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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
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  • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
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  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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  • H10K85/649—Aromatic compounds comprising a hetero atom
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  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
  • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

• the present invention relates to a light emitting element capable of converting electric energy into light. More specifically, the present invention relates to a light emitting element that can be used in fields such as a display element, a flat panel display, a backlight, illumination, interior, a sign, a signboard, an electrophotographic machine, and an optical signal generator.
• organic thin-film light-emitting elements can be obtained in various light-emitting colors by using various light-emitting materials for the light-emitting layer.
• three primary color luminescent materials research on the green luminescent material is the most advanced, and at present, intensive research is being conducted to improve the characteristics of the red and blue luminescent materials.
• Organic thin-film light-emitting elements must satisfy improved luminous efficiency, lower drive voltage, and improved durability.
• the compatibility between luminous efficiency and durability is a major issue.
• a light emitting material and an electron transport material having pyrene as a basic skeleton have been developed (see, for example, Patent Documents 1 to 5).
• JP 2007-131723 A Japanese Patent Laid-Open No. 2007-159591 JP 2011-14886 A International Publication No. 2004/63159 European Patent Application No. 1808912
• An object of the present invention is to provide a light-emitting element that solves the problems of the prior art and enables an organic thin-film light-emitting element with high-efficiency light emission and excellent durability.
• the present invention is a light emitting device material comprising a compound represented by the following general formula (1) or (2).
• R 1 to R 16 may be the same or different and are each a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl ether group, an arylthioether Selected from the group consisting of a group, an aryl group, a heteroaryl group, a halogen, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a silyl group, and —P ( ⁇ O) R 17 R 18 .
• R 17 and R 18 are an aryl group or a heteroaryl group.
• R 1 to R 8 and R 9 to R 16 may form a ring with adjacent substituents.
• X is a group represented by the general formula (3)
• Y is a group represented by the general formula (4).
• L 1 represents a single bond, a substituted or unsubstituted arylene group having 6 to 40 nuclear carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 nuclear carbon atoms.
• Ar 1 represents a residue derived from a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms, or a residue derived from a substituted or unsubstituted heteroaryl group having 2 to 14 nuclear carbon atoms.
• L 2 represents a single bond, a residue derived from a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms, or a residue derived from a substituted or unsubstituted heteroaryl group having 2 to 14 nuclear carbon atoms.
• HAr 1 and HAr 2 represent a heteroaryl group having a substituted or unsubstituted electron-accepting nitrogen.
• n is an integer of 1 to 5.
• n is 2 to 5
• HAr 1 may be the same or different
• m is 2 to 5
• HAr 2 may be the same or different.
• X and Y are not the same group.
• an organic electroluminescent device having high efficiency light emission and excellent durability.
• R 1 to R 16 may be the same or different and are each a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl ether group, an arylthioether Selected from the group consisting of a group, an aryl group, a heteroaryl group, a halogen, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a silyl group, and —P ( ⁇ O) R 17 R 18 .
• R 17 and R 18 are an aryl group or a heteroaryl group.
• R 1 to R 8 and R 9 to R 16 may form a ring with adjacent substituents.
• X is a group represented by the general formula (3)
• Y is a group represented by the general formula (4).
• L 1 represents a single bond, a substituted or unsubstituted arylene group having 6 to 40 nuclear carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 nuclear carbon atoms.
• Ar 1 represents a residue derived from a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms, or a residue derived from a substituted or unsubstituted heteroaryl group having 2 to 14 nuclear carbon atoms.
• L 2 represents a single bond, a residue derived from a substituted or unsubstituted aryl group having 6 to 14 nuclear carbon atoms, or a residue derived from a substituted or unsubstituted heteroaryl group having 2 to 14 nuclear carbon atoms.
• HAr 1 and HAr 2 represent a heteroaryl group having a substituted or unsubstituted electron-accepting nitrogen.
• n is an integer of 1 to 5.
• n is 2 to 5
• HAr 1 may be the same or different
• m is 2 to 5
• HAr 2 may be the same or different.
• X and Y are not the same group.
• the alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. It may or may not have a substituent.
• a substituent There is no restriction
• the number of carbon atoms of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 and more preferably 1 to 8 from the viewpoint of availability and cost.
• the cycloalkyl group refers to, for example, a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, which may or may not have a substituent.
• carbon number of an alkyl group part is not specifically limited, Usually, it is the range of 3-20.
• the heterocyclic group refers to an aliphatic ring having atoms other than carbon, such as a pyran ring, a piperidine ring, and a cyclic amide, in the ring, which may or may not have a substituent. .
• carbon number of a heterocyclic group is not specifically limited, Usually, it is the range of 2-20.
• alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may or may not have a substituent.
• carbon number of an alkenyl group is not specifically limited, Usually, it is the range of 2-20.
• the cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, which may have a substituent. You don't have to.
• the alkynyl group indicates, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent.
• carbon number of an alkynyl group is not specifically limited, Usually, it is the range of 2-20.
• the alkoxy group refers to, for example, a functional group having an aliphatic hydrocarbon group bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group may have a substituent. It may not have. Although carbon number of an alkoxy group is not specifically limited, Usually, it is the range of 1-20.
• the alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.
• the hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Usually, it is the range of 1-20.
• An aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Good. Although carbon number of an aryl ether group is not specifically limited, Usually, it is the range of 6-40.
• the aryl thioether group is a group in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom.
• the aromatic hydrocarbon group in the aryl ether group may or may not have a substituent. Although carbon number of an aryl ether group is not specifically limited, Usually, it is the range of 6-40.
• the aryl group refers to, for example, an aromatic hydrocarbon group such as a phenyl group, a biphenylyl group, a fluorenyl group, a naphthyl group, a phenanthryl group, or a terphenyl group.
• the aryl group may or may not have a substituent.
• the number of nuclear carbon atoms of the aryl group is not particularly limited, but is usually in the range of 6 or more and 40 or less. The number of nuclear carbons does not include substituent carbon. This is common to the following description.
• a heteroaryl group is a furanyl group, thiophenyl group, pyridyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, naphthyridyl group, benzofuranyl group, benzothiophenyl group, imidazolyl group, benzoimidazolyl group, indolyl group, dibenzofuranyl
• the number of nuclear carbon atoms of the heteroaryl group is not particularly limited, but is usually in the range of 2 to 30.
• Halogen means fluorine, chlorine, bromine and iodine.
• the carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, or phosphine oxide group may or may not have a substituent.
• substituents include an alkyl group, a cycloalkyl group, An aryl group, a heteroaryl group, etc. are mentioned, These substituents may be further substituted.
• the silyl group refers to, for example, a functional group having a bond to a silicon atom such as a trimethylsilyl group, which may or may not have a substituent.
