Patent Application
20200052212
The present invention relates to organic electroluminescence devices and electronic devices.
An organic electroluminescence device (hereinafter “electroluminescence” may be simply referred to as “EL”) generally comprises an anode, a cathode, and one or more organic thin film layers sandwiched between the anode and the cathode. When a voltage is applied between the electrodes, electrons from the cathode and holes from the anode are injected into a light emitting region. The injected electrons recombine with the injected holes in the light emitting region to form excited state. When the excited state returns to the ground state, the energy is released as light.
Many researches have been made on the applications of organic EL device to display, etc. because the organic EL device has a wide range of selection of emission colors by using various emitting materials in a light emitting layer. Particularly, the research on the emitting materials which emit three primary red, green, and blue colors has been made actively, and the intensive research has been made to improve their properties.
The materials for organic EL devices and organic EL devices have been proposed, for example, in Patent Literatures 1 to 7.
Patent Literature 1: JP 2014-73965A
Patent Literature 2: WO 2016/006925
Patent Literature 3: CN 104119347B
Patent Literature 4: WO 2011/128017
Patent Literature 5: KR 10-2015-0135125B
Patent Literature 6: WO 2013/077344
Patent Literature 7: WO 2016/195441
An object of the invention is to provide an organic EL device having a lifetime further improved.
As a result of extensive research to solve the above problem, the inventors have found that a light emitting layer comprising a dopant material having a specific structure, a host material having a specific structure, and a co-host material having a specific structure solves the above problem.
(1) In an aspect of the invention, provided is an organic electroluminescence device comprising a cathode, an anode and an organic layer disposed between the cathode and the anode, wherein the organic layer comprises a fluorescent emitting layer and the fluorescent emitting layer comprises at least one dopant material selected from the compounds represented by formulae (D1) and (D2), at least one first compound selected from the compounds represented by formulae (19), (21), (22), and (23), and at least one second compound selected from the compounds represented by formulae (2a), (2b), and (2c):
wherein:
Z is CRA or N;
π1 is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50 ring atoms;
π2 is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50 ring atoms;
RA, RB, and RC are each independently a hydrogen atom or a substituent, wherein the substituent is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an amino group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 50 ring carbon atoms, a group represented by —Si(R101)(R102)(R103), a group represented by —N(R104)(R105), a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
R101 to R105 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
n and m are each independently an integer of 1 to 4;
adjacent two RA's are bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure;
adjacent two RB's are bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure;
adjacent two RC's are bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure;
wherein:
a ring α, a ring β, and a ring γ are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50 ring atoms;
Ra and Rb are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms;
Ra may be bonded to one or both of the ring α and the ring β directly or via a linker;
Rb may be bonded to one or both of the ring α and the ring γ directly or via a linker;
wherein:
R101 to R110 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC; provided that at least one of R101 to R110 is -L-Ar;
each L is independently a single bond or a linker, wherein the linker is a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms;
each Ar is independently a substituted or unsubstituted single ring group having 5 to 50 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, or a monovalent group wherein two or more selected from the single ring and the fused ring are bonded to each other via a single bond;
wherein:
R201 to R212 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC; provided that at least one of R201 to R212 is -L2-Ar21;
each L2 is independently a single bond or a linker, wherein the linker is a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms; and
each Ar21 is independently a substituted or unsubstituted single ring group having 5 to 50 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, or a monovalent group wherein two or more selected from the single ring and the fused ring are bonded to each other via a single bond;
wherein:
R301 to R310 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC;
provided that at least one of R301 to R310 is -L3-Ar1;
each L3 is independently a single bond or a linker, wherein the linker is a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms; and
each Ar31 is independently a substituted or unsubstituted single ring group having 5 to 50 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, or a monovalent group wherein two or more selected from the single ring and the fused ring are bonded to each other via a single bond;
wherein:
R401 to R410 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC;
provided that at least one of R401 to R410 is -L4-Ar41;
each L4 is independently a single bond or a linker, wherein the linker is a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms;
each Ar41 is independently a substituted or unsubstituted single ring group having 5 to 50 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50 ring atoms, or a monovalent group wherein two or more selected from the single ring and the fused ring are bonded to each other via a single bond; and
adjacent two selected from R401 and R402, R402 and R403, R403 and R404, R405 and R406, R406 and R407, and R407 and R408 may be bonded to each other to form a substituted or unsubstituted ring structure;
wherein:
Ar11, Ar22, and Ar33 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
L11, L22, and L33 are each independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms; and
p, q, and r are each independently 0, 1, or 2, when p is 0, L11 is a single bond, when q is 0, L22 is a single bond, and when r is 0, L33 is a single bond;
wherein:
one selected from R71 to R78 is a single bond bonded to *a;
one selected from R81 to R88 is a single bond bonded to *b;
R71 to R78 and R81 to R88 not the single bond are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
adjacent two selected from R71 to R74 not the single bond, adjacent two selected from R75 to R78 not the single bond, adjacent two selected from R81 to R84 not the single bond, and adjacent two selected from R85 to R88 not the single bond may be bonded to each other to form a substituted or unsubstituted ring structure;
Ar44 and Ar55 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
L44, L55, and L66 are each independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms;
m4, m5, and m6 are each independently 0, 1, or 2, when m4 is 0, L44 is a single bond, when m5 is 0, L55 is a single bond, and when m6 is 0, L66 is a single bond; and
(Ar80)(Ar81)N-(L80)-N(Ar82)(Ar83) (2c)
wherein:
Ar80 to Ar83 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
L80 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms.
(2) In another aspect of the invention, an electronic device comprising the organic EL device mentioned above in (1) is provided.
The organic EL device of the invention has an excellent lifetime.
The term of “XX to YY carbon atoms” referred to by “a substituted or unsubstituted group ZZ having XX to YY carbon atoms” used herein is the number of carbon atoms of the unsubstituted group ZZ and does not include any carbon atom in the substituent of the substituted group ZZ.
The term of “XX to YY atoms” referred to by “a substituted or unsubstituted group ZZ having XX to YY atoms” used herein is the number of atoms of the unsubstituted group ZZ and does not include any atom in the substituent of the substituted group ZZ.
The number of “ring carbon atoms” referred to herein means the number of the carbon atoms included in the atoms which are members forming the ring itself of a compound in which a series of atoms is bonded to form the ring (for example, a monocyclic compound, a fused ring compound, a cross-linked compound, a carbocyclic compound, and a heterocyclic compound). If the ring has a substituent, the carbon atom in the substituent is not included in the ring carbon atom. The same applies to the number of “ring carbon atom” described below, unless otherwise noted. For example, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridinyl group has 5 ring carbon atoms, and a furanyl group has 4 ring carbon atoms. If a benzene ring or a naphthalene ring has, for example, an alkyl substituent, the carbon atom in the alkyl substituent is not counted as the ring carbon atom of the benzene or naphthalene ring. In case of a fluorene ring to which a fluorene substituent is bonded (inclusive of a spirofluorene ring), the carbon atom in the fluorene substituent is not counted as the ring carbon atom of the fluorene ring.
The number of “ring atom” referred to herein means the number of the atoms which are members forming the ring itself (for example, a monocyclic ring, a fused ring, and a ring assembly) of a compound in which a series of atoms is bonded to form the ring (for example, a monocyclic compound, a fused ring compound, a cross-linked compound, a carbocyclic compound, and a heterocyclic compound). The atom not forming the ring (for example, hydrogen atom(s) for saturating the valence of the atom which forms the ring) and the atom in a substituent, if the ring is substituted, are not counted as the ring atom. The same applies to the number of “ring atoms” described below, unless otherwise noted. For example, a pyridine ring has 6 ring atoms, a quinazoline ring has 10 ring atoms, and a furan ring has 5 ring atoms. The hydrogen atom on the ring carbon atom of a pyridine ring or a quinazoline ring and the atom in a substituent are not counted as the ring atom. In case of a fluorene ring to which a fluorene substituent is bonded (inclusive of a spirofluorene ring), the atom in the fluorene substituent is not counted as the ring atom of the fluorene ring
The definition of “hydrogen atom” used herein includes isotopes different in the neutron numbers, i.e., light hydrogen (protium), heavy hydrogen (deuterium), and tritium.
The organic electroluminescence device in an aspect of the invention comprises a cathode, an anode, and an organic layer disposed between the cathode and the anode, wherein the organic layer comprises a fluorescent emitting layer and the fluorescent emitting layer comprises at least one first compound selected from the compounds represented by formula (19), (21), (22), and (23) each described below, at least one second compound selected from the compounds represented by formulae (2a), (2b), and (2c) each described below, and at least one dopant material selected from the compounds represented by the following formulae (D1) and (D2).
The dopant material used in the organic EL device of the invention is preferably at least one compound selected from a compound represented by formula (D1) (“dopant material 1”) and a compound represented by formula (D2) (“dopant material 2”) and more preferably a compound represented by formula (D1) (“dopant material 1”).
The dopant material 1 is represented by formula (D1):
wherein:
each Z is independently CRA or N;
a ring π1 is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50 ring atoms;
a ring π2 is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50 ring atoms;
RA, RB, and RC are each independently a hydrogen atom or a substituent, wherein the substituent is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, a group represented by —Si(R101)(R102)(R103), or a group represented by —N(R104)(R105);
R101 to R105 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
n and m are each independently an integer of 1 to 4;
adjacent two RA's are bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure;
adjacent two RB's are bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure; and
adjacent two RC's are bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure.
The ring π1 and the ring π2 are each independently an aromatic hydrocarbon ring having 6 to 50, preferably 6 to 24, and more preferably 6 to 18 ring carbon atoms or an aromatic heterocyclic ring having 5 to 50, preferably 5 to 24, and more preferably 5 to 13 ring atoms.
Examples of the aromatic hydrocarbon ring having 6 to 50 ring carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a benzanthracene ring, a phenanthrene ring, a benzophenanthrene ring, a fluorene ring, a benzofluorene ring, a dibenzofluorene ring, a picene ring, a tetracene ring, a pentacene ring, a pyrene ring, a chrysene ring, a benzochrysene ring, a s-indacene ring, an as-indacene ring, a fluoranthene ring, a benzofluoranthene ring, a triphenylene ring, a benzotriphenylene ring, a perylene ring, a coronene ring, and a dibenzanthracene ring.
Examples of the aromatic heterocyclic ring having 5 to 50 ring atoms include a pyrrole ring, a pyrazole ring, an isoindole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a dibenzothiophene ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an imidazopyridine ring, an indole ring, an indazole ring, a benzimidazole ring, a quinoline ring, an acridine ring, a pyrrolidine ring, a dioxane ring, a piperidine ring, a morpholine ring, a piperazine ring, a carbazole ring, a furan ring, a thiophene ring, an oxazole ring, an oxadiazole ring, a benzoxazole ring, a thiazole ring, a thiadiazole ring, a benzothiazole ring, a triazole ring, an imidazole ring, a benzimidazole ring, a pyran ring, a dibenzofuran ring, a benzo[c]dibenzofuran ring, a purine ring, and an acridine ring.
Each RB is bonded to a ring atom of the aromatic hydrocarbon ring or the aromatic heterocyclic ring (ring π1). Each RC is bonded to a ring atom of the aromatic hydrocarbon ring or the aromatic heterocyclic ring (ring π2).
The substituents represented by RA, RB, and RC are described below.
The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
Examples of the alkyl group of the substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group (inclusive of isomeric groups), a hexyl group (inclusive of isomeric groups), a heptyl group (inclusive of isomeric groups), an octyl group (inclusive of isomeric groups), a nonyl group (inclusive of isomeric groups), a decyl group (inclusive of isomeric groups), an undecyl group (inclusive of isomeric groups), and a dodecyl group (inclusive of isomeric groups). Preferred are a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and a pentyl group (inclusive of isomeric groups), more preferred are a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group, and a t-butyl group, and still more preferred are a methyl group, an ethyl group, an isopropyl group, and a t-butyl group.
The substituted alkyl group is preferably a fluoroalkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms. The fluoroalkyl group is a group derived from the above alkyl group having 1 to 20 carbon atoms by replacing at least one hydrogen atom, preferably 1 to 7 hydrogen atoms, or all hydrogen atoms with a fluorine atom. The fluoroalkyl group is preferably a heptafluoropropyl group (inclusive of isomeric groups), a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, or a trifluoromethyl group, more preferably a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, or a trifluoromethyl group, and still more preferably a trifluoromethyl group.
Examples of the alkenyl group of the substituted or unsubstituted alkenyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms include a vinyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 4-pentenyl group, a 2-methyl-2-propenyl group, a 2-methyl-2-butenyl group, and a 3-methyl-2-butenyl group.
