TWI602809B - Method for producing n-type organic semiconductor thin film - Google Patents
Method for producing n-type organic semiconductor thin film Download PDFInfo
- Publication number
- TWI602809B TWI602809B TW103128787A TW103128787A TWI602809B TW I602809 B TWI602809 B TW I602809B TW 103128787 A TW103128787 A TW 103128787A TW 103128787 A TW103128787 A TW 103128787A TW I602809 B TWI602809 B TW I602809B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- thin film
- semiconductor thin
- organic semiconductor
- type organic
- Prior art date
Links
- 239000004065 semiconductor Substances 0.000 title claims description 50
- 239000010409 thin film Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000010408 film Substances 0.000 claims description 47
- -1 decylamino group Chemical group 0.000 claims description 44
- 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 description 29
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 6
- 125000003147 glycosyl group Chemical group 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 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 claims description 4
- 125000005011 alkyl ether group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 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
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 150000007970 thio esters Chemical group 0.000 claims description 3
- 125000004149 thio group Chemical group *S* 0.000 claims description 3
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 2
- 125000000837 carbohydrate group Chemical group 0.000 claims 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 25
- 229910003472 fullerene Inorganic materials 0.000 description 13
- 238000010304 firing Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000001720 carbohydrates Chemical group 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000002402 hexoses Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000005259 measurement Methods 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
- 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
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 150000002972 pentoses Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 125000000548 ribosyl group Chemical group C1([C@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical group NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 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
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000770 erythrosyl group Chemical group C1([C@H](O)[C@H](O)CO1)* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 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
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002772 monosaccharides Chemical class 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
- 239000003973 paint Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 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
- 125000004024 talosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 2
- 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
- YXZSONCKKBKMRZ-UHFFFAOYSA-N 1-tert-butyl-1,2-dimethylhydrazine Chemical compound CNN(C)C(C)(C)C YXZSONCKKBKMRZ-UHFFFAOYSA-N 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
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 125000000824 D-ribofuranosyl group Chemical group [H]OC([H])([H])[C@@]1([H])OC([H])(*)[C@]([H])(O[H])[C@]1([H])O[H] 0.000 description 1
- 206010056474 Erythrosis Diseases 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 125000000089 arabinosyl group Chemical group C1([C@@H](O)[C@H](O)[C@H](O)CO1)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 125000006310 cycloalkyl amino 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([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
- DXVWRJRZCMCNEU-UHFFFAOYSA-N dimercaptoamine Chemical group SNS DXVWRJRZCMCNEU-UHFFFAOYSA-N 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
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000001503 gulosyl group Chemical group C1([C@H](O)[C@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001288 lysyl group Chemical group 0.000 description 1
- 125000003796 lyxosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 description 1
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 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
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- XDRYMKDFEDOLFX-UHFFFAOYSA-N pentamidine Chemical group C1=CC(C(=N)N)=CC=C1OCCCCCOC1=CC=C(C(N)=N)C=C1 XDRYMKDFEDOLFX-UHFFFAOYSA-N 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
- 230000001737 promoting effect Effects 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000005629 sialic acid group Chemical group 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 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
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- 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
-
- 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
-
- 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
-
- 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
Description
本發明係關於n型有機半導體薄膜之製造方法，更詳細而言，關於包含由具有單糖或糖醇殘基之富勒烯衍生物所構成之n型半導體之大表面積薄膜之製造方法。 The present invention relates to a method for producing an n-type organic semiconductor thin film, and more particularly to a method for producing a large-surface-surface film comprising an n-type semiconductor composed of a fullerene derivative having a monosaccharide or a sugar alcohol residue.
富勒烯具有優異電子輸送性(電子接收性)及耐熱性，故泛用作為有機薄膜太陽能電池等之有機裝置之n型半導體材料。 Since fullerene has excellent electron transport properties (electron acceptability) and heat resistance, it is widely used as an n-type semiconductor material as an organic device such as an organic thin film solar cell.
然而，由於無修飾之富勒烯對於各種有機溶劑之溶解性差，故難以由濕式製程進行成膜，此成膜通常係施行乾式製程之蒸鍍法。 However, since unmodified fullerene has poor solubility in various organic solvents, it is difficult to form a film by a wet process, and this film formation is usually performed by a dry process vapor deposition method.
又，作為能以濕式製程進行成膜之富勒烯衍生物，已知有如PCBM，但PCBM僅能溶解於特定之有機溶劑，不僅在單體下之成膜性差，並且與無修飾之富勒烯相比，在電子輸送性上亦差。 Further, as a fullerene derivative which can be formed by a wet process, it is known as PCBM, but PCBM can only be dissolved in a specific organic solvent, and the film formation property is not only poor under the monomer, but also rich in no modification. Compared with the olefin, it is also inferior in electron transport properties.
有機薄膜太陽能電池係具備具有電洞輸送性(電子供給性)之p型半導體與具有電子輸送性(電子接 收性)之n型半導體，主要係p型半導體吸收來自外部之光而激發，所產生之激子擴散至此等2個半導體之界面，因此電子移動至n型半導體，進而引起電動所必需之電荷分離。提高此電荷分離之效率則係連繫於有機薄膜太陽能電池之光電轉換效率之提升，作為達成此之1個方法，可舉出如增大各半導體彼此之接觸面積。 The organic thin film solar cell system has a p-type semiconductor having hole transportability (electron supply property) and has electron transportability (electronic connection) The n-type semiconductor is mainly a p-type semiconductor that absorbs light from the outside and is excited. The generated excitons diffuse to the interface of the two semiconductors, so that the electrons move to the n-type semiconductor, thereby causing the electric charge necessary for the electric motor. Separation. Increasing the efficiency of the charge separation is an improvement in the photoelectric conversion efficiency of the organic thin film solar cell. As one of the methods for achieving this, the contact area between the semiconductors is increased.