• carbon number of a silyl group is not specifically limited, Usually, it is the range of 3-20.
• the number of silicon is usually 1 or more and 6 or less.
• R 1 to R 8 and R 9 to R 16 may combine with adjacent substituents to form a conjugated or non-conjugated ring.
• the ring may contain nitrogen, oxygen, sulfur, phosphorus, silicon atoms, or may be condensed with another ring.
• R 1 or R 5 is preferable in the general formula (1)
• R 9 or R 12 is preferable in the general formula (2).
• R 1 to R 8 or R 9 to R 16 are all hydrogen or deuterium.
• the arylene group is a divalent group derived from an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenylyl group, a fluorenyl group, a phenanthryl group, or an anthracenyl group, which may have a substituent. You don't have to.
• the number of carbon atoms of the arylene group is not particularly limited, but is usually in the range of 6 to 40.
• a heteroarylene group is a pyridyl group, pyrazinyl group, pyrimidyl group, triazyl group, quinolinyl group, benzoquinolinyl group, quinoxalinyl group, naphthyridyl group, acridyl group, phenanthrolinyl group, thiophenyl group, benzothiophenyl group, dibenzothiophenyl group
• the number of nuclear carbon atoms of the heteroarylene group is not particularly limited, but is usually in the range of 2 to 40.
• Heteroaryl groups having electron-accepting nitrogen are pyridyl, quinolinyl, isoquinolinyl, benzoquinolinyl, quinoxanyl, naphthyridyl, pyrazinyl, pyrimidyl, pyridazinyl, phenanthrolinyl, imidazopyridyl, triazyl
• At least one electron-accepting nitrogen atom as an atom other than carbon among the heteroaryl groups such as a group, an acridyl group, an imidazolyl group, a benzimidazolyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group
• a plurality of cyclic aromatic groups in a ring are shown, which may be unsubstituted or substituted.
• the electron-accepting nitrogen mentioned here represents a nitrogen atom forming a multiple bond with an adjacent atom. Since the nitrogen atom has a high electronegativity, the multiple bond has an electron accepting property. Therefore, an aromatic heterocycle containing electron-accepting nitrogen has a high electron affinity.
• the number of nuclear carbon atoms of the heteroaryl group having electron-accepting nitrogen is not particularly limited, but is usually 2 or more and 40 or less.
• the compound represented by the general formula (1) or (2) is a compound in which the 1,6-position or the 1,8-position of the pyrene skeleton is substituted with a substituent containing a heteroaryl group containing an electron-accepting nitrogen. is there.
• the 1,6-position or 1,8-position is substituted with an aromatic substituent, the electronic state of the pyrene skeleton is greatly changed, and the conjugated system is expanded. Therefore, by substituting such a position with a substituent containing a heteroaryl group containing electron-accepting nitrogen, the energy level of LUMO (minimum unoccupied orbital) localized in the pyrene skeleton is greatly stabilized. be able to.
• the compound represented by the general formula (1) or (2) can easily receive electrons from the cathode, and the electron mobility of the organic layer containing the compound represented by the general formula (1) or (2) is also increased. Since it improves, it is preferable. Furthermore, the energy level of the HOMO (maximum occupied orbital) of the compound represented by the general formula (1) or (2) is greatly stabilized and becomes stable against oxidation. That is, the compound represented by the general formula (1) or (2) is not easily radically cationized, and the hole blocking property is improved. Therefore, when the compound represented by the general formula (1) or (2) is used as the electron transport layer, the material can contribute to the improvement of the light emission efficiency.
• the HOMO maximum occupied orbital
• X and Y are p- (pyridyl) phenyl groups
• X and Y are p- (pyridyl) phenyl groups
• X and Y are also used.
• substituents For example, p- (2- (4-methyl) pyridyl) phenyl group and p- (2- (5-methyl) pyridyl) phenyl group are different substituents.
• Ar 1 is a residue derived from an aryl group having 6 to 14 nuclear carbon atoms
• examples of the case where Ar 1 is a residue derived from an aryl group having 6 to 14 nuclear carbon atoms include, but are not limited to, a phenyl group, a naphthyl group, a biphenylyl group, a fluorenyl group, an anthracenyl group, Or the residue guide
• a residue derived from a phenyl group, a naphthyl group, a biphenylyl group, or a fluorenyl group is more preferable, and a residue derived from a phenyl group is more preferable from the viewpoint of synthesis cost and resistance to heat load during vapor deposition.
• examples of the case where Ar 1 is a residue derived from a heteroaryl group having 2 to 14 nuclear carbon atoms are not particularly limited, but specifically, pyridyl group, pyrazinyl group, pyrimidyl group, triazyl group, quinolinyl Group, isoquinolinyl group, benzoquinolinyl group, quinoxalinyl group, naphthyridyl group, acridyl group, phenanthrolinyl group, thiophenyl group, benzothiophenyl group, dibenzothiophenyl group, furanyl group, benzofuranyl group, dibenzofuranyl group, indolyl group, Examples thereof include residues derived from a carbazolyl group, an imidazolyl group, a benzimidazolyl group, and the like.
• a residue derived from a pyridyl group, a pyrazinyl group, or a pyrimidyl group is particularly preferable from the viewpoints of resistance to heat load during vapor deposition and synthesis cost.
• L 1 examples include, but are not limited to, a divalent residue derived from a single bond, a phenylene group, a naphthalenylene group, a biphenylene group, a terphenylene group, a fluorenylene group, an anthracenylene group, a pyridylene group, or a pyrimidine.
• a single bond, a phenylene group, a biphenylene group, a naphthalenylene group, a fluorenylene group, a pyridylene group, a divalent residue derived from pyrimidine, a divalent residue derived from pyrazine, a divalent residue derived from quinoline Or a divalent residue derived from isoquinoline is more preferred. More preferred are a single bond, a phenylene group, and a pyridylene group.
• HAr 1 is a heteroaryl group containing an electron-accepting nitrogen, and is not particularly limited.
• a pyridyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxanyl group, a naphthyridyl group, a pyrazinyl group, a pyrimidyl group examples include a pyridazinyl group, a phenanthrolinyl group, an imidazopyridyl group, a triazyl group, an acridyl group, an imidazolyl group, a benzoimidazolyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, and a benzothiazolyl group.
• those not containing a 5-membered ring are preferable from the viewpoint of chemical or thermal stability during vapor deposition, and include pyridyl group, quinolinyl group, isoquinolinyl group, benzoquinolinyl group, quinoxanyl group, naphthyridyl group, pyrazinyl group, pyrimidyl group.
• pyridazinyl group, a phenanthrolinyl group, a triazyl group, or an acridyl group is more preferable.
• a pyridyl group a pyrimidyl group, a quinolinyl group, and an isoquinolinyl group are more preferable, and a pyridyl group is particularly preferable.
