JP2006070100A - Organic-organometallic compound-doped dendrimer - Google Patents
Organic-organometallic compound-doped dendrimer Download PDFInfo
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- JP2006070100A JP2006070100A JP2004252781A JP2004252781A JP2006070100A JP 2006070100 A JP2006070100 A JP 2006070100A JP 2004252781 A JP2004252781 A JP 2004252781A JP 2004252781 A JP2004252781 A JP 2004252781A JP 2006070100 A JP2006070100 A JP 2006070100A
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- dendrimer
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- organometallic compound
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- 239000000412 dendrimer Substances 0.000 title claims abstract description 96
- 229920000736 dendritic polymer Polymers 0.000 title claims abstract description 92
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 17
- 150000001768 cations Chemical class 0.000 claims abstract description 16
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000012776 electronic material Substances 0.000 claims abstract description 6
- -1 aromatic cation Chemical class 0.000 claims description 45
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 claims description 3
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 239000010409 thin film Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 150000002892 organic cations Chemical class 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 230000003321 amplification Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012377 drug delivery Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000009918 complex formation Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000004303 annulenes Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical group 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920004010 poly(benzyl ether) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229930192474 thiophene Chemical group 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Polyethers (AREA)
- Electroluminescent Light Sources (AREA)
- Medicinal Preparation (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、発光材料、電子デバイス、ドラックデリバリーシステム（ＤＤＳ）、触媒、印刷、写真等の広範囲な分野において有用な、新しい機能物質としての有機・有機金属内包デンドリマーとその応用に関するものである。 The present invention relates to an organic / organic metal-containing dendrimer as a new functional substance useful in a wide range of fields such as a light emitting material, an electronic device, a drug delivery system (DDS), a catalyst, printing, and photography, and its application.
特異な樹状分子構造をもつデンドリマーあるいはデンドロンが新しい機能性分子として注目されている。しかしながら、その機能の発現については、分子構造やその複合構造の観点から多くの解決すべき課題がある。 Dendrimers or dendrons with a unique dendritic molecular structure are attracting attention as new functional molecules. However, there are many problems to be solved about the expression of the function from the viewpoint of the molecular structure and the composite structure.
たとえば、有機ＥＬ素子への応用について概観してみると、まず、有機ＥＬ素子は透明ガラス電極（ＩＴＯ）と電子注入層の低仕事関数金属の間に有機層として正孔輸送層、発光層、電子輸送層などを挟んで、発光層において正孔と電子の再結合により生成される励起子（エキシトン）の失活する際の放出する光エネルギー（蛍光・燐光）を利用する表示素子である。従来、正孔輸送層としては室温で安定なガラス転移を示すアモルファスの低分子系が用いられており、その代表的な例としては低分子系としてはトリフェニルアミン誘導体、さらに有機ＥＬ素子の高効率、高安定性を高めるためにトリフェニルアミン基とビニル基を結合させたジスチルベンゼン誘導体や電子輸送材として知られているオキサジアゾール基と結合させた誘導体などが用いられている。または、強い蛍光特性を示す希土類金属錯体系も利用されている。高分子系の場合はπ共役系のポリフェニレンビニレン、非共役系のポリビニルカルバゾール誘導体などもそれぞれ発光層、正孔輸送層材として用いられている。このような有機ＥＬ素子を実用するうえで、高輝度、高効率の発光材料の開発のみならず、素子寿命の向上も重要課題である。そのため、薄膜である各々層の膜形成状態、すなわち薄膜のモルフォロジー安定性が極めて要求されている。さらに、有機ＥＬ素子の更なる安定性のためには電気化学的安定性（可逆的な酸化還元）も優れた化合物が望まれている。 For example, when reviewing the application to organic EL elements, first, the organic EL element is an organic layer between a transparent glass electrode (ITO) and a low work function metal of an electron injection layer, a hole transport layer, a light emitting layer, It is a display element that utilizes light energy (fluorescence / phosphorescence) emitted when an exciton (exciton) generated by recombination of holes and electrons in a light-emitting layer is sandwiched between an electron transport layer and the like. Conventionally, an amorphous low molecular weight system that exhibits a stable glass transition at room temperature has been used as the hole transport layer. Typical examples of such a low molecular weight system are triphenylamine derivatives, and organic EL device high molecular weight devices. In order to enhance efficiency and high stability, a distilbenzene derivative in which a triphenylamine group and a vinyl group are bonded, a derivative bonded to an oxadiazole group, which is known as an electron transport material, and the like are used. Alternatively, a rare earth metal complex system exhibiting strong fluorescence characteristics is also used. In the case of a polymer system, π-conjugated polyphenylene vinylene and non-conjugated polyvinyl carbazole derivatives are also used as the light emitting layer and hole transport layer material, respectively. In practical use of such an organic EL element, not only development of a high-luminance and high-efficiency light-emitting material, but also improvement of the element lifetime is an important issue. Therefore, the film formation state of each layer which is a thin film, that is, the morphological stability of the thin film is extremely required. Furthermore, a compound having excellent electrochemical stability (reversible oxidation-reduction) is desired for further stability of the organic EL device.
