WO2022045272A1 - 有機電界発光素子 - Google Patents

有機電界発光素子 Download PDF

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WO2022045272A1
WO2022045272A1 PCT/JP2021/031430 JP2021031430W WO2022045272A1 WO 2022045272 A1 WO2022045272 A1 WO 2022045272A1 JP 2021031430 W JP2021031430 W JP 2021031430W WO 2022045272 A1 WO2022045272 A1 WO 2022045272A1
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carbon atoms
substituted
group
unsubstituted
aromatic
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French (fr)
Japanese (ja)
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紗友里 木寺
匡志 多田
棟智 井上
絢香 寺田
智 浮海
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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Priority to KR1020237003012A priority Critical patent/KR102881326B1/ko
Priority to EP21861694.4A priority patent/EP4206301A1/en
Priority to US18/018,005 priority patent/US20230276644A1/en
Priority to CN202180056523.6A priority patent/CN116194549B/zh
Priority to JP2022545715A priority patent/JP7754821B2/ja
Publication of WO2022045272A1 publication Critical patent/WO2022045272A1/ja
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Definitions

  • the present invention relates to an organic electroluminescent device (referred to as an organic EL device).
  • the phosphorescent organic EL element that uses light emission by triplet excitons can increase the internal quantum efficiency to 100% when intersystem crossing is efficiently performed from the singlet excitons. Has been done. However, extending the life of a blue phosphorescent organic EL device has become a technical issue.
  • Patent Document 1 discloses an organic EL device using a TTF (Triplet-Triplet Fusion) mechanism, which is one of the mechanisms of delayed fluorescence.
  • TTF Triplet-Triplet Fusion
  • the TTF mechanism utilizes the phenomenon that singlet excitons are generated by the collision of two triplet excitons, and it is considered that the internal quantum efficiency can be theoretically increased to 40%.
  • the efficiency is lower than that of the phosphorescent light emitting type organic EL element, further improvement in efficiency is required.
  • Patent Document 2 discloses an organic EL element using a TADF (Thermally Activated Delayed Fluorescence) mechanism.
  • the TADF mechanism utilizes the phenomenon that an intersystem crossing from a triplet exciter to a singlet exciter occurs in a material with a small energy difference between the singlet level and the triplet level, and theoretically determines the internal quantum efficiency. It is believed that it can be increased to 100%. However, as with the phosphorescent light emitting device, further improvement in life characteristics is required.
  • Patent Document 4 discloses an organic EL device in which two types of host materials typified by the following compounds and a TADF material are contained in a light emitting layer as light emitting dopants.
  • Patent Document 3 and Patent Document 5 disclose an organic EL element using a TADF material composed of a polycyclic aromatic compound represented by the following compound as a light emitting dopant.
  • Patent Document 6 discloses an organic EL device in which a boron-based compound, a TADF material, and a carbazole compound (a3) are mixed and used in a light emitting layer.
  • Patent Document 7 discloses an organic EL device in which a boron-based compound, a TADF material, and a carbazole compound are mixed and used in a light emitting layer.
  • Patent Document 8 discloses an organic EL element in which a boron-based compound (a7), a nitrogen-containing 6-membered ring compound (a8), and a carbazole compound (a9) are mixed and used in a light emitting layer.
  • An object of the present invention is to provide a practically useful organic EL device having characteristics of high efficiency and long life.
  • an organic EL element including one or more light emitting layers between an opposing anode and a cathode
  • at least one light emitting layer is a first host selected from a compound represented by the following general formula (1).
  • An organic EL element comprising a second host selected from the compound represented by the following general formula (2) and a polycyclic aromatic compound represented by the following general formula (4) as a luminescent dopant. Is.
  • R1 is independently a heavy hydrogen, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 substituted or unsubstituted carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 3 to 17 carbon atoms.
  • a, c and d independently represent an integer of 0 to 4
  • b independently represents an integer of 0 to 3
  • e independently represents an integer of 1 to 4
  • f represents an integer of 1 or 2.
  • X 1 independently represents N or CR 2 , but at least one X 1 represents N.
  • Ar 2 is independently hydrogen, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted or unsubstituted, an aromatic heterocyclic group having 3 to 17 carbon atoms substituted or unsubstituted, or an aromatic ring thereof. Represents a substituted or unsubstituted linked aromatic group composed of 2 to 8 linked aromatic groups. However, not all of Ar 2 is hydrogen.
  • R2 is independently hydrogen, a hydrocarbon, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 3 to 17 carbon atoms. Represents the aromatic heterocyclic group of.