• a pyridyl group a 3-pyridyl group or a 4-pyridyl group is preferable, and a 4-pyridyl group is most preferable.
• X is a substituent represented by the general formula (3) because the intermolecular interaction becomes strong. Further, it is more preferable that X is a substituent represented by the general formula (5), since the intermolecular interaction becomes stronger and the movement of the molecule can be suppressed.
• L 1 and HAr 1 are as described above.
• R 19 to R 21 are the same as those described above for R 1 to R 16 .
• Two HAr 1 may be the same or different.
• a nitrogen atom in a heteroaryl group having electron-accepting nitrogen forms a hydrogen bond with a hydrogen atom in an adjacent molecule.
• the substituent represented by the general formula (5) has a heteroaryl group containing an electron-accepting nitrogen having a hydrogen bonding property as described above, at the meta position and the meta ′ position of the benzene ring. Therefore, the compound having a substituent represented by the general formula (5) can form a strong hydrogen bonding network between adjacent molecules, and can suppress the movement of molecules due to the application of an electric field as described above. .
• R 19 to R 21 include hydrogen or deuterium, an alkyl group, an aryl group, and a heteroaryl group, with hydrogen or deuterium being more preferred.
• L 2 include, but are not limited to, those similar to Ar 1 in addition to a single bond.
• a single bond or a residue derived from a phenyl group, biphenylyl group, fluorenyl group, naphthalenyl group, pyridyl group, pyrimidyl group, quinolinyl group or isoquinolinyl group is preferable. More preferably, it is a residue derived from a single bond or a phenyl group, biphenylyl group or fluorenyl group, and a residue derived from a single bond or a phenyl group is particularly preferred. The particularly preferred reasons are described below.
• the heteroaryl group HAr 2 having electron-accepting nitrogen contained in Y plays a role of adjusting the energy level of LUMO mainly localized in the pyrene skeleton.
• the LUMO energy level is closely related to the ease with which electrons are received from the cathode and the ease with which electrons are injected into the light-emitting layer, and is one of the major factors involved in improving the light-emitting efficiency and lifetime of light-emitting elements.
• the ease of adjustment of the LUMO energy level is affected by the distance between the HAr 2 and the pyrene skeleton and the spread of ⁇ conjugate.
• the energy level of LUMO localized in pyrene skeleton is influenced electron accepting possessed by HAr 2 This makes it easier for the LUMO energy level to change. That is, when L 2 is a single bond in which the distance between pyrene and HAr 2 is the shortest or a residue derived from a phenyl group that is relatively short and ⁇ -conjugated, the LUMO energy level is HAR 2 . Be susceptible.
• the LUMO energy level of the optimal electron transport material varies depending on the cathode material and the light-emitting material used, and it becomes possible to finely adjust the LUMO energy level by changing the type of HAr 2.
• Compounds with the optimal LUMO energy level can be found.
• L 2 is particularly preferably a single bond or a residue derived from a phenyl group.
• n represents an integer of 1 to 5 when L 2 is other than a single bond, but when m is 4 or 5, the molecular weight becomes too large and there is a concern of thermal decomposition during vapor deposition.
• HAr 2 is the same as HAr 1 .
• a pyridyl group, a quinolinyl group, an isoquinolinyl group, a pyrazinyl group, a pyrimidyl group, a triazyl group, or an acridyl group is more preferable.
• a pyridyl group, a quinolinyl group, an isoquinolinyl group, a pyrazinyl group, or a pyrimidyl group is more preferable from the viewpoint that a high electron mobility can be obtained and the voltage of the light emitting element can be lowered.
• a pyridyl group particularly preferred is a pyridyl group, and among the pyridyl groups, a 3-pyridyl group or a 4-pyridyl group is more preferred.
• the compound represented by the general formula (1) or (2) can be synthesized by combining known reactions such as halogenation and Suzuki coupling reaction. As an example, a synthesis scheme is shown below. The synthesis method is not limited to this. In this synthetic route, by changing the type of boronic acid used in the first step reaction, the substitution position of HAr 1 and the number of substitutions n can be adjusted, and the type of boronic acid used in the third step reaction is changed. Thus, the type of HAr 2 can be selected. That is, compounds having various LUMO energy levels can be easily synthesized.
• the compound represented by the general formula (1) or (2) is not particularly limited, but specific examples include the following.
• the light emitting device of the present invention has an anode and a cathode, and an organic layer interposed between the anode and the cathode, and the organic layer includes at least a light emitting layer and an electron transport layer, and the light emitting layer emits light by electric energy. To do.
• the organic layer is composed of only the light emitting layer / electron transport layer, 1) hole transport layer / light emitting layer / electron transport layer and 2) hole transport layer / light emitting layer / electron transport layer / electron injection layer, 3) Laminate structure such as hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer can be mentioned.
• Each of the layers may be a single layer or a plurality of layers.
• the compound represented by the general formula (1) or (2) may be used in any layer in the above device configuration, it is excellent in electron injection and transport properties, and therefore has an electron transport layer or electron injection. It is preferable to use it for the layer.
• the anode and the cathode have a role of supplying a sufficient current for light emission of the device, and it is desirable that at least one of them is transparent or translucent in order to extract light.
• the anode formed on the substrate is a transparent electrode.
• the material used for the anode is a material that can efficiently inject holes into the organic layer, and is transparent or translucent to extract light.
• Tin oxide, indium oxide, indium tin oxide (ITO) indium zinc oxide (IZO) Although not particularly limited, such as conductive metal oxides such as, metals such as gold, silver and chromium, inorganic conductive materials such as copper iodide and copper sulfide, conductive polymers such as polythiophene, polypyrrole and polyaniline It is particularly desirable to use ITO glass or Nesa glass. These electrode materials may be used alone, or a plurality of materials may be laminated or mixed.
• the resistance of the transparent electrode is not limited as long as a current sufficient for light emission of the element can be supplied, but it is desirable that the resistance be low from the viewpoint of power consumption of the element.
• an ITO substrate with a resistance of 300 ⁇ / ⁇ or less will function as a device electrode, but since it is now possible to supply a substrate with a resistance of approximately 10 ⁇ / ⁇ , use a substrate with a low resistance of 20 ⁇ / ⁇ or less. Is particularly desirable.
• the thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 100 to 300 nm.
• the light emitting element is preferably formed over a substrate.
• a glass substrate such as soda glass or non-alkali glass is preferably used.
• the thickness of the glass substrate it is sufficient that the thickness is sufficient to maintain the mechanical strength.
• alkali-free glass is preferred because it is better that there are fewer ions eluted from the glass.
• soda lime glass provided with a barrier coat such as SiO 2 is also commercially available and can be used.
• the substrate need not be glass, and for example, an anode may be formed on a plastic substrate.
