KR102185609B1 - Method for manufacturing n-type organic semiconductor thin film - Google Patents
Method for manufacturing n-type organic semiconductor thin film Download PDFInfo
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- KR102185609B1 KR102185609B1 KR1020157035781A KR20157035781A KR102185609B1 KR 102185609 B1 KR102185609 B1 KR 102185609B1 KR 1020157035781 A KR1020157035781 A KR 1020157035781A KR 20157035781 A KR20157035781 A KR 20157035781A KR 102185609 B1 KR102185609 B1 KR 102185609B1
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- thin film
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- organic semiconductor
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- 239000010409 thin film Substances 0.000 title claims abstract description 57
- 239000004065 semiconductor Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 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 claims abstract description 31
- 238000010304 firing Methods 0.000 claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- -1 p-methoxybenzyl group Chemical group 0.000 claims description 46
- 239000010408 film Substances 0.000 claims description 20
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- 125000000611 organothio group Chemical group 0.000 claims description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005011 alkyl ether group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 150000007970 thio esters Chemical group 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 claims description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 125000000625 hexosyl group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001805 pentosyl group Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 125000000089 arabinosyl group Chemical group C1([C@@H](O)[C@H](O)[C@H](O)CO1)* 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002519 galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 2
- 125000001503 gulosyl group Chemical group C1([C@H](O)[C@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 125000000548 ribosyl group Chemical group C1([C@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 150000005846 sugar alcohols Chemical group 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical group OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000006310 cycloalkyl amino group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000770 erythrosyl group Chemical group C1([C@H](O)[C@H](O)CO1)* 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004351 phenylcyclohexyl group Chemical group C1(=CC=CC=C1)C1(CCCCC1)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000005629 sialic acid group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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- H01L51/4253—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H99/00—Subject matter not provided for in other groups of this subclass
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- H01L51/0047—
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- H01L51/424—
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L2031/0344—Organic materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
식 (1)로 표시되는 풀러렌 유도체를 포함하는 용액을 기재에 도포하고, 450℃ 이상에서 소성하여 n형 유기 반도체 박막을 제조함으로써 적합한 이온화 포텐셜을 가짐과 아울러, 성막면에 미소한 요철이나 미세구멍을 갖는 n형 유기 반도체 박막이 얻어진다.
(식 중, R1∼R5는, 각각 독립하여, 수소 원자, 당기, 또는 당기의 임의의 수산기가 치환기에 의해 치환된 당기인 치환 당기를 나타내고, R6은 탄소수 1∼5의 알킬기를 나타낸다. 단, R1∼R5 중 적어도 1개는 상기 당기 또는 치환 당기이다.)Applying a solution containing a fullerene derivative represented by the formula (1) to a substrate and firing at 450°C or higher to prepare an n-type organic semiconductor thin film has an appropriate ionization potential, and minute irregularities or micropores on the film-forming surface An n-type organic semiconductor thin film is obtained.
(In the formula, R 1 to R 5 each independently represent a hydrogen atom, a sugar, or a substituted sugar in which an arbitrary hydroxyl group of the sugar is substituted by a substituent, and R 6 represents an alkyl group having 1 to 5 carbon atoms. However, at least one of R 1 to R 5 is the aforementioned sugar or substituted sugar.)
Description
본 발명은 n형 유기 반도체 박막의 제조 방법에 관한 것으로, 더욱 상세히 설명하면, 단당이나 당알코올 잔기를 갖는 풀러렌 유도체로 이루어지는 n형 반도체를 포함하는 표면적이 큰 박막의 제조 방법에 관한 것이다. The present invention relates to a method of manufacturing an n-type organic semiconductor thin film, and more particularly, to a method of manufacturing a thin film with a large surface area including an n-type semiconductor made of a fullerene derivative having a monosaccharide or sugar alcohol residue.
풀러렌은 우수한 전자 수송성(전자 수용성) 및 내열성을 갖고, 유기 박막 태양전지 등의 유기 디바이스의 n형 반도체 재료로서 범용되고 있다. Fullerene has excellent electron transport properties (electron acceptability) and heat resistance, and is widely used as an n-type semiconductor material for organic devices such as organic thin film solar cells.
그러나, 무수식의 풀러렌은 각종 유기 용매에 대한 용해성이 부족하기 때문에, 습식 프로세스에 의한 성막은 곤란하여, 그 성막은 통상 건식 프로세스인 증착법에 의해 행해진다. However, since anhydrous fullerene lacks solubility in various organic solvents, it is difficult to form a film by a wet process, and the film formation is usually performed by a vapor deposition method which is a dry process.
또한 습식 프로세스로 성막 가능한 풀러렌 유도체로서 PCBM이 알려져 있지만, PCBM은 특정 유기 용매에밖에 용해되지 않아, 단일체로의 성막성이 나쁜데다, 무수식의 풀러렌과 비교하면 전자 수송성이 뒤떨어진다. In addition, although PCBM is known as a fullerene derivative that can be formed by a wet process, PCBM is only soluble in a specific organic solvent, so that the film-forming property in a single body is poor, and electron transport properties are inferior compared to anhydrous fullerene.
유기 박막 태양전지는, 정공 수송성(전자 공여성)을 갖는 p형 반도체와 전자 수송성(전자 수용성)을 갖는 n형 반도체를 구비하고, 주로 p형 반도체가 외부로부터의 광을 흡수하여 여기되고, 발생한 여기자가 이들 2개의 반도체의 계면까지 확산되고, 거기에서 전자가 n형 반도체로 이동함으로써 기전에 필요한 전하 분리가 일어난다. 이 전하 분리의 효율을 높이는 것이 유기 박막 태양전지의 광전 변환 효율의 향상으로 이어지고, 그것을 위한 하나의 방법으로서 각 반도체끼리의 접촉 면적의 증대화를 들 수 있다. An organic thin-film solar cell includes a p-type semiconductor having hole transporting (electron donating) and an n-type semiconductor having electron transporting (electron accepting), and mainly p-type semiconductors are excited by absorbing light from the outside and generated. The excitons diffuse to the interface of these two semiconductors, and electrons move from there to the n-type semiconductor, whereby charge separation required for the mechanism occurs. Increasing the efficiency of charge separation leads to an improvement in the photoelectric conversion efficiency of the organic thin-film solar cell, and one method for this is increasing the contact area between semiconductors.