Examples of the alkynyl group of the substituted or unsubstituted alkynyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms include a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, a 5-hexynyl group, a 1-methyl-2-propynyl group, a 1-methyl-2-butynyl group, and a 1,1-dimethyl-2-propynyl group.
Examples of the cycloalkyl group of the substituted or unsubstituted cycloalkyl group having 3 to 20, preferably 3 to 6, and more preferably 5 or 6 ring carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group, with a cyclopentyl group and a cyclohexyl group being preferred.
The details of the alkyl portion of the substituted or unsubstituted alkoxy group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms are as described above with respect to the alkyl group having 1 to 20 carbon atoms.
The substituted alkoxy group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms is preferably a fluoroalkoxy group. The details of the fluoroalkyl portion of the fluoroalkoxy group are as described above with respect to the fluoroalkyl group having 1 to 20 carbon atoms.
The aryl group of the substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 may be a fused aryl group or a non-fused aryl group. Examples thereof include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an acenaphthylenyl group, an anthryl group, a benzanthryl group, an aceanthryl group, a phenanthryl group, a benzo[c]phenanthryl group, a phenalenyl group, a fluorenyl group, a picenyl group, a pentaphenyl group, a pyrenyl group, a chrysenyl group, a benzo[g]chrysenyl group, a s-indacenyl group, an as-indacenyl group, a fluoranthenyl group, a benzo[k]fluoranthenyl group, a triphenylenyl group, a benzo[b]triphenylenyl group, and a perylenyl group. Preferred are a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a fluoranthenyl group, with a phenyl group, a biphenylyl group, and a terphenylyl group being more preferred and a phenyl group being still more preferred.
The substituted aryl group is preferably a 9,9-dimethylfluorenyl group, a 9,9-diphenyl fluorenyl group, a 9,9′-spirobifluorenyl group, a 9,9-di(4-methylphenyl)fluorenyl group, a 9,9-di(4-isopropylphenyl)fluorenyl group, a 9,9-di(4-t-butylphenyl)fluorenyl group, a para-methylphenyl group, a meta-methylphenyl group, an ortho-methylphenyl group, a para-isopropylphenyl group, a meta-isopropylphenyl group, an ortho-isopropylphenyl group, a para-t-butylphenyl group, a meta-t-butylphenyl group, or an ortho-t-butylphenyl group.
The details of the aryl portion of the aryloxy group in the substituted or unsubstituted aryloxy group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 are as described above with respect to the aryl group having 6 to 50 ring carbon atoms.
The details of the alkyl portion of the alkylthio group in the substituted or unsubstituted alkylthio group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms are as described above with respect to the alkyl group having 1 to 20 carbon atoms.
The details of the aryl portion of the arylthio group in the substituted or unsubstituted arylthio group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 are as described above with respect to the aryl group having 6 to 50 ring carbon atoms.
The heteroaryl group of the substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms includes at least one, preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 3 ring hetero atoms. Examples of the ring hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom, with a nitrogen atom and an oxygen atom being preferred. The free valance of the heteroaryl group is present on a ring carbon atom or may be present on a ring nitrogen atom, if structurally possible.
Examples the heteroaryl group include the a pyrrolyl group, a furyl group, a thienyl group, a pyridyl group, an imidazopyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyrazolyl group, an isoxazolyl group, an isothiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a triazolyl group, a tetrazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, an isobenzofuranyl group, a benzothiophenyl group (a benzothienyl group), an isobenzothiophenyl group (an isobenzothienyl group), an indolizinyl group, a quinolizinyl group, a quinolyl group, an isoquinolyl group, a cinnolyl group, a phthalazinyl group, a quinazolinyl group, a quinoxalinyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, an indazolyl group, a benzisoxazolyl group, a benzisothiazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group (a dibenzothienyl group), a carbazolyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a phenothiazinyl group, a phenoxazinyl group, and a xanthenyl group.
Other examples of the heteroaryl group include the following groups:
wherein X is an oxygen atom or a sulfur atom, Y is an oxygen atom, a sulfur atom, NRa, or CRb2, and each of Ra and Rb is a hydrogen atom.
Preferred heteroaryl groups are a pyridyl group, an imidazopyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a benzimidazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a phenanthrolinyl group, and a quinazolinyl group.
Examples of the substitute heteroaryl group include a (9-phenyl)carbazolyl group, a (9-biphenylyl)carbazolyl group, a (9-phenyl)phenylcarbazolyl group, a (9-naphthyl)carbazolyl group, a diphenylcarbazole-9-yl group, a phenyldibenzofuranyl group, a phenyldibenzothiophenyl group (phenyldibenzothienyl group), and the following groups:
wherein X is an oxygen atom or a sulfur atom, Y is NRa or CRb2, and Ra and Rb are each independently selected from the alkyl group having 1 to 20 carbon atoms mentioned above and the aryl group having 6 to 50 ring carbon atoms mentioned above.
In the group represented by —Si(R101)(R102)(R103) and the group represented by —N(R104)(R105), R101 to R105 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms.
The details of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and the substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms are as described above.
Examples of the group represented by —Si(R101)(R102)(R103) include a monoalkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, a monoarylsilyl group, a diarylsilyl group, a triarylsilyl group, a monoalkyldiarylsilyl group, and a dialkylmonoarylsilyl group.
Preferred are a trialkylsilyl group and a triarylsilyl group and more preferred are a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a t-butyldimethylsilyl group, a triphenylsilyl group, and a tritolylsilyl group.
Examples of the group represented by —N(R104)(R105) include an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, a monoheteroarylamino group, a diheteroarylamino group, a monoalkylmonoarylamino group, a monoalkylmonoheteroarylamino group, and a monoarylmonoheteroarylamino group. Preferred are a dialkylamino group, a diarylamino group, a diheteroarylamino group, and a monoarylmonoheteroarylamino group and more preferred are a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, a bis(alkyl-substituted phenyl)amino group, and a bis(aryl-substituted phenyl)amino group.
Two or more groups represented by —Si(R101)(R102)(R103) in formula (D1) may be the same or different. Two or more groups represented by —N(R104)(R105) in formula (D1) may be the same or different.
The compound represented by formula (D1) preferably includes a compound represented by formula (D1a):
wherein:
Z1 is CR1 or N, Z2 is CR2 or N, Z3 is CR3 or N, Z4 is CR4 or N, Z5 is CR5 or N, Z6 is CR6 or N, Z7 is CR7 or N, Z8 is CR8 or N, Z9 is CR9 or N, Z10 is CR10 or N, and Z11 is CR11 or N;
R1 to R11 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC of formula (D1);
adjacent two selected from R1 to R8 may be bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure;
adjacent two selected from R4 to R7 may be bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure;
adjacent two selected from R8 to R11 may be bonded to each other to form a substituted or unsubstituted ring structure or not bonded to each other, thereby failing to form a ring structure.
The compound represented by formula (D1) preferably includes a compound represented by formula (1):
wherein:
Rn and Rn+1 (n is an integer selected from 1, 2, 4 to 6, and 8 to 10) may be bonded to each other to form, together with two ring carbon atoms to which Rn and Rn+1 are bonded, a substituted or unsubstituted ring structure having 3 or more ring atoms, or Rn and Rn+1 may be not bonded to each other, thereby failing to form a ring structure;
the ring atom is selected from a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
an optional substituent of the ring structure having 3 or more ring atoms is as described above with respect to the substituent of RA, RB, and RC of formula (D1) and adjacent two optional substituents may be bonded to each other to form a substituted or unsubstituted ring structure; and
R1 to R11 not forming the substituted or unsubstituted ring structure having 3 or more ring atoms is a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC of formula (D1).
When Rn and Rn+1, i.e., R1 and R2, R2 and R3, R4 and R5, R5 and R6, R6 and R7, R8 and R9, R9 and R10, or R10 and R11, are bonded to each other to form, together with two ring carbon atoms to which Rn and Rn+1 are bonded, the substituted or unsubstituted ring structure having 3 or more ring atoms, Rn—Rn+1, i.e., R1-R2, R2-R3, R4-R5, R5-R6, R6-R7, R8-R9, R9-R10, or R10-R11 represents CH2, NH, O, or S, or represents a group of atoms wherein two or more selected from CH2, CH, NH, N, O, and S are successively bonded to each other via a single bond, a double bond, or an aromatic bond. The hydrogen atom of CH2, CH, and NH may be substituted by the substituent mentioned above. The aromatic bond is a bond bonding two adjacent atoms in an aromatic ring and having a bond order between 1 and 2 (about 1.5).
In an embodiment of the invention, the compound of formula (1) preferably has two substituted or unsubstituted ring structures each having 3 or more ring atoms.
In another embodiment of the invention, the compound of formula (1) preferably has three ring structures and more preferably has one ring structure on each of the three different benzene rings, i.e., one ring structure on each of the ring A, the ring B, and the ring C.
In still another embodiment of the invention, the compound of formula (1) preferably has four or more ring structures.
In an embodiment of the invention, a pair of Rp and Rp+1 and a pair of Rp+1 and Rp+2 (wherein p is 1, 4, 5, 8, or 9) preferably do not form the substituted or unsubstituted ring structure having 3 or more ring atoms at the same time. Namely, a pair of R1 and R2 and a pair of R2 and R3; a pair of R4 and R5 and a pair of R5 and R6; a pair of R5 and R6 and a pair of R6 and R7; a pair of R8 and R9 and a pair of R9 and R10; and a pair of R9 and R10 and a pair of R10 and R11 preferably do not form the ring structure at the same time.
In an embodiment of the invention, when the compound of formula (1) has two or more substituted or unsubstituted ring structures each having 3 or more ring atoms, the two or more ring structures are preferably present on two or three rings selected from the ring A, the ring B, and the ring C. The two or more ring structures may be the same or different.
The details of the optional substituent of the substituted or unsubstituted ring structure having 3 or more ring atoms are as described above with respect to the substituent of RA, RB, and RC of formula (D1).
The number of ring atoms of the substituted or unsubstituted ring structure having 3 or more ring atoms is preferably 3 to 7 and more preferably 5 or 6, although not limited thereto.
The substituted or unsubstituted ring structure having 3 or more ring atoms is preferably a ring structure represented by any of formulae (2) to (8):
wherein:
*1 and *2, *3 and *4, *5 and *6, *7 and *8, *9 and *10, *11 and *12, and *13 and *14 are two ring carbon atoms to which Rn and Rn+1 are bonded, wherein R may be bonded to either of the two ring carbon atoms;
X is selected from C(R23)(R24), NR25, O, and S;
R12 to R25 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC; and
adjacent two selected from R12 to R15, R16 and R17, and R23 and R24 may be bonded to each other to form a substituted or unsubstituted ring structure.
A ring structure selected from formulae (9) to (11) are also preferred as the substituted or unsubstituted ring structure having 3 or more ring atoms:
wherein:
*1 and *2, and *3 and *4 are as defined above;
R12, R14, R15, and X are as defined above;
R31 to R38 and R41 to R44 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC of formula (D1); and
adjacent two selected from R12, R15, and R31 to R34, adjacent two selected from R14, R15, and R35 to R38, and adjacent two selected from R41 to R44 may be bonded to each other to form a substituted or unsubstituted ring structure.
Preferably, in formula (1), at least one of R2, R4, R5, R10, and R11, preferably at least one of R2, R5, and R10, and more preferably R2 does not form the substituted or unsubstituted ring structure having 3 or more ring atoms.
Preferably, in formula (1), the optional substituent of the ring structure having 3 or more ring atoms is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a group represented by —N(R104)(R105), a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or any of the following groups:
wherein:
each Rc is independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC of formula (D1);
X is as defined above;
p1 is an integer of 0 to 5, p2 is an integer of 0 to 4, p3 is an integer of 0 to 3, and p4 is an integer of 0 to 7.
Preferably, R1 to R11 of formula (1) not forming the substituted or unsubstituted ring structure having 3 or more ring atoms and R12 to R22, R31 to R38, and R41 to R44 of formulae (2) to (11) are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a group represented by —N(R104)(R105), a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or any of the following groups:
wherein Re, X, p1, p2, p3, and p4 are as defined above.
The compound of formula (1) is preferably represented by any of formulae (1-1) to (1-6), more preferably represented by any of formulae (1-1) to (1-3) and (1-5), and still more preferably represented by formula (1-1) or (1-5):
wherein:
R1 to R11 are as defined above; and
the rings a to f are each independently the substituted or unsubstituted ring structure having 3 or more ring atoms.
In formulae (1-1) to (1-6), adjacent two optional substituents on the ring structure having 3 or more ring atoms may be bonded to each other to form a substituted or unsubstituted ring structure.
The number of ring atoms of the rings a to f is preferably 3 to 7 and more preferably 5 or 6, although not limited thereto. Preferably, the rings a to f are each independently any of the rings selected from formulae (2) to (11).