  • ring D, ring E, ring F, ring G, and ring H are independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 24 carbon atoms, or substituted or unsubstituted aromatic hydrocarbon rings having 3 to 3 carbon atoms.
  • Each of R 3 is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an substituted or unsubstituted aromatic group having 3 to 17 carbon atoms.
  • heterocyclic group X 2 is independently O, N-Ar 3 , S or Se, respectively.
  • Ar 3 is independently substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms, or 2 to 8 of them linked.
  • a substituted or unsubstituted linked aromatic group consisting of N—Ar 3 even if it is bonded to any of ring D, ring E, ring F, ring G, or ring H to form a heterocycle containing N.
  • At least one hydrogen in ring D, ring E, ring F, ring G, and ring H may be substituted with deuterium.
  • Ar 1 in the formula (1) is an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 17 carbon atoms. It is mentioned that it is a fused aromatic heterocyclic group of.
  • a preferred embodiment of the polycyclic aromatic compound represented by the general formula (4) is a boron-containing polycyclic aromatic compound represented by the following formula (5).
  • X 3 independently represents N-Ar 4 , O, or S, but at least one X 3 represents N-Ar 4 .
  • Ar 4 has independently substituted or unsubstituted aromatic hydrocarbon groups having 6 to 18 carbon atoms, substituted or unsubstituted aromatic heterocyclic groups having 3 to 17 carbon atoms, or 2 to 2 of these aromatic rings. Represents a substituted or unsubstituted linked aromatic group composed of eight linked aromatic groups.
  • N-Ar 4 may be bonded to the benzene ring to which it is bonded to form a heterocycle containing N.
  • R4 is independently a cyano group, a hydrocarbon, a diarylamino group having 12 to 44 carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an substituted or unsubstituted aromatic hydrocarbon having 6 to 18 carbon atoms.
  • g and h independently represent an integer of 0 to 4
  • i and j independently represent an integer of 0 to 3
  • k represents an integer of 0 to 2.
  • Preferred embodiments of the general formula (2) include the following formula (6), the following formula (7) or the formula (8).
  • Ar 2 and X 1 agree with the general formula (2).
  • R 5 and R 6 are independently heavy hydrogens, aliphatic hydrocarbon groups having 1 to 10 carbon atoms, triarylsilyl groups having 18 to 36 carbon atoms, and substituted or unsubstituted aromatic hydrocarbons having 6 to 18 carbon atoms, respectively.
  • l, m, n, o, p and q each independently represent an integer of 0 to 4.
  • the difference ( ⁇ EST) between the excited singlet energy (S1) and the excited triplet energy (T1) of the luminescent dopant is preferably 0.20 eV or less, and more preferably 0.10 eV or less.
  • the organic EL device of the present invention has the characteristics of high luminous efficiency and long life.
  • the reason why the organic EL element of the present invention has high light emission efficiency is that the excitons generated on the host move rapidly to the light emitting dopant, so that the energy loss is small, and the excitons generated on the light emitting dopant are the hosts. It is considered that the energy loss is small because it is difficult to move to.
  • the carbazole compound has the property that holes are easily injected and the nitrogen-containing 6-membered ring compound has the property that electrons are easily injected, the balance between holes and electrons in the light emitting layer should be maintained. It is presumed that this is also a factor that leads to high luminous efficiency.
  • the reason why the organic EL element of the present invention has a long life is that when a voltage is applied to the organic EL element, holes are sent to the first host made of the biscarbazole compound and electrons are sent to the second host made of the nitrogen-containing 6-membered ring compound. It is presumed that this is because the electrochemical load on the luminescent dopant is reduced by preferentially injecting.
  • the polycyclic aromatic compound can emit blue light with high efficiency by using the TADF mechanism, but its resistance to holes and electrons is low, so that the device life tends to be shortened.
  • the first host used in the present invention is likely to be injected with holes, and electrons are also easily injected by the second host, the electrochemical load on the luminescent dopant is reduced, and long-life device characteristics can be exhibited. it is conceivable that. Further, since the first host and the second host have higher resistance to holes and electrons than known host materials, it is presumed that they can be organic EL devices having a longer life.
  • the organic EL element of the present invention has one or more light emitting layers between the facing anode and the cathode, and at least one light emitting layer is selected from the compound represented by the above general formula (1). It contains a host, a second host selected from the compound represented by the general formula (2), and a polycyclic aromatic compound represented by the general formula (4) as a luminescent dopant.
  • Ar 1 is an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms, or an aromatic thereof.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a substituted or unsubstituted fused aromatic heterocyclic group having 6 to 17 carbon atoms, or 2 to 4 aromatic rings thereof are linked.