• the ITO film forming method is not particularly limited, such as an electron beam method, a sputtering method, and a chemical reaction method.
• the material used for the cathode is not particularly limited as long as it can efficiently inject electrons into the light emitting layer.
• metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys and multilayer stacks of these metals with low work function metals such as lithium, sodium, potassium, calcium, and magnesium Is preferred.
• aluminum, silver, and magnesium are preferable as the main component from the viewpoints of electrical resistance, ease of film formation, film stability, luminous efficiency, and the like.
• magnesium and silver are preferable because electron injection into the electron transport layer and the electron injection layer in the present invention is facilitated and low voltage driving is possible.
• metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, polyvinyl chloride
• an organic polymer compound such as a hydrocarbon polymer compound is laminated on the cathode as a protective film layer.
• the compound represented by General formula (1) or (2) can also be utilized as this protective film layer.
• the protective film layer is selected from materials that are light transmissive in the visible light region.
• the production method of these electrodes is not particularly limited, such as resistance heating, electron beam, sputtering, ion plating and coating.
• the hole transport layer is formed by a method of laminating or mixing one or more hole transport materials or a method using a mixture of a hole transport material and a polymer binder.
• the hole transport material needs to efficiently transport holes from the positive electrode between electrodes to which an electric field is applied, has high hole injection efficiency, and can efficiently transport injected holes. desirable.
• the material has an appropriate ionization potential, has a high hole mobility, is excellent in stability, and does not easily generate trapping impurities during manufacture and use.
• a substance satisfying such conditions is not particularly limited.
• the compound represented by the general formula (1) or (2) has excellent electron injecting and transporting properties, when this is used in the electron transporting layer, electrons are not recombined in the light emitting layer, and some holes are transported. There is a concern that even the layer will leak. Therefore, it is preferable to use a compound having an excellent electron blocking property for the hole transport layer.
• a compound containing a carbazole skeleton is preferable because it has excellent electron blocking properties and can contribute to high light emission efficiency of the light emitting element.
• the compound containing the carbazole skeleton contains a good carbazole dimer, carbazole trimer, or carbazole tetramer skeleton because it has both good electron blocking properties and hole injection / transport properties. Furthermore, when a compound containing a carbazole skeleton is used for the hole transport layer, the compound having the carbazole skeleton also has a high triplet exciton blocking function if the combined light-emitting layer contains a phosphorescent material described later. Therefore, it is more preferable because high luminous efficiency can be achieved.
• the compound containing a triphenylene skeleton which is excellent in having high hole mobility, in the hole transport layer because the effects of improving the carrier balance and improving the light emission efficiency and durability are obtained.
• the compound containing a triphenylene skeleton has two or more diarylamino groups.
• the compound containing a carbazole skeleton or the compound containing a triphenylene skeleton may be used alone as a hole transport layer, or may be used as a mixture with each other. Further, other materials may be mixed within a range not impairing the effects of the present invention. In the case where the hole transport layer is composed of a plurality of layers, any one layer may contain a compound containing a carbazole skeleton or a compound containing a triphenylene skeleton.
• a hole injection layer may be provided between the anode and the hole transport layer. Providing the hole injection layer lowers the voltage of the light emitting element and improves the durability life.
• a material having a smaller ionization potential than that of the material normally used for the hole transport layer is preferably used. Specifically, a benzidine derivative such as TPD232 and a starburst arylamine material group can be used, and a phthalocyanine derivative can also be used. It is also preferred that the hole injection layer is composed of an acceptor compound alone, or that the acceptor compound is doped into another hole transport material.
• acceptor compounds include metal chlorides such as iron (III) chloride, aluminum chloride, gallium chloride, indium chloride, antimony chloride, metal oxides such as molybdenum oxide, vanadium oxide, tungsten oxide, ruthenium oxide, A charge transfer complex such as tris (4-bromophenyl) aminium hexachloroantimonate (TBPAH).
• metal chlorides such as iron (III) chloride, aluminum chloride, gallium chloride, indium chloride, antimony chloride, metal oxides such as molybdenum oxide, vanadium oxide, tungsten oxide, ruthenium oxide,
• a charge transfer complex such as tris (4-bromophenyl) aminium hexachloroantimonate (TBPAH).
• organic compounds having a nitro group, cyano group, halogen or trifluoromethyl group in the molecule quinone compounds, acid anhydride compounds, fullerenes, and the like are also preferably used.
• these compounds include hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, tetracyanoquinodimethane (TCNQ), tetrafluorotetracyanoquinodimethane (F4-TCNQ), 2, 3, 6, 7 , 10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN6), p-fluoranyl, p-chloranil, p-bromanyl, p-benzoquinone, 2,6-dichlorobenzoquinone 2,5-dichlorobenzoquinone, tetramethylbenzoquinone, 1,2,4,5-tetracyanobenzene, o-dicyanobenzene, p-dicyanobenzene, 1,4-dicyanotetrafluorobenzene, 2,3-dichloro-5 , 6-Dicyanobenzoquinone, p-
• metal oxides and cyano group-containing compounds are preferable because they are easy to handle and can be easily deposited, so that the above-described effects can be easily obtained.
• preferred metal oxides include molybdenum oxide, vanadium oxide, or ruthenium oxide.
• cyano group-containing compounds (a) a compound having at least one electron-accepting nitrogen other than the nitrogen atom of the cyano group in the molecule and further having a cyano group, (b) a halogen and a cyano group in the molecule (C) a compound having both a carbonyl group and a cyano group in the molecule, or (d) an electron-accepting nitrogen other than the nitrogen atom of the cyano group, a halogen and a cyano group.
• a compound having all is more preferable because it becomes a strong electron acceptor. Specific examples of such a compound include the following compounds.
• the hole injection layer is composed of an acceptor compound alone or when the hole injection layer is doped with an acceptor compound
• the hole injection layer may be a single layer, A plurality of layers may be laminated.
• the hole injection material used in combination when the acceptor compound is doped is the same compound as the compound used for the hole transport layer from the viewpoint that the hole injection barrier to the hole transport layer can be relaxed. Is more preferable.
• the light emitting layer may be either a single layer or a plurality of layers, each formed of a light emitting material (host material, dopant material), which may be a mixture of a host material and a dopant material or a host material alone. It may be either. That is, in the light emitting element of the present invention, only the host material or the dopant material may emit light in each light emitting layer, or both the host material and the dopant material may emit light. From the viewpoint of efficiently using electric energy and obtaining light emission with high color purity, the light emitting layer is preferably composed of a mixture of a host material and a dopant material. Further, the host material and the dopant material may be either one kind or a plurality of combinations, respectively.
• a light emitting material host material, dopant material
• the dopant material may be included in the entire host material or may be partially included.
• the dopant material may be laminated or dispersed.
