Patent Application
20230371375
The present invention relates to a light-emitting material and an organic electroluminescent device (also referred to as an organic EL device) including the light-emitting material as a light emitting layer.
When a voltage is applied to an organic EL device, holes and electrons are injected from the anode and the cathode, respectively, into the light emitting layer. Then, the injected holes and electrons are recombined in the light emitting layer to thereby generate excitons. At this time, according to the electron spin statistics theory, singlet excitons and triplet excitons are generated at a ratio of 1:3. In the fluorescent organic EL device that uses emission caused by singlet excitons, the limit of the internal quantum efficiency is said to be 25%. On the other hand, it has been known that, in the phosphorescent organic EL device that uses emission caused by triplet excitons, the internal quantum efficiency can be enhanced up to 100% when intersystem crossing efficiently occurs from singlet excitons.
A technology for extending the lifetime of a phosphorescent organic EL device has advanced in recent years, and the device is being applied to a display of a mobile phone and others. Regarding a blue organic EL device, however, a practical phosphorescent organic EL device has not been developed, and thus the development of a blue organic EL device having high efficiency and a long lifetime is desired.
Further, a highly efficient delayed fluorescence organic EL device utilizing delayed fluorescence has been developed, in recent years. For example, Patent Literature 1 discloses an organic EL device utilizing the Triplet-Triplet Fusion (TTF) mechanism, which is one of the mechanisms of delayed fluorescence. The TTF mechanism utilizes a phenomenon in which a singlet exciton is generated by the collision of two triplet excitons, and it is believed that the internal quantum efficiency can be enhanced up to 40%, in theory. However, its efficiency is low as compared with the efficiency of the phosphorescent organic EL device, and thus further improvement in efficiency is desired.
On the other hand, Patent Literature 2 discloses an organic EL device utilizing the Thermally Activated Delayed Fluorescence (TADF) mechanism. The TADF mechanism utilizes a phenomenon in which reverse intersystem crossing occurs from the triplet exciton to the singlet exciton in a material having a small energy difference between the singlet level and the triplet level, and it is believed that the internal quantum efficiency can be enhanced up to 100%, in theory. Specifically, Patent Literature 2 discloses an indolocarbazole compound as a thermally activated delayed fluorescence material.
Patent Literature 3, Patent Literature 4, and Patent Literature 5 each disclose an emission material including a polycyclic aromatic compound containing a boron atom, and an organic EL device including the emission material.
In view of applying an organic EL device to a display device such as a flat panel display and a light source, it is necessary to improve the emission efficiency of the device and sufficiently ensure the stability of the device at the time of driving, at the same time. The present invention has been made under such circumstances, and an object thereof is to provide an emission material that can be used to obtain a practically useful organic EL device having high emission efficiency and high driving stability, and an organic EL device including the emission material.
Specifically, the present invention is an emission material represented by the following general formula (1) and also an organic EL device comprising one or more light emitting layers between an anode and a cathode opposite to each other, wherein at least one of the light emitting layers contains the emission material.
In the formula, B represents a boron atom, a ring A represents a heterocycle fused with an adjacent ring at any position and represented by formula (1a), and a ring C represents a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic ring having 2 to 30 carbon atoms, or a substituted or unsubstituted linked aromatic ring formed by linking 2 to 3 aromatic rings of aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group. A ring D represents a benzene ring.
X represents O, S, or N—Ar1.
Ar1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 4 aromatic rings of aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group, and Ar1 is optionally bonded with the ring C or the ring D by a single bond or a linked group to thereby form a ring.
Y represents O, S, or N—Ar2.
Ar2 represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 4 aromatic rings of aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group.
Z independently represents a cyano group, deuterium, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms; and when Z represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms, Z is optionally bonded with the ring D by a single bond to thereby form a ring.
L represents O, S, or C(R2)2.
R2 independently represents hydrogen, or an aliphatic group having 1 to 8 carbon atoms.
R1 independently represents a cyano group, deuterium, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms.
a represents an integer of 0 to 3, b and d each represent an integer of 0 to 4, and c and e represent 0 or 1.
In the general formula (1), X is preferably represented by N—Ar1.
In the general formula (1a), Y is preferably represented by N—Ar2.
In the general formula (1), the ring C is preferably represented by a substituted or unsubstituted benzene ring, or a substituted or unsubstituted aromatic heterocyclic ring having 2 to 30 carbon atoms.
The emission material represented by the general formula (1) is preferably represented by the following general formula (2).
In the formula, ring C, X, Y, Z, L, a and e are the same as those defined in the general formula (1).
The present invention is an organic electroluminescent device comprising one or more light emitting layers between an anode and a cathode opposite to each other, wherein at least one of the light emitting layers contains the above emission material.
In the organic electroluminescent device of the present invention, the light emitting layer containing the emission material preferably contains a host material.
In the organic electroluminescent device of the present invention, the host material is more preferably a triazine compound or an anthracene compound.
A practically useful organic EL device having high emission efficiency and high driving stability can be obtained by the emission material of the present invention.
The organic EL device of the present invention has one or more light emitting layers between an anode and a cathode opposite to each other, and at least one layer of the light emitting layers contains the emission material represented by the general formula (1). The organic EL device has a plurality of layers between an anode and a cathode opposite to each other, at least one layer of the plurality of layers is a light emitting layer, and the light emitting layer may contain a host material, as necessary.
The general formula (1) will be described below.
First, B represents a boron atom, and a ring A represents a heterocycle fused with an adjacent ring at any position and represented by formula (1a).
A ring C represents a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic ring having 2 to 30 carbon atoms, or a substituted or unsubstituted linked aromatic ring formed by linking 2 to 3 aromatic rings of aromatic groups selected from the aromatic hydrocarbon ring group and the aromatic heterocyclic group. The ring C preferably represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted aromatic heterocyclic ring having 2 to 30 carbon atoms, or a substituted or unsubstituted linked aromatic ring formed by linking 2 to 3 aromatic rings of aromatic groups selected from the aromatic hydrocarbon ring group and the aromatic heterocyclic group. The ring C more preferably represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted aromatic heterocyclic ring having 2 to 20 carbon atoms, or a substituted or unsubstituted linked aromatic ring formed by linking 2 to 3 aromatic rings of aromatic groups selected from the aromatic hydrocarbon ring group and the aromatic heterocyclic group.