このような状況において注目されているのがデンドリマーあるいはデンドロンである。たとえば具体的にはモルフォロジー安定性を向上するために簡便にキャストのみできれいに製膜できる樹状の高分子デンドリマーを用いる試みが行われている（たとえば特許文献１−２参照）。 Dendrimers or dendrons are attracting attention in such situations. For example, specifically, an attempt has been made to use a dendritic polymer dendrimer that can be easily formed cleanly only by casting in order to improve morphological stability (see, for example, Patent Document 1-2).
また、ホール移動度の向上のためにデンドリマーの末端に芳香族アミン構造を導入する例もある（特許文献３）。 There is also an example in which an aromatic amine structure is introduced at the end of a dendrimer in order to improve hole mobility (Patent Document 3).
また、薬剤伝達システムに関しては、近年ドラッグデリバリーシステム（ＤＤＳ）を確立し、副作用の少ない薬剤の開発が進められており、細胞膜、毛細血管の小さな穴を透過するためにはナノサイズであることが必要であることから、デンドリマーはその点で有効であると考えられている。薬剤を内包させ、電気化学、ｐＨなどの外部刺激、外部環境の変化によって薬剤を放出させることができると期待されている。そして実際にも、デンドリマーを用いたものがすでに提案されている（特許文献４）。 In addition, regarding drug delivery systems, drug delivery systems (DDS) have recently been established, and development of drugs with few side effects has been promoted, and it must be nano-sized to penetrate small holes in cell membranes and capillaries. Because it is necessary, dendrimers are considered effective in that respect. It is expected that drugs can be released by encapsulating drugs and by external stimuli such as electrochemistry and pH, and changes in the external environment. In fact, one using a dendrimer has already been proposed (Patent Document 4).
そしてまた、有機カチオン、有機金属カチオンは反応性があり、高濃度に３ｎｍ程度の空間に集積できるため、高触媒能が期待でき、さらに発光能を持つ色素も多く、濃度消光や色素の分解を抑えるために、これらをデンドリマー内に共有結合によって取込むことが考えられている（特許文献５）。 In addition, organic cations and organometallic cations are reactive and can be accumulated in a space of about 3 nm at a high concentration, so that a high catalytic ability can be expected. In order to suppress these, it is considered that these are incorporated into the dendrimer by a covalent bond (Patent Document 5).
しかしながら、これまでに提案されているデンドリマーやその修飾体の場合には、各種の機能を顕著に高め、しかもこれを薄膜や粒子の状態において安定なものとすることは必ずしも満足できるものとなってはいない。また、デンドリマーの構造を修飾するとの従来の提案については、合成そのものが容易ではないという大きな問題があった。 However, in the case of the dendrimer and the modified product proposed so far, it is not always satisfactory to remarkably enhance various functions and to make it stable in the state of a thin film or particles. No. Further, the conventional proposal to modify the structure of the dendrimer has a big problem that the synthesis itself is not easy.
そして、これらの問題を解決に際しては、フェニルアゾメチンデンドリマーのように、デンドリマー単独では絶縁性のためにデバイス（素子）に利用することが難しいという基本的な問題があった。
本発明は、以上のとおりの背景から、従来の問題点を解消し、その合成が比較的容易であって、しかも薄膜や粒子等としての成形の難しさもほとんどなく、高い機能性を安定して発現することができ、デバイスとしての構成も可能な、新しいデンドリマー（デンドロン）物質を提供し、またそのデバイス等への応用の方策も提供することを課題としている。 The present invention eliminates the conventional problems from the background as described above, is relatively easy to synthesize, and has almost no difficulty in forming as a thin film or particle, and stably has high functionality. It is an object to provide a new dendrimer (dendron) substance that can be expressed and can be configured as a device, and to provide a method for application to the device.
本発明は、上記の課題を解決するものとして、以下のことを特徴としている。 The present invention is characterized by the following in order to solve the above problems.
＜１＞電子供与性の結合もしくは原子を含むデンドリマーもしくはデンドロンに、有機化合物および有機金属化合物の１種以上のカチオンもしくはカチオンラジカルが内包あるいは複合化されている有機・有機金属化合物内包デンドリマー。 <1> An organic / organic metal compound-encapsulated dendrimer in which one or more cations or cation radicals of an organic compound and an organometallic compound are encapsulated or complexed in a dendrimer or dendron containing an electron-donating bond or atom.
＜２＞デンドリマーは、フェニルアゾメチンデンドリマー、ポリアミドアミンデンドリマー、ポリアルキレンイミンデンドリマーおよびポリアリールアルキルエーテルデンドリマーのうちの少くとも１種である上記の有機・有機金属化合物内包デンドリマー。 <2> The above-mentioned organic / organometallic compound-containing dendrimer, wherein the dendrimer is at least one of phenylazomethine dendrimer, polyamidoamine dendrimer, polyalkyleneimine dendrimer and polyarylalkyl ether dendrimer.