• the dopant material can control the emission color. If the amount of the dopant material is too large, a concentration quenching phenomenon occurs, so that it is preferably used at 20% by weight or less, more preferably 10% by weight or less with respect to the host material.
• the doping method can be formed by a co-evaporation method with a host material, but may be simultaneously deposited after being previously mixed with the host material.
• the light emitting layer may be either a single layer or a plurality of layers, each formed by a light emitting material (host material, dopant material), which may be a mixture of a host material and a dopant material or a host material alone, Either is acceptable. That is, in the light emitting element of the present invention, only the host material or the dopant material may emit light in each light emitting layer, or both the host material and the dopant material may emit light. From the viewpoint of efficiently using electric energy and obtaining light emission with high color purity, the light emitting layer is preferably composed of a mixture of a host material and a dopant material. Further, the host material and the dopant material may be either one kind or a plurality of combinations, respectively.
• a light emitting material host material, dopant material
• the dopant material may be included in the entire host material or may be partially included.
• the dopant material may be laminated or dispersed.
• the dopant material can control the emission color. If the amount of the dopant material is too large, a concentration quenching phenomenon occurs, so that it is preferably used at 20% by weight or less, more preferably 10% by weight or less with respect to the host material.
• the doping method can be formed by a co-evaporation method with a host material, but may be simultaneously deposited after being previously mixed with the host material.
• the light-emitting material includes condensed ring derivatives such as anthracene and pyrene, which have been known as light emitters, metal chelated oxinoid compounds such as tris (8-quinolinolato) aluminum, bisstyrylanthracene derivatives and diesters.
• condensed ring derivatives such as anthracene and pyrene, which have been known as light emitters
• metal chelated oxinoid compounds such as tris (8-quinolinolato) aluminum, bisstyrylanthracene derivatives and diesters.
• Bisstyryl derivatives such as styrylbenzene derivatives, tetraphenylbutadiene derivatives, indene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, dibenzofuran derivatives, carbazole
• polyphenylene vinylene derivatives, polyparaphenylene derivatives, polythiophene derivatives, etc. can be used, but are not particularly limited. Not shall.
• the host material contained in the light emitting material is not particularly limited, but is a compound having a condensed aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, indene, and derivatives thereof, N, Aromatic amine derivatives such as N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1,1′-diamine, metal chelating oxinoids including tris (8-quinolinato) aluminum (III) Compounds, bisstyryl derivatives such as distyrylbenzene derivatives, tetraphenylbutadiene derivatives, indene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, pyr
• the dopant material is not particularly limited, but is a compound having a condensed aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, triphenylene, perylene, fluoranthene, fluorene, indene or a derivative thereof (for example, 2- (benzothiazole-2) -Yl) -9,10-diphenylanthracene, 5,6,11,12-tetraphenylnaphthacene), furan, pyrrole, thiophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzo Compounds having heteroaryl rings such as thiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine
• a phosphorescent material may be included in the light emitting layer.
• a phosphorescent material is a material that exhibits phosphorescence even at room temperature. As a dopant, it is basically necessary to obtain phosphorescence even at room temperature, but it is not particularly limited, and iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum ( An organometallic complex compound containing at least one metal selected from the group consisting of Pt), osmium (Os), and rhenium (Re) is preferable. Among these, from the viewpoint of having a high phosphorescence emission yield even at room temperature, an organometallic complex having iridium or platinum is more preferable.
• Hosts of phosphorescent materials include indole derivatives, carbazole derivatives, indolocarbazole derivatives, pyridine, pyrimidine, nitrogen-containing aromatic compound derivatives having a triazine skeleton, polyarylbenzene derivatives, spirofluorene derivatives, truxene derivatives, triphenylene derivatives, etc.
• a compound containing a chalcogen element such as an aromatic hydrocarbon compound derivative, a dibenzofuran derivative or a dibenzothiophene derivative, or an organometallic complex such as a beryllium quinolinol complex is preferably used.
• Two or more triplet light-emitting dopants may be contained, or two or more host materials may be contained. Further, one or more triplet light emitting dopants and one or more fluorescent light emitting dopants may be contained.
• Preferred phosphorescent host or dopant is not particularly limited, but specific examples include the following.
• the electron transport layer is a layer in which electrons are injected from the cathode and further transports electrons.
• the electron transport layer has high electron injection efficiency, and it is desired to efficiently transport injected electrons. Therefore, it is desirable that the electron transport layer is made of a material having a high electron affinity, a high electron mobility, excellent stability, and a trapping impurity that is unlikely to be generated during manufacture and use.
• the electron transport layer in the present invention includes a hole blocking layer that can efficiently block the movement of holes as the same meaning.
• the compound represented by the general formula (1) or (2) is a compound that satisfies the above conditions, and has a high electron injecting and transporting capability, and thus is suitably used as an electron transporting material.
• the compound represented by the general formula (1) or (2) contains a heteroaryl group having an electron-accepting nitrogen at the 1,6-position or 1,8-position of the pyrene skeleton, the electron injecting and transporting property, electrochemical Excellent stability.
• the introduction of the substituent improves compatibility in a thin film state with a donor compound described later, and exhibits higher electron injecting and transporting ability.
• the transport of electrons from the cathode to the light emitting layer is promoted, and both high luminous efficiency and low driving voltage can be achieved.
• the electron transport material used in the present invention need not be limited to only one kind of each compound represented by the general formula (1) or (2) of the present invention, and a plurality of pyrene compounds of the present invention may be used in combination.
• One or more other electron transport materials may be mixed with the pyrene compound of the present invention as long as the effects of the present invention are not impaired.
• the electron transport material that can be mixed is not particularly limited, but is a compound having a condensed aryl ring such as naphthalene, anthracene, or pyrene or a derivative thereof, or a styryl-based fragrance represented by 4,4′-bis (diphenylethenyl) biphenyl.
• Ring derivatives perylene derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives, quinolinol complexes such as tris (8-quinolinolato) aluminum (III) and hydroxy Examples include hydroxyazole complexes such as phenyloxazole complexes, azomethine complexes, tropolone metal complexes, and flavonol metal complexes.
• the donor compound in the present invention is a compound that facilitates electron injection from the cathode or the electron injection layer to the electron transport layer by improving the electron injection barrier, and further improves the electrical conductivity of the electron transport layer. That is, the light-emitting device of the present invention is more preferably a compound obtained by doping an electron transport layer with a donor compound in order to improve the electron transport capability in addition to the compound represented by the general formula (1) or (2). preferable.
• Preferred examples of the donor compound in the present invention include an alkali metal, an inorganic salt containing an alkali metal, a complex of an alkali metal and an organic substance, an alkaline earth metal, an inorganic salt containing an alkaline earth metal, or an alkaline earth metal. And a complex of organic substance.