이러한 관점에서, 예를 들면, p형 반도체 재료와 n형 반도체 재료를 혼합한 용액을 조제하고, 도포법에 의해 활성층을 형성함으로써 얻어지는 태양전지의 변환 효율이 대폭 상승하는 것이 보고되어 있다(비특허문헌 1). 이 수법에 의해 얻어지는 활성층은, 도너/억셉터 계면이 활성층의 벌크 전체에 형성되는 점에서, 일반적으로 벌크 헤테로 정크션이라고 불린다. From this point of view, for example, it has been reported that the conversion efficiency of a solar cell obtained by preparing a solution of a mixture of a p-type semiconductor material and an n-type semiconductor material and forming an active layer by a coating method increases significantly (non-patent Document 1). The active layer obtained by this method is generally called a bulk heterojunction because the donor/acceptor interface is formed over the entire bulk of the active layer.
또한 광전 변환 효율 향상을 도모할 수 있는 그 밖의 이상적인 구조로서 초계층 나노 구조가 제안되어 있다(비특허문헌 2). 이 구조에서는, 전극 근방에서의 캐리어의 재결합을 방지하기 위하여, 헤테로 정크션과는 달리, p형 반도체와 n형 반도체의 각각이 분리되어 전극에 배치되어 있는 한편, 이들 2개의 반도체끼리가 나노 단위 수준의 간격으로 정연하게 접촉하고 있으므로, 발생한 캐리어의 재결합을 억제하면서 고이동도를 발현할 수 있고, 또한, 도너/억셉터 계면을 고밀도로 형성할 수 있다고 하고 있다. In addition, as another ideal structure capable of improving photoelectric conversion efficiency, a superlayer nanostructure has been proposed (Non-Patent Document 2). In this structure, in order to prevent recombination of carriers in the vicinity of the electrode, unlike heterojunction, each of the p-type semiconductor and the n-type semiconductor are separated and disposed on the electrode, while these two semiconductors are separated by nano-units. It is said that since they are in regular contact at intervals of a level, high mobility can be exhibited while suppressing recombination of generated carriers, and a donor/acceptor interface can be formed with high density.
이상의 2개의 기술은 광전 변환 효율을 향상시키는 수법으로서 잘 알려져 있는 것이지만, 벌크 헤테로 정크션에서는, p형 반도체 재료와 n형 반도체 재료의 혼합액을 도포하여 계면을 형성하므로, 적합한 계면을 재현성 좋게 얻는 것이 곤란할 뿐만 아니라, 막 형성에 필요한 소성시의 열에 의해, 계면의 변화가 일어난다고 하는 문제가 있다. The above two techniques are well known as methods of improving photoelectric conversion efficiency, but in bulk heterojunction, since an interface is formed by applying a mixture of a p-type semiconductor material and an n-type semiconductor material, it is desirable to obtain a suitable interface with good reproducibility. In addition to being difficult, there is a problem that the interface changes due to the heat during firing required for film formation.
그 때문에, 광전 변환 효율의 향상과 소자의 신뢰성 향상을 위해서는, 초계층 나노 구조가 적합하다고 할 수 있지만, 그 구조를 실현하기 위해서는 반도체층의 다공질화나 요철화 등의 표면적의 증대화가 필요하게 된다. Therefore, in order to improve the photoelectric conversion efficiency and improve the reliability of the device, it can be said that the superlayer nanostructure is suitable, but in order to realize the structure, it is necessary to increase the surface area such as porosity and irregularities of the semiconductor layer.
본 발명은 이러한 사정을 감안하여 이루어진 것으로, 적합한 이온화 포텐셜을 가짐과 아울러 성막면에 미소한 요철이나 미세구멍을 갖는 습식 프로세스를 사용한 n형 유기 반도체 박막의 제조 방법을 제공하는 것을 목적으로 한다. The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for producing an n-type organic semiconductor thin film using a wet process having a suitable ionization potential and having minute irregularities or micropores on the film formation surface.
본 출원인은 당 잔기나 당알코올 잔기를 갖는 풀러렌 화합물이 유기 용매에 대한 용해성이 양호하며, 이 화합물을 포함하는 바니시로부터 얻어진 박막의 균일성이 양호한 것, 및 당해 화합물이 n형 반도체로서 구동하여, 유기 박막 태양전지에 적용할 수 있는 것을 이미 보고했다(특허문헌 1, 2). 이 특허문헌 1, 2의 기술에서는, 당 잔기 등을 갖는 풀러렌 화합물을 유기 용매에 녹인 바니시를 기재 위에 도포하고, 대기하 또는 진공하에, 80∼100℃에서 소성하여 용매를 제거함으로써 균일성 및 평탄성이 양호한 n형 반도체 박막을 형성하고 있다. Applicants argue that a fullerene compound having a sugar residue or a sugar alcohol residue has good solubility in an organic solvent, and the uniformity of a thin film obtained from a varnish containing this compound is good, and the compound is driven as an n-type semiconductor, It has already reported that it can be applied to an organic thin film solar cell (Patent Documents 1 and 2). In the techniques of
본 발명자는, 이 특허문헌 1, 2의 기술에 있어서, 박막 형성시의 소성 온도를 높임으로써 100℃ 정도의 저온 소성시에 비해, 성막면의 미소한 요철이나 미세구멍이 증가하는 것, 및 소성 온도를 더욱 높여 감으로써 n형 반도체로서 사용하는데 적합한 이온화 포텐셜을 갖는 박막도 형성할 수 있는 것을 발견하고, 본 발명을 완성했다. In the techniques of
즉, 본 발명은,That is, the present invention,
1. 식 (1)로 표시되는 풀러렌 유도체를 포함하는 용액을 기재에 도포하고, 450℃ 이상에서 소성하는 것을 특징으로 하는 n형 유기 반도체 박막의 제조 방법,1. A method for producing an n-type organic semiconductor thin film, characterized in that a solution containing a fullerene derivative represented by formula (1) is applied to a substrate and fired at 450°C or higher,
(식 중, R1∼R5는, 각각 독립하여, 수소 원자, 당기, 또는 당기의 임의의 수산기가 치환기에 의해 치환된 당기인 치환 당기를 나타내고, R6은 탄소수 1∼5의 알킬기를 나타낸다. 단, R1∼R5 중 적어도 1개는 상기 당기 또는 치환 당기이다.)(In the formula, R 1 to R 5 each independently represent a hydrogen atom, a sugar, or a substituted sugar in which an arbitrary hydroxyl group of the sugar is substituted by a substituent, and R 6 represents an alkyl group having 1 to 5 carbon atoms. However, at least one of R 1 to R 5 is the aforementioned sugar or substituted sugar.)
