Patent Application
20240023436
The present invention relates to an organic electroluminescence device and an electronic device.
An organic electroluminescence device (hereinafter, occasionally referred to as “organic EL device”) has found its application in a full-color display for mobile phones, televisions and the like. When a voltage is applied to an organic EL device, holes and electrons are injected from an anode and a cathode, respectively, into an emitting layer. The injected holes and electrons are recombined in the emitting layer to form excitons. Specifically, according to the electron spin statistics theory, singlet excitons and triplet excitons are generated at a ratio of 25%:75%.
Various studies have been made for compounds to be used for the organic EL device in order to enhance the performance of the organic EL device (see, for instance, Patent Literature 1). The performance of the organic EL device is evaluable in terms of, for instance, luminance, emission wavelength, chromaticity, luminous efficiency, drive voltage, and lifetime.
An object of the invention is to provide an organic electroluminescence device with improved performance. Another object of the invention is to provide an organic electroluminescence device with improved luminous efficiency. Still another object of the invention is to provide an organic electroluminescence device emitting light with a long lifetime. A further object of the invention is to provide an electronic device including the organic electroluminescence device.
According to an aspect of the invention, there is provided an organic electroluminescence device including: an anode; a cathode; a first emitting layer provided between the anode and the cathode and containing a first compound; and a second emitting layer provided between the anode and the cathode and containing a second compound, in which at least one of the first emitting layer or the second emitting layer contains a compound having at least one deuterium atom, and at least one of the first emitting layer or the second emitting layer contains a compound having a fused ring that includes four or more rings.
According to another aspect of the invention, an electronic device including the organic electroluminescence device according to the above aspect of the invention is provided.
According to the above aspect of the invention, an organic electroluminescence device with enhanced performance can be provided. Further, according to the above aspect of the invention, an organic electroluminescence device with enhanced luminous efficiency can be provided. Furthermore, according to the above aspect of the invention, an organic electroluminescence device emitting light with a long lifetime can be provided. Moreover, according to the above aspect of the invention, an electronic device including the organic electroluminescence device can be provided.
Herein, a hydrogen atom includes isotope having different numbers of neutrons, specifically, protium, deuterium and tritium.
In chemical formulae herein, it is assumed that a hydrogen atom (i.e. protium, deuterium and tritium) is bonded to each of bondable positions that are not annexed with signs “R” or the like or “D” representing a deuterium.
Herein, the ring carbon atoms refer to the number of carbon atoms among atoms forming a ring of a compound (e.g., a monocyclic compound, fused-ring compound, cross-linking compound, carbon ring compound, and heterocyclic compound) in which the atoms are bonded to each other to form the ring. When the ring is substituted by a substituent(s), carbon atom(s) contained in the substituent(s) is not counted in the ring carbon atoms. Unless otherwise specified, the same applies to the “ring carbon atoms” described later. For instance, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridine ring has 5 ring carbon atoms, and a furan ring has 4 ring carbon atoms. Further, for instance, 9,9-diphenylfluorenyl group has 13 ring carbon atoms and 9,9′-spirobifluorenyl group has 25 ring carbon atoms.
When a benzene ring is substituted by a substituent in a form of, for instance, an alkyl group, the number of carbon atoms of the alkyl group is not counted in the number of the ring carbon atoms of the benzene ring. Accordingly, the benzene ring substituted by an alkyl group has 6 ring carbon atoms. When a naphthalene ring is substituted by a substituent in a form of, for instance, an alkyl group, the number of carbon atoms of the alkyl group is not counted in the number of the ring carbon atoms of the naphthalene ring. Accordingly, the naphthalene ring substituted by an alkyl group has 10 ring carbon atoms.
Herein, the ring atoms refer to the number of atoms forming a ring of a compound (e.g., a monocyclic compound, fused-ring compound, cross-linking compound, carbon ring compound, and heterocyclic compound) in which the atoms are bonded to each other to form the ring (e.g., monocyclic ring, fused ring, and ring assembly). Atom(s) not forming the ring (e.g., hydrogen atom(s) for saturating the valence of the atom which forms the ring) and atom(s) in a substituent by which the ring is substituted are not counted as the ring atoms. Unless otherwise specified, the same applies to the “ring atoms” described later. For instance, a pyridine ring has 6 ring atoms, a quinazoline ring has 10 ring atoms, and a furan ring has 5 ring atoms. For instance, the number of hydrogen atom(s) bonded to a pyridine ring or the number of atoms forming a substituent are not counted as the pyridine ring atoms. Accordingly, a pyridine ring bonded to a hydrogen atom(s) or a substituent(s) has 6 ring atoms. For instance, the hydrogen atom(s) bonded to carbon atom(s) of a quinazoline ring or the atoms forming a substituent are not counted as the quinazoline ring atoms. Accordingly, a quinazoline ring bonded to hydrogen atom(s) or a substituent(s) has 10 ring atoms.
Herein, “XX to YY carbon atoms” in the description of “substituted or unsubstituted ZZ group having XX to YY carbon atoms” represent carbon atoms of an unsubstituted ZZ group and do not include carbon atoms of a substituent(s) of the substituted ZZ group. Herein, “YY” is larger than “XX,” “XX” representing an integer of 1 or more and “YY” representing an integer of 2 or more.
Herein, “XX to YY atoms” in the description of “substituted or unsubstituted ZZ group having XX to YY atoms” represent atoms of an unsubstituted ZZ group and does not include atoms of a substituent(s) of the substituted ZZ group. Herein, “YY” is larger than “XX,” “XX” representing an integer of 1 or more and “YY” representing an integer of 2 or more.
Herein, an unsubstituted ZZ group refers to an “unsubstituted ZZ group” in a “substituted or unsubstituted ZZ group,” and a substituted ZZ group refers to a “substituted ZZ group” in a “substituted or unsubstituted ZZ group.”
Herein, the term “unsubstituted” used in a “substituted or unsubstituted ZZ group” means that a hydrogen atom(s) in the ZZ group is not substituted with a substituent(s). The hydrogen atom(s) in the “unsubstituted ZZ group” is protium, deuterium, or tritium.
Herein, the term “substituted” used in a “substituted or unsubstituted ZZ group” means that at least one hydrogen atom in the ZZ group is substituted with a substituent. Similarly, the term “substituted” used in a “BB group substituted by AA group” means that at least one hydrogen atom in the BB group is substituted with the AA group.
Substituents mentioned herein will be described below.
An “unsubstituted aryl group” mentioned herein has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
An “unsubstituted heterocyclic group” mentioned herein has, unless otherwise specified herein, 5 to 50, preferably 5 to 30, more preferably 5 to 18 ring atoms.
An “unsubstituted alkyl group” mentioned herein has, unless otherwise specified herein, 1 to 50, preferably 1 to 20, more preferably 1 to 6 carbon atoms.
An “unsubstituted alkenyl group” mentioned herein has, unless otherwise specified herein, 2 to 50, preferably 2 to 20, more preferably 2 to 6 carbon atoms.
An “unsubstituted alkynyl group” mentioned herein has, unless otherwise specified herein, 2 to 50, preferably 2 to 20, more preferably 2 to 6 carbon atoms.
An “unsubstituted cycloalkyl group” mentioned herein has, unless otherwise specified herein, 3 to 50, preferably 3 to 20, more preferably 3 to 6 ring carbon atoms.
An “unsubstituted arylene group” mentioned herein has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
An “unsubstituted divalent heterocyclic group” mentioned herein has, unless otherwise specified herein, 5 to 50, preferably 5 to 30, more preferably 5 to 18 ring atoms.
An “unsubstituted alkylene group” mentioned herein has, unless otherwise specified herein, 1 to 50, preferably 1 to 20, more preferably 1 to 6 carbon atoms.
Specific examples (specific example group G1) of the “substituted or unsubstituted aryl group” mentioned herein include unsubstituted aryl groups (specific example group G1A) below and substituted aryl groups (specific example group G11B). (Herein, an unsubstituted aryl group refers to an “unsubstituted aryl group” in a “substituted or unsubstituted aryl group”, and a substituted aryl group refers to a “substituted aryl group” in a “substituted or unsubstituted aryl group.”) A simply termed “aryl group” herein includes both of an “unsubstituted aryl group” and a “substituted aryl group.”
The “substituted aryl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted aryl group” with a substituent. Examples of the “substituted aryl group” include a group derived by substituting at least one hydrogen atom in the “unsubstituted aryl group” in the specific example group G1A below with a substituent, and examples of the substituted aryl group in the specific example group G1B below. It should be noted that the examples of the “unsubstituted aryl group” and the “substituted aryl group” mentioned herein are merely exemplary, and the “substituted aryl group” mentioned herein includes a group derived by further substituting a hydrogen atom bonded to a carbon atom of a skeleton of a “substituted aryl group” in the specific example group G1B below, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted aryl group” in the specific example group G1B below.
The “heterocyclic group” mentioned herein refers to a cyclic group having at least one hetero atom in the ring atoms. Specific examples of the hetero atom include a nitrogen atom, oxygen atom, sulfur atom, silicon atom, phosphorus atom, and boron atom.
The “heterocyclic group” mentioned herein is a monocyclic group or a fused-ring group.
The “heterocyclic group” mentioned herein is an aromatic heterocyclic group or a non-aromatic heterocyclic group.
Specific examples (specific example group G2) of the “substituted or unsubstituted heterocyclic group” mentioned herein include unsubstituted heterocyclic groups (specific example group G2A) and substituted heterocyclic groups (specific example group G2B). (Herein, an unsubstituted heterocyclic group refers to an “unsubstituted heterocyclic group” in a “substituted or unsubstituted heterocyclic group,” and a substituted heterocyclic group refers to a “substituted heterocyclic group” in a “substituted or unsubstituted heterocyclic group.”) A simply termed “heterocyclic group” herein includes both of “unsubstituted heterocyclic group” and “substituted heterocyclic group.”
The “substituted heterocyclic group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted heterocyclic group” with a substituent. Specific examples of the “substituted heterocyclic group” include a group derived by substituting at least one hydrogen atom in the “unsubstituted heterocyclic group” in the specific example group G2A below with a substituent, and examples of the substituted heterocyclic group in the specific example group G2B below. It should be noted that the examples of the “unsubstituted heterocyclic group” and the “substituted heterocyclic group” mentioned herein are merely exemplary, and the “substituted heterocyclic group” mentioned herein includes a group derived by further substituting a hydrogen atom bonded to a ring atom of a skeleton of a “substituted heterocyclic group” in the specific example group G2B below, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted heterocyclic group” in the specific example group G2B below.
The specific example group G2A includes, for instance, unsubstituted heterocyclic groups including a nitrogen atom (specific example group G2A1) below, unsubstituted heterocyclic groups including an oxygen atom (specific example group G2A2) below, unsubstituted heterocyclic groups including a sulfur atom (specific example group G2A3) below, and monovalent heterocyclic groups (specific example group G2A4) derived by removing a hydrogen atom from cyclic structures represented by formulae (TEMP-16) to (TEMP-33) below.
The specific example group G2B includes, for instance, substituted heterocyclic groups including a nitrogen atom (specific example group G2B1) below, substituted heterocyclic groups including an oxygen atom (specific example group G2B2) below, substituted heterocyclic groups including a sulfur atom (specific example group G2B3) below, and groups derived by substituting at least one hydrogen atom of the monovalent heterocyclic groups (specific example group G2B4) derived from the cyclic structures represented by formulae (TEMP-16) to (TEMP-33) below.
In the formulae (TEMP-16) to (TEMP-33), XA and YA are each independently an oxygen atom, a sulfur atom, NH or CH2, with a proviso that at least one of XA or YA is an oxygen atom, a sulfur atom, or NH.
When at least one of XA or YA in the formulae (TEMP-16) to (TEMP-33) is NH or CH2, the monovalent heterocyclic groups derived from the cyclic structures represented by the formulae (TEMP-16) to (TEMP-33) include a monovalent group derived by removing one hydrogen atom from NH or CH2.
The “at least one hydrogen atom of a monovalent heterocyclic group” means at least one hydrogen atom selected from a hydrogen atom bonded to a ring carbon atom of the monovalent heterocyclic group, a hydrogen atom bonded to a nitrogen atom of at least one of XA or YA in a form of NH, and a hydrogen atom of one of XA and YA in a form of a methylene group (CH2).
Specific examples (specific example group G3) of the “substituted or unsubstituted alkyl group” mentioned herein include unsubstituted alkyl groups (specific example group G3A) and substituted alkyl groups (specific example group G3B) below. (Herein, an unsubstituted alkyl group refers to an “unsubstituted alkyl group” in a “substituted or unsubstituted alkyl group,” and a substituted alkyl group refers to a “substituted alkyl group” in a “substituted or unsubstituted alkyl group.”) A simply termed “alkyl group” herein includes both of “unsubstituted alkyl group” and “substituted alkyl group.”
The “substituted alkyl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted alkyl group” with a substituent. Specific examples of the “substituted alkyl group” include a group derived by substituting at least one hydrogen atom of an “unsubstituted alkyl group” (specific example group G3A) below with a substituent, and examples of the substituted alkyl group (specific example group G3B) below. Herein, the alkyl group for the “unsubstituted alkyl group” refers to a chain alkyl group. Accordingly, the “unsubstituted alkyl group” include linear “unsubstituted alkyl group” and branched “unsubstituted alkyl group.” It should be noted that the examples of the “unsubstituted alkyl group” and the “substituted alkyl group” mentioned herein are merely exemplary, and the “substituted alkyl group” mentioned herein includes a group derived by further substituting a hydrogen atom of a skeleton of the “substituted alkyl group” in the specific example group G3B, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted alkyl group” in the specific example group G3B.
Specific examples (specific example group G4) of the “substituted or unsubstituted alkenyl group” mentioned herein include unsubstituted alkenyl groups (specific example group G4A) and substituted alkenyl groups (specific example group G4B). (Herein, an unsubstituted alkenyl group refers to an “unsubstituted alkenyl group” in a “substituted or unsubstituted alkenyl group,” and a substituted alkenyl group refers to a “substituted alkenyl group” in a “substituted or unsubstituted alkenyl group.”) A simply termed “alkenyl group” herein includes both of “unsubstituted alkenyl group” and “substituted alkenyl group.”
The “substituted alkenyl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted alkenyl group” with a substituent. Specific examples of the “substituted alkenyl group” include an “unsubstituted alkenyl group” (specific example group G4A) substituted by a substituent, and examples of the substituted alkenyl group (specific example group G4B) below. It should be noted that the examples of the “unsubstituted alkenyl group” and the “substituted alkenyl group” mentioned herein are merely exemplary, and the “substituted alkenyl group” mentioned herein includes a group derived by further substituting a hydrogen atom of a skeleton of the “substituted alkenyl group” in the specific example group G4B with a substituent, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted alkenyl group” in the specific example group G4B with a substituent.
The “substituted alkynyl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted alkynyl group” with a substituent. Specific examples of the “substituted alkynyl group” include a group derived by substituting at least one hydrogen atom of the “unsubstituted alkynyl group” (specific example group G5A) below with a substituent.
Unsubstituted Alkynyl Group (Specific Example Group G5A): ethynyl group.
Specific examples (specific example group G6) of the “substituted or unsubstituted cycloalkyl group” mentioned herein include unsubstituted cycloalkyl groups (specific example group G6A) and substituted cycloalkyl groups (specific example group G6B). (Herein, an unsubstituted cycloalkyl group refers to an “unsubstituted cycloalkyl group” in a “substituted or unsubstituted cycloalkyl group,” and a substituted cycloalkyl group refers to a “substituted cycloalkyl group” in a “substituted or unsubstituted cycloalkyl group.”) A simply termed “cycloalkyl group” herein includes both of “unsubstituted cycloalkyl group” and “substituted cycloalkyl group.”
The “substituted cycloalkyl group” refers to a group derived by substituting at least one hydrogen atom of an “unsubstituted cycloalkyl group” with a substituent. Specific examples of the “substituted cycloalkyl group” include a group derived by substituting at least one hydrogen atom of the “unsubstituted cycloalkyl group” (specific example group G6A) below with a substituent, and examples of the substituted cycloalkyl group (specific example group G6B) below. It should be noted that the examples of the “unsubstituted cycloalkyl group” and the “substituted cycloalkyl group” mentioned herein are merely exemplary, and the “substituted cycloalkyl group” mentioned herein includes a group derived by substituting at least one hydrogen atom bonded to a carbon atom of a skeleton of the “substituted cycloalkyl group” in the specific example group G6B with a substituent, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted cycloalkyl group” in the specific example group G6B with a substituent.
Specific examples (specific example group G7) of the group represented herein by —Si(R901)(R902)(R903) include: —Si(G1)(G1)(G1); —Si(G1)(G2)(G2); —Si(G1)(G1)(G2); —Si(G2)(G2)(G2); —Si(G3)(G3)(G3); and —Si(G6)(G6)(G6), where:
Specific examples (specific example group G8) of a group represented by —O—(R904) herein include: —O(G1); —O(G2); —O(G3); and —O(G6), where:
Specific examples (specific example group G9) of a group represented herein by —S—(R905) include: —S(G1); —S(G2); —S(G3); and —S(G6), where:
Specific examples (specific example group G10) of a group represented herein by —N(R906)(R907) include: —N(G1)(G1); —N(G2)(G2); —N(G1)(G2); —N(G3)(G3); and —N(G6)(G6), where:
Specific examples (specific example group G11) of “halogen atom” mentioned herein include a fluorine atom, chlorine atom, bromine atom, and iodine atom.
The “substituted or unsubstituted fluoroalkyl group” mentioned herein refers to a group derived by substituting at least one hydrogen atom bonded to at least one of carbon atoms forming an alkyl group in the “substituted or unsubstituted alkyl group” with a fluorine atom, and also includes a group (perfluoro group) derived by substituting all of hydrogen atoms bonded to carbon atoms forming the alkyl group in the “substituted or unsubstituted alkyl group” with fluorine atoms. An “unsubstituted fluoroalkyl group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, more preferably 1 to 18 carbon atoms. The “substituted fluoroalkyl group” refers to a group derived by substituting at least one hydrogen atom in a “fluoroalkyl group” with a substituent. It should be noted that the examples of the “substituted fluoroalkyl group” mentioned herein include a group derived by further substituting at least one hydrogen atom bonded to a carbon atom of an alkyl chain of a “substituted fluoroalkyl group” with a substituent, and a group derived by further substituting at least one hydrogen atom of a substituent of the “substituted fluoroalkyl group” with a substituent. Specific examples of the “substituted fluoroalkyl group” include a group derived by substituting at least one hydrogen atom of the “alkyl group” (specific example group G3) with a fluorine atom.
The “substituted or unsubstituted haloalkyl group” mentioned herein refers to a group derived by substituting at least one hydrogen atom bonded to carbon atoms forming the alkyl group in the “substituted or unsubstituted alkyl group” with a halogen atom, and also includes a group derived by substituting all hydrogen atoms bonded to carbon atoms forming the alkyl group in the “substituted or unsubstituted alkyl group” with halogen atoms. An “unsubstituted haloalkyl group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, and more preferably 1 to 18 carbon atoms. The “substituted haloalkyl group” refers to a group derived by substituting at least one hydrogen atom in a “haloalkyl group” with a substituent. It should be noted that the examples of the “substituted haloalkyl group” mentioned herein include a group derived by further substituting at least one hydrogen atom bonded to a carbon atom of an alkyl chain of a “substituted haloalkyl group” with a substituent, and a group derived by further substituting at least one hydrogen atom of a substituent of the “substituted haloalkyl group” with a substituent. Specific examples of the “substituted haloalkyl group” include a group derived by substituting at least one hydrogen atom of the “alkyl group” (specific example group G3) with a halogen atom. The haloalkyl group is sometimes referred to as a halogenated alkyl group.