• alkali metals and alkaline earth metals include alkali metals such as lithium, sodium and cesium, which have a low work function and a large effect of improving the electron transport ability, and alkaline earth metals such as magnesium and calcium.
• inorganic salts include oxides such as LiO and Li 2 O, nitrides, fluorides such as LiF, NaF, and KF, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Rb 2 CO 3 , Examples thereof include carbonates such as Cs 2 CO 3 .
• a preferable example of the alkali metal or alkaline earth metal is lithium from the viewpoint that the raw materials are inexpensive and easy to synthesize.
• Preferred examples of the organic substance in the complex with the organic substance include quinolinol, benzoquinolinol, flavonol, hydroxyimidazopyridine, hydroxybenzazole, hydroxytriazole and the like.
• a complex of an alkali metal and an organic substance is preferable, a complex of lithium and an organic substance is more preferable, and lithium quinolinol is particularly preferable. Two or more of these donor compounds may be mixed and used.
• the preferred doping concentration varies depending on the material and the thickness of the doped region.
• the deposition rate ratio of the electron transport material and the donor compound is 10,000: It is preferable to use an electron transport layer by co-evaporation so as to be in the range of 1 to 2: 1.
• the deposition rate ratio is more preferably 100: 1 to 5: 1, and further preferably 100: 1 to 10: 1.
• the donor compound is a complex of a metal and an organic substance
• the electron transport layer and the donor compound are co-deposited so that the deposition rate ratio of the electron transport material and the donor compound is in the range of 100: 1 to 1: 100. Is preferred.
• the deposition rate ratio is more preferably 10: 1 to 1:10, and more preferably 7: 3 to 3: 7.
• the electron transport layer in which the compound represented by the general formula (1) or (2) is doped with a donor compound is used as a charge generation layer in a tandem structure type element that connects a plurality of light emitting elements. It may be done.
• the method of improving the electron transport ability by doping a donor compound in the electron transport layer is particularly effective when the thin film layer is thick. It is particularly preferably used when the total film thickness of the electron transport layer and the light emitting layer is 50 nm or more.
• the total film thickness of the electron transport layer and the light emitting layer is 50 nm or more.
• the total film thickness of the electron transport layer and the light-emitting layer is 50 nm or more, and in the case of long-wavelength light emission such as red, it may be a thick film near 100 nm. .
• the thickness of the electron transport layer to be doped may be a part or all of the electron transport layer.
• the donor compound is in direct contact with the light emitting layer, it may adversely affect the light emission efficiency. In that case, it is desirable to provide a non-doped region at the light emitting layer / electron transport layer interface.
• an electron injection layer may be provided between the cathode and the electron transport layer.
• the electron injection layer is inserted for the purpose of assisting injection of electrons from the cathode to the electron transport layer, but in the case of insertion, a compound having a heteroaryl ring structure containing electron-accepting nitrogen may be used.
• a layer containing the above donor compound may be used.
• the compound represented by the general formula (1) or (2) may be included in the electron injection layer.
• An insulator or a semiconductor inorganic substance can also be used for the electron injection layer. Use of these materials is preferable because a short circuit of the light emitting element can be effectively prevented and the electron injection property can be improved.
• preferred alkali metal chalcogenides include, for example, Li 2 O, Na 2 S, and Na 2 Se
• preferred alkaline earth metal chalcogenides include, for example, CaO, BaO, SrO, BeO, BaS, and CaSe. Is mentioned.
• preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl.
• preferable alkaline earth metal halides include fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 and BeF 2 , and halides other than fluorides.
• a complex of an organic substance and a metal is also preferably used.
• organometallic complexes include quinolinol, benzoquinolinol, pyridylphenol, flavonol, hydroxyimidazopyridine, hydroxybenzazole, hydroxytriazole, and the like as preferred examples of the organic substance in a complex with an organic substance.
• a complex of an alkali metal and an organic substance is preferable, a complex of lithium and an organic substance is more preferable, and lithium quinolinol is particularly preferable.
• each layer constituting the light emitting element is not particularly limited, such as resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, coating method, etc., but resistance heating vapor deposition or electron beam vapor deposition is usually used in terms of element characteristics. preferable.
• the thickness of the organic layer is not limited because it depends on the resistance value of the luminescent material, but is preferably 1 to 1000 nm.
• the film thicknesses of the light emitting layer, the electron transport layer, and the hole transport layer are each preferably 1 nm to 200 nm, and more preferably 5 nm to 100 nm.
• the light emitting element of the present invention has a function of converting electrical energy into light.
• a direct current is mainly used as the electric energy, but a pulse current or an alternating current can also be used.
• the current value and voltage value are not particularly limited, but should be selected so that the maximum luminance can be obtained with as low energy as possible in consideration of the power consumption and lifetime of the device.
• the light-emitting element of the present invention is suitably used as a display for displaying in a matrix and / or segment system, for example.
• pixels for display are arranged two-dimensionally such as a lattice shape or a mosaic shape, and characters and images are displayed by a set of pixels.
• the shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 ⁇ m or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become.
• monochrome display pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type.
• the matrix driving method may be either a line sequential driving method or an active matrix. Although the structure of the line sequential drive is simple, the active matrix may be superior in consideration of the operation characteristics, and it is necessary to use it depending on the application.
• the segment system in the present invention is a system in which a pattern is formed so as to display predetermined information and an area determined by the arrangement of the pattern is caused to emit light.
• a pattern is formed so as to display predetermined information and an area determined by the arrangement of the pattern is caused to emit light.
• the time and temperature display in a digital clock or a thermometer can be mentioned.
• the matrix display and the segment display may coexist in the same panel.
• the light emitting device of the present invention is also preferably used as a backlight for various devices.
• the backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like.
• the light-emitting element of the present invention is preferably used for a backlight for a liquid crystal display device, particularly a personal computer for which a reduction in thickness is being considered, and a backlight that is thinner and lighter than conventional ones can be provided.
• this solid was dispersed and washed with 300 ml of water for 30 minutes and then collected by filtration, and then dispersed and washed with 300 ml of methanol for 30 minutes and then collected by filtration and dried to obtain 3.4 g of a crude solid.
• This solid was recrystallized twice more to obtain 2.5 g of solid. Further, this solid was purified by sublimation to obtain 2.0 g of Compound D.
• the results of 1 H-NMR analysis of the obtained solid are as follows.
• this solid was dispersed and washed with 300 ml of water for 30 minutes and then collected by filtration, and then dispersed and washed with 300 ml of methanol for 30 minutes, and then collected by filtration and dried to obtain 3.3 g of a crude solid.
• This solid was recrystallized twice more to obtain 2.4 g of solid. Further, this solid was purified by sublimation to obtain 1.9 g of compound E.
• the results of 1 H-NMR analysis of the obtained solid are as follows.