＜３＞デンドリマーもしくはデンドロンは、次式（１） <3> Dendrimer or dendron has the following formula (1)
のデンドロンである。〕
で表わされるフェニルアゾメチンデンドリマーもしくはコア構造を持たないデンドロンである上記の有機・有機金属化合物内包デンドリマー。
The dendron. ]
A phenylazomethine dendrimer represented by the above or a dendron containing no organic or organometallic compound, which is a dendron having no core structure.
＜４＞Ｘの分子基は、次式（３）で表わされるいずれかのものである上記の有機・有機金属化合物内包デンドリマー。 <4> The above-mentioned organic / organometallic compound-containing dendrimer, wherein the molecular group of X is any one represented by the following formula (3).
＜６＞上記いずれかの有機・有機金属化合物内包デンドリマーをその構成の少くとも一部としていることを特徴とする発光材料。 <6> A light emitting material characterized in that any one of the above-mentioned organic / organometallic compound-containing dendrimers is at least a part of the constitution.
＜７＞上記発光材料を構成の一部としていることを特徴とする有機ＥＬ素子もしくは装置。 <7> An organic EL element or apparatus characterized in that the light emitting material is part of the structure.
＜８＞上記いずれかの有機・有機金属化合物内包デンドリマーをその構成の少くとも一部としていることを特徴とする電子材料。 <8> An electronic material characterized in that any one of the above-mentioned organic / organometallic compound-encapsulating dendrimers is at least a part of its constitution.
＜９＞上記電子材料を構成の一部としていることを特徴とする電子素子もしくは装置。 <9> An electronic element or apparatus characterized in that the electronic material is part of the configuration.
＜１０＞上記の素子もしくは装置である太陽電池。 <10> A solar cell which is the above element or device.
＜１１＞上記いずれかの有機・有機金属化合物内包デンドリマーをその構成の少くとも一部としていることを特徴とする薬剤伝達体。 <11> A drug transmitter characterized in that any one of the above-mentioned organic / organometallic compound-containing dendrimers is at least a part of the constitution.
＜１２＞上記いずれかの有機・有機金属化合物内包デンドリマーをその構成の少くとも一部としていることを特徴とする触媒。 <12> A catalyst characterized in that any one of the above organic / organometallic compound-encapsulating dendrimers is at least a part of its constitution.
以上のとおりの本発明は、従来、フェニルアゾメチンデンドリマー等のデンドリマー単体では絶縁性のため、デバイスに利用することは難しく、また有機カチオン、有機金属カチオン単体では製膜性、安定性が悪く、デバイスに利用することが難しかったが、合成などの手間を省き、簡単に両者を複合化されることにより、有機カチオンやカチオンラジカル、有機金属カチオンをデンドリマーへ錯形成反応を利用して導入すると、アモルファス状態で製膜できるようになり、ホール移動度、導電性、発光特性等が発現させ、この機能が安定して維持されることが発明者により見出され、この知見に基づいて完成されたものである。そしてその背景には、すでに発明者が見出しているフェニルアゾメチンデンドリマーの電子供与性のＣ＝Ｎ結合と金属塩（たとえば塩化鉄、塩化スズ、塩化金）などが錯形成するとの知見が踏まえられている。 The present invention as described above is conventionally difficult to use in devices because of the insulating properties of dendrimers such as phenylazomethine dendrimers, and it is difficult to use in organic cation and organometallic cation alone. However, it is difficult to use it for synthesis, and it is easy to combine both of them by combining them. It has been found by the inventor that the film can be formed in a state, exhibits hole mobility, conductivity, light emission characteristics, etc., and this function is stably maintained, and has been completed based on this knowledge It is. And the background is based on the knowledge that the inventor has already found that the electron donating C═N bond of phenylazomethine dendrimer and a metal salt (for example, iron chloride, tin chloride, gold chloride) are complexed. Yes.
上記の本発明によれば、簡便な合成によって複合化された有機・有機金属化合物内包デンドリマー（デンドロン）として、特徴のある優れた機能を安定して発現でき、デバイス、粒子等への成形も容易に可能とされる。 According to the present invention described above, as an organic / organometallic compound-encapsulated dendrimer (dendron) complexed by simple synthesis, it can stably exhibit a characteristic and excellent function and can be easily formed into a device, particle, or the like. Is possible.
このため、本発明の有機・有機金属化合物内包デンドリマー（デンドロン）は、たとえば、発光材料をはじめ、ＥＬ素子、太陽電池、トランジスタ、ダイオード、キャパシター、電池などの電子デバイスに用いることができる。 For this reason, the organic-organometallic compound inclusion dendrimer (dendron) of this invention can be used for electronic devices, such as an EL element, a solar cell, a transistor, a diode, a capacitor, a battery, for example including a luminescent material.