Specific examples of a “substituted or unsubstituted alkoxy group” mentioned herein include a group represented by —O(G3), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3. An “unsubstituted alkoxy group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, more preferably 1 to 18 carbon atoms.
Specific examples of a “substituted or unsubstituted alkylthio group” mentioned herein include a group represented by —S(G3), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3. An “unsubstituted alkylthio group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, more preferably 1 to 18 carbon atoms.
Specific examples of a “substituted or unsubstituted aryloxy group” mentioned herein include a group represented by —O(G1), G1 being the “substituted or unsubstituted aryl group” in the specific example group G1. An “unsubstituted aryloxy group” has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
Specific examples of a “substituted or unsubstituted arylthio group” mentioned herein include a group represented by —S(G1), G1 being the “substituted or unsubstituted aryl group” in the specific example group G1. An “unsubstituted arylthio group” has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
Specific examples of a “trialkylsilyl group” mentioned herein include a group represented by —Si(G3)(G3)(G3), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3. The plurality of G3 in —Si(G3)(G3)(G3) are mutually the same or different. Each of the alkyl groups in the “trialkylsilyl group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 20, more preferably 1 to 6 carbon atoms.
Specific examples of a “substituted or unsubstituted aralkyl group” mentioned herein include a group represented by (G3)-(G1), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3, G1 being the “substituted or unsubstituted aryl group” in the specific example group G1. Accordingly, the “aralkyl group” is a group derived by substituting a hydrogen atom of the “alkyl group” with a substituent in a form of the “aryl group,” which is an example of the “substituted alkyl group.” An “unsubstituted aralkyl group,” which is an “unsubstituted alkyl group” substituted by an “unsubstituted aryl group,” has, unless otherwise specified herein, 7 to 50 carbon atoms, preferably 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms.
Specific examples of the “substituted or unsubstituted aralkyl group” include a benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, and 2-β-naphthylisopropyl group.
Preferable examples of the substituted or unsubstituted aryl group mentioned herein include, unless otherwise specified herein, a phenyl group, p-biphenyl group, m-biphenyl group, o-biphenyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-terphenyl-4-yl group, o-terphenyl-3-yl group, o-terphenyl-2-yl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, fluorenyl group, 9,9′-spirobifluorenyl group, 9,9-dimethylfluorenyl group, and 9,9-diphenylfluorenyl group.
Preferable examples of the substituted or unsubstituted heterocyclic group mentioned herein include, unless otherwise specified herein, a pyridyl group, pyrimidinyl group, triazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, benzimidazolyl group, phenanthrolinyl group, carbazolyl group (1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, or 9-carbazolyl group), benzocarbazolyl group, azacarbazolyl group, diazacarbazolyl group, dibenzofuranyl group, naphthobenzofuranyl group, azadibenzofuranyl group, diazadibenzofuranyl group, dibenzothiophenyl group, naphthobenzothiophenyl group, azadibenzothiophenyl group, diazadibenzothiophenyl group, (9-phenyl)carbazolyl group ((9-phenyl)carbazole-1-yl group, (9-phenyl)carbazole-2-yl group, (9-phenyl)carbazole-3-yl group, or (9-phenyl)carbazole-4-yl group), (9-biphenylyl)carbazolyl group, (9-phenyl)phenylcarbazolyl group, diphenylcarbazole-9-yl group, phenylcarbazole-9-yl group, phenyltriazinyl group, biphenylyltriazinyl group, diphenyltriazinyl group, phenyldibenzofuranyl group, and phenyldibenzothiophenyl group.
The carbazolyl group mentioned herein is, unless otherwise specified herein, specifically a group represented by one of formulae below.
The (9-phenyl)carbazolyl group mentioned herein is, unless otherwise specified herein, specifically a group represented by one of formulae below.
In the formulae (TEMP-Cz1) to (TEMP-Cz9), * represents a bonding position.
The dibenzofuranyl group and dibenzothiophenyl group mentioned herein are, unless otherwise specified herein, each specifically represented by one of formulae below.
In the formulae (TEMP-34) to (TEMP-41), * represents a bonding position.
Preferable examples of the substituted or unsubstituted alkyl group mentioned herein include, unless otherwise specified herein, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.
The “substituted or unsubstituted arylene group” mentioned herein is, unless otherwise specified herein, a divalent group derived by removing one hydrogen atom on an aryl ring of the “substituted or unsubstituted aryl group.” Specific examples of the “substituted or unsubstituted arylene group” (specific example group G12) include a divalent group derived by removing one hydrogen atom on an aryl ring of the “substituted or unsubstituted aryl group” in the specific example group G1.
The “substituted or unsubstituted divalent heterocyclic group” mentioned herein is, unless otherwise specified herein, a divalent group derived by removing one hydrogen atom on a heterocycle of the “substituted or unsubstituted heterocyclic group.” Specific examples of the “substituted or unsubstituted divalent heterocyclic group” (specific example group G13) include a divalent group derived by removing one hydrogen atom on a heterocyclic ring of the “substituted or unsubstituted heterocyclic group” in the specific example group G2.
The “substituted or unsubstituted alkylene group” mentioned herein is, unless otherwise specified herein, a divalent group derived by removing one hydrogen atom on an alkyl chain of the “substituted or unsubstituted alkyl group.” Specific examples of the “substituted or unsubstituted alkylene group” (specific example group G14) include a divalent group derived by removing one hydrogen atom on an alkyl chain of the “substituted or unsubstituted alkyl group” in the specific example group G3.
The substituted or unsubstituted arylene group mentioned herein is, unless otherwise specified herein, preferably any one of groups represented by formulae (TEMP-42) to (TEMP-68) below.
In the formulae (TEMP-42) to (TEMP-52), Q1 to Q10 each independently are a hydrogen atom or a substituent.
In the formulae (TEMP-42) to (TEMP-52), * represents a bonding position.
In the formulae (TEMP-53) to (TEMP-62), Q1 to Q10 each independently are a hydrogen atom or a substituent.
In the formulae, Q9 and Q10 may be mutually bonded through a single bond to form a ring.
In the formulae (TEMP-53) to (TEMP-62), * represents a bonding position.
In the formulae (TEMP-63) to (TEMP-68), Q1 to Q8 each independently are a hydrogen atom or a substituent.
In the formulae (TEMP-63) to (TEMP-68), * represents a bonding position.
The substituted or unsubstituted divalent heterocyclic group mentioned herein is, unless otherwise specified herein, preferably a group represented by any one of formulae (TEMP-69) to (TEMP-102) below.
In the formulae (TEMP-69) to (TEMP-82), Q1 to Q9 each independently are a hydrogen atom or a substituent.
In the formulae (TEMP-83) to (TEMP-102), Q1 to Qs each independently are a hydrogen atom or a substituent.
The substituent mentioned herein has been described above.
Instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring, mutually bonded to form a substituted or unsubstituted fused ring, or not mutually bonded” mentioned herein refer to instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring, “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted fused ring,” and “at least one combination of adjacent two or more (of . . . ) are not mutually bonded.”
Instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring” and “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted fused ring” mentioned herein (these instances will be sometimes collectively referred to as an instance of “bonded to form a ring” hereinafter) will be described below. An anthracene compound having a basic skeleton in a form of an anthracene ring and represented by a formula (TEMP-103) below will be used as an example for the description.
For instance, when “at least one combination of adjacent two or more of R921 to R930 are mutually bonded to form a ring,” the combination of adjacent ones of R921 to R930 (i.e. the combination at issue) is a combination of R921 and R922, a combination of R922 and R923, a combination of R923 and R924, a combination of R924 and R930, a combination of R930 and R925, a combination of R925 and R926, a combination of R926 and R927, a combination of R927 and R928, a combination of R928 and R929, or a combination of R929 and R921.
The term “at least one combination” means that two or more of the above combinations of adjacent two or more of R921 to R930 may simultaneously form rings. For instance, when R921 and R922 are mutually bonded to form a ring QA and R925 and R926 are simultaneously mutually bonded to form a ring QB, the anthracene compound represented by the formula (TEMP-103) is represented by a formula (TEMP-104) below.
The instance where the “combination of adjacent two or more” form a ring means not only an instance where the “two” adjacent components are bonded but also an instance where adjacent “three or more” are bonded. For instance, R921 and R922 are mutually bonded to form a ring QA and R922 and R923 are mutually bonded to form a ring Qc, and mutually adjacent three components (R921, R922 and R923) are mutually bonded to form a ring fused to the anthracene basic skeleton. In this case, the anthracene compound represented by the formula (TEMP-103) is represented by a formula (TEMP-105) below. In the formula (TEMP-105) below, the ring QA and the ring QC share R922.
The formed “monocyclic ring” or “fused ring” may be, in terms of the formed ring in itself, a saturated ring or an unsaturated ring. When the “combination of adjacent two” form a “monocyclic ring” or a “fused ring,” the “monocyclic ring” or “fused ring” may be a saturated ring or an unsaturated ring. For instance, the ring QA and the ring QB formed in the formula (TEMP-104) are each independently a “monocyclic ring” or a “fused ring.” Further, the ring QA and the ring Qc formed in the formula (TEMP-105) are each a “fused ring.” The ring QA and the ring Qc in the formula (TEMP-105) are fused to form a fused ring. When the ring QA in the formula (TEMP-104) is a benzene ring, the ring QA is a monocyclic ring. When the ring QA in the formula (TEMP-104) is a naphthalene ring, the ring QA is a fused ring.
The “unsaturated ring” represents an aromatic hydrocarbon ring or an aromatic heterocycle. The “saturated ring” represents an aliphatic hydrocarbon ring or a non-aromatic heterocycle.
Specific examples of the aromatic hydrocarbon ring include a ring formed by terminating a bond of a group in the specific example of the specific example group G1 with a hydrogen atom.
Specific examples of the aromatic heterocycle include a ring formed by terminating a bond of an aromatic heterocyclic group in the specific example of the specific example group G2 with a hydrogen atom.
Specific examples of the aliphatic hydrocarbon ring include a ring formed by terminating a bond of a group in the specific example of the specific example group G6 with a hydrogen atom.
The phrase “to form a ring” herein means that a ring is formed only by a plurality of atoms of a basic skeleton, or by a combination of a plurality of atoms of the basic skeleton and one or more optional atoms. For instance, the ring QA formed by mutually bonding R921 and R922 shown in the formula (TEMP-104) is a ring formed by a carbon atom of the anthracene skeleton bonded to R921, a carbon atom of the anthracene skeleton bonded to R922, and one or more optional atoms. Specifically, when the ring QA is a monocyclic unsaturated ring formed by R921 and R922, the ring formed by a carbon atom of the anthracene skeleton bonded to R921, a carbon atom of the anthracene skeleton bonded to R922, and four carbon atoms is a benzene ring.
The “optional atom” is, unless otherwise specified herein, preferably at least one atom selected from the group consisting of a carbon atom, nitrogen atom, oxygen atom, and sulfur atom. A bond of the optional atom (e.g. a carbon atom and a nitrogen atom) not forming a ring may be terminated by a hydrogen atom or the like or may be substituted by an “optional substituent” described later. When the ring includes an optional element other than carbon atom, the resultant ring is a heterocycle.
The number of “one or more optional atoms” forming the monocyclic ring or fused ring is, unless otherwise specified herein, preferably in a range from 2 to 15, more preferably in a range from 3 to 12, further preferably in a range from 3 to 5.
Unless otherwise specified herein, the ring, which may be a “monocyclic ring” or “fused ring,” is preferably a “monocyclic ring.”
Unless otherwise specified herein, the ring, which may be a “saturated ring” or “unsaturated ring,” is preferably an “unsaturated ring.”
Unless otherwise specified herein, the “monocyclic ring” is preferably a benzene ring.
Unless otherwise specified herein, the “unsaturated ring” is preferably a benzene ring.
When “at least one combination of adjacent two or more” (of . . . ) are “mutually bonded to form a substituted or unsubstituted monocyclic ring” or “mutually bonded to form a substituted or unsubstituted fused ring,” unless otherwise specified herein, at least one combination of adjacent two or more of components are preferably mutually bonded to form a substituted or unsubstituted “unsaturated ring” formed of a plurality of atoms of the basic skeleton, and 1 to 15 atoms of at least one element selected from the group consisting of carbon, nitrogen, oxygen and sulfur.
When the “monocyclic ring” or the “fused ring” has a substituent, the substituent is the substituent described in later-described “optional substituent.” When the “monocyclic ring” or the “fused ring” has a substituent, specific examples of the substituent are the substituents described in the above under the subtitle “Substituent Mentioned Herein.”
When the “saturated ring” or the “unsaturated ring” has a substituent, the substituent is the substituent described in later-described “optional substituent.” When the “monocyclic ring” or the “fused ring” has a substituent, specific examples of the substituent are the substituents described in the above under the subtitle “Substituent Mentioned Herein.”
The above is the description for the instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring” and “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted fused ring” mentioned herein (sometimes referred to as an instance of “bonded to form a ring”).
In an exemplary embodiment herein, a substituent for the substituted or unsubstituted group (sometimes referred to as an “optional substituent” hereinafter) is, for instance, a group selected from the group consisting of an unsubstituted alkyl group having 1 to 50 carbon atoms, an unsubstituted alkenyl group having 2 to 50 carbon atoms, an unsubstituted alkynyl group having 2 to 50 carbon atoms, an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, —Si(R901)(R902)(R903), —O—(R904), —S—(R905), —N(R906)(R907), a halogen atom, a cyano group, a nitro group, an unsubstituted aryl group having 6 to 50 ring carbon atoms, and an unsubstituted heterocyclic group having 5 to 50 ring atoms; R901 to R907 each independently are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
In an exemplary embodiment, a substituent for the substituted or unsubstituted group is selected from the group consisting of an alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 ring carbon atoms, and a heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, a substituent for the substituted or unsubstituted group is selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 ring carbon atoms, and a heterocyclic group having 5 to 18 ring atoms.
Specific examples of the above optional substituent are the same as the specific examples of the substituent described in the above under the subtitle “Substituent Mentioned Herein.”
Unless otherwise specified herein, adjacent ones of the optional substituents may form a “saturated ring” or an “unsaturated ring,” preferably a substituted or unsubstituted saturated five-membered ring, a substituted or unsubstituted saturated six-membered ring, a substituted or unsubstituted unsaturated five-membered ring, or a substituted or unsubstituted unsaturated six-membered ring, more preferably a benzene ring.
Unless otherwise specified herein, the optional substituent may further include a substituent. Examples of the substituent for the optional substituent are the same as the examples of the optional substituent.
Herein, numerical ranges represented by “AA to BB” represent a range whose lower limit is the value (AA) recited before “to” and whose upper limit is the value (BB) recited after “to.”
An organic electroluminescence device according to a first exemplary embodiment includes: an anode; a cathode; a first emitting layer provided between the anode and the cathode and containing a first compound; and a second emitting layer provided between the anode and the cathode and containing a second compound, in which at least one of the first emitting layer or the second emitting layer contains a compound having at least one deuterium atom, and at least one of the first emitting layer or the second emitting layer contains a compound having a fused ring that includes four or more rings.
The fused ring that includes four or more rings means that the number of rings forming the fused ring is four or more. For example, phenyl-substituted anthracene has an anthracene ring having three rings and a benzene ring having one ring. The number of rings forming the fused ring, however, is three. Thus, phenyl-substituted anthracene does not have a fused ring that includes four or more rings.
When the organic EL device according to the exemplary embodiment contains a plurality of compounds each of which has a fused ring including four or more rings, the fused rings in the plurality of compounds are mutually the same or different.
The fused ring that includes four or more rings is preferably a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heterocycle, and more preferably a substituted or unsubstituted aromatic hydrocarbon ring. The four or more rings included in the fused ring are mutually the same or different. The four or more rings included in the fused ring are preferably each independently a five-membered ring or a six-membered ring. The fused ring that includes four or more rings may include both a five-membered ring and a six-membered ring. The fused ring that includes four or more rings includes, for instance, fluoranthene.
In the organic electroluminescence device according to the exemplary embodiment, at least one of the first emitting layer or the second emitting layer preferably contains a compound having a fused ring that includes 4 or more and 14 or less rings, and more preferably contains a compound having a fused ring that includes 4 or more and 10 or less rings.
In the organic electroluminescence device according to the exemplary embodiment, a structure of the first compound is the same as or different from a structure of the second compound, preferably the first compound and the second compound are different in structure.
In the organic electroluminescence device according to the exemplary embodiment, at least one of the first emitting layer or the second emitting layer preferably contains a compound having at least one deuterium atom and having a fused ring that includes four or more rings.
In the organic electroluminescence device according to the exemplary embodiment, at least the first emitting layer preferably contains a compound having at least one deuterium atom.
In the organic electroluminescence device according to the exemplary embodiment, the first compound also preferably has at least one deuterium atom.
In the organic electroluminescence device according to the exemplary embodiment, the first compound also preferably has a fused ring that includes four or more rings.
In the organic electroluminescence device according to the exemplary embodiment, the first compound also preferably has at least one deuterium atom and a fused ring that includes four or more rings.
In the organic electroluminescence device according to the exemplary embodiment, the second compound also preferably has at least one deuterium atom.
In the organic electroluminescence device according to the exemplary embodiment, the second compound also preferably has a fused ring that includes four or more rings.
In the organic electroluminescence device according to the exemplary embodiment, the second compound also preferably has at least one deuterium atom and a fused ring that includes four or more rings.
In the organic electroluminescence device according to the exemplary embodiment, the first compound in the first emitting layer and the second compound in the second emitting layer preferably satisfy any of conditions for Device A1 to Device A9 shown in Table 1 below.
In columns of “Having fused ring that includes four or more rings” of Table 1, “Y” means that a compound has a fused ring that includes four or more rings, and “N” means that a compound does not have a fused ring that includes four or more rings.
In columns of “Having at least one deuterium atom” of Table 1, “Y” means that a compound has at least one deuterium atom, and “N” means that a compound has no deuterium atom.
For instance, Device A1 of Table 1 means that the first emitting layer contains the first compound having at least one deuterium atom and a fused ring that includes four or more rings, and the second emitting layer contains the second compound having at least one deuterium atom and a fused ring that includes four or more rings.
For instance, Device A3 of Table 1 means that the first emitting layer contains the first compound having at least one deuterium atom and a fused ring that includes four or more rings, and the second emitting layer contains the second compound not having a fused ring that includes four or more rings and having at least one deuterium atom.
In the organic electroluminescence device according to the exemplary embodiment, a compound not having a fused ring that includes four or more rings is at least one of a compound having a fused ring that includes two or three rings or a compound having a monocyclic ring formed by one ring.
The fused ring that includes two or three rings and the monocyclic ring are preferably each independently a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heterocycle, and more preferably each independently a substituted or unsubstituted aromatic hydrocarbon ring. The two or three rings included in the fused ring are mutually the same or different. The two or three rings included in the fused ring and the monocyclic ring are preferably each independently a five-membered ring or a six-membered ring.
In the organic electroluminescence device according to the exemplary embodiment, a compound not having a fused ring that includes four or more rings is preferably a compound having a fused ring that includes two or three rings, and also preferably a compound having a monocyclic ring and a fused ring that includes two or three rings.
In the organic electroluminescence device according to the exemplary embodiment, it is also preferable that one of the first compound and the second compound substantially has no deuterium atom.
