WO2012050002A1 - 含窒素芳香族化合物、有機半導体材料及び有機電子デバイス - Google Patents
含窒素芳香族化合物、有機半導体材料及び有機電子デバイス Download PDFInfo
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- WO2012050002A1 WO2012050002A1 PCT/JP2011/072783 JP2011072783W WO2012050002A1 WO 2012050002 A1 WO2012050002 A1 WO 2012050002A1 JP 2011072783 W JP2011072783 W JP 2011072783W WO 2012050002 A1 WO2012050002 A1 WO 2012050002A1
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- 0 CC(C)([n]1c(-c2c(*3)cccc2)c3c2c1cccc2)IC(*)(C*)[n]1c(cccc2)c2c-2c1*c1ccccc-21 Chemical compound CC(C)([n]1c(-c2c(*3)cccc2)c3c2c1cccc2)IC(*)(C*)[n]1c(cccc2)c2c-2c1*c1ccccc-21 0.000 description 3
- JEOCDKRZELMZJF-UHFFFAOYSA-N C#Cc1ccccc1NO Chemical compound C#Cc1ccccc1NO JEOCDKRZELMZJF-UHFFFAOYSA-N 0.000 description 1
- ZQEBXDLOLAVKTQ-UHFFFAOYSA-N C[N+](C)(c1c(CC(c2ccccc2N=O)=O)cccc1)[O-] Chemical compound C[N+](C)(c1c(CC(c2ccccc2N=O)=O)cccc1)[O-] ZQEBXDLOLAVKTQ-UHFFFAOYSA-N 0.000 description 1
- DKMWQUJRRODVPW-UHFFFAOYSA-N C[O-][NH+](c1ccccc1C#C)[O-] Chemical compound C[O-][NH+](c1ccccc1C#C)[O-] DKMWQUJRRODVPW-UHFFFAOYSA-N 0.000 description 1
- FSAQLJQKYNYWQK-UHFFFAOYSA-N C[Si](C)(C)C#Cc(cccc1)c1N(O)OI Chemical compound C[Si](C)(C)C#Cc(cccc1)c1N(O)OI FSAQLJQKYNYWQK-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a novel nitrogen-containing aromatic compound and an organic electronic device using the same, and further relates to a light emitting element, a thin film transistor, and a photovoltaic element using the compound as an organic semiconductor material.
- organic electronics devices using organic compounds as semiconductor materials have made remarkable progress.
- Typical applications include organic electroluminescence elements (hereinafter sometimes referred to as “organic EL elements”) that are expected as next-generation flat panel displays, and thin film transistors used for pixel driving of displays.
- organic thin-film transistors (hereinafter sometimes referred to as “organic TFTs”) that are attracting attention because they can be manufactured by low-cost processes such as printing, and can be applied to flexible substrates, and photovoltaic elements (organic thin-films) as lightweight and flexible power supplies Solar cell).
- a high-temperature process and a high-vacuum process are essential for forming a thin film. Since a high-temperature process is required, it is difficult to form a thin film of silicon on a plastic substrate or the like. Therefore, it has been difficult to impart flexibility and weight reduction to a product incorporating a semiconductor element. In addition, since a high vacuum process is required, it is difficult to increase the area and cost of a product incorporating a semiconductor element.
- organic compounds are easier to process than inorganic silicon, it is expected that low-cost devices will be realized by using organic compounds as semiconductor materials.
- a semiconductor device using an organic compound can be manufactured at a low temperature, and thus can be applied to a wide variety of substrates including a plastic substrate.
- organic compound semiconductor materials are structurally flexible, by using a combination of a plastic substrate and an organic compound semiconductor material, application to organic semiconductor products that take advantage of these characteristics, such as organic EL panels and It is expected to realize devices such as flexible displays such as electronic paper, liquid crystal displays, information tags, electronic artificial skin sheets, and large area sensors such as sheet type scanners.
- Organic semiconductor materials used in such organic electronic devices are used for improving the luminous efficiency of organic EL elements, extending their lifetime and driving voltage, lowering the threshold voltage of organic TFT elements, and improving switching speed. There is a need to improve the charge mobility of the organic thin film solar cells and the photoelectric conversion efficiency of organic thin film solar cells.
- a host material that is responsible for charge transport in the light emitting layer is important in order to increase the light emission efficiency.
- the carbazole compound 4,4′-bis (9-carbazolyl) biphenyl (hereinafter referred to as CBP) introduced in Patent Document 1 and introduced in Non-Patent Document 1 1,3-dicarbazolylbenzene (hereinafter referred to as mCP).
- CBP carbazole compound 4,4′-bis (9-carbazolyl) biphenyl
- mCP 1,3-dicarbazolylbenzene
- FIrpic blue phosphorescent materials represented by bis [2- (4,6-difluorophenyl) pyridinato-N, C2 ′] (picolinato) iridium complex
- a host material that is balanced in both charge (hole / electron) injection and transport characteristics is required. Further, a compound that is electrochemically stable and has high heat resistance and excellent amorphous stability is desired, and further improvement is required.
- organic TFT element materials organic semiconductor materials having charge transportability comparable to amorphous silicon have been reported in recent years.
- pentacene which is a hydrocarbon-based acene-type polycyclic aromatic molecule in which five benzene rings are linearly condensed
- Non-Patent Document 2 as an amorphous semiconductor
- Patent Document 2 proposes a method of forming a pentacene crystal in a dilute solution of o-dichlorobenzene without using a vacuum deposition method.
- the manufacturing method is difficult and a stable element has not been obtained.
- a hydrocarbon-based acene-type polycyclic aromatic molecule such as pentacene also has a low oxidation stability.
- organic thin-film solar cells have been initially studied with a single-layer film using a merocyanine dye or the like, but a multi-layer film having a p-layer that transports holes and an n-layer that transports electrons is used.
- a multi-layer film having a p-layer that transports holes and an n-layer that transports electrons is used.
- the materials used when the multilayer film began to be studied were copper phthalocyanine (CuPc) for the p layer and peryleneimides (PTCBI) for the n layer.
- microlayer separation is achieved by using conductive polymers as the material for the p layer, mixing fullerene (C60) derivatives as the material for the n layer, and heat-treating them.
- C60 fullerene
- the material system used here was mainly poly-3-hexylthiophene (P3HT) as the material for the p-layer and C60 derivative (PCBM) as the material for the n-layer.
- Patent Document 3 discloses an organic thin film solar cell using a compound having a fluoranthene skeleton, but does not provide satisfactory photoelectric conversion efficiency.
- Patent Document 4 an organic EL element using the following compounds is disclosed.
- the present invention aims to provide a novel nitrogen-containing aromatic compound that can be used as an organic semiconductor material that solves the problems of the prior art as described above.
- the present invention relates to a nitrogen-containing aromatic compound represented by the general formula (1).
- L is an m + n-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic heterocyclic group having 3 to 30 carbon atoms that does not include four or more condensed heterocyclic rings, or 9 to 30 carbon atoms. Or a group derived from a diarylsulfone having 6 to 24 carbon atoms.
- X represents NA, O, S, or Se, and each A independently represents an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a carbon number.
- R is independently hydrogen, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or 6 to 30 carbon atoms.
- n represents an integer of 0 to 3.
- the total number of m and n is an integer from 2 to 4.
- the present invention also relates to an organic semiconductor material containing the nitrogen-containing aromatic compound. Moreover, this invention relates to the organic electronic device containing the said nitrogen-containing aromatic compound.
- the compound of the present invention is represented by the general formula (1).
- the nitrogen-containing aromatic compound of the present invention is also referred to as a nitrogen-containing aromatic compound or a compound of the present invention.
- L represents an n + m-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, an aromatic heterocyclic group having 3 to 30 carbon atoms, or a triarylamine having 9 to 30 carbon atoms. And a group derived from a diaryl sulfone having 6 to 24 carbon atoms.
- L is an n-valent aromatic hydrocarbon group having 6 to 24 carbon atoms, an aromatic heterocyclic group having 3 to 24 carbon atoms, a group derived from a triarylamine having 9 to 22 carbon atoms, or a group having 6 to 20 carbon atoms.
- the aromatic heterocyclic group does not include four or more condensed heterocyclic rings.