• Example 1 A glass substrate (manufactured by Geomat Co., Ltd., 11 ⁇ / ⁇ , sputtered product) on which ITO transparent conductive film was deposited at 165 nm was cut into 38 ⁇ 46 mm and etched. The obtained substrate was ultrasonically cleaned with “Semico Clean 56” (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 15 minutes and then with ultrapure water. This substrate was subjected to UV-ozone treatment for 1 hour immediately before producing the device, placed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 5 ⁇ 10 ⁇ 4 Pa or less.
• “Semico Clean 56” trade name, manufactured by Furuuchi Chemical Co., Ltd.
• HAT-CN6 was deposited as a hole injection layer at 5 nm and HT-1 as a hole transport layer was deposited at 60 nm by a resistance heating method.
• a host material compound H-1 and a dopant material compound D-1 were deposited to a thickness of 40 nm so that the doping concentration was 5 wt%.
• Compound E-1 was deposited as an electron transport layer to a thickness of 25 nm and laminated.
• 1000 nm of aluminum was vapor-deposited to form a cathode, and a 5 ⁇ 5 mm square device was fabricated.
• the film thickness referred to here is a crystal oscillation type film thickness monitor display value.
• the characteristics of this light emitting device at 1000 cd / m 2 were a driving voltage of 4.2 V and an external quantum efficiency of 4.9%. Further, when the initial luminance was set to 1000 cd / m 2 and driven at a constant current, the time for the luminance to decrease by 20% was 330 hours.
• HAT-CN6, HT-1, H-1, D-1, and E-1 are the compounds shown below.
• Examples 2 to 23 A light emitting device was prepared and evaluated in the same manner as in Example 1 except that the compounds described in Table 1 were used for the electron transport layer and the hole transport layer. The results are shown in Table 1. E-2 to E-15, HT-2, and 3 are the compounds shown below.
• Comparative Examples 1-18 A light emitting device was prepared and evaluated in the same manner as in Example 1 except that the compounds described in Table 2 were used for the electron transport layer and the hole transport layer. The results are shown in Table 2. E-16 to E-21 are the compounds shown below.
• Example 24 A glass substrate (manufactured by Geomat Co., Ltd., 11 ⁇ / ⁇ , sputtered product) on which ITO transparent conductive film was deposited at 165 nm was cut into 38 ⁇ 46 mm and etched. The obtained substrate was ultrasonically cleaned with “Semico Clean 56” (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 15 minutes and then with ultrapure water. This substrate was subjected to UV-ozone treatment for 1 hour immediately before producing the device, placed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 5 ⁇ 10 ⁇ 4 Pa or less.
• “Semico Clean 56” trade name, manufactured by Furuuchi Chemical Co., Ltd.
• HAT-CN6 was deposited as a hole injection layer at 5 nm and HT-1 as a hole transport layer was deposited at 60 nm by a resistance heating method.
• the compound H-1 was used as the host material and the compound D-1 was used as the dopant material, and vapor deposition was performed to a thickness of 40 nm with a doping concentration of 5% by weight.
• Compound E-1 was deposited to a thickness of 10 nm as a first electron transport layer and laminated.
• E-1 was used as an electron transport material for the second electron transport layer
• cesium was used as a donor compound
• a layer having a thickness of 15 nm was laminated so that the deposition rate ratio of E-1 and cesium was 20: 1.
• the film thickness referred to here is a crystal oscillation type film thickness monitor display value.
• the characteristics of this light emitting element at 1000 cd / m 2 were a driving voltage of 3.9 V and an external quantum efficiency of 5.2%.
• Examples 25-29 A light emitting device was prepared and evaluated in the same manner as in Example 14 except that the compounds described in Table 3 were used for the first electron transport layer and the second electron transport layer. The results are shown in Table 3.
• Example 30 A glass substrate (manufactured by Geomat Co., Ltd., 11 ⁇ / ⁇ , sputtered product) on which ITO transparent conductive film was deposited at 165 nm was cut into 38 ⁇ 46 mm and etched. The obtained substrate was ultrasonically cleaned with “Semico Clean 56” (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 15 minutes and then with ultrapure water. This substrate was subjected to UV-ozone treatment for 1 hour immediately before producing the device, placed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 5 ⁇ 10 ⁇ 4 Pa or less.
• “Semico Clean 56” trade name, manufactured by Furuuchi Chemical Co., Ltd.
• HAT-CN6 was deposited as a hole injection layer at 5 nm and HT-1 as a hole transport layer was deposited at 60 nm by a resistance heating method.
• the compound H-1 was used as the host material and the compound D-1 was used as the dopant material, and vapor deposition was performed to a thickness of 40 nm with a doping concentration of 5% by weight.
• Compound E-1 was deposited to a thickness of 10 nm as a first electron transport layer and laminated.
• E-1 was used as the electron transport material for the second electron transport layer
• lithium was used as the donor compound
• the layer was laminated to a thickness of 15 nm so that the deposition rate ratio of E-1 to lithium was 100: 1.
• 1000 nm of aluminum was vapor-deposited to form a cathode, and a 5 ⁇ 5 mm square device was fabricated.
• the film thickness referred to here is a crystal oscillation type film thickness monitor display value.
• the characteristics of this light emitting element at 1000 cd / m 2 were a driving voltage of 3.9 V and an external quantum efficiency of 5.1%.
• the initial luminance was set to 1000 cd / m 2 and driven at a constant current, the time for a 20% decrease in luminance was 420 hours.
• Examples 31-35 A light emitting device was prepared and evaluated in the same manner as in Example 30 except that the compounds described in Table 3 were used for the first electron transport layer and the second electron transport layer. The results are shown in Table 3.
• Example 36 A glass substrate (manufactured by Geomat Co., Ltd., 11 ⁇ / ⁇ , sputtered product) on which ITO transparent conductive film was deposited at 165 nm was cut into 38 ⁇ 46 mm and etched. The obtained substrate was ultrasonically cleaned with “Semico Clean 56” (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 15 minutes and then with ultrapure water. This substrate was subjected to UV-ozone treatment for 1 hour immediately before producing the device, placed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 5 ⁇ 10 ⁇ 4 Pa or less.
• “Semico Clean 56” trade name, manufactured by Furuuchi Chemical Co., Ltd.
• HAT-CN6 was deposited as a hole injection layer at 5 nm and HT-1 as a hole transport layer was deposited at 60 nm by a resistance heating method.
• Compound H-1 was used as the host material
• Compound D-1 was used as the dopant material
• vapor deposition was performed to a thickness of 40 nm so that the doping concentration was 5% by weight.
• E-1 was used as an electron transport material as an electron transport layer
• Liq was used as a donor compound
• a layer having a thickness of 25 nm was laminated so that the deposition rate ratio of E-1 and Liq was 1: 1.