Specific examples of the unsubstituted ring C include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, carbazole, and a linked aromatic ring in which 2 to 3 aromatic rings represented by these aromatic groups are linked. Preferred examples thereof include benzene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, carbazole, and a linked aromatic ring in which 2 to 3 aromatic rings represented by these aromatic groups are linked. More preferred examples thereof include benzene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, quinoxaline, quinazoline, indole, benzofuran, dibenzofuran, dibenzothiophene, carbazole, and a linked aromatic ring in which 2 to 3 aromatic rings represented by these aromatic groups are linked.
A ring D represents a benzene ring.
X represents O, S, or N—Ar1, and preferably represents N—Ar1.
Y represents O, S, or N—Ar2, and preferably represents N—Ar2.
Ar1 and Ar2 represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 4 aromatic rings of aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group. These preferably represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 20 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 3 aromatic rings of aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group. These more preferably represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 10 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 3 aromatic rings of aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group.
Ar1 can be bonded with the ring C or the ring D by a single bond or a linked group to thereby form a ring.
The linked group is preferably an ether group (—O—), a sulfide group (—S—), or a methylene group (—C(R2)2—). R2 here independently represents hydrogen, or an aliphatic group having 1 to 8 carbon atoms, and specifically represents, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group.
Specific examples of the unsubstituted Ar1 and Ar2 include a group produced by removing one hydrogen atom from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, carbazole, and a compound formed by linking 2 to 4 of these compounds. Preferred examples thereof include a group produced by removing one hydrogen atom from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, carbazole, and a compound formed by linking 2 to 3 of these compounds. More preferred examples thereof include a group produced by removing one hydrogen atom from benzene, naphthalene, azulene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, and a compound formed by linking 2 to 3 of these compounds.
Herein, each of the aromatic hydrocarbon rings, aromatic heterocyclic groups, and linked aromatic rings, forming the ring C, and each of the aromatic hydrocarbon groups, aromatic heterocyclic groups, and linked aromatic groups, forming Ar1 or Ar2, may have a substituent. When these groups have a substituent, the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a diarylamino group having 12 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or an arylthio group having 6 to 18 carbon atoms. The number of substituents is 0 to 5, and preferably 0 to 2. When each of the aromatic hydrocarbon groups, aromatic hydrocarbon rings and aromatic heterocyclic groups, and the aromatic heterocyclic rings has a substituent, the number of carbon atoms of the substituent is not included in the calculation of the number of carbon atoms. However, it is preferred that the total number of carbon atoms including the number of carbon atoms of the substituent satisfy the above range.
Specific examples of the above substituent include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranilamino, diphenanthrenylamino, methoxy, ethoxy, phenol, diphenyloxy, methylthio, ethylthio, thiophenol, and diphenylthio. Preferred examples thereof include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, dinaphthylamino, phenol, and thiophenol.
Z independently represents a cyano group, deuterium, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms. Z preferably represents a cyano group, deuterium, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 24 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 20 carbon atoms. Z more preferably represents a substituted or unsubstituted diarylamino group having 12 to 18 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 10 carbon atoms.
When Z represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms, Z is optionally bonded with the ring D by a single bond to thereby form a ring.
L represents O, S, or C(R2)2, and preferably represents O, or S.
R2 here independently represents hydrogen, or an aliphatic group having 1 to 8 carbon atoms, and specifically represents, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group.
When Z represents a diarylamino group or an aliphatic hydrocarbon group, specific examples of Z include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dianthranilamino, diphenanthrenylamino, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Preferred examples thereof include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. More preferred examples thereof include diphenylamino and phenylbiphenylamino.
When Z represents an aromatic hydrocarbon group or an aromatic heterocyclic group, specific examples include a group produced by removing one hydrogen atom from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, and carbazole. Preferred examples thereof include a group produced by removing one hydrogen atom from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, and carbazole. More preferred examples thereof include a group produced by removing one hydrogen atom from benzene, naphthalene, azulene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, and chromone.
R1 independently represents a cyano group, deuterium, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 30 carbon atoms. R1 preferably represents a cyano group, deuterium, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic amino group having 12 to 24 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 20 carbon atoms. R1 more preferably represents a substituted or unsubstituted diarylamino group having 12 to 18 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 2 to 10 carbon atoms.
a represents an integer of 0 to 3, preferably represents an integer of 0 to 1, and more preferably represents an integer of 0.
e represents an integer of 0 to 1, and preferably represents an integer of 0.
b and d each represent an integer of 0 to 4, preferably represent an integer of 0 to 1, and more preferably represent 0.
c represents 0 or 1, and preferably represents 0.
When R1 is a diarylamino group or an aliphatic hydrocarbon group, specific examples of R1 include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dianthranilamino, diphenanthrenylamino, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Preferred examples thereof include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. More preferred examples thereof include diphenylamino and phenylbiphenylamino.
When R1 is an aromatic hydrocarbon group or an aromatic heterocyclic group, specific examples of R1 include a group produced by removing one hydrogen atom from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, and carbazole. Preferred examples thereof include a group produced by removing one hydrogen atom from benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, and carbazole. More preferred examples thereof include a group produced by removing one hydrogen atom from benzene, naphthalene, azulene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, and chromone.
Specific examples of the emission materials represented by the general formula (1) are shown below, but the materials are not limited to these exemplified compounds.
By incorporating the emission material represented by the general formula (1) into a light emitting layer, a practically excellent organic EL device having high emission efficiency and high driving stability can be provided.
The light emitting layer can also contain a host material together with the emission material represented by the general formula (1), as necessary. A more excellent organic EL device can be provided by incorporating the host material.