また薬剤に有機金属カチオンまたは有機カチオン部位を導入、デンドリマーの中へ内包させることができる。またカチオンとイミンの孤立電子対との間の静電相互作用によって内包させているため、電気化学、ｐＨなどの外部刺激、外部環境の変化によって薬剤を放出させることができる。機能性触媒への応用についても同様である。 In addition, an organometallic cation or an organic cation moiety can be introduced into a drug and encapsulated in a dendrimer. Moreover, since it is included by the electrostatic interaction between the lone pair of a cation and imine, a chemical | medical agent can be discharge | released by external stimuli, such as electrochemistry and pH, and the change of external environment. The same applies to functional catalysts.
本発明において、電子供与性の結合または原子を含むデンドリマーまたはデンドロンとしては、その代表的なものとしてフェニルアゾメチンデンドリマーを例示することができる。このフェニルアゾメチンデンドリマーは、前記の式（１）（２）で示すことができるものであって、式中のフェニル基は、Ｃ、Ｎ、Ｏ等の原子を含む置換基、たとえばアルキル基、アリール基、アミノ基、アミド基、ニトリル基、ヒドロキシル基、アルコキシル基、エステル基、カルバメート基等を適宜に有していてもよい。 In the present invention, a typical example of a dendrimer or dendron containing an electron-donating bond or atom is a phenylazomethine dendrimer. This phenylazomethine dendrimer can be represented by the above formulas (1) and (2), and the phenyl group in the formula is a substituent containing an atom such as C, N, O, etc., for example, an alkyl group, aryl A group, an amino group, an amide group, a nitrile group, a hydroxyl group, an alkoxyl group, an ester group, a carbamate group and the like may be appropriately included.
また、この式（１）（２）においては、Ｙは、フェニルアゾメチン結合からなる第ｎ世代までのデンドロンを示し、Ｚは、デンドリマーの置換数を示している。ｎについては、特に制限はないが、代表的には１〜８の範囲を、置換数Ｚについては、代表的には１〜６の範囲を好適なものとして例示することができる。 In the formulas (1) and (2), Y represents a dendron up to the nth generation composed of a phenylazomethine bond, and Z represents the number of substitutions of the dendrimer. n is not particularly limited, but typically a range of 1 to 8 can be typically exemplified, and a substitution number Z can typically be exemplified by a range of 1 to 6 as suitable.
そして、コアの骨格としてのＸについては、特に限定的ではないが、たとえば、フェニルアミン基などを含むアミン誘導体、ベンゼン基、ナフタレン基などの芳香環を含む炭素環誘導体、ピロール、チオフェン、オキサジアゾル基などを含むヘテロ環誘導体、ポルフィリン誘導体、フタロシアニン誘導体などが例示される。そして合成反応によりＹの導入が可能であれば特に限定されない。 X as a core skeleton is not particularly limited, but examples thereof include amine derivatives containing phenylamine groups, carbocyclic derivatives containing aromatic rings such as benzene groups and naphthalene groups, pyrrole, thiophene, and oxadiazole groups. And the like, such as heterocyclic derivatives, porphyrin derivatives, phthalocyanine derivatives and the like. And if Y can be introduce | transduced by a synthesis reaction, it will not specifically limit.
前記式（３）は、このＸについての代表例を具体例として示したものである。この場合も、上記同様に置換基を有していてもよい。 The above formula (3) shows a typical example of X as a specific example. Also in this case, it may have a substituent as described above.
そして、本発明においては、以上のようなフェニルアゾメチンデンドリマーに限られることはなく、コアとしてのデンドリマーの骨格は電子供与体になる孤立電子対を持つＮ、Ｏ原子などを含むデンドリマーでもいい。たとえばポリアミドアミンデンドリマーやポリプロピレンイミンデンドリマー等のポリアルキレンイミンデンドリマー、ポリベンジルエーテルデンドリマー等のポリアリールアルキルエーテルデンドリマーなどがある。 In the present invention, the dendrimer is not limited to the phenylazomethine dendrimer as described above, and the skeleton of the dendrimer as the core may be a dendrimer containing N, O atoms having a lone electron pair that becomes an electron donor. Examples thereof include polyalkyleneimine dendrimers such as polyamidoamine dendrimers and polypropyleneimine dendrimers, and polyarylalkyl ether dendrimers such as polybenzyl ether dendrimers.
さらに、本発明においては、以上のようなコア骨格のＸを有するものだけでなく、Ｘ＝Ｈ原子のようにコアのないデンドロンであってもよい。 Furthermore, in the present invention, not only those having the core skeleton X as described above, but also dendrons without a core such as X = H atoms may be used.
また、これらのデンドリマー、デンドロンの末端構造にも特段の限定はない。 Further, there is no particular limitation on the terminal structure of these dendrimers and dendrons.