In an exemplary embodiment, only one of the first emitting layer and the second emitting layer contains a compound having at least one deuterium atom, and the other of the first emitting layer and the second emitting layer does not substantially contain a compound having a deuterium atom.
Here, “emitting layer does not substantially contain a compound having a deuterium atom” means that the emitting layer contains no deuterium atom or that the emitting layer is allowed to contain a deuterium atom approximately at the natural abundance ratio. The natural abundance ratio of the deuterium atom (mole fraction or atomic fraction) is, for instance, 0.015% or less.
That is, “emitting layer contains a compound having at least one deuterium atom” means that the emitting layer contains a compound having a deuterium atom at a content exceeding the natural abundance ratio.
Whether the compound has a deuterium atom is verified by mass spectrometry or 1H-NMR spectrometry. A bonding position of a deuterium atom in the compound is specified by the 1H-NMR spectrometry. Details are described below.
Mass spectrometry is performed on a target compound. When a molecular weight of the target compound is increased by, for example, one as compared with a related compound in which all the hydrogen atoms in the target compound are replaced by protium atoms, it can be determined that the target compound has a deuterium atom. Further, since a signal of a deuterium atom does not appear in 1H-NMR spectrometry, the number of deuterium atoms in a molecule can be determined by an integral value obtained by performing 1H-NMR spectrometry on the target compound. Furthermore, a bonding position of a deuterium atom can be determined by conducting 1H-NMR spectrometry on the target compound to perform signal assignment.
In the organic electroluminescence device according to the exemplary embodiment, the first compound preferably has at least one skeleton selected from the group consisting of a pyrene skeleton, benzanthracene skeleton, xanthene skeleton, chrysene skeleton, fluoranthene skeleton, benzofluoranthene skeleton, triphenylene skeleton, benzoxanthene skeleton, benzophenanthrene skeleton, and benzochrysene skeleton. Each of the above skeletons may have a substituent.
In the organic electroluminescence device according to the exemplary embodiment, the second compound preferably has at least one skeleton selected from the group consisting of a pyrene skeleton, benzanthracene skeleton, xanthene skeleton, chrysene skeleton, fluoranthene skeleton, benzofluoranthene skeleton, triphenylene skeleton, benzoxanthene skeleton, benzophenanthrene skeleton, and benzochrysene skeleton. Each of the above skeletons may have a substituent.
In an exemplary embodiment, the first compound and the second compound have or do not have the same skeleton.
In the organic electroluminescence device according to the exemplary embodiment, the compound having the fused ring that includes four or more rings preferably has no anthracene skeleton.
In an exemplary embodiment, the compound having the fused ring that includes four or more rings is a compound represented by a formula (1) below and having at least one group represented by a formula (11) below.
In the formula (1)
In the compound represented by the formula (1), R901, R902, R903, R904, R905, R906, R907, R801 and R802 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
In the organic electroluminescence device according to the exemplary embodiment, at least one of R101 to R110 not being the group represented by the formula (11) is also preferably a deuterium atom.
In the organic electroluminescence device according to the exemplary embodiment, L101 also preferably has at least one deuterium atom.
In the organic electroluminescence device according to the exemplary embodiment, Ar101 also preferably has at least one deuterium atom.
In the organic EL device according to the exemplary embodiment, the group represented by the formula (11) is preferably a group represented by a formula (111) below.
In the formula (111):
Among positions *1 to *8 of carbon atoms in a cyclic structure represented by a formula (111a) below in a group represented by the formula (111), L111 is bonded to one of the positions *1 to *4, R121 is bonded to each of three positions of the rest of *1 to *4, L112 is bonded to one of the positions *5 to *8, and R122 is bonded to each of three positions of the rest of *5 to *8.
For instance, in the group represented by the formula (111), when L111 is bonded to a carbon atom at a position *2 in the cyclic structure represented by the formula (111a) and L112 is bonded to a carbon atom at a position *7 in the cyclic structure represented by the formula (111a), the group represented by the formula (111) is represented by a formula (111b) below.
In the formula (111b):
In the organic EL device according to the exemplary embodiment, the group represented by the formula (111) is preferably a group represented by the formula (111b).
In the organic EL device according to the exemplary embodiment, it is preferable that ma is 0, 1, or 2 and mb is 0, 1, or 2.
In the organic EL device according to the exemplary embodiment, it is preferable that ma is 0 or 1 and mb is 0 or 1.
In the organic EL device according to the exemplary embodiment, Ar101 is preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, Ar101 is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted fluorenyl group.
In the organic EL device according to the exemplary embodiment, Ar101 is also preferably a group represented by a formula (12), a formula (13), or a formula (14) below.
In the formulae (12), (13), and (14):
In the organic EL device according to the exemplary embodiment, the compound represented by the formula (1) is preferably represented by a formula (101) below.
In the formula (101):
In a compound represented by the formula (101), it is preferable that:
In the organic EL device according to the exemplary embodiment, the compound represented by the formula (1) is preferably represented by a formula (1010), a formula (1011), a formula (1012), a formula (1013), a formula (1014), or a formula (1015) below.
In the formulae (1010) to (1015):
The compound represented by the formula (1010) corresponds to a compound, in which R103 represents a bonding position to L101 and R120 represents a bonding position to L101.
The compound represented by the formula (1011) corresponds to a compound, in which R103 represents a bonding position to L101 and R111 represents a bonding position to L101.
The compound represented by the formula (1012) corresponds to a compound, in which R103 represents a bonding position to L101 and R118 represents a bonding position to L101.
The compound represented by the formula (1013) corresponds to a compound, in which R102 represents a bonding position to L101 and R111 represents a bonding position to L101.
The compound represented by the formula (1014) corresponds to a compound, in which R102 represents a bonding position to L101 and R118 represents a bonding position to L101.
The compound represented by the formula (1015) corresponds to a compound, in which R105 represents a bonding position to L101 and R118 represents a bonding position to L101.
In the organic EL device according to the exemplary embodiment, the compound represented by the formula (1) is preferably represented by the formula (1010).
In the organic EL device according to the exemplary embodiment, R101 to R110 not being the bonding position to L101 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the organic EL device according to the exemplary embodiment, R101 to R110 not being the bonding position to L101 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, R101 to R110 not being the bonding position to L101 are each preferably a hydrogen atom.
In the organic EL device according to the exemplary embodiment, R111 to R120 not being the bonding position to L101 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the organic EL device according to the exemplary embodiment, R111 to R120 not being the bonding position to L101 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, R111 to R120 not being the bonding position to L101 are each preferably a hydrogen atom.
In the organic EL device according to the exemplary embodiment, L101 is preferably a single bond, or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, L101 is also preferably a single bond, a substituted or unsubstituted arylene group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 18 ring atoms.
In the organic EL device according to the exemplary embodiment, L101 is also preferably a single bond, or a substituted or unsubstituted arylene group having 6 to 18 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, L101 is also preferably a substituted or unsubstituted arylene group having 6 to 18 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, L101 is also preferably a single bond, a substituted or unsubstituted arylene group having 6 to 13 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 13 ring atoms.
In the organic EL device according to the exemplary embodiment, L101 is also preferably a single bond, or a substituted or unsubstituted arylene group having 6 to 13 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, L101 is also preferably a substituted or unsubstituted arylene group having 6 to 13 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, mx is also preferably 1, 2, or 3.
In the organic EL device according to the exemplary embodiment, mx is also preferably 1 or 2.
In the organic EL device according to the exemplary embodiment, it is also preferable that mx is 1, 2, or 3; and L101 is a substituted or unsubstituted arylene group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 18 ring atoms.
In the organic EL device according to the exemplary embodiment, it is also preferable that mx is 1 or 2; and L101 is a substituted or unsubstituted arylene group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 18 ring atoms.
In the organic EL device according to the exemplary embodiment, it is also preferable that mx is 1 or 2; and L101 is a substituted or unsubstituted arylene group having 6 to 18 ring carbon atoms.
In the organic electroluminescence device according to the exemplary embodiment, it is preferable that at least one of R101 to R110 not being the bonding position to L111 is a deuterium atom; and at least one of R111 to R120 not being the bonding position to L112 is a deuterium atom.
In the organic EL device according to the exemplary embodiment, the compound represented by the formula (1) is also preferably represented by a formula (102) below.
In the formula (102):
In the compound represented by the formula (102), it is preferable that ma is 0, 1, or 2; and mb is 0, 1, or 2.
In the compound represented by the formula (102), it is preferable that ma is 0 or 1; and mb is 0 or 1.
In the compound represented by the formula (102), L111 and L112 are preferably each independently a single bond, a substituted or unsubstituted arylene group having 6 to 24 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 24 ring atoms.
In the compound represented by the formula (102), ma is 1, 2, or 3; mb is 1, 2, or 3; and ma+mb is 2, 3, or 4.
In the compound represented by the formula (102), it is preferable that ma is 1 or 2; and mb is 1 or 2.
In the compound represented by the formula (102), it is preferable that ma is 1; and mb is 1.
In the organic EL device according to the exemplary embodiment, R101 to R110 not being the bonding position to L111 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the organic EL device according to the exemplary embodiment, R101 to R110 not being the bonding position to L111 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, R101 to R110 not being the bonding position to L111 are each preferably a hydrogen atom.
In the organic EL device according to the exemplary embodiment, R111 to R120 not being the bonding position to L112 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the organic EL device according to the exemplary embodiment, R111 to R120 not being the bonding position to L112 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, R111 to R120 not being the bonding position to L112 are each preferably a hydrogen atom.
In the organic EL device of the exemplary embodiment, two or more of R101 to R110 are each preferably a group represented by the formula (11).
In the organic EL device according to the exemplary embodiment, it is preferable that two or more of R101 to R110 are each a group represented by the formula (11); and Ar101 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, it is also preferable that:
In the organic EL device according to the exemplary embodiment, it is preferable that R101 to R110 not being the group represented by the formula (11) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the organic EL device according to the exemplary embodiment, it is preferable that R101 to R110 not being the group represented by the formula (11) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, R101 to R110 not being the group represented by the formula (11) are each preferably a hydrogen atom.
In the organic EL device according to the exemplary embodiment, for instance, two of R101 to R110 in the compound represented by the formula (1) are each a group represented by the formula (11).
In the organic EL device according to the exemplary embodiment, for instance, three of R101 to R110 in the compound represented by the formula (1) are each a group represented by the formula (11).
In the organic EL device according to the exemplary embodiment, for instance, four of R101 to R110 in the compound represented by the formula (1) are each a group represented by the formula (11).
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), and mx is 1 or more.
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), mx is 0, and Ar101 is a substituted or unsubstituted aryl group.
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), mx is 0, and Ar101 is a substituted or unsubstituted heterocyclic group including a nitrogen atom.
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), mx is 0, and Ar101 is a substituted or unsubstituted heterocyclic group including a sulfur atom.
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), mx is 0, and Ar101 is a substituted or unsubstituted furyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, xanthenyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, benzoxazolyl group, benzisoxazolyl group, phenoxazinyl group, morpholino group, dinaphthofuranyl group, azadibenzofuranyl group, diazadibenzofuranyl group, azanaphthobenzofuranyl group, and diazanaphthobenzofuranyl group.
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), mx is 0, and Ar101 is at least one group selected from the group consisting of unsubstituted furyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, xanthenyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, benzoxazolyl group, benzisoxazolyl group, phenoxazinyl group, morpholino group, dinaphthofuranyl group, azadibenzofuranyl group, diazadibenzofuranyl group, azanaphthobenzofuranyl group, and diazanaphthobenzofuranyl group.
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), mx is 0, and Ar101 is a substituted or unsubstituted dibenzofuranyl group.
In the organic EL device according to the exemplary embodiment, for instance, one of R101 to R110 in the compound represented by the formula (1) is a group represented by the formula (11), mx is 0, and Ar101 is an unsubstituted dibenzofuranyl group.
In the organic EL device according to the exemplary embodiment, for instance, mx in the compound represented by the formula (101) is 2 or more.
In the organic EL device according to the exemplary embodiment, for instance, mx in the compound represented by the formula (101) is 1 or more, and L101 is an arylene group having 6 to 24 ring carbon atoms or a divalent heterocyclic group having 5 to 24 ring atoms.
In the organic EL device according to the exemplary embodiment, for instance, mx in the compound represented by the formula (101) is 1 or more, and L101 is an arylene group having 6 to 18 ring carbon atoms or a divalent heterocyclic group having 5 to 18 ring atoms.
The compound represented by the formula (1) can be manufactured by a known method. The compound represented by the formula (1) can also be manufactured based on a known method through a known alternative reaction using a known material(s) tailored for the target compound.
Specific examples of the compound represented by the formula (1) include the following compounds. It should however be noted that the invention is not limited to the specific examples.
In the specific examples of the compound herein, D represents a deuterium atom, Me represents a methyl group, and tBu represents a tert-butyl group.
In an exemplary embodiment, the compound having the fused ring that includes four or more rings is a compound represented by a formula (1X) below and having at least one group represented by a formula (11X) below.
In the formula (1X):
In the compound represented by the formula (1X), R901, R902, R903, R904, R905, R801 and R802 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
In the compound represented by the formula (1X), at least one of R1101 to R1112 not being the group represented by the formula (11X) is also preferably a deuterium atom.
In the compound represented by the formula (1X), L1101 also preferably has at least one deuterium atom.
In the compound represented by the formula (1X), Ar1101 also preferably has at least one deuterium atom.
In the compound represented by the formula (1X), Ar1101 is preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (1X), Ar1101 is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted benz[a]anthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted fluorenyl group.
The compound represented by the formula (1X) is also preferably represented by a formula (101X) below.
In the formula (101X):
In the compound represented by the formula (1X), L1101 is preferably a single bond, or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (1X), the group represented by the formula (11X) is also preferably a group represented by a formula (11AX) below or a group represented by a formula (11 BX) below.
In the formulae (11AX) and (11BX):
The compound represented by the formula (1X) is also preferably represented by a formula (103X) below.
In the formula (103X):
In the compound represented by the formula (1X), L1131 is also preferably a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (1X), L1132 is also preferably a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (1X), it is also preferable that two or more of R1101 to R1112 are each a group represented by the formula (11X).
In the compound represented by the formula (1X), it is preferable that two or more of R1101 to R1112 are each a group represented by the formula (11X); and Ar1101 in the formula (11X) is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (1X), it is also preferable that R1111 and R1112 are each a group represented by the formula (11X).
The compound represented by the formula (1X) is also preferably represented by a formula (1101X) below.
In the formula (1101X), R1101 to R1110 each independently represent the same as R1101 to R1110 in the formula (1X); Ar1141 and Ar1142 each independently represent the same as Ar1101 in the formula (11X); L1141 and L1142 each independently represent the same as L1101 in the formula (11X); and mx11 and mx12 each independently represent the same as mx1 in the formula (11X).
In the compound represented by the formula (1X), it is also preferable that Ar1101 is not a substituted or unsubstituted benz[a]anthryl group; L1101 is not a substituted or unsubstituted benz[a]anthrylene group; and the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms as R1101 to R1110 not being the group represented by the formula (11X) is not a substituted or unsubstituted benz[a]anthryl group.
In the compound represented by the formula (1X), R1101 to R1112 not being the group represented by the formula (11X) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the compound represented by the formula (1X), R1101 to R1112 not being the group represented by the formula (11X) are each preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
In the compound represented by the formula (1X), R1101 to R1112 not being the group represented by the formula (11X) are each preferably a hydrogen atom.
The compound represented by the formula (1X) can be manufactured by a known method. The compound represented by the formula (1X) can also be manufactured based on a known method through a known alternative reaction using a known material(s) tailored for the target compound.
Specific examples of the compound represented by the formula (1X) include the following compounds. It should however be noted that the invention is not limited to the specific examples.
In an exemplary embodiment, the compound having the fused ring that includes four or more rings is a compound represented by a formula (14X) below and having at least one group represented by a formula (141) below.
In the formula (14X):
In the compound represented by the formula (14X), R901, R902, R903, R904, R905, R801 and R802 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
In the compound represented by the formula (14X), at least one of R1401 to R1410 not being the group represented by the formula (141) is also preferably a deuterium atom.
In the compound represented by the formula (14X), L1401 also preferably has at least one deuterium atom.
In the compound represented by the formula (14X), Ar1401 also preferably has at least one deuterium atom.
In the compound represented by the formula (14X), Ar1401 is preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (14X), it is also preferable that two or more of R1401 to R1410 are each a group represented by the formula (141).
In the compound represented by the formula (14X), it is preferable that two or more of R1401 to R1410 are each a group represented by the formula (141); and Ar1401 in the formula (141) is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (14X), L1401 is preferably a single bond, or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In the compound represented by the formula (14X), R1401 to R1410 not being the group represented by the formula (141) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the compound represented by the formula (14X), R1401 to R1410 not being the group represented by the formula (141) are each preferably a hydrogen atom.
The compound represented by the formula (14X) can be manufactured by a known method. The compound represented by the formula (14X) can also be manufactured based on a known method through a known alternative reaction using a known material(s) tailored for the target compound.
Specific examples of the compound represented by the formula (14X) include the following compounds. It should however be noted that the invention is not limited to the specific examples.
In the organic electroluminescence device according to the exemplary embodiment, the second emitting layer preferably contains a compound represented by a formula (2) below.
In the formula (2):
In the compound represented by the formula (2), R901, R902, R903, R904, R905, R906, R907, R801 and R802 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
In the organic EL device according to the exemplary embodiment, it is preferable that:
In the organic EL device according to the exemplary embodiment, it is preferable that:
In the organic EL device according to the exemplary embodiment, it is preferable that Ar201 and Ar202 are each independently a phenyl group, naphthyl group, phenanthryl group, biphenyl group, terphenyl group, diphenylfluorenyl group, dimethylfluorenyl group, benzodiphenylfluorenyl group, benzodimethylfluorenyl group, dibenzofuranyl group, dibenzothienyl group, naphthobenzofuranyl group, or naphthobenzothienyl group.
In the organic EL device according to the exemplary embodiment, at least one group of L201, L202, Ar201, or Ar202 preferably has at least one deuterium atom.
In the organic EL device according to the exemplary embodiment, at least one of Ar201 or Ar202 is also preferably a group represented by a formula (21), a formula (22), a formula (23), or a formula (24) below.
In the formulae (21) to (24),
At least one of R211 to R214 or R216 to R219 is preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms that has at least one deuterium atom, more preferably a substituted or unsubstituted phenyl group having at least one deuterium atom, and further preferably a phenyl group having four deuterium atoms.
In the organic EL device according to the exemplary embodiment, at least one of L201 or L202 is also preferably a group represented by a formula (L21), a formula (L22), a formula (L23), or a formula (L24) below.
In the formulae (L21) to (L24),
At least one of R221 to R224 or R226 to R229 is preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms that has at least one deuterium atom, more preferably a substituted or unsubstituted phenyl group having at least one deuterium atom, and further preferably a phenyl group having four deuterium atoms.
In the organic EL device according to the exemplary embodiment, the compound represented by the formula (2) is preferably a compound represented by a formula (201), a formula (202), a formula (203), a formula (204), a formula (205), a formula (206), a formula (207), a formula (208), or a formula (209) below.
In the formulae (201) to (209):
The compound represented by the formula (2) is also preferably a compound represented by a formula (221), a formula (222), a formula (223), a formula (224), a formula (225), a formula (226), a formula (227), a formula (228), or a formula (229) below.