At least one of such host materials is preferably a triazine compound or an anthracene compound.
More preferred examples of the host material include compounds represented by the following general formulas.
In the formulas, each Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 20 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 3 aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group. Each Ar preferably represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 15 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 15 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 3 aromatic groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group. Each Ar more preferably represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 15 carbon atoms, or a substituted or unsubstituted linked aromatic group formed by linking 2 to 3 aromatic groups selected from the aromatic hydrocarbon group.
Specific examples of the unsubstituted Ar include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo[a]anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, carbazole, and a group formed by linking 2 to 3 these aromatic groups. Preferred examples thereof include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, phenanthrene, fluorene, pyridine, pyrimidine, triazine, thiophene, isothiazole, thiazole, pyridazine, pyrrole, pyrazole, imidazole, triazole, thiadiazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, thiadiazole, phthalazine, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzisothiazole, benzothiadiazole, purine, pyranone, coumarin, isocoumarin, chromone, dibenzofuran, dibenzothiophene, dibenzoselenophene, carbazole, and a linked aromatic group formed by linking 2 to 3 these aromatic groups. More preferred examples thereof include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, phenanthrene, fluorene, and a linked aromatic group formed by linking 2 to 3 these aromatic groups.
Preferred examples of the host specifically include, but are not particularly limited to, the following.
Next, the structure of the organic EL device of the present invention will be described with reference to the drawing, but the structure of the organic EL device of the present invention is not limited thereto.
It is also possible to have a structure that is the reverse of the structure shown in
—Substrate—
The organic EL device of the present invention is preferably supported on a substrate. The substrate is not particularly limited and may be a substrate conventionally used for organic EL devices, and for example, a substrate made of glass, transparent plastic, or quartz can be used.
—Anode—
As the anode material in the organic EL device, a material made of a metal, alloy, or conductive compound having a high work function (4 eV or more), or a mixture thereof is preferably used. Specific examples of such an electrode material include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO2, and ZnO. An amorphous material capable of producing a transparent conductive film such as IDIXO (In2O3—ZnO) may also be used. As the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and then a pattern of a desired form may be formed by photolithography. Alternatively, when a highly precise pattern is not required (about 100 μm or more), a pattern may be formed through a mask of a desired form at the time of vapor deposition or sputtering of the above electrode materials. Alternatively, when a coatable material such as an organic conductive compound is used, a wet film forming method such as a printing method and a coating method can also be used. When light is extracted from the anode, the transmittance is desirably more than 10%, and the sheet resistance as the anode is preferably several hundred Ω/square or less. The film thickness is selected within a range of usually 10 to 1,000 nm, and preferably 10 to 200 nm, although it depends on the material.
—Cathode—
On the other hand, a material made of a metal (referred to as an electron injection metal), alloy, or conductive compound having a low work function (4 eV or less) or a mixture thereof is used as the cathode material. Specific examples of such an electrode material include sodium, a sodium-potassium alloy, magnesium, lithium, a magnesium/copper mixture, a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al2O3) mixture, indium, a lithium/aluminum mixture, and a rare earth metal. Among them, in terms of electron injection properties and durability against oxidation and the like, a mixture of an electron injection metal with a second metal that has a higher work function value than the electron injection metal and is stable, for example, a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al2O3) mixture, a lithium/aluminum mixture, or aluminum is suitable. The cathode can be produced by forming a thin film from these cathode materials by a method such as vapor deposition and sputtering. The sheet resistance as the cathode is preferably several hundred Ω/square or less, and the film thickness is selected within a range of usually 10 nm to 5 μm, and preferably 50 to 200 nm. To transmit the light emitted, either one of the anode and the cathode of the organic EL device is favorably transparent or translucent because light emission brightness is improved.
The above metal is formed to have a film thickness of 1 to 20 nm, and then a conductive transparent material mentioned in the description of the anode is formed on the metal, so that a transparent or translucent cathode can be produced. By applying this process, a device in which both anode and cathode have transmittance can be produced.
—Light Emitting Layer—
The light emitting layer is a layer that emits light after holes and electrons respectively injected from the anode and the cathode are recombined to form exciton. For the light emitting layer, the emission material represented by the general formula (1) may be used alone, or the emission material may be used in combination with a host material. When the emission material is used together with the host material, the emission material serves as a light emitting dopant.
The emission material represented by the general formula (1) may also be used together with a fluorescence material other than those represented by the general formula (1). When the emission material represented by the general formula (1) is used together with the fluorescence material, the emission material may be further used together with a host material. When the emission material represented by the general formula (1) is used with a fluorescence material, the fluorescence material serves as a light emitting dopant.
The content of the light emitting dopant is preferably 0.1 to 50 wt %, and more preferably 0.1 to 40 wt % based on the host material.
The host material in the light emitting layer can be a known host material used for a phosphorescent device or a fluorescent device, other than the host material shown above. A usable known host material is a compound having the ability to transport hole, the ability to transport electron, and a high glass transition temperature, and preferably has a higher triplet excited energy (T1) than the triplet excited energy (T1) of the emission material represented by the general formula (1). A TADF-active compound may also be used as the host material, and the TADF-active compound preferably has a difference (ΔEST=S1−T1) between the singlet excited energy (S1) and the triplet excited energy (T1), of 0.20 eV or less.
Here, S1 and T1 are measured as follows.
A sample compound (thermally activated delayed fluorescence material) is deposited on a quartz substrate by a vacuum deposition method under conditions of a degree of vacuum of 10−4 Pa or less to form a deposition film having a thickness of 100 nm. For S1, the emission spectrum of this deposition film is measured, a tangent is drawn to the rise of the emission spectrum on the short-wavelength side, and the wavelength value λedge [nm] of the point of intersection of the tangent and the horizontal axis is substituted into the following equation (i) to calculate S1.
S1 [eV]=1239.85/λedge (i)
For T1, on the other hand, the phosphorescence spectrum of the above deposition film is measured, a tangent is drawn to the rise of the phosphorescence spectrum on the short-wavelength side, and the wavelength value λedge [nm] of the point of intersection of the tangent and the horizontal axis is substituted into the following equation (ii) to calculate T1.