2. 상기 당기 또는 치환 당기가 식 (2), 식 (3) 및 식 (4)로부터 선택되는 적어도 1개의 기인 1의 n형 유기 반도체 박막의 제조 방법,2. A method for producing an n-type organic semiconductor thin film of 1 wherein the sugar or substituted sugar is at least one group selected from formulas (2), (3) and (4),
(식 중, R7∼R15는, 각각 독립하여, 수소 원자, 아미노기, 싸이올기, 카복실기, 인산기, 인산에스터기, 에스터기, 싸이오에스터기, 아마이드기, 나이트로기, 1가 탄화 수소기, 오가노아미노기, 오가노실릴기, 오가노싸이오기, 아실기, 알킬에터기, 또는 설폰기를 나타낸다.)(In the formula, R 7 to R 15 are each independently a hydrogen atom, an amino group, a thiol group, a carboxyl group, a phosphoric acid group, a phosphate ester group, an ester group, a thioester group, an amide group, a nitro group, or a monovalent hydrocarbon. Group, organoamino group, organosilyl group, organothio group, acyl group, alkyl ether group, or sulfone group.)
3. 상기 치환기가 탄소수 1∼10의 알킬기, 벤질기, p-메톡시벤질기, 메톡시메틸기, 2-테트라하이드로파이란일기, 에톡시에틸기, 아세틸기, 피발로일기, 벤조일기, 트라이메틸실릴기, 트라이에틸실릴기, t-뷰틸메틸실릴기, 트라이아이소프로필실릴기, 또는 t-뷰틸다이페닐실릴기인 1 또는 2의 n형 유기 반도체 박막의 제조 방법,3. The substituent is an alkyl group having 1 to 10 carbon atoms, benzyl group, p-methoxybenzyl group, methoxymethyl group, 2-tetrahydropyranyl group, ethoxyethyl group, acetyl group, pivaloyl group, benzoyl group, trimethylsilyl Group, triethylsilyl group, t-butylmethylsilyl group, triisopropylsilyl group, or t-butyldiphenylsilyl group 1 or 2 n-type organic semiconductor thin film manufacturing method,
4. 1∼3 중 어느 하나의 제조 방법으로 얻어진 n형 유기 반도체 박막,4. An n-type organic semiconductor thin film obtained by the manufacturing method of any one of 1 to 3,
5. 산술평균 거칠기 Ra가 막 두께의 2% 이상이며, 최대높이 Rz가 막 두께의 40% 이상이며, 이온화 포텐셜이 6.0eV 이상인 n형 유기 반도체 박막,5. An n-type organic semiconductor thin film having an arithmetic mean roughness Ra of 2% or more of the film thickness, a maximum height Rz of 40% or more of the film thickness, and an ionization potential of 6.0 eV or more,
6. 4 또는 5의 n형 유기 반도체 박막을 갖는 유기 태양전지6. Organic solar cell having 4 or 5 n-type organic semiconductor thin films
를 제공한다. Provides.
본 발명의 제조 방법에 의하면, 적합한 이온화 포텐셜을 갖는 성막면에 미소한 요철이나 미세구멍이 형성된 n형 유기 반도체 박막을 형성할 수 있다. 본 발명의 제조 방법에서 얻어진 박막을 사용하면, 적층법에 의해 인접하여 형성되는 p층과의 p/n 접합 계면의 면적을, 이상적인 에너지 준위의 관계를 유지하면서 비약적으로 향상시키는 것이 가능하게 되기 때문에, 유기 태양전지의 변환 효율 향상에 기여할 수 있다. 특히 고온 소성으로 제작한 박막은, 무수식 풀러렌과 동등한 이온화 포텐셜을 갖는 대표면적 n형 유기 반도체 박막이므로, 전자 디바이스, 특히, p형 반도체와의 접촉 면적 증대에 의해 직접적으로 특성 향상이 기대되는 유기 태양전지의 n형 반도체로서 적합하다. According to the manufacturing method of the present invention, it is possible to form an n-type organic semiconductor thin film in which minute irregularities or fine pores are formed on a film-forming surface having a suitable ionization potential. When the thin film obtained in the manufacturing method of the present invention is used, it is possible to dramatically improve the area of the p/n junction interface with the p-layer formed adjacent to each other by the lamination method while maintaining the relationship of the ideal energy level. , It can contribute to improving the conversion efficiency of organic solar cells. In particular, the thin film produced by high-temperature firing is a representative area n-type organic semiconductor thin film having an ionization potential equivalent to that of anhydrous fullerene. Therefore, it is expected that properties can be directly improved by increasing the contact area with electronic devices, especially p-type semiconductors. It is suitable as an n-type semiconductor for solar cells.
