JP2016139710A - Organic transistor with organic semiconductor layer containing organic semiconductor material characterized by bent thienothiophene skeleton having thiophenes at ends - Google Patents
Organic transistor with organic semiconductor layer containing organic semiconductor material characterized by bent thienothiophene skeleton having thiophenes at ends Download PDFInfo
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- JP2016139710A JP2016139710A JP2015013913A JP2015013913A JP2016139710A JP 2016139710 A JP2016139710 A JP 2016139710A JP 2015013913 A JP2015013913 A JP 2015013913A JP 2015013913 A JP2015013913 A JP 2015013913A JP 2016139710 A JP2016139710 A JP 2016139710A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 28
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical group S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229930192474 thiophene Natural products 0.000 title claims abstract description 17
- 150000003577 thiophenes Chemical class 0.000 title abstract 3
- 239000000126 substance Substances 0.000 claims description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 125000001424 substituent group Chemical group 0.000 claims description 36
- -1 n -Hexyl Chemical group 0.000 claims description 35
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000000304 alkynyl group Chemical group 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 claims description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000004991 fluoroalkenyl group Chemical group 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000005743 methylethenyl group Chemical group [H]\C(*)=C(\[H])C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl 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])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 229920000052 poly(p-xylylene) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 235000019423 pullulan Nutrition 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical class CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RWBMMASKJODNSV-UHFFFAOYSA-N [1]benzothiolo[2,3-g][1]benzothiole Chemical compound C1=CC=C2C3=C(SC=C4)C4=CC=C3SC2=C1 RWBMMASKJODNSV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical group C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- BOCFGAMKSYQRCI-UHFFFAOYSA-N dinaphtho[2,3-b:2',3'-d]furan Chemical compound C1=CC=C2C=C3C4=CC5=CC=CC=C5C=C4OC3=CC2=C1 BOCFGAMKSYQRCI-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- VGWBXRXNERKBSJ-UHFFFAOYSA-N dithieno[2,3-a:2',3'-d]thiophene Chemical compound C1=CSC2=C1SC1=C2SC=C1 VGWBXRXNERKBSJ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QHIRVZBLPRTQQO-UHFFFAOYSA-I pentafluorotungsten Chemical compound F[W](F)(F)(F)F QHIRVZBLPRTQQO-UHFFFAOYSA-I 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 230000005610 quantum mechanics Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical group C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000005428 wave function Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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Abstract
Description
本発明は、本願発明者等が先にした特許出願（特願２０１４−２６６９１９ 出願日：平２６．１２．２８ 以下、先出願とする。）に係わる、末端にチオフェンを有する屈曲型のチエノチオフェン骨格を特徴とする有機半導体材料（以下、先出願に係わる有機半導体材料とする。）を使用する有機トランジスタの特性に関する。 The present invention relates to a bent-type thienothiophene having a thiophene at the end according to a patent application previously filed by the inventors of the present application (Japanese Patent Application No. 2014-266919 filing date: Hei 26.12.28, hereinafter referred to as a prior application). The present invention relates to characteristics of an organic transistor using an organic semiconductor material characterized by a skeleton (hereinafter referred to as an organic semiconductor material according to an earlier application).
本願は先出願に係わる有機半導体材料を使用する有機トランジスタに関する発明であり、本願では、先出願の記載を引用する場合が多くあることに留意されたい。 It should be noted that the present application is an invention related to an organic transistor using an organic semiconductor material according to an earlier application, and the description of the earlier application is often cited in the present application.
有機半導体は、有機ＥＬや電子ペーパーなどのフレキシブルディスプレーへの応用が期待され、ウェットプロセスである塗布や印刷によって大面積の素子を、シリコン半導体よりも低コストで作製できることが期待されている。このようなウェットプロセスへ適応させるために、溶媒への溶解性を高め、また熱安定性や耐酸化性等の安定性のある有機半導体材料が求められている。 Organic semiconductors are expected to be applied to flexible displays such as organic EL and electronic paper, and it is expected that a large-area element can be produced at a lower cost than silicon semiconductors by application or printing, which are wet processes. In order to adapt to such a wet process, there is a demand for an organic semiconductor material having improved solubility in a solvent and having stability such as thermal stability and oxidation resistance.
高いキャリア移動度を有するペンタセンやテトラセン等のポリアセン化合物は、有機半導体材料として古くから知られている。しかし、このポリアセン化合物は、光や酸化に対して不安定であり、更に有機溶媒への溶解性が低いためウェットプロセスに利用することが困難である。そこで、化学的安定性や溶解度を改善するため、アセン骨格の一部に硫黄やセレン等のカルコゲン元素を導入したベンゾチエノベンゾチオフェン (以下、ＢＴＢＴとする。)やジナフトチエノチオフェン (以下、ＤＮＴＴとする。 )などが多数検討されている。 Polyacene compounds such as pentacene and tetracene having high carrier mobility have long been known as organic semiconductor materials. However, this polyacene compound is unstable to light and oxidation, and further has low solubility in an organic solvent, so that it is difficult to use it in a wet process. Therefore, in order to improve chemical stability and solubility, benzothienobenzothiophene (hereinafter referred to as BTBT) or dinaphthothienothiophene (hereinafter referred to as DNTT) in which a chalcogen element such as sulfur or selenium is introduced into a part of the acene skeleton. ) Etc. are being studied.