由此般觀點，例如已提出有，藉由調製混合p型半導體材料與n型半導體材料之溶液，以塗佈法形成活性層，即可大幅提升取得之太陽能電池之轉換效率(非專利文獻1)。藉此手法取得之活性層由於供體/受體界面係形成於活性層之層體全體，故一般稱為體異質接面(Bulk heterojunction)。 From this point of view, for example, it has been proposed that the conversion efficiency of the obtained solar cell can be greatly improved by preparing a solution in which a p-type semiconductor material and an n-type semiconductor material are mixed and forming an active layer by a coating method (Non-Patent Document 1) ). The active layer obtained by this method is generally referred to as a bulk heterojunction because the donor/acceptor interface is formed on the entire layer of the active layer.
又，作為能謀求光電轉換效率提升之其他理想構造，已提出有超階層奈米構造(非專利文獻2)。此構造中，為了防止電極附近之載體之再結合，而係與異質接面相異，p型半導體與n型半導體係各自分離而配置於電極，而另一方面此等2個半導體彼此係以奈米級程度之間隔整齊地接觸，故據說可抑制所產生之載體之再結合並同時發現高移動度，且能以高密度形成供體/受體界面。 Further, as another ideal structure capable of improving the photoelectric conversion efficiency, a super-layered nanostructure has been proposed (Non-Patent Document 2). In this configuration, in order to prevent recombination of the carrier in the vicinity of the electrode, the heterojunction is different from each other, and the p-type semiconductor and the n-type semiconductor are separated from each other and disposed on the electrode, and on the other hand, the two semiconductors are connected to each other. The level of the rice level is neatly contacted, so it is said that the recombination of the generated carrier can be suppressed and high mobility can be found at the same time, and the donor/acceptor interface can be formed at a high density.
以上之2種技術係周知作為提升光電轉換效率之手法者，在體異質接面中由於係塗佈p型半導體材料與n型半導體材料之混合液而形成界面，故不僅難以再現性良好地取得適宜界面，同時亦有因形成膜所需之燒成時之熱，而引起界面變化之問題。 The above two techniques are known as methods for improving the photoelectric conversion efficiency, and the interface between the p-type semiconductor material and the n-type semiconductor material is formed in the bulk heterojunction to form an interface, so that it is difficult to obtain good reproducibility. The interface is suitable, and there is also a problem that the interface changes due to the heat required for the formation of the film.
因此，為了提升光電轉換效率與提升元件之信賴性，超階層奈米構造可謂係適宜者，但為了實現該構造則必須進行半導體層之多孔質化或凹凸化等之表面積之增大化。 Therefore, in order to improve the photoelectric conversion efficiency and the reliability of the lifting element, the super-layered nanostructure can be said to be suitable. However, in order to realize this structure, it is necessary to increase the surface area of the semiconductor layer such as porosity or unevenness.
[專利文獻1] 國際公開第2010/055898號 [Patent Document 1] International Publication No. 2010/055898
[專利文獻2] 日本特開2011-258944號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-258944
[非專利文獻1] Science, 1995, 270, pp. 1789-1791 [Non-Patent Document 1] Science, 1995, 270, pp. 1789-1791
[非專利文獻2] Chem. Rev., 2007, 107, pp. 1324-1338 [Non-Patent Document 2] Chem. Rev., 2007, 107, pp. 1324-1338
本發明係有鑑於此種情事所完成者，以提供具有適宜游離電位且於成膜面具有微小凹凸或細孔之使用濕式製程之n型有機半導體薄膜之製造方法為目的。 The present invention has been made in view of such circumstances, and it is intended to provide a method for producing an n-type organic semiconductor thin film using a wet process having a suitable free potential and having fine irregularities or pores on a film formation surface.
本案申請人既已提出具有糖殘基或糖醇殘基之富勒烯化合物對於有機溶劑之溶解性為良好，由包含此化合物之塗漆所得之薄膜之均勻性為良好，及該化合物可驅動作為n型半導體，且可適用於有機薄膜太陽能電池 (專利文獻1、2)。此專利文獻1、2之技術係將使具有糖殘基等之富勒烯化合物溶解於有機溶劑而成之塗漆塗佈於基材上，並在大氣下或真空下，以80~100℃進行燒成而去除溶劑，進而形成均勻性及平坦性良好之n型半導體薄膜。 The applicant of the present invention has proposed that the fullerene compound having a sugar residue or a sugar alcohol residue has good solubility in an organic solvent, the uniformity of the film obtained from the paint containing the compound is good, and the compound can be driven. As an n-type semiconductor, and can be applied to organic thin film solar cells (Patent Documents 1 and 2). The techniques of Patent Documents 1 and 2 apply a paint obtained by dissolving a fullerene compound having a sugar residue or the like in an organic solvent onto a substrate, and 80 to 100 ° C under air or under vacuum. The solvent is removed by firing to form an n-type semiconductor film having good uniformity and flatness.