T1 [eV]=1239.85/λedge (ii)
Such host materials are known in a large number of Patent Literatures and the like, and hence may be selected from them. Specific examples of the host material include, but are not particularly limited to, various metal complexes typified by metal complexes of indole compounds, carbazole compounds, indolocarbazole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, triazole compounds, oxazole compounds, oxadiazole compounds, imidazole compounds, phenylenediamine compounds, arylamine compounds, anthracene compounds, fluorenone compounds, stilbene compounds, triphenylene compounds, carborane compounds, porphyrin compounds, phthalocyanine compounds, and 8-quinolinol compounds, and metal phthalocyanine, and metal complexes of benzoxazole and benzothiazole compounds; and polymer compounds such as poly(N-vinyl carbazole) compounds, aniline-based copolymer compounds, thiophene oligomers, polythiophene compounds, polyphenylene compounds, polyphenylene vinylene compounds, and polyfluorene compounds. Preferred examples thereof include carbazole compounds, indolocarbazole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, anthracene compounds, triphenylene compounds, carborane compounds, and porphyrin compounds.
Only one host may be contained or two or more hosts may be used in one light emitting layer. When two or more hosts are used, at least one thereof is preferably an electron-transporting compound, for example, the triazine compounds or anthracene compounds described above, and other host is preferably a hole-transporting compound, for example, the carbazole compounds or indolocarbazole compounds. When a plurality of hosts is used, each host is deposited from different deposition sources, or a plurality of hosts is premixed before vapor deposition to form a premix, whereby a plurality of hosts can be simultaneously deposited from one deposition source.
As the method of premixing, a method by which hosts can be mixed as uniformly as possible is desirable, and examples thereof include, but are not limited to, milling, a method of heating and melting hosts under reduced pressure or under an inert gas atmosphere such as nitrogen, and sublimation.
The host and a premix thereof may be in the form of powder, sticks, or granules.
When a fluorescence material other than those represented by the general formula (1) is used in the light emitting layer, preferred examples of the other fluorescence material include fused polycyclic aromatic derivatives, styrylamine derivatives, fused ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, and indolocarbazole derivatives. Among them, fused ring amine derivatives, boron-containing compounds, carbazole derivatives, and indolocarbazole derivatives are preferred.
Examples of the fused ring amine derivatives include diaminepyrene derivatives, diaminochrysene derivatives, diaminoanthracene derivatives, diaminofluorenone derivatives, and diaminofluorene derivatives fused with one or more benzofuro backbones.
Examples of the boron-containing compounds include pyrromethene derivatives and trriphenylborane derivatives.
Preferred examples of the fluorescence material other than those represented by the general formula (1) are not particularly limited, but specific examples thereof include the following.
—Injection Layer—
The injection layer refers to a layer provided between the electrode and the organic layer to reduce the driving voltage and improve the light emission brightness, and includes the hole injection layer and the electron injection layer. The injection layer may be present between the anode and the light emitting layer or the hole transport layer, as well as between the cathode and the light emitting layer or the electron transport layer. The injection layer may be provided as necessary.
—Hole Blocking Layer—
The hole blocking layer has the function of the electron transport layer in a broad sense, is made of a hole blocking material having a very small ability to transport holes while having the function of transporting electrons, and can improve the recombination probability between the electrons and the holes in the light emitting layer by blocking the holes while transporting the electrons. For the hole blocking layer, a known hole blocking material can be used. A plurality of hole blocking materials may be used in combination.
—Electron Blocking Layer—
The electron blocking layer has the function of the hole transport layer in a broad sense, and can improve the recombination probability between the electrons and the holes in the light emitting layer by blocking the electrons while transporting the holes. As the material for the electron blocking layer, a known material for the electron blocking layer can be used.
—Exciton Blocking Layer—
The exciton blocking layer is a layer to block the diffusion of the excitons generated by recombination of the holes and the electrons in the light emitting layer into a charge transport layer, and insertion of this layer makes it possible to efficiently keep the excitons in the light emitting layer, so that the emission efficiency of the device can be improved. The exciton blocking layer can be inserted between two light emitting layers adjacent to each other in the device in which two or more light emitting layers are adjacent to each other. As the material for such an exciton blocking layer, a known material for the exciton blocking layer can be used.
The layer adjacent to the light emitting layer includes the hole blocking layer, the electron blocking layer, and the exciton blocking layer, and when these layers are not provided, the adjacent layer is the hole transport layer, the electron transport layer, and the like.
—Hole Transport Layer—
The hole transport layer is made of a hole transport material having the function of transporting holes, and the hole transport layer may be provided as a single layer or a plurality of layers.
The hole transport material has any of hole injection properties, hole transport properties, or electron barrier properties, and may be either an organic material or an inorganic material. As the hole transport layer, any of conventionally known compounds may be selected and used. Examples of such a hole transport material include porphyrin derivatives, arylamine derivatives, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, particularly, thiophene oligomers. Porphyrin derivatives, arylamine derivatives, and styrylamine derivatives are preferably used, and arylamine compounds are more preferably used.
—Electron Transport Layer—
The electron transport layer is made of a material having the function of transporting electrons, and the electron transport layer may be provided as a single layer or a plurality of layers.
The electron transport material (may also serve as the hole blocking material) has the function of transmitting electrons injected from the cathode to the light emitting layer. As the electron transport layer, any of conventionally known compounds may be selected and used, and examples thereof include polycyclic aromatic derivatives such as naphthalene, anthracene, and phenanthroline, tris(8-quinolinolato)aluminum (III) derivatives, phosphine oxide derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, bipyridine derivatives, quinoline derivatives, oxadiazole derivatives, benzimidazole derivatives, benzothiazole derivatives, and indolocarbazole derivatives. Further, polymer materials in which these materials are introduced in the polymer chain or these materials constitute the main chain of the polymer can also be used.