ＤＮＴＴの中でも非特許文献１、特許文献１に記載のジナフト［２，３−ｂ：２’，３’−ｆ］チエノ［３，２−ｂ］チエノチオフェン（以下，本非特許文献１の提案者は、この有機半導体をＤＮＴＴと称しているが、ここでは２，３−ＤＮＴＴとする。）は、キャリアー移動度が２．０ｃｍ２／Ｖｓと高い値を示すことが報告されている。しかし、２，３−ＤＮＴＴは、溶液状態で安定であるが、その溶解度は、室温でジクロロメタン１リットル中３．４４ｍｇであり、溶解性が低く、ウェットプロセスに利用することが困難である。
Among the DNTTs, dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thienothiophene described in
そこで、本願発明者等は、２，３−ＤＮＴＴとは別に溶媒中で安定であり、かつ、溶解性の高いジナフト［２，１−ｂ：２’，１’−ｆ］チエノ［３，２−ｂ］チオフェン（以下２，１−ＤＮＴＴとする。）を開発し特許権を取得した。(特許文献２、特許文献３)
また、２，１−ＤＮＴＴと異性体関係にあるジナフト［１，２−ｂ：１‘，２’−ｆ］チエノ［３，２−ｂ］チオフェン（以下１，２−ＤＮＴＴとする。）も特許文献２、３と同一の出願人により特許されている(特許文献４)。
Therefore, the inventors of the present application have found that dinaphtho [2,1-b: 2 ′, 1′-f] thieno [3,2] that is stable in a solvent apart from 2,3-DNTT and has high solubility. -B] thiophene (hereinafter referred to as 2,1-DNTT) was developed and patented. (
In addition, dinaphtho [1,2-b: 1 ′, 2′-f] thieno [3,2-b] thiophene (hereinafter referred to as 1,2-DNTT) which has an isomer relationship with 2,1-DNTT is also used. Patented by the same applicant as
以下に、２，３−ＤＮＴＴ、２，１−ＤＮＴＴ、１，２−ＤＮＴＴの一般式を下記の［化Ａ１］、［化Ａ２］、［化Ａ３］に示す。
［化Ａ１］
[Chemical A1]
一方、２，３−ＤＮＴＴ類似の構造を有する縮合多環芳香族化合物において、中心のヘテロ環部分に隣接する芳香族環に置換基を導入することによって、縮合多環芳香族化合物の溶解度が改良されることを見出した特許出願もある(特許文献５)。 On the other hand, in a condensed polycyclic aromatic compound having a structure similar to 2,3-DNTT, the solubility of the condensed polycyclic aromatic compound is improved by introducing a substituent into the aromatic ring adjacent to the central heterocyclic portion. There is also a patent application that has been found (Patent Document 5).
また、有機半導体では、分子構造が直線的な場合、温度が高くなるに従い動きやすくなり、それによって分子状態が変化し不安定となる傾向があることが明らかとなっている。そのため、ジグザグな構造を求められ、化学的及び物理的に安定で、かつ、高いキャリア移動度を示すＷ型構造を取るジナフトチオフェン及びジナフトチオフェン以外の化合物を有機半導体とする特許文献もある(特許文献６)。特許文献６のＷ型構造の化学式を［化Ａ４］に示す。
［化Ａ４］
[Chemical A4]
本願発明者等の特許権に係わる発明である２，１−ＤＮＴＴの末端のベンゼン環をチオフェン環に置き換えた屈曲型のチエノチオフェン骨格の有機半導体材料、ジ(ベンゾ［ｂ］チエノ)［５，４―ｂ：５’，４’―ｆ］チエノ［３，２―ｂ］チオフェン（以下、略称を５４ＤＢＴ３とする。）を検討した結果、特許文献７にジ(ベンゾ［ｂ］チエノ)［４，５―ｂ：４’，５’―ｆ］チエノ［３，２―ｂ］チオフェン（以下、略称４５ＤＢＴ３とする。）が見出された。４５ＤＢＴ３の一般式を［化Ａ５］に示す。
なお、４５ＤＢＴ３は１，２−ＤＮＴＴの端末のベンゼン環をチオフェン環に置き換えた有機半導体材料である。
［化Ａ５］
Incidentally, 45DBT 3 is an organic semiconductor material replacing the benzene ring of the
[Chemical A5]
これまで、２，１−ＤＮＴＴ誘導体よりも１，２−ＤＮＴＴ誘導体は、溶解性が悪く、閾値電圧が高いという問題があった。この理由の一つとして、１，２−ＤＮＴＴのＨＯＭＯレベル（計算値）が−５．５６ｅＶと、２，１−ＤＮＴＴのＨＯＭＯレベル（計算値）の−５．４０ｅＶよりも深く、電極の仕事関数との差が大きくなり、正孔注入障壁が大きくなるものと考えられた。 So far, 1,2-DNTT derivatives have poor solubility and higher threshold voltage than 2,1-DNTT derivatives. One reason for this is that the HOMO level (calculated value) of 1,2-DNTT is −5.56 eV, which is deeper than the HOMO level (calculated value) of −5.40 eV of 2,1-DNTT. It was thought that the difference from the function increased and the hole injection barrier increased.