- aromatic hydrocarbon group or the aromatic heterocyclic group examples include benzene, pentalene, indene, naphthalene, azulene, heptalene, octalene, indacene, acenaphthylene, phenalene, phenanthrene, anthracene, tridene, fluoranthene, acephenanthrylene, ASEANTRylene, Triphenylene, Pyrene, Chrysene, Tetraphen, Tetracene, Pleiaden, Picene, Perylene, Pentaphene, Pentacene, Tetraphenylene, Cholantolylene, Helicene, Hexaphene, Rubicene, Coronene, Trinaphthylene, Heptaphene, Pyrantrene, Furan, Benzofuran, Iso Benzofuran, xanthene, oxatolene, dibenzofuran, perixant
- the number to be linked is preferably 2 to 10, more preferably 2 to 7, and the linked aromatic rings may be the same. It may be different.
- the bonding position of L bonded to nitrogen is not limited, and it may be a ring at the end of a linked aromatic ring or a ring at the center.
- the aromatic ring is a generic term for an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
- the linked aromatic ring contains at least one heterocyclic ring, it is included in the aromatic heterocyclic group.
- the monovalent group generated by connecting a plurality of aromatic rings is represented by the following formula, for example.
- Ar 1 to Ar 6 represent a substituted or unsubstituted aromatic ring.
- Specific examples of the group formed by linking a plurality of the aromatic rings include, for example, biphenyl, terphenyl, bipyridine, bipyrimidine, vitriazine, terpyridine, bistriazylbenzene, dicarbazolylbenzene, carbazolylbiphenyl, dicarbazolylbiphenyl.
- the aromatic heterocyclic group not containing 4 or more condensed heterocyclic rings means a monocyclic aromatic heterocyclic group or 2 to 3 condensed aromatic heterocyclic groups, and this aromatic heterocyclic group The group may have a substituent.
- the aromatic heterocyclic group is a group formed by linking a plurality of aromatic rings as represented by the formula (11), for example, a monovalent or divalent aromatic heterocyclic ring contained in the aromatic group
- the group is not a condensed ring group having 4 or more rings.
- the aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent, and when these have a substituent, the substituent may be an alkyl group having 1 to 4 carbon atoms, or a group having 3 to 6 carbon atoms.
- An alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a secondary amino group having 6 to 15 carbon atoms is preferable.
- L is an aromatic hydrocarbon group or an aromatic heterocyclic group and has a substituent
- the total number of substituents is 1 to 10.
- it is 1-6, more preferably 1-4.
- it may be the same or different.
- L is a group derived from a triarylamine having 9 to 30 carbon atoms, these carbon number is preferably 9 to 24, more preferably 9 to 18.
- the group generated from the triarylamine is an n-valent group generated by removing n hydrogens from Ar of the triarylamine represented by the following formula (5).
- Ars are 1 to (m + n + 1) valent aromatic groups, but the three Ars may be the same or different, and may have different valences.
- Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 18 carbon atoms that does not include a condensed heterocyclic ring having 4 or more rings.
- Preferred is a phenyl group, a naphthyl group, a pyridyl group, a quinolyl group, or a carbazolyl group, and more preferred is a phenyl group.
- Ar may have a substituent, and when it has a substituent, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, An acetyl group.
- L is a group derived from a diaryl sulfone having 6 to 24 carbon atoms, these carbon number is preferably 6 to 20, more preferably 6 to 18.
- the group generated from diarylsulfone is an n-valent group generated by removing m + n hydrogen atoms from any Ar of diarylsulfone represented by the following formula (3).
- Ar has the same meaning as Ar in Formula (2).
- X represents NA, O, S or Se.
- N-A, O or S is preferable, and N-A is more preferable.
- A is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or a silyl group having 3 to 18 carbon atoms.
- it is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.
- an aromatic heterocyclic group having 3 to 30 carbon atoms is an aromatic heterocyclic group having 3 to 30 carbon atoms.
- the aromatic heterocyclic group does not include four or more condensed heterocyclic rings.
- A is an alkyl group having 1 to 30 carbon atoms
- the carbon number is preferably 1 to 20, more preferably 1 to 8.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, preferably a methyl group, an ethyl group, and a propyl group.
- the alkyl group may be linear or branched.
- the alkyl group may have a substituent, and when these have a substituent, examples of the substituent include a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a carbon number. 3 to 18 aromatic heterocyclic groups.
- the total number of substituents is 1-10. Preferably it is 1-6, more preferably 1-4. Moreover, when it has two or more substituents, they may be the same or different.
- the carbon number is preferably 3 to 20, more preferably 5 to 6.
- Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexyl group, and a decahydronaphthyl group, preferably a cyclopentyl group or a cyclohexyl group. Is mentioned.
- the cycloalkyl group may have a substituent, and when these have a substituent, the substituent may be an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a carbon number. 3 to 18 aromatic heterocyclic groups.
- the total number of substituents is 1-10. Preferably it is 1-6, more preferably 1-4. Moreover, when it has two or more substituents, they may be the same or different.
- alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms these carbon numbers are preferably 2 to 20, more preferably 2 to 10.
- specific examples of the alkenyl group or alkynyl group include ethylenyl group, propylenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, acetylenyl group, propynyl group, butynyl group, or pentynyl group, preferably Examples include an ethylenyl group, a propylenyl group, a butenyl group, an acetylenyl group, and a propynyl group.
- the alkenyl group and alkynyl group may be linear or branched.
- the alkenyl group or alkynyl group may have a substituent.
- substituents include a cycloalkyl group having 3 to 11 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Or an aromatic heterocyclic group having 3 to 18 carbon atoms.
- A is a silyl group having 3 to 18 carbon atoms, these carbon numbers are preferably 3 to 12, more preferably 3 to 9.
- the silyl group is represented by —SiZ 3 , where Z is hydrogen or a hydrocarbon group, preferably all Z are hydrocarbon groups.
- Preferred examples of the hydrocarbon group include an alkyl group and a phenyl group. The three Zs may be the same or different, and the carbon number is calculated as the sum of these. An alkylsilyl group is preferred.
- alkylsilyl group examples include, for example, a trimethylsilyl group, a triethylsilyl group, a tri (n-propyl) silyl group, a tri (n-butyl) silyl group, a trivinylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, Tri (isopropoxy) silyl group, tri (n-butoxy) silyl group, tri (s-butoxy) silyl group, tri (t-butoxy) silyl group, triisopropylsilyl group, tricyclohexylsilyl group, tri (s-butyl) ) Silyl group, triethynylsilyl group, triallylsilyl group, tripropargylsilyl group, triphenylsilyl group, t-butyldimethylsilyl group, t-butyldiethylsilyl group, is
- A is an acyl group having 2 to 19 carbon atoms, these carbon numbers are preferably 6 to 19, more preferably 7 to 13.
- the acyl group is preferably a monovalent group represented by the following formula (4).
- Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 3 to 18 carbon atoms that does not include four or more condensed heterocyclic rings.
- Preferred is a phenyl group, a naphthyl group, a pyridyl group, a quinolyl group, or a carbazolyl group, and more preferred is a phenyl group.
- Ar may have a substituent, and when it has a substituent, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, An acetyl group.
- A is an aromatic hydrocarbon group having 6 to 50 carbon atoms or an aromatic heterocyclic group having 3 to 50 carbon atoms
- the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms.
- the aromatic heterocyclic group preferably has 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms.
- the aromatic heterocyclic group does not include four or more condensed heterocyclic rings.
- A is a group selected from an aromatic hydrocarbon group or an aromatic heterocyclic group
- aromatic hydrocarbon group or the aromatic heterocyclic group constituting the above L except that they are monovalent It is the same.
- each R is independently hydrogen, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms.
- alkyl group having 1 to 20 carbon atoms Preferably, hydrogen, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aromatic carbonization having 6 to 20 carbon atoms It represents a hydrogen group or an aromatic heterocyclic group having 3 to 20 carbon atoms.
- alkyl group, cycloalkyl group, alkenyl group or alkynyl group are the same as those of the alkyl group, cycloalkyl group, alkenyl group or alkynyl group constituting L.
- the case where these alkyl group, cycloalkyl group, alkenyl group or alkynyl group has a substituent is the same as in L.