  • Ar 1 is an unsubstituted aromatic hydrocarbon group, an aromatic heterocyclic group, or a linked aromatic group
  • Ar 1 is an unsubstituted aromatic hydrocarbon group, an aromatic heterocyclic group, or a linked aromatic group
  • benzene naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysen, pyrene, and phenanthrene.
  • benzene, naphthalene, acenaphthene, acenaphthylene, azulene, dibenzofuran, dibenzothiophene, carbazole or a group formed by taking f hydrogens from a compound composed of 2 to 4 linkages thereof can be mentioned. More preferably, a group formed by taking f hydrogens from a compound composed of benzene, naphthalene or a benzene ring linked by 2 to 3 can be mentioned.
  • the linked aromatic group refers to a group in which the aromatic rings of an aromatic hydrocarbon group or an aromatic heterocyclic group are linked by a single bond, and these are branched even if they are linearly linked. They may be linked and the aromatic rings may be the same or different.
  • R1 is independently a heavy hydrogen, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 3 to 17 carbon atoms.
  • it is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 15 carbon atoms. be.
  • Ar 1 and R 1 are not groups derived from pyridine, pyrimidine, or triazine.
  • a, c and d independently represent an integer of 0 to 4
  • b independently represents an integer of 0 to 3
  • e independently represents an integer of 1 to 4
  • f represents an integer of 1 or 2.
  • a, b, c and d are independently integers of 0 to 1
  • e is an integer of 1 to 2. These are the number of substitutions.
  • the general formula (1) may be symmetric or asymmetric.
  • R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl.
  • R 1 is an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms are the same as described in Ar 1 above.
  • Preferred are groups formed by taking one hydrogen from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, dibenzofuran, dibenzothiophene, or carbazole. More preferably, a group formed by taking one hydrogen from benzene, naphthalene, or carbazole may be mentioned.
  • Ar 1 to Ar 3 and R 1 to R 5 are aromatic hydrocarbon groups or aromatic complex. When it is a ring group or a linked aromatic group, these may have a substituent, and the substituents include a hydrocarbon, a cyano group, a triarylsilyl group having 18 to 36 carbon atoms, and 1 to 10 carbon atoms.
  • the aliphatic hydrocarbon group of the above, a diarylamino group having 12 to 44 carbon atoms is preferable.
  • the substituent is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, it may be linear, branched, or cyclic.
  • the number of substituents is preferably 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent.
  • substituents include cyano, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, diphenylamino and naphthylphenylamino. , Dinaphthylamino, dianthranylamino, diphenanthrenylamino, dipyrenylamino, triphenylsilyl and the like.
  • Preferred examples include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • hydrogen may be deuterium. That is, in the above general formulas (1) to (8), a part or all of H having a carbazole skeleton and a substituent such as R 1 or Ar 1 may be deuterium.
  • X 1 independently represents N or CR 2 , but at least one X 1 represents N. Preferably two X 1s represent N. More preferably, it is a triazine compound in which three X 1s are N.
  • Preferred embodiments of the general formula (2) include the formulas (6), (7) and (8), but the formula (7) is more preferable.
  • the formula (6), the formula (7) and the formula (8) the common symbols have the same meaning.
  • l, m, n, o, p and q each independently represent an integer of 0 to 4, preferably an integer of 0 to 2.
  • Ar 2 is independently hydrogen, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted or unsubstituted, an aromatic heterocyclic group having 3 to 17 carbon atoms substituted or unsubstituted, or an aromatic ring thereof.
  • an aromatic hydrocarbon group having 6 to 12 carbon atoms substituted or unsubstituted, an aromatic heterocyclic group having 3 to 12 carbon atoms substituted or unsubstituted, or 2 to 6 aromatic rings thereof are linked to each other.
  • substituted or unsubstituted aromatic hydrocarbon groups having 6 to 10 carbon atoms, substituted or unsubstituted aromatic heterocyclic groups having 6 to 12 carbon atoms, or 2 to 4 of these aromatic rings are linked.
  • at least one of Ar 2 is the above aromatic hydrocarbon group, aromatic heterocyclic group, or linked aromatic group.
  • aromatic hydrocarbon group in which Ar 2 is substituted or the aromatic heterocyclic group in which Ar 2 is substituted are the same as in the case where Ar 1 or R 1 is these.
  • the unsubstituted linked aromatic group is the same as in the case where Ar 1 is these.