本發明者在此專利文獻1、2之技術中，發現藉由提高薄膜形成時之燒成溫度，在與100℃程度之低溫燒成時相比，成膜面之微小凹凸或細孔增加，及再更加提高燒成溫度，即亦能形成作為n型半導體使用之具有適宜游離電位之薄膜，進而完成本發明。 In the techniques of Patent Documents 1 and 2, the present inventors have found that the fine unevenness or pores of the film formation surface are increased as compared with the case of firing at a low temperature of about 100 ° C by increasing the firing temperature at the time of film formation. Further, by further increasing the firing temperature, a film having a suitable free potential which is used as an n-type semiconductor can be formed, and the present invention can be completed.
即，本發明為提供下述者： That is, the present invention provides the following:
1.一種n型有機半導體薄膜之製造方法，其特徵為將包含式(1)所表示之富勒烯衍生物之溶液塗佈於基材上，並以450℃以上進行燒成；
2.如1之n型有機半導體薄膜之製造方法，其中前述糖基或取代糖基為選自式(2)、式(3)及式(4)之至少一種之基；
3.如1或2之n型有機半導體薄膜之製造方法，其中前述取代基為碳數1~10之烷基、苄基、p-甲氧基苄基、甲氧基甲基、2-四氫吡喃基、乙氧基乙基、乙醯基、三甲基乙醯基、苄醯基、三甲基矽基、三乙基矽基、t-丁基二甲基矽基、三異丙基矽基、或t-丁基二苯基矽基。 3. The method for producing an n-type organic semiconductor thin film according to 1 or 2, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a benzyl group, a p-methoxybenzyl group, a methoxymethyl group, and a 2-four group. Hydropyranyl, ethoxyethyl, ethoxymethyl, trimethylethenyl, benzindenyl, trimethylsulfonyl, triethylsulfonyl, t-butyldimethylguanidino, triiso Propyl fluorenyl, or t-butyldiphenyl fluorenyl.
4.一種n型有機半導體薄膜，其係藉由如1~3中任一項之製造方法所得者。 An n-type organic semiconductor thin film obtained by the production method according to any one of 1 to 3.
5.一種n型有機半導體薄膜，其係算術平均粗度Ra為膜厚之2%以上，最大高度Rz為膜厚之40%以上，游離電位為6.0eV以上。 An n-type organic semiconductor thin film having an arithmetic mean roughness Ra of 2% or more of a film thickness, a maximum height Rz of 40% or more of a film thickness, and a free potential of 6.0 eV or more.
6.一種有機太陽能電池，其係具有如4或5之n型有機半導體薄膜。 6. An organic solar cell having an n-type organic semiconductor thin film such as 4 or 5.
根據本發明之製造方法，可形成具有適宜游離電位且於成膜面形成有微小凹凸或細孔之n型有機半導體薄膜。若使用由本發明之製造方法所得之薄膜，能在保持理想之能階關係下，同時極顯著地提高與藉由積層法而鄰接形成之p層之p/n接合界面面積，故能賦予有機太陽能電池之轉換效率提升。尤其，由高溫燒成所製成之薄膜由於係為具有與無修飾富勒烯同等之游離電位之大表面積n型有機半導體薄膜，故可適宜作為電子裝置，特別係適宜作為因與p型半導體之接觸面積增加而可直接期待特性提高之有機太陽能電池之n型半導體。 According to the production method of the present invention, an n-type organic semiconductor thin film having a suitable free potential and having minute irregularities or fine pores formed on the film formation surface can be formed. When the film obtained by the manufacturing method of the present invention is used, the organic light energy can be imparted while maintaining a desired energy level relationship while significantly increasing the p/n bonding interface area of the p layer adjacently formed by the lamination method. The conversion efficiency of the battery is improved. In particular, since the film produced by firing at a high temperature is a large surface area n-type organic semiconductor film having a free potential equivalent to that of the unmodified fullerene, it can be suitably used as an electronic device, particularly as a p-type semiconductor. As the contact area is increased, an n-type semiconductor of an organic solar cell having improved characteristics can be directly expected.
又，本發明之製造方法中，由於係使用變更其取代基及糖骨架而可容易衍生成各種類似物之富勒烯衍生物，故因應鄰接形成之p層之種類或其形成方法，而能控制其游離電位或表面積。因此，根據本發明之製造方法，即可製造具有最佳化之p/n接合界面且更高轉換效率之有機太陽能電池。 Further, in the production method of the present invention, since the fullerene derivative of various analogs can be easily derivatized by changing the substituent and the sugar skeleton, the type of the p layer formed adjacent thereto or the method for forming the same can be used. Control its free potential or surface area. Therefore, according to the manufacturing method of the present invention, an organic solar cell having an optimized p/n bonding interface and higher conversion efficiency can be manufactured.
並且，本發明之製造方法中，由於可藉由濕式製程而薄膜化，故與乾式製程相比，元件之大面積化變得容易，且亦變得能減低製造成本，其結果係能賦予有機太陽能電池、有機EL元件之低成本化。 Further, in the production method of the present invention, since the film can be formed by a wet process, the area of the device can be made larger than that of the dry process, and the manufacturing cost can be reduced. The cost of organic solar cells and organic EL elements is reduced.
[圖1]展示實施例1中製成之富勒烯薄膜之AFM觀察結果圖。 Fig. 1 is a graph showing the results of AFM observation of a fullerene film produced in Example 1.
[圖2]展示比較例1中製成之富勒烯薄膜之AFM觀察結果圖。 Fig. 2 is a graph showing the results of AFM observation of a fullerene film produced in Comparative Example 1.
[圖3]展示比較例2中製成之富勒烯薄膜之AFM觀察結果圖。 Fig. 3 is a graph showing the results of AFM observation of a fullerene film produced in Comparative Example 2.