- aromatic hydrocarbon group or aromatic heterocyclic group are the same as those of the aromatic hydrocarbon group or aromatic heterocyclic group constituting L, except that the total carbon number is different.
- aromatic hydrocarbon groups or aromatic heterocyclic groups have a substituent is the same as in L.
- n represents an integer of 1 to 4.
- it is an integer of m2 to 3, more preferably m is 2.
- N represents an integer of 0 to 3.
- n is 0 or 1, more preferably 0.
- the total number of m and n is 2-4. Preferably it is 2 or 3, more preferably 2.
- the nitrogen-containing aromatic compound of the present invention can be synthesized using a known method by selecting an indole derivative as a starting material, selecting the starting material according to the structure of the target compound.
- skeletons having the condensation mode of [2,3-b] skeletons in which X is NA are JCSChem.Comm., 1,975,911-912 and JournalJof Chemical Research, 1988,272-273. Can be synthesized according to the following reaction formula with reference to the synthesis example shown in FIG.
- a skeleton in which X is represented by any of O, S, and Se can also be synthesized using the above synthesis example.
- a skeleton in which X is represented by S can be synthesized by the following reaction formula with reference to a synthesis example shown in Tetrahedoron, 2003, vol. 59, 3737-3744.
- the nitrogen-containing nitrogen represented by the general formula (1) is obtained by substituting the hydrogen on the nitrogen of various compounds obtained by the above reaction formula with a corresponding linking group or substituent by a coupling reaction such as an Ullmann reaction.
- Aromatic compounds can be synthesized.
- the organic semiconductor material of the present invention and the organic electronic device of the present invention will be described. Since the nitrogen-containing aromatic compound of the present invention itself has a function as an organic semiconductor material, it is useful as an organic semiconductor material.
- the organic semiconductor material of the present invention contains the nitrogen-containing aromatic compound of the present invention.
- the organic semiconductor material of the present invention only needs to contain the nitrogen-containing aromatic compound of the present invention.
- the organic semiconductor material may be used by mixing with other organic semiconductor materials, or may contain various dopants. Good.
- the dopant for example, when used as a light emitting layer of an organic EL device, coumarin, quinacridone, rubrene, stilbene derivatives and fluorescent dyes, noble metal complexes such as iridium complexes and platinum complexes can be used.
- the organic electronic device of the present invention is an organic electronic device using the organic semiconductor material of the present invention. That is, the organic electronic device of the present invention is an organic electronic device containing the nitrogen-containing aromatic compound of the present invention. Specifically, the organic electronic device of the present invention includes at least one organic layer, and at least one of the organic layers includes the above-described compound of the present invention.
- the organic electronic device of the present invention can be in various forms, and an organic EL element can be cited as one of preferred embodiments.
- an organic electronic device comprising an organic EL device in which an anode, an organic layer including a phosphorescent light emitting layer, and a cathode are laminated on a substrate, wherein the organic layer includes the above-described compound of the present invention. It is an electronic device.
- FIG. 1 is a cross-sectional view showing a structural example of a general organic EL device used in the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, and 5 is a light emitting layer. , 6 represents an electron transport layer, and 7 represents a cathode.
- the organic EL device of the present invention may have an exciton blocking layer adjacent to the light emitting layer, and may have an electron blocking layer between the light emitting layer and the hole injection layer.
- the exciton blocking layer can be inserted on either the anode side or the cathode side of the light emitting layer, or both can be inserted simultaneously.
- the organic EL device of the present invention has a substrate, an anode, a light emitting layer and a cathode as essential layers, but it is preferable to have a hole injecting and transporting layer and an electron injecting and transporting layer in layers other than the essential layers, and further emit light. It is preferable to have a hole blocking layer between the layer and the electron injecting and transporting layer.
- the hole injection / transport layer means either or both of a hole injection layer and a hole transport layer
- the electron injection / transport layer means either or both of an electron injection layer and an electron transport layer.
- the compound of the present invention can be used in any layer in an organic EL device. It is preferably used in a light emitting layer, a hole transport layer, an electron blocking layer, a hole blocking layer and an electron transport layer, and particularly preferably used as a light emitting layer, a hole transport layer and an electron blocking layer.
- the organic EL element of the present invention is preferably supported on a substrate.
- the substrate is not particularly limited as long as it is conventionally used for an organic EL element.
- a substrate made of glass, transparent plastic, quartz, or the like can be used.
- an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
- electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO.
- conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO.
- an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used.
- these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not so high (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply
- the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
- the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
- the cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
- an electron injecting metal a material having a low work function (4 eV or less) metal
- an alloy a material having a low work function (4 eV or less) metal
- an alloy a material having a low work function (4 eV or less) metal
- an alloy referred to as an electron injecting metal
- an alloy referred to as an electron injecting metal
- a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture
- Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
- the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
- the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
- the light emission luminance is improved, which is convenient.
- a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a thickness of 1 to 20 nm on the cathode.
- an element in which both the anode and the cathode are transmissive can be manufactured.
- the light emitting layer may be either a fluorescent light emitting layer or a phosphorescent light emitting layer, but is preferably a phosphorescent light emitting layer.
- the fluorescent light emitting material may be at least one kind of fluorescent light emitting material, but it is preferable to use the fluorescent light emitting material as a fluorescent light emitting dopant and include a host material. .
- the compound of the present invention represented by the general formula (1) can be used. However, when the compound is used in any other organic layer, a large number of patent documents, etc. You can also choose from them.
- Preferred examples include condensed aromatic compounds, styryl compounds, diketopyrrolopyrrole compounds, oxazine compounds, pyromethene metal complexes, transition metal complexes, and lanthanoid complexes. More preferred are naphthacene, pyrene, chrysene, triphenylene, benzo [c] phenanthrene.
- the amount of the fluorescent light emitting dopant contained in the light emitting layer is 0.01 to 20% by weight, preferably 0.1 to 10% by weight. It should be in range.
- an organic EL element injects electric charges into a luminescent material from both an anode and a cathode, generates an excited luminescent material, and emits light.
- a charge injection type organic EL element it is said that 25% of the generated excitons are excited to the excited singlet state and the remaining 75% are excited to the excited triplet state.
- certain fluorescent materials are excited triplet states by intersystem crossing etc.
- An organic EL device using the compound of the present invention can also exhibit delayed fluorescence. In this case, both fluorescence emission and delayed fluorescence emission can be included. However, light emission from the host material may be partly or partly emitted.
- the luminescent layer when it is a phosphorescent layer, it includes a phosphorescent dopant and a host material.
- the phosphorescent dopant material preferably contains an organometallic complex containing at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold.
- organometallic complexes are known in the prior art documents and the like, and these can be selected and used.
- Preferred phosphorescent dopants include complexes such as Ir (ppy) 3 having a noble metal element such as Ir as a central metal, complexes such as (Bt) 2 Iracac, and complexes such as (Btp) Ptacac. Specific examples of these complexes are shown below, but are not limited to the following compounds.
- the amount of phosphorescent dopant contained in the light emitting layer is preferably in the range of 1 to 50% by weight. More preferably, it is 5 to 30% by weight.
- the compound of the present invention represented by the general formula (1) is preferably used.
- the material used for the light emitting layer may be a host material other than the compound of the present invention.
- a plurality of known host materials may be used in combination.
- a known host compound that can be used is preferably a compound that has a hole transporting ability or an electron transporting ability, prevents the emission of light from becoming longer, and has a high glass transition temperature.
- Such other host materials are known from a large number of patent documents and can be selected from them.
- Specific examples of the host material are not particularly limited, but include indole derivatives, carbazole derivatives, indolocarbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, Pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrins Compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivative
- metal complexes represented by tetracarboxylic acid anhydrides metal complexes of phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes of benzoxazole and benzothiazole derivatives, polysilane compounds, poly (N-vinylcarbazole) derivatives, Examples include aniline-based copolymers, thiophene oligomers, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives.
- the injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission.
- the injection layer can be provided as necessary.
- the compound of the present invention represented by the general formula (1) can be used. When the compound is used in any other organic layer, any of the conventionally known compounds can be used. A thing can be selected and used.
- the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
- the compound of the present invention represented by the general formula (1) is preferably used.