In the formulae (221), (222), (223), (224), (225), (226), (227), (228) and (229):
The compound represented by the formula (2) is also preferably a compound represented by a formula (241), a formula (242), a formula (243), a formula (244), a formula (245), a formula (246), a formula (247), a formula (248), or a formula (249) below.
In the formulae (241), (242), (243), (244), (245), (246), (247), (248) and (249):
In the compound represented by the formula (2), R201 to R208 not being the group represented by the formula (21) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, or a group represented by —Si(R901)(R902)(R903).
It is preferable that L101 is a single bond, or an unsubstituted arylene group having 6 to 22 ring carbon atoms; and Ar101 is a substituted or unsubstituted aryl group having 6 to 22 ring carbon atoms.
In the organic EL device according to the exemplary embodiment, R201 to R208 in the compound represented by the formula (2) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, or a group represented by —Si(R901)(R902)(R903).
In the organic EL device according to the exemplary embodiment, R201 to R208 in the compound represented by the formula (2) are each preferably a hydrogen atom.
In the compound represented by the formula (2), the groups specified to be “substituted or unsubstituted” are each preferably an “unsubstituted” group.
In the organic EL device according to the exemplary embodiment, for instance, Ar201 in the compound represented by the formula (2) is a substituted or unsubstituted dibenzofuranyl group.
In the organic EL device according to the exemplary embodiment, for instance, Ar201 in the second compound represented by the formula (2) is an unsubstituted dibenzofuranyl group.
In the organic EL device according to the exemplary embodiment, for instance, the compound represented by the formula (2) has at least one hydrogen atom that includes at least one deuterium atom.
In the organic EL device according to the exemplary embodiment, the compound represented by the formula (2) preferably has at least one deuterium atom.
In the organic EL device according to the exemplary embodiment, at least one of R201 to R208 is preferably a deuterium atom.
In the organic EL device according to the exemplary embodiment, at least one of L201 or L202 preferably has at least one deuterium atom.
In the organic electroluminescence device according to the exemplary embodiment, at least one of Ar201 or Ar202 preferably has at least one deuterium atom.
In the organic EL device according to the exemplary embodiment, for instance, L201 in the compound represented by the formula (2) is one of TEMP-63 to TEMP-68
In the organic EL device according to the exemplary embodiment, for instance, Ar201 in the compound represented by the formula (2) is at least one group selected from the group consisting of substituted or unsubstituted anthryl group, benzanthryl group, phenanthryl group, benzophenanthryl group, phenalenyl group, pyrenyl group, chrysenyl group, benzochrysenyl group, triphenylenyl group, benzotriphenylenyl group, tetracenyl group, pentacenyl group, fluoranthenyl group, benzofluoranthenyl group, and perylenyl group.
In the organic EL device according to the exemplary embodiment, for instance, Ar201 in the compound represented by the formula (2) is a substituted or unsubstituted fluorenyl group.
In the organic EL device according to the exemplary embodiment, for instance, Ar201 in the compound represented by the formula (2) is a substituted or unsubstituted xanthenyl group.
In the organic EL device according to the exemplary embodiment, for instance, Ar201 in the compound represented by the formula (2) is a benzoxanthenyl group.
The compound represented by the formula (2) can be manufactured by a known method. The second compound can also be manufactured based on a known method through a known alternative reaction using a known material(s) tailored for the target compound.
Specific examples of the compound represented by the formula (2) include the following compounds. It should however be noted that the invention is not limited to the specific examples.
In the organic EL device according to the exemplary embodiment, it is also preferable that the first emitting layer further contains a third compound that emits fluorescence.
In the organic EL device according to the exemplary embodiment, it is also preferable that the second emitting layer further contains a fourth compound that emits fluorescence.
When the first emitting layer contains the third compound and the second emitting layer contains the fourth compound, the third compound and the fourth compound are mutually the same or different.
The third compound and the fourth compound are each independently at least one compound selected from the group consisting of a compound represented by a formula (3), a compound represented by a formula (4), a compound represented by a formula (5), a compound represented by a formula (6), a compound represented by a formula (7), a compound represented by a formula (8), a compound represented by a formula (9), and a compound represented by a formula (10).
The compound represented by the formula (3) will be described.
In the formula (3):
In the formula (31):
In the third and fourth compounds, R901, R902, R903, R904, R905, R906, and R907 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
In the formula (3), it is preferable that two of R301 to R310 are each a group represented by the formula (31).
In an exemplary embodiment, the compound represented by the formula (3) is a compound represented by a formula (33) below.
In the formula (33):
In the formula (31), L301 is preferably a single bond, and L302 and L303 are each preferably a single bond.
In an exemplary embodiment, the compound represented by the formula (3) is represented by a formula (34) or a formula (35) below.
In the formula (34):
In the formula (35):
In the formula (31), at least one of Ar301 or Ar302 is preferably a group represented by a formula (36) below.
In the formulae (33) to (35), at least one of Ar312 or Ar313 is preferably a group represented by the formula (36) below.
In the formulae (33) to (35), at least one of Ar315 or Ar316 is preferably a group represented by the formula (36) below.
In the formula (36):
X3 is preferably an oxygen atom.
At least one of R321 to R327 is preferably a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the formula (31), it is preferable that Ar301 is a group represented by the formula (36); and Ar302 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the formulae (33) to (35), it is preferable that Ar312 is a group represented by the formula (36); and Ar313 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the formulae (33) to (35), it is preferable that Ar315 is a group represented by the formula (36); and Ar316 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the compound represented by the formula (3) is represented by a formula (37) below.
In the formula (37):
Specific examples of the compound represented by the formula (3) include compounds shown below.
The compound represented by the formula (4) will be described.
In the formula (4):
The “aromatic hydrocarbon ring” for the A1 ring and A2 ring has the same structure as a compound formed by introducing a hydrogen atom to the “aryl group” described above.
Ring atoms of the “aromatic hydrocarbon ring” for the A1 ring and the A2 ring include two carbon atoms on a fused bicyclic structure at the center of the formula (4).
Specific examples of the “substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms” include a compound formed by introducing a hydrogen atom to the “aryl group” described in the specific example group G1.
The “heterocycle” for the A1 ring and A2 ring has the same structure as a compound formed by introducing a hydrogen atom to the “heterocyclic group” described above.
Ring atoms of the “heterocycle” for the A1 ring and the A2 ring include two carbon atoms on a fused bicyclic structure at the center of the formula (4).
Specific examples of the “substituted or unsubstituted heterocycle having 5 to 50 ring atoms” include a compound formed by introducing a hydrogen atom to the “heterocyclic group” described in the specific example group G2.
Rb is bonded to any one of carbon atoms forming the aromatic hydrocarbon ring for the A1 ring or any one of the atoms forming the heterocycle for the A1 ring.
Rc is bonded to any one of carbon atoms forming the aromatic hydrocarbon ring for the A2 ring or any one of the atoms forming the heterocycle for the A2 ring.
At least one of Ra, Rb, or Rc is preferably a group represented by a formula (4a) below. More preferably, at least two of Ra, Rb, and Rc are each a group represented by the formula (4a).
[Formula 482]
*-L401-Ar401 (4)
In the formula (4a):
In the formula (4b):
In an exemplary embodiment, the compound represented by the formula (4) is represented by a formula (42) below.
In the formula (42):
At least one of R401 to R411 is preferably a group represented by the formula (4a). More preferably, at least two of R401 to R411 are each a represented by the formula (4a).
In an exemplary embodiment, the compound represented by the formula (4) is a compound formed by bonding a structure represented by a formula (4-1) or a formula (4-2) below to the A1 ring.
Further, in an exemplary embodiment, the compound represented by the formula (42) is a compound formed by bonding a structure represented by the formula (4-1) or the formula (4-2) to the ring bonded with R404 to R407.
In the formula (4-1), two bonds * are each independently bonded to a ring-forming carbon atom of the aromatic hydrocarbon ring or a ring atom of the heterocycle for the A1 ring in the formula (4) or bonded to one of R404 to R407 in the formula (42).
In the formula (4-2), three bonds * are each independently bonded to a ring-forming carbon atom of the aromatic hydrocarbon ring or a ring atom of the heterocycle for the A1 ring in the formula (4) or bonded to one of R404 to R407 in the formula (42);
In an exemplary embodiment, the compound represented by the formula (4) is a compound represented by a formula (41-3), a formula (41-4), or a formula (41-5) below.
In the formulae (41-3), (41-4) and (41-5):
In an exemplary embodiment, a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms for the A1 ring in the formula (41-5) is a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted fluorene ring.
In an exemplary embodiment, a substituted or unsubstituted heterocycle having 5 to 50 ring atoms for the A1 ring in the formula (41-5) is a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted carbazole ring, or a substituted or unsubstituted dibenzothiophene ring.
In an exemplary embodiment, the compound represented by the formula (4) or the formula (42) is selected from the group consisting of compounds represented by formulae (461) to (467) below.
In the formulae (461), (462), (463), (464), (465), (466) and (467):
In an exemplary embodiment, in the compound represented by the formula (42), at least one combination of adjacent two or more of R401 to R411 are mutually bonded to form a substituted or unsubstituted monocyclic ring or a substituted or unsubstituted fused ring. The compound represented by the formula (42) in the exemplary embodiment is described in detail as a compound represented by a formula (45).
The compound represented by the formula (45) will be described.
In the formula (45):
In the formula (45), Rn and Rn+1 (n being an integer selected from 461, 462, 464 to 466, and 468 to 470) are mutually bonded to form a substituted or unsubstituted monocyclic ring or fused ring together with two ring-forming carbon atoms bonded with Rn and Rn+1. The ring is preferably formed of atoms selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom, and is preferably made of 3 to 7, more preferably 5 or 6 atoms.
The number of the above cyclic structures in the compound represented by the formula (45) is, for instance, 2, 3, or 4. The two or more of the cyclic structures may be present on the same benzene ring on the basic skeleton represented by the formula (45) or may be present on different benzene rings. For instance, when three cyclic structures are present, each of the cyclic structures may be present on corresponding one of the three benzene rings of the formula (45).
Examples of the above cyclic structures in the compound represented by the formula (45) include structures represented by formulae (451) to (460) below.
In the formulae (451) to (457):
In the formulae (458) to (460):
In the formula (45), it is preferable that at least one of R462, R464, R465, R470 or R471 (preferably, at least one of R462, R465 or R470, more preferably R462) is a group forming no cyclic structure.
In the formulae (461) to (464):
In the third and fourth compounds, R901 to R907 represent the same as those as described above.
In an exemplary embodiment, the compound represented by the formula (45) is represented by one of formulae (45-1) to (45-6) below.
In the formulae (45-1) to (45-6):
In an exemplary embodiment, the compound represented by the formula (45) is represented by one of formulae (45-7) to (45-12) below.
In the formulae (45-7) to (45-12):
In an exemplary embodiment, the compound represented by the formula (45) is represented by one of formulae (45-13) to (45-21) below.
In the formulae (45-13) to (45-21):
When the ring g or the ring h further has a substituent, examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a group represented by the formula (461), a group represented by the formula (463), and a group represented by the formula (464).
In an exemplary embodiment, the compound represented by the formula (45) is represented by one of formulae (45-22) to (45-25) below.
In the formulae (45-22) to (45-25):
In an exemplary embodiment, the compound represented by the formula (45) is represented by a formula (45-26) below.
In the formula (45-26):
Specific examples of the compound represented by the formula (4) include compounds shown below. In the specific examples below, Ph represents a phenyl group, and D represents a deuterium atom.
The compound represented by the formula (5) will be described. The compound represented by the formula (5) corresponds to a compound represented by the formula (41-3).
In the formula (5):
“A combination of adjacent two or more of R501 to R507 and R511 to R517” refers to, for instance, a combination of R501 and R502, a combination of R502 and R503, a combination of R503 and R504, a combination of R505 and R506, a combination of R506 and R507, and a combination of R501, R502, and R503.
In an exemplary embodiment, at least one, preferably two of R501 to R507 and R511 to R517 are groups represented by —N(R906)(R907).
In an exemplary embodiment, R501 to R507 and R511 to R517 are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compound represented by the formula (5) is a compound represented by a formula (52) below.
In the formula (52):
In an exemplary embodiment, the compound represented by the formula (5) is a compound represented by a formula (53) below.
In the formula (53), R551, R552 and R561 to R564 each independently represent the same as R551, R552 and R561 to R564 in the formula (52).
In an exemplary embodiment, R561 to R564 in the formulae (52) and (53) are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms (preferably a phenyl group).
In an exemplary embodiment, R521 and R522 in the formula (5) and R551 and R552 in the formulae (52) and (53) are each a hydrogen atom.
In an exemplary embodiment, the substituent for the “substituted or unsubstituted” group in the formulae (5), (52) and (53) is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Specific examples of the compound represented by the formula (5) include compounds shown below.
In the formulae, Ph is a phenyl group.
The compound represented by the formula (6) will be described.
In the formula (6):
The a ring, b ring and c ring are each a ring (a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocycle having 5 to 50 ring atoms) fused with a fused bicyclic structure formed of a boron atom and two nitrogen atoms at the center of the formula (6).
The “aromatic hydrocarbon ring” for the a, b, and c rings has the same structure as a compound formed by introducing a hydrogen atom to the “aryl group” described above.
Specific examples of the “substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms” include a compound formed by introducing a hydrogen atom to the “aryl group” described in the specific example group G1.
The “heterocycle” for the a, b, and c rings has the same structure as a compound formed by introducing a hydrogen atom to the “heterocyclic group” described above.
Ring atoms of the “heterocycle” for the a ring include three carbon atoms on the fused bicyclic structure at the center of the formula (6). Ring atoms of the “heterocycle” for the b ring and c ring include two carbon atoms on the fused bicyclic structure at the center of the formula (6). Specific examples of the “substituted or unsubstituted heterocycle having 5 to 50 ring atoms” include a compound formed by introducing a hydrogen atom to the “heterocyclic group” described in the specific example group G2.
R601 and R602 are optionally each independently bonded with the a ring, b ring, or c ring to form a substituted or unsubstituted heterocycle. The “heterocycle” in this arrangement includes a nitrogen atom on the fused bicyclic structure at the center of the formula (6). The heterocycle in the above arrangement optionally includes a hetero atom other than the nitrogen atom. R601 and R602 bonded with the a ring, b ring, or c ring specifically means that atoms forming R601 and R602 are bonded with atoms forming the a ring, b ring, or c ring. For instance, R601 may be bonded with the a ring to form a bicyclic (or tri-or-more cyclic) fused nitrogen-containing heterocycle, in which the ring including R601 and the a ring are fused. Specific examples of the nitrogen-containing heterocycle include a compound corresponding to the nitrogen-containing bi(or-more)cyclic fused heterocyclic group in the specific example group G2.
The same applies to R601 bonded with the b ring, R602 bonded with the a ring, and R602 bonded with the c ring.
In an exemplary embodiment, the a ring, b ring and c ring in the formula (6) are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the a ring, b ring and c ring in the formula (6) are each independently a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring.
In an exemplary embodiment, R601 and R602 in the formula (6) are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the compound represented by the formula (6) is a compound represented by a formula (62) below.
In the formula (62):
R601A and R602A in the formula (62) are groups corresponding to R601 and R602 in the formula (6), respectively.
For instance, R601A and R611 are optionally bonded with each other to form a bicyclic (or tri-or-more cyclic) fused nitrogen-containing heterocycle, in which the ring including R601A and R611 and a benzene ring corresponding to the a ring are fused. Specific examples of the nitrogen-containing heterocycle include a compound corresponding to the nitrogen-containing bi(or-more)cyclic fused heterocyclic group in the specific example group G2. The same applies to R601A bonded with R621, R602A bonded with R613, and R602A bonded with R614.
At least one combination of adjacent two or more of R611 to R621 may be mutually bonded to form a substituted or unsubstituted monocyclic ring, or mutually bonded to form a substituted or unsubstituted fused ring.
For instance, R611 and R612 are optionally mutually bonded to form a structure in which a benzene ring, indole ring, pyrrole ring, benzofuran ring, benzothiophene ring or the like is fused to the six-membered ring bonded with R611 and R612, the resultant fused ring forming a naphthalene ring, carbazole ring, indole ring, dibenzofuran ring, or dibenzothiophene ring, respectively.
In an exemplary embodiment, R611 to R621 not contributing to ring formation are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R611 to R621 not contributing to ring formation are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R611 to R621 not contributing to ring formation are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, R611 to R621 not contributing to ring formation are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and
In an exemplary embodiment, the compound represented by the formula (62) is a compound represented by a formula (63) below.
In the formula (63):
R631 are optionally bonded with R646 to form a substituted or unsubstituted heterocycle. For instance, R631 and R646 are optionally bonded with each other to form a tri-or-more cyclic fused nitrogen-containing heterocycle, in which a benzene ring bonded with R646, a ring including a nitrogen atom, and a benzene ring corresponding to the a ring are fused. Specific examples of the nitrogen-containing heterocycle include a compound corresponding to the nitrogen-containing tri(-or-more)cyclic fused heterocyclic group in the specific example group G2. The same applies to R633 bonded with R647, R634 bonded with R651, and R641 bonded with R642.
In an exemplary embodiment, R631 to R651 not contributing to ring formation are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R631 to R651 not contributing to ring formation are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R631 to R651 not contributing to ring formation are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, R631 to R651 not contributing to ring formation are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and
In an exemplary embodiment, the compound represented by the formula (63) is a compound represented by a formula (63A) below.
In the formula (63A):
In an exemplary embodiment, R661 to R665 are each independently a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R661 to R665 are each independently a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, the compound represented by the formula (63) is a compound represented by a formula (63B) below.
In the formula (63B):
In an exemplary embodiment, the compound represented by the formula (63) is a compound represented by a formula (63B′) below.
In the formula (63B′), R672 to R675 each independently represent the same as R672 to R675 in the formula (63B).
In an exemplary embodiment, at least one of R671 to R675 is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a group represented by —N(R906)(R907), or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R672 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a group represented by —N(R906)(R907), or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; and
In an exemplary embodiment, the compound represented by the formula (63) is a compound represented by a formula (63C) below.
In the formula (63C):
In an exemplary embodiment, the compound represented by the formula (63) is a compound represented by a formula (63C′) below.
In the formula (63C′), R683 to R686 each independently represent the same as R683 to R686 in the formula (63C).
In an exemplary embodiment, R681 to R686 are each independently a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R681 to R686 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
The compound represented by the formula (6) is producible by initially bonding the a ring, b ring and c ring with linking groups (a group including N—R601 and a group including N—R602) to form an intermediate (first reaction), and bonding the a ring, b ring and c ring with a linking group (a group including a boron atom) to form a final product (second reaction). In the first reaction, an amination reaction (e.g. Buchwald-Hartwig reaction) is applicable. In the second reaction, Tandem Hetero-Friedel-Crafts Reactions or the like is applicable.
Specific examples of the compound represented by the formula (6) are shown below. It should however be noted that these specific examples are merely exemplary and do not limit the compound represented by the formula (6).
The compound represented by the formula (7) will be described below.
In the formula (7):
In the formula (7), each of the p ring, q ring, r ring, s ring, and t ring is fused with an adjacent ring(s) sharing two carbon atoms. The fused position and orientation are not limited but may be defined as required.
In an exemplary embodiment, in the formula (72) or the formula (73) representing the r ring, m1=0 or m2=0 is satisfied.
In an exemplary embodiment, the compound represented by the formula (7) is represented by any one of formulae (71-1) to (71-6) below.
In the formulae (71-1) to (71-6), R701, X7, Ar701, Ar702, L701, m1 and m3 respectively represent the same as R701, X7, Ar701, Ar702, L701, m1 and m3 in the formula (7).