１，２−ＤＮＴＴと２，１−ＤＮＴＴの関係のような、４５ＤＢＴ３とは異なり、より屈折した分子構造を持つ異性体の方が、ＨＯＭＯレベルも浅くなると推察され、また、２，１−ＤＮＴＴの端末のベンゼン環をチオフェン環に置き換えることで、末端の硫黄原子によって、２，１−ＤＮＴＴよりも分子間相互作用が強くなり、耐熱性も向上すると推測されることから、合成を試みた。その結果、耐熱性に優れ、有機溶媒に溶けやすい、末端にチオフェンを有する屈曲型のチエノチオフェン骨格を特徴とする有機半導体材料を発明し、これを先出願とした。
1, 2-DNTT and like
そして、先出願に係わる有機半導体材料(以下、本有機半導体材料とする場合がある。)の物性を検討するため、４５ＤＢＴ３と本有機半導体材料との分子軌道計算を行った。その結果は後述するが、後者の方が、前者に比較し、ＨＯＭＯレベルがＡｕ電極の仕事関数に近いため、正孔の注入障壁が小さく、Ａｕ電極から半導体層へ正孔が注入しやすくなり、より低電圧で駆動するようになり、トランジスタ性能が向上すると推察された。 Then, in order to examine the physical properties of the organic semiconductor material (hereinafter sometimes referred to as the present organic semiconductor material) according to the previous application, molecular orbital calculation between 45DBT 3 and the present organic semiconductor material was performed. Although the result will be described later, the latter has a lower HOMO level than the work function of the Au electrode, and therefore has a smaller hole injection barrier and facilitates the injection of holes from the Au electrode into the semiconductor layer. It is assumed that the transistor performance is improved by driving at a lower voltage.
解決しようとする課題は、先出願に係わる末端にチオフェンを有する屈曲型のチエノチオフェン骨格を特徴とする有機半導体材料を、有機半導体層に使用し、良好なトランジスタ性能を有する有機トランジスタを提供するものである。 The problem to be solved is to provide an organic transistor having good transistor performance by using an organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at the terminal according to the prior application for an organic semiconductor layer It is.
参考のため、先出願に係わる有機半導体材料の一般式を［化８］に示す。
［化８］
[Chemical 8]
すなわち、第１発明は、下記の化学式［化１］で示される末端にチオフェンを有する屈曲型のチエノチオフェン骨格を特徴とする化合物を有機半導体層に使用する有機トランジスタである。
［化１］
[Chemical 1]
化学式〔化１〕中の置換基Ｒ１からＲ８は、水素原子及びハロゲン原子、炭素数が３から６０のアリール基、炭素数が３から６０の複素環基、炭素数が１から３０のアルキル基、炭素数が２から３０のアルケニル基、炭素数が２から３０のアルキニル基、炭素数が１から３０のアルコキシル基、炭素数が１から６０のアミノ基、炭素数が１から３０のアミド基、炭素数が１から３０のイミノ基、炭素数が１から３０のカルボキシル基、ヒドロキシル基、炭素数が１から３０のエステル基、ニトロ基、ニトリル基、炭素数が１から３０のスルフィド基、メルカプト基、炭素数が１から３０のスルホニル基、炭素数が１から６０のシリル基のうち、少なくとも一つを含み、これらの各基は置換基を有していてもよい。なお、置換基Ｒ１からＲ８の好ましい例は、水素原子、フッ素原子、アリール基、複素環基、アルキル基、アルケニル基、アルキニル基、アミノ基である。 The substituents R 1 to R 8 in the chemical formula [Chemical Formula 1] are a hydrogen atom and a halogen atom, an aryl group having 3 to 60 carbon atoms, a heterocyclic group having 3 to 60 carbon atoms, and 1 to 30 carbon atoms. Alkyl group, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 30 carbon atoms, alkoxyl group having 1 to 30 carbon atoms, amino group having 1 to 60 carbon atoms, 1 to 30 carbon atoms Amido group, imino group having 1 to 30 carbon atoms, carboxyl group having 1 to 30 carbon atoms, hydroxyl group, ester group having 1 to 30 carbon atoms, nitro group, nitrile group, sulfide having 1 to 30 carbon atoms It includes at least one of a group, a mercapto group, a sulfonyl group having 1 to 30 carbon atoms, and a silyl group having 1 to 60 carbon atoms, and each of these groups may have a substituent. Preferred examples of the substituents R 1 to R 8 are a hydrogen atom, a fluorine atom, an aryl group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, and an amino group.
置換基Ｒ１からＲ８における、ハロゲン原子はフッ素、塩素、臭素、ヨウ素であり、好ましい例はフッ素原子である。 In the substituents R 1 to R 8 , the halogen atom is fluorine, chlorine, bromine or iodine, and a preferred example is a fluorine atom.
置換基Ｒ１からＲ８における、アリール基は炭素数が３から６０の芳香環基で、例えば、フェニル基、１−ナフチル基、２−ナフチル基、ビフェニル基、ターフェニル基、アントリル基、フェナントリル基、クリセンなどが挙げられ、これらの各基は置換基を有していてもよい。 In the substituents R 1 to R 8 , the aryl group is an aromatic ring group having 3 to 60 carbon atoms, such as a phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl group, terphenyl group, anthryl group, phenanthryl. Group, chrysene and the like, and each of these groups may have a substituent.
置換基Ｒ１からＲ８における、複素環基は炭素数が３から６０の複素環基で、ピリジン、ピラジン、トリアジン、ピロール、キノリン、チオフェン、ベンゾチオフェン、ジベンゾチオフェン、チエノチオフェン、フラン、ベンゾフラン、ジベンゾフラン、チアゾール、ベンゾチアゾールなどが挙げられ、これらの各基は置換基を有していてもよい。 The heterocyclic group in the substituents R 1 to R 8 is a heterocyclic group having 3 to 60 carbon atoms, such as pyridine, pyrazine, triazine, pyrrole, quinoline, thiophene, benzothiophene, dibenzothiophene, thienothiophene, furan, benzofuran, Dibenzofuran, thiazole, benzothiazole and the like can be mentioned, and each of these groups may have a substituent.