또한 본 발명의 제조 방법에서는, 그 치환기 및 당 골격을 변경하여 여러 유사체로 용이하게 유도할 수 있는 풀러렌 유도체를 사용하고 있기 때문에, 인접하여 형성되는 p층의 종류나 그 형성 방법에 따라 그 이온화 포텐셜이나 표면적의 컨트롤이 가능하다. 그 때문에 본 발명의 제조 방법에 의하면, 최적화된 p/n 접합 계면을 갖는 보다 고변환 효율의 유기 태양전지를 제조할 수 있다. In addition, in the production method of the present invention, since a fullerene derivative that can be easily induced into various analogs by changing its substituent and sugar skeleton is used, its ionization potential is determined depending on the type of p-layer formed adjacent to it and the method of its formation. Or the surface area can be controlled. Therefore, according to the manufacturing method of the present invention, an organic solar cell with higher conversion efficiency can be manufactured having an optimized p/n junction interface.
또한, 본 발명의 제조 방법에서는, 습식 프로세스에 의해 박막화하므로, 건식 프로세스와 비교하여 소자의 대면적화가 용이하게 됨과 아울러, 제조 비용의 저감이 가능하게 되고, 그 결과, 유기 태양전지, 유기 EL 소자의 저비용화에 기여할 수 있다. In addition, in the manufacturing method of the present invention, since the thin film is formed by a wet process, it becomes easier to increase the area of the device compared to the dry process, and it is possible to reduce the manufacturing cost. As a result, organic solar cells and organic EL devices Can contribute to lowering the cost of the product.
도 1은 실시예 1에서 제작한 풀러렌 박막의 AFM 관찰 결과를 도시하는 도면이다.
도 2는 비교예 1에서 제작한 풀러렌 박막의 AFM 관찰 결과를 도시하는 도면이다.
도 3은 비교예 2에서 제작한 풀러렌 박막의 AFM 관찰 결과를 도시하는 도면이다.1 is a diagram showing AFM observation results of a fullerene thin film prepared in Example 1. FIG.
FIG. 2 is a diagram showing AFM observation results of a fullerene thin film prepared in Comparative Example 1. FIG.
3 is a diagram showing AFM observation results of a fullerene thin film prepared in Comparative Example 2. FIG.
이하, 본 발명에 대해 더욱 상세하게 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명에 따른 n형 유기 반도체 박막의 제조 방법은, 식 (1)로 표시되는 풀러렌 유도체를 포함하는 용액을 기재에 도포하고, 450℃ 이상으로 소성하는 것이다. In the method for producing an n-type organic semiconductor thin film according to the present invention, a solution containing a fullerene derivative represented by Formula (1) is applied to a substrate and fired at 450°C or higher.
식 (1)에서, R1∼R5는, 각각 독립하여, 수소 원자, 당기, 또는 당기의 임의의 수산기가 치환기에 의해 치환된 당기인 치환 당기를 나타내지만, R1∼R5 중 적어도 1개는 당기 또는 치환 당기이다. In the formula (1), R 1 to R 5 each independently represent a hydrogen atom, a sugar, or a substituted sugar in which any hydroxyl group of the sugar is substituted by a substituent, but at least one of R 1 to R 5 Dog is a pull or substitution pull.
여기에서, 당기 또는 치환 당기로서는 특별히 한정되는 것은 아니고, 임의의 테트로스기, 펜토스기, 헥소스기 및 그것들의 임의의 수산기가 치환된 치환 당기를 채용할 수 있다. Here, the sugar or substituted sugar is not particularly limited, and a substituted sugar in which an arbitrary tetros group, a pentose group, a hexose group, and an arbitrary hydroxyl group thereof is substituted can be employed.
테트로스기로서는 에리트로스기인 에리트로실기 등을 들 수 있다. Examples of the tetros group include an erythrosyl group which is an erythros group.
펜토스기로서는 아라비노스기인 아라비노실기, 릭소스기인 릭소실기, 리보스기인 리보실기, 자일로스기인 자일로실기 등을 들 수 있다. Examples of the pentose group include arabinosyl group, which is an arabinose group, lixosyl group, which is a rixos group, ribosyl group, which is a ribose group, and xylosyl group, which is a xylose group.
헥소스기로서는 아로스기인 아로실기, 프룩토스기인 프룩토실기, 갈락토스기인 갈락토실기, 글루코스기인 글루코실기, 굴로스기인 굴로실기, 만노스기인 만노실기, 타가로스기인 타가로실기, 타로스기인 타로실기, 시알산기 등을 들 수 있다.Hexose groups include arosyl group, fructose group, fructosyl group, galactose group, galactosyl group, glucose group, glucosyl group, gulose group, gulosyl group, mannose group, mannosyl group, tagaros group, tagarosyl group, taros group, tarosyl group, A sialic acid group, etc. are mentioned.
이것들 중에서도, 본 발명에서는, 헥소스기가 바람직하고, 특히, 갈락토실기, 글루코실기가 적합하다. Among these, in the present invention, a hexose group is preferable, and in particular, a galactosyl group and a glucosyl group are preferable.
보다 구체적으로는, 식 (2)∼(4)로 표시되는 테트로스기, 펜토스기, 헥소스기가 적합하며, 특히, 식 (4)로 표시되는 헥소스기가 바람직하다. More specifically, a tetros group, a pentose group, and a hexose group represented by formulas (2) to (4) are suitable, and in particular, a hexose group represented by formula (4) is preferred.
(식 중, R7∼R15는, 각각 독립하여, 수소 원자, 아미노기, 싸이올기, 카복실기, 인산기, 인산 에스터기, 에스터기, 싸이오에스터기, 아마이드기, 나이트로기, 1가 탄화 수소기, 오가노아미노기, 오가노실릴기, 오가노싸이오기, 아실기, 알킬에터기, 또는 설폰기를 나타낸다.)(In the formula, R 7 to R 15 are each independently a hydrogen atom, an amino group, a thiol group, a carboxyl group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, or a monovalent hydrocarbon. Group, organoamino group, organosilyl group, organothio group, acyl group, alkyl ether group, or sulfone group.)