The compound of formula (1) is preferably represented by any of formulae (2-1) to (2-6) and more preferably represented by formula (2-2) or (2-5):
wherein
R1 and R3 to R11 are as defined above;
the rings a to c are as defined above; and
the rings g and h are each independently the substituted or unsubstituted ring structure having 3 or more ring atoms.
In formulae (2-1) to (2-6), adjacent two optional substituents on the ring structure having 3 or more ring atoms may be bonded to each other to form a substituted or unsubstituted ring structure.
The number of ring atoms of the rings a to c, g, and h is preferably 3 to 7 and more preferably 5 or 6, although not limited thereto. Preferably, the rings a to c, g, and h are each independently any of the rings selected from formulae (2) to (11).
The compound of formula (1) is more preferably represented by any of formulae (3-1) to (3-9) and still more preferably represented by formula (3-1):
wherein R1, R3 to R11, and the rings a to h are as defined above.
Preferably, in formulae (1-1) to (1-6), (2-1) to (2-6), and (3-1) to (3-9), the optional substituent of the rings a to h is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a group represented by —N(R104)(R105), a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or any of the following groups:
wherein Rc, X, p1, p2, p3, and p4 are as defined above.
Preferably, in formulae (1-1) to (1-6), (2-1) to (2-6), and (3-1) to (3-9), R1 to R11 not forming the rings a to h is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a group represented by —N(R104)(R105), a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or any of the following groups:
wherein Rc, X, p1, p2, p3, and p4 are as defined above.
The compound of formula (1) is preferably represented by any of formulae (4-1) to (4-4):
wherein:
R1 to R11 and X are as defined above; and
R51 to R58 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC of formula (D1)
The compound of formula (1) is preferably represented by formula (5-1):
wherein:
R5, R4, R7, R8, R11, and R51 to R58 are as defined above; and
R59 to R62 are each independently a hydrogen atom or a substituent, wherein the substituent is as described above with respect to the substituent of RA, RB, and RC of formula (D1).
Examples of the dopant material represented by formula (D1) which is used in the present invention are shown below, although not limited thereto. In the following exemplary compounds, Ph is a phenyl group and D is a heavy hydrogen atom.
The dopant material 2 is a boron-containing compound represented by formula (D2):
wherein:
a ring α, a ring β, and a ring γ are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50 ring atoms;
Ra and Rb are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms;
Ra may be bonded to one or both of the ring α and the ring β directly or via a linker; and
Rb may be bonded to one or both of the ring α and the ring γ directly or via a linker.
Examples of the aromatic hydrocarbon ring having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms include a benzene ring, a biphenyl ring, a naphthalene ring, a terphenyl ring (m-terphenyl ring, o-terphenyl ring, p-terphenyl ring), an anthracene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a fluoranthene ring, a pyrene ring, a naphthacene ring, a perylene ring, and a pentacene ring.
The aromatic heterocyclic ring having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms includes at least one, preferably 1 to 5 ring hetero atoms. The ring hetero atom is selected, for example, from a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of the aromatic heterocyclic ring include a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, a phenazine ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a furazan ring, an oxadiazole ring, and a thianthrene ring.
Each of the ring α, the ring β, and the ring γ is preferably a five-membered ring or a six-membered ring.
The optional substituent of the ring α, the ring β, and the ring γ is selected from a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms; a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms; a diarylamino group, a diheteroarylamino group, or an arylheteroarylamino group each having a substituent selected from a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms; a substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms; and a substituted or unsubstituted aryloxy group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms.
The optional substituent may be substituted with an aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms; a heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms; or an alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.
Adjacent two on each of the ring α, the ring β, and the ring γ may be bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms. The details of the aromatic hydrocarbon ring and the aromatic heterocyclic ring are as described above with respect to the ring α, the ring β, and the ring γ.
The optional substituent of the ring thus formed is selected from an aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms; a heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms; and an alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.
Ra and Rb are each independently a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.
The details of the aryl group, the heteroaryl group, the alkyl group, the alkoxy group, and the aryloxy group mentioned with respect to the ring α, the ring β, and the ring γ and the details of the aryl group, the heteroaryl group, and the alkyl group of Ra and Rb are the same as those of corresponding groups described above with respect to RA, RB, and RC of formula (D1).
The linker is —O—, —S—, or —CRcRd—. Rc and Rd are each independently a hydrogen atom or an alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.
The details of the alkyl group are as described above with respect to the alkyl group of RA, RB, and RC of formula (D1).
Formula (D2) is preferably represented by formula (D2a):
In formula (D2a), Ra and Rb are as defined above.
Rc to Ro are each independently a hydrogen atom or an optional substituent that is described above with respect to the ring α, the ring β, and the ring γ.
Adjacent two selected from Re to Rg, adjacent two selected from Rh to Rk, and adjacent two selected from Rl to Ro may be bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic ring having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms.
The details of the ring thus formed are as described above with respect to the ring formed by adjacent two bonded to each other on the ring α, the ring β, and the ring γ.
The dopant material 2 may be an oligomer, preferably a dimer to a hexamer, more preferably a dimer or a trimer, and still more preferably a dimer each comprising a unit structure represented by formula (D2) preferably formula (D2a). The oligomer may be a compound wherein two or more structural units are bonded to each other directly or via a linker, such as an alkylene group having 1 to 3 carbon atoms, a phenylene group and a naphthylene group; a compound wherein the ring α, the ring β, the ring γ, or the ring formed by the substituents on the ring α, the ring β, or the ring γ is commonly owned by two or more structural units; or a compound wherein the ring α, the ring β, the ring γ, or the ring formed by the substituents on the ring α, the ring β, or the ring γ in one structural unit is fused to any of the rings of another structural unit.
Examples of the oligomer having a ring commonly owned or the oligomer having a fused ring are shown below, wherein each R on the ring α, the ring β, or the ring γ is omitted for conciseness.
Examples of the compound represented by formula (D2) preferably formula (D2a) are shown below, although not limited thereto.
The first compound is used in the fluorescent emitting layer of the organic EL device of the invention together with the dopant material and the second compound and works as the host material (main host material) of the fluorescent emitting layer.
The first compound is at least one selected from an anthracene skeleton-containing compound represented by formula (19), a chrysene skeleton-containing compound represented by formula (21), a pyrene skeleton-containing compound represented by formula (22), and a fluorene skeleton-containing compound represented by formula (23).
An anthracene skeleton-containing compound represented by formula (19) is usable as the first compound.
In formula (19), R101 to R110 are each independently a hydrogen atom, a substituent, or -L-Ar, provided that at least one of R101 to R110 is -L-Ar.
The details of the substituent are as described above with respect to the substituent of RA, RB, and RC.
L is independently a single bond or a linker, wherein the linker is a substituted or unsubstituted arylene group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms.
Ar is independently a substituted or unsubstituted single ring group having 5 to 50, preferably 5 to 30, more preferably 5 to 24, and still more preferably 5 to 18 ring atoms, a substituted or unsubstituted fused ring group having 8 to 50, preferably 8 to 30, more preferably 8 to 24, and still more preferably 8 to 18 ring atoms, or a monovalent group wherein two or more selected from the single ring and the fused ring are bonded to each other via a single bond.
The single ring group having 5 to 50 ring atoms is a group having only a single ring structure and having no fused ring, for example, preferably an aryl group, such as a phenyl group, a biphenylyl group, a terphenylyl group, and a quaterphenylyl group, and a heteroaryl group, such as a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a triazinyl group, a furyl group, and a thienyl group, and more preferably a phenyl group, a biphenylyl group, and a terphenylyl group.
The fused ring group having 8 to 50 ring atoms is a group having a fused ring structure wherein two or more rings are fused. Examples thereof are preferably a fused aryl group, such as a naphthyl group, a phenanthryl group, an anthryl group, a chrysenyl group, a benzanthryl group, a benzophenanthryl group, a triphenylenyl group, a benzochrysenyl group, an indenyl group, a fluorenyl group, a 9,9-dimethylfluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a fluoranthenyl group, and a benzofluoranthenyl group, and a fused heteroaryl group, such as a benzofuranyl group, a benzothiophenyl group, an indolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a quinolyl group, and a phenanthrolinyl group, with a naphthyl group, a phenanthryl group, an anthryl group, a 9,9-dimethylfluorenyl group, a fluoranthenyl group, a benzanthryl group, a dibenzothiophenyl group, a dibenzofuranyl group, and a carbazolyl group being more preferred.
The optional substituent of Ar is preferably the single ring group or the fused ring group each mentioned above.
The arylene group of the substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms represented by L is a divalent group derived by removing two hydrogen atoms from an aromatic hydrocarbon compound selected from benzene, naphthylbenzene, biphenyl, terphenyl, naphthalene, acenaphthylene, anthracene, benzanthracene, aceanthracene, phenanthrene, benzo[c]phenanthrene, phenalene, fluorene, picene, pentaphene, pyrene, chrysene, benzo[g]chrysene, s-indacene, as-indacene, fluoranthene, benzo[k]fluoranthene, triphenylene, benzo[b]triphenylene, and perylene. Preferred are a phenylene group, a biphenyldiyl group, a terphenyldiyl group, and a naphthalenediyl group, with a phenylene group, a biphenyldiyl group, and a terphenyldiyl group being more preferred and a phenylene group being still more preferred.
The heteroarylene group of the substituted or unsubstituted heteroarylene group having 5 to 30 ring carbon atoms represented by L is a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having at least one and preferably 1 to 5 ring hetero atom, for example, a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of the aromatic heterocyclic ring include pyrrole, furan, thiophene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, oxadiazole, thiadiazole, triazole, tetrazole, indole, isoindole, benzofuran, isobenzofuran, benzothiophene, isobenzothiophene, indolizine, quinolizine, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, benzimidazole, benzoxazole, benzothiazole, indazole, benzisoxazole, benzoisothiazole, dibenzofuran, dibenzothiophene, carbazole, phenanthridine, acridine, phenanthroline, phenazine, phenothiazine, phenoxazine, and xanthene. Preferred examples of the heteroarylene group are divalent groups obtained by removing two hydrogen atoms from furan, thiophene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, benzothiophene, dibenzofuran, and dibenzothiophene, with divalent groups obtained by removing two hydrogen atoms from benzofuran, benzothiophene, dibenzofuran, and dibenzothiophene being more preferred.
The compound of formula (19) is preferably an anthracene derivative represented by formula (20):
wherein:
R101 to R108 are as defined in formula (19);
L1 is as defined above with respect to L of formula (19); and
Ar11 and Ar12 are as defined above with respect to Ar of formula (19).
The anthracene derivative represented by formula (20) is preferably any of the anthracene derivatives (A), (B), and (C), which are selected according to the structure of the organic EL device and required properties.
The anthracene derivative (A) is a compound of formula (20), wherein Ar11 and Ar12 are independently a substituted or unsubstituted fused ring group having 8 to 50 ring atoms. Ar11 and Ar12 may be the same or different, preferably different.
Examples of the fused ring group having 8 to 50 ring atoms are as described above with respect to formula (19) and preferably a naphthyl group, a phenanthryl group, a benzanthryl group, a 9,9-dimethylfluorenyl group, and a dibenzofuranyl group.
The anthracene derivative (B) is a compound of formula (20), wherein one of Ar11 and Ar12 is a substituted or unsubstituted single ring group having 5 to 50 ring atoms and the other is a substituted or unsubstituted fused ring group having 8 to 50 ring atoms.
The details of the single ring group having 5 to 50 ring atoms and the fused ring group having 8 to 50 ring atoms are as described above with respect to formula (19).
In an embodiment of the invention, Ar12 is preferably a naphthyl group, a phenanthryl group, a benzanthryl group, a 9,9-dimethylfluorenyl group, or a dibenzofuranyl group and Ar11 is preferably an unsubstituted phenyl group or a phenyl group substituted with a single ring group or a fused ring group, for example, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a 9,9-dimethylfluorenyl group, or a dibenzofuranyl group.
In another embodiment of the invention, Ar12 is preferably a substituted or unsubstituted fused ring group having 8 to 50 ring atoms and Ar11 is an unsubstituted phenyl group. The fused ring group is particularly preferably a phenanthryl group, a 9,9-dimethylfluorenyl group, a dibenzofuranyl group, or a benzanthryl group.
The anthracene derivative (C) is a compound of formula (20), wherein Ar11 and Ar12 are each independently a substituted or unsubstituted single ring group having 5 to 50 ring atoms.
Preferably, each of Ar11 and Ar12 is a substituted or unsubstituted phenyl group. More preferably, Ar11 is an unsubstituted phenyl group and Ar12 is phenyl group substituted with a single ring group or a fused ring group, or Ar11 and Ar12 are each independently a phenyl group substituted with a single ring group or a fused ring group.