以下，更詳細說明關於本發明。 Hereinafter, the present invention will be described in more detail.
本發明之n型有機半導體薄膜之製造方法，其係將包含式(1)所表示之富勒烯衍生物之溶液塗佈於基材上，在450℃以上進行燒成者。 In the method for producing an n-type organic semiconductor thin film of the present invention, a solution containing a fullerene derivative represented by the formula (1) is applied onto a substrate, and baked at 450 ° C or higher.
式(1)中，R1~R5係各自獨立表示氫原子、糖基、或糖基之任意羥基被取代基所取代之糖基即取代糖基，但R1~R5之中之任意一個為糖基或取代糖基。 In the formula (1), R 1 to R 5 each independently represent a sugar atom, that is, a substituted sugar group, in which a hydrogen atom, a sugar group or a hydroxy group is substituted with a substituent, but any of R 1 to R 5 One is a glycosyl group or a substituted sugar group.
在此，作為糖基或取代糖基，並非係受到特別限定 者，可採用任意之丁糖基、戊糖基、己糖基及此等之任意羥基被取代之取代糖基。 Here, as the glycosyl group or the substituted sugar group, it is not particularly limited. Any of the glycosyl groups, pentose groups, hexose groups, and substituted saccharides substituted with any of these hydroxy groups may be employed.
作為丁糖基，可舉出如赤蘚糖(erythrose)之基即赤蘚糖基(erythrosyl)等。 Examples of the butyose group include erythrosyl groups such as erythrose.
作為戊糖基，可舉出如***糖(arabinose)之基即***糖基(Arabinosyl)、來蘇糖(lyxose)之基即來蘇糖基(lyxosyl)、核糖(ribose)之基即核糖基(ribosyl)、木糖(xylose)之基即木糖基(xylosyl)等。 Examples of the pentose group include a ribose group, i.e., arabinosyl, a lyxose group, that is, a lyxyl group or a ribose group, that is, a ribose group. (ribosyl), the base of xylose is xylosyl and the like.
作為己糖基，可舉出如阿洛糖(allose)之基即阿洛糖基(allosyl)、果糖(fructose)之基即果糖基(fructosyl)、半乳糖(galactose)之基即半乳糖基(galactosyl)、葡萄糖(glucose)之基即葡萄糖基(glucosyl)、古洛糖(gulose)之基即古洛糖基(gulosyl)、甘露糖(mannose)之基即甘露糖基(mannosyl)、塔格酮糖(tagalose)之基即塔格糖酮基(tagalosyl)、太洛糖(talose)之基即太洛糖基(talosyl)、唾液酸基等。 Examples of the hexose group include a lysyl group which is a radical of allose, a fructosyl group which is a group of fructose, and a galactose group which is a galactose group. (galactosyl), the basis of glucose (glucosyl), the base of gulose, gulosyl, mannose, mannosyl, tower The base of the tagalose is the tagalosyl group, the talose group, the talosyl group, the sialic acid group and the like.
於本發明中，此等之中係以己糖基為佳，特別係以半乳糖基、葡萄糖基為適宜。 In the present invention, among these, a hexose group is preferred, and a galactosyl group or a glucosyl group is particularly preferred.
更具體而言，適宜為式(2)~(4)所示之丁糖基、戊糖基、己糖基，尤其係以式(4)所示之己糖基為佳。 More specifically, it is preferably a butylosyl group, a pentose group or a hexose group represented by the formulae (2) to (4), and particularly preferably a hexose group represented by the formula (4).
作為一價烴基，例如可舉出，甲基、乙基、n-丙基、i-丙基、n-丁基、i-丁基、t-丁基、n-己基、n-辛基、2-乙基己基、癸基等之烷基、環戊基、環己基等之環烷基、雙環己基等之雙環烷基、乙烯基、1-丙烯基、2-丙烯基、異丙烯基、1-甲基-2-丙烯基、1或2或3-丁烯基、己烯基等之烯基、苯基、茬基、甲苯基、聯苯基、萘基等之芳基、苄基、苯基乙基、苯基環己基等之芳烷基等，或此等一價烴基之氫原子之一部分或全部被鹵素原子(氟原子、氯原子、溴原子、碘原子)、羥基、烷氧基(甲氧基、乙氧基等)等所取代者。 Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and an n-octyl group. a cycloalkyl group such as a 2-ethylhexyl group or a fluorenyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a bicycloalkyl group such as a dicyclohexyl group; a vinyl group; a 1-propenyl group; a 2-propenyl group; an isopropenyl group; An aryl group such as a 1-methyl-2-propenyl group, a 1 or 2 or 3-butenyl group, a hexenyl group or the like, an aryl group such as a phenyl group, a decyl group, a tolyl group, a biphenyl group or a naphthyl group; Or an aralkyl group such as a phenylethyl group or a phenylcyclohexyl group, or a part or all of a hydrogen atom of the monovalent hydrocarbon group is partially or wholly a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a hydroxyl group or an alkane. An oxy group (methoxy group, ethoxy group, etc.) or the like is substituted.