1가 탄화 수소기로서는 예를 들면, 메틸기, 에틸기, n-프로필기, i-프로필기, n-뷰틸기, i-뷰틸기 ,t-뷰틸기, n-헥실기, n-옥틸기, 2-에틸헥실기, 데실기 등의 알킬기, 사이클로펜틸기, 사이클로헥실기 등의 사이클로알킬기, 바이사이클로헥실기 등의 바이사이클로알킬기, 바이닐기, 1-프로펜일기, 2-프로펜일기, 아이소프로펜일기, 1-메틸-2-프로펜일기, 1 또는 2 또는 3-뷰텐일기, 헥센일기 등의 알켄일기, 페닐기, 자일릴기, 톨릴기, 바이페닐기, 나프틸기 등의 아릴기, 벤질기, 페닐에틸기, 페닐사이클로헥실기 등의 아르알킬기 등이나, 이들 1가 탄화 수소기의 수소 원자의 일부 또는 전부가 할로젠 원자(불소 원자, 염소 원자, 브로민 원자, 아이오딘 원자), 수산기, 알콕시기(메톡시기, 에톡시기 등) 등으로 치환된 것을 들 수 있다. As a monovalent hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2 -Alkyl groups such as ethylhexyl and decyl groups, cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, bicycloalkyl groups such as bicyclohexyl groups, vinyl groups, 1-propenyl groups, 2-propenyl groups, isopro Alkenyl groups such as fenyl group, 1-methyl-2-propenyl group, 1 or 2 or 3-butenyl group, hexenyl group, phenyl group, xylyl group, tolyl group, biphenyl group, aryl group such as naphthyl group, benzyl group, Aralkyl groups such as phenylethyl group and phenylcyclohexyl group, and some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, alkoxy What is substituted with a group (methoxy group, ethoxy group, etc.) etc. is mentioned.
오가노아미노기로서는 예를 들면, 메틸아미노기, 에틸아미노기, 프로필아미노기, 뷰틸아미노기, 펜틸아미노기, 헥실아미노기, 헵틸아미노기, 옥틸아미노기, 노닐아미노기, 데실아미노기, 라우릴아미노기 등의 알킬아미노기, 다이메틸아미노기, 다이에틸아미노기, 다이프로필아미노기, 다이뷰틸아미노기, 다이펜틸아미노기, 다이헥실아미노기, 다이헵틸아미노기, 다이옥틸아미노기, 다이노닐아미노기, 다이데실아미노기 등의 다이알킬아미노기, 사이클로헥실아미노기 등의 사이클로알킬아미노기, 모폴리노기 등을 들 수 있다. Examples of the organoamino group include alkylamino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, laurylamino group, dimethylamino group, Dialkylamino groups such as diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, cycloalkylamino groups such as cyclohexylamino group, And morpholino groups.
오가노실릴기로서는 예를 들면, 트라이메틸실릴기, 트라이에틸실릴기, 트라이프로필실릴기, 트라이뷰틸실릴기, 트라이펜틸실릴기, 트라이헥실실릴기, 펜틸다이메틸실릴기, 헥실다이메틸실릴기, 옥틸다이메틸실릴기, 데실다이메틸실릴기 등을 들 수 있다. As the organosilyl group, for example, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group , Octyldimethylsilyl group, decyldimethylsilyl group, and the like.
오가노싸이오기로서는, 예를 들면, 메틸싸이오기, 에틸싸이오기, 프로필싸이오기, 뷰틸싸이오기, 펜틸싸이오기, 헥실싸이오기, 헵틸싸이오기, 옥틸싸이오기, 노닐싸이오기, 데실싸이오기, 라우릴싸이오기 등의 알킬싸이오기 등을 들 수 있다.As an organothio, for example, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, Alkylthio, such as laurylthio, etc. are mentioned.
아실기로서는 예를 들면, 폼일기, 아세틸기, 프로피온일기, 뷰틸일기, 아이소뷰틸일기, 발레릴기, 아이소발레릴기, 벤조일기 등을 들 수 있다. Examples of the acyl group include formyl group, acetyl group, propionyl group, butylyl group, isobutylyl group, valeryl group, isovaleryl group, and benzoyl group.
또한 R6은 탄소수 1∼5의 알킬기이며, 그 구체예로서는 메틸기, 에틸기, n-프로필기, i-프로필기, n-뷰틸기, i-뷰틸기, t-뷰틸기, n-펜틸기 등을 들 수 있지만, 특히, 메틸기가 바람직하다. In addition, R 6 is an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, etc. Although mentioned, in particular, a methyl group is preferable.
특히, 상기 풀러렌 유도체의 유기 용매에 대한 용해성을 보다 향상시키는 것을 고려하면, 당 잔기가 갖는 수산기의 적어도 1개가 임의의 치환기에 의해 치환되어 있는 것이 바람직하고, 모든 수산기가 치환기에 의해 치환되어 있는 것이 보다 바람직하다. In particular, in consideration of further improving the solubility of the fullerene derivative in an organic solvent, it is preferable that at least one of the hydroxyl groups of the sugar moiety is substituted by an arbitrary substituent, and that all hydroxyl groups are substituted by a substituent. More preferable.