- a known hole blocking layer material is used. It may be used.
- the material of the electron carrying layer mentioned later can be used as needed.
- the electron blocking layer is made of a material that has a function of transporting holes and has a very small ability to transport electrons.
- the electron blocking layer blocks the electrons while transporting holes, and the probability of recombination of electrons and holes. Can be improved.
- the compound of the present invention represented by the general formula (1) can be used as a material for the electron blocking layer.
- a hole transport layer described later is used. These materials can be used as needed.
- the thickness of the electron blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.
- the exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved.
- the exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
- the compound of the present invention represented by the general formula (1) can be used, and any one of conventionally known compounds can be selected and used. Examples thereof include 1,3-dicarbazolylbenzene (mCP) and bis (2-methyl-8-quinolinolato) -4-phenylphenolatoaluminum (III) (BAlq).
- mCP 1,3-dicarbazolylbenzene
- BAlq bis (2-methyl-8-quinolinolato) -4-phenylphenolatoaluminum
- the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
- the hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic. It is preferable to use the compound of the present invention represented by the general formula (1) for the hole transport layer. However, when the compound is used for any other organic layer, any of conventionally known compounds can be used. Can be selected and used. Examples of known hole transporting materials that can be used include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, aromatic amine derivatives, amino-substituted chalcone derivatives, oxazole derivatives.
- Styrylanthracene derivatives fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, styrylamine compounds, and conductive polymer oligomers, particularly thiophene oligomers. It is preferable to use an aromatic tertiary amine compound and a styrylamine compound, and it is more preferable to use an aromatic tertiary amine compound.
- the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
- the compound of the present invention represented by the general formula (1) is preferably used for the electron transport layer.
- any of the conventionally known compounds can be used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, etc. It is done.
- a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
- an organic TFT element As another preferred embodiment of the organic electronic device containing the compound of the present invention, there is an organic TFT element. Specifically, an organic electronic device comprising an organic TFT element having a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode and a drain electrode on a substrate, wherein the organic semiconductor layer is as described above. It is an organic electronic device containing the compound of this invention.
- Electrodes 13 represent drain electrodes.
- substrate is not specifically limited, For example, it can be set as a conventionally well-known structure.
- the substrate include glass (for example, quartz glass), silicon, ceramic, and plastic.
- the plastic include general-purpose resin substrates such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate.
- the resin substrate is preferably a laminate of gas barrier films for reducing the permeability of gases such as oxygen and water vapor.
- a gate electrode is not specifically limited, For example, it can be set as a conventionally well-known structure.
- the gate electrode for example, gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium, calcium, or an alloy thereof, polysilicon, amorphous silicon, graphite, ITO, zinc oxide, conductive A material such as a conductive polymer can be used.
- a gate insulating layer is not specifically limited, For example, it can be set as a conventionally well-known structure.
- the gate insulating layer SiO 2 , Si 3 N 4 , SiON, Al 2 O 3 , Ta 2 O 5 , amorphous silicon, polyimide resin, polyvinyl phenol resin, polyparaxylylene resin, polymethyl methacrylate resin, fluororesin ( Materials such as PTFE, PFA, PETFE, PCTFE, and CYTOP (registered trademark) can be used.
- organic-semiconductor layer will not be specifically limited if it is a layer containing the compound of this invention.
- it may be a layer consisting essentially only of the compound of the present invention, or a layer containing a substance other than the compound of the present invention.
- the source electrode and the drain electrode are not particularly limited, and for example, a conventionally known configuration can be used.
- any of metals such as gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium, calcium or alloys thereof, polysilicon, amorphous silicon, graphite, ITO, Materials such as zinc oxide and conductive polymer can be used.
- the laminated structure in the organic TFT element includes a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode and a drain electrode in this order from the substrate side (i), and a gate electrode from the substrate side. And any of the configurations (ii) having the gate insulating layer, the source and drain electrodes, and the organic semiconductor layer in this order.
- the manufacturing method of the organic TFT element is not particularly limited. In the case of the configuration (i), for example, a gate electrode, a gate insulating layer, an organic semiconductor layer, a drain electrode, and a source electrode are sequentially stacked on the substrate. In the case of the configuration (ii), there is a bottom contact method in which a gate electrode, a gate insulating layer, a drain electrode and a source electrode, and an organic semiconductor layer are sequentially stacked on the substrate.
- the formation method of the gate electrode, the gate insulating layer, the source electrode, and the drain electrode is not particularly limited.
- any of the above materials can be used, for example, a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, It can be formed by a known film production method such as spin coating or printing.
- the formation method of the organic semiconductor layer is not particularly limited.
- the organic semiconductor layer can be formed by a known film production method such as a vacuum deposition method, a spin coating method, an inkjet method, or a printing method using the above-described compound (1). it can.
- the organic TFT element is not particularly limited in use, but is preferably used as a TFT element for driving a flexible display using a plastic substrate, for example.
- a process such as a vacuum deposition method, a spin coating method, an ink jet method, a printing method, etc. is used as described above, and a high temperature process is not used.
- a TFT element for driving a pixel can be formed thereon.
- the compound (1) used in the present invention is soluble in general-purpose organic solvents such as chloroform, tetrahydrofuran, and toluene, low-cost processes such as spin coating, ink jet, and printing can be applied. It is suitable for making inexpensive paper-like (flexible) displays.
- the organic electronic device containing the compound of the present invention there is a photovoltaic element.
- a photovoltaic device having a positive electrode, an organic semiconductor layer, and a negative electrode on a substrate, and the organic semiconductor device includes the above-described compound of the present invention.
- FIG. 4 is a cross-sectional view showing an example of the structure of a general photovoltaic device used in the present invention, wherein 14 is a substrate, 15 is a positive electrode, 16 is an organic semiconductor layer, and 17 is a negative electrode.
- FIG. 5 is a cross-sectional view showing a structural example in the case where organic semiconductor layers are stacked. 16-a is an electron donating organic semiconductor layer, and 16-b is an electron accepting organic semiconductor layer.
- substrate is not specifically limited, For example, it can be set as a conventionally well-known structure. It is preferable to use a glass substrate or a transparent resin film having mechanical and thermal strength and transparency.
- Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone.
- an electrode material it is preferable to use a conductive material having a high work function for one electrode and a conductive material having a low work function for the other electrode.
- An electrode using a conductive material having a large work function is a positive electrode.
- Conductive materials with a large work function include metals such as gold, platinum, chromium and nickel, transparent metal oxides such as indium and tin, composite metal oxides (indium tin oxide (ITO), indium Zinc oxide (IZO) or the like is preferably used.
- the conductive material used for the positive electrode is preferably an ohmic junction with the organic semiconductor layer.
- a hole transport layer described later it is preferable that the conductive material used for the positive electrode is an ohmic contact with the hole transport layer.
- An electrode using a conductive material having a small work function serves as a negative electrode.
- the conductive material having a small work function alkali metal or alkaline earth metal, specifically, lithium, magnesium, or calcium is used. Tin, silver, and aluminum are also preferably used.
- an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used.
- the conductive material used for the negative electrode is preferably one that is in ohmic contact with the organic semiconductor layer.
- an electron transport layer described later it is preferable that the conductive material used for the negative electrode is in ohmic contact with the electron transport layer.
- the organic semiconductor layer contains the compound of the present invention. That is, an electron donating organic material and an electron accepting organic material containing the compound of the present invention represented by the general formula (1) are included. These materials are preferably mixed, and the electron-donating organic material and the electron-accepting organic material are preferably compatible or phase-separated at the molecular level.
- the domain size of this phase separation structure is not particularly limited, but is usually 1 nm or more and 50 nm or less.
- the organic semiconductor layer preferably has a thickness of 5 nm to 500 nm, more preferably 30 nm to 300 nm.
- the layer having the electron donating organic material of the present invention preferably has a thickness of 1 nm to 400 nm, more preferably 15 nm to 150 nm.
- the electron donating organic material may be composed of only the compound of the present invention represented by the general formula (1) or may contain other electron donating organic materials.
- Examples of other electron-donating organic materials include polythiophene polymers, benzothiadiazole-thiophene derivatives, benzothiadiazole-thiophene copolymers, poly-p-phenylene vinylene polymers, poly-p-phenylene polymers.