以上のようなデンドリマーやデンドロンについては、公知の方法をはじめとして、本発明者らが提案している方法等の各種の方法で合成することができる。たとえば四塩化チタンやパラトルエンスルホン酸などの酸存在下で、ジアミノベンゾフェノンの脱水反応によってデンドリマーの世代数（ｎ）を増やしていくことができる。 The dendrimer and dendron as described above can be synthesized by various methods such as a method proposed by the present inventors including a known method. For example, the generation number (n) of dendrimers can be increased by the dehydration reaction of diaminobenzophenone in the presence of an acid such as titanium tetrachloride or p-toluenesulfonic acid.
本発明における有機あるいは有機金属化合物のカチオン、カチオンラジカルについて説明すると、有機カチオンもしくはカチオンラジカルとは、炭素、窒素、硫黄、ケイ素などにカチオンまたはカチオンラジカルが立ったものを指している（Ｃ+，Ｃ+ ●，Ｎ+ ●，Ｓ+，Ｓｉ+）。以下に例を示すが、特に制限はなく、目的に応じて適宜選択することができる。 The cation or cation radical of the organic or organometallic compound in the present invention will be described. The organic cation or cation radical refers to a cation or cation radical standing on carbon, nitrogen, sulfur, silicon or the like (C + , C + ● , N + ● , S + , Si + ). Although an example is shown below, there is no restriction | limiting in particular and it can select suitably according to the objective.
すなわち、Ｃ+，Ｃ+ ●はＲ3Ｃ4（Ｒ＝Ｈ，Ｐｈ，ＣＨ3やその誘導体等）などのメチリウムや、トロピリウム、シクロプロペニルカチオン、ベンジルカチオン等のチャージのある芳香族カチオン、アズレン、ナフタレン、アントラセン、アヌレンなど不飽和炭化水素のカチオン及びカチオンラジカル、またはヘテロ環化合物のカチオンラジカル、フラーレンのカチオン等を指す。Ｎ+ ●はＲ3Ｎ+ ●（Ｒ＝Ｐｈ，ＢｒＰｈ等）などのアミニウム、ポルフィリンやフタロシアニン等の環状配位子のカチオンラジカル、またピリジニウムなどの芳香族。Ｓ、Ｓｉはカチオン及びカチオンラジカルなどである。 That is, C + , C + ● are methylium such as R 3 C 4 (R = H, Ph, CH 3 and derivatives thereof), aromatic cation having a charge such as tropylium, cyclopropenyl cation, benzyl cation, and azulene. , Cation radicals and cation radicals of unsaturated hydrocarbons such as naphthalene, anthracene and annulene, cation radicals of heterocyclic compounds, cations of fullerenes and the like. N + ● is an aminium such as R 3 N + ● (R = Ph, BrPh, etc.), a cation radical of a cyclic ligand such as porphyrin or phthalocyanine, or an aromatic such as pyridinium. S and Si are cations and cation radicals.
これらの代表例を次に示す。 Typical examples of these are as follows.
また本発明の有機金属カチオン、有機カチオン、カチオンラジカル内包デンドリマー錯体の合成については、前記各種の方法により合成されたデンドリマーもしくはデンドロンに、有機カチオン、カチオンラジカル、もしくは有機金属カチオンを、カウンターアニオンとともに、もしくはそのものを、混合することで、一般的には、配位錯体を生成させることで可能とされる。この場合配位数については、デンドリマーのアゾメチン結合の総数の範囲内において、所定モル数の金属化合物の混合によって調整が可能とされる。 In addition, for the synthesis of the organometallic cation, organic cation, and cation radical encapsulating dendrimer complex of the present invention, the organic cation, cation radical, or organometallic cation, together with the counter anion, to the dendrimer or dendron synthesized by the various methods described above, Or, by mixing them, it is generally possible to form a coordination complex. In this case, the coordination number can be adjusted by mixing a predetermined number of moles of the metal compound within the range of the total number of azomethine bonds of the dendrimer.
なお、本発明における内包もしくは複合化は、デンドリマーもしはデンドロンと上記のカチオンまたはカチオンラジカルとの混合の結果として得られた状態を示している。この状態は、錯位錯体の形成によるものと推定されるが、より現象的に、混合形成体として把握されてもよい。 The inclusion or complexing in the present invention indicates a state obtained as a result of mixing the dendrimer or dendron and the above cation or cation radical. This state is presumed to be due to the formation of a complex complex, but may be grasped more phenomenologically as a mixed formation.
この内包もしくは複合化のための混合は、通常は室温（１０〜２５℃）において行ってよいが、さらに低温、あるいはより高い温度であってもよい。大気中もしくは不活性ガス（Ｎ2、希ガス等）雰囲気下とすることができる。また、溶媒が適宜に使用されてよい。 The mixing for inclusion or compounding may be usually performed at room temperature (10 to 25 ° C.), but may be performed at a lower temperature or a higher temperature. The atmosphere may be an atmosphere or an inert gas (N 2 , rare gas, etc.) atmosphere. A solvent may be used as appropriate.