  • benzene, naphthalene, acenaphthene, acenaphthylene, azulene, pyridine, triazine, dibenzofuran, dibenzothiophene, carbazole, or a group formed by taking one hydrogen from a compound composed of 2 to 6 linkages thereof can be mentioned. .. More preferably, there is a group formed by taking one hydrogen from a compound composed of benzene, carbazole, dibenzofuran, dibenzothiophene, or a compound composed of 2 to 4 benzene rings linked.
  • R 2 is independently hydrogen, a hydrocarbon, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon number 3 Represents ⁇ 17 aromatic heterocyclic groups.
  • Preferred are hydrogen, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 3 to 15 carbon atoms. More preferably, it is an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • R5 and R6 are independently heavy hydrogens, aliphatic hydrocarbon groups having 1 to 10 carbon atoms, triarylsilyl groups having 18 to 36 carbon atoms, substituted or substituted. It represents an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 3 to 15 carbon atoms is preferable. More preferably, it is an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an substituted or unsubstituted aromatic heterocyclic group having 3 to 15 carbon atoms.
  • R2 , R5 and R6 are aliphatic hydrocarbon groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 18 carbon atoms, or substituted or unsubstituted aromatic hydrocarbon groups having 3 to 17 carbon atoms.
  • Specific examples of the case of representing an aromatic heterocyclic group are the same as those described in R1 .
  • Preferred are groups formed by taking one hydrogen from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, dibenzofuran, dibenzothiophene, or carbazole. More preferably, a group formed by taking one hydrogen from benzene, naphthalene, or carbazole may be mentioned.
  • the luminescent dopant used in the organic EL device of the present invention is a polycyclic aromatic compound represented by the above general formula (4).
  • a boron-containing polycyclic aromatic compound represented by the above formula (5) is preferable.
  • the ring D, the ring E, the ring F, the ring G, and the ring H are independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 24 carbon atoms or substituted or unsubstituted. It is an aromatic hydrocarbon ring having 3 to 17 carbon atoms, preferably an substituted or unsubstituted aromatic hydrocarbon ring having 6 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon ring having 3 to 15 carbon atoms. Is shown. Since the rings D to H are aromatic hydrocarbon rings or aromatic heterocycles as described above, they are also referred to as aromatic rings.
  • unsubstituted aromatic ring examples include benzene, naphthalene, acenaphthene, acenaphtylene, azulene, anthracene, chrysen, pyrene, phenanthrene, triphenylene, fluorene, benzo [a] anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole.
  • Preferred examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a triphenylene ring, a phenanthrene ring, a pyrene ring, a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring.
  • the aromatic hydrocarbon ring or the aromatic heterocycle may have a substituent, and the substituents are independently cyano groups, respectively.
  • a diarylamino group having 12 to 36 carbon atoms Preferably, a diarylamino group having 12 to 36 carbon atoms, an arylheteroarylamino group having 12 to 36 carbon atoms, a diheteroarylamino group having 12 to 36 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. It is an aromatic heterocycle having 3 to 15 carbon atoms. More preferably, a diarylamino group having 12 to 24 carbon atoms, an arylheteroarylamino group having 12 to 24 carbon atoms, a diheteroarylamino group having 12 to 24 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the like. Alternatively, it is an aromatic heterocyclic group having 3 to 12 carbon atoms.
  • the substituent is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, it may be linear, branched, or cycl
  • diarylamino group having 12 to 44 carbon atoms When representing the above-mentioned diarylamino group having 12 to 44 carbon atoms, an arylheteroarylamino group having 12 to 44 carbon atoms, a diheteroarylamino group having 12 to 44 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
  • diphenylamino diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino, diphenanthrenylamino, dipyrenylamino, dibenzofuranylphenylamino, dibenzofuranylbiphenylamino, Dibenzofuranylnaphthylamino, dibenzofuranylanthranylamino, dibenzofuranylphenanslenylamino, dibenzofuranylpyrenylamino, bisdibenzofuranylamino, carbazolylphenylamino, carbazolylnaphthylamino, carbazolylanthranylamino , Carbazolylphenanthrenylamino, carbazolylpyrenylamino, dicarbazolylamino, methyl, ethyl, prop
  • Preferred examples thereof include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino, diphenanthrenylamino, or dipyrenylamino. More preferably, diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dibenzofuranylphenylamino, or carbazolylphenylamino are mentioned.
  • Each of R 3 is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an substituted or unsubstituted aromatic group having 3 to 17 carbon atoms. It is a heterocyclic group. Preferably, it is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 15 carbon atoms. be. More preferably, it is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 12 carbon atoms.
  • R 3 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms. As a specific example in a certain case, it is the same as the case where R 1 in the general formula (1) is these groups.