- Conjugated polymers such as polyfluorene polymer, polypyrrole polymer, polyaniline polymer, polyacetylene polymer, polythienylene vinylene polymer, H2 phthalocyanine (H2Pc), copper phthalocyanine (CuPc), zinc Phthalocyanine derivatives such as phthalocyanine (ZnPc), porphyrin derivatives, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine (TPD), N , N′-Dinaphthyl-N, N′-diphenyl-4,4′-diphenyl- Triarylamine derivatives such as 1,1′-diamine (NPD), carbazole derivatives such as 4,4′-di (carbazol-9-yl) biphenyl (CBP), oligothiophene derivatives (terthiophene, quarterthiophene, s
- the photovoltaic device material of the present invention further includes an electron-accepting organic material (n-type organic semiconductor). ) Is preferably contained.
- the electron-accepting organic material used in the photovoltaic device of the present invention is an organic material exhibiting n-type semiconductor characteristics, such as 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), 3,4 , 9,10-perylenetetracarboxylic dianhydride (PTCDA), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), N, N′-dioctyl-3,4,9,10-naphthyl Tetracarboxydiimide (PTCDI-C8H), 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD), 2,5-di (1-naphthyl) ) -1,3,4-oxadiazole (BND) and other oxazole derivatives, 3- (4-biphenylyl) -4-phen Triazo
- a hole transport layer may be provided between the positive electrode and the organic semiconductor layer.
- conductive polymers such as polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, phthalocyanine derivatives (H2Pc, CuPc, ZnPc, etc.), Low molecular organic compounds exhibiting p-type semiconductor properties such as porphyrin derivatives are preferably used.
- PEDOT polyethylenedioxythiophene
- PEDOT polyethylenedioxythiophene
- PEDOT polyethylenedioxythiophene
- PEDOT polyethylenedioxythiophene
- PEDOT polystyrene sulfonate
- the thickness of the hole transport layer is preferably 5 nm to 600 nm, more preferably 30 nm to 200 nm.
- an electron transport layer may be provided between the organic semiconductor layer and the negative electrode.
- the material for forming the electron transport layer is not particularly limited, but the above-described electron-accepting organic materials (NTCDA, PTCDA, PTCDI-C8H, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerene compounds, Organic materials exhibiting n-type semiconductor properties such as CNT and CN-PPV are preferably used.
- the thickness of the electron transport layer is preferably 5 nm to 600 nm, more preferably 30 nm to 200 nm.
- two or more organic semiconductor layers may be stacked (tandemized) via one or more intermediate electrodes to form a series junction.
- a laminated structure of substrate / positive electrode / first organic semiconductor layer / intermediate electrode / second organic semiconductor layer / negative electrode can be given.
- the open circuit voltage can be improved.
- the hole transport layer described above may be provided between the positive electrode and the first organic semiconductor layer and between the intermediate electrode and the second organic semiconductor layer, and between the first organic semiconductor layer and the intermediate electrode.
- the hole transport layer described above may be provided between the second organic semiconductor layer and the negative electrode.
- At least one layer of the organic semiconductor layer contains the compound of the present invention represented by the general formula (1), and the other layers do not reduce the short-circuit current.
- the donating organic material preferably contains an electron donating organic material having a different band gap. Examples of such electron-donating organic materials include the above-mentioned polythiophene polymers, poly-p-phenylene vinylene polymers, poly-p-phenylene polymers, polyfluorene polymers, polypyrrole polymers, polyaniline.
- Conjugated polymers such as polymer, polyacetylene polymer, polythienylene vinylene polymer, phthalocyanine derivatives such as H2 phthalocyanine (H2Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), porphyrin derivatives, N , N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine (TPD), N, N′-dinaphthyl-N, N′-diphenyl- Triarylamine derivatives such as 4,4′-diphenyl-1,1′-diamine (NPD), Bazoru-9-yl) carbazole derivatives, such as biphenyl (CBP), oligothiophene derivatives (terthiophene, quarter thiophene, sexithiophene, etc. oct thiophene) include low molecular
- the material for the intermediate electrode used here is preferably a material having high conductivity, for example, the above-mentioned metals such as gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, and transparent Metal oxides such as indium and tin, composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), etc.), alloys composed of the above metals and laminates of the above metals, polyethylene Examples include dioxythiophene (PEDOT) and those obtained by adding polystyrene sulfonate (PSS) to PEDOT.
- the intermediate electrode preferably has a light transmission property, but even a material such as a metal having a low light transmission property can often ensure a sufficient light transmission property by reducing the film thickness.
- organic semiconductor layer formation spin coating, blade coating, slit die coating, screen printing coating, bar coater coating, mold coating, printing transfer method, dip pulling method, ink jet method, spray method, vacuum deposition method, etc. This method may be used, and the formation method may be selected according to the characteristics of the organic semiconductor layer to be obtained, such as film thickness control and orientation control.
- the organic semiconductor material of the present invention has high charge mobility, solvent solubility, oxidation stability, and good film forming properties, and an organic semiconductor device using the material exhibits high characteristics.
- Specific organic semiconductor devices that can make use of the characteristics of the organic semiconductor material of the present invention include, for example, organic field effect transistors and organic thin-film solar cells. Furthermore, by incorporating these organic semiconductor devices, It can be applied to large area sensors such as displays such as EL panels and electronic paper, liquid crystal displays, information tags, electronic artificial skin sheets and sheet-type scanners.
- Intermediate A-8 was obtained in the same manner as Intermediates A-6 and A-7, except that 1-bromo-3- (N-carbazolyl) benzene was used in place of 3-bromobiphenyl.
- Intermediate A-12 was used in the same manner as A-6 and A-7, except that intermediate A-12 was used instead of intermediate A-4 and iodobenzene was used instead of 1-bromo-3- (N-carbazolyl) benzene. Body A-13 was obtained.
- intermediate A-14 was 15 g (57 mmol)
- 2,6-dibromopyridine was 20 g (84 mmol)
- copper iodide 1.0 g (5.2 mmol)
- tripotassium phosphate 36 g (170 mmol)
- Trans-1,2-cyclohexanediamine 6.5 g (57 mmol)
- 1,4-dioxane 200 ml were added and stirred for 6 hours while heating at 120 ° C.
- the precipitated crystals were collected by filtration, and the solvent was distilled off under reduced pressure.
- the obtained residue was purified by silica gel column chromatography to obtain 11 g (26 mmol, 46% yield) of intermediate A-15 as a pale yellow solid.
- a white solid was prepared in the same manner as Intermediate A-15 except that Intermediate A-11 was used instead of Intermediate A-14, and 1-bromo-3-iodobenzene was used instead of 2,6-dibromopyridine.
- Intermediate A-16 was obtained.
- Example 14 Each thin film was laminated at a vacuum degree of 4.0 ⁇ 10 ⁇ 5 Pa by a vacuum deposition method on a glass substrate on which an anode made of ITO having a thickness of 110 nm was formed.
- copper phthalocyanine (CuPC) was formed to a thickness of 25 nm on ITO.
- NPB 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
- the compound 1-2 obtained in Example 1 as a host material and tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) as a phosphorescent dopant are used.
- a light emitting layer was formed to a thickness of 40 nm by co-evaporation from different deposition sources. The concentration of Ir (ppy) 3 in the light emitting layer was 10.0 wt%.
- tris (8-hydroxyquinolinato) aluminum (III) (Alq3) was formed to a thickness of 20 nm as an electron transport layer.
- lithium fluoride (LiF) was formed to a thickness of 1.0 nm as an electron injection layer.
- aluminum (Al) was formed as an electrode to a thickness of 70 nm to produce an organic EL element.
- the organic EL element had the light emission characteristics as shown in Table 1.
- Table 1 the luminance, voltage, and luminous efficiency show values at 10 mA / cm 2 .
- the maximum wavelength of the device emission spectrum was 530 nm, and it was found that light was emitted from Ir (ppy) 3 .
- Example 15 An organic EL device was produced in the same manner as in Example 15 except that Compound 1-7 was used as the host material for the light emitting layer.
- Example 16 An organic EL device was produced in the same manner as in Example 15 except that Compound 1-8 was used as the host material for the light emitting layer.