In an exemplary embodiment, the compound represented by the formula (7) is represented by any one of formulae (71-11) to (71-13) below.
In the formulae (71-11) to (71-13), R701, X7, Ar701, Ar702, L701, m1, m3 and m4 respectively represent the same as R701, X7, Ar701, Ar702, L701, m1, m3 and m4 in the formula (7).
In an exemplary embodiment, the compound represented by the formula (7) is represented by any one of formulae (71-21) to (71-25) below.
In the formulae (71-21) to (71-25), R701, X7, Ar701, Ar702, L701, m1 and m4 respectively represent the same as R701, X7, Ar701, Ar702, L701, m1 and m4 in the formula (7).
In an exemplary embodiment, the compound represented by the formula (7) is represented by any one of formulae (71-31) to (71-33) below.
In the formulae (71-31) to (71-33), R701, X7, Ar701, Ar702, L701, and m2 to m4 respectively represent the same as R701, X7, Ar701, Ar702, L701, and m2 to m4 in the formula (7).
In an exemplary embodiment, Ar701 and Ar702 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, one of Ar701 and Ar702 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and the other of Ar701 and
Ar702 is a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Specific examples of the compound represented by the formula (7) include compounds shown below.
The compound represented by the formula (8) will be described below.
In the formula (8):
At least one of R801 to R804 not forming the divalent group represented by the formula (82) or R811 to R814 is a monovalent group represented by a formula (84) below;
In the formula (84):
In the formula (8), the positions for the divalent group represented by the formula (82) and the divalent group represented by the formula (83) to be formed are not specifically limited but the divalent groups may be formed at any possible positions on R801 to R808.
In an exemplary embodiment, the compound represented by the formula (8) is represented by any one of formulae (81-1) to (81-6) below.
In the formulae (81-1) to (81-6):
In an exemplary embodiment, the compound represented by the formula (8) is represented by any one of formulae (81-7) to (81-18) below.
In the formulae (81-7) to (81-18):
R801 to R8os not forming the divalent group represented by the formula (82) or (83) and not being the monovalent group represented by the formula (84), and R811 to R814 and R821 to R824 not being the monovalent group represented by the formula (84) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
The monovalent group represented by the formula (84) is preferably represented by a formula (85) or (86) below.
In the formula (85):
In the formula (86):
In the formula (87):
Specific examples of the compound represented by the formula (8) include compounds shown below as well as the compounds disclosed in WO 2014/104144.
The compound represented by the formula (9) will be described below.
In the formula (9):
In the formula (92):
At least one ring selected from the group consisting of A91 ring and A92 ring is bonded to a bond * of a structure represented by the formula (92). In other words, the ring-forming carbon atoms of the aromatic hydrocarbon ring or the ring atoms of the heterocycle of the A91 ring in an exemplary embodiment are bonded to the bonds * in a structure represented by the formula (92). Further, the ring-forming carbon atoms of the aromatic hydrocarbon ring or the ring atoms of the heterocycle of the A92 ring in an exemplary embodiment are bonded to the bonds * in a structure represented by the formula (92).
In an exemplary embodiment, a group represented by a formula (93) below is bonded to one or both of the A91 ring and A92 ring.
In the formula (93):
In an exemplary embodiment, in addition to the A91 ring, the ring-forming carbon atoms of the aromatic hydrocarbon ring or the ring atoms of the heterocycle of the A92 ring are bonded to * in a structure represented by the formula (92). In this case, the structures represented by the formula (92) may be mutually the same or different.
In an exemplary embodiment, R91 and R92 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R91 and R92 are mutually bonded to form a fluorene structure.
In an exemplary embodiment, the rings A91 and A92 are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, example of which is a substituted or unsubstituted benzene ring.
In an exemplary embodiment, the ring A93 is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, example of which is a substituted or unsubstituted benzene ring.
In an exemplary embodiment, X9 is an oxygen atom or a sulfur atom.
Specific examples of the compound represented by the formula (9) include compounds shown below.
The compound represented by the formula (10) will be described below.
In the formula (10):
Ax1 ring is a ring represented by the formula (10a) and fused with adjacent ring(s) at any position(s);
In an exemplary embodiment, Ar1001 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, Ax3 ring is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, example of which is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted anthracene ring.
In an exemplary embodiment, R1003 and R1004 are each independently a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, ax is 1.
Specific examples of the compound represented by the formula (10) include compounds shown below.
In an exemplary embodiment, the emitting layer contains, as at least one of the third compound or the fourth compound, at least one compound selected from the group consisting of a compound represented by the formula (4), a compound represented by the formula (5), a compound represented by the formula (7), a compound represented by the formula (8), a compound represented by the formula (9), and a compound represented by a formula (63a ) below.
In the formula (63a ):
In an exemplary embodiment, the compound represented by the formula (4) is a compound represented by the formula (41-3), the formula (41-4), or the formula (41-5), the A1 ring in the formula (41-5) being a substituted or unsubstituted fused aromatic hydrocarbon ring having 10 to 50 ring carbon atoms, or a substituted or unsubstituted fused heterocycle having 8 to 50 ring atoms.
In an exemplary embodiment, the substituted or unsubstituted fused aromatic hydrocarbon ring having 10 to 50 ring carbon atoms in the formulae (41-3), (41-4) and (41-5) is a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, or a substituted or unsubstituted fluorene ring; and
In an exemplary embodiment, the substituted or unsubstituted fused aromatic hydrocarbon ring having 10 to 50 ring carbon atoms in the formula (41-3), (41-4) or (41-5) is a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted fluorene ring; and
In an exemplary embodiment, the compound represented by the formula (4) is selected from the group consisting of a compound represented by a formula (461) below, a compound represented by a formula (462) below, a compound represented by a formula (463) below, a compound represented by a formula (464) below, a compound represented by a formula (465) below, a compound represented by a formula (466) below, and a compound represented by a formula (467) below.
In the formulae (461) to (467):
In an exemplary embodiment, R421 to R427 and R440 to R445 are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R421 to R427 and R440 to R447 are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms, and a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In an exemplary embodiment, the compound represented by the formula (41-3) is a compound represented by a formula (41-3-1) below.
In the formula (41-3-1), R423, R425, R426, R442, R444 and R445 each independently represent the same as R423, R425, R426, R442, R444 and R445 in the formula (41-3).
In an exemplary embodiment, the compound represented by the formula (41-3) is a compound represented by a formula (41-3-2) below.
In the formula (41-3-2):
In an exemplary embodiment, two of R421 to R427 and R440 to R446 in the formula (41-3-2) are each a group represented by —N(R906)(R907).
In an exemplary embodiment, the compound represented by the formula (41-3-2) is a compound represented by a formula (41-3-3) below.
In the formula (41-3-3):
In an exemplary embodiment, the compound represented by the formula (41-3-3) is a compound represented by a formula (41-3-4) below.
In the formula (41-3-4), R447, R448, RA, RB, RC and RD each independently represent the same as R447, R448, RA, RB, RC and RD in the formula (41-3-3).
In an exemplary embodiment, RA, RB, RC, and RD are each independently a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms.
In an exemplary embodiment, RA, RB, RC, and RD are each independently a substituted or unsubstituted phenyl group.
In an exemplary embodiment, R447 and R448 are each a hydrogen atom.
In an exemplary embodiment, the substituent for “the substituted or unsubstituted” group in each of the formulae is an unsubstituted alkyl group having 1 to 50 carbon atoms, an unsubstituted alkenyl group having 2 to 50 carbon atoms, an unsubstituted alkynyl group having 2 to 50 carbon atoms, an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, —Si(R901a)(R902a)(R903a), —O—(R904a), —S—(R905a), —N(R906a)(R907a), a halogen atom, a cyano group, a nitro group, an unsubstituted aryl group having 6 to 50 ring carbon atoms, or an unsubstituted heterocyclic group having 5 to 50 ring atoms;
In an exemplary embodiment, the substituent “for the substituted or unsubstituted” group in each of the formulae is an unsubstituted alkyl group having 1 to 50 carbon atoms, an unsubstituted aryl group having 6 to 50 ring carbon atoms, or an unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the substituent for “the substituted or unsubstituted” group in each of the formulae is an unsubstituted alkyl group having 1 to 18 carbon atoms, an unsubstituted aryl group having 6 to 18 ring carbon atoms, or an unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the organic electroluminescence device according to the exemplary embodiment, it is preferable that the first emitting layer further contains the third compound; and the third compound is a compound that emits light having a maximum peak wavelength in a range from 430 nm to 480 nm. The third compound in the first emitting layer is more preferably a compound that emits fluorescence. The third compound is more preferably a compound that emits fluorescence having a maximum peak wavelength in a range from 430 nm to 480 nm.
In the organic electroluminescence device according to the exemplary embodiment, it is preferable that the second emitting layer further contains the fourth compound; and the fourth compound is a compound that emits light having a maximum peak wavelength in a range from 430 nm to 480 nm. The fourth compound in the second emitting layer is more preferably a compound that emits fluorescence. The fourth compound is more preferably a compound that emits fluorescence having a maximum peak wavelength in a range from 430 nm to 480 nm.
A measurement method of the maximum peak wavelength of a compound is as follows. A toluene solution of a measurement target compound at a concentration ranging from 10−6 mol/L to 10−5 mol/L is prepared and put in a quartz cell. An emission spectrum (ordinate axis: luminous intensity, abscissa axis: wavelength) of the thus-obtained sample is measured at a normal temperature (300K). The emission spectrum is measurable using a spectrophotometer (machine name: F-7000) manufactured by Hitachi High-Tech Science Corporation. It should be noted that the machine for measuring the emission spectrum is not limited to the machine used herein.
A peak wavelength of the emission spectrum exhibiting the maximum luminous intensity is defined as a maximum peak wavelength. Herein, the maximum peak wavelength of fluorescence is occasionally referred to as a maximum fluorescence peak wavelength (FL-peak).
In the organic electroluminescence device according to the exemplary embodiment, the groups specified to be “substituted or unsubstituted” are each preferably an “unsubstituted” group.
In the first compound and the second compound according to the exemplary embodiment, the groups specified to be “substituted or unsubstituted” are each preferably an “unsubstituted” group.
In the organic electroluminescence device according to the exemplary embodiment, the first compound is preferably a host material. The first compound as a host material is occasionally referred to as a first host material.
When the first emitting layer of the organic EL device according to the exemplary embodiment contains the first compound and the third compound, the first compound is preferably a host material (occasionally also referred to as a matrix material) and the third compound is preferably a dopant material (occasionally also referred to as a guest material, emitter or luminescent material).
When the first emitting layer of the organic EL device according to the exemplary embodiment contains the first compound and the third compound, a singlet energy S1(H1) of the first compound and a singlet energy S1(D3) of the third compound preferably satisfy a relationship of a numerical formula (Numerical Formula 1) below.
S1(H1)>S1(D3) (Numerical Formula 1)
The singlet energy S1 means an energy difference between the lowest singlet state and the ground state.
In the organic electroluminescence device according to the exemplary embodiment, the second compound is preferably a host material. The second compound as a host material is occasionally referred to as a second host material.
In the organic EL device according to the exemplary embodiment, when the second emitting layer contains the second compound and the fourth compound, the second compound is preferably a host material (occasionally also referred to as a matrix material) and the fourth compound is preferably a dopant material (occasionally also referred to as a guest material, emitter or luminescent material).
When the second emitting layer of the organic EL device according to the exemplary embodiment contains the second compound and the fourth compound, a singlet energy S1(H2) of the second compound and a singlet energy S1(D4) of the fourth compound preferably satisfy a relationship of a numerical formula (Numerical Formula 2) below.
S1(H2)>S1(D4) (Numerical Formula 2)
In the organic EL device according to the exemplary embodiment, it is also preferable that the first emitting layer contains the first host material as the first compound and a dopant material as the third compound (occasionally referred to as a first dopant material); and the second emitting layer contains the second host material as the second compound and a dopant material as the fourth compound (occasionally referred to as a second dopant material).
Herein, the “host material” refers to, for instance, a material that accounts for “50 mass % or more of the layer.” The first emitting layer thus contains, for instance, 50 mass % or more of the first compound with respect to a total mass of the first emitting layer. The second emitting layer contains, for instance, 50 mass % or more of the second compound with respect to a total mass of the second emitting layer. Further, for instance, the “host material” may account for 60 mass % or more of the layer, 70 mass % or more of the layer, 80 mass % or more of the layer, 90 mass % or more of the layer, or 95 mass % or more of the layer.
The compound having at least one deuterium atom is preferably at least one of a host material or a dopant material. In an exemplary embodiment, the compound having at least one deuterium atom is a host material. In an exemplary embodiment, the compound having at least one deuterium atom is a host material, and a dopant material has no deuterium atom.
In an exemplary embodiment, when deuterium atoms in the first and second compounds are substituted with protium atoms, chemical structures of the first and the second compounds are mutually the same or different, preferably mutually different.
In an exemplary embodiment, dopant materials in the first and second emitting layers are mutually the same or different, preferably mutually the same.
The compound having at least one deuterium atom preferably has 1 to 100 deuterium atoms, more preferably has 1 to 80 deuterium atoms.
The compound having at least one deuterium atom as a dopant material preferably has 1 to 100 deuterium atoms, and more preferably has 1 to 80 deuterium atoms.
The compound having at least one deuterium atom as a host material preferably has 1 to 50 deuterium atoms, and more preferably has 1 to 40 deuterium atoms.
In an exemplary embodiment, at least one of the first emitting layer or the second emitting layer contains one or more of host materials.
The emitting layer containing two or more of host materials may contain a host material having a deuterium atom. In that case, only one of the host materials may be a compound having a deuterium atom and the other may be a compound having no deuterium atom, or both of the host materials may each be a compound having a deuterium atom.
A method of measuring a singlet energy S1 with use of a solution (occasionally referred to as a solution method) is exemplified by a method below.
A toluene solution of a measurement target compound at a concentration ranging from 10−5 mol/L to 10−4 mol/L is prepared and put in a quartz cell. An absorption spectrum (ordinate axis: absorption intensity, abscissa axis: wavelength) of the thus-obtained sample is measured at a normal temperature (300K). A tangent is drawn to the fall of the absorption spectrum close to the long-wavelength region, and a wavelength value λedge (nm) at an intersection of the tangent and the abscissa axis is assigned to a conversion equation (F2) below to calculate the singlet energy.
S1 [eV]=1239.85/λedge Conversion Equation (F2):
Any device for measuring absorption spectrum is usable. For instance, a spectrophotometer (U3310 manufactured by Hitachi, Ltd.) is usable.
The tangent to the fall of the absorption spectrum close to the long-wavelength region is drawn as follows. While moving on a curve of the absorption spectrum from the local maximum value closest to the long-wavelength region, among the local maximum values of the absorption spectrum, in a long-wavelength direction, a tangent at each point on the curve is checked. An inclination of the tangent is decreased and increased in a repeated manner as the curve falls (i.e., a value of the ordinate axis is decreased). A tangent drawn at a point where the inclination of the curve is the local minimum closest to the long-wavelength region (except when absorbance is 0.1 or less) is defined as the tangent to the fall of the absorption spectrum close to the long-wavelength region.
The local maximum absorbance of 0.2 or less is not counted as the above-mentioned local maximum absorbance closest to the long-wavelength region.
In the organic electroluminescence device according to the exemplary embodiment, a triplet energy T1(M1) of the first compound is preferably different from a triplet energy T1(M2) of the second compound.
A method of measuring triplet energy T1 is exemplified by a method below.
A measurement target compound is dissolved in EPA (diethylether:isopentane:ethanol=5:5:2 in volume ratio) so as to fall within a range from 10−5 mol/L to 10−4 mol/L, and the obtained solution is put in a quartz cell to provide a measurement sample. A phosphorescence spectrum (ordinate axis: phosphorescent luminous intensity, abscissa axis: wavelength) of the measurement sample is measured at a low temperature (77K). A tangent is drawn to the rise of the phosphorescence spectrum close to the short-wavelength region. An energy amount is calculated by a conversion equation (F1) below on a basis of a wavelength value λedge [nm] at an intersection of the tangent and the abscissa axis. The calculated energy amount is defined as triplet energy T1.
T1 [eV]=1239.85/λedge Conversion Equation (F1):
The tangent to the rise of the phosphorescence spectrum close to the short-wavelength region is drawn as follows. While moving on a curve of the phosphorescence spectrum from the short-wavelength region to the local maximum value closest to the short-wavelength region among the local maximum values of the phosphorescence spectrum, a tangent is checked at each point on the curve toward the long-wavelength of the phosphorescence spectrum. An inclination of the tangent is increased along the rise of the curve (i.e., a value of the ordinate axis is increased). A tangent drawn at a point of the local maximum inclination (i.e., a tangent at an inflection point) is defined as the tangent to the rise of the phosphorescence spectrum close to the short-wavelength region.
A local maximum point where a peak intensity is 15% or less of the maximum peak intensity of the spectrum is not counted as the above-mentioned local maximum peak intensity closest to the short-wavelength region. The tangent drawn at a point that is closest to the local maximum peak intensity closest to the short-wavelength region and where the inclination of the curve is the local maximum is defined as a tangent to the rise of the phosphorescence spectrum close to the short-wavelength region.
For phosphorescence measurement, a spectrophotofluorometer body F-4500 (manufactured by Hitachi High-Technologies Corporation) is usable. Any device for phosphorescence measurement is usable. A combination of a cooling unit, a low temperature container, an excitation light source and a light-receiving unit may be used for phosphorescence measurement.
The first emitting layer and the second emitting layer preferably do not contain a phosphorescent material (dopant material).
The first emitting layer and the second emitting layer preferably do not contain a heavy metal complex and a phosphorescent rare earth metal complex. Examples of the heavy-metal complex herein include iridium complex, osmium complex, and platinum complex.
In the organic electroluminescence device according to the exemplary embodiment, the first emitting layer also preferably contains no metal complex.
In the organic electroluminescence device according to the exemplary embodiment, the second emitting layer also preferably contains no metal complex.
Both of the first and second emitting layers also preferably contain no metal complex.
The film thickness of the emitting layer of the organic EL device according to the exemplary embodiment is preferably in a range from 5 nm to 50 nm, more preferably in a range from 7 nm to 50 nm, and further preferably in a range from 10 nm to 50 nm. When the film thickness of the emitting layer is 5 nm or more, the emitting layer is easily formable and chromaticity is easily adjustable. When the film thickness of the emitting layer is 50 nm or less, a rise in the drive voltage is easily reducible. The film thickness of first and second emitting layers may be mutually the same or different.
When the first emitting layer contains the first compound and the third compound, a content ratio of each of the first compound and the third compound in the first emitting layer preferably falls, for instance, within a range below.
The content ratio of the first compound is preferably in a range from 80 mass % to 99 mass %, more preferably in a range from 90 mass % to 99 mass %, and further preferably in a range from 95 mass % to 99 mass %.
The content ratio of the third compound is preferably in a range from 1 mass % to 10 mass %, more preferably in a range from 1 mass % to 7 mass %, and further preferably in a range from 1 mass % to 5 mass %.
The upper limit of the total of the content ratios of the first compound and the third compound in the first emitting layer is 100 mass %.
It is not excluded that the first emitting layer of the exemplary embodiment further contains a material(s) other than the first and third compounds.
The first emitting layer may contain a single type of the first compound or may contain two or more types of the first compound. The first emitting layer may contain a single type of the third compound or may contain two or more types of the third compound.