作為有機胺基，例如可舉出，甲基胺基、乙基胺基、丙基胺基、丁基胺基、戊基胺基、己基胺基、庚基胺基、辛基胺基、壬基胺基、癸基胺基、十二基胺基等之烷基胺基、二甲基胺基、二乙基胺基、二丙基胺基、二丁基胺基、二戊基胺基、二己基胺基、二庚基胺基、二辛 基胺基、二壬基胺基、二癸基胺基等之二烷基胺基、環己基胺基等之環烷基胺基、嗎啉基等。 Examples of the organic amine group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, and an anthracene group. Alkylamino group, dimethylamino group, dodecylamino group, etc., alkylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diamylamino group , dihexylamino, diheptylamino, dioctyl A cycloalkylamino group such as a dialkylamino group such as a arylamino group, a dinonylamino group or a dimercaptoamine group; a cyclohexylamino group; and a morpholinyl group.
作為有機矽基，例如可舉出，三甲基矽基、三乙基矽基、三丙基矽基、三丁基矽基、三戊基矽基、三己基矽基、戊基二甲基矽基、己基二甲基矽基、辛基二甲基矽基、癸基二甲基矽基等。 Examples of the organic thiol group include a trimethylsulfonyl group, a triethylsulfonyl group, a tripropylsulfonyl group, a tributylsulfonyl group, a tripentylsulfonyl group, a trihexylsulfonyl group, and a pentyldimethyl group. Mercapto, hexyl dimethyl fluorenyl, octyl dimethyl fluorenyl, decyl dimethyl fluorenyl and the like.
作為有機硫基，例如可舉出，甲硫基、乙硫基、丙硫基、丁硫基、戊硫基、己硫基、庚硫基、辛硫基、壬硫基、癸硫基、十二硫基等之烷硫基等。 Examples of the organic sulfur group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, an anthracenylthio group, an anthracenylthio group, and the like. An alkylthio group such as a dodecyl group or the like.
作為醯基，例如可舉出，甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、異戊醯基、苄醯基等。 Examples of the mercapto group include a mercapto group, an ethenyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group, and the like.
又，R6為碳數1~5之烷基，作為其具體例，可舉出如甲基、乙基、n-丙基、i-丙基、n-丁基、i-丁基、t-丁基、n-戊基等，特別係以甲基為佳。 Further, R 6 is an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and t. - butyl, n-pentyl, etc., especially methyl.
尤其，若考量到更加提升上述富勒烯衍生物對於有機溶劑之溶解性時，以糖殘基所具有之羥基之至少一個被任意之取代基所取代為佳，以全部羥基被取代基所取代為較佳。 In particular, when it is considered that the solubility of the above fullerene derivative in an organic solvent is further improved, it is preferred that at least one of the hydroxyl groups of the sugar residue is substituted with an arbitrary substituent, and all of the hydroxyl groups are substituted with a substituent. It is better.
作為具體例，可舉出與在R7~R15中例示者同樣之取代基，尤其係以碳數1~10之烷基、苄基、p-甲氧基苄基、甲氧基甲基、2-四氫吡喃基、乙氧基乙基、乙醯基、三甲基乙醯基、苄醯基、三甲基矽基、三乙基矽基、t-丁基二甲基矽基、三異丙基矽基、t-丁基二苯基矽基等為佳，以乙醯基為較佳。 Specific examples thereof include the same substituents as those exemplified in R 7 to R 15 , and particularly, an alkyl group having 1 to 10 carbon atoms, a benzyl group, a p-methoxybenzyl group, or a methoxymethyl group. , 2-tetrahydropyranyl, ethoxyethyl, ethenyl, trimethylethenyl, benzamidine, trimethylsulfonyl, triethylsulfonyl, t-butyldimethylhydrazine A group, a triisopropyl fluorenyl group, a t-butyldiphenyl fluorenyl group and the like are preferred, and an acetamino group is preferred.
式(1)所示之富勒烯衍生物係可根據“具有糖單位之水溶性富勒烯衍生物之合成與電化學特性”(2002年3月日本化學會第81回春季年會)中揭示之具有單糖基之富勒烯化合物之合成方法，專利文獻1、2，國際公開第2011/108365號等記載之方法而合成。若例舉出其之一例，則如以下之反應流程所示。 The fullerene derivative represented by the formula (1) can be based on "synthesis and electrochemical properties of a water-soluble fullerene derivative having a sugar unit" (March 81, Annual Meeting of the Chemical Society of Japan, March 2002) A method for synthesizing a fullerene compound having a monosaccharide group is disclosed in the methods described in Patent Documents 1 and 2, International Publication No. 2011/108365. If one of them is exemplified, it is as shown in the following reaction scheme.
作為調製包含式(1)所表示之富勒烯衍生物之溶液所用之有機溶劑，只要係具有溶解上述富勒烯衍生物之能力者，即非係受到特別限定者，例如可使用如苯、甲苯、茬、氯苯等之芳香族或鹵化芳香族烴溶劑；二乙基醚、四氫呋喃、二噁烷等之醚系溶劑、丙酮等之酮系溶劑、乙酸乙酯等之酯系溶劑；二氯乙烷、氯仿、二氯甲烷等之鹵化烴溶劑；二硫化碳等。 The organic solvent used for preparing the solution containing the fullerene derivative represented by the formula (1) is not particularly limited as long as it has the ability to dissolve the above fullerene derivative, and for example, benzene can be used. An aromatic or halogenated aromatic hydrocarbon solvent such as toluene, hydrazine or chlorobenzene; an ether solvent such as diethyl ether, tetrahydrofuran or dioxane; a ketone solvent such as acetone; and an ester solvent such as ethyl acetate; a halogenated hydrocarbon solvent such as ethyl chloride, chloroform or dichloromethane; carbon disulfide or the like.