- Example 17 An organic EL device was produced in the same manner as in Example 15 except that Compound 1-24 was used as the host material for the light emitting layer.
- Example 18 An organic EL device was produced in the same manner as in Example 15 except that Compound 1-34 was used as the host material for the light emitting layer.
- Example 19 An organic EL device was produced in the same manner as in Example 15 except that Compound 1-49 was used as the host material for the light emitting layer.
- Example 20 An organic EL device was produced in the same manner as in Example 15 except that Compound 1-58 was used as the host material for the light emitting layer.
- Comparative Example 1 An organic EL device was produced in the same manner as in Example 15 except that 4,4′-bis (9-carbazolyl) biphenyl (CBP) was used as the host material of the light emitting layer.
- CBP 4,4′-bis (9-carbazolyl) biphenyl
- the maximum wavelengths of the emission spectra of the devices prepared in Examples 15 to 20 and Comparative Example 1 were all 530 nm, indicating that light emission from Ir (ppy) 3 was obtained.
- the emission characteristics are shown in Table 1.
- Example 21 Each thin film was laminated at a vacuum degree of 4.0 ⁇ 10 ⁇ 5 Pa by a vacuum deposition method on a glass substrate on which an anode made of ITO having a thickness of 110 nm was formed.
- copper phthalocyanine (CuPC) was formed to a thickness of 25 nm on ITO.
- NPB was formed to a thickness of 55 nm as a hole transport layer.
- the compound 1-39 obtained in Example 6 as a host material and bis (2- (2′-benzo [4,5-a] thienyl) pyridinato as a phosphorescent dopant are used.
- iridium (acetylacetonate) [(Btp) 2 Iracac] was co-evaporated from different deposition sources to form a light emitting layer with a thickness of 47.5 nm.
- concentration of (Btp) 2 Iracac in the light emitting layer was 8.0 wt%.
- Alq3 was formed to a thickness of 30 nm as an electron transport layer.
- LiF was formed on the electron transport layer to a thickness of 1.0 nm as an electron injection layer.
- Al was formed as an electrode to a thickness of 200 nm, and an organic EL device was produced.
- the organic EL element had the light emission characteristics as shown in Table 2.
- Table 2 the luminance, voltage, and luminous efficiency show values at 10 mA / cm 2 .
- the maximum wavelength of the device emission spectrum was 620 nm, and it was found that light emission from (Btp) 2 Iracac was obtained.
- Example 22 An organic EL device was produced in the same manner as in Example 22 except that Compound 1-41 was used as the host material for the light emitting layer.
- Example 23 An organic EL device was produced in the same manner as in Example 22 except that Compound 1-53 was used as the host material for the light emitting layer.
- Example 24 An organic EL device was produced in the same manner as in Example 22 except that Compound 2-11 was used as the host material for the light emitting layer.
- Comparative Example 2 An organic EL device was produced in the same manner as in Example 22 except that bis (2-methyl-8-quinolinolato) -4-phenylphenolato aluminum (III) (BAlq) was used as the host material for the light emitting layer.
- bis (2-methyl-8-quinolinolato) -4-phenylphenolato aluminum (III) (BAlq) was used as the host material for the light emitting layer.
- the maximum wavelengths of the device emission spectra prepared in Examples 22 to 24 and Comparative Example 2 are all 620 nm, indicating that light emission from (Btp) 2 Iracac is obtained. It was.
- the light emission characteristics are shown in Table 2.
- Example 25 An organic TFT element having the configuration shown in FIG. 2 was produced, and the characteristics of the organic semiconductor material of the present invention were evaluated.
- a silicon wafer (n-doped) having a thermally grown silicon oxide layer having a thickness of about 300 nm was washed with a sulfuric acid-hydrogen peroxide aqueous solution, boiled with isopropyl alcohol, and then dried.
- the obtained silicon wafer was spin-coated with a photoresist, and then exposed with an exposure machine through a photomask. Subsequently, after developing with a developing solution, it wash
- chromium and 50 nm gold were further deposited by vacuum deposition.
- the silicon wafer was immersed in a remover solution to produce a source electrode and a drain electrode on the silicon wafer.
- the silicon wafer on which the source and drain electrodes were formed was washed with acetone, further boiled with isopropyl alcohol and dried, and then immersed in an approximately 1 ⁇ 10 ⁇ 6 M toluene solution of octyltrichlorosilane overnight. Thereafter, the substrate was washed with toluene and isopropyl alcohol, and then heated at 110 ° C.
- an organic TFT substrate subjected to octyltrichlorosilane (OTS) treatment.
- OTS octyltrichlorosilane
- a chlorobenzene solution (1 wt%) of compound 1-2 was filtered using a 0.2 ⁇ m syringe filter, and spin-coated on the OTS-treated substrate at room temperature, 1000 rpm, and 30 seconds. It was then dried at 80 ° C. for 30 minutes. At this time, the thickness of the organic semiconductor layer was 50 nm. In this way, an organic TFT element having the structure shown in FIG. 2 was obtained.
- a voltage of -10 to -100 V is applied between the source electrode and the drain electrode of the obtained organic TFT element, the gate voltage is changed in the range of -30 to -80 V, and the voltage-current curve is 25 ° C.
- the transistor characteristics were evaluated at temperature.
- Field-effect mobility (mu) was calculated using the following equation representing the drain current I d of (I).
- I d (W / 2L) ⁇ C i (V g ⁇ V t ) 2 (I)
- L is the gate length and W is the gate width.
- C i is a capacitance per unit area of the insulating layer, V g is a gate voltage, and V t is a threshold voltage.
- the on / off ratio was calculated from the ratio between the maximum and minimum drain current values (I d ). Table 3 shows the characteristics of the obtained organic TFT element.
- Example 26 In Example 25, a chloroform solution (1 wt%) of compound 1-8 was used in place of the chlorobenzene solution (1 wt%) of compound 1-2, and spin coating was performed at room temperature at 1000 rpm for 30 seconds.
- the organic TFT element was produced in the same manner as described above. Table 3 shows the characteristics of the obtained organic TFT element.
- Example 27 An organic TFT substrate was produced in the same manner as in Example 25.
- a compound 3-6 was deposited on the organic TFT substrate by vacuum deposition under the condition of a vacuum degree of 5.0 ⁇ 10 ⁇ 4 Pa, and a thin film of compound 3-6 was formed at a thickness of 100 nm at 0.3 nm / second. By forming with a thickness, an organic TFT element having the structure shown in FIG. 2 was obtained. Table 3 shows the characteristics of the obtained organic TFT element.
- Table 3 shows that the nitrogen-containing aromatic compound of the present invention has high characteristics as an organic semiconductor.
- the skeleton of the nitrogen-containing aromatic compound of the present invention can control various energy values of ionization potential, electron affinity, and triplet excitation energy by a heterocyclic ring and a linking group condensed with indole. It is considered that charge stability is improved by having a plurality of such condensed indole skeletons in the same molecule.
- the nitrogen-containing aromatic compound of the present invention is considered to have high charge transfer characteristics. Therefore, it is considered that the organic electronic device using the nitrogen-containing aromatic compound of the present invention can exhibit high characteristics. For example, it can be applied to displays such as organic EL panels and electronic paper, liquid crystal displays, organic field effect transistors, organic thin-film solar cells, information tags, electronic artificial skin sheets, large area sensors such as sheet-type scanners, etc. Technical value is great.