以上のような本発明の有機・有機金属化合物内包（複合）デンドリマーによって、以下の実施例においても例示しているように、発光材料、有機ＥＬ素子、電子材料、太陽電池等をはじめ、薬物搬送ＤＤＳシステム体、触媒等が構成されることになる。 With the organic / organometallic compound-encapsulating (composite) dendrimer of the present invention as described above, as exemplified in the following examples, drug delivery including luminescent materials, organic EL elements, electronic materials, solar cells, etc. A DDS system body, a catalyst, etc. will be comprised.
たとえば実施例にも例示したように、有機ＥＬ素子においては、本発明のデンドリマー（デンドロン）をたとえばスピンキャスト法により成膜して正孔輸送層として構成することや、太陽電池においては、同様にスピンキャスト法により電荷増幅層として構成することができる。 For example, as exemplified in the examples, in the organic EL element, the dendrimer (dendron) of the present invention is formed by, for example, spin casting to form a hole transport layer, It can be configured as a charge amplification layer by spin casting.
そこで以下に実施例を示す。もちろん以下の例によって発明が限定されることはない。 Therefore, examples will be shown below. Of course, the invention is not limited by the following examples.
＜実施例１＞
Ｚが２、Ｙのｎが４であるフェニルアゾメチンデンドリマー第四世代のクロロホルム：アセトニトリル＝１：１混合溶液にテトラフルオロホウ酸トリフェニルメチリウムのアセトニトリル溶液を添加すると、４１０ｎｍ付近の錯形成に由来する吸収が増加し、２９０ｎｍ付近のイミンの吸収が減少した。第四世代のデンドリマーに約２４個ものトリフェニルメチリウムが内包されることが分光化学的に確認された。
<Example 1>
Phenylazomethine dendrimer in which Z is 2 and Y is 4 is added to a fourth generation chloroform: acetonitrile = 1: 1 mixed solution with acetonitrile solution of triphenylmethylium tetrafluoroborate, resulting from complex formation around 410 nm Absorption increased and the absorption of imine near 290 nm decreased. It was spectrochemically confirmed that about 24 triphenylmethylium was encapsulated in the fourth generation dendrimer.
またクロロホルム：アセトニトリル中、またはアセトニトリル中でのイミン部位とテトラフルオロホウ酸トリフェニルメチリウムの錯形成定数は１０H〔Ｍ-1〕と見積ることができた。これは非常に大きな値で、テトラフルオロホウ酸トリフェニルメチリウム溶液をデンドリマー溶液に添加するとほぼ定量的に錯形成する。
＜実施例２＞
Ｚが２、Ｙのｎが４であるフェニルアゾメチンデンドリマー第四世代のクロロホルム：アセトニトリル＝１：１混合溶媒にヘキサクロロアンチモン（Ｖ）トリス（４−プロモフェニル）アミニウムのアセトニトリル溶液を添加すると、４１０ｎｍ付近の錯形成に由来する吸収が増加し、２９０ｎｍ付近のイミンの吸収が減少した。第四世代のデンドリマーに約２０個ものトリス（４−プロモフェニル）アミニウムが内包されることを分光化学的に確認した。
＜実施例３＞有機ＥＬ素子
有機ＥＬ素子を図１に沿って構成した。すなわちガラス基板１に形成したＩＴＯ電極２上に前記式（１）の構造においてＸがｐ−フェニレンジアミン、Ｚが２、Ｙのｎが４であるフェニルアゾメチンデンドリマー第四世代にヘキサクロロアンチモン（Ｖ）トリス（４−プロモフェニル）アミニウムを少量（０．１〜１当量）添加した有機カチオンラジカル内包錯体のクロロホルム溶液をスピンクアスト法により成膜し、厚さ５００オングストロームの正孔輸送層３を形成した。ついで発光・電子輸送層４としてアルミニウム−キノリノール錯体（Ａｌｑ）を真空蒸着により厚さ５００オングストロームに形成した。その後背面電極５としてＡｌを厚さ１０００オングストロームに形成し、面積０．１平方センチの素子を製作した。
The complex formation constant of imine moiety in chloroform: acetonitrile or acetonitrile and triphenylmethylium tetrafluoroborate was estimated to be 10 H [M −1 ]. This is a very large value, and when the triphenylmethylium tetrafluoroborate solution is added to the dendrimer solution, it is complexed almost quantitatively.
<Example 2>
When a solution of hexachloroantimony (V) tris (4-promophenyl) aminium in acetonitrile is added to a fourth-generation chloroform: acetonitrile = 1: 1 mixed solvent in which Z is 2, Y n is 4, and the vicinity of 410 nm. The absorption resulting from the complexation of γ increased and the absorption of imine near 290 nm decreased. It was spectrochemically confirmed that about 20 tris (4-promophenyl) aminium was encapsulated in the fourth generation dendrimer.