  • X 2 is independently O, N-Ar 3 , S or Se, preferably O, N-Ar 3 or S, and more preferably O or N-Ar 3 .
  • Ar 3 is independently substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms, or 2 to 8 of them linked. It is a linked aromatic group. It is preferably a phenyl group, a biphenyl group, or a terphenyl group.
  • Ar 3 is an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms, or a linked aromatic group in which 2 to 8 of them are linked. As a specific example of the case, it is the same as the case where Ar 1 in the general formula (1) is these groups.
  • Ar 3 is a substituted aromatic hydrocarbon group having 6 to 18 carbon atoms and a substituted aromatic heterocyclic group having 3 to 17 carbon atoms
  • the substituents include a heavy hydrogen, a hydroxyl group, a sulfite group and a cyano group.
  • a triarylsilyl group having 18 to 36 carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms are preferable.
  • the substituent is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, it may be linear, branched, or cyclic.
  • substituents include cyano, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, diphenylamino and naphthylphenylamino. , Dinaphthylamino, dianthranylamino, diphenanthrenylamino, dipyrenylamino, triphenylsilyl and the like.
  • Preferred examples include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • N-Ar 3 may be combined with an aromatic ring selected from ring D, ring E, ring F, ring G, or ring H to form a heterocycle containing N.
  • Ar 3 has a substituent, it is bonded to an aromatic ring selected from ring D, ring E, ring F, ring G, or ring H via the substituent to form a heterocycle containing N.
  • at least one hydrogen in Ar 3 may be substituted with deuterium.
  • Examples of the polycyclic aromatic compound include compounds represented by the general formula (4) or the formula (5).
  • the general formula (4) and the formula (5) the common symbols have the same meaning.
  • g and h each independently represent an integer of 0 to 4
  • i and j each independently represent an integer of 0 to 3
  • k represents an integer of 0 to 2.
  • g, h, i, j and k are independently 0 or 1.
  • X 3 independently represents N-Ar 4 , O, or S, but at least one X 3 represents N-Ar 4 , preferably N-Ar 4 , or O. be.
  • Ar 4 is in agreement with Ar 3 in the general formula (4).
  • N-Ar 4 may be bonded to the above aromatic ring (benzene ring corresponding to rings D to H) to form a heterocycle containing N.
  • R4 is independently a cyano group, a hydrocarbon, a diarylamino group having 12 to 44 carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an substituted or unsubstituted aromatic hydrocarbon having 6 to 18 carbon atoms.
  • it is a diarylamino group having 12 to 36 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an substituted or unsubstituted aromatic heterocycle having 3 to 15 carbon atoms.
  • it is a diarylamino group having 12 to 24 carbon atoms, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or an substituted or unsubstituted aromatic heterocyclic group having 3 to 12 carbon atoms. ..
  • R4 represents a diarylamino group having 12 to 44 carbon atoms or an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • Preferred examples thereof include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino, diphenanthrenylamino, or dipyrenylamino. More preferably, diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, or dinaphthylamino can be mentioned.
  • Preferred embodiments of the polycyclic aromatic compound of the general formula (4) or the formula (5) include the following formulas (4-d), (4-e), (4-f), and formula (4-h). be. More preferably, it is the following formula (4-f).
  • the polycyclic aromatic compounds represented by the formulas (4-d), the formula (4-e), and the formula (4-f) are, for example, the formulas (4-67), the formula (4-68), and the formula (4-f) described later. It corresponds to a compound as represented by 4-69).
  • the polycyclic aromatic compound represented by the formula (4-h) is, for example, a formula (4-71), a formula (4-72), a formula (4-73), a formula (4-74), a formula (4-74), which will be described later. Corresponds to the compound represented by 4-75).
  • polycyclic aromatic compound represented by the general formula (4) or the formula (5) are shown below, but the present invention is not limited to these exemplary compounds.
  • the organic light emitting material used as a light emitting dopant in the organic EL device of the present invention preferably has ⁇ EST of 0.20 eV or less. It is more preferably 0.15 eV or less, still more preferably 0.10 eV or less.
  • ⁇ EST represents the difference between the excited singlet energy (S1) and the excited triplet energy (T1).
  • S1 and T1 are according to the method described in the examples.
  • a material selected from the polycyclic aromatic compound represented by the general formula (4) (hereinafter, also referred to as a polycyclic aromatic compound material) is used as a luminescent dopant, and the compound represented by the general formula (1) is used.
  • An excellent organic EL element can be provided by using the material selected from the above as the first host and the material selected from the compound represented by the general formula (2) as the second host.