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Abstract
Description
本発明の有機EL素子は、基板に支持されていることが好ましい。この基板については、特に制限はなく、従来から有機EL素子に慣用されているものであればよく、例えば、ガラス、透明プラスチック、石英などからなるものを用いることができる。
有機EL素子における陽極としては、仕事関数の大きい(4eV以上)金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具体例としてはAu等の金属、CuI、インジウムチンオキシド(ITO)、SnO2、ZnO等の導電性透明材料が挙げられる。また、IDIXO(In2O3-ZnO)等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの電極物質を蒸着やスパッタリング等の方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、あるいはパターン精度をあまり必要としない場合は(100μm以上程度)、上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。あるいは、有機導電性化合物のように塗布可能な物質を用いる場合には、印刷方式、コーティング方式等湿式成膜法を用いることもできる。この陽極より発光を取り出す場合には、透過率を10%より大きくすることが望ましく、また陽極としてのシート抵抗は数百Ω/□以下が好ましい。更に膜厚は材料にもよるが、通常10~1000nm、好ましくは10~200nmの範囲で選ばれる。
一方、陰極としては、仕事関数の小さい(4eV以下)金属(電子注入性金属と称する)、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム-カリウム合金、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、インジウム、リチウム/アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性及び酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、リチウム/アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電極物質を蒸着やスパッタリング等の方法により薄膜を形成させることにより、作製することができる。また、陰極としてのシート抵抗は数百Ω/□以下が好ましく、膜厚は通常10nm~5μm、好ましくは50~200nmの範囲で選ばれる。なお、発光した光を透過させるため、有機EL素子の陽極又は陰極のいずれか一方が、透明又は半透明であれば発光輝度が向上し好都合である。
発光層は蛍光発光層、燐光発光層のいずれでも良いが、燐光発光層であることが好ましい。
注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、正孔注入層と電子注入層があり、陽極と発光層又は正孔輸送層の間、及び陰極と発光層又は電子輸送層との間に存在させてもよい。注入層は必要に応じて設けることができる。注入材料としては、一般式(1)で表される本発明の化合物を用いることができるが、該化合物を他の何れかの有機層に使用する場合は、従来公知の化合物の中から任意のものを選択して用いることができる。
正孔阻止層とは広い意味では電子輸送層の機能を有し、電子を輸送する機能を有しつつ正孔を輸送する能力が著しく小さい正孔阻止材料からなり、電子を輸送しつつ正孔を阻止することで電子と正孔の再結合確率を向上させることができる。
電子阻止層とは、正孔を輸送する機能を有しつつ電子を輸送する能力が著しく小さい材料から成り、正孔を輸送しつつ電子を阻止することで電子と正孔が再結合する確率を向上させることができる。
励起子阻止層とは、発光層内で正孔と電子が再結合することにより生じた励起子が電荷輸送層に拡散することを阻止するための層であり、本層の挿入により励起子を効率的に発光層内に閉じ込めることが可能となり、素子の発光効率を向上させることができる。励起子阻止層は発光層に隣接して陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。
正孔輸送層とは正孔を輸送する機能を有する正孔輸送材料からなり、正孔輸送層は単層又は複数層設けることができる。
電子輸送層とは電子を輸送する機能を有する材料からなり、電子輸送層は単層又は複数層設けることができる。
基板は、特に限定されず、例えば、従来公知の構成とすることができる。基板としては、例えば、ガラス(例えば、石英ガラス)、シリコン、セラミック、プラスチックが挙げられる。プラスチックとしては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート等の汎用の樹脂基板が挙げられる。樹脂基板は、酸素、水蒸気等のガスの透過性を低くするためのガスバリア膜を積層したものであることが好ましい。
ゲート電極は、特に限定されず、例えば、従来公知の構成とすることができる。ゲート電極としては、例えば、金、白金、クロム、タングステン、タンタル、ニッケル、銅、アルミニウム、銀、マグネシウム、カルシウム等の金属またはそれらの合金、ポリシリコン、アモルファスシリコン、グラファイト、ITO、酸化亜鉛、導電性ポリマー等の材料を用いることができる。
ゲート絶縁層は、特に限定されず、例えば、従来公知の構成とすることができる。ゲート絶縁層としては、SiO2、Si3N4、SiON、Al2O3、Ta2O5、アモルファスシリコン、ポリイミド樹脂、ポリビニルフェノール樹脂、ポリパラキシリレン樹脂、ポリメチルメタクリレート樹脂、フッ素樹脂(PTFE、PFA、PETFE、PCTFE、CYTOP(登録商標)等)等の材料を用いることができる。
有機半導体層は、本発明の化合物を含む層であれば、特に限定されない。例えば、実質的に本発明の化合物のみからなる層であってもよく、本発明の化合物以外の他の物質を含有する層であってもよい。
ソース電極およびドレイン電極は、いずれも特に限定されず、例えば、従来公知の構成とすることができる。ソース電極およびドレイン電極としては、いずれも、金、白金、クロム、タングステン、タンタル、ニッケル、銅、アルミニウム、銀、マグネシウム、カルシウム等の金属またはそれらの合金、ポリシリコン、アモルファスシリコン、グラファイト、ITO、酸化亜鉛、導電性ポリマー等の材料を用いることができる。
基板は、特に限定されず、例えば、従来公知の構成とすることができる。機械的、熱的強度を有し、透明性を有するガラス基板や透明性樹脂フィルムを使用することが好ましい。透明性樹脂フィルムとしては、ポリエチレン、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体、ポリプロピレン、ポリスチレン、ポリメチルメタアクリレート、ポリ塩化ビニル、ポリビニルアルコール、ポリビニルブチラール、ナイロン、ポリエーテルエーテルケトン、ポリサルホン、ポリエーテルサルフォン、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体、ポリビニルフルオライド、テトラフルオロエチレン-エチレン共重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、ポリエステル、ポリカーボネート、ポリウレタン、ポリイミド、ポリエーテルイミド、ポリイミド、ポリプロピレン等が挙げられる。
電極材料としては、一方の電極には仕事関数の大きな導電性素材、もう一方の電極には仕事関数の小さな導電性素材を使用することが好ましい。仕事関数の大きな導電性素材を用いた電極は正極となる。この仕事関数の大きな導電性素材としては金、白金、クロム、ニッケルなどの金属のほか、透明性を有するインジウム、スズなどの金属酸化物、複合金属酸化物(インジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)など)が好ましく用いられる。ここで、正極に用いられる導電性素材は、有機半導体層とオーミック接合するものであることが好ましい。さらに、後述する正孔輸送層を用いた場合においては、正極に用いられる導電性素材は正孔輸送層とオーミック接合するものであることが好ましい。
有機半導体層は本発明の化合物を含む。すなわち、一般式(1)で表される本発明の化合物を含む電子供与性有機材料および電子受容性有機材料を含む。これらの材料は混合されていることが好ましく、電子供与性有機材料と電子受容性有機材料が分子レベルで相溶しているか、相分離していることが好ましい。この相分離構造のドメインサイズは特に限定されるものではないが通常1nm以上50nm以下のサイズである。また、電子供与性有機材料と電子受容性有機材料が積層されている場合は、p型半導体特性を示す電子供与性有機材料を有する層が正極側、n型半導体特性を示す電子受容性有機材料を有する層が負極側であることが好ましい。有機半導体層は5nm~500nmの厚さが好ましく、より好ましくは30nm~300nmである。積層されている場合は、本発明の電子供与性有機材料を有する層は上記厚さのうち1nm~400nmの厚さを有していることが好ましく、より好ましくは15nm~150nmである。
APCI-TOFMS, m/z 791 [M+H]+
APCI-TOFMS, m/z 969 [M+H]+、1H-NMR測定結果(測定溶媒:THF-d8)を図6に示す。