Example 3 Organic EL Element An organic EL element was constructed according to FIG. That is, on the ITO electrode 2 formed on the glass substrate 1, in the structure of the above formula (1), X is p-phenylenediamine, Z is 2, Y is n is 4. Phenylazomethine dendrimer fourth generation is hexachloroantimony (V) Forming a hole transport layer 3 having a thickness of 500 angstroms by forming a chloroform solution of an organic cation radical inclusion complex containing a small amount (0.1 to 1 equivalent) of tris (4-promophenyl) aminium by the Spink Ast method. did. Next, an aluminum-quinolinol complex (Alq) was formed as the light emitting / electron transporting layer 4 to a thickness of 500 Å by vacuum deposition. Thereafter, Al was formed as a back electrode 5 to a thickness of 1000 angstroms, and an element having an area of 0.1 square centimeter was manufactured.
この有機ＥＬ素子について、室温大気下において電圧−電流、電圧−輝度の測定を行った。本実施例により製作した素子の電圧−輝度特性を図２（実線）に示した１１Ｖで最高輝度２５００ｃｄ／ｍ2を示し、輝度３００ｃｄ／ｍ2における発光効率は１．５ｌｍ／Ｗと高い発光効率を示した。さらに０．１ｃｄ／ｍ2に達するｔｕｒｎ−ｏｎ電圧は３Ｖとなり、比較例１に示した有機カチオンラジカル錯体を利用しない素子よりもおよそ２Ｖ低下しており、素子の低消費電力化が可能となった。このように比較例１と比べて、有機カチオンラジカルが集積（錯形成）されたデンドリマーを正孔輸送層として利用することにより素子の高発光効率さらに低ｔｕｒｎ−ｏｎ電圧特性を有するのは正孔注入電極であるＩＴＯと正孔輸送間のエネルギーギャップがより小さくなり、正孔輸送層への正孔の注入効率が高くなるためである。
＜比較例１＞
正孔輸送層３をＺが２、Ｙのｎが４であるフェニルアゾメチンデンドリマー第四世代のクロロホルム溶液をキャストすることにより形成し、実施例３とに記載された方法と同様に作製し、素子の特性を測定した。この素子の電圧−輝度特性を図２（点線）に示した。ＩＴＯ電極を正極として５Ｖ以上の電圧を印加することによりＡｌｑ由来の緑色発光が確認され、１２Ｖ最高輝度３００ｃｄ／ｍ2を示し、０．１ｃｄ／ｍ2に達するｔｕｒｎ−ｏｎ電圧は５Ｖ、輝度３００ｃｄ／ｍ2における発光効率は０．５ｌｍ／Ｗであった。
＜実施例４＞有機太陽電池素子
有機太陽電池素子を図３に従って構成した。
With respect to this organic EL element, voltage-current and voltage-luminance were measured at room temperature in the atmosphere. Voltage of the element fabricated by the present embodiment - the highest luminance 2500 cd / m 2 at 11V illustrating luminance characteristics in FIG. 2 (solid line), the light emission efficiency at a luminance of 300 cd / m 2 is 1.5 lm / W and higher luminous efficiency showed that. Further, the turn-on voltage reaching 0.1 cd / m 2 is 3 V, which is approximately 2 V lower than the element not using the organic cation radical complex shown in Comparative Example 1, and the power consumption of the element can be reduced. It was. Thus, in comparison with Comparative Example 1, the use of a dendrimer in which organic cation radicals are accumulated (complex formation) as a hole transport layer has a high luminous efficiency and a low turn-on voltage characteristic. This is because the energy gap between ITO serving as the injection electrode and hole transport becomes smaller, and the efficiency of hole injection into the hole transport layer becomes higher.
<Comparative Example 1>
A hole transport layer 3 is formed by casting a fourth-generation chloroform solution of a phenylazomethine dendrimer in which Z is 2, Y is n, and is produced in the same manner as described in Example 3. The characteristics of were measured. The voltage-luminance characteristics of this element are shown in FIG. 2 (dotted line). By applying a voltage of 5 V or more with the ITO electrode as a positive electrode, green light emission derived from Alq was confirmed, showing a 12 V maximum luminance of 300 cd / m 2 , a turn-on voltage reaching 0.1 cd / m 2 was 5 V, and a luminance of 300 cd. The luminous efficiency at / m 2 was 0.5 lm / W.
Example 4 Organic Solar Cell Element An organic solar cell element was constructed according to FIG.