有機溶液中之富勒烯衍生物之含有量，只要係能溶解於有機溶劑中之量，即非係受到特別限定者，在考量到塗佈性等之操作性等時，則以0.01~20質量%為佳，以0.5~3質量%為較佳。 The content of the fullerene derivative in the organic solution is not particularly limited as long as it is soluble in the organic solvent, and is 0.01 to 20 in consideration of workability such as coatability. The mass % is preferably 0.5 to 3% by mass.
作為塗佈溶液之方法，可舉出如浸漬法、旋轉塗佈法、轉印印刷法、輥塗法、毛刷塗佈、噴墨法、噴霧法、狹縫塗佈法等，但並非意指係限於此等者。 Examples of the method of applying the solution include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an inkjet method, a spray method, and a slit coating method, but are not intended to be used. Fingering is limited to these.
作為燒成方法，並非係受到特別限定者，例如，使用加熱板或烤箱等，在適當環境下，即氮等之惰性氣體、真空中等進行加熱即可，但以在惰性氣體下進行加熱為佳。 The method of firing is not particularly limited. For example, it may be heated in an appropriate environment, that is, an inert gas such as nitrogen or a vacuum, using a hot plate or an oven. However, it is preferable to perform heating under an inert gas. .
燒成溫度係必須作成450℃以上，若未滿450℃時，則有無法充分形成表面之凹凸，無法實現適宜游離電位(Ip)之情形。燒成溫度係以460℃以上為佳，較佳為470℃以上，較更佳為480℃以上，再更較佳為490℃以上。另一方面，燒成溫度之上限值只要係不使富勒烯衍生物分解，即非係受到特別限定者，通常為800℃程度。 The firing temperature must be 450 ° C or higher, and if it is less than 450 ° C, the surface unevenness cannot be sufficiently formed, and a suitable free potential (Ip) cannot be achieved. The firing temperature is preferably 460 ° C or higher, preferably 470 ° C or higher, 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 it does not decompose the fullerene derivative, and is usually about 800 °C.
尚且，於燒成時，以促進形成表面之凹凸等為目的，亦可加入2階段以上之溫度變化。 Further, in the case of firing, it is also possible to add a temperature change of two or more stages for the purpose of promoting the formation of irregularities on the surface.
由本發明之製造方法所得之n型有機半導體薄膜之膜厚由於係可因應用途而適宜決定，故無法一律規定，在使用作為有機薄膜太陽能電池之n型半導體時，適宜為40~300nm程度。作為使膜厚變化之方法，則有如使有機溶液中之固形分濃度變化，變化塗布時之基材上之溶 液量等之方法。 The film thickness of the n-type organic semiconductor thin film obtained by the production method of the present invention is appropriately determined depending on the application, and therefore it cannot be uniformly defined. When an n-type semiconductor as an organic thin film solar cell is used, it is preferably about 40 to 300 nm. As a method of changing the film thickness, for example, the solid content concentration in the organic solution is changed, and the dissolution on the substrate at the time of coating is changed. The method of liquid amount and the like.
藉由以上所說明之製造方法所得之薄膜係於表面具有眾多凹凸，因此不僅具有較大表面積，且具有游離電位為6.0eV以上之特別適宜使用於n型半導體之特徵。 Since the film obtained by the above-described production method has a large number of irregularities on the surface, it has a large surface area and has a free potential of 6.0 eV or more, which is particularly suitable for use as an n-type semiconductor.
由本發明之製造方法所得之n型有機半導體薄膜之算術平均粗度Ra，在相對於膜厚而言，通常為2%以上，以3%以上為佳，較佳為4%以上，較更佳為5%以上，再更佳為6%以上。另一方面，Ra之上限值並非係受到特別限定者，但通常為15%程度。 The arithmetic mean roughness Ra of the n-type organic semiconductor thin film obtained by the production method of the present invention is usually 2% or more, preferably 3% or more, more preferably 4% or more, and more preferably, relative to the film thickness. It is 5% or more, and more preferably 6% or more. On the other hand, the Ra upper limit is not particularly limited, but is usually about 15%.
又，由本發明之製造方法所得之n型有機半導體薄膜之最大高度Rz，在相對於膜厚而言，通常在40%以上，以45%以上為佳，較佳為50%以上，較更佳為55%以上，再更佳為60%以上。另一方面，Rz之上限值係通常為90%程度，從維持薄膜強度之觀點，以80%以下為佳。 Further, 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, more preferably 45% or more, and most preferably 50% or more, more preferably, relative to the film thickness. It is 55% or more, and more preferably 60% or more. On the other hand, the upper limit of Rz is usually about 90%, and from the viewpoint of maintaining the strength of the film, it is preferably 80% or less.
尚且，算術平均粗度Ra及最大高度Rz係依據JIS B0601所測得之值。 Further, the arithmetic mean roughness Ra and the maximum height Rz are values measured in accordance with JIS B0601.
由本發明之製造方法所得之n型有機半導體薄膜之游離電位之下限值，通常在6.0eV以上，以6.025eV以上為佳，較佳為6.05eV以上，較更佳為6.075eV以上，上限值係通常在6.3eV以下，以6.275eV以下為佳，較佳為6.25eV以下，較更佳為6.225eV以下，再更佳為6.2eV。游離電位之值係能藉由變更燒成溫度進行調整。 The lower limit of the free 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, preferably 6.05 eV or more, more preferably 6.075 eV or more, and the upper limit. The value is usually 6.3 eV or less, preferably 6.275 eV or less, preferably 6.25 eV or less, more preferably 6.225 eV or less, still more preferably 6.2 eV. The value of the free potential can be adjusted by changing the firing temperature.