APCI-TOFMS, m/z 599 [M+H]+
APCI-TOFMS, m/z 974 [M+H]+
APCI-TOFMS, m/z 640 [M+H]+
APCI-TOFMS, m/z 718 [M+H]+
APCI-TOFMS, m/z 717 [M+H]+、1H-NMR測定結果(測定溶媒:THF-d8)を図7に示す。
APCI-TOFMS, m/z 806 [M+H]+
APCI-TOFMS, m/z 871 [M+H]+
APCI-TOFMS, m/z 661 [M+H]+
APCI-TOFMS, m/z 561 [M+H]+
APCI-TOFMS, m/z 564 [M+H]+
APCI-TOFMS, m/z 1148 [M+H]+
膜厚110 nmのITOからなる陽極が形成されたガラス基板上に、各薄膜を真空蒸着法にて、真空度4.0×10-5 Paで積層した。まず、ITO上に銅フタロシアニン(CuPC)を25 nmの厚さに形成した。次に、正孔輸送層として4,4'-ビス[N-(1-ナフチル)-N-フェニルアミノ]ビフェニル(NPB)を40 nmの厚さに形成した。次に、正孔輸送層上に、ホスト材料として実施例1で得た化合物1-2と、燐光発光ドーパントとしてのトリス(2‐フェニルピリジン)イリジウム(III)(Ir(ppy)3)とを異なる蒸着源から、共蒸着し、40 nmの厚さに発光層を形成した。発光層中のIr(ppy)3の濃度は10.0 wt%であった。次に、電子輸送層としてトリス(8-ヒドロキシキノリナト)アルミニウム(III)(Alq3)を20 nmの厚さに形成した。更に、電子輸送層上に、電子注入層としてフッ化リチウム(LiF)を1.0 nmの厚さに形成した。最後に、電子注入層上に、電極としてアルミニウム(Al)を70 nmの厚さに形成し、有機EL素子を作製した。
発光層のホスト材料として、化合物1-7を用いた以外は実施例15と同様にして有機EL素子を作製した。
発光層のホスト材料として、化合物1-8を用いた以外は実施例15と同様にして有機EL素子を作製した。
発光層のホスト材料として、化合物1-24を用いた以外は実施例15と同様にして有機EL素子を作製した。
発光層のホスト材料として、化合物1-34を用いた以外は実施例15と同様にして有機EL素子を作製した。
発光層のホスト材料として、化合物1-49を用いた以外は実施例15と同様にして有機EL素子を作製した。
発光層のホスト材料として、化合物1-58を用いた以外は実施例15と同様にして有機EL素子を作製した。
発光層のホスト材料として、4,4'-ビス(9-カルバゾリル)ビフェニル(CBP)を用いた以外は実施例15と同様にして有機EL素子を作製した。
膜厚110 nmのITOからなる陽極が形成されたガラス基板上に、各薄膜を真空蒸着法にて、真空度4.0×10-5 Paで積層した。まず、ITO上に銅フタロシアニン(CuPC)を25 nmの厚さに形成した。次に、正孔輸送層としてNPBを55 nmの厚さに形成した。次に、正孔輸送層上に、ホスト材料としての実施例6で得た化合物1-39と、燐光発光ドーパントとしてのビス(2-(2'-ベンゾ[4,5-a]チエニル)ピリジナト-N,C3)イリジウム(アセチルアセトネート)〔(Btp)2Iracac〕とを異なる蒸着源から、共蒸着し、47.5 nmの厚さに発光層を形成した。発光層中の(Btp)2Iracacの濃度は8.0 wt%であった。次に、電子輸送層としてAlq3を30 nmの厚さに形成した。更に、電子輸送層上に、電子注入層としてLiFを1.0 nmの厚さに形成した。最後に、電子注入層上に、電極としてAlを200 nmの厚さに形成し、有機EL素子を作製した。
発光層のホスト材料として、化合物1-41を用いた以外は実施例22と同様にして有機EL素子を作製した。
発光層のホスト材料として、化合物1-53を用いた以外は実施例22と同様にして有機EL素子を作製した。
発光層のホスト材料として、化合物2-11を用いた以外は実施例22と同様にして有機EL素子を作製した。
発光層のホスト材料として、ビス(2-メチル-8-キノリノラト)-4-フェニルフェノラトアルミニウム(III)(BAlq)を用いた以外は実施例22と同様にして有機EL素子を作製した。
図2に示す構成の有機TFT素子を作製し、本発明の有機半導体材料の特性を評価した。まず、約300 nmの厚みの熱成長酸化ケイ素層を有するシリコンウェハ(nドープ)を、硫酸-過酸化水素水溶液で洗浄し、イソプロピルアルコールで煮沸した後、乾燥した。得られたシリコンウェハにフォトレジストをスピンコート後、フォトマスクを介して露光機により露光した。次いで、現像液で現像を行った後、イオン交換水で洗浄し、空気乾燥した。そのパターニングされたフォトレジストが塗布されたシリコンウェハ上に、真空蒸着法により、厚さ3 nmのクロム、更にその上に50 nmの金を蒸着した。そのシリコンウェハを、リムーバー溶液に浸すことでシリコンウェハ上にソース電極およびドレイン電極を作製した。ソース電極およびドレイン電極が作製されたシリコンウェハをアセトンで洗浄し、さらに、イソプロピルアルコールで煮沸し乾燥した後、オクチルトリクロロシランの約1×10-6M トルエン溶液中に、一晩浸漬した。その後、トルエン、イソプロピルアルコールで洗浄した後、110 ℃で約10 分間加熱することで、オクチルトリクロロシラン(OTS)処理を行った有機TFT基板を作製した。チャネル長はL=25 μm、チャネル幅はW=15.6 μmであった。次に化合物1-2のクロロベンゼン溶液(1重量%)を0.2 μmのシリンジフィルターを用いてろ過し、OTS処理を行った基板上に、室温、1000 rpm、30 秒間の条件でスピンコートした。次いでそれを80 ℃で30 分間乾燥した。この時、有機半導体層の厚さは50 nmであった。このようにして図2に示す構造を有する有機TFT素子を得た。
Id=(W/2L)μCi(Vg-Vt)2 (I)
実施例25において、化合物1-2のクロロベンゼン溶液(1重量%)の代わりに、化合物1-8のクロロホルム溶液(1重量%)を使用し、室温にて1000 rpm、30 秒の条件でスピンコートを行ったほかは同様の操作を行い、有機TFT素子を作製した。得られた有機TFT素子の特性を表3に示す。
実施例25と同様の方法により、有機TFT基板を作製した。チャネル長はL=25 μm、チャネル幅はW=15.6μmであった。次に、有機TFT基板上に真空蒸着法にて、真空度5.0×10-4Pa の条件にて化合物3-6を蒸着し、化合物3-6の薄膜を0.3 nm/秒にて100 nmの厚さで形成する事により、図2に示す構造を有する有機TFT素子を得た。得られた有機TFT素子の特性を表3に示す。
Claims (9)
- 一般式(1)で表される含窒素芳香族化合物。
式(1)中、Lはm+n価の炭素数6~30の芳香族炭化水素基又は4環以上の縮合複素環を含まない炭素数3~30の芳香族複素環基、炭素数9~30のトリアリールアミンから生じる基、又は炭素数6~24のジアリールスルホンから生じる基を表す。XはN-A、O、S又はSeを表し、Aはそれぞれ独立して炭素数1~30のアルキル基、炭素数3~30のシクロアルキル基、炭素数2~30のアルケニル基、炭素数2~30のアルキニル基、炭素数3~18のシリル基、炭素数2~19のアシル基、炭素数6~50の芳香族炭化水素基又は4環以上の縮合複素環を含まない炭素数3~50の芳香族複素環基を表す。Rはそれぞれ独立して水素、炭素数1~30のアルキル基、炭素数3~30のシクロアルキル基、炭素数2~30のアルケニル基、炭素数2~30のアルキニル基、炭素数6~30の芳香族炭化水素基又は4環以上の縮合複素環を含まない炭素数3~30の芳香族複素環基を表す。mは1~4の整数を表し、nは0~3の整数を表す。mとnの総数は2~4である。 - 一般式(1)において、nが0である請求項1に記載の含窒素芳香族化合物。
- 一般式(1)において、XがN-Aであることを特徴とする請求項1に記載の含窒素芳香族化合物。
- 一般式(1)において、mが2又は3であることを特徴とする請求項1に記載の化合物。
- 請求項1~4のいずれかに記載の含窒素芳香族化合物を含むことを特徴とする有機半導体材料。
- 請求項5に記載の有機半導体材料で形成されることを特徴とする有機半導体薄膜。
- 請求項5に記載の有機半導体材料を使用したことを特徴とする有機電子デバイス。
- 有機電子デバイスが、発光素子、薄膜トランジスタ、又は光起電力素子のいずれかである請求項7に記載の有機電子デバイス。
- 発光素子が、有機電界発光素子である請求項8に記載の有機電子デバイス。
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US8766249B2 (en) | 2014-07-01 |
TW201242125A (en) | 2012-10-16 |
TWI508343B (zh) | 2015-11-11 |
CN103154005B (zh) | 2015-08-26 |
KR101902767B1 (ko) | 2018-10-01 |
CN103154005A (zh) | 2013-06-12 |
EP2628743B1 (en) | 2016-02-24 |
JP5767237B2 (ja) | 2015-08-19 |
EP2628743A1 (en) | 2013-08-21 |
US20130184458A1 (en) | 2013-07-18 |
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