The single ring group and the fused ring group as the optional substituent of Ar11 and Ar12 are as described above with respect to formula (19). The single ring group is preferably a phenyl group or a biphenyl group and the fused ring group is preferably a naphthyl group, a phenanthryl group, a 9,9-dimethylfluorenyl group, a dibenzofuranyl group, or a benzanthryl group.
Examples of the anthracene derivative represented by formula (19) or (20) are shown below.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
As the chrysene skeleton-containing compound, a compound represented by formula (21) is usable:
wherein:
R201 to R212 are each independently a hydrogen atom, a substituent, or -L2-Ar21, provided that at least one of R201 to R212 is -L2-Ar21—;
the details of the substituent are as described above with respect to the substituent of RA, RB, and RC of formula (D1),
the details of L2 are Ar21 are as described above with respect to L and Ar of formula (0.19), respectively; and
one or both of R204 and R210 are preferably -L2-Ar21.
Examples of the chrysene derivative represented by formula (21) are shown below, although not particularly limited thereto.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene mugs.
In the following compounds, the six-membered rings are all benzene rings.
As the pyrene derivative, a compound represented by formula (22) is usable:
wherein:
R301 to R310 are each independently a hydrogen atom, a substituent, or -L3-Ar31, provided that at least one of R301 to R310 is -L3-Ar31;
the details of the substituent are as described above with respect to the substituent of RA, RB, and RC of formula (D1);
the details of L3 and Ar31 are as described above with respect to L and Ar of formula (19), respectively; and
at least one of R301, R303, R306, and R308 is preferably -L3-Ar31.
Examples of the pyrene derivative represented by formula (22) are shown below, although not particularly limited thereto.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six-membered rings are all benzene rings.
In the following compounds, the six membered rings are all benzene rings.
As the fluorene derivative, a compound represented by formula (23) is usable:
wherein:
R401 to R410 are each independently a hydrogen atom, a substituent, or -L4-Ar41, provided that at least one of R401 to R410 is -L4-Ar41;
the details of the substituent are as described above with respect to the substituent of RA, RB, and RC;
the details of L4 and Ar41 are as described above with respect to L and Ar of formula (19), respectively;
in at least one pair selected from R401 and R402, R402 and R403, R403 and R404, R405 and R406, R406 and R407, and R407 and R408, adjacent two may be bonded to each other to form a substituted or unsubstituted ring structure;
each of R402 and R407 is preferably -L4-Ar41;
each of R409 and R410 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or -L4-Ar41; and
the details of the alkyl group having 1 to 20 carbon atoms are as described above with respect to the alkyl group of RA, RB, and RC of formula (D1),
Examples of the fluorene derivative represented by formula (23) are shown below, although not particularly limited.
The second compound is used in a fluorescent emitting layer of the organic EL device of the invention together with the dopant material and the first compound and works as a co-host material of the fluorescent emitting layer.
The second compound is at least one compound selected from an amine compound represented by formula (2a), a biscarbazole compound represented by formula (2b), and a diamine compound represented by formula (2c).
The second compound is preferably at least one compound selected from an amine compound represented by formula (2a) and a biscarbazole compound represented by formula (2b).
The amine compound is represented by formula (2a):
wherein:
Ar11, Ar22, and Ar33 are each independently a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms;
the details of the aryl group having 6 to 50 ring carbon atoms and the heteroaryl group having 5 to 50 ring atoms are as described above with respect to the aryl group having 6 to 50 ring carbon atoms and the heteroaryl group having 5 to 50 ring atoms of RA, RB, and RC of formula (D1), respectively;
L11, L22, and L33 are each independently a substituted or unsubstituted arylene group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms;
the details of the arylene group having 6 to 50 ring carbon atoms and the heteroarylene group having 5 to 50 ring atoms are as described above with respect to the arylene group having 6 to 50 ring carbon atoms and the heteroarylene group having 5 to 50 ring atoms of L in formula (19), respectively;
p, q, and r are each independently 0, 1, or 2 and preferably 0 or 1; and
when p is 0, L11 is a single bond, when q is 0, L22 is a single bond, and when r is 0, L33 is a single bond.
Examples of the compound represented by formula (2a) are shown below, although not limited thereto.
The biscarbazole compound is represented by formula (2b):
wherein:
one selected from R71 to R78 is a single band bonded to *a and one selected from R81 to R88 is a single bond bonded to *b;
R71 to R78 and R81 to R88 not the single bond are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 24, and still more preferably 6 to 18 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 18, and still more preferably 5 to 13 ring atoms;
the details of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 50 ring carbon atoms, and the heteroaryl group having 5 to 50 ring atoms are as described above with respect to the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 50 ring carbon atoms, and the heteroaryl group having 5 to 50 ring atoms of RA, RB, and RC of formula (D1), respectively;
adjacent two selected from R71 to R74 not the single bond, adjacent two selected from R75 to R78 not the single bond, adjacent two selected from R81 to R84 not the single bond, and adjacent two selected from R85 to R88 not the single bond may be bonded to each other to form a substituted or unsubstituted ring structure or not form the ring structure;
the ring structure is selected, for example, from the aromatic hydrocarbon ring having 6 to 50 ring carbon atoms and the aromatic heterocyclic ring having 5 to 50 ring atoms that are described above with respect to the ring π1 and ring π2 of formula (D1) and preferably selected from formulae (2) to (11) described above with respect to formula (1);
Ar44 and Ar55 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms;
the details of the aryl group having 6 to 50 ring carbon atoms and the heteroaryl group having 5 to 50 ring atoms are as described above with respect to the aryl group having 6 to 50 ring carbon atoms and the heteroaryl group having 5 to 50 ring atoms of RA, RB, and RC of formula (D1), respectively;
L44, L55, and L66 are each independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms;
the details of the arylene group having 6 to 50 ring carbon atoms and the heteroarylene group having 5 to 50 ring atoms are as described above with respect to the arylene group having 6 to 50 ring carbon atoms and the heteroarylene group having 5 to 50 ring atoms of L in formula (19), respectively;
m4, m5, and m6 are each independently 0, 1, or 2 and preferably 0 or 1; and
when m4 is 0, L44 is a single bond, when m5 is 0, L55 is a single bond, and when m6 is 0, L66 is a single bond.
Formula (2b) is preferably represented by any of formulae (2b-1) to (2b-3):
Examples of the compound represented by formula (2b) are shown below, although not limited thereto.
The diamine compound is represented by formula (2c):
(Ar80)(Ar81)N-(L80)-N(Ar82)(Ar83) (2c)
wherein:
Ar80 to Ar83 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms
the details of the aryl group having 6 to 50 ring carbon atoms and the heteroaryl group having 5 to 50 ring atoms are as described above with respect to the aryl group having 6 to 50 ring carbon atoms and the heteroaryl group having 5 to 50 ring atoms of RA, RB, and RC of formula (D1), respectively;
L80 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms; and
the details of the arylene group having 6 to 50 ring carbon atoms and the heteroarylene group having 5 to 50 ring atoms are as described above with respect to the arylene group having 6 to 50 ring carbon atoms and the heteroarylene group having 5 to 50 ring atoms of L in formula (19), respectively.
Examples of the compound represented by formula (2c) are shown below, although not limited thereto.
The content of the second compound in the fluorescent emitting layer is preferably less than that of the first compound in the fluorescent emitting layer.
The content of the second compound in the fluorescent emitting layer is preferably 30% by mass or less, more preferably 2 to 30% by mass, and still more preferably 2 to 20% by mass, each based on the total amount of the first compound, the second compound, and the dopant material. Within the above ranges, the region of high excitation density comes close to the central portion of the fluorescent emitting layer to increase the lifetime.
The content of the dopant material in the fluorescent emitting layer is preferably 10% by mass or less, more preferably 1 to 10% by mass, and still more preferably 1 to 8% by mass, each based on the total amount of the first compound, the second compound and the dopant material. Within the above rages, the self-absorption is reduced to increase the emission efficiency.
The substituent referred to by “substituent” or “substituted or unsubstituted” each mentioned above is, unless otherwise noted, preferably at least one selected from an alkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms; a cycloalkyl group having 3 to 50, preferably 3 to 1.0, more preferably 3 to 8, and still more preferably 5 or 6 ring carbon atoms; an aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 1.8 ring carbon atoms; an aralkyl group having 7 to 51, preferably 7 to 30, and more preferably 7 to 20 carbon atoms, which has an aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; an amino group; a mono- or di-substituted amino group having a substituent selected from an alkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms and an aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; an alkoxy group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms; an aryloxy group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; a mono-, di-, or tri-substituted silyl group having a substituent selected from an alkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms and an aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; a heteroaryl group having 5 to 50, preferably 5 to 24, and more preferably 5 to 13 ring atoms; a haloalkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms; a halogen atom; a cyano group; a nitro group; a sulfonyl group having a substituent selected from an alkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms and an aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; a di-substituted phosphoryl group having a substituent selected from an alkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms and an aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; an alkylsulfonyloxy group; an arylsulfonyloxy group; an alkylcarbonyloxy group; an arylcarbonyloxy group; a boron-containing group; a zinc-containing group; a tin-containing group; a silicon-containing group; a magnesium-containing group; a lithium-containing group; a hydroxyl group; an alkyl-substituted or aryl-substituted carbonyl group; a carboxyl group; a vinyl group; a (meth)acryloyl group; an epoxy group; and an oxetanyl group, although not particularly limited thereto.
The substituent may be further substituted with the optional substituent mentioned above and adjacent two substituents may be bonded to each other to form a ring structure.
The substituent is more preferably a substituted or unsubstituted an alkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms; a substituted or unsubstituted a cycloalkyl group having 3 to 50, preferably 3 to 10, more preferably 3 to 8, and still more preferably 5 or 6 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; a mono- or di-substituted amino group having a substituent selected from a substituted or unsubstituted alkyl group having 1 to 50, preferably 1 to 18, and more preferably 1 to 8 carbon atoms and a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms; a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 24, and more preferably 5 to 13 ring atoms, a halogen atom, or a cyano group.
Examples of the alkyl group having 1 to 50 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group (inclusive of isomeric groups), a hexyl group (inclusive of isomeric groups), a heptyl group (inclusive of isomeric groups), an octyl group (inclusive of isomeric groups), a nonyl group (inclusive of isomeric groups), a decyl group (inclusive of isomeric groups), an undecyl group (inclusive of isomeric groups), and a dodecyl group (inclusive of isomeric groups). Preferred are a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and a pentyl group (inclusive of isomeric groups), with a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a s-butyl group, and a t-butyl group being more preferred and a methyl group, an ethyl group, an isopropyl group, and a t-butyl group being particularly preferred.
Examples of the cycloalkyl group having 3 to 50 ring carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group, with a cyclopentyl group and a cyclohexyl group being preferred.
Examples of the aryl group having 6 to 50 ring carbon atoms include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an acenaphthylenyl group, an anthryl group, a benzanthryl group, an aceanthryl group, a phenanthryl group, a benzo[c]phenanthryl group, a phenalenyl group, a fluorenyl group, a picenyl group, a pentaphenyl group, a pyrenyl group, a chrysenyl group, a benzo[g]chrysenyl group, a s-indacenyl group, an as-indacenyl group, a fluoranthenyl group, a benzo[k]fluoranthenyl group, a triphenylenyl group, a benzo[b]triphenylenyl group, and a perylenyl group. Preferred are a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a fluoranthenyl group, with a phenyl group, a biphenylyl group, and a terphenylyl group being more preferred and a phenyl group being still more preferred.
In the aralkyl group having 7 to 51 carbon atoms which includes an aryl group having 6 to 50 ring carbon atoms, the details of the aryl portion are as described above with respect to the aryl group having 6 to 50 ring carbon atoms and the details of the alkyl portion are as described above with respect to the alkyl group having 1 to 50 carbon atoms.
In the mono- or di-substituted amino group having a substituent selected from an alkyl group having 1 to 50 carbon atoms and an aryl group having 6 to 50 ring carbon atoms, the details of the aryl portion are as described above with respect to the aryl group having 6 to 50 ring carbon atoms and the details of the alkyl portion are as described above with respect to the alkyl group having 1 to 50 carbon atoms.
The details of the alkyl portion of the alkoxy group having 1 to 50 carbon atoms are as described above with respect to the alkyl group having 1 to 50 carbon atoms.
The details of the aryl portion of the aryloxy group having 6 to 50 ring carbon atoms are as described above with respect to the aryl group having 6 to 50 ring carbon atoms.
Examples of the mono-, di-, or tri-substituted silyl group having a substituent selected from an alkyl group having 1 to 50 carbon atoms and an aryl group having 6 to 50 ring carbon atoms include a monoalkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, a monoarylsilyl group, a diarylsilyl group, a triarylsilyl group, a monoalkyldiarylsilyl group, and a dialkylmonoarylsilyl group. The details of the alkyl portion are as described above with respect to the alkyl group having 1 to 50 carbon atoms and the details of the aryl portion are as described above with respect to the aryl group having 6 to 50 ring carbon atoms.
