layer, hole blocking layer, electron blocking layer, exciton blocking layer, hole transport layer, electron transport layer, etc. can emit delayed fluorescence and allow intramolecular proton transfer May be used.
  • the method for forming these layers is not particularly limited, and the layer may be formed by either a dry process or a wet process.
  • preferable materials that can be used for the organic electroluminescence element are shown below.
  • the material that can be used in the present invention is not limited to the following exemplary compounds. Moreover, even if it is a compound illustrated as a material which has a specific function, it can also be diverted as a material which has another function.
  • the organic electroluminescent device produced by the above-described method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the light is emitted by excited singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In addition, in the case of light emission by excited triplet energy, a wavelength corresponding to the energy level is confirmed as phosphorescence. Since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence, the emission lifetime can be distinguished from fluorescence and delayed fluorescence.
  • phosphorescence is hardly observable at room temperature in ordinary organic compounds such as the compounds of the present invention because the excited triplet energy is unstable and converted to heat, etc., and has a short lifetime and immediately deactivates.
  • the excited triplet energy of a normal organic compound it can be measured by observing light emission under extremely low temperature conditions.
  • the organic electroluminescence element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix.
  • an organic light-emitting device having greatly improved light emission efficiency can be obtained by including in the light-emitting layer a compound that emits delayed fluorescence and allows intramolecular proton transfer.
  • the organic light emitting device such as the organic electroluminescence device of the present invention can be further applied to various uses. For example, it is possible to produce an organic electroluminescence display device using the organic electroluminescence element of the present invention.
  • organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.
  • the organic light emitting device of the present invention may be an organic light emitting transistor.
  • An organic light emitting transistor has a structure in which, for example, a gate electrode is stacked on an active layer that also serves as a light emitting layer via a gate insulating layer, and a source electrode and a drain electrode are connected to the active layer.
  • 2-Bromo-4,6-diphenyltriazine (1.56 g, 5.0 mmol), 9-acridone (1.17 g, 6.0 mmol), tetrafluoroboric acid-tri-t-butylphosphine (0.085 g, 0.8 mmol).
  • 30 mmol sodium-t-butoxide (0.575 g, 6.0 mmol), tris (dibenzylideneacetone) -dipalladium (0.090 g, 0.10 mmol), dehydrated toluene (60 mL) in a three-necked flask under a nitrogen atmosphere. And stirred at 120 ° C. overnight.
  • 9,9-dimethylacridan (0.42 g, 2 mmol), 1-bromodibenzofuran (0.24 g, 1 mmol), tetrafluoroborate-tri-t-butylphosphine (35 mg, 0.12 mmol), sodium-t- Butoxide (0.23 g, 2.4 mmol) and tris (dibenzylideneacetone) dibaradium (0) (37 mg, 0.04 mmol) were placed in a three-necked flask, dehydrated toluene (40 mL) was added, and the mixture was stirred and refluxed overnight. After confirming that all the raw materials were consumed by thin layer chromatography (TLC), the reaction was stopped and allowed to cool.
  • TLC thin layer chromatography
  • 9,9-dimethylacridan (0.71 g, 3.4 mmol), 2-bromodibenzofuran (1.0 g, 4 mmol), tetrafluoroboric acid-tri-t-butylphosphine (70 mg, 0.24 mmol), sodium- t-Butoxide (0.46 g, 4.8 mmol) and tris (dibenzylideneacetone) dibaladium (0) (73 mg, 0.08 mmol) were placed in a three-necked flask, dehydrated toluene (40 mL) was added, and the mixture was stirred and refluxed overnight. After confirming that all the raw materials were consumed by TLC, the reaction was stopped and allowed to cool.
  • 9,9-dimethylacridan (0.84 g, 4 mmol), 3-bromodibenzofuran (1.2 g, 5 mmol), tetrafluoroborate-tri-t-butylphosphine (70 mg, 0.24 mmol), sodium-t- Butoxide (0.46 g, 4.8 mmol) and tris (dibenzylideneacetone) dibaradium (0) (73 mg, 0.08 mmol) were placed in a three-necked flask, dehydrated toluene (40 mL) was added, and the mixture was stirred and refluxed overnight. After confirming that all the raw materials were consumed by TLC, the reaction was stopped and allowed to cool.