그 구체예로서는 R7∼R15에서 예시한 것과 동일한 치환기를 들 수 있지만, 특히, 탄소수 1∼10의 알킬기, 벤질기, p-메톡시벤질기, 메톡시메틸기, 2-테트라하이드로파이란일기, 에톡시에틸기, 아세틸기, 피발로일기, 벤조일기, 트라이메틸실릴기, 트라이에틸실릴기, t-뷰틸메틸실릴기, 트라이아이소프로필실릴기, t-뷰틸다이페닐실릴기 등이 바람직하고, 아세틸기가 보다 바람직하다. Specific examples thereof include the same substituents as those illustrated for R 7 to R 15 , but in particular, a C 1 to
식 (1)로 표시되는 풀러렌 유도체는 "당 단위를 갖는 수용성 풀러렌 유도체의 합성과 전기화학 특성"(2002년 3월 일본화학회 제81회 춘계 연회)에 게재되어 있는 단 당기를 갖는 풀러렌 화합물의 합성 방법, 특허문헌 1, 2, 국제공개 제2011/108365호 등에 기재된 방법에 준하여 합성할 수 있다. 그 일례를 들면, 이하의 반응식과 같다. The fullerene derivative represented by the formula (1) is the synthesis and electrochemical properties of a water-soluble fullerene derivative having a sugar unit (March 2002, the 81st Spring Annual Meeting of the Japanese Chemical Society). It can be synthesized according to the method described in the synthesis method,
식 (1)로 표시되는 풀러렌 유도체를 포함하는 용액을 조제하기 위한 유기 용매로서는 상기 풀러렌 유도체의 용해능을 갖는 것이면 특별히 한정되는 것은 아니며, 예를 들면, 벤젠, 톨루엔, 자일렌, 클로로벤젠 등의 방향족 또는 할로젠화 방향족 탄화 수소 용매; 다이에틸에터, 테트라하이드로퓨란, 다이옥세인 등의 에터계 용매, 아세톤 등의 케톤계 용매, 아세트산 에틸 등의 에스터계 용매; 다이클로로에테인, 클로로폼, 다이클로로메테인 등의 할로젠화 탄화 수소 용매; 이황화 탄소 등을 사용할 수 있다. The organic solvent for preparing a solution containing the fullerene derivative represented by formula (1) is not particularly limited as long as it has a solubility of the fullerene derivative. For example, benzene, toluene, xylene, chlorobenzene, etc. Aromatic or halogenated aromatic hydrocarbon solvents; Ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ketone solvents such as acetone; ester solvents such as ethyl acetate; Halogenated hydrocarbon solvents such as dichloroethane, chloroform, and dichloromethane; Carbon disulfide and the like can be used.
유기 용액 중의 풀러렌 유도체의 함유량은 유기 용매에 용해하는 양이면 특별히 한정되는 것은 아니지만, 도포성 등의 조작성 등을 고려하면, 0.01∼20질량%가 바람직하고, 0.5∼3질량%가 보다 바람직하다. The content of the fullerene derivative in the organic solution is not particularly limited as long as it is an amount dissolved in an organic solvent, but in consideration of operability such as coatability, etc., 0.01 to 20% by mass is preferable, and 0.5 to 3% by mass is more preferable.
용액을 도포하는 방법으로서는 디핑법, 스핀코팅법, 전사인쇄법, 롤 코팅법, 브러싱법, 잉크젯법, 스프레이법, 슬릿 코팅법 등을 들 수 있지만, 이것들에 한정되는 것은 아니다. Examples of the method of applying the solution include, but are not limited to, a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brushing method, an inkjet method, a spray method, and a slit coating method.
소성 방법으로서는 특별히 한정되는 것은 아니고, 예를 들면, 핫플레이트나 오븐 등을 사용하여, 적절한 분위기하에, 즉, 질소 등의 불활성 가스, 진공중 등에서 가열하면 되지만, 불활성 가스하에서 가열하는 것이 바람직하다. The firing method is not particularly limited, for example, using a hot plate or an oven, and heating in an appropriate atmosphere, that is, in an inert gas such as nitrogen, vacuum, or the like, but heating under an inert gas is preferable.
소성 온도는 450℃ 이상으로 할 필요가 있고, 450℃ 미만이면, 표면의 요철이 충분히 형성되지 않거나, 적합한 이온화 포텐셜(Ip)을 실현할 수 없거나 하는 경우가 있다. 소성 온도는, 바람직하게는 460℃ 이상, 보다 바람직하게는 470℃ 이상, 더한층 바람직하게는 480℃ 이상, 더욱 바람직하게는 490℃ 이상이다. 한편, 소성 온도의 상한값은 풀러렌 유도체가 분해되지 않는 한에 있어서 특별히 한정되는 것은 아니지만, 통상 800℃ 정도이다. The firing temperature needs to be 450° C. or higher, and if it is less than 450° C., surface irregularities may not be sufficiently formed, or an appropriate ionization potential Ip may not be realized. The firing temperature is preferably 460°C or higher, more preferably 470°C or higher, still more preferably 480°C or higher, and still more preferably 490°C or higher. On the other hand, the upper limit of the firing temperature is not particularly limited as long as the fullerene derivative is not decomposed, but is usually about 800°C.
또한, 소성시에, 표면의 요철 형성을 촉진하는 것 등을 목적으로 하여, 2단계 이상의 온도 변화를 주어도 된다. Further, at the time of firing, for the purpose of promoting the formation of irregularities on the surface, etc., two or more temperature changes may be applied.
본 발명의 제조 방법에서 얻어지는 n형 유기 반도체 박막의 막 두께는 용도 에 따라 적당히 결정하기 때문에 일률적으로 규정할 수는 없지만, 유기 박막 태양전지의 n형 반도체로서 사용하는 경우, 40∼300nm 정도가 적합하다. 막 두께를 변화시키는 방법으로서는 유기 용액 중의 고형분 농도를 변화시키거나, 도포시의 기재 상의 용액량을 변화시키거나 하는 등의 방법이 있다. The film thickness of the n-type organic semiconductor thin film obtained in the manufacturing method of the present invention cannot be uniformly defined because it is appropriately determined according to the application, but when used as an n-type semiconductor of an organic thin film solar cell, about 40 to 300 nm is suitable. Do. As a method of changing the film thickness, there are methods such as changing the solid content concentration in the organic solution or changing the amount of the solution on the substrate at the time of application.
이상에서 설명한 제조 방법에 의해 얻어지는 박막은 표면에 많은 요철을 갖고, 그 때문에 큰 표면적을 가질 뿐만 아니라, 이온화 포텐셜이 6.0eV 이상이라고 하는 n형 반도체에 사용하는데 특히 적합한 특징을 갖는다. The thin film obtained by the above-described manufacturing method has a large number of irregularities on its surface, and therefore not only has a large surface area, but also has a characteristic suitable for use in an n-type semiconductor having an ionization potential of 6.0 eV or more.