Examples of the heteroaryl group having 5 to 50 ring atoms include a pyrrolyl group, a furyl group, a thienyl group, a pyridyl group, an imidazopyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyrazolyl group, an isoxazolyl group, an isothiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a triazolyl group, a tetrazolyl group, an indolyl group, an isoindolyl group, a benzofuranyl group, an isobenzofuranyl group, a benzothiophenyl group, an isobenzothiophenyl group, an indolizinyl group, a quinolizinyl group, a quinolyl group, an isoquinolyl group, a cinnolyl group, a phthalazinyl group, a quinazolinyl group, a quinoxalinyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, an indazolyl group, a benzisoxazolyl group, a benzisothiazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a phenothiazinyl group, a phenoxazinyl group, and a xanthenyl group. Preferred are a pyridyl group, an imidazopyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a benzimidazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a phenanthrolinyl group, and a quinazolinyl group.
The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The haloalkyl group having 1 to 50 carbon atoms is a group derived from the alkyl group having 1 to 50 carbon atoms by replacing at least one hydrogen atom with a halogen atom.
The details of the aryl portion and the alkyl portion of the sulfonyl group having a substituent selected from an alkyl group having 1 to 50 carbon atoms and an aryl group having 6 to 50 ring carbon atoms, the di-substituted phosphoryl group having a substituent selected from an alkyl group having 1 to 50 carbon atoms and an aryl group having 6 to 50 ring carbon atoms, the alkylsulfonyloxy group, the arylsulfonyloxy group, the alkylcarbonyloxy group, the arylcarbonyloxy group, and the alkyl-substitute or aryl-substituted carbonyl group are as described above with respect to the aryl group having 6 to 50 ring carbon atoms and the alkyl group having 1 to 50 carbon atoms, respectively.
An embodiment wherein examples, preferred examples, more preferred examples, etc. of a substituent are combined with examples, preferred examples, more preferred examples, etc. of another substituent is included in the scope of the invention. The same applies to the compounds, the ranges of the number of carbon atoms, and the ranges of the number of atoms. In addition, the substituents, the compounds, the ranges of the number of carbon atoms, and the ranges of the number of atoms may be combined freely and such a combination is included in the scope of the invention.
The organic EL device of the invention is described below in detail. In the following, the “light emitting layer” means a fluorescent emitting layer and a phosphorescent emitting layer, unless otherwise noted.
As described above, the organic EL device of the invention comprises a cathode, an anode, and an organic layer disposed between the cathode and the anode, wherein the organic layer comprises a fluorescent emitting layer and the fluorescent emitting layer comprises at least one first compound selected from the compounds represented by formulae (19), (21), (22), and (23), at least one second compound selected from the compounds represented by formulae (2a), (2b), and (2c), and at least one dopant material selected from the compounds represented by formulae (D1) and (D2).
The fluorescent emitting layer may be a TADF-based (thermally activated delayed fluorescence-based) light emitting layer. The fluorescent emitting layer does not contain a phosphorescent heavy metal complex, for example, an iridium complex, a platinum complex, an osmium complex, a rhenium complex, and a ruthenium complex.
The organic EL device of the invention may be any of a single color emitting device using fluorescence or thermally activated delayed fluorescence; a white-emitting hybrid device comprising two or more single color emitting devices; an emitting device of a simple type having a single emission unit; and an emitting device of a tandem type having two or more emission units. The “emission unit” referred to herein is the smallest unit for emitting light by the recombination of injected holes and injected electrons, which comprises one or more organic layers wherein at least one layer is a light emitting layer.
Representative device structures of the simple-type organic EL device are shown below.
The emission unit described below includes at least one fluorescent emitting layer. The emission unit may be a layered structure comprising two or more light emitting layers selected from a phosphorescent light emitting layer, a fluorescent light emitting layer, and a thermally activated delayed fluorescence-based light emitting layer. A space layer may be disposed between two light emitting layers to prevent the diffusion of excitons generated in the phosphorescent emitting layer into the fluorescent emitting layer. Representative layered structures of the emission unit are shown below, wherein the layer in the parenthesis is optional:
(a) (Hole injecting layer/)Hole transporting layer/Fluorescent emitting layer(/Electron transporting layer/Electron injecting layer);
(b) (Hole injecting layer/)Hole transporting layer/First fluorescent emitting layer/Second fluorescent emitting layer(/Electron transporting layer/Electron injecting layer);
(c) (Hole injecting layer/)Hole transporting layer/Phosphorescent emitting layer/Space layer/Fluorescent emitting layer(/Electron transporting layer/Electron injecting layer);
(d) (Hole injecting layer/)Hole transporting layer/First phosphorescent emitting layer/Second phosphorescent emitting layer/Space layer/Fluorescent emitting layer(/Electron transporting layer/Electron injecting layer);
(e) (Hole injecting layer/)Hole transporting layer/First phosphorescent emitting layer/Space layer/Second phosphorescent emitting layer/Space layer/Fluorescent emitting layer(/Electron transporting layer/Electron injecting layer);
(f) (Hole injecting layer/)Hole transporting layer/Phosphorescent emitting layer/Space layer/First fluorescent emitting layer/Second fluorescent emitting layer(/Electron transporting layer/Electron injecting layer); and
(g) (Hole injecting layer/)First hole transporting layer/Second hole transporting layer/Fluorescent emitting layer/First electron transporting layer/Second electron transporting layer(/Electron injecting layer).
The emission colors of the phosphorescent emitting layers and the fluorescent emitting layer may be different. For example, the layered structure (d) may be Hole transporting layer/First phosphorescent emitting layer (red)/Second phosphorescent emitting layer (green)/Space layer/Fluorescent emitting layer (blue)/Electron transporting layer.
An electron blocking layer may be disposed between the light emitting layer and the hole transporting layer or between the light emitting layer and the space layer, if necessary. Also, a hole blocking layer may be disposed between the light emitting layer and the electron transporting layer, if necessary. With such an electron blocking layer or a hole blocking layer, electrons and holes are confined in the light emitting layer to facilitate the charge recombination in the light emitting layer, thereby improving the emission efficiency.
Representative device structure of the tandem-type organic EL device is shown below.
The layered structure of the first emission unit and the second emission unit may be independently selected from those described above with respect to the emission unit.
Generally, the intermediate layer is also called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron withdrawing layer, a connecting layer, or an intermediate insulating layer. The intermediate layer may be formed by known materials so as to supply electrons to the first emission unit and holes to the second emission unit.
A schematic structure of an example of the organic EL device of the invention is shown in
In the present invention, a host material is referred to as a fluorescent host material when combinedly used with a fluorescent dopant material and as a phosphorescent host material when combinedly used with a phosphorescent dopant material. Therefore, the fluorescent host material and the phosphorescent host material are not distinguished from each other merely by the difference in their molecular structures. Namely, in the present invention, the term “fluorescent host material” means a material for constituting a fluorescent emitting layer which contains a fluorescent dopant material and does not mean a material that cannot be used as a material for a phosphorescent emitting layer. The same applies to the phosphorescent host material.
The organic EL device of the invention is formed on a light-transmissive substrate. The light-transmissive substrate serves as a support for the organic EL device and preferably a flat substrate having a transmittance of 50% or more to 400 to 700 nm visible light. Examples of the substrate include a glass plate and a polymer plate. The glass plate may include a plate made of soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz. The polymer plate may include a plate made of polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, or polysulfone.
The anode of the organic EL device injects holes to the hole transporting layer or the light emitting layer, and an anode having a work function of 4.5 eV or more is effective. Examples of the material for anode include an indium tin oxide alloy (ITO), tin oxide (NESA), an indium zinc oxide alloy, gold, silver, platinum, and cupper. The anode is formed by making the electrode material into a thin film by a method, such as a vapor deposition method or a sputtering method. When getting the light emitted from the light emitting layer through the anode, the transmittance of anode to visible light is preferably 10% or more. The sheet resistance of anode is preferably several hundreds Ω/□ or less. The film thickness of anode depends upon the kind of material and generally 10 nm to 1 m, preferably 10 to 200 nm.
The cathode injects electrons to the electron injecting layer, the electron transporting layer or the light emitting layer, and is formed preferably by a material having a small work function. Examples of the material for cathode include, but not limited to, indium, aluminum, magnesium, a magnesium-indium alloy, a magnesium-aluminum alloy, an aluminum-lithium alloy, an aluminum-scandium-lithium alloy, and a magnesium-silver alloy. Like the anode, the cathode is formed by making the material into a thin film by a method, such as the vapor deposition method and the sputtering method. The light emitted from a light emitting layer may be taken through the cathode, if necessary.
The hole injecting layer comprises a material having a high hole injecting ability (hole injecting material).
Examples of the hole injecting material include an aromatic amine compound, molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, and manganese oxide.
The hole transporting layer is an organic layer formed between the light emitting layer and the anode and transports holes from the anode to the light emitting layer. When the hole transporting layer is formed by two or more layers, the layer closer to the anode may be defined as a hole injecting layer in some cases. The hole injecting layer injects holes from the anode to the organic layer unit efficiently.
An aromatic amine compound, for example, the aromatic amine derivative represented by formula (I) is preferably used as a material for the hole transporting layer:
wherein:
Ar1 to Ar4 are each independently a substituted or unsubstituted non-fused aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms, a substituted or unsubstituted fused aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms, a substituted or unsubstituted non-fused heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms, a substituted or unsubstituted fused heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms, or a group wherein the non-fused aryl group or the fused aryl group is bonded to the non-fused heteroaryl group or the fused heteroaryl group;
Ar1 and Ar2, and Ar3 and Ar4 may be bonded to each other to form a ring; and
L represents a substituted or unsubstituted non-fused arylene group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms, a substituted or unsubstituted fused arylene group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms, a substituted or unsubstituted non-fused heteroarylene group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms, or a substituted or unsubstituted fused heteroarylene group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms.
Examples of the compound represented by formula (I) are shown below.
An aromatic amine represented by formula (II) is also preferred as the hole transporting layer material:
wherein Ar1 to Ar3 are as defined above with respect to Ar1 to Ar4 of formula (I).
Examples of the compound represented by formula (II) are shown below, although not limited thereto.
The hole transporting layer may be made into two-layered structure of a first hole transporting layer (anode side) and a second hole transporting layer (cathode side).
The thickness of the hole transporting layer is preferably 10 to 200 nm, although not particularly limited thereto. If the hole transporting layer is of a two-layered structure of a first hole transporting layer (anode side) and a second hole transporting layer (cathode side), the thickness is preferably 50 to 150 nm and more preferably 50 to 110 nm for the first hole transporting layer, and preferably 5 to 50 nm and more preferably 5 to 30 nm for the second hole transporting layer.
A layer comprising an acceptor material may be disposed in contact with the anode side of the hole transporting layer or the first hole transporting layer. With such a layer, it is expected that the driving voltage is lowered and the production cost is reduced.
The acceptor material is preferably a compound represented by the following formula:
The thickness of the layer comprising the acceptor material is preferably 5 to 20 nm, although not particularly limited thereto.
The light emitting layer is an organic layer having a light emitting function and contains a host material and a dopant material when a doping system is employed. The major function of the host material is to promote the recombination of electrons and holes and confine excitons in the light emitting layer. The dopant material causes the excitons generated by recombination to emit light efficiently.
In case of a phosphorescent device, the major function of the host material is to confine the excitons generated on the dopant in the light emitting layer.
The light emitting layer may be made into a double dopant layer, in which two or more kinds of dopant materials having high quantum yield are combinedly used and each dopant material emits light with its own color. For example, a yellow-emitting layer is obtained by co-depositing a host material, a red-emitting dopant material and a green-emitting dopant material into a single emitting layer.
The easiness of hole injection to the light emitting layer and the easiness of electron injection to the light emitting layer may be different from each other. Also, the hole transporting ability expressed by hole mobility and the electron transporting ability expressed by electron mobility in the light emitting layer may be different from each other.
The light emitting layer is formed, for example, by a known method, such as a vapor deposition method, a spin coating method, and LB method. The light emitting layer may be also formed by making a solution of a binder, such as resin, and a material for the light emitting layer into a thin film by a method such as spin coating.
The light emitting layer is preferably a molecular deposit film. The molecular deposit film is a thin film formed by depositing a vaporized material or a film formed by solidifying a material in the form of solution or liquid. The molecular deposit film can be distinguished from a thin film formed by LB method (molecular build-up film) by the differences in the assembly structures and higher order structures and the functional difference due to the structural differences.
The thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and still more preferably 10 to 50 nm. If being 5 nm or more, the light emitting layer is formed easily. If being 50 nm or less, the driving voltage is prevented from increasing.
The fluorescent dopant material (fluorescent emitting material) is a compound emitting light by releasing the energy of excited singlet state. A fluorescent dopant material other than the compounds represented by formulae (D1) and (D2) may be used. Such a fluorescent dopant material is not particularly limited as long as emitting light by releasing the energy of excited singlet state. Examples thereof include a fluoranthene derivative, a styrylarylene derivative, a pyrene derivative, an arylacetylene derivative, a fluorene derivative, a boron complex, a perylene derivative, an oxadiazole derivative, an anthracene derivative, a styrylamine derivative, and an arylamine derivative, with an anthracene derivative, a fluoranthene derivative, a styrylamine derivative, an arylamine derivative, a styrylarylene derivative, a pyrene derivative, and a boron complex being preferred, and an anthracene derivative, a fluoranthene derivative, a styrylamine derivative, an arylamine derivative, and a boron complex compound being more preferred.
The phosphorescent dopant material (phosphorescent emitting material) is a compound emitting light by releasing the energy of excited triplet state. Examples of the phosphorescent dopant material include a metal complex, such as an iridium complex, a platinum complex, an osmium complex, a rhenium complex, and a ruthenium complex.
In an embodiment of the invention, the fluorescent emitting layer comprises the first compound as the host material (main host material) and the second compound as the co-host material. Another host material usable in the light emitting layer may include, for example, a metal complex, such as an aluminum complex, a beryllium complex, and a zinc complex; a heterocyclic compound, such as an oxadiazole derivative, a benzimidazole derivative, and a phenanthroline derivative; a fused aromatic compound, such as a carbazole derivative, an anthracene derivative, a phenanthrene derivative, a pyrene derivative, a chrysene derivative, and a fluorene derivative; and an aromatic amine compound, such as a triarylamine derivative and a fused aromatic polycyclic amine derivative.
The electron transporting layer is an organic layer disposed between the light emitting layer and the cathode and transports electrons from the cathode to the light emitting layer.
An aromatic heterocyclic compound having one or more hetero atoms in its molecule is preferably used as an electron transporting material used in the electron transporting layer, and a nitrogen-containing ring derivative is particularly preferred. In addition, the nitrogen-containing ring derivative is preferably an aromatic heterocyclic compound having a nitrogen-containing, 6- or 5-membered ring, or a fused aromatic heterocyclic compound having a nitrogen-containing, 6- or 5-membered ring.
The nitrogen-containing ring derivative is preferably, for example, a metal chelate complex of a nitrogen-containing ring represented by formula (A):
wherein:
each of R2 to R7 independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydrocarbon group having 1 to 40, preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6 carbon atoms, an alkoxy group having 1 to 40, preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6 carbon atoms, an aryloxy group having 6 to 40, preferably 6 to 20, and more preferably 6 to 12 ring carbon atoms, an alkoxycarbonyl group having 2 to 40, preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 5 carbon atoms, or an aromatic heterocyclic group having 9 to 40, preferably 9 to 30, and more preferably 9 to 20 ring atoms, each optionally having a substituent;
M is aluminum, gallium, or indium, with In being preferred; and
L is a group represented by formula (A′) or (A″):
wherein:
each R8 to R12 in formula (A′) independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 40, preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6 carbon atoms and adjacent two may form a ring structure;
each of R13 to R27 in formula (A″) independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 40, preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6 carbon atoms and adjacent two may form a ring structure.
Examples of the divalent group formed by adjacent two of R8 to R12 and R13 to R27 which completes the ring structure include a tetramethylene group, a pentamethylene group, a hexamethylene group, a diphenylmethane-2,2′-diyl group, a diphenylethane-3,3′-diyl group, and a diphenylpropane-4,4′-diyl group.
A metal complex including 8-hydroxyquinoline or its derivative, an oxadiazole derivative, and a nitrogen-containing heterocyclic derivative are also preferably as the electron transporting material for used in the electron transporting layer,
An electron transporting material having a good thin film forming property is preferably used. Examples of the electron transporting compound are shown below.
A compound having a nitrogen-containing heterocyclic group represented, by any of the following formulae is also preferred as the electron transporting material for the electron transporting layer.
wherein
R is a non-used aryl group having 6 to 40 ring carbon atoms, a fused aromatic hydrocarbon group having 10 to 40 ring carbon atoms, a non-fused heteroaryl group having 3 to 40 ring atoms, a fused heteroaryl group having 3 to 40 ring atoms, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;
n is an integer of 0 to 5 and
when n is an integer of 2 or more, groups R may be the same or different.
The electron transporting layer particularly preferably comprises at least one compound selected from the nitrogen-containing heterocyclic derivatives represented by formulae (60) to (62):
wherein:
Z11, Z12, and Z13 are each independently a nitrogen atom or a carbon atom;
RA and RB are each independently a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms, a substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, or a substituted or unsubstituted alkoxyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms;
n is an integer of 0 to 5, when n is an integer of 2 or more, RA's may be the same or different, and adjacent two RA's may be bonded to each other to form a substituted or unsubstituted hydrocarbon ring;
Ar11 is a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms;
Ar12 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms;
provided that one of Ar11 and Ar12 is a substituted or unsubstituted fused aryl group having 10 to 50, preferably 10 to 30, more preferably 10 to 20, and still more preferably 10 to 14 ring carbon atoms or a substituted or unsubstituted fused heteroaryl group having 9 to 50, preferably 9 to 30, more preferably 9 to 20, and still more preferably 9 to 14 ring atoms;
Ar13 is a substituted or unsubstituted arylene group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50, preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12 ring atoms; and
L11, L12, and L13 each independently represent a single bond, a substituted or unsubstituted arylene group having 6 to 50, preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12 ring carbon atoms or a substituted or unsubstituted divalent fused aromatic heterocyclic group having 9 to 50, preferably 9 to 30, more preferably 9 to 20, and still more preferably 9 to 14 ring atoms.
Examples of the nitrogen-containing heterocyclic derivative represented by formulae (60) to (62) are shown below.
The electron transporting layer of the organic EL device of the invention may be made into two-layered structure of a first electron transporting layer (anode side) and a second electron transporting layer (cathode side).
The thickness of the electron transporting layer is preferably 1 to 100 nm, although not particularly limited thereto. If the electron transporting layer is of a two-layered structure of a first electron transporting layer (anode side) and a second electron transporting layer (cathode side), the thickness is preferably 5 to 60 nm and more preferably 10 to 40 nm for the first electron transporting layer, and preferably 1 to 20 nm and more preferably 1 to 10 nm for the second electron transporting layer.
The electron injecting layer is a layer for transporting electrons from the cathode to the organic layer unit efficiently.
The material for the electron injecting layer may be selected from the nitrogen-containing heterocyclic derivative. In addition, an inorganic compound, such as an insulating material and a semiconductor is preferably used. The electron injecting layer formed by the insulating material or the semiconductor effectively prevents the leak of electric current to enhance the electron injecting properties.
The insulating material is preferably at least one metal compound selected from the group consisting of an alkali metal chalcogenide, an alkaline earth metal chalcogenide, an alkali metal halide and an alkaline earth metal halide. The alkali metal chalcogenide, etc. mentioned above are preferred because the electron injecting properties of the electron injecting layer are further enhanced. Example of preferred alkali metal chalcogenide includes Li2O, K2O, Na2S, Na2Se and Na2O, and example of preferred alkaline earth metal chalcogenide includes CaO, BaO, SrO, BeO, BaS and CaSe. Example of preferred alkali metal halide includes LiF, NaF, KF, LiCl, KCl and NaCl. Example of the alkaline earth metal halide includes a fluoride, such as CaF2, BaF2, SrF2, MgF2 and BeF2, and a halide other than the fluoride.
Example of the semiconductor includes an oxide, a nitride or an oxynitride of at least one element selected from the group consisting of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn. The semiconductor may be used alone or in combination of two or more. The inorganic compound in the electron injecting layer preferably forms a microcrystalline or amorphous insulating thin film. If the electron injecting layer is formed from such an insulating thin film, the pixel defects, such as dark spots, can be decreased because a more uniform thin film is formed.
The thickness of the electron injecting layer including the insulating material or the semiconductor is preferably about 0.1 to 15 nm. The electron injecting layer preferably contains the electron-donating dopant mentioned below.
The electron mobility in the electron injecting layer is preferably 10−6 cm2/Vs or more at an electric field strength of 0.04 to 0.5 MV/cm, because the electron injection from the cathode to the electron transporting layer is promoted to promote the electron injection to the adjacent blocking layer and the light emitting layer, thereby enabling the operation at a lower driving voltage.
The organic EL device of the invention preferably comprises an electron-donating dopant at an interfacial region between the cathode and the emitting unit. With such a construction, the organic EL device has an improved luminance and an elongated lifetime. The electron-donating dopant is a metal having a work function of 3.8 eV or less and a compound including such a metal. Examples thereof include at least one selected from alkali metal, alkali metal complex, alkali metal compound, alkaline earth metal, alkaline earth metal complex, alkaline earth metal compound, rare earth metal, rare earth metal complex, and rare earth metal compound.
Examples of the alkali metal include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), and Cs (work function: 1.95 eV), with those having a work function of 2.9 eV or less being particularly preferred. Examples of the alkaline earth metal include Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), and Ba (work function: 2.52 eV), with those having a work function of 2.9 eV or less being particularly preferred. Examples of the rare earth metal include Sc, Y, Ce, Tb, and Yb, with those having a work function of 2.9 eV or less being particularly preferred.
Examples of the alkali metal compound include alkali oxide, such as Li2O, Cs2O, K2O, and alkali halide, such as LiF, NaF, CsF, and KF, with LiF, Li2O, and NaF being preferred. Examples of the alkaline earth metal compound include BaO, SrO, CaO, and mixture thereof, such as BaxSr1-xO (0<x<1) and BaxCA1-xO (0<x<1), with BaO, SrO, and CaO being preferred. Examples of the rare earth metal compound include YbF3, ScF3, ScO3, Y2O3, Ce2O3, GdF3, and TbF3, with YbF3, ScF3, and TbF3 being preferred.
Examples of the alkali metal complex, alkaline earth metal complex, and rare earth metal are not particularly limited as long as containing at least one metal ion selected from an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion, respectively. The ligand is preferably, but not limited to, quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azomethines, and derivative thereof.
The electron-donating dopant material is preferably formed into a layer or island in the interfacial region, which is formed by co-depositing the electron-donating dopant material with an organic compound (light emitting material, electron injecting material) for forming the interfacial region by a resistance heating deposition method, thereby dispersing the electron-donating dopant material into the organic material. The disperse concentration expressed by the ratio of organic material:electron-donating dopant material is 100:1 to 1:100 by mole.
When the electron-donating dopant material is formed into a form of layer, a light emitting material or an electron injecting material is formed into an interfacial organic layer, and then, the electron-donating dopant material alone is deposited by a resistance heating deposition method into a layer having a thickness of preferably 0.1 to 15 nm. When the electron-donating dopant material is formed into a form of island, a light emitting material or an electron injecting material is made into an interfacial island, and then, the electron-donating dopant material alone is deposited by a resistance heating deposition method into a form of island having a thickness of preferably 0.05 to 1 nm.
The molar ratio of the main component and the electron-donating dopant in the organic EL device of the invention is preferably 5:1 to 1:5.
N/P doping
As described in JP 3695714B, the carrier injecting properties into the hole transporting layer and the electron transporting layer is controlled by the doping (n) with a donor material or the doping (p) with an acceptor material.
A typical example of the n-doping is an electron transporting material doped with a metal, such as Li and Cs, and a typical example of the p-doping is a hole transporting material doped with an acceptor material, such as F4TCNQ.
For example, in an organic EL device wherein a fluorescent emitting layer and a phosphorescent emitting layer are stacked, a space layer is disposed between the fluorescent emitting layer and the phosphorescent emitting layer to prevent the diffusion of excitons generated in the phosphorescent emitting layer to the fluorescent emitting layer or to control the carrier balance. The space layer may be disposed between two or more phosphorescent emitting layers.
Since the space layer is disposed between the light emitting layers, a material combining the electron transporting ability and the hole transporting ability is preferably used for forming the space layer. To prevent the diffusion of triplet energy in the adjacent phosphorescent emitting layer, the triplet energy of the material for the space layer is preferably 2.6 eV or more. The materials described with respect to the hole transporting layer are usable as the material for the space layer.