When the organic EL device of the present invention is produced, the film formation method of each layer is not particularly limited, and the layers may be produced by either a dry process or a wet process.
Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples.
The compounds used in Examples and Comparative Examples are shown below.
As shown in the above reaction scheme, 6.9 g of a starting material (A), 20.0 g of a starting material (B), 57.8 g of cesium carbonate, and 200 ml of N,N-dimethylacetamide (DMAc) were put in a three-necked flask under a nitrogen atmosphere and stirred at 180° C. for 18 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered, and the filtrate was put in a flask containing 800 ml of water, and stirred for 1 hour. The precipitated solid was collected by filtering, and then dissolved in tetrahydrofuran and extracted with toluene. The organic layer was washed with water, and then concentrated. The concentrate was purified by silica gel column chromatography and thereafter the resulting solid was dried under reduced pressure to yield 7.6 g of an intermediate (C) (yield: 32%).
APCI-TOFMS m/z 667[M+1]+
Then, 7.6 g of the intermediate (C) obtained above, 200.0 g of a starting material (D), 4.7 g of copper, and 17.3 g of potassium carbonate were put in a three-necked flask under a nitrogen atmosphere and stirred at 190° C. for 24 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered, the resulting solution was concentrated, and the concentrate was purified by silica gel column chromatography. The resulting solid was dried under reduced pressure to yield 7.5 g of an intermediate (E) (yield: 80%).
APCI-TOFMS m/z 819[M+1]+
To a 500-mL Schlenk flask were added 4.1 g of the intermediate (E) obtained above and 250 mL of anhydrous t-butylbenzene. After purging with nitrogen, (1.64 mol/l) 3.3 mL of n-butyllithium was added at −30° C. in small amounts, and the resultant was stirred for 1 hour. Subsequently, 0.6 mL of boron tribromide was added at −30° C. in small amounts, and the resultant was stirred at room temperature for 1 hour. Subsequently, 1.7 mL of N,N-diisopropylethylamine was added at 0° C., and the resultant was stirred at 140° C. overnight. The reaction solution was cooled to room temperature, and methanol was added in small amounts to take the resulting precipitate by filtering. Thereafter, the precipitate was washed sequentially with methanol, toluene, and hexane in the listed order, and the resulting solid was dried under reduced pressure to yield 1.3 g of a compound (52) (yield: 35%).
APCI-TOFMS m/z 747[M+1]+
Each thin film shown below was laminated on the glass substrate on which an anode made of ITO having a film thickness of 70 nm was formed by a vacuum deposition method at a degree of vacuum of 4.0×10−5 Pa. First, the previously presented HAT-CN was formed on ITO to a thickness of 10 nm as a hole injection layer, and then HT-1 was formed to a thickness of 25 nm as a hole transport layer. Then, HT-2 was formed to a thickness of 5 nm as an electron blocking layer. Then, BH-1 as the host and the compound (52) in the exemplified compounds previously presented as specific examples of the general formula (1), as the dopant, were co-deposited from different deposition sources to form a light emitting layer having a thickness of 30 nm. At this time, they were co-deposited under deposition conditions such that the concentration of the compound (52) was 2% by mass. Then, ET-2 was formed to a thickness of 5 nm as a hole blocking layer. Then, ET-1 was formed to a thickness of 40 nm as an electron transport layer. Further, lithium fluoride (LiF) was formed on the electron transport layer to a thickness of 1 nm as an electron injection layer. Finally, aluminum (Al) was formed on the electron injection layer to a thickness of 70 nm as a cathode, whereby an organic EL device according to Example 1 was produced.
Each organic EL device was produced in the same manner as in Example 1, except that BD-1 was used as the dopant.
The maximum emission wavelength of the emission spectrum, external quantum efficiency, and lifetime of each organic EL device produced are shown in Table 1. The maximum emission wavelength and the external quantum efficiency were values at a driving current density of 2.5 mA/cm2 and were initial characteristics. The time taken for the luminance to reduce to 70% of the initial luminance when the driving current density was 2.5 mA/cm2 was measured as the lifetime.
Each thin film shown below was laminated on the glass substrate on which an anode made of ITO having a film thickness of 70 nm was formed by a vacuum deposition method at a degree of vacuum of 4.0×10−5 Pa. First, the previously presented HAT-CN was formed on ITO to a thickness of 10 nm as a hole injection layer, and then HT-1 was formed to a thickness of 25 nm as a hole transport layer. Then, HT-2 was formed to a thickness of 5 nm as an electron blocking layer. Then, BH-1 as the first host, the compound BH-2 as the second host, and the compound (52) as the dopant were co-deposited from different deposition sources to form a light emitting layer having a thickness of 30 nm. At this time, they were co-deposited under deposition conditions such that the concentration of BH-1 was 29% by mass, the concentration of BH-2 was 69% by mass, and the concentration of the compound (52) was 2% by mass. Then, ET-2 was formed to a thickness of 5 nm as a hole blocking layer. Then, ET-1 was formed to a thickness of 40 nm as an electron transport layer. Further, lithium fluoride (LiF) was formed on the electron transport layer to a thickness of 1 nm as an electron injection layer. Finally, aluminum (Al) was formed on the electron injection layer to a thickness of 70 nm as a cathode, whereby an organic EL device according to Example 2 was produced.
Each organic EL device was produced in the same manner as in Example 2, except that the dopant was changed to the BD-1.
The maximum emission wavelength of the emission spectrum, external quantum efficiency, and lifetime of each organic EL device produced are shown in Table 2. The maximum emission wavelength and the external quantum efficiency were values at a driving current density of 2.5 mA/cm2 and were initial characteristics. The time taken for the luminance to reduce to 70% of the initial luminance when the driving current density was 2.5 mA/cm2 was measured as the lifetime.