藉由以上所說明之製造方法所得之n型半導體薄膜，由於其之大表面積及游離電位，故適宜使用於有機薄膜太陽能電池，尤其係適宜使用於具有超階層奈米構造之半導體層之太陽能電池。 The n-type semiconductor thin film obtained by the above-described manufacturing method is suitably used for an organic thin film solar cell due to its large surface area and free potential, and is particularly suitable for use in a solar cell having a semiconductor layer of a super-hierarchical nanostructure. .
以下，例舉實施例及比較例更具體地說明本發明，但本發明並非係受到下述實施例所限定者。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples.
(1)表面觀察：Dimension ICON(Bruker AXS公司製) (1) Surface observation: Dimension ICON (manufactured by Bruker AXS)
(2)游離電位測量：AC-3(理研計器(股)製) (2) Measurement of free potential: AC-3 (manufactured by Rikenji Co., Ltd.)
(3)膜厚測量：S-4300型電場釋出型掃描電子顯微鏡((股)日立高科技製) (3) Film thickness measurement: S-4300 electric field release scanning electron microscope ((Hybrid) Hitachi High-Tech)
在氮環境下，混合以國際公開第2010/055898號中記載之方法所合成之式(4a)所表示之富勒烯衍生物50mg與氯仿1.0mL，在室溫充分攪拌而調製成溶液。在同樣環境下，藉由旋轉塗佈法(1500rpm、30秒)將取得之濃褐色透明溶液塗佈於矽晶圓上，使用加熱板，以500℃燒成10分鐘而形成富勒烯薄膜。 In a nitrogen atmosphere, 50 mg of the fullerene derivative represented by the formula (4a) synthesized by the method described in International Publication No. 2010/055898 and 1.0 mL of chloroform were mixed and stirred at room temperature to prepare a solution. In the same environment, the obtained thick brown transparent solution was applied onto a ruthenium wafer by a spin coating method (1500 rpm, 30 seconds), and fired at 500 ° C for 10 minutes using a hot plate to form a fullerene film.
確認製成之薄膜之膜厚剖面之結果，膜厚為170nm。 As a result of confirming the film thickness profile of the produced film, the film thickness was 170 nm.
除以350℃燒成10分鐘以外，與實施例1相同之方法形成富勒烯薄膜。 A fullerene film was formed in the same manner as in Example 1 except that it was baked at 350 ° C for 10 minutes.
確認製成之薄膜之膜厚剖面之結果，膜厚為220nm。 As a result of confirming the film thickness profile of the produced film, the film thickness was 220 nm.
除以100℃燒成10分鐘以外，與實施例1相同之方法形成富勒烯薄膜。 A fullerene film was formed in the same manner as in Example 1 except that it was baked at 100 ° C for 10 minutes.
施行實施例1及比較例1、2中製成之富勒烯薄膜之表面觀察及游離電位之測量。分別將實施例1及比較例1、2之富勒烯薄膜之表面照片展示於圖1~3。又，將各薄膜之算術平均粗度(Ra)、最大高度(Rz)及游離電位展示於表1。 The surface observation and the measurement of the free potential of the fullerene film prepared in Example 1 and Comparative Examples 1 and 2 were carried out. The surface photographs of the fullerene films of Example 1 and Comparative Examples 1 and 2 are shown in Figs. 1 to 3, respectively. Further, the arithmetic mean roughness (Ra), the maximum height (Rz), and the free potential of each film are shown in Table 1.
如表1及圖1~3所示，可得知實施例1及比較例1之富勒烯薄膜之表面粗度(Ra及Rz)係較比較例2之薄膜還高，藉由在350℃以上之高溫下進行燒成，即可形成更多數之更具有高低差之凹凸。 As shown in Table 1 and Figures 1 to 3, it was found that the surface roughness (Ra and Rz) of the fullerene films of Example 1 and Comparative Example 1 was higher than that of the film of Comparative Example 2, at 350 ° C. When the above-mentioned high temperature is fired, a larger number of irregularities having a height difference can be formed.
更進一步，亦得知在500℃下燒成之實施例1之薄膜具有6.0eV以上之適宜n型半導體之游離電位，且與無修飾富勒烯具有相同程度之游離電位(6.1eV)，且也得知藉由在高溫進行燒成，可提升薄膜之游離電位。 Further, it is also known that the film of Example 1 fired at 500 ° C has a free potential of a suitable n-type semiconductor of 6.0 eV or more and has the same degree of free potential (6.1 eV) as the unmodified fullerene, and It is also known that the free potential of the film can be raised by firing at a high temperature.