  • FIG. 1 is a cross-sectional view showing a structural example of a general organic EL device used in the present invention, in which 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, and 5 is a light emitting layer. , 6 represent an electron transport layer, and 7 represents a cathode.
  • the organic EL device of the present invention may have an exciton blocking layer adjacent to the light emitting layer, or may have an electron blocking layer between the light emitting layer and the hole injection layer.
  • the exciton blocking layer can be inserted into either the anode side or the cathode side of the light emitting layer, and both can be inserted at the same time.
  • the organic EL device of the present invention has an anode, a light emitting layer, and a cathode as essential layers, but it is preferable to have a hole injection transport layer and an electron injection transport layer in addition to the essential layers, and further, a light emitting layer and an electron injection. It is preferable to have a hole blocking layer between the transport layers.
  • the hole injection transport layer means either or both of the hole injection layer and the hole transport layer
  • the electron injection transport layer means either or both of the electron injection layer and the electron transport layer.
  • the organic EL element of the present invention is preferably supported by a substrate.
  • the substrate is not particularly limited as long as it is conventionally used for an organic EL element, and for example, a substrate made of glass, transparent plastic, quartz or the like can be used.
  • anode material in the organic EL element a material having a large work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • an electrode material include a metal such as Au, and a conductive transparent material such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 -ZnO) capable of producing a transparent conductive film may be used.
  • a thin film may be formed by forming a thin film of these electrode materials by a method such as thin film deposition or sputtering, and a pattern of a desired shape may be formed by a photolithography method, or when pattern accuracy is not required so much (about 100 ⁇ m or more). May form a pattern through a mask having a desired shape during vapor deposition or sputtering of the electrode material.
  • a coatable substance such as an organic conductive compound
  • a wet film forming method such as a printing method or a coating method can also be used.
  • the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, but is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • the cathode material a material consisting of a metal having a small work function (4 eV or less) (referred to as an electron-injectable metal), an alloy, an electrically conductive compound, or a mixture thereof 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 ) Examples include mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injectable 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 mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) mixture, lithium / aluminum mixture, aluminum and the like are suitable.
  • the cathode can be produced by forming a thin film of these cathode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance of 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 brightness is improved, which is convenient.
  • a transparent or translucent cathode can be produced. By applying this, it is possible to manufacture an element in which both the anode and the cathode have transparency.
  • 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 cathode, and the light emitting layer contains a light emitting dopant and a host.
  • the luminescent dopant and the host can be used, for example, so that the luminescent dopant is 0.10 to 10% and the host is 99.9 to 90%.
  • the luminescent dopant is preferably 1.0 to 5.0% and the host 99 to 95%, and more preferably the luminescent dopant 1.0 to 3.0% and the host 99 to 97%. In the present specification,% is mass% unless otherwise specified.
  • the first host and the second host are used as the host in the light emitting layer.
  • the first host and the second host can be used by, for example, 10 to 90% of the first host and 90 to 10% of the second host.
  • the first host is 30 to 70%
  • the second host is 70 to 30%
  • more preferably the first host is 50 to 70% and the second host is 50 to 30%.
  • one or a plurality of known hosts may be used in combination, but the amount used may be 50% or less, preferably 25% or less of the total amount of host materials. good.
  • Other known hosts that can be used are compounds having hole transporting ability and electron transporting ability and having a high glass transition temperature, and preferably have T1 larger than T1 of the luminescent dopant. ..
  • the T1 of the host is preferably 0.010 eV or more higher than the T1 of the luminescent dopant, more preferably 0.030 eV or more, and even more preferably 0.10 eV or more.
  • a TADF-active compound may be used as the host material, and this compound preferably has a ⁇ EST of 0.20 eV or less.
  • the other known hosts mentioned above are known from a large number of patent documents and the like, and can be selected from them. Specific examples of the host are not particularly limited, but are limited to indole derivative, carbazole derivative, indolocarbazole derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, phenylenediamine derivative, arylamine derivative, and styryl.
  • Anthracene derivatives fluorenone derivatives, stylben derivatives, triphenylene derivatives, carborane derivatives, porphyrin derivatives, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives and metal phthalocyanine, various metal complexes represented by metal complexes of benzoxazole and benzothiazole derivatives, poly Examples thereof include polymer compounds such as (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives.
  • polymer compounds such as (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives.
  • each host can be vapor-deposited from different vapor deposition sources, or multiple types of hosts can be simultaneously vapor-deposited from one vapor deposition source by premixing them before vapor deposition to form a premixture. ..