Each thin film shown below was laminated on the glass substrate on which an anode made of ITO having a film thickness of 70 nm was formed by a vacuum deposition method at a degree of vacuum of 4.0×10−5 Pa. First, the previously presented HAT-CN was formed on ITO to a thickness of 10 nm as a hole injection layer, and then HT-3 was formed to a thickness of 25 nm as a hole transport layer. Then, HT-4 was formed to a thickness of 5 nm as an electron blocking layer. Then, BH-3 as the host and the compound (52) as the dopant were co-deposited from different deposition sources to form a light emitting layer having a thickness of 30 nm. At this time, they were co-deposited under deposition conditions such that the concentration of the compound (52) was 2% by mass. Then, BH-3 was formed to a thickness of 5 nm as a hole blocking layer. Then, Alq3 was formed to a thickness of 40 nm as an electron transport layer. Further, lithium fluoride (LiF) was formed on the electron transport layer to a thickness of 1 nm as an electron injection layer. Finally, aluminum (Al) was formed on the electron injection layer to a thickness of 70 nm as a cathode, whereby an organic EL device according to Example 3 was produced.
Each organic EL device was produced in the same manner as in Example 3, except that the dopant was changed to the BD-1.
The maximum emission wavelength of the emission spectrum, external quantum efficiency, and lifetime of each organic EL device produced are shown in Table 3. The maximum emission wavelength and the external quantum efficiency were values at a driving current density of 2.5 mA/cm2 and were initial characteristics. The time taken for the luminance to reduce to 95% of the initial luminance when the driving current density was 10 mA/cm2 was measured as the lifetime.
From the respective comparisons of the data of Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3 as shown in Tables 1 to 3, the organic EL device including, as a light emitting dopant, the emission material represented by the general formula (1), in which a backbone having a specific 5-ring-fused ring structure was combined with a boron atom, showed excellent results in efficiency and lifetime and showed excellent results particularly in lifetime characteristics. It is considered that the reason for this is as follows: the use of a backbone having a specific 5-ring-fused ring structure expanded conjugation, and improved the stability against oxidation and reduction, and lifetime characteristics.
As shown in the above reaction scheme, 12.0 g of the starting material (A), 10.4 g of a starting material (F), 101.3 g of cesium carbonate, and 300 ml of N,N-dimethylacetamide (DMAc) were put in a three-necked flask under a nitrogen atmosphere and stirred at 90° C. for 24 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered, and the filtrate was put in a flask containing 800 ml of water, and stirred for 1 hour. The precipitated solid was collected by filtering, and then dissolved in tetrahydrofuran and extracted with toluene. The organic layer was washed with water, and then concentrated. The concentrate was purified by silica gel column chromatography and thereafter the resulting solid was dried under reduced pressure to yield 6.0 g of an intermediate (G) (yield: 27%).
APCI-TOFMS m/z 341[M+1]+
As shown in the above reaction scheme, 6.0 g of an intermediate (G), 5.0 g of the starting material (B), 28.5 g of cesium carbonate, and 300 ml of N,N-dimethylacetamide (DMAc) were put in a three-necked flask under a nitrogen atmosphere and stirred at 180° C. for 5 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered, and the filtrate was put in a flask containing 800 ml of water, and stirred for 1 hour. The precipitated solid was collected by filtering, and then dissolved in tetrahydrofuran and extracted with toluene. The organic layer was washed with water, and then concentrated. The concentrate was purified by silica gel column chromatography and thereafter the resulting solid was dried under reduced pressure to yield 7.1 g of an intermediate (H) (yield: 72%).
APCI-TOFMS m/z 577[M+1]+
Then, 7.1 g of the intermediate (H) obtained above, 100.0 g of the starting material (D), 5.1 g of copper, and 18.8 g of potassium carbonate were put in a three-necked flask under a nitrogen atmosphere and stirred at 180° C. for 24 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered, the resulting solution was concentrated, and the concentrate was purified by silica gel column chromatography. The resulting solid was dried under reduced pressure to yield 6.7 g of an intermediate (I) (yield: 82%).
APCI-TOFMS m/z 653[M+1]+
To a 500-mL Schlenk flask were added 5.0 g of the intermediate (I) obtained above and 250 mL of anhydrous t-butylbenzene. After purging with nitrogen, (1.64 mol/l) 5.2 mL of n-butyllithium was added at −30° C. in small amounts, and the resultant was stirred for 2 hours. Subsequently, 0.9 mL of boron tribromide was added at −30° C. in small amounts, and the resultant was stirred at room temperature for 1 hour. Subsequently, 2.7 mL of N,N-diisopropylethylamine (DIEA) was added at 0° C., and the resultant was stirred at 140° C. overnight. The reaction solution was cooled to room temperature, and methanol was added in small amounts to take the resulting precipitate by filtering. Thereafter, the precipitate was washed sequentially with methanol, toluene, and hexane in the listed order, and the resulting solid was dried under reduced pressure to yield 1.2 g of a compound (38) (yield: 28%).
APCI-TOFMS m/z 582[M+1]+
As shown in the above reaction scheme, 5.0 g of a starting material (J), 5.0 g of the starting material (B), 13.0 g of cesium carbonate, and 40 ml of N,N-dimethylacetamide (DMAc) were put in a three-necked flask under a nitrogen atmosphere and stirred at 160° C. for 5 hours. The reaction solution was cooled to room temperature, and then extracted with toluene. The organic layer was washed with water, and then concentrated. The concentrate was subjected to reslurry with methanol, and the resulting solid was dried under reduced pressure to yield 7.8 g of an intermediate (K) (yield: 81%).
APCI-TOFMS m/z 489[M+1]+
Then, 4.0 g of the intermediate (K) obtained above, 38.0 g of a starting material (L), 3.1 g of copper, and 12.4 g of potassium carbonate were put in a three-necked flask under a nitrogen atmosphere and stirred at 180° C. for 24 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered, the resulting solution was concentrated, and the concentrate was purified by silica gel column chromatography. The resulting solid was dried under reduced pressure to yield 4.1 g of an intermediate (M) (yield: 79%).