置換基Ｒ１からＲ８における、アルキル基は炭素数が１から３０の直鎖型、分岐型、環状型のアルキル基であり、例えば、メチル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、イソプロピル基、ｔ-ブチル基、シクロプロピル基、シクロヘキシル基、アダマンチル基、ｎ−トリフルオロメチル基などが挙げられ、これらの各基は置換基を有していてもよい。 In the substituents R 1 to R 8 , the alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, such as a methyl group, n-butyl group, n-pentyl group, n -Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, isopropyl, t-butyl, cyclopropyl , A cyclohexyl group, an adamantyl group, an n-trifluoromethyl group, and the like, and each of these groups may have a substituent.
置換基Ｒ１からＲ８における、アルケニル基は炭素数が２から３０のアルケニル基で、例えば、エテニル基、メチルエテニル基、（ｎ−オクチル）エテニル基、フェニルエテニル基、ナフチルエテニル基、ビフェニルエテニル基、ターフェニルエテニル基、パーフルオロフェニルエテニル基などが挙げられ、これらの各基は置換基を有していてもよい。 In the substituents R 1 to R 8 , the alkenyl group is an alkenyl group having 2 to 30 carbon atoms such as ethenyl group, methylethenyl group, (n-octyl) ethenyl group, phenylethenyl group, naphthylethenyl group, biphenylethenyl group. Group, terphenyl ethenyl group, perfluorophenyl ethenyl group and the like, and each of these groups may have a substituent.
置換基Ｒ1からＲ８における、アルキニル基は炭素数が２から３０のアルキニル基で、例えば、エチニル基、メチルエチニル基、（ｎ−オクチル）エチニル基、フェニルエチニル基、ナフチルエチニル基、ビフェニルエチニル基、ターフェニルエチニル基、パーフルオロフェニルエチニル基などが挙げられ、これらの各基は置換基を有していてもよい。 In the substituents R 1 to R 8 , the alkynyl group is an alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, methylethynyl group, (n-octyl) ethynyl group, phenylethynyl group, naphthylethynyl group, biphenylethynyl group. Group, terphenylethynyl group, perfluorophenylethynyl group and the like, and each of these groups may have a substituent.
置換基Ｒ１からＲ８における、アミノ基は炭素数が１から６０のアミノ基で、例えば、ジフェニルアミノ基、ジナフチルアミノ基、ジチエニルアミノ基、ジピリジルアミノ基などが挙げられ、これらの各基は置換基を有していてもよい。 In the substituents R 1 to R 8 , the amino group is an amino group having 1 to 60 carbon atoms, and examples thereof include a diphenylamino group, a dinaphthylamino group, a dithienylamino group, and a dipyridylamino group. The group may have a substituent.
前記置換基とは、水素原子及びハロゲン原子、アリール基、複素環基、アルキル基、フルオロアルキル基、アルケニル基、フルオロアルケニル基、アルキニル基、フルオロアルキニル基、アルコキシル基、フルオロアルコキシル基、アミノ基、アミド基、イミノ基、カルボキシル基、ヒドロキシル基、エステル基、ニトロ基、ニトリル基、スルフィド基、メルカプト基、スルホニル基、シリル基が挙げられる。 Examples of the substituent include a hydrogen atom and a halogen atom, an aryl group, a heterocyclic group, an alkyl group, a fluoroalkyl group, an alkenyl group, a fluoroalkenyl group, an alkynyl group, a fluoroalkynyl group, an alkoxyl group, a fluoroalkoxyl group, an amino group, Examples include amide group, imino group, carboxyl group, hydroxyl group, ester group, nitro group, nitrile group, sulfide group, mercapto group, sulfonyl group, and silyl group.
［化１］の正式名はジ(ベンゾ［ｂ］チエノ)［６，７―ｂ：６’，７’―ｆ］チエノ［３，２―ｂ］チオフェンであり、以下、略して６７ＤＢＴ３とする。 The formal name of [Chemical Formula 1] is di (benzo [b] thieno) [6,7-b: 6 ′, 7′-f] thieno [3,2-b] thiophene, hereinafter referred to as 67DBT 3 for short. To do.
第１発明に記載の化学式［化１］の６７ＤＢＴ３の有機半導体材料の合成過程を反応式［化４］に示すが、下記の合成法に限定されるものではなく、公知の反応を組み合わせて合成することが可能である。
［化４］
[Chemical formula 4]
２−ブロモチオフェノールを塩基性条件下で、２−ブロモアセトアルデヒドジエチルアセタールを作用させ、次にポリリン酸を作用させると、化合物Ａを合成することができる。上記以外の化合物Ａの合成法として、公知のベンゾ［ｂ］チオフェンの合成法を用いることができる。例えば、ｏ−ジブロモベンゼンや１−ブロモー２−ヨードベンゼンなどｏ−ジハロベンゼンに、ｎ−ＢｕＬｉなどの公知の有機リチウム試薬やＭｇなどを用いて有機金属化合物とし、硫黄を作用させ、２−ブロモアセトアルデヒドジエチルアセタールなど、２−ハロゲン化アセトアルデヒドジアルキルアセタールを用い、さらにポリリン酸や二リン酸等の酸触媒を用いることで化合物Ａを合成することができる。 Compound A can be synthesized by reacting 2-bromothiophenol under basic conditions with 2-bromoacetaldehyde diethyl acetal and then with polyphosphoric acid. As a method for synthesizing Compound A other than the above, a known method for synthesizing benzo [b] thiophene can be used. For example, an o-dihalobenzene such as o-dibromobenzene or 1-bromo-2-iodobenzene is converted into an organometallic compound using a known organolithium reagent such as n-BuLi or Mg, and sulfur is allowed to act on 2-bromoacetaldehyde. Compound A can be synthesized by using 2-halogenated acetaldehyde dialkyl acetal such as diethyl acetal and further using an acid catalyst such as polyphosphoric acid or diphosphoric acid.