• This electron transport layer is shown as a second electron transport layer in Table 2.
• the film thickness referred to here is a crystal oscillation type film thickness monitor display value.
• the characteristics of this light-emitting element at 1000 cd / m 2 were a driving voltage of 4.0 V and an external quantum efficiency of 5.3%. Further, when the initial luminance was set to 1000 cd / m 2 and driven at a constant current, the time for the luminance to decrease by 20% was 440 hours. Liq is a compound shown below.
• Examples 37-41 A light emitting device was prepared and evaluated in the same manner as in Example 36 except that the compounds listed in Table 3 were used for the electron transport layer. The results are shown in Table 3.
• Comparative Examples 19-23 A light emitting device was prepared and evaluated in the same manner as in Example 24 except that the compounds described in Table 4 were used for the first electron transport layer and the second electron transport layer. The results are shown in Table 4.
• Comparative Examples 24-28 A light emitting device was prepared and evaluated in the same manner as in Example 30 except that the compounds described in Table 4 were used for the first electron transport layer and the second electron transport layer. The results are shown in Table 4.
• Comparative Examples 29 to 33 A light emitting device was prepared and evaluated in the same manner as in Example 36 except that the compounds listed in Table 4 were used for the electron transport layer. The results are shown in Table 4.
• Example 42 A glass substrate (manufactured by Geomat Co., Ltd., 11 ⁇ / ⁇ , sputtered product) on which ITO transparent conductive film was deposited at 165 nm was cut into 38 ⁇ 46 mm and etched. The obtained substrate was ultrasonically cleaned with “Semico Clean 56” (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 15 minutes and then with ultrapure water. This substrate was subjected to UV-ozone treatment for 1 hour immediately before producing the device, placed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 5 ⁇ 10 ⁇ 4 Pa or less.
• “Semico Clean 56” trade name, manufactured by Furuuchi Chemical Co., Ltd.
• HAT-CN6 was deposited as a hole injection layer at 5 nm and HT-1 as a hole transport layer was deposited at 60 nm by a resistance heating method. This hole transport layer is shown in Table 3 as the first hole transport layer.
• a host material compound H-2 and a dopant material compound D-2 were deposited to a thickness of 40 nm so that the dope concentration was 10 wt%.
• Compound E-1 was deposited as an electron transport layer to a thickness of 25 nm and laminated.
• the film thickness referred to here is a crystal oscillation type film thickness monitor display value.
• the characteristics of this light emitting device at 4000 cd / m 2 were a driving voltage of 4.2 V and an external quantum efficiency of 12.0%. Further, when the initial luminance was set to 4000 cd / m 2 and driven at a constant current, the time required for the luminance to decrease by 20% was 300 hours. H-2 and D-2 are the compounds shown below.
• Example 43 A glass substrate (manufactured by Geomat Co., Ltd., 11 ⁇ / ⁇ , sputtered product) on which ITO transparent conductive film was deposited at 165 nm was cut into 38 ⁇ 46 mm and etched. The obtained substrate was ultrasonically cleaned with “Semico Clean 56” (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 15 minutes and then with ultrapure water. This substrate was subjected to UV-ozone treatment for 1 hour immediately before producing the device, placed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 5 ⁇ 10 ⁇ 4 Pa or less.
• “Semico Clean 56” trade name, manufactured by Furuuchi Chemical Co., Ltd.
• HAT-CN6 was deposited as a hole injection layer at a thickness of 5 nm and HT-1 as a first hole transport layer was deposited at a thickness of 50 nm by a resistance heating method. Further, HT-4 was deposited to a thickness of 10 nm as the second hole transport layer.
• a host material compound H-2 and a dopant material compound D-2 were deposited to a thickness of 40 nm so that the dope concentration was 10 wt%.
• Compound E-1 was deposited as an electron transport layer to a thickness of 25 nm and laminated.
• the film thickness referred to here is a crystal oscillation type film thickness monitor display value.
• the characteristics of this light emitting element at 4000 cd / m 2 were a driving voltage of 4.3 V and an external quantum efficiency of 13.9%. Further, when the initial luminance was set to 4000 cd / m 2 and driven at a constant current, the time required for the luminance to decrease by 20% was 350 hours.
• HT-4 is a compound shown below.
• Examples 44 and 45 A light emitting device was prepared and evaluated in the same manner as in Example 43 except that the compounds described in Table 5 were used as the second hole transport layer. The results are shown in Table 5.
• HT-5 and HT-6 are the compounds shown below.
• Example 46 A light emitting device was prepared and evaluated in the same manner as in Example 42 except that E-5 was used as the electron transport layer. The results are shown in Table 3.
• Examples 47-49 A device was prepared and evaluated in the same manner as in Example 43 except that the compounds shown in Table 5 were used as the second hole transport layer and E-5 was used as the electron transport layer. The results are shown in Table 5.
• Example 50 A light emitting device was prepared and evaluated in the same manner as in Example 42 except that E-12 was used as the electron transport layer. The results are shown in Table 3.
• Examples 51-53 A device was prepared and evaluated in the same manner as in Example 43 except that the compounds shown in Table 5 were used as the second hole transport layer and E-12 was used as the electron transport layer. The results are shown in Table 5.
• Comparative Example 34 A light emitting device was prepared and evaluated in the same manner as in Example 42 except that E-16 was used for the electron transport layer. The results are shown in Table 6.
• Comparative Examples 35 to 37 A device was prepared and evaluated in the same manner as in Example 43 except that the compounds shown in Table 6 were used as the second hole transport layer and E-16 was used as the electron transport layer. The results are shown in Table 6.
• Comparative Example 38 A light emitting device was prepared and evaluated in the same manner as in Example 42 except that E-17 was used for the electron transport layer. The results are shown in Table 6. Comparative Examples 39 to 41 A device was prepared and evaluated in the same manner as in Example 43 except that the compounds shown in Table 6 were used as the second hole transport layer and E-17 was used as the electron transport layer. The results are shown in Table 6.
• Comparative Example 42 A light emitting device was prepared and evaluated in the same manner as in Example 42 except that E-18 was used for the electron transport layer. The results are shown in Table 6.
• Comparative Examples 43-45 A device was prepared and evaluated in the same manner as in Example 43 except that the compounds shown in Table 6 were used as the second hole transport layer and E-18 was used as the electron transport layer. The results are shown in Table 6.
• Comparative Example 46 A light emitting device was prepared and evaluated in the same manner as in Example 42 except that E-19 was used for the electron transport layer. The results are shown in Table 6.
• Comparative Examples 47-49 A device was prepared and evaluated in the same manner as in Example 43 except that the compounds shown in Table 6 were used as the second hole transport layer and E-19 was used as the electron transport layer. The results are shown in Table 6.

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