A blocking layer, such as an electron blocking layer, a hole blocking layer, and a triplet blocking layer, is preferably disposed adjacent to the light emitting layer. The electron blocking layer is a layer for preventing the diffusion of electrons from the light emitting layer to the hole transporting layer and disposed between the light emitting layer and the hole transporting layer. The hole blocking layer is a layer for preventing the diffusion of holes from the light emitting layer to the electron transporting layer and disposed between the light emitting layer and the electron transporting layer. The triplet blocking layer prevents the diffusion of triplet excitons generated in the light emitting layer to adjacent layers and confines the triplet excitons in the light emitting layer, thereby preventing the energy of the triplet excitons from being deactivated on the molecules other than the emitting dopant, i.e., on the molecules in the electron transporting layer.
The organic EL device comprising the compound of the invention is of high performance and is usable in electronic device, for example, as display parts, such as organic EL panel module, display devices of television sets, mobile phones, personal computer, etc., and light emitting sources of lighting equipment and vehicle lighting equipment.
The present invention will be described below in more details with reference to the examples. However, it should be noted that the scope of the invention is not limited thereto.
Under argon atmosphere, a solution of 2,4,6-trichloroaniline (1.0 g, 5.09 mmol), 2-bromonaphthalene (2.21 g, 10.7 mmol), palladium acetate (22 mg, 0.102 mmol), tri-t-butylphosphine tetrafluoroborate (59 mg, 0.204 mmol), and sodium t-butoxide (1.38 g, 15.3 mmol) in toluene (15 mL) was stirred at 100° C. for 6 h. After the reaction, water was added and the reaction solution was extracted with dichloromethane. The collected organic layers were concentrated. The obtained solid was purified by column chromatography to obtain a white solid (1.5 g), which was identified as the target Intermediate 3 by the result of mass spectrometric analysis (m/e=448 to the molecular weight of 448.77). (yield: 66%)
Under argon atmosphere, a solution of Intermediate 3 (100 mg, 0.223 mmol), palladium acetate (2.5 mg, 0.0111 mmol), tricyclohexylphosphine tetrafluoroborate (6.4 mg, 0.0222 mmol), and potassium carbonate (92 mg, 0.669 mmol) in dimethylacetamide (3 mL) was heated at 140° C. for 6 h. After the reaction, water was added and the reaction solution was extracted with dichloromethane. The collected organic layers were concentrated. The obtained solid was purified by flash column chromatography to obtain a yellow solid (26 mg), which was identified as the target Intermediate 4 by the result of mass spectrometric analysis (m/e=375 to the molecular weight of 375.85). (yield: 30%)
Under argon atmosphere, a mixture of Intermediate 4 (20 mg, 0.0532 mmol), 4-tert-butylphenylboronic acid (9.3 mg, 0.0639 mmol), palladium acetate (1.2 mg, 0.00532 mmol), tri-t-butylphosphine tetrafluoroborate (3.1 mg, 0.0106 mmol), and potassium carbonate (14.7 mg, 0.106 mmol) in dimethoxyethane (2 mL) and water (0.5 mL) was stirred at 80° C. for 12 h. After the reaction, water was added and the reaction solution was extracted with dichloromethane. The collected organic layers were concentrated. The obtained solid was purified by column chromatography to obtain a yellow solid (16 mg), which was identified as the target Compound BD-1 by the result of mass spectrometric analysis (m/e=473 to the molecular weight of 473.61). (yield: 64%)
Under argon atmosphere, a solution of 2,7-dibromonaphthalene (5.0 g, 17 mmol) in a mixed solvent of anhydrous tetrahydrofuran (80 mL) and anhydrous toluene (40 mL) was cooled to −48° C. in a dry ice/acetone bath, to which a n-butyllithium/hexane solution (10.6 mL, 1.64 mol/L, 17 mmol) was added. The resultant solution was stirred at −45° C. for 20 min, and then stirred at −72° C. for 30 min. After adding a tetrahydrofuran solution of iodine (4.9 g, 19 mmol), the reaction mixture was stirred at −72° C. for one hour and then stirred at room temperature for 2.5 h. The reaction was deactivated by adding a 10% by mass aqueous solution of sodium sulfite (60 mL) and then extracted with toluene (150 mL). The organic layer was washed with a saturated brine (30 mL) and dried over magnesium sulfate. The solvent was evaporated off and the residue was dried under reduced pressure to obtain a pale yellow solid (5.66 g), which was identified as the target Intermediate 13 by the result of mass spectrometric analysis (m/e=339 to the molecular weight of 339). (yield: 99%)
Under argon atmosphere, into a suspension of 9H-carbazole (2.55 g, 15 mmol), 2-bromo-7-iodonaphthalene (5.7 g, 17 mmol), capper iodide (30 mg, 0.16 mmol), and tripotassium phosphate (7.5 g, 35 mmol) in anhydrous 1,4-dioxane (20 mL), trans-1,2-diaminocyclohexane (0.19 mmol) was added, and the resultant mixture was refluxed for 10 h. After the reaction, toluene (200 mL) was added and the inorganic substances were removed by filtration. The filtrate was concentrated and the obtained brawn solid (6.5 g) was purified by column chromatography to obtain a white acicular crystal (3.8 g), which was identified as the target Intermediate 14 by the result of mass spectrometric analysis (m/e=332 to the molecular weight of 332). (yield: 68%)
Under argon atmosphere, a solution of 2,2,6,6-tetramethylpiperidine (2.9 g, 20.6 mmol) in anhydrous tetrahydrofuran (30 mL) was cooled to −43° C. in a dry ice/acetone bath, to which a n-butyllithium/hexane solution (12.5 mL, 1.64 mol/L, 20.5 mmol) was added. The resultant solution was stirred at −36° C. for 20 min and then cooled to −70° C., to which triisopropoxyborane (7 mL, 30 mmol) was added dropwise and then a solution of Intermediate 14 (3.8 g, 10.2 mmol) in tetrahydrofuran (20 mL) was added. The resultant solution was stirred in a cooling bath for 10 h. After the reaction, a 5% by mass hydrochloric acid (100 mL) was added. The resultant solution was stirred at room temperature for 30 min and then extracted with ethyl acetate (150 mL). The organic layer was washed with a saturated brine (30 mL) and dried over magnesium sulfate. The solvent was evaporated off to obtain a yellow amorphous solid (4.9 g). The obtained solid was purified by column chromatography to obtain a yellow solid (2.9 g), which was identified as the target Intermediate 15 by the result of mass spectrometric analysis (m/e=415 to the molecular weight of 415). (yield: 68%)
Under argon atmosphere, into a suspension of 2,6-diiodo-4-tert-butylaniline (1.27 g, 3.2 mmol), Intermediate 15 (2.9 g, 7.0 mmol), tetrakis(triphenylphosphine)palladium (0.36 g, 0.31 mmol), and sodium hydrogen carbonate (2.1 g, 25 mmol) in 1,2-dimethoxyethane (40 mL), water (21 mL) was added and the resultant suspension was refluxed for 11 h. After the reaction, the reaction mixture was extracted with dichloromethane (200 mL). The organic layer was dried over magnesium sulfate and the solvent was evaporated off to obtain a yellow amorphous solid (3.5 g). The obtained solid was purified by column chromatography to obtain a white solid (2.0 g), which was identified as the target Intermediate 16 by the result of mass spectrometric analysis (m/e=887 to the molecular weight of 887). (yield: 70%)
Under argon atmosphere, a suspension in Intermediate 16 (1.0 g, 1.1 mmol), tris(dibenzylideneacetone)dipalladium(0) (41 mg, 451 μmol), SPhos (5 mg, 0.1.8 mmol), cesium carbonate (2.2 g, 6.7 mmol) in anhydrous xylene (100 mL) was refluxed for 10 h. After the reaction, the suspension was filtered and the residue was washed with water and methanol and dried under reduced pressure to obtain a pale green solid (0.427 g). The obtained solid was purified by column chromatography to obtain a yellow solid (0.37 g), which was identified as the target Compound BD-2 by the result of mass spectrometric analysis (nm/e=727 to the molecular weight of 727). (yield: 47%)
Under argon atmosphere, into a solution of 4-tert-butylphenylboronic acid (3.0 g, 17 mmol), 2-bromo-7-iodonaphthalene (5.66 g, 1.7 mmol), and tetrakis(triphenylphosphine)palladium (0.35 g, 0.30 mmol) in 1,2-dimethoxyethane (45 mL), a 2 M aqueous solution of sodium carbonate (23 mL, 45 mmol) was added and the resultant solution was refluxed for 11 h. After the reaction, the reaction solution was extracted with toluene (150 mL). The organic layer was washed with a saturated brine (30 mL) and dried over magnesium sulfate. The solvent was evaporated off to obtain a brown solid (9.2 g). The obtained solid was purified by column chromatography to obtain a white solid (4.4-5 g), which was identified as the target Intermediate 19 by the result of mass spectrometric analysis (m/e=338 to the molecular weight of 338). (yield: 77%)
Under argon atmosphere, a solution of 2,2,6,6-tetramethylpiperidine (2.8 g, 20 mmol) in anhydrous tetrahydrofuran (30 mL) was cooled to −40° C. in a dry ice/acetone bath, to which a n-butyllithium/hexane solution (12 mL, 1.64 mol/L, 20 mmol) was added, and the resultant solution was stirred at −54° C. for 20 min. After the reaction, the solution was cooled to −65° C., to which triisopropoxyborane (6 mL, 26 mmol) was added dropwise and then a solution of Intermediate 19 (4.45 g, 13 mmol) in tetrahydrofuran (20 mL) was added. The resultant solution was stirred for 10 h in a cooling bath. After the reaction, a 5% by mass hydrochloric acid (70 mL) was added and the reaction solution was stirred at room temperature for 30 min and extracted with ethyl acetate (200 mL). The organic layer was washed with a saturated brine (30 mL) and dried over magnesium sulfate. The solvent was evaporated off to obtain a yellow amorphous solid (5.5 g). The obtained solid was purified by column chromatography to obtain a white solid (3.19 g), which was identified as the target Intermediate 20 by the result of mass spectrometric analysis (m/e=382 to the molecular weight of 382). (yield: 64%)
Under argon atmosphere, into a suspension of Intermediate 20 (3.19 g, 8.3 mmol), 2,6-diiodo-4-tert-butylaniline (1.5 g, 3.7 mmol), tetrakis(triphenylphosphine)palladium (0.43 g, 0.37 mmol), and sodium hydrogen carbonate (2.5 g, 30 mmol) in 1,2-dimethoxyethane (50 mL), water (25 mL) was added and the resultant suspension was stirred for 11 h. The reaction mixture was extracted with dichloromethane (200 mL). The organic layer was dried over magnesium sulfate and the solvent was evaporated off to obtain a yellow amorphous solid (4.14 g). The obtained solid was purified by column chromatography to obtain a white solid (2.47 g), which was identified as the target Intermediate 21 by the result of mass spectrometric analysis (m/e=821 to the molecular weight of 821). (yield: 81%)
Under argon atmosphere, a suspension of Intermediate 21 (2.47 g, 3.0 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.11 g, 0.12 mmol), SPhos (0.20 g, 0.49 mmol), and cesium carbonate (5.9 g, 18 mmol) in anhydrous xylene (250 m L) was refluxed for 11 h. After the reaction, the reaction mixture was filtered and the residue was successively washed with water and methanol and dried under reduced pressure to obtain a pale yellow acicular crystal (1.88 g). The obtained crystal was purified by column chromatography to obtain a yellow solid (1.03 g) which was identified as the target Compound BD-3 by the result of mass spectrometric analysis (m/e=661 to the molecular weight of 661). (yield: 52%)
Under argon atmosphere, a solution of 2,2,6,6-tetramethylpiperidine (8.80 g, 62.4 mmol. 2 eq) in anhydrous THF (90 mL) was cooled to −50° C. in a dry ice/acetone bath, to which a n-BuLi/hexane solution (155 mol/L, 4.0.3 mL, 62.5 mmol, 1 eq) was added. The resultant solution was stirred at −50° C. for 30 min and cooled to −70° C. B(OiPr), (20.0 mL, 86.7 mmol, 2.8 eq) was added dropwise and 5 main thereafter a 3-bromo-9-phenylcarbazole/THF solution (10.1 g, 31.4 mmol/45 mL) was added. The reaction mixture was stirred for 10 h in a cooling bath, to which a 10% HCl (13.0 mL) was added. The reaction mixture was stirred at room temperature for 30 min and extracted with ethyl acetate (200 mL). The organic layer was washed with a saturated brine (30 mL) and dried over MgSO4. The solvent was evaporated off and the residue was dried under reduced pressure to obtain a yellow amorphous solid (10.6 g). The obtained solid was purified by column chromatography to obtain a pale yellow solid (4.20 g, yield: 37%), which was identified as the target Intermediate 22 by the result of mass spectrometric analysis (m/e=366 to the molecular weight of 366.02).