化合物Ａにｎ−ＢｕＬｉなどの公知の有機リチウム試薬やＭｇなどを用いて、有機金属化合物とし、ＤＭＦやＮ−メチルホルムアニリドなど公知のホルミル化剤を作用させると、化合物Ｂを合成することができる。
化合物Ｂに臭素などのハロゲンや塩化チオニル等の公知のハロゲン化剤と硫黄を作用させることで、６７ＤＢＴ３を合成することができる。
Compound B can be synthesized by using a known organolithium reagent such as n-BuLi or Mg or the like as an organometallic compound and allowing a known formylating agent such as DMF or N-methylformanilide to act on compound A. it can.
67DBT 3 can be synthesized by allowing compound B to react with a halogen such as bromine or a known halogenating agent such as thionyl chloride and sulfur.
続いて、第２発明は、化学式［化２］で示される末端にチオフェンを有する屈曲型のチエノチオフェン骨格を特徴とする化合物を有機半導体層に使用する有機トランジスタである。
［化２］
[Chemical formula 2]
化学式［化２］の正式名はジ(ベンゾ［ｂ］チエノ)［５，４―ｂ：５’，４’―ｆ］チエノ［３，２―ｂ］チオフェンであり、５４ＤＢＴ３とする。 Full name of the chemical formula [Formula 2] is di (benzo [b] thieno) [5,4-b: 5 ' , 4'-f] a thieno [3,2-b] thiophene, and 54DBT 3.
化学式［化２］の化合物は、第１発明の化合物［化１］と同様にアルデヒドに臭素などのハロゲンや塩化チオニル等の公知のハロゲン化剤と硫黄を作用させることで、５４ＤＢＴ３を合成することができる。反応式を［化５］に示す。
［化５］
[Chemical formula 5]
続いて、第３発明は、化学式［化３］で示される末端にチオフェンを有する屈曲型のチエノチオフェン骨格を特徴とする化合物を有機半導体層に使用する有機トランジスタである。
［化３］
[Chemical formula 3]
化学式［化３］の正式名はジ(ベンゾ［ｃ］チエノ)［５，４―ｂ：５’，４’―ｆ］チエノ［３，２―ｂ］チオフェンであり、５４ＤＢＴ３−ｃとする。 The formal name of the chemical formula [Chemical Formula 3] is di (benzo [c] thieno) [5,4-b: 5 ′, 4′-f] thieno [3,2-b] thiophene, which is 54DBT 3 -c. .
化合物［化３］は［化１］と同様にアルデヒドに臭素などのハロゲンや塩化チオニル等の公知のハロゲン化剤と硫黄を作用させることで、５４ＤＢＴ３−ｃを合成することができる。反応式を［化６］に示す。
［化６］
[Chemical 6]
続いて、第４発明は、第１発明から第３発明に記載の化学式［化１］、［化２］、［化３］のいずれかの有機半導体材料の複数を組み合わせて有機半導体層に使用する有機トランジスタである。 Subsequently, the fourth invention is used for the organic semiconductor layer by combining a plurality of organic semiconductor materials of any one of the chemical formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 3] described in the first to third inventions. It is an organic transistor.
化学式［化１］、［化２］、［化３］のいずれかの有機半導体材料の中から２種類の有機半導体材料を選択し組み合わせる、又は３種類のすべてを選択し組み合わせてなる有機トランジスタである。 An organic transistor formed by selecting and combining two types of organic semiconductor materials from any one of the chemical formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 3], or by selecting and combining all three types. is there.
本発明の有機トランジスタを製作する際、有機半導体材料は、高純度化のために不純物の除去等の精製が必要になるが、本発明の化合物は、液体クロマトグラフィー法、昇華法、ゾーンメルティング法、ゲルパーミェーションクロマトグラフィー法、再結晶法などによって精製できる。 When producing the organic transistor of the present invention, the organic semiconductor material needs to be purified to remove impurities in order to achieve high purity. However, the compound of the present invention can be obtained by liquid chromatography, sublimation, zone melting. Purification by gel permeation chromatography method, recrystallization method and the like.
また、本発明の有機トランジスタを製作する際、有機半導体材料は、主として薄膜の形態で用いられるが、その薄膜作製法として、ウェットプロセスとドライプロセスどちらを使用してもよい。本発明の化合物は、有機溶媒等への溶解させることにより、産業上メリットの大きいウェットプロセスに適応できる。 Further, when the organic transistor of the present invention is manufactured, the organic semiconductor material is mainly used in the form of a thin film, and either a wet process or a dry process may be used as a method for forming the thin film. The compound of the present invention can be applied to a wet process having a large industrial merit by dissolving it in an organic solvent or the like.