  • 9,9-dimethylacridan 2.1 g, 10 mmol
  • 4-bromodibenzofuran 2.2 g, 9 mmol
  • tetrafluoroboric acid-tri-t-butylphosphine 0.16 g, 0.54 mmol
  • sodium t-Butoxide 1.0 g, 11 mmol
  • tris (dibenzylideneacetone) dibaradium (0) 0.17 g, 0.54 mmol
  • 9,9-dimethylacridan (1.5 g, 7 mmol), 2,8-dibromodibenzofuran (0.98 g, 3 mmol), tetrafluoroboric acid-tri-t-butylphosphine (70 mg, 0.24 mmol), sodium t-Butoxide (0.46 g, 4.8 mmol) and tris (dibenzylideneacetone) dibaladium (0) (73 mg, 0.08 mmol) were placed in a three-necked flask, dehydrated toluene (40 mL) was added, and the mixture was stirred and refluxed overnight. After confirming that all the raw materials were consumed by TLC, the reaction was stopped and allowed to cool.
  • 9,9-dimethylacridan (1.1 g, 5 mmol), intermediate 6 (0.65 g, 2 mmol), tetrafluoroboric acid-tri-t-butylphosphine (87 mg, 0.3 mmol), sodium-t-butoxide (0.58 g, 6 mmol) and tris (dibenzylideneacetone) dibaladium (0) (92 mg, 0.1 mmol) were placed in a three-necked flask, dehydrated toluene (40 mL) was added, and the mixture was stirred and refluxed overnight. After confirming that all the raw materials were consumed by TLC, the reaction was stopped and allowed to cool.
  • reaction solution was washed with water, and the organic layer was taken out and dried using sodium sulfate. After removing sodium sulfate by filtration under reduced pressure, toluene was removed using an evaporator. The residue was purified using column chromatography (silica gel, chloroform) and washed with ethanol to obtain Compound 8 as a pale yellow powder in a yield of 0.63 g and a yield of 55%.
  • 9,9-dimethylacridan (1.1 g, 5 mmol), 4,6-dibromodibenzofuran (0.65 g, 2 mmol), tetrafluoroborate-tri-t-butylphosphine (87 mg, 0.3 mmol), sodium t-Butoxide (0.58 g, 6 mmol) and tris (dibenzylideneacetone) dibaladium (0) (92 mg, 0.1 mmol) were placed in a three-necked flask, dehydrated toluene (40 mL) was added, and the mixture was stirred and refluxed overnight. After confirming that all the raw materials were consumed by TLC, the reaction was stopped and allowed to cool.
  • Example 1 Preparation and Evaluation of Solution Compound 1 and Compound 2 were dissolved in toluene to prepare 1.0 ⁇ 10 ⁇ 5 mol / L toluene solutions, respectively.
  • UV-visible absorption, fluorescence, and phosphorescence spectra of a toluene solution of Compound 1 were measured.
  • the fluorescence maximum wavelength was 425 nm, and the phosphorescence maximum wavelength was 443 nm.
  • S1 estimated from the emission end of the fluorescence and phosphorescence spectra 2.92 eV, T1 is 2.80 eV, the value of Delta] E ST was 0.12 eV.
  • the light emission quantum yield (PLQY) was measured about each when the bubbling of nitrogen gas was not performed and when it performed.
  • the fluorescence intensity decay curve was measured to determine the lifetime ⁇ p of the immediate fluorescence component and the lifetime ⁇ d of the delayed fluorescence component. The measurement results are shown in Table 1. Since the emission quantum yield and the lifetime are improved by bubbling nitrogen gas, it was confirmed that the delayed component is delayed fluorescence via the T 1 excited state.