APCI-TOFMS m/z 643[M+1]+
Then, 4.2 g of the intermediate (M) obtained above, 2.7 g of a starting material (N), 0.2 g of palladium acetate, 0.3 g of tri-t-butylphosphine, 3.1 g of sodium t-butoxide, and 60 ml of toluene were put in a three-necked flask under a nitrogen atmosphere and stirred at 80° C. for 1 hour. The reaction solution was cooled to room temperature, and then washed with water and concentrated. The concentrate was purified by silica gel column chromatography. The resulting solid was dissolved in tetrahydrofuran (THF), put in a flask containing methanol, and re-precipitated. The precipitated solid was collected by filtering and dried under reduced pressure to yield 4.2 g of an intermediate (O) (yield: 79%).
APCI-TOFMS m/z 819[M+1]+
Then, 2.1 g of the intermediate (O) obtained above, 25 mL of anhydrous toluene, and 1.0 mL of boron tribromide were put in a three-necked flask under a nitrogen atmosphere and stirred at 125° C. for 8 hours. The reaction solution was cooled to room temperature, and water was added thereto. The reaction solution was extracted with dichloromethane, and concentrated. The concentrate was purified by silica gel column chromatography. The resulting solid was dried under reduced pressure to yield 2.0 g of a compound (165) (yield: 95%).
APCI-TOFMS m/z 827[M+1]+
As shown in the above reaction scheme, 10.1 g of the starting material (J), 10.0 g of a starting material (P), 31.8 g of cesium carbonate, and 78 ml of N,N-dimethylacetamide (DMAc) were put in a three-necked flask under a nitrogen atmosphere and stirred at 160° C. for 4.5 hours. After the reaction solution was cooled to room temperature, the reaction solution was put in a flask containing 500 ml of water, and stirred for 30 minutes. The precipitated solid was collected by filtering, and then subjected to reslurry with 2-propanol and m-xylene in the listed order, and the resulting solid was dried under reduced pressure to yield 17.0 g of an intermediate (Q) (yield: 86%).
APCI-TOFMS m/z 490[M+1]+
Then, 10.0 g of the intermediate (Q) obtained above, 8.3 g of the starting material (N), 0.5 g of palladium acetate, 0.8 g of tri-t-butylphosphine, 9.8 g of sodium t-butoxide, and 200 ml of toluene were put in a three-necked flask under a nitrogen atmosphere and stirred at 80° C. for 2 hours. The reaction solution was cooled to room temperature, and then washed with water and concentrated. The concentrate was subjected to reslurry with 2-propanol and tetrahydrofuran (THF) in the listed order, and the resulting solid was dried under reduced pressure to yield 11.5 g of an intermediate (R) (yield: 85%).
APCI-TOFMS m/z 668[M+1]+
Then, 3.0 g of the intermediate (R) obtained above, 150 mL of anhydrous toluene, and 1.7 mL of boron tribromide were put in a three-necked flask under a nitrogen atmosphere and stirred at 120° C. for 24 hours. The reaction solution was cooled to room temperature, and water was added thereto. The reaction solution was extracted with dichloromethane, and concentrated. The concentrate was purified by silica gel column chromatography. The purified product was heated and dissolved in m-xylene, and crystallized with n-heptane. The resulting solid was dried under reduced pressure to yield 1.6 g of a compound (32) (yield: 53%).
APCI-TOFMS m/z 676[M+1]+
As shown in the above reaction scheme, 7.7 g of a starting material (S), 7.5 g of the starting material (B), 25.9 g of cesium carbonate, and 60 ml of N,N-dimethylacetamide (DMAc) were put in a three-necked flask under a nitrogen atmosphere and stirred at 160° C. for 5 hours. The reaction solution was cooled to room temperature, and then extracted with toluene. The organic layer was washed with water and then concentrated, and the concentrate was purified by silica gel column chromatography. The resulting solid was dissolved in tetrahydrofuran (THF), put in a flask containing methanol, and re-precipitated. The precipitated solid was collected by filtering and dried under reduced pressure to yield 8.8 g of an intermediate (T) (yield: 66%).
APCI-TOFMS m/z 445[M+1]+
Then, 8.8 g of the intermediate (T) obtained above, 120.7 g of the starting material (D), 22.6 g of copper, and 30.0 g of potassium carbonate were put in a three-necked flask under a nitrogen atmosphere and stirred at 180° C. for 16 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered, the resulting solution was concentrated, and the concentrate was purified by silica gel column chromatography. The resulting solid was dried under reduced pressure to yield 8.5 g of an intermediate (U) (yield: 82%).
APCI-TOFMS m/z 521[M+1]+
Then, 7.5 g of the intermediate (U) obtained above, 2.2 g of the starting material (F), 0.2 g of copper iodide, 0.4 g of 8-quinolinol, 3.6 g of potassium carbonate, and 25 ml of 1,3-dimethyl-2-imidazolidinone (DMI) were put in a three-necked flask under a nitrogen atmosphere and stirred at 140° C. for 3 hours. After the reaction solution was cooled to room temperature, the reaction solution was put in a flask containing 200 ml of water and stirred for 30 minutes. The precipitated solid was collected by filtering, and then subjected to reslurry with methanol, and the resulting solid was purified by silica gel column chromatography. The purified product was heated and dissolved in toluene, and crystallized with methanol. The resulting solid was dried under reduced pressure to yield 5.0 g of an intermediate (V) (yield: 63%).
APCI-TOFMS m/z 608 [M+1]+
Then, 4.6 g of the intermediate (V) obtained above, 1.4 g of the starting material (N), 70 mg of tris(dibenzylideneacetone)dipalladium, 86 mg of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), 1.4 g of sodium t-butoxide, and 75 ml of toluene were put in a three-necked flask under a nitrogen atmosphere and stirred at 120° C. for 1.5 hours. The reaction solution was cooled to room temperature, and then washed with water. The organic layer was filtered with activated white earth, and concentrated. The resulting solid was dissolved in tetrahydrofuran (THF), put in a flask containing methanol, and re-precipitated. The precipitated solid was collected by filtering, and purified by silica gel column chromatography. The resulting solid was dried under reduced pressure to yield 3.0 g of an intermediate (W) (yield: 54%).