ここで、有機溶媒としては、例えば、ジクロロメタン、クロロホルム、クロロベンゼン、シクロヘキサノール、トルエン、キシレン、ニトロベンゼン、メチルエチルケトン、ジグライム、テトラヒドロフランなど、これまで公知のものが使用できる。これらの溶媒は、一種類もしくは二種類以上の混合物を用いても良い。また、本発明の化合物を有機溶媒等へ溶解させる場合、温度や圧力に特に制限は無いが、溶解させる温度に関しては、０〜２００℃の範囲が好ましく、さらに好ましくは、１０〜１５０℃の範囲である。また、溶解させる圧力に関しては、０．１〜１００ＭＰａの範囲が好ましく、さらに好ましくは、０．１〜１０ＭＰａの範囲である。また、有機溶媒の代わりに、超臨界二酸化炭素のようなものを用いることも可能である。 Here, as the organic solvent, for example, known solvents such as dichloromethane, chloroform, chlorobenzene, cyclohexanol, toluene, xylene, nitrobenzene, methyl ethyl ketone, diglyme, and tetrahydrofuran can be used. These solvents may be used singly or as a mixture of two or more. In addition, when the compound of the present invention is dissolved in an organic solvent or the like, the temperature and pressure are not particularly limited, but the temperature for dissolution is preferably in the range of 0 to 200 ° C, more preferably in the range of 10 to 150 ° C. It is. Moreover, regarding the pressure to melt | dissolve, the range of 0.1-100 MPa is preferable, More preferably, it is the range of 0.1-10 MPa. Moreover, it is also possible to use something like supercritical carbon dioxide instead of the organic solvent.
ここで言うウェットプロセスとは、スピンコート法、ディップコート法、バーコート法、スプレーコート法、インクジェット法、スクリーン印刷法、平板印刷法、凹版印刷法、凸版印刷法などを示しており、これら公知の方法が利用できる。
また、ここで言うドライプロセスとは、真空蒸着法、スパッタリング法、ＣＶＤ法、レーザー蒸着法、分子線エピタキシャル成長法、気相輸送成長法などを示しており、これら公知の方法が利用できる。
The wet process here refers to a spin coating method, a dip coating method, a bar coating method, a spray coating method, an ink jet method, a screen printing method, a lithographic printing method, an intaglio printing method, a relief printing method, and the like. Can be used.
In addition, the dry process mentioned here indicates a vacuum deposition method, a sputtering method, a CVD method, a laser deposition method, a molecular beam epitaxial growth method, a vapor phase transport growth method, and the like, and these known methods can be used.
本発明の有機トランジスタには、電極が使用されるが、その導電性材料としては特に限定はなく、例えば、金、銅、銀、ニッケル、クロム、鉄、スズ、アルミニウム、インジウム、パラジウム、ゲルマニウム、カルシウム、ナトリウム、カリウム、マグネシウム、マンガン、チタン、リチウム、亜鉛、タングステン、モリブデン、酸化スズ、酸化インジウム、銀ペースト、カーボンペースト、ＩＴＯ、ＰＥＤＯＴ／ＰＳＳなどが挙げられる。これらの電極は、一種類もしくは二種類以上の混合物を用いても良い。 An electrode is used for the organic transistor of the present invention, but the conductive material is not particularly limited. For example, gold, copper, silver, nickel, chromium, iron, tin, aluminum, indium, palladium, germanium, Examples include calcium, sodium, potassium, magnesium, manganese, titanium, lithium, zinc, tungsten, molybdenum, tin oxide, indium oxide, silver paste, carbon paste, ITO, and PEDOT / PSS. These electrodes may use one kind or a mixture of two or more kinds.
本発明の有機トランジスタには、ゲート絶縁膜が使用されるが、その絶縁膜としては特に限定はなく、ポリメチルメタクリレート、パリレン、ポリスチレン、ポリアクリロニトリル、ポリイミド、ポリアミド、ポリビニルフェノール、ポリビニルアルコール、ポリフッ化ビニリデン、シアノエチルプルラン、ＣＹＴＯＰ
のような有機絶縁膜や、酸化ケイ素、酸化アルミニウム、酸化タンタル、酸化チタン、酸化スズ、チタン酸バリウム、チタン酸ストロンチウムなどの無機絶縁膜を用いることができる。なお、ＣＹＴＯＰとは、アモルファス（非晶質）構造を有するフッ素樹脂で、透明性があり、コーティング剤、絶縁膜等に使用される。
In the organic transistor of the present invention, a gate insulating film is used, but the insulating film is not particularly limited, and polymethyl methacrylate, parylene, polystyrene, polyacrylonitrile, polyimide, polyamide, polyvinyl phenol, polyvinyl alcohol, polyfluoride. Vinylidene, cyanoethyl pullulan, CYTOP
An inorganic insulating film such as silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, barium titanate, strontium titanate, or the like can be used. Note that CYTOP is a fluororesin having an amorphous structure and is transparent and is used for a coating agent, an insulating film, and the like.