  • Example 2 Production and Evaluation of Thin Film
  • a thin film made of only Compound 1 was formed on a Si substrate by a vacuum deposition method. Separately, compound 1 and dibenzothiophene-2,8-bis-diphenylphosphine oxide (PPT: HOMO energy level ⁇ 6.6 eV, LUMO energy level ⁇ 2.9 eV) on a Si substrate.
  • PPT dibenzothiophene-2,8-bis-diphenylphosphine oxide
  • a co-evaporation film containing 5% by weight of Compound 1 was produced.
  • the thin film consisting only of Compound 1 was subjected to photoelectron yield spectroscopy measurement and UV-visible absorption spectrum measurement using AC-3 manufactured by Riken Keiki Co., Ltd.
  • the HOMO energy level of Compound 1 estimated from the photoelectron yield spectroscopic measurement result and the absorption edge wavelength of the UV-visible absorption spectrum was ⁇ 6.1 eV, and the LUMO energy level was ⁇ 3.0 eV.
  • the emission spectrum was measured for each of the thin film consisting only of Compound 1 and the co-deposited film, the same fluorescence spectrum was obtained for each film, and the maximum emission wavelength was 485 nm.
  • the light emission quantum yield (PLQY) of the co-deposited film was measured and found to be 17% under the atmosphere and 21% under the argon stream. Further, FIG.
  • the compounds 3, 4, 8, and 9 were co-evaporated with the host materials shown in Table 3 to prepare a co-evaporated film having a concentration of 6% by weight.
  • Table 3 shows the results of measuring the light emission quantum yield (PLQY) of each co-deposited film under the atmosphere and argon.
  • FIG. 3 shows the results of measuring the emission intensity decay curves of the vapor deposition film of compound 9 at temperatures of 30K, 100K, 200K, and 300K with a streak camera. Since the fluorescence delay component increased with the temperature rise, it was confirmed that Compound 9 is a thermally activated delayed fluorescence material.
  • Example 3 Production and Evaluation of Organic Electroluminescence Element
  • a glass substrate manufactured by Atsugi Micro Co., Ltd.
  • an ITO transparent electrode was patterned with a film thickness of 100 nm was cut into a size of 25 nm in length and 25 nm in width and washed.
  • the following layers were formed on this substrate at 3 to 7 ⁇ 10 ⁇ 4 Pa using a vacuum vapor deposition machine (manufactured by ALS Technology).
  • ⁇ -NPD was formed on ITO to a thickness of 35 nm, and mCP was formed thereon to a thickness of 10 nm.
  • Compound 1 and PPT were co-evaporated from different vapor deposition sources to form a 20 nm thick layer as a light emitting layer. At this time, the concentration of Compound 1 was 5% by weight.
  • PPT is formed to a thickness of 40 nm, lithium fluoride (LiF) is further vacuum-deposited to 0.8 nm, and then aluminum (Al) is evaporated to a thickness of 80 nm to form a cathode. A luminescence element was obtained. When the emission spectrum of the produced organic electroluminescence device was measured, it almost coincided with the emission spectrum of the co-deposited film of Example 2.
  • the driving voltage of 10 mA / cm 2 was 12 V
  • the luminous flux was 2.98 ⁇ 10 ⁇ 3 cd / cm 2. Met.
  • the external quantum efficiency at 0.15 mA / cm 2 was 2.2%.
  • an OLED integrating sphere (PMA-12 manufactured by Hamamatsu Photonics) and a luminance light distribution measuring device (A10119 manufactured by Hamamatsu Photonics) were used.

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  • Electroluminescent Light Sources (AREA)
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Abstract

Selon l'invention, (A) un composé possédant une structure dans laquelle au moins deux sortes de groupe accepteur sont liés, (B) un composé possédant une structure dans laquelle un groupe donneur faible et un groupe accepteur faible sont liés, et (C) un composé possédant une structure dans laquelle au moins deux sortes de groupe donneur sont liés, sont avantageux en tant que matériaux luminescents.
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