본 발명의 제조 방법으로 얻어지는 n형 유기 반도체 박막의 산술평균 거칠기 Ra는 막 두께에 대하여 통상 2% 이상이지만, 바람직하게는 3% 이상, 보다 바람직하게는 4% 이상, 더한층 바람직하게는 5% 이상, 더욱 바람직하게는 6% 이상이다. 한편, Ra의 상한값은 특별히 한정되는 것은 아니지만, 통상 15% 정도이다. The arithmetic average roughness Ra of the n-type organic semiconductor thin film obtained by the production method of the present invention is usually 2% or more with respect to the film thickness, but is preferably 3% or more, more preferably 4% or more, and even more preferably 5% or more. , More preferably 6% or more. On the other hand, the upper limit of Ra is not particularly limited, but is usually about 15%.
또한 본 발명의 제조 방법으로 얻어지는 n형 유기 반도체 박막의 최대 높이 Rz는 막 두께에 대하여 통상 40% 이상이지만, 바람직하게는 45% 이상, 보다 바람직하게는 50% 이상, 더한층 바람직하게는 55% 이상, 더욱 바람직하게는 60% 이상이다. 한편, Rz의 상한값은 통상 90% 정도이며, 박막의 강도를 유지하는 관점에서 80% 이하가 바람직하다. In addition, the maximum height Rz of the n-type organic semiconductor thin film obtained by the production method of the present invention is usually 40% or more, but preferably 45% or more, more preferably 50% or more, and even more preferably 55% or more with respect to the film thickness. , More preferably 60% or more. On the other hand, the upper limit of Rz is usually about 90%, and 80% or less is preferable from the viewpoint of maintaining the strength of the thin film.
또한, 산술평균 거칠기 Ra 및 최대 높이 Rz는 JIS B0601에 근거하는 값이다. In addition, arithmetic mean roughness Ra and maximum height Rz are values based on JIS B0601.
본 발명의 제조 방법으로 얻어지는 n형 유기 반도체 박막의 이온화 포텐셜의 하한값은 통상 6.0eV 이상이지만, 바람직하게는 6.025eV 이상이고, 보다 바람직하게는 6.05eV 이상이고, 더한층 바람직하게는 6.075eV 이상이며, 상한값은 통상 6.3eV 이하이고, 바람직하게는 6.275eV 이하이고, 보다 바람직하게는 6.25eV 이하이고, 더한층 바람직하게는 6.225eV 이하이며, 더욱 바람직하게는 6.2eV이다. 이온화 포텐셜의 값은 소성 온도를 변경함으로써, 조정하는 것이 가능하다. The lower limit of the ionization potential of the n-type organic semiconductor thin film obtained by the production method of the present invention is usually 6.0 eV or more, preferably 6.025 eV or more, more preferably 6.05 eV or more, and even more preferably 6.075 eV or more, The upper limit value is usually 6.3 eV or less, preferably 6.275 eV or less, more preferably 6.25 eV or less, further preferably 6.225 eV or less, and still more preferably 6.2 eV. The value of the ionization potential can be adjusted by changing the firing temperature.
이상에서 설명한 제조 방법에 의해 얻어지는 n형 반도체 박막은, 그 큰 표면적 및 이온화 포텐셜 때문에, 유기 박막 태양전지, 특히, 초계층 나노 구조의 반도체층을 갖는 태양전지에 사용하는데 적합하다. The n-type semiconductor thin film obtained by the above-described manufacturing method is suitable for use in an organic thin-film solar cell, in particular, a solar cell having a superlayer nanostructured semiconductor layer because of its large surface area and ionization potential.
실시예Example
이하, 실시예 및 비교예를 들어 본 발명을 보다 구체적으로 설명하지만, 본 발명은 하기의 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
[1] 사용한 장치[1] Device used
(1) 표면관찰: Dimension ICON(브루커 에이엑스에스사제)(1) Surface observation: Dimension ICON (manufactured by Bruker AXS)
(2) 이온화 포텐셜 측정: AC-3(리켄케키(주)제)(2) Ionization potential measurement: AC-3 (manufactured by Rikenkeki Co., Ltd.)
(3) 막 두께 측정: S-4300형 전해 방출형 주사전자현미경((주) 히타치하이테크놀러지즈제)(3) Film thickness measurement: S-4300 type electrolytic emission scanning electron microscope (manufactured by Hitachi High Technologies)
[2] 박막의 제작[2] thin film fabrication
[실시예 1][Example 1]
질소 분위기하에서, 국제공개 제2010/055898호 기재의 방법으로 합성한 식 (4a)로 표시되는 풀러렌 유도체 50mg과 클로로폼 1.0mL를 혼합하고, 실온에서 잘 교반하여 용액을 조제했다. 동일한 분위기하에서, 얻어진 농갈색 투명 용액을, 스핀 코팅법(1500rpm, 30초)에 의해 실리콘 웨이퍼 위에 도포하고, 핫플레이트를 사용하여, 500℃에서 10분간 소성하여 풀러렌 박막을 형성했다. In a nitrogen atmosphere, 50 mg of a fullerene derivative represented by formula (4a) synthesized by the method described in International Publication No. 2010/055898 and 1.0 mL of chloroform were mixed, and stirred well at room temperature to prepare a solution. In the same atmosphere, the obtained dark brown transparent solution was applied onto a silicon wafer by spin coating (1500 rpm, 30 seconds), and baked at 500°C for 10 minutes using a hot plate to form a fullerene thin film.
제작한 박막의 막 두께의 단면을 확인한 결과 막 두께는 170nm이었다. As a result of checking the cross section of the film thickness of the produced thin film, the film thickness was 170 nm.
[비교예 1][Comparative Example 1]
350℃에서 10분간 소성한 이외는 실시예 1과 동일한 방법으로 풀러렌 박막을 형성했다. A fullerene thin film was formed in the same manner as in Example 1 except that it was baked at 350°C for 10 minutes.
제작한 박막의 막 두께의 단면을 확인한 결과 막 두께는 220nm이었다. As a result of checking the cross section of the film thickness of the produced thin film, the film thickness was 220 nm.
[비교예 2][Comparative Example 2]
100℃에서 10분간 소성한 이외는 실시예 1과 동일한 방법으로 풀러렌 박막을 형성했다. A fullerene thin film was formed in the same manner as in Example 1 except for firing at 100°C for 10 minutes.