  • a method capable of mixing as uniformly as possible is desirable, and examples thereof include pulverization mixing, heating and melting under reduced pressure or in an atmosphere of an inert gas such as nitrogen, sublimation, and the like. It is not limited to the method.
  • the form of the premixture may be powder, stick or granular.
  • the above-mentioned polycyclic aromatic compound material can be used as the light emitting dopant in the light emitting layer.
  • the light emitting layer may contain two or more types of light emitting dopants.
  • it may be a luminescent dopant composed of the above polycyclic aromatic compound material and another compound.
  • the luminescent dopant composed of the other compounds preferably has a ⁇ EST of 0.20 eV or less, but is not limited thereto.
  • the first dopant is a compound represented by the general formula (4) or the formula (5)
  • the second dopant is a known compound. It may be used together as a dopant.
  • the first dopant is preferably 0.050 to 50% with respect to the host material
  • the second dopant is preferably 0.050 to 50% with respect to the host material
  • the first dopant is used.
  • the total content of the second dopant does not exceed 50% with respect to the host material.
  • luminescent dopants are known from a large number of patent documents and the like, they can be selected from them.
  • the dopant include, but are not limited to, fused ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysen, benzoxazole derivatives and benzothiazole derivatives.
  • Benzoimidazole derivative benzotriazole derivative, oxazole derivative, oxadiazole derivative, thiazole derivative, imidazole derivative, thiadiazole derivative, triazole derivative, pyrazoline derivative, stilben derivative, thiophene derivative, tetraphenylbutadiene derivative, cyclopentadiene derivative, bisstyrylanthracene derivative And bisstyryl derivatives such as distyrylbenzene derivatives, bisstyrylarylene derivatives, diazaindacene derivatives, furan derivatives, benzofuran derivatives, isobenzofuran derivatives, dibenzofuran derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives.
  • the luminescent dopant and the first host, or the second host are vapor-deposited from different vapor deposition sources, or premixed before vapor deposition to form a premixture, so that the luminescent dopant and the first host, or the first host, can be deposited from one vapor deposition source.
  • the second host can also be deposited at the same time.
  • the injection layer is a layer provided between the electrode and the organic layer in order to reduce the driving voltage and improve the emission brightness.
  • the injection layer includes a hole injection layer and an electron injection layer, and is located between the anode and the light emitting layer or the hole transport layer. And may be present between the cathode and the light emitting layer or the electron transporting layer.
  • the injection layer can be provided as needed.
  • the hole blocking layer has the function of an electron transporting layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and a significantly small ability to transport holes, and is composed of a hole blocking material while transporting electrons. It is possible to improve the recombination probability of electrons and holes in the light emitting layer by blocking the above.
  • a known hole blocking material can be used for the hole blocking layer.
  • the material used as the second host can also be used as the material of the hole blocking layer. Further, a plurality of types of hole blocking materials may be used in combination.
  • the electron blocking layer has a function of a hole transporting layer in a broad sense, and by blocking electrons while transporting holes, the probability of recombination of electrons and holes in the light emitting layer can be improved. ..
  • As the material of the electron blocking layer a known electron blocking layer material can be used. In order to bring out the characteristics of the luminescent dopant, the material used as the first host can also be used as the material of the electron blocking layer.
  • the film thickness of the electron blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.
  • the exciton blocking layer is a layer for blocking excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer, and excitons are inserted by inserting this layer. It is possible to efficiently confine it in the light emitting layer, and it is possible to improve the light emitting efficiency of the element.
  • the exciton blocking layer can be inserted between two adjacent light emitting layers in an element in which two or more light emitting layers are adjacent to each other.
  • As the material of the exciton blocking layer a known exciton blocking layer material can be used.
  • the layers adjacent to the light emitting layer include a hole blocking layer, an electron blocking layer, an exciton blocking layer, and the like, but if these layers are not provided, the hole transport layer, the electron transport layer, and the like are adjacent layers. Become.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer may be provided with a single layer or a plurality of layers.
  • the hole transport material has any of hole injection, transport, and electron barrier properties, and may be either an organic substance or an inorganic substance. Any compound can be selected and used for the hole transport layer from conventionally known compounds. Examples of such hole transport materials include porphyrin derivatives, arylamine derivatives, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, and styrylanthracene.
  • Examples thereof include derivatives, fluorenone derivatives, hydrazone derivatives, stylben derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, especially thiophene oligomers, but porphyrin derivatives, arylamine derivatives and styrylamine derivatives may be used. It is preferable to use an arylamine compound, and it is more preferable to use an arylamine compound.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer may be provided with 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.
  • any conventionally known compound can be selected and used, for example, a polycyclic aromatic derivative such as naphthalene, anthracene, phenanthroline, tris (8-quinolinolate) aluminum (III).