本発明のトランジスタにおいて、有機半導体層は、ドーピング処理を施されていてもよい。ドーパントとしては、ドナー性のドーパントとアクセプター性のドーパントを用いることができる。ドナー性のドーパントとしては、有機半導体に、電子を供与できる化合物であれば、好適に用いる事ができる。例えば、リチウム、ナトリウム、カリウムなどのアルカリ金属や、カルシウム、ストロンチウム、バリウムなどのアルカリ土類金属。イットリウム、ランタン、ユーロピウム、などの希土類金属。テトラアルキルアンモニウム、テトラアルキルホスホニウムなどのカチオンが挙げられる。 In the transistor of the present invention, the organic semiconductor layer may be subjected to doping treatment. As the dopant, a donor-type dopant and an acceptor-type dopant can be used. As the donor dopant, any compound that can donate electrons to the organic semiconductor can be preferably used. For example, alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as calcium, strontium and barium. Rare earth metals such as yttrium, lanthanum and europium. Cations such as tetraalkylammonium and tetraalkylphosphonium can be mentioned.
アクセプター性のドーパントとしては、有機半導体から、電子を取り去ることができる化合物であれば好適に用いる事ができる。例えば、塩素、臭素、ヨウ素、塩化ヨウ素、臭化ヨウ素などのハロゲン化合物。五フッ化リン、三フッ化ホウ素、三塩化ホウ素、三臭化ホウ素などのルイス酸、フッ化水素、硫酸、硝酸などのプロトン酸、酢酸、ギ酸、アミノ酸などの有機酸。三塩化鉄、四塩化チタン、四塩化ジルコニウム、五フッ化タングステン、六塩化タングステンなどの遷移金属化合物塩化物イオン、臭化物イオン、ヨウ化物イオン、スルホン酸アニオンなどの電解質アニオンなどが挙げられる。 As the acceptor dopant, any compound that can remove electrons from an organic semiconductor can be preferably used. For example, halogen compounds such as chlorine, bromine, iodine, iodine chloride, iodine bromide. Lewis acids such as phosphorus pentafluoride, boron trifluoride, boron trichloride and boron tribromide, proton acids such as hydrogen fluoride, sulfuric acid and nitric acid, and organic acids such as acetic acid, formic acid and amino acids. Examples include transition metal compounds such as iron trichloride, titanium tetrachloride, zirconium tetrachloride, tungsten pentafluoride, tungsten hexachloride, electrolyte anions such as chloride ions, bromide ions, iodide ions, and sulfonate anions.
また、本発明の有機トランジスタは、物理的損傷から保護するために、有機トランジスタの全面あるいは一部に保護層を設けることもできる。保護層を形成する材料としては、特に限定はなく、ポリメチルメタクリレート、パリレン、ポリスチレン、ポリアクリロニトリル、ポリイミド、ポリアミド、ポリビニルフェノール、ポリビニルアルコール、ポリフッ化ビニリデン、シアノエチルプルラン、ＣＹＴＯＰのような有機化合物や、酸化ケイ素、酸化アルミニウム、酸化タンタル、酸化チタン、酸化スズ、チタン酸バリウム、チタン酸ストロンチウムなどの無機化合物を用いることができる。 Moreover, in order to protect the organic transistor of this invention from a physical damage, a protective layer can also be provided in the whole surface or a part of organic transistor. The material for forming the protective layer is not particularly limited, and an organic compound such as polymethyl methacrylate, parylene, polystyrene, polyacrylonitrile, polyimide, polyamide, polyvinyl phenol, polyvinyl alcohol, polyvinylidene fluoride, cyanoethyl pullulan, CYTOP, Inorganic compounds such as silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, barium titanate, and strontium titanate can be used.
本発明の有機トランジスタの使用例を、図１及び図２に示す。図１、図２では、電界効果型トランジスタ（以下ＦＥＴとする）での使用例を挙げている。ＦＥＴはその特徴から、スイッチング素子や増幅素子として利用される。ゲート電流が低いことに加え、構造が平面的であるため、ウェットプロセスによる作製や集積化が容易であり大面積化を可能とする。ここでは、本発明に使用する化合物は、主にｐ型半導体として利用されているが、置換基、溶剤によってｎ型半導体として機能する場合もある。 Examples of use of the organic transistor of the present invention are shown in FIGS. 1 and 2 show examples of use in a field effect transistor (hereinafter referred to as FET). FETs are used as switching elements and amplifying elements because of their characteristics. In addition to a low gate current, the structure is planar, so that fabrication and integration by a wet process are easy and a large area can be achieved. Here, although the compound used for this invention is mainly utilized as a p-type semiconductor, it may function as an n-type semiconductor by a substituent and a solvent.
第１発明ないし第３発明では、チエノチオフェン骨格を特徴とする有機半導体材料であるジナフト［２，１−ｂ：２’，１’−ｆ］チエノ［３，２−ｂ］チオフェン（略称２，１−ＤＮＴＴ）を用いた有機トランジスタと比較し、電界効果移動度や熱安定性が高く、かつ、本発明に係わる有機半導体の異性体である、ジ(ベンゾ［ｂ］チエノ)［４，５―ｂ：４’，５’―ｆ］チエノ［３，２―ｂ］チオフェン（略称４５ＤＢＴ３）よりも、ＨＯＭＯレベルが浅く、低電圧で駆動できると推定され、有機溶媒への溶解性が高くなるため、この有機半導体をウェットプロセスで有機トランジスタに使用することが容易になり、安価に生産することが可能となる。第４発明によれば請求項１ないし請求項３の化合物の有機トランジスタへの用途を明らかにして化合物の有効利用をより図ることができる。
In the first to third inventions, dinaphtho [2,1-b: 2 ′, 1′-f] thieno [3,2-b] thiophene (abbreviated as 2, an organic semiconductor material characterized by a thienothiophene skeleton) Di (benzo [b] thieno) [4,5, which is an isomer of the organic semiconductor according to the present invention and has high field effect mobility and thermal stability as compared with an organic transistor using 1-DNTT). -B: 4 ', 5'-f] thieno [3,2-b] thiophene (abbreviation: 45DBT 3 ) is estimated to have a shallow HOMO level and can be driven at a low voltage, and has high solubility in organic solvents. Therefore, it becomes easy to use this organic semiconductor for an organic transistor by a wet process, and it becomes possible to produce it at low cost. According to the fourth invention, it is possible to clarify the application of the compounds of
本発明の代表的な実施例を以下に挙げる。 Representative examples of the present invention are listed below.