[3] 표면 관찰 및 이온화 포텐셜의 측정[3] Surface observation and measurement of ionization potential
실시예 1 및 비교예 1, 2에서 제작한 풀러렌 박막의 표면의 관찰 및 이온화 포텐셜의 측정을 행했다. 실시예 1 및 비교예 1, 2의 풀러렌 박막의 표면 사진을 도 1∼3에 각각 나타낸다. 또한 각 박막의 산술평균 거칠기(Ra), 최대 높이(Rz) 및 이온화 포텐셜을 표 1에 나타낸다.The surface of the fullerene thin film produced in Example 1 and Comparative Examples 1 and 2 was observed and the ionization potential was measured. Surface photographs of the fullerene thin films of Example 1 and Comparative Examples 1 and 2 are shown in Figs. 1 to 3, respectively. In addition, the arithmetic mean roughness (Ra), maximum height (Rz) and ionization potential of each thin film are shown in Table 1.
막 두께
Film thickness
이온화 포텐셜
Ionization potential
표 1 및 도 1∼3에 나타내어지는 바와 같이, 실시예 1 및 비교예 1의 풀러렌 박막의 표면 거칠기(Ra 및 Rz)는 비교예 2의 박막보다도 높고, 350℃ 이상이라고 하는 고온에서 소성함으로써 보다 고저차가 있는 요철이 보다 다수 형성되는 것을 알 수 있다. As shown in Table 1 and Figs. 1 to 3, the surface roughness (Ra and Rz) of the fullerene thin films of Example 1 and Comparative Example 1 is higher than that of the thin film of Comparative Example 2, and by firing at a high temperature of 350°C or higher, It can be seen that more irregularities with a difference in elevation are formed.
게다가, 500℃에서 소성한 실시예 1의 박막은 6.0eV 이상이라고 하는 n형 반도체에 적합한 이온화 포텐셜을 가지고 있어, 무수식 풀러렌과 동일한 정도의 이온화 포텐셜(6.1eV)인 것을 알 수 있으며, 또한 고온에서 소성함으로써 박막의 이온화 포텐셜이 향상되는 것도 알 수 있다. In addition, the thin film of Example 1 fired at 500°C has an ionization potential suitable for an n-type semiconductor of 6.0 eV or more, and it can be seen that it has the same degree of ionization potential (6.1 eV) as an anhydrous fullerene, and also at high temperature. It can also be seen that the ionization potential of the thin film is improved by firing at.
이상으로부터, 본 발명의 n형 반도체는 그 이온화 포텐셜 특성 때문에 무수식 풀러렌 대신에 사용하는 것이 가능하며, 또한 그 높은 표면적 때문에, 이것을 유기 태양전지의 n형 반도체로서 사용함으로써, 무수식 풀러렌에서는 실현할 수 없었던 고변환 효율을 기대할 수 있다. From the above, the n-type semiconductor of the present invention can be used instead of anhydrous fullerene because of its ionization potential characteristics, and because of its high surface area, it can be realized in anhydrous fullerene by using it as an n-type semiconductor of an organic solar cell. High conversion efficiency can be expected.
Claims (6)
(식 중, R1∼R5는, 각각 독립하여, 수소 원자, 당기, 또는 당기의 임의의 수산기가 치환기에 의해 치환된 당기인 치환 당기를 나타내고, R6은 탄소수 1∼5의 알킬기를 나타낸다. 단, R1∼R5 중 적어도 1개는 상기 당기 또는 치환 당기이다.)A method for producing an n-type organic semiconductor thin film, comprising applying a solution containing a fullerene derivative represented by formula (1) to a substrate and firing at 450°C or higher.
(In the formula, R 1 to R 5 each independently represent a hydrogen atom, a sugar, or a substituted sugar in which an arbitrary hydroxyl group of the sugar is substituted by a substituent, and R 6 represents an alkyl group having 1 to 5 carbon atoms. However, at least one of R 1 to R 5 is the aforementioned sugar or substituted sugar.)
상기 당기 또는 치환 당기가 식 (2), 식 (3) 및 식 (4)로부터 선택되는 적어도 1개의 기인 것을 특징으로 하는 n형 유기 반도체 박막의 제조 방법.
(식 중, R7∼R15는, 각각 독립하여, 수소 원자, 아미노기, 싸이올기, 카복실기, 인산기, 인산 에스터기, 에스터기, 싸이오에스터기, 아마이드기, 나이트로기, 1가 탄화 수소기, 오가노아미노기, 오가노실릴기, 오가노싸이오기, 아실기, 알킬에터기, 또는 설폰기를 나타낸다.)The method of claim 1,
The method for producing an n-type organic semiconductor thin film, wherein the sugar or substituted sugar is at least one group selected from formulas (2), (3) and (4).
(In the formula, R 7 to R 15 are each independently a hydrogen atom, an amino group, a thiol group, a carboxyl group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, or a monovalent hydrocarbon. Group, organoamino group, organosilyl group, organothio group, acyl group, alkyl ether group, or sulfone group.)
상기 치환기가 탄소수 1∼10의 알킬기, 벤질기, p-메톡시벤질기, 메톡시메틸기, 2-테트라하이드로파이란일기, 에톡시에틸기, 아세틸기, 피발로일기, 벤조일기, 트라이메틸실릴기, 트라이에틸실릴기, t-뷰틸메틸실릴기, 트라이아이소프로필실릴기, 또는 t-뷰틸다이페닐실릴기인 것을 특징으로 하는 n형 유기 반도체 박막의 제조 방법.The method according to claim 1 or 2,
The substituent is an alkyl group having 1 to 10 carbon atoms, benzyl group, p-methoxybenzyl group, methoxymethyl group, 2-tetrahydropyranyl group, ethoxyethyl group, acetyl group, pivaloyl group, benzoyl group, trimethylsilyl group, Triethylsilyl group, t-butylmethylsilyl group, triisopropylsilyl group, or t-butyldiphenylsilyl group, characterized in that the manufacturing method of the n-type organic semiconductor thin film.
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