すなわち、既知方法により作られた酸化チタンペーストを導電性酸化スズ電極付きガラス基板上にスピンキャスト法により塗布し（面積０．３ｃｍ2）、室温で１時間乾燥後、さらに４５０℃の電気炉で３０分間焼成により、膜厚約１０μｍの金属酸化物半導体層を形成した。電子輸送・電荷分離層は、市販のルテニウム錯体（〔Ｒｕ（２，２’−bipyridil −４，４−dicarboxilate （ＴＢＡ））2（ＮＣＳ）2ｌ）を５×１０-5ｍｏｌ／１のエタノール溶液を用い、前記の酸化物半導体層の電極をその溶液の中に１日間浸漬した後、エタノールで洗浄、乾燥により電子輸送・電荷分離層を形成した。電荷増幅層である電位傾斜型デンドリマー層は、前記式（１）の構造においてＸがｐ−フェニンジアミン、Ｚが２、Ｙのｎが４であるフェニルアゾメチンデンドリマー第四世代のクロロホルム：アセトニトリル＝１：１溶液（３×１０-4ｍｏｌ／１）へ、ヘキサクロロアンチモン（Ｖ）トリス（４−プロモフェニル）アミニウムを１当量加えた溶液を用いて、電子輸送・電荷分離層が塗布された半導体電極上にスピンキャスト後、乾燥により膜厚約３μｍの電荷増幅デンドリマー層を形成した。電解質溶液としては、ヨウ化リチウム、ヨウ素をそれぞれ０．２モル、０．０１モル／リットルの３−メトキシプロピオニトリル溶液を用いた。対極としては金属白金膜をスパッタ法により形成した導電性ガラスを用いた。 That is, a titanium oxide paste made by a known method is applied onto a glass substrate with a conductive tin oxide electrode by spin casting (area 0.3 cm 2 ), dried at room temperature for 1 hour, and further in an electric furnace at 450 ° C. A metal oxide semiconductor layer having a thickness of about 10 μm was formed by baking for 30 minutes. The electron transport / charge separation layer was made of a commercially available ruthenium complex ([Ru (2,2′-bipyridil-4,4-dicarboxilate (TBA)) 2 (NCS) 2 l) in 5 × 10 −5 mol / 1 ethanol. The electrode of the oxide semiconductor layer was immersed in the solution for 1 day using a solution, washed with ethanol, and dried to form an electron transport / charge separation layer. The potential gradient dendrimer layer, which is a charge amplification layer, is a phenylazomethine dendrimer fourth generation chloroform in which X is p-pheninediamine, Z is 2 and Y is 4 in the structure of the above formula (1): acetonitrile = A semiconductor in which an electron transport / charge separation layer is applied using a solution obtained by adding 1 equivalent of hexachloroantimony (V) tris (4-promophenyl) aminium to a 1: 1 solution (3 × 10 −4 mol / 1) After spin casting on the electrode, a charge amplification dendrimer layer having a film thickness of about 3 μm was formed by drying. As the electrolyte solution, a 3-methoxypropionitrile solution containing 0.2 mol and 0.01 mol / liter of lithium iodide and iodine, respectively, was used. As the counter electrode, conductive glass in which a metal platinum film was formed by sputtering was used.
上記の電荷増幅層であるデンドリマー層が形成された酸化物半導体層電極の上に導電性ガラスを重てクリップなどにより止めた後、電解質を入れ、光電変換素子を得た。素子の特性評価は、キセノンランプを光源として紫外線、赤外線遮断フィルターを通して強度が５０Ｗ／ｃｍ2の模擬太陽光を用いた。本発明の変換素子にこの光を照射したところ、変換効率は３．２％であった。次の比較例２と比べることによりフェニルアゾメチンデンドリマーへ有機アミニウムを添加したものが変換効率が向上していることが確認された。
＜比較例２＞
電荷増幅層をヘキサクロロアンチモン（Ｖ）トリス（４−プロモフェニル）アミニウムを添加していないデンドリマーのみの溶液を用い、実施例４に記載された方法と同様に作製し、特性を測定した結果、変換効率は１．６％であった。
A conductive glass was placed on the oxide semiconductor layer electrode on which the dendrimer layer as the charge amplification layer was formed, and stopped with a clip, and then an electrolyte was added to obtain a photoelectric conversion element. The characteristics of the device were evaluated using simulated sunlight having an intensity of 50 W / cm 2 through an ultraviolet and infrared cut filter using a xenon lamp as a light source. When this light was irradiated to the conversion element of the present invention, the conversion efficiency was 3.2%. By comparing with the following Comparative Example 2, it was confirmed that the conversion efficiency of the phenylazomethine dendrimer added with organic aminium was improved.
<Comparative example 2>
A charge amplification layer was prepared in the same manner as described in Example 4 using a dendrimer-only solution to which hexachloroantimony (V) tris (4-promophenyl) aminium was not added. The efficiency was 1.6%.
Claims (12)
で表わされるフェニルアゾメチンデンドリマーもしくはコア構造を持たないデンドロンであることを特徴とする請求項１または２の有機・有機金属化合物内包デンドリマー。 Dendrimer or dendron is represented by the following formula (1)
3. The organic / organometallic compound-encapsulating dendrimer according to claim 1, wherein the dendrimer is a phenylazomethine dendrimer represented by the formula (1) or a dendron having no core structure.
A catalyst characterized in that the organic / organometallic compound-containing dendrimer according to any one of claims 1 to 5 is at least a part of its constitution.
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