When the second emitting layer contains the second compound and the fourth compound, a content ratio of each of the second compound and the fourth compound in the second emitting layer preferably falls, for instance, within a range below.
The content ratio of the second compound is preferably in a range from 80 mass % to 99 mass %, more preferably in a range from 90 mass % to 99 mass %, and further preferably in a range from 95 mass % to 99 mass %.
The content ratio of the fourth compound is preferably in a range from 1 mass % to 10 mass %, more preferably in a range from 1 mass % to 7 mass %, and further preferably in a range from 1 mass % to 5 mass %.
The upper limit of the total of the content ratios of the second compound and the fourth compound in the second emitting layer is 100 mass %.
It is not excluded that the second emitting layer of the exemplary embodiment further contains a material(s) other than the second and fourth compounds.
The second emitting layer may contain a single type of the second compound or may contain two or more types of the second compound. The second emitting layer may contain a single type of the fourth compound or may contain two or more types of the fourth compound.
The organic electroluminescence device of the exemplary embodiment preferably emits light having a maximum peak wavelength in a range from 430 nm to 480 nm when being driven.
The maximum peak wavelength of the light emitted from the organic EL element when being driven is measured as follows. Voltage is applied on the organic EL device such that a current density is 10 mA/cm2, where spectral radiance spectrum is measured by a spectroradiometer CS-2000 (manufactured by Konica Minolta, Inc.). A peak wavelength of an emission spectrum, at which the luminous intensity of the resultant spectral radiance spectrum is at the maximum, is measured and defined as the maximum peak wavelength (unit: nm).
In the organic EL device according to the exemplary embodiment, the second emitting layer is also preferably provided between the first emitting layer and the cathode. Specifically, the first emitting layer and the second emitting layer are also preferably laminated in this order from the anode.
In the organic EL device according to the exemplary embodiment, the second emitting layer is also preferably provided between the first emitting layer and the anode. Specifically, the second emitting layer and the first emitting layer are also preferably laminated in this order from the anode.
When the first emitting layer and the second emitting layer are laminated in this order from the anode in the organic EL device according to the exemplary embodiment, an electron mobility μe(H1) of the first host material and an electron mobility μe(H2) of the second host material satisfy a relationship of a numerical formula (Numerical Formula 30) below.
μe(H2)>μe(H1) (Numerical Formula 30)
When the first host material and the second host material satisfy the relationship of the numerical formula (Numerical Formula 30), a recombination ability between holes and electrons in the first emitting layer is improved.
When the first emitting layer and the second emitting layer are laminated in this order from the anode in the organic EL device according to the exemplary embodiment, a hole mobility μh(H1) of the first host material and a hole mobility μh(H2) of the second host material also preferably satisfy a relationship of a numerical formula (Numerical Formula 31) below.
μh(H1)>μh(H2) (Numerical Formula 31)
When the first emitting layer and the second emitting layer are laminated in this order from the anode in the organic EL device according to the exemplary embodiment, the hole mobility μh(H1) of the first host material, the electron mobility μe(H1) of the first host material, the hole mobility μh(H2) of the second host material, and the electron mobility μe(H2) of the second host material also preferably satisfy a relationship of a numerical formula (Numerical Formula 32) below.
(μe(H2)/μh(H2))>(μe(H1)/μh(H1)) (Numerical Formula 32)
The electron mobility can be measured according to an impedance measurement using a mobility evaluation device manufactured by the following steps. The mobility evaluation device is, for instance, manufactured by the following steps.
A compound Target, which is to be measured for an electron mobility, is vapor-deposited on a glass substrate having an aluminum electrode (anode) so as to cover the aluminum electrode, thereby forming a measurement target layer. A compound ET-A below is vapor-deposited on this measurement target layer to form an electron transporting layer. LiF is vapor-deposited on the formed electron transporting layer to form an electron injecting layer. Metal aluminum (Al) is vapor-deposited on the formed electron injecting layer to form a metal cathode.
An arrangement of the mobility evaluation device above is roughly shown as follows.
Numerals in parentheses represent a film thickness (nm).
The mobility evaluation device for an electron mobility is set in an impedance measurement device to perform an impedance measurement. In the impedance measurement, a measurement frequency is swept from 1 Hz to 1 MHz. At this time, an alternating current amplitude of 0.1 V and a direct current voltage V are applied to the device. A modulus M is calculated from a measured impedance Z using a relationship of a calculation formula (C1) below.
M=jωZ Calculation Formula (C1):
In the calculation formula (C1), j is an imaginary unit whose square is −1 and ω is an angular frequency [rad/s].
In a bode plot in which an imaginary part of the modulus M is represented by an ordinate axis and the frequency [Hz] is represented by an abscissa axis, an electrical time constant T of the mobility evaluation device is obtained from a frequency fmax showing a peak using a calculation formula (C2) below.
τ=1/(2πf max) Calculation Formula (C2):
π in the calculation formula (C2) is a symbol representing a circumference ratio.
An electron mobility μe is calculated from a relationship of a calculation formula (C3-1) below using τ.
μe=d2/(VT) Calculation Formula (C3-1):
The hole mobility can be measured according to an impedance measurement using a mobility evaluation device manufactured by the following steps. The mobility evaluation device is, for instance, manufactured by the following steps.
A compound HA-2 below is vapor-deposited on a glass substrate having an ITO transparent electrode (anode) so as to cover the transparent electrode, thereby forming a hole injecting layer. A compound HT-A below is vapor-deposited on the formed hole injecting layer to form a hole transporting layer. Subsequently, a compound Target, which is to be measured for a hole mobility, is vapor-deposited to form a measurement target layer. Metal aluminum (Al) is vapor-deposited on this measurement target layer to form a metal cathode.
An arrangement of the mobility evaluation device above is roughly shown as follows.
The mobility evaluation device for a hole mobility is set in an impedance measurement device to perform an impedance measurement. In the impedance measurement, a measurement frequency is swept from 1 Hz to 1 MHz. At this time, an alternating current amplitude of 0.1 V and a direct current voltage V are applied to the device. A modulus M is calculated from a measured impedance Z using the relationship of the calculation formula (C1).
In a bode plot in which an imaginary part of the modulus M is represented by an ordinate axis and the frequency [Hz] is represented by an abscissa axis, an electrical time constant τ of the mobility evaluation device is obtained from a frequency fmax showing a peak using the calculation formula (C2).
A hole mobility μh is calculated from a relationship of a calculation formula (C3-2) below using T obtained from the calculation formula (C2).
μh=d2/(VT) Calculation Formula (C3-2):
The electron mobility and the hole mobility herein are each a value obtained in a case where a square root of an electric field intensity meets E1/2=500 [V1/2/cm1/2]. The square root of the electric field intensity, E1/2, can be calculated from a relationship of a calculation formula (C4) below.
E1/2=V1/2/d1/2 Calculation Formula (C4):
For the impedance measurement, a 1260 type by Solartron Analytical is used as the impedance measurement device, and for a higher accuracy, a 1296 type dielectric constant measurement interface by Solartron Analytical can be used together therewith.
The organic EL device according to the exemplary embodiment may include one or more organic layer(s) in addition to the first emitting layer and the second emitting layer. Examples of the organic layer include at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an emitting layer, an electron injecting layer, an electron transporting layer, a hole blocking layer, and an electron blocking layer.
In the organic EL device according to the exemplary embodiment, the organic layer may consist of the first emitting layer and the second emitting layer. Alternatively, the organic layer may further include, for instance, at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, a hole blocking layer, and an electron blocking layer.
It is preferable that the organic electroluminescence device of the exemplary embodiment includes a hole transporting layer between the anode and one of the first emitting layer and the second emitting layer provided closer to the anode.
It is preferable that the organic electroluminescence device of the exemplary embodiment includes an electron transporting layer between the cathode and one of the first emitting layer and the second emitting layer provided closer to the cathode.
An organic EL device 1 includes a light-transmissive substrate 2, an anode 3, a cathode 4, and an organic layer 10 provided between the anode 3 and the cathode 4. The organic layer 10 includes a hole injecting layer 6, a hole transporting layer 7, a first emitting layer 51, a second emitting layer 52, an electron transporting layer 8, and an electron injecting layer 9, these of which are laminated in this order from the anode 3.
The invention is not limited to a structure of the organic EL device shown in
In the organic EL device of the exemplary embodiment, the first emitting layer and the second emitting layer are preferably in direct contact with each other.
Herein, a layer arrangement in which the first emitting layer and the second emitting layer are in direct contact with each other may include one of embodiments (LS1), (LS2) and (LS3) below.
When the first emitting layer and the second emitting layer are not in direct contact with each other in the organic EL device of the exemplary embodiment, at least one organic layer may be provided between the first emitting layer and the second emitting layer.
The organic EL device according to the exemplary embodiment may include an interposed layer as an organic layer disposed between the first emitting layer and the second emitting layer.
In the exemplary embodiment, in order to inhibit an overlap between a Singlet emitting region and a TTF emitting region, the interposed layer contains no emitting compound or may contain an emitting compound in an insubstantial amount provided that the overlap can be inhibited.
For instance, the interposed layer contains 0 mass % of an emitting compound. Alternatively, for instance, the interposed layer may contain an emitting compound provided that the emitting compound contained is a component accidentally mixed in a manufacturing process or a component contained as impurities in a material.
For instance, when the interposed layer consists of a material A, a material B, and a material C, the content ratios of the materials A, B, and C in the interposed layer are each 10 mass % or more, and the total of the content ratios of the materials A, B, and C is 100 mass %.
In the following, the interposed layer is occasionally referred to as a “non-doped layer”. A layer containing an emitting compound is occasionally referred to as a “doped layer”.
It is considered that the Singlet emitting region and the TTF emitting region are typically likely to be separated from each other in laminated emitting layers, thus improving luminous efficiency.
In the organic EL device according to the exemplary embodiment, when the interposed layer (non-doped layer) is disposed between the first emitting layer and the second emitting layer in the emitting region, it is expected that a region where the Singlet emitting region and the TTF emitting region overlap with each other is reduced to inhibit a decrease in TTF efficiency caused by collision between triplet excitons and carriers. That is, it is considered that providing the interposed layer (non-doped layer) between the emitting layers contributes to the improvement in the efficiency of TTF emission.
The interposed layer is a non-doped layer.
The interposed layer contains no metal atom. The interposed layer thus contains no metal complex.
The interposed layer contains an interposed layer material. The interposed layer material is not an emitting compound.
The interposed layer material may be any material except for the emitting compound.
Examples of the interposed layer material include: 1) a heterocyclic compound such as an oxadiazole derivative, benzimidazole derivative, or phenanthroline derivative; 2) a fused aromatic compound such as a carbazole derivative, anthracene derivative, phenanthrene derivative, pyrene derivative or chrysene derivative; and 3) an aromatic amine compound such as a triarylamine derivative or a fused polycyclic aromatic amine derivative.
One or both of the first host material and the second host material may be used as the interposed layer material. The interposed layer material may be any material provided that the Singlet emitting region and the TTF emitting region are separated from each other and the Singlet emission and the TTF emission are not hindered.
In the organic EL device according to the exemplary embodiment, the respective content ratios of all the materials forming the interposed layer in the interposed layer are 10 mass % or more.
The interposed layer contains the interposed layer material as a material forming the interposed layer.
The interposed layer preferably contains 60 mass % or more of the interposed layer material, more preferably contains 70 mass % or more of the interposed layer material, further preferably contains 80 mass % or more of the interposed layer material, more further preferably 90 mass % or more of the interposed layer material, and still further more preferably 95 mass % or more of the interposed layer material, with respect to a total mass of the interposed layer.
The interposed layer may contain a single type of the interposed layer material or may contain two or more types of the interposed layer material.
When the interposed layer contains two or more types of the interposed layer material, the upper limit of the total of the content ratios of the two or more types of the interposed layer material is 100 mass %.
It should be noted that the interposed layer of the exemplary embodiment may further contain material(s) other than the interposed layer material.
The interposed layer may be provided in the form of a single layer or a laminate of two or more layers.
As long as the overlap between the Singlet emitting region and the TTF emitting region is inhibited, the film thickness of the interposed layer is not particularly limited but each layer in the interposed layer is preferably in a range from 3 nm to 15 nm, more preferably in a range from 5 nm to 10 nm.
The interposed layer having a film thickness of 3 nm or more easily separates the Singlet emitting region from the emitting region derived from TTF.
The interposed layer having a film thickness of 15 nm or less easily inhibits a phenomenon where the host material of the interposed layer emits light.
An arrangement of an organic EL device will be further described below. It should be noted that the reference numerals will be occasionally omitted below.
The substrate is used as a support for the organic EL device. For instance, glass, quartz, plastics and the like are usable for the substrate. A flexible substrate is also usable. The flexible substrate is a bendable substrate, which is exemplified by a plastic substrate. Examples of the material for the plastic substrate include polycarbonate, polyarylate, polyethersulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, and polyethylene naphthalate. Moreover, an inorganic vapor deposition film is also usable.
Metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a large work function (specifically, 4.0 eV or more) is preferably used as the anode formed on the substrate. Specific examples of the material include ITO (Indium Tin Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, indium oxide containing tungsten oxide and zinc oxide, and graphene. In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chrome (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), and nitrides of a metal material (e.g., titanium nitride) are usable.
The material is typically formed into a film by a sputtering method. For instance, the indium oxide-zinc oxide can be formed into a film by the sputtering method using a target in which zinc oxide in a range from 1 mass % to 10 mass % is added to indium oxide. Moreover, for instance, the indium oxide containing tungsten oxide and zinc oxide can be formed by the sputtering method using a target in which tungsten oxide in a range from 0.5 mass % to 5 mass % and zinc oxide in a range from 0.1 mass % to 1 mass % are added to indium oxide. In addition, the anode may be formed by a vacuum deposition method, a coating method, an inkjet method, a spin coating method or the like.
Among the organic layers formed on the anode, since the hole injecting layer adjacent to the anode is formed of a composite material into which holes are easily injectable irrespective of the work function of the anode, a material usable as an electrode material (e.g., metal, an alloy, an electroconductive compound, a mixture thereof, and the elements belonging to the group 1 or 2 of the periodic table) is also usable for the anode.
A material having a small work function such as elements belonging to Groups 1 and 2 in the periodic table of the elements, specifically, an alkali metal such as lithium (Li) and cesium (Cs), an alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), alloys (e.g., MgAg and AlLi) including the alkali metal or the alkaline earth metal, a rare earth metal such as europium (Eu) and ytterbium (Yb), alloys including the rare earth metal are also usable for the anode. It should be noted that the vacuum deposition method and the sputtering method are usable for forming the anode using the alkali metal, alkaline earth metal and the alloy thereof. Further, when a silver paste is used for the anode, the coating method and the inkjet method are usable.
It is preferable to use metal, an alloy, an electroconductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less) for the cathode. Examples of the material for the cathode include elements belonging to Groups 1 and 2 in the periodic table of the elements, specifically, the alkali metal such as lithium (Li) and cesium (Cs), the alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), alloys (e.g., MgAg and AlLi) including the alkali metal or the alkaline earth metal, the rare earth metal such as europium (Eu) and ytterbium (Yb), and alloys including the rare earth metal.
It should be noted that the vacuum deposition method and the sputtering method are usable for forming the cathode using the alkali metal, alkaline earth metal and the alloy thereof. Further, when a silver paste is used for the cathode, the coating method and the inkjet method are usable.
By providing the electron injecting layer, various conductive materials such as Al, Ag, ITO, graphene, and indium oxide-tin oxide containing silicon or silicon oxide may be used for forming the cathode regardless of the work function. The conductive materials can be formed into a film using the sputtering method, inkjet method, spin coating method and the like.
The hole injecting layer is a layer containing a substance exhibiting a high hole injectability. Examples of the substance exhibiting a high hole injectability include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chrome oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, and manganese oxide.
In addition, the examples of the highly hole-injectable substance further include: an aromatic amine compound, which is a low-molecule organic compound, such as 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), 4,4′-bis(N-{4-[N′-(3-methylphenyl)-N′-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTPD), 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B), 3-[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), and 3-[N-(1-naphthyl)-N-(9-phenylcarbazole-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1); and dipyrazino[2,3-f:20,30-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN).
In addition, a high polymer compound (e.g., oligomer, dendrimer and polymer) is usable as the substance exhibiting a high hole injectability. Examples of the high-molecule compound include poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide](abbreviation: PTPDMA), and poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (abbreviation: Poly-TPD). Moreover, an acid-added high polymer compound such as poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) and polyaniline/poly(styrene sulfonic acid) (PAni/PSS) are also usable.
The hole transporting layer is a layer containing a highly hole-transporting substance. An aromatic amine compound, carbazole derivative, anthracene derivative and the like are usable for the hole transporting layer. Specific examples of a material for the hole transporting layer include an aromatic amine compound such as 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4-phenyl-4′-(9-phenylfluorene-9-yl)triphenylamine (abbreviation: BAFLP), 4,4′-bis[N-(9,9-dimethylfluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: DFLDPBi), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), and 4,4′-bis[N-(spiro-9,9′-bifluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB). The above-described substances mostly have a hole mobility of 10−6 cm2/(V-s) or more.
For the hole transporting layer, a carbazole derivative such as CBP, 9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (CzPA), and 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (PCzPA) and an anthracene derivative such as t-BuDNA, DNA, and DPAnth may be used. A high polymer compound such as poly(N-vinylcarbazole) (abbreviation: PVK) and poly(4-vinyltriphenylamine) (abbreviation: PVTPA) is also usable.
However, in addition to the above substances, any substance exhibiting a higher hole transportability than an electron transportability may be used. It should be noted that the layer containing the substance exhibiting a high hole transportability may be not only a single layer but also a laminate of two or more layers formed of the above substance(s).
The electron transporting layer is a layer containing a highly electron-transporting substance. For the electron transporting layer, 1) a metal complex such as an aluminum complex, beryllium complex, and zinc complex, 2) a hetero aromatic compound such as imidazole derivative, benzimidazole derivative, azine derivative, carbazole derivative, and phenanthroline derivative, and 3) a high polymer compound are usable. Specifically, as a low-molecule organic compound, a metal complex such as Alq, tris(4-methyl-8-quinolinato)aluminum (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato)beryllium (abbreviation: BeBq2), BAlq, Znq, ZnPBO and ZnBTZ is usable. In addition to the metal complex, a heteroaromatic compound such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis[5-(ptert-butylphenyl)-1,3,4-oxadiazole-2-yl]benzene (abbreviation: OXD-7), 3-(4-tert-butylphenyl)-4-phenyl-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: TAZ), 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), and 4,4′-bis(5-methylbenzoxazole-2-yl)stilbene (abbreviation: BzOs) is usable. In the exemplary embodiment, a benzimidazole compound is preferably usable. The above-described substances mostly have an electron mobility of 10−6 cm2/Vs or more. It should be noted that any substance other than the above substance may be used for the electron transporting layer as long as the substance exhibits a higher electron transportability than the hole transportability. The electron transporting layer may be provided in the form of a single layer or a laminate of two or more layers of the above substance(s).
Specific examples of the compound usable for the electron transporting layer include compounds below. It should however be noted that the invention is not limited to the specific examples of the compound.
Further, a high polymer compound is usable for the electron transporting layer. For instance, poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)](abbreviation: PF-Py), poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridine-6,6′-diyl)](abbreviation: PF-BPy) and the like are usable.