Under argon atmosphere, a suspension of Intermediate 22 (4.20 g, 11.5 mmol, 2.3 eq), 4-(tert-butyl)-2,6-diiodoaniline (2.00 g, 4.99 mmol), Pd(PPh3)4 (0.58 g, 0.50 mmol, 5% Pd), and NaHCO3 (3.5 g, 3.6 eq) in 1,2-dimethoxyethane (70 mL) was refluxed for 11 h after adding H2O (35 mL). The reaction mixture was extracted with CH2Cl2 (250 mL) and the extract was dried over magnesium sulfate. The solvent was evaporated off and the residue was dried under reduced pressure to obtain a yellow amorphous solid (5.6 g). The obtained solid was purified by column chromatography to obtain a white solid (3.25 g, yield: 82%), which was identified as the target Intermediate 23 by the result of mass spectrometric analysis (m/e=789 to the molecular weight of 789.6).
Under argon atmosphere, a suspension of Intermediate 23 (3.25 g, 4.12 mmol), Pd2(dba)3 (0.15 g, 0.16 mol, 4% Pd), SPhos (0.27 g, 0.66 mmol), and Cs2CO3 (8.1 g, 24.8 mmol) in anhydrous xylene (320 mL) was refluxed for 11 h. The reaction mixture was filtered and the solvent of the filtrate was evaporated off. The residue was dried under reduced pressure to obtain a brown solid (3.27 g). The obtained solid was purified by column chromatography to obtain a yellow solid (1.40 g). The obtained solid was recrystallized from toluene (40 mL) to obtain a yellow plate crystal (1.14 g, yield: 54%), which was identified as the target Compound BD-4 by the result of mass spectrometric analysis (m/e=627 to the molecular weight of 627.77).
Under argon atmosphere, into a suspension of 2 bromo-7-iodonaphthalene (2.83 g, 16.7 mmol), diphenylamine (5.57 g, 16.7 mmol), cupper iodide (30 mg, 0.16 mmol), and sodium t-butoxide (2.2 g, 23 mmol) in anhydrous 1,4-dioxane (20 ml), trans-1,2-diaminocyclohexane (0.19 mL, 1.6 mmol) was added. The resultant suspension was stirred at 110° C. for 10 h. The reaction mixture was filtered through a silica pad and the residue was washed with toluene (100 mL). The solvent of the filtrate was evaporated off and the residue was dried under reduced pressure to obtain a dark brown oil (6.7 g). The obtained oil was purified by column chromatography to obtain a white solid (4.56 g), which was identified as the target Intermediate 24 by the result of mass spectrometric analysis (m/e=373 to the molecular weight of 373). (yield: 68%)
(2) Synthesis of intermediate 25
Under argon atmosphere, a solution of 2,2,6,6-tetramethylpiperidine (3.4 g, 24 mmol) in anhydrous tetrahydrofuran (35 ml) was cooled to −30° C. in a dry ice/acetone bath, to which a n-butyllithium/hexane solution (14.7 mL, 1.64 mol/L, 24 mmol) was added. The resultant solution was stirred at −20° C. for 20 min and cooled to −75° C., to which triisopropoxyborane (8.3 mL, 36 mmol) was added dropwise and 5 min thereafter a solution of Intermediate 24 (4.5 g, 12 mmol) in tetrahydrofuran (20 mL) was added. The resultant solution was stirred for 10 h in a cooling bath. After the reaction, a 5% by mass hydrochloric acid (100 mL) was added and the solution was stirred at room temperature for 30 min and extracted with ethyl acetate (150 mL). The organic layer was washed with a saturated brine (30 mL) and dried over magnesium sulfate. The solution was evaporated off to obtain a reddish brown amorphous solid (5.8 g). The obtained solid was purified by column chromatography to obtain a pale yellow solid (2.94 g), which was identified as the target Intermediate 25 by the result of mass spectrometric analysis (m/e=417 to the molecular weight of 417). (yield: 59%)
Under argon atmosphere, into a suspension of Intermediate 25 (2.94 g, 7.0 mmol, 2.2 eq), 4-(4-tert-butylphenyl)-2,6-diiodoaniline (3.05 g, 6.40 mmol), Pd(PPh3)4 (0.74 g, 0.64 mmol, 5% Pd), and NaHCO3 (4.3 g, 51 mmol, 3.6 eq) in 1,2-dimethoxyethane (80 mL), H2O (40 mL) was added and the resultant suspension was refluxed for 11 h. The reaction mixture was extracted with CH2Cl2 (200 mL) and the extract was dried over MgSO4. The solvent was evaporated off and the residue was dried under reduced pressure to obtain a brown amorphous solid (7.78 g). The obtained solid was purified by column chromatography to obtain a yellow solid (4.80 g, yield: 77%), which was identified as the target Intermediate 26 by the result of mass spectrometric analysis (m/e=969 to the molecular weight of 969.8).
Under argon atmosphere, a suspension of Intermediate 26 (4.00 g, 4.12 mmol), Pd2(dba)3 (0.15 g, 0.164 mmol, 4% Pd), SPhos (0.27 g, 0.658 mmol), and Cs2CO3 (8.1 g, 24.8 mmol) in anhydrous xylene (400 mL) was refluxed for 11 h. The reaction mixture was filtered. The solvent of the filtrate was evaporated off and the residue was dried under reduced pressure to obtain a dark yellow solid. The obtained solid was purified by column chromatography to obtain a yellow solid (2.43 g, yield: 73%), which was identified as the target Compound BD-5 by the result of mass spectrometric analysis (m/e=808 to the molecular weight of 808.04).
Each of Compounds BD-1 to BD-6 (dopant material) synthesized in Synthesis Example 1 to 5 was measured for the half width in the following manner.
The dopant material was dissolved in toluene in a concentration of 10-6 mol/L or more and 10-5 mol/L or less to prepare a test sample. The fluorescence spectrum (vertical coordinate: fluorescence intensity, horizontal coordinate: wavelength) was measured by irradiating the test sample in a quartz cell with an excitation light at room temperature (300 K) by using Fluorescent Spectrophotometer F-7000 manufactured by Hitachi High-Tech Science Corporation.
The half width (nm) of the dopant material was determined from the obtained fluorescence spectrum. The results are shown in Tables 1 and 2.
The hole mobility of each of the first compound and the second compound was measured by using a device for evaluating hole mobility prepared in the following manner.
A 25 mm×75 mm×1.1 mm glass substrate having ITO transparent electrode (anode) (product of Geomatec Company) was ultrasonically cleaned in isopropyl alcohol for 5 min and then UV/ozone cleaned for 30 min. The thickness of ITO transparent electrode was 130 nm.
The cleaned glass substrate was mounted to a substrate holder of a vacuum vapor deposition apparatus. First, Compound HI-1 was vapor-deposited on the surface having the transparent electrode so as to cover the transparent electrode to form a hole injecting layer with a thickness of 5 nm.
On the hole injecting layer, Compound HT-1 was vapor-deposited to form a hole transporting layer with a thickness of 10 nm.
Successively thereafter, a compound (target) selected from the following first compounds and the following second compounds was vapor-deposited to form a target film with a thickness of 200 nm.
Finally, metallic aluminum was vapor-deposited on the target film to form a metallic cathode with a thickness of 80 nm.
The layered structure of the device for evaluating hole mobility thus prepared is shown below.
ITO (130)/HI-1 (5)/HT-1 (10)/target (200)/Al (80)
The numeral in each parenthesis is the thickness (nm).
The device for evaluating hole mobility was measured for the impedance by using an impedance measuring apparatus.
The impedance was measured by sweeping the measuring frequency from 1 Hz to 1 MHz while applying a DC voltage V and an AC amplitude of 0.1 V simultaneously to the device.
The modulus M was calculated from the measured impedance Z according to the following relational expression:
M=jωZ
wherein j is an imaginary unit and ω is an angular frequency (rad/s).
The electrical time constant r of the device for evaluating hole mobility was calculated according to the following expression:
τ=1/(2πfmax)
wherein:
fmax is the frequency at the peak on a Bode plot in which the imaginary part of the modulus M is plotted on the vertical axis and the frequency (Hz) is plotted on the horizontal axis; and π is the ratio of a circle's circumference to its diameter.
Using the obtained τ, the hole mobility μ (cm2/V·s) was calculated according to the following expression:
μ=d2/(Vτ)
wherein d is the total thickness of the organic thin films constituting the device, i.e., d=5+10+200=215 (nm) for the above device for evaluating hole mobility.
The hole mobility referred to herein is the value at a root of electric field strength E1/2 of 500 V1/2/cm1/2. The root of electric field strength E1/2 is calculated from the following relational expression:
E
1/2
=V
1/2
/d
1/2.
In the examples, the impedance was measured by using Solartron 1260. To obtain highly accurate results, Solartron 1296 Dielectric Interface System was used in combination.
The measured results of the hole mobility of the first compound and the second compound are shown in Tables 1 and 2.
25 mm×75 mm×1.1 mm glass substrate having ITO transparent electrode (anode) (product of Geomatec Company) was ultrasonically cleaned in isopropyl alcohol for 5 min and then UV/ozone cleaned for 30 min. The thickness of ITO transparent electrode was 130 nm.
The cleaned glass substrate was mounted to a substrate holder of a vacuum vapor deposition apparatus. First, Compound HI-1 was vapor-deposited on the surface having the transparent electrode so as to cover the transparent electrode to form a hole injecting layer with a thickness of 5 nm.
On the hole injecting layer, Compound HT-1 was vapor-deposited to form a first hole transporting layer with a thickness of 80 nm.
Then, on the first hole transporting layer, Compound HT-2 was vapor-deposited to form a second hole transporting layer with a thickness of 10 nm.
Successively after forming the second hole transporting layer, Compound BH1-1 (first compound), Compound BH2-1 (second compound), and Compound BD-1 (dopant material) were vapor co-deposited to form a light emitting layer with a thickness of 25 nm. The concentration in the light emitting layer was 86% by mass for Compound BH1-1, 12% by mass for BH2-1, and 2% by mass for Compound BD-1.
On the light emitting layer, Compound ET-1 was vapor-deposited to form a first electron transporting layer with a thickness of 10 nm.
Successively after forming the first electron transporting layer, Compound ET-2 was vapor-deposited to form a second electron transporting layer with a thickness of 15 nm.
Then, on the second electron transporting layer, lithium fluoride (LiF) was vapor-deposited to form an electron injecting electrode with a thickness of 1 nm.
Then, metallic aluminum (Al) was vapor-deposited on the electron injecting electrode to form a metallic cathode with a thickness of 80 nm.
The layered structure of the organic EL device is shown below.
ITO (130)/HI-1 (5)/HT-1 (80)/HT-2 (10)/BH1-1:BH2-1:BD-1 (25, 86:12:2% by mass)/ET-1 (10)/ET-2 (15)/LiF (1)/Al (80)
The numeral in each parenthesis is the thickness (nm).
The organic EL device thus produced was measured for the main peak wavelength λp and the lifetime LT90 in the following manners.
A spectral radiance spectrum was measured by applying direct voltage to the organic EL device so as to reach a current density of 10 mA/cm2. The main peak wavelength λp (unit of measure: nm) was determined from the obtained spectral radiance spectrum. The spectral radiance spectrum was measured by using a spectroradiometer CS-1000 manufactured by Konica Minolta.
A direct current was allowed to continuously flow the organic EL device at an initial current density of 50 mA/cm2 and the time taken until the luminance was reduced to 90% of the initial luminance was measured. The measured time was taken as the lifetime LT90.
The results are shown in Table 1.
Each organic EL device containing the first compound, the second compound, and the dopant material in the ratio by mass shown in Table 1 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1,
The materials used in Examples 1 to 13 and Comparative Examples 1 to 10 are shown below.
As compared with the single-host organic EL devices of Comparative Examples 1 to 10 each containing the first compound and the dopant material, the co-host organic EL devices of Examples 1 to 13 each containing the second compound in addition to the first compound and the dopant material had longer lifetimes. Namely, comparing the organic EL devices that are different from each other only in the presence or absence of the second compound, the organic EL devices of the invention showed longer lifetimes.
Like the single-host organic EL device, the co-host organic EL devices emitted light in a blue region.
Each organic EL device containing the first compound, the second compound, and the dopant material in the ratio by mass shown in Table 2 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.
The materials used in Examples 14 to 20 and Comparative Examples 11 to 13 are shown below.
As compared with the single-host organic EL devices of Comparative Examples 11 to 13 each containing the first compound and the dopant material, the co-host organic EL devices of Examples 14 to 20 each containing the second compound in addition to the first compound and the dopant material had longer lifetimes. Namely, comparing the organic EL devices that are different from each other only in the presence or absence of the second compound, the organic EL devices of the invention showed longer lifetimes.
Like the single-host organic EL device, the co-host organic EL devices emitted light in a blue region.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-074064 | Apr 2017 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2018/014284 | 4/3/2018 | WO | 00 |