如以上所述，本發明之n型半導體由於其之游離電位特性，故係為能取代無修飾富勒烯而使用者，又，由於其之高表面積，藉由將此使用作為有機太陽能電池之n型半導體，即可期待無修飾富勒烯所無法實現之高轉換效率。 As described above, the n-type semiconductor of the present invention is a user capable of replacing unmodified fullerenes due to its free potential characteristics, and because of its high surface area, it is used as an organic solar cell. An n-type semiconductor can expect high conversion efficiency that cannot be achieved without modified fullerene.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013129443 | 2013-06-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201500346A TW201500346A (en) | 2015-01-01 |
| TWI602809B true TWI602809B (en) | 2017-10-21 |
Family
ID=52104619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW103128787A TWI602809B (en) | 2013-06-20 | 2014-06-20 | Method for producing n-type organic semiconductor thin film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6222229B2 (en) |
| KR (1) | KR102185609B1 (en) |
| CN (1) | CN105308729B (en) |
| TW (1) | TWI602809B (en) |
| WO (1) | WO2014203887A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106463564A (en) * | 2014-07-31 | 2017-02-22 | 富士胶片株式会社 | Photoelectric conversion element and imaging element |
| KR20210153243A (en) | 2020-06-10 | 2021-12-17 | 박문석 | A mixture for the production of the N-type semiconductor of piezoelectric element of P, N semiconductor type |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7850778B2 (en) * | 2005-09-06 | 2010-12-14 | Lemaire Charles A | Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4853779B2 (en) * | 2006-08-01 | 2012-01-11 | 独立行政法人産業技術総合研究所 | Organic thin film solar cell |
| JPWO2009084078A1 (en) * | 2007-12-27 | 2011-05-12 | パイオニア株式会社 | Organic semiconductor device, organic solar cell and display panel |
| TWI477489B (en) * | 2008-11-14 | 2015-03-21 | 學校法人君淵學園 崇城大學 | An n-type semiconductor composed of a fullerene compound |
| CN102939673B (en) * | 2010-04-08 | 2018-05-15 | 密歇根大学董事会 | The bulk heterojunction device of the enhancing prepared by heat and solvent vapo(u)r annealing method |
| WO2011136800A1 (en) * | 2010-04-30 | 2011-11-03 | Northwestern University | Organic photovoltaic device with interfacial layer and method of fabricating same |
| JP2011258944A (en) * | 2010-05-13 | 2011-12-22 | Nissan Chem Ind Ltd | Organic solar cell prepared using fullerene derivative |
| JP5979710B2 (en) * | 2012-04-12 | 2016-08-31 | 日産化学工業株式会社 | Fullerene derivative and organic solar cell using the same |
-
2014
- 2014-06-17 WO PCT/JP2014/066006 patent/WO2014203887A1/en active Application Filing
- 2014-06-17 JP JP2015522928A patent/JP6222229B2/en active Active
- 2014-06-17 KR KR1020157035781A patent/KR102185609B1/en active IP Right Grant
- 2014-06-17 CN CN201480034764.0A patent/CN105308729B/en active Active
- 2014-06-20 TW TW103128787A patent/TWI602809B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7850778B2 (en) * | 2005-09-06 | 2010-12-14 | Lemaire Charles A | Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160022824A (en) | 2016-03-02 |
| KR102185609B1 (en) | 2020-12-02 |
| WO2014203887A1 (en) | 2014-12-24 |
| JP6222229B2 (en) | 2017-11-01 |
| CN105308729A (en) | 2016-02-03 |
| JPWO2014203887A1 (en) | 2017-02-23 |
| TW201500346A (en) | 2015-01-01 |
| CN105308729B (en) | 2018-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Phung et al. | Enhanced self-assembled monolayer surface coverage by ALD NiO in pin perovskite solar cells | |
| Niu et al. | Interfacial engineering at the 2D/3D heterojunction for high-performance perovskite solar cells | |
| Xie et al. | Enhanced performance of perovskite CH3NH3PbI3 solar cell by using CH3NH3I as additive in sequential deposition | |
| ES2897728T3 (en) | Two-stage deposition process | |
| ES2399728T3 (en) | Copper complexes for optoelectronic applications | |
| Camacho et al. | Carbon nanotube arrays for photovoltaic applications | |
| Zhao et al. | Facile deposition of high-quality Cs2AgBiBr6 films for efficient double perovskite solar cells | |
| US20140326981A1 (en) | Heteroleptic copper complexes for optoelectronic uses | |
| KR102550275B1 (en) | Composition comprising an organic semiconductor and a metal complex | |
| Chen et al. | Fully solution processed pin organic solar cells with an industrial pigment–Quinacridone | |
| Gao et al. | Freestanding atomically-thin cuprous oxide sheets for improved visible-light photoelectrochemical water splitting | |
| US20130255762A1 (en) | Passivation layer for solar cells and method for manufacturing the same | |
| TW201522679A (en) | Amine precursors for depositing graphene | |
| Tockhorn et al. | Improved quantum efficiency by advanced light management in nanotextured solution-processed perovskite solar cells | |
| Dai et al. | Formulation engineering for optimizing ternary electron acceptors exemplified by isomeric PC 71 BM in planar perovskite solar cells | |
| TWI602809B (en) | Method for producing n-type organic semiconductor thin film | |
| JP2016508137A (en) | Binuclear metal (I) complexes for optoelectronic applications | |
| CN110194718B (en) | Preparation method of highly stable lead-based organic-inorganic hybrid perovskite nanosheet | |
| CN104716263A (en) | Method for preparing mixed halide compound perovskite CH3NH3PbI3-xClx gradient optical film | |
| Gu et al. | Growth of covalently bonded Sierpiński triangles up to the second generation | |
| Abisdris et al. | Electrophoretic deposition of supramolecular complexes for the formation of carbon nitride films | |
| Adhikari et al. | Structural, optical, electrochemical and photovoltaic studies of spider web like silver indium diselenide quantum dots synthesized by ligand mediated colloidal sol-gel approach | |
| Yin et al. | CH3NH3PbBr3–x I x Quantum Dots Enhance Bulk Crystallization and Interface Charge Transfer for Efficient and Stable Perovskite Solar Cells | |
| Cao et al. | Precursor Engineering of Vapor-Exchange Processes for 20%-Efficient 1 cm2 Inverted-Structure Perovskite Solar Cells | |
| JP5979710B2 (en) | Fullerene derivative and organic solar cell using the same |