The electron injecting layer is a layer containing a highly electron-injectable substance. Examples of a material for the electron injecting layer include an alkali metal, alkaline earth metal and a compound thereof, examples of which include lithium (Li), cesium (Cs), calcium (Ca), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), and lithium oxide (LiOx). In addition, the alkali metal, alkaline earth metal or the compound thereof may be added to the substance exhibiting the electron transportability in use. Specifically, for instance, magnesium (Mg) added to Alq may be used. In this case, the electrons can be more efficiently injected from the cathode.
Alternatively, the electron injecting layer may be provided by a composite material in a form of a mixture of the organic compound and the electron donor. Such a composite material exhibits excellent electron injectability and electron transportability since electrons are generated in the organic compound by the electron donor. In this case, the organic compound is preferably a material excellent in transporting the generated electrons. Specifically, the above examples (e.g., the metal complex and the hetero aromatic compound) of the substance forming the electron transporting layer are usable. As the electron donor, any substance exhibiting electron donating property to the organic compound is usable. Specifically, the electron donor is preferably alkali metal, alkaline earth metal and rare earth metal such as lithium, cesium, magnesium, calcium, erbium and ytterbium. The electron donor is also preferably alkali metal oxide and alkaline earth metal oxide such as lithium oxide, calcium oxide, and barium oxide. Moreover, a Lewis base such as magnesium oxide is usable. Further, the organic compound such as tetrathiafulvalene (abbreviation: TTF) is usable.
A method for forming each layer of the organic EL device in the exemplary embodiment is subject to no limitation except for the above particular description. However, known methods of dry film-forming such as vacuum deposition, sputtering, plasma or ion plating and wet film-forming such as spin coating, dipping, flow coating or ink-jet are applicable.
A film thickness of each of the organic layers of the organic EL device in the exemplary embodiment is not limited unless otherwise specified in the above. In general, the thickness preferably ranges from several nanometers to 1 μm because excessively small film thickness is likely to cause defects (e.g. pin holes) and excessively large thickness leads to the necessity of applying high voltage and consequent reduction in efficiency.
In the organic EL device according to the exemplary embodiment, at least one of the first emitting layer that contains the first compound or the second emitting layer that contains the second compound contains a compound having at least one deuterium atom, and at least one of the first emitting layer or the second emitting layer contains a compound having a fused ring that includes four or more rings. Laminating the first emitting layer and the second emitting layer as described above can provide at least one of an organic EL device with enhanced luminous efficiency, an organic EL device emitting light with a long lifetime, or an organic EL device with enhanced luminous efficiency that emits light with a long lifetime.
An electronic device according to a second exemplary embodiment is installed with any one of the organic EL devices according to the above exemplary embodiment. Examples of the electronic device include a display device and a light-emitting unit. Examples of the display device include a display component (e.g., an organic EL panel module), TV, mobile phone, tablet and personal computer. Examples of the light-emitting unit include an illuminator and a vehicle light.
The scope of the invention is not limited to the above-described exemplary embodiments but includes any modification and improvement as long as such modification and improvement are compatible with the invention.
For instance, the number of emitting layers is not limited to two, and more than two emitting layers may be provided and laminated with each other. When the organic EL device includes more than two emitting layers, it is only necessary that at least two of the emitting layers should satisfy the requirements mentioned in the above exemplary embodiment. For instance, the rest of the emitting layers may be a fluorescent emitting layer or a phosphorescent emitting layer with use of emission caused by electron transfer from the triplet excited state directly to the ground state.
When the organic EL device includes a plurality of emitting layers, these emitting layers may be mutually adjacently provided, or may form a so-called tandem organic EL device, in which a plurality of emitting units are layered via an intermediate layer.
An arrangement of the organic EL device including three or more emitting layers is as follows.
An organic electroluminescence device includes: an anode; a cathode; a first emitting layer provided between the anode and the cathode and containing a first compound; a second emitting layer provided between the first emitting layer and the cathode and containing a second compound; and a third emitting layer provided between the anode and the cathode and being not in direct contact with any of the first emitting layer and the second emitting layer, in which
The third emitting layer also preferably contains the first compound.
The third emitting layer also preferably contains the second compound.
The organic electroluminescence device preferably includes an intermediate layer between the third emitting layer and the first emitting layer and/or an intermediate layer between the third emitting layer and the second emitting layer.
The intermediate layer is generally also referred to as an intermediate electrode, intermediate conductive layer, charge generating layer, electron drawing layer, connection layer, or intermediate insulative layer.
The intermediate layer supplies electrons to a layer that is close to the anode with respect to the intermediate layer, and supplies holes to a layer that is close to the cathode with respect to the intermediate layer. The intermediate layer can be formed from a known material. The intermediate layer may be a single layer, or may be provided by two or more layers. A unit formed by two or more intermediate layers is occasionally referred to as an intermediate unit. The compositions of the plurality of intermediate layers of the intermediate unit are mutually the same or different.
Further, a plurality of layers including the emitting layer that are disposed between the intermediate layer/intermediate unit and the anode/cathode are occasionally referred to as an emitting unit. Examples of the device arrangement of the organic EL device including a plurality of emitting units include (TND1) to (TND4) below.
The number of the emitting units and the intermediate layers (or intermediate units) is not limited to the examples shown above.
The first emitting layer and the second emitting layer are preferably included in at least one of the first emitting unit, the second emitting unit, or the third emitting unit.
The first emitting layer and the second emitting layer are also preferably included in all of the emitting units of the organic EL device.
For instance, a blocking layer may be provided adjacent to at least one of a side of the emitting layer close to the anode or a side of the emitting layer close to the cathode. The blocking layer is preferably provided in contact with the emitting layer to block at least any of holes, electrons, or excitons.
For instance, when the blocking layer is provided in contact with the side of the emitting layer close to the cathode, the blocking layer permits transport of electrons and blocks holes from reaching a layer provided closer to the cathode (e.g., the electron transporting layer) beyond the blocking layer. When the organic EL device includes the electron transporting layer, the blocking layer is preferably interposed between the emitting layer and the electron transporting layer.
When the blocking layer is provided in contact with the side of the emitting layer close to the anode, the blocking layer permits transport of holes and blocks electrons from reaching a layer provided closer to the anode (e.g., the hole transporting layer) beyond the blocking layer. When the organic EL device includes the hole transporting layer, the blocking layer is preferably interposed between the emitting layer and the hole transporting layer.
Alternatively, the blocking layer may be provided adjacent to the emitting layer so that excitation energy does not leak out from the emitting layer toward neighboring layer(s). The blocking layer blocks excitons generated in the emitting layer from being transferred to a layer(s) (e.g., the electron transporting layer and the hole transporting layer) closer to the electrode(s) beyond the blocking layer.
The emitting layer is preferably bonded with the blocking layer.
Specific structure, shape and the like of the components in the invention may be designed in any manner as long as an object of the invention can be achieved.
The invention will be described in further detail with reference to Examples. The scope of the invention is by no means limited to Examples.
Structures of compounds used for manufacturing organic EL devices in Examples, Reference Examples, and Comparative Examples are shown below.
Structures of other compounds used for manufacturing organic EL devices in Examples, Reference Examples and Comparative Examples are shown below.
Organic EL devices were manufactured and evaluated as follows.
A glass substrate (size: 25 mm×75 mm×1.1 mm thick, manufactured by Geomatec Co., Ltd.) having an ITO (Indium Tin Oxide) transparent electrode (anode) was ultrasonic-cleaned in isopropyl alcohol for five minutes, and then UV-ozone-cleaned for 30 minutes. A film thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate having the transparent electrode line was attached to a substrate holder of a vacuum deposition apparatus. Initially, a compound HT1 and the compound HA2 were co-deposited on a surface provided with the transparent electrode line to cover the transparent electrode, thereby forming a 5-nm-thick hole injecting layer (HI). The ratios of the compound HT1 and the compound HA2 in the hole injecting layer were 97 mass % and 3 mass %, respectively.
After the formation of the hole injecting layer, the compound HT1 was vapor-deposited to form an 80-nm-thick first hole transporting layer (HT).
After the formation of the first hole transporting layer, a compound HT9 was vapor-deposited to form a 10-nm-thick second hole transporting layer (also referred to as an electron blocking layer (EBL)).
A compound BH1-84 (first host material (BH)) and a compound BD2 (dopant material (BD)) were co-deposited on the second hole transporting layer such that the ratio of the compound BD2 accounted for 2 mass %, thereby forming a 5-nm-thick first emitting layer.
A compound BH2-3 (second host material (BH)) and the compound BD2 (dopant material (BD)) were co-deposited on the first emitting layer such that the ratio of the compound BD2 accounted for 2 mass %, thereby forming a 20-nm-thick second emitting layer.
A compound ET7 was vapor-deposited on the second emitting layer to form a 10-nm-thick first electron transporting layer (also referred to as a hole blocking layer (HBL)).
A compound ET2 was vapor-deposited on the first electron transporting layer to form a 15-nm-thick second electron transporting layer (ET).
LiF was vapor-deposited on the second electron transporting layer to form a 1-nm-thick electron injecting layer.
Metal (Al) was vapor-deposited on the electron injecting layer to form an 80-nm-thick cathode.
A device arrangement of the organic EL device in Example 1 is roughly shown as follows.
Numerals in parentheses represent a film thickness (unit: nm).
The numerals (97%:3%) represented by percentage in the same parentheses indicate a ratio (mass %) between the compound HT1 and the compound HA2 in the hole injecting layer, and the numerals (98%:2%) represented by percentage in the same parentheses indicate a ratio (mass %) between the host material (the compound BH1-84 or the compound BH2-3) and the compound BD2 in the first emitting layer or the second emitting layer. Similar notations apply to the description below.
The organic EL devices of Examples 2 and 3 were each manufactured in the same manner as that of Example 1 except that the compound BH1-84 (first host material) in the first emitting layer was replaced with the first compound listed in Table 2.
The organic EL device of Example 4 was manufactured in the same manner as that of Example 1 except that the compound BH2-3 (second host material) in the second emitting layer was replaced with the second compound listed in Table 2.
The organic EL device of Reference Example 1 was manufactured in the same manner as that of Example 4 except that the compound BH1-84 (first host material) in the first emitting layer was replaced with the first compound listed in Table 2.
As shown in Table 2, the organic EL devices of Reference Examples 2 to 4 were each manufactured in the same manner as that of Example 1 except that a 25-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the compound BH1-84 (first host material) in the first emitting layer was replaced with the first compound listed in Table 2.
As shown in Table 2, the organic EL device of Comparative Example 1 was manufactured in the same manner as that of Example 1 except that a 25-nm-thick second emitting layer was formed as the emitting layer on the second hole transporting layer without forming the first emitting layer.
As shown in Table 2, the organic EL device of Comparative Example 2 was manufactured in the same manner as that of Reference Example 1 except that a 25-nm-thick first emitting layer was formed as the emitting layer, and the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer.
As shown in Table 2, the organic EL device of Comparative Example 3 was manufactured in the same manner as that of Reference Example 1 except that a 25-nm-thick second emitting layer was formed as the emitting layer on the second hole transporting layer without forming the first emitting layer.
The organic EL devices manufactured were evaluated as follows. Tables 2 to 17 show the evaluation results. In Tables, the first compound corresponds to the first host material and the second compound corresponds to the second host material.
Voltage was applied on the organic EL devices so that a current density was 10 mA/cm2, where spectral radiance spectrum was measured by a spectroradiometer (CS-2000 manufactured by Konica Minolta, Inc.). The external quantum efficiency EQE (unit: %) was calculated based on the obtained spectral-radiance spectra, assuming that the spectra was provided under a Lambertian radiation.
Voltage was applied on the resultant organic EL devices so that a current density was 50 mA/cm2, where a time (LT95 (unit: hr)) elapsed before a luminance intensity was reduced to 95% of the initial luminance intensity was measured.
The organic EL devices of Examples 5 to 8 were each manufactured in the same manner as that of Example 1 except that at least one of the compound BH1-84 (first host material) in the first emitting layer or the compound BH2-3 in the second emitting layer was replaced with the compound listed in Table 3.
The organic EL devices of Reference Examples 5 and 6 were each manufactured in the same manner as that of Example 1 except that at least one of the compound BH1-84 (first host material) in the first emitting layer or the compound BH2-3 in the second emitting layer was replaced with the compound listed in Table 3.
As shown in Table 3, the organic EL device of Reference Example 7 was manufactured in the same manner as that of Example 1 except that a 25-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the compound BH1-84 (first host material) in the first emitting layer was replaced with the first compound listed in Table 3.
As shown in Table 3, the organic EL device of Comparative Example 4 was manufactured in the same manner as that of Comparative Example 2 except that a compound BH1-87 (first host material) in the first emitting layer of Comparative Example 2 was replaced with the first compound listed in Table 3.
The organic EL devices of Examples 9 to 12 were each manufactured in the same manner as that of Example 1 except that at least one of the compound BH1-84 (first host material) in the first emitting layer or the compound BH2-3 in the second emitting layer was replaced with the compound listed in Table 4.
The organic EL devices of Reference Examples 8 and 9 were each manufactured in the same manner as that of Example 1 except that at least one of the compound BH1-84 (first host material) in the first emitting layer or the compound BH2-3 in the second emitting layer was replaced with the compound listed in Table 4.
As shown in Table 4, the organic EL device of Reference Example 10 was manufactured in the same manner as that of Example 1 except that a 25-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the compound BH1-84 (first host material) in the first emitting layer was replaced with the first compound listed in Table 4.
As shown in Table 4, the organic EL device of Comparative Example 5 was manufactured in the same manner as that of Comparative Example 2 except that the compound BH1-87 (first host material) in the first emitting layer of Comparative Example 2 was replaced with the first compound listed in Table 4.
A glass substrate (size: 25 mm×75 mm×1.1 mm thick, manufactured by Geomatec Co., Ltd.) having an ITO (Indium Tin Oxide) transparent electrode (anode) was ultrasonic-cleaned in isopropyl alcohol for five minutes, and then UV-ozone-cleaned for 30 minutes. A film thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate having the transparent electrode line was attached to a substrate holder of a vacuum deposition apparatus. Initially, a compound HA1 was vapor-deposited on a surface provided with the transparent electrode line to cover the transparent electrode, thereby forming a 10-nm-thick hole injecting layer (HI).
After the formation of the hole injecting layer, a compound HT2 was vapor-deposited to form an 80-nm-thick first hole transporting layer (HT).
After the formation of the first hole transporting layer, a compound HT3 was vapor-deposited to form a 5-nm-thick second hole transporting layer (also referred to as an electron blocking layer (EBL)).
A compound BH1-81 (first host material (BH)) and a compound BD1 (dopant material (BD)) were co-deposited on the second hole transporting layer such that the ratio of the compound BD1 accounted for 2 mass %, thereby forming a 5-nm-thick first emitting layer.
A compound BH2-11 (second host material (BH)) and the compound BD1 (dopant material (BD)) were co-deposited on the first emitting layer such that the ratio of the compound BD1 accounted for 2 mass %, thereby forming a 20-nm-thick second emitting layer.
The compound ET7 was vapor-deposited on the second emitting layer to form a 3-nm-thick first electron transporting layer (also referred to as a hole blocking layer (HBL)).
A compound ET3 was vapor-deposited on the first electron transporting layer to form a 20-nm-thick second electron transporting layer (ET).
LiF was vapor-deposited on the second electron transporting layer to form a 1-nm-thick electron injecting layer.
Metal (Al) was vapor-deposited on the electron injecting layer to form an 80-nm-thick cathode.
A device arrangement of the organic EL device of Example 13 is roughly shown as follows.
Numerals in parentheses represent a film thickness (unit: nm).
The numerals (98%:2%) represented by percentage in the same parentheses indicate a ratio (mass %) between the host material (compound BH1-81 or BH2-11) and the compound BD1 in the first emitting layer or the second emitting layer. Similar notations apply to the description below.
The organic EL devices of Examples 14 to 16 were each manufactured in the same manner as that of Example 13 except that compounds listed in Table 5 were used as the first compound (first host material) of the first emitting layer and the second compound (second host material) of the second emitting layer.
As shown in Table 5, the organic EL devices of Comparative Examples 6 to 8 were each manufactured in the same manner as that of Example 13 except that a 25-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the first compound listed in Table 5 was used as the first compound (first host material) of the first emitting layer.
The organic EL devices of Examples 17 to 22 were each manufactured in the same manner as that of Example 13 except that compounds listed in Table 6 were used as the first compound (first host material) of the first emitting layer and the second compound (second host material) of the second emitting layer.
As shown in Table 6, the organic EL devices of Comparative Examples 9 to 11 were each manufactured in the same manner as that of Example 13 except that a 25-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the compound listed in Table 6 was used as the first compound (first host material) of the first emitting layer.
The organic EL devices of Examples 23 to 26 were each manufactured in the same manner as that of Example 13 except that compounds listed in Table 7 were used as the first compound (first host material) of the first emitting layer and the second compound (second host material) of the second emitting layer.
As shown in Table 7, the organic EL devices of Comparative Examples 12 and 13 were each manufactured in the same manner as that of Example 13 except that a 25-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the compound listed in Table 7 was used as the first compound (first host material) of the first emitting layer.
The organic EL devices of Examples 27 and 28 were each manufactured in the same manner as that of Example 13 except that the film thickness of the first emitting layer was changed to 3 nm, the film thickness of the second emitting layer was changed to 15 nm, and compounds listed in Table 8 were used as the first compound (first host material) of the first emitting layer and the second compound (second host material) of the second emitting layer.
As shown in Table 8, the organic EL devices of Comparative Examples 14 and 15 were each manufactured in the same manner as that of Example 13 except that an 18-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the compound listed in Table 8 was used as the first compound (first host material) of the first emitting layer.
The organic EL devices of Examples 29 and 30 were each manufactured in the same manner as that of Example 13 except that the film thickness of the first emitting layer was changed to 8 nm, the film thickness of the second emitting layer was changed to 12 nm, and compounds listed in Table 9 were used as the first compound (first host material) of the first emitting layer and the second compound (second host material) of the second emitting layer.
As shown in Table 9, the organic EL devices of Comparative Examples 16 and 17 were each manufactured in the same manner as that of Example 13 except that a 20-nm-thick first emitting layer was formed as the emitting layer, the first electron transporting layer was formed on the first emitting layer without forming the second emitting layer, and the compound listed in Table 9 was used as the first compound (first host material) of the first emitting layer.
A glass substrate (size: 25 mm×75 mm×1.1 mm thick, manufactured by Geomatec Co., Ltd.) having an ITO (Indium Tin Oxide) transparent electrode (anode) was ultrasonic-cleaned in isopropyl alcohol for five minutes, and then UV-ozone-cleaned for 30 minutes. A film thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate having the transparent electrode line was attached to a substrate holder of a vacuum deposition apparatus. Initially, the compound HA1 was vapor-deposited on a surface provided with the transparent electrode line to cover the transparent electrode, thereby forming a 10-nm-thick hole injecting layer (HI).
After the formation of the hole injecting layer, the compound HT1 was vapor-deposited to form an 80-nm-thick first hole transporting layer (HT).
After the formation of the first hole transporting layer, a compound EBL was vapor-deposited to form a 10-nm-thick second hole transporting layer (also referred to as an electron blocking layer (EBL)).
A compound BH1-90 (first host material (BH)) and the compound BD2 (dopant material (BD)) were co-deposited on the second hole transporting layer such that the ratio of the compound BD2 accounted for 2 mass %, thereby forming a 12.5-nm-thick first emitting layer.
A compound BH2-18 (second host material (BH)) and the compound BD2 (dopant material (BD)) were co-deposited on the first emitting layer such that the ratio of the compound BD2 accounted for 2 mass %, thereby forming a 12.5-nm-thick second emitting layer.