  • Derivatives phosphine oxide derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide, fleolenilidene methane derivatives, anthracinodimethane and antron derivatives, bipyridine derivatives, quinoline derivatives, oxadiazole derivatives, benzoimidazole Derivatives, benzothiazole derivatives, indrocarbazole derivatives and the like can be mentioned. Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • the film forming method for each layer when producing the organic EL element of the present invention is not particularly limited, and may be produced by either a dry process or a wet process.
  • S1 and T1 of the compounds BD1, (4-110) and (4-121) were measured.
  • S1 and T1 were measured as follows.
  • S1 measures the emission spectrum of this vapor-deposited film, draws a tangent to the rising edge of the emission spectrum on the short wavelength side, and formulates the wavelength value ⁇ edge [nm] at the intersection of the tangent and the horizontal axis by the following equation ( Substitute in i) to calculate S1.
  • S1 [eV] 1239.85 / ⁇ edge (i)
  • T1 measures the phosphorescence spectrum of the vapor deposition film, draws a tangent line with respect to the rising edge of the phosphorescence spectrum on the short wavelength side, and sets the wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis in the equation (ii).
  • T1 [eV] 1239.85 / ⁇ edge (ii)
  • Example 1 Each thin film was laminated on a glass substrate having an anode made of ITO having a film thickness of 70 nm by a vacuum vapor deposition method at a vacuum degree of 4.0 ⁇ 10-5 Pa.
  • HAT-CN was formed on ITO as a hole injection layer to a thickness of 10 nm
  • HT-1 was formed as a hole transport layer to a thickness of 25 nm.
  • compound (1-58) was formed to a thickness of 5 nm as an electron blocking layer.
  • compound (1-58) as the first host, compound (2-6) as the second host, and compound (4-121) as the luminescent dopant were co-deposited from different deposition sources to a thickness of 30 nm.
  • a light emitting layer was formed to a thickness.
  • co-deposited under the vapor deposition conditions where the concentration of the compound (4-121) was 2% and the compounding ratio of the first host and the second host was 70:30.
  • compound (2-6) was formed to a thickness of 5 nm as a hole blocking layer.
  • ET-1 was formed to a thickness of 40 nm as an electron transport layer.
  • Lithium fluoride (LiF) was formed on the electron transport layer as an electron injection layer to a thickness of 1 nm.
  • aluminum (Al) was formed on the electron injection layer as a cathode to a thickness of 70 nm to produce an organic EL device.
  • Examples 2-9 An organic EL device was produced in the same manner as in Example 1 except that the luminescent dopant, the first host, the second host, and the compounding ratio of the first host and the second host were the compounds shown in Table 2.
  • Comparative Example 1 Each thin film was laminated on a glass substrate having an anode made of ITO having a film thickness of 70 nm by a vacuum vapor deposition method at a vacuum degree of 4.0 ⁇ 10-5 Pa.
  • HAT-CN was formed on ITO as a hole injection layer to a thickness of 10 nm
  • HT-1 was formed as a hole transport layer to a thickness of 25 nm.
  • compound (1-58) was formed to a thickness of 5 nm as an electron blocking layer.
  • compound (1-58) as the first host and compound (4-121) as the luminescent dopant were co-deposited from different vapor deposition sources to form a light emitting layer to a thickness of 30 nm.
  • Comparative Examples 3, 5, 7 An organic EL device was produced in the same manner as in Comparative Example 1, except that the luminescent dopant and the first host (without the second host) were the compounds shown in Table 2.
  • Comparative Examples 2 and 6 An organic EL device was produced in the same manner as in Comparative Example 1, except that the luminescent dopant and the second host (without the first host) were the compounds shown in Table 2.
  • Comparative Examples 4, 8, 9, 10 An organic EL device was produced in the same manner as in Example 1 except that the luminescent dopant, the first host, and the second host were the compounds and compounding ratios shown in Table 2.
  • Table 3 shows the maximum emission wavelength, external quantum efficiency, and lifetime of the emission spectrum of the organic EL device produced in Examples and Comparative Examples.
  • the maximum emission wavelength and the external quantum efficiency are values when the luminance is 500 cd / m 2 , which are initial characteristics.
  • the lifetime was measured by measuring the time until the brightness attenuated to 50% of the initial brightness at an initial brightness of 500 cd / m 2 .
  • the organic EL element of the embodiment has characteristics of high efficiency and long life, and emits blue light from the maximum emission wavelength.
  • the organic EL element of the present invention has high luminous efficiency and long life.

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