APCI-TOFMS m/z 741[M+1]+
Then, 3.1 g of the intermediate (W) obtained above, 100 mL of o-dichlorobenzene, and 4.8 mL of boron tribromide were put in a three-necked flask under a nitrogen atmosphere, and stirred at 70° C. for 3 hours and stirred at 100° C. for 4.5 hours. The reaction solution was cooled to room temperature, and water was added thereto. The reaction solution was extracted with dichloromethane, and the organic layer was put in a flask containing hexane and stirred for 30 minutes. The precipitated solid was collected by filtering, and then subjected to reslurry with acetonitrile, and the resulting solid was dried under reduced pressure to yield 2.6 g of a compound (44) (yield: 83%).
APCI-TOFMS m/z 749[M+1]+
Each thin film shown below was laminated on the glass substrate on which an anode made of ITO having a film thickness of 70 nm was formed, by a vacuum deposition method at a degree of vacuum of 4.0×10−5 Pa. First, the previously presented HAT-CN was formed on ITO to a thickness of 10 nm as a hole injection layer, and then HT-1 was formed to a thickness of 25 nm as a hole transport layer. Then, HT-2 was formed to a thickness of 5 nm as an electron blocking layer. Then, BH-1 as the host and the compound (38) in the exemplified compounds previously presented as specific examples of the general formula (1), as the dopant, were co-deposited from different deposition sources to form a light emitting layer having a thickness of 30 nm. At this time, they were co-deposited under deposition conditions such that the concentration of the compound (38) was 2% by mass. Then, ET-2 was formed to a thickness of 5 nm as a hole blocking layer. Then, ET-1 was formed to a thickness of 40 nm as an electron transport layer. Further, lithium fluoride (LiF) was formed on the electron transport layer to a thickness of 1 nm as an electron injection layer. Finally, aluminum (Al) was formed on the electron injection layer to a thickness of 70 nm as a cathode, whereby an organic EL device according to Example 4 was produced.
The maximum emission wavelength of the emission spectrum, external quantum efficiency, and lifetime of each organic EL device produced are shown in Table 4. The maximum emission wavelength and the external quantum efficiency were values at a driving current density of 2.5 mA/cm2 and were initial characteristics. The time taken for the luminance to reduce to 70% of the initial luminance when the driving current density was 2.5 mA/cm2 was measured as the lifetime.
Each thin film shown below was laminated on the glass substrate on which an anode made of ITO having a film thickness of 70 nm was formed by a vacuum deposition method at a degree of vacuum of 4.0×10−5 Pa. First, the previously presented HAT-CN was formed on ITO to a thickness of 10 nm as a hole injection layer, and then HT-3 was formed to a thickness of 25 nm as a hole transport layer. Then, HT-4 was formed to a thickness of 5 nm as an electron blocking layer. Then, BH-3 as the host and the compound (38) as the dopant were co-deposited from different deposition sources to form a light emitting layer having a thickness of 30 nm. At this time, they were co-deposited under deposition conditions such that the concentration of the compound (38) was 2% by mass. Then, BH-3 was formed to a thickness of 5 nm as a hole blocking layer. Then, Alq3 was formed to a thickness of 40 nm as an electron transport layer. Further, lithium fluoride (LiF) was formed on the electron transport layer to a thickness of 1 nm as an electron injection layer. Finally, aluminum (Al) was formed on the electron injection layer to a thickness of 70 nm as a cathode, whereby an organic EL device according to Example 5 was produced.
The maximum emission wavelength of the emission spectrum, external quantum efficiency, and lifetime of each organic EL device produced are shown in Table 5. The maximum emission wavelength and the external quantum efficiency were values at a driving current density of 2.5 mA/cm2 and were initial characteristics. The time taken for the luminance to reduce to 95% of the initial luminance when the driving current density was 10 mA/cm2 was measured as the lifetime.
Each thin film shown below was laminated on the glass substrate on which an anode made of ITO having a film thickness of 70 nm was formed by a vacuum deposition method at a degree of vacuum of 4.0×10−5 Pa. First, the previously presented HAT-CN was formed on ITO to a thickness of 10 nm as a hole injection layer, and then HT-1 was formed to a thickness of 25 nm as a hole transport layer. Then, HT-2 was formed to a thickness of 5 nm as an electron blocking layer. Then, HT-2 as the first host, the compound ET-2 as the second host, and the compound (165) as the dopant were co-deposited from different deposition sources to form a light emitting layer having a thickness of 30 nm. At this time, they were co-deposited under deposition conditions such that the concentration of HT-2 was 49% by mass, the concentration of ET-2 was 49% by mass, and the concentration of the compound (165) was 2% by mass. Then, ET-2 was formed to a thickness of 5 nm as a hole blocking layer. Then, ET-1 was formed to a thickness of 40 nm as an electron transport layer. Further, lithium fluoride (LiF) was formed on the electron transport layer to a thickness of 1 nm as an electron injection layer. Finally, aluminum (Al) was formed on the electron injection layer to a thickness of 70 nm as a cathode, whereby an organic EL device according to Example 6 was produced.
Each organic EL device was produced in the same manner as in Example 6, except that the dopant was changed to the compound (44).
Each organic EL device was produced in the same manner as in Example 6, except that the dopant was changed to the compound (32).
Each organic EL device was produced in the same manner as in Example 6, except that the dopant was changed to the BD-2.
The maximum emission wavelength of the emission spectrum, external quantum efficiency, and lifetime of each organic EL device produced are shown in Table 6. The maximum emission wavelength and the external quantum efficiency were values at a driving current density of 2.5 mA/cm2 and were initial characteristics. The time taken for the luminance to reduce to 70% of the initial luminance when the driving current density was 2.5 mA/cm2 was measured as the lifetime.
1 substrate, 2 anode, 3 hole injection layer, 4 hole transport layer, 5 light emitting layer, 6 electron transport layer, 7 cathode.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-176205 | Oct 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/038271 | 10/15/2021 | WO |