A compound HBL was vapor-deposited on the second emitting layer to form a 3-nm-thick first electron transporting layer (also referred to as a hole blocking layer (HBL)).
The compound ET2 was vapor-deposited on the first electron transporting layer to form a 20-nm-thick second electron transporting layer (ET).
LiF was vapor-deposited on the second electron transporting layer to form a 1-nm-thick electron injecting layer.
Metal (Al) was vapor-deposited on the electron injecting layer to form an 80-nm-thick cathode.
A device arrangement of the organic EL device of Example 31 is roughly shown as follows.
Numerals in parentheses represent a film thickness (unit: nm).
The numerals (98%:2%) represented by percentage in the same parentheses indicate a ratio (mass %) between the host material (compound BH1-90 or BH2-18) and the compound BD2 in the first emitting layer or the second emitting layer. Similar notations apply to the description below.
The organic EL devices of Examples 32 to 35 were each manufactured in the same manner as that of Example 31 except that the compound BH1-90 in the first emitting layer and the compound BH2-18 in the second emitting layer were replaced with the first compound and the second compound listed in Tables 11 to 14.
The organic EL devices of Examples 36 to 38 were each manufactured in the same manner as that of Example 31 except that the compounds BH1-90 and BD2 in the first emitting layer and the compounds BH2-18 and BD2 in the second emitting layer were replaced with the first compound, the second compound, the third compound and the fourth compound listed in Tables 15 to 17.
The organic EL devices of Reference Examples 11 to 15 were each manufactured in the same manner as that of Example 31 except that the compound BH1-90 in the first emitting layer and the compound BH2-18 in the second emitting layer were replaced with the first compound and the second compound listed in Tables 10 to 14.
The organic EL devices of Reference Examples 16 and 17 were each manufactured in the same manner as that of Example 31 except that the compounds BH1-90 and BD2 in the first emitting layer and the compounds BH2-18 and BD2 in the second emitting layer were replaced with the first compound, the second compound, the third compound and the fourth compound listed in Tables 15 and 16.
As shown in Tables 10 to 14, the organic EL devices of Comparative Examples 18 to 27 were each manufactured in the same manner as that of Example 31 except that a 25-nm-thick second emitting layer was formed as the emitting layer on the second hole transporting layer without forming the first emitting layer, and the compound listed in Tables 10 to 14 was used as the second compound (second host material) of the second emitting layer.
As shown in Tables 15 to 17, the organic EL devices of Comparative Examples 28 to 32 were manufactured in the same manner as that of Example 31 except that a 25-nm-thick second emitting layer was formed as the emitting layer on the second hole transporting layer without forming the first emitting layer, and the compound listed in Table 10 was used as the second compound (second host material) and the fourth compound.
In order to easily compare Examples, Reference Examples, and Comparative Examples, some of Reference Examples and Comparative Examples are repeatedly listed in Tables 10 to 17.
As shown in Tables 10 to 17, when the compound of the second emitting layer used as the second host material is a compound having at least one deuterium atom, the organic EL device has a long lifetime. An increase in lifetime of the organic EL devices in which the first and second emitting layers were laminated as shown in Examples 31 to 38 was greater than that of the organic EL device only including the second emitting layer as the emitting layer.
Preparation of Toluene Solution
The compound BD1 was dissolved in toluene at a concentration of 4.9×10−6 mol/L to prepare a toluene solution of the compound BD1.
The compound BD2 was dissolved in toluene at a concentration of 4.9×10−6 mol/L to prepare a toluene solution of the compound BD2.
The compound BD3 was dissolved in toluene at a concentration of 4.9×10−6 mol/L to prepare a toluene solution of the compound BD3.
Using a fluorescence spectrometer (spectrophotofluorometer F-7000 manufactured by Hitachi High-Tech Science Corporation), the toluene solution of the compound BD1, the toluene solution of the compound BD2, and the toluene solution of the compound BD3 were respectively excited at 390 nm, where a maximum fluorescence peak wavelength was measured.
The maximum fluorescence peak wavelength of the compound BD1 was 451 nm.
The maximum fluorescence peak wavelength of the compound BD2 was 455 nm.
The maximum fluorescence peak wavelength of the compound BD3 was 458 nm.
A measurement target compound was dissolved in EPA (diethylether:isopentane:ethanol=5:5:2 in volume ratio) at a concentration of 10 μmol/L, and the obtained solution was put in a quartz cell to provide a measurement sample. A phosphorescence spectrum (ordinate axis: phosphorescent luminous intensity, abscissa axis: wavelength) of the measurement sample is measured at a low temperature (77K). A tangent is drawn to the rise of the phosphorescence spectrum close to the short-wavelength region. An energy amount is calculated by a conversion equation (F1) below on a basis of a wavelength value λedge [nm] at an intersection of the tangent and the abscissa axis. The calculated energy amount is defined as triplet energy T1.
T1 [eV]=1239.85/λedge Conversion Equation (F1):
The tangent to the rise of the phosphorescence spectrum close to the short-wavelength region is drawn as follows. While moving on a curve of the phosphorescence spectrum from the short-wavelength region to the local maximum value closest to the short-wavelength region among the local maximum values of the phosphorescence spectrum, a tangent is checked at each point on the curve toward the long-wavelength of the phosphorescence spectrum. An inclination of the tangent is increased along the rise of the curve (i.e., a value of the ordinate axis is increased). A tangent drawn at a point of the local maximum inclination (i.e., a tangent at an inflection point) is defined as the tangent to the rise of the phosphorescence spectrum close to the short-wavelength region.
A local maximum point where a peak intensity is 15% or less of the maximum peak intensity of the spectrum is not counted as the above-mentioned local maximum peak intensity closest to the short-wavelength region. The tangent drawn at a point that is closest to the local maximum peak intensity closest to the short-wavelength region and where the inclination of the curve is the local maximum is defined as a tangent to the rise of the phosphorescence spectrum close to the short-wavelength region.
For phosphorescence measurement, a spectrophotofluorometer body F-4500 manufactured by Hitachi High-Technologies Corporation was used.
Table 18 shows measurement results of triplet energy T1 of the respective compounds.
The compound BH2-11 was synthesized in accordance with a synthesis scheme below.
Under argon atmosphere, 20.0 g of (2,6-dimethoxyphenyl)boronic acid, 39.7 g of 4-bromo-2-fluoro-1-iodobenzene, 2.54 g of tetrakis (triphenylphosphine)palladium(0), 385 mL of 1,2-dimethoxyethane, and 165 ml of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography, and the obtained sample was dried in a vacuum at room temperature for three hours to obtain 25.2 g of 4-bromo-2-fluoro-2′,6′-dimethoxy-1,1′-biphenyl (a yield of 74%).
Under argon atmosphere, 25.2 g of 4-bromo-2-fluoro-2′,6′-dimethoxy-1,1′-biphenyl and 162 mL of (dehydrated) dichloromethane were put into a flask, and cooled to 0 degrees C. Boron tribromide dichloromethane solution (1.0 mol/I, 243 mL) was added thereto, and the reaction solution was stirred at room temperature for four hours. After the reaction, the solution was cooled to −78 degrees C. The solution was carefully deactivated with methanol and then deactivated with a sufficient amount of water. The reaction solution was extracted with dichloromethane. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate, and then origin impurities were removed through a silica gel short column. The solution was concentrated and the obtained sample was dried in a vacuum at room temperature for three hours to obtain 21.6 g of 4′-bromo-2′-fluoro-[1,1′-biphenyl]-2,6-diol (a yield of 94%).
Under argon atmosphere, 21.6 g of 4′-bromo-2′-fluoro-[1,1′-biphenyl]-2,6-diol, 450 mL of (dehydrated)N-methyl-2-pyrrolidinone, and 21.1 g of K2CO3 were put into a flask, and stirred at 180 degrees C. for 2 hours. After the reaction, the solution was cooled to room temperature. The reaction solution was extracted with ethyl acetate. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then purified by silica gel column chromatography. The obtained sample was dried in a vacuum at room temperature for three hours to obtain 13.4 g of 7-bromodibenzo[b,d]furan-1-ol (a yield of 67%).
Under argon atmosphere, 13.4 g of 7-bromodibenzo[b,d]furan-1-ol, 7.06 g of (phenyl-d5)boronic acid, 1.17 g of tetrakis (triphenylphosphine)palladium(0), 177 mL of 1,2-dimethoxyethane, and 76 ml of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography. The obtained sample was dried in a vacuum at room temperature for three hours to obtain 11.7 g of 7-(phenyl-d5)dibenzo[b,d]furan-1-ol (a yield of 87%).
Under argon atmosphere, 11.7 g of 7-(phenyl-d5)dibenzo[b,d]furan-1-ol, 540 mg of N,N-dimethyl-4-aminopyridine, 14.9 g of trifluoro methane sulfonic acid anhydride, and 27 mL of (dehydrated) dichloromethane were put into a flask, and cooled to 0 degrees C. 5.34 mL of (dehydrated) pyridine was added dropwise and then stirred at room temperature for two hours. After the reaction, the solution was deactivated with a sufficient amount of water. The reaction solution was extracted with dichloromethane. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate, and then origin impurities were removed through a silica gel short column. The solution was concentrated and the obtained sample was dried in a vacuum at room temperature for three hours to obtain 16.1 g of 7-(phenyl-d5)dibenzo[b,d]furan-1-yl trifluoromethanesulfonate as a white solid (a yield of 92%).
Under argon atmosphere, 16.1 g of 7-(phenyl-d5)dibenzo[b,d]furan-1-yl trifluoromethanesulfonate, 12.7 g of (10-phenylanthracen-9-yl)boronic acid, 936 mg of tetrakis(triphenylphosphine)palladium(0), 142 mL of 1,4-dioxane, and 61 ml of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography. The obtained sample was dried in a vacuum at 60 degrees C. for three hours to obtain 11.4 g of 7-(phenyl-d5)-1-(10-phenylanthracen-9-yl)dibenzo[b,d]furan (a yield of 56%). As a result of mass spectroscopy analysis, the solid was the compound 2-11, and m/e was equal to 501 while a calculated molecular weight was 501.64.
A compound BH2-12 was synthesized in accordance with a synthesis scheme below.
In Synthesis Example 2, the compound BH2-12 was synthesized using (10-(phenyl-d5)anthracen-9-yl)boronic acid synthesized by a known method in place of (10-phenylanthracen-9-yl)boronic acid. Except for the above, the same reaction as in (6) of Synthesis Example 1 was performed to obtain a white solid. As a result of mass spectroscopy analysis, the white solid was the compound BH2-12, and m/e was equal to 506 while a calculated molecular weight was 506.67.
A compound BH2-13 was synthesized in accordance with a synthesis scheme below.
In Synthesis Example 3, the compound BH2-13 was synthesized using (phenyl)boronic acid in place of (phenyl-d5)boronic acid. Except for the above, the same reaction as in Synthesis Example 1 or 2 was performed to obtain a white solid. As a result of mass spectroscopy analysis, the white solid was the compound BH2-13, and m/e was equal to 501 while a calculated molecular weight was 501.64.
A compound BH2-14 was synthesized in accordance with a synthesis scheme below.
Under argon atmosphere, 4.32 g of 4-bromo-1,1′-biphenyl-2′,3′,4′,5′,6′-d5, 7.39 g of (10-(dibenzo[b,d]furan-2-yl)anthracen-9-yl)boronic acid, 419 mg of tetrakis(triphenylphosphine)palladium(0), 64 mL of 1,4-dioxane, and 27 m1 of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography to obtain 5.58 g of 2-(10-([1,1′-biphenyl]-4-yl-2′,3′,4′,5′,6′-d5)anthracen-9-yl)dibenzo[b,d]furan (a yield of 61%). As a result of mass spectroscopy analysis, the solid was the compound BH2-14, and m/e was equal to 501 while a calculated molecular weight was 501.64.
A compound BH2-15 was synthesized in accordance with a synthesis scheme below.
In Synthesis Example 5, the compound BH2-15 was synthesized using naphtho[1,2-b]benzofuran-7-yl trifluoromethanesulfonate synthesized by a known method in place of 7-(phenyl-d5)dibenzo[b,d]furan-1-yl trifluoromethanesulfonate. Except for the above, the same reaction as in (6) of Synthesis Example 1 was performed to obtain a white solid. As a result of mass spectroscopy analysis, the white solid was the compound BH2-15, and m/e was equal to 475 while a calculated molecular weight was 475.60.
A compound BH2-16 was synthesized in accordance with a synthesis scheme below.
In Synthesis Example 6, the compound BH2-16 was synthesized using naphtho[2,3-b]benzofuran-1-yl trifluoromethanesulfonate synthesized by a known method in place of naphtho[1,2-b]benzofuran-7-yl trifluoromethanesulfonate. Except for the above, the same reaction as in Synthesis Example 2 was performed to obtain a white solid. As a result of mass spectroscopy analysis, the white solid was the compound BH2-16, and m/e was equal to 475 while a calculated molecular weight was 475.60.
A compound BH2-17 was synthesized in accordance with a synthesis scheme below.
In Synthesis Example 7, the compound BH2-17 was synthesized using 4-bromo-1-fluoro-2-iodobenzene in place of 4-bromo-2-fluoro-1-iodobenzene. Except for the above, the same reaction as in Synthesis Example 1 or 2 was performed to obtain a white solid. As a result of mass spectroscopy analysis, the white solid was the compound BH2-17, and m/e was equal to 506 while a calculated molecular weight was 506.67.
The compound BH1-81 was synthesized in accordance with a synthesis scheme below.
Under argon atmosphere, 3.00 g of 1,4-dibromobenzene-2,3,5,6-d4, 6.22 g of (pyren-1-yl-d9)boronic acid, 578 mg of tetrakis(triphenylphosphine)palladium(0), 44 mL of 1,2-dimethoxyethane, and 19 m1 of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography. The obtained sample was dried in a vacuum at room temperature for three hours to obtain 3.32 g of 1,1′-(1,4-phenylene-d4)bis(pyrene-2,3,4,5,6,7,8,9,10-d9) (a yield of 53%). As a result of mass spectroscopy analysis, the solid was the compound BH1-81, and m/e was equal to 500 while a calculated molecular weight was 500.73.
A compound BH1-82 was synthesized in accordance with a synthesis scheme below.
In Synthesis Example 9, the compound BH1-82 was synthesized using pyren-1-ylboronic acid synthesized by a known method in place of (pyren-1-yl-d9)boronic acid. Except for the above, the same reaction as in Synthesis Example 8 was performed to obtain a white solid. As a result of mass spectroscopy analysis, the white solid was the compound BH1-82, and m/e was equal to 482 while a calculated molecular weight was 482.62.
The compound BH1-84 was synthesized in accordance with a synthesis scheme below.
Under argon atmosphere, 3.17 g of 1,3,5-tribromobenzene-2,4,6-d3, 1.3 g of (phenyl-d5)boronic acid, 461 mg of tetrakis(triphenylphosphine)palladium(0), 35 mL of 1,2-dimethoxyethane, and 15 ml of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography. The obtained sample was dried in a vacuum at room temperature for three hours to obtain 1.34 g of 1,1′-(1,4-phenylene-d4)bis(pyrene-2,3,4,5,6,7,8,9,10-d9) (a yield of 42%).
Under argon atmosphere, 13.4 g of 1,1′-(1,4-phenylene-d4)bis(pyrene-2,3,4,5,6,7,8,9,10-d9), 2.08 g of (pyren-1-yl-d9)boronic acid, 194 mg of tetrakis(triphenylphosphine)palladium(0), 15 mL of 1,2-dimethoxyethane, and 6.3 ml of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography. The obtained sample was dried in a vacuum at room temperature for three hours to obtain 1.17 g of 1,1′-([1,1′-biphenyl]-3,5-diyl-d8)bis(pyrene-2,3,4,5,6,7,8,9,10-d9) (a yield of 48%). As a result of mass spectroscopy analysis, the solid was the compound BH1-84, and m/e was equal to 581 while a calculated molecular weight was 580.85.
A compound BH1-86 was synthesized in accordance with a synthesis scheme below.
In Synthesis Example 11, the compound BH1-86 was synthesized using 1,3,5-tribromobenzene in place of 1,3,5-tribromobenzene-2,4,6-d3 and using pyren-1-ylboronic acid in place of (pyren-1-yl-d9)boronic acid. Except for the above, the same reaction as in Synthesis Example 10 was performed to obtain a white solid. As a result of mass spectroscopy analysis, the white solid was the compound BH1-86, and m/e was equal to 560 while a calculated molecular weight was 559.72.
A compound BH1-83 was synthesized in accordance with a synthesis scheme below.
Under argon atmosphere, 4.20 g of 1,3,5-tribromobenzene-2,4,6-d3, 6.57 g of (pyren-1-yl-d9)boronic acid, 611 mg of tetrakis(triphenylphosphine)palladium(0), 46 mL of 1,2-dimethoxyethane, and 20 ml of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography. The obtained sample was dried in a vacuum at room temperature for three hours to obtain 2.91 g of 1,1′-(5-bromo-1,3-phenylene-2,4,6-d3)bis(pyrene-2,3,4,5,6,7,8,9,10-d9) (a yield of 38%).
Under argon atmosphere, 2.91 g of 1,1′-(5-bromo-1,3-phenylene-2,4,6-d3)bis(pyrene-2,3,4,5,6,7,8,9,10-d9) and 25 mL of (dehydrated) tetrahydrofuran were put into a flask, and cooled to −78 degrees C. 3.9 mL of n-BuLi (1.55 M in hexane) was added thereto, and stirred for 30 minutes. Next, 2.0 mL of (iPrO)3B was added, stirred at −78 degrees C. for five minutes, and then stirred at room temperature for one hour. After the reaction, 25 mL of 1 M HCl aq. was added, and stirred at room temperature for one hour. The reaction solution was extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and concentrated, and then washed with hexane to obtain 2.10 g of (3,5-bis(pyren-1-yl-d9)phenyl-2,4,6-d3)boronic acid (a yield of 77%).
Under argon atmosphere, (3,5-bis(pyren-1-yl-d9)phenyl-2,4,6-d3)boronic acid 2.10, 2.91 g of naphtho[2,3-b]benzofuran-2-yl-d9 trifluoromethanesulfonate, 247 mg of tetrakis(triphenylphosphine)palladium(0), 20 mL of 1,2-dimethoxyethane, and 8.0 ml of 2M sodium carbonate aqueous solution were put into a flask and stirred at reflux for eight hours. The reaction solution was cooled to room temperature, and then extracted with toluene. After an aqueous phase was removed, an organic phase was washed with saturated saline. The organic phase was dried with anhydrous sodium sulfate and then concentrated. The residue was purified by silica gel column chromatography. The obtained sample was dried in a vacuum at room temperature for three hours to obtain 1.43 g of 2-(3,5-bis(pyren-1-yl-d9)phenyl-2,4,6-d3)naphtho[2,3-b]benzofuran-1,3,4,6,7,8,9,10,11-d9 (a yield of 37%). As a result of mass spectroscopy analysis, the solid was the compound BH1-83, and m/e was equal to 725 while a calculated molecular weight was 725.01.
1 . . . organic EL device, 2 . . . substrate, 3 . . . anode, 4 . . . cathode, 51 . . . first emitting layer, 52 . . . second emitting layer, 6 . . . hole injecting layer, 7 . . . hole transporting layer, 8 . . . electron transporting layer, 9 . . . electron injecting layer
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-073089 | Apr 2020 | JP | national |
| 2020-111889 | Jun 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/009835 | 3/11/2021 | WO |