前記反応式［化４］の６７ＤＢＴ３の合成過程の詳細を示す。しかし、本発明はこれらの実施例のみに限定されるものではない。
また、目的の化合物は必要に応じてＭＳ（質量分析スペクトル）、１Ｈ―ＮＭＲおよび１３Ｃ−ＮＭＲにより決定した。使用した機器は以下の通りである。
ＭＳ：ＡＢＳＣＩＥＸ Ｑ−ＳＴＡＲ
１Ｈ―ＮＭＲおよび１３Ｃ−ＮＭＲ：Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ ＭｅｒｃｕｒｙＰｌｕｓ
Showing details of the synthesis process of 67DBT 3 in the reaction [formula 4]. However, the present invention is not limited only to these examples.
The target compound was determined by MS (mass spectrometry spectrum), 1 H-NMR and 13 C-NMR as required. The equipment used is as follows.
MS: ABSCIEX Q-STAR
1 H-NMR and 13 C-NMR: Agilent Technologies MercuryPlus
ナトリウムｔ−ブトキシド０．５９ｇ（５．３ｍｍｏｌ）のＴＨＦ溶液１０ｍｌに２−ブロモベンゼンチオール０．５ｇ（２．６ｍｍｏｌ）のＴＨＦ溶液５ｍｌを滴下した。３０分撹拌後、２−ブロモアセトアルデヒドジエチルアセタール０．６２ｇ（３．２ｍｍｏｌ、１．２ｅｑ）を滴下し、室温で１時間撹拌した。反応液に水を加え、トルエンで抽出し、有機層を減圧濃縮後、ポリリン酸０．５ｇを加え、一晩撹拌した。反応液に水を加え、トルエンで抽出し、有機層を減圧濃縮後、化合物Ａ０．３ｇを収率５４％で得た。 To 10 ml of a THF solution of 0.59 g (5.3 mmol) of sodium t-butoxide, 5 ml of a THF solution of 0.5 g (2.6 mmol) of 2-bromobenzenethiol was added dropwise. After stirring for 30 minutes, 0.62 g (3.2 mmol, 1.2 eq) of 2-bromoacetaldehyde diethyl acetal was added dropwise, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with toluene. The organic layer was concentrated under reduced pressure, 0.5 g of polyphosphoric acid was added, and the mixture was stirred overnight. Water was added to the reaction solution, extraction was performed with toluene, and the organic layer was concentrated under reduced pressure to obtain 0.3 g of Compound A in a yield of 54%.
化合物Ａの１Ｈ−ＮＭＲおよび１３Ｃ−ＮＭＲの測定結果を以下に示す。
１Ｈ―ＮＭＲ（ＣＤＣｌ３， ４００．４ＭＨｚ）δ＝７．２３（１Ｈ，ｔ，Ｊ＝８．６Ｈｚ），７．４１（１Ｈ，ｄ，Ｊ＝５．５Ｈｚ），７．４７（１Ｈ，ｄ，Ｊ＝８．６Ｈｚ），７．４７（１Ｈ，ｄ，Ｊ＝５．３Ｈｚ），７．７４（１Ｈ，ｄｄ，Ｊ＝０．８Ｈｚ，８．６Ｈｚ）．
１３Ｃ−ＮＭＲ（ＣＤＣｌ３， １００．７ＭＨｚ）δ＝１１６．１，１２２．７，１２４．９，１２５．７，１２７．３，１２７．４，１４０．７，１４１．８．
The measurement results of 1 H-NMR and 13 C-NMR of Compound A are shown below.
1H-NMR (CDCl3, 400.4 MHz) δ = 7.23 (1H, t, J = 8.6 Hz), 7.41 (1H, d, J = 5.5 Hz), 7.47 (1H, d, J = 8.6 Hz), 7.47 (1H, d, J = 5.3 Hz), 7.74 (1H, dd, J = 0.8 Hz, 8.6 Hz).
13 C-NMR (CDCl 3 , 100.7 MHz) δ = 116.1, 122.7, 124.9, 125.7, 127.3, 127.4, 140.7, 141.8.
操作２
窒素雰囲気下、化合物Ａ０．３ｇ（１．４ｍｍｏｌ）のＴＨＦ溶液１０ｍｌにｉ−ＰｒＭｇＣｌ・ＬｉＣｌ（１Ｍ−ＴＨＦ溶液）を２．８ｍｌ（２．８ｍｍｏｌ、２ｅｑ）滴下し、室温で２時間撹拌後、０℃でＮ，Ｎ−ジメチルホルムアミド０．２９ｍｌ（４．２ｍｍｏｌ、３ｅｑ）を滴下し、滴下後室温に昇温後、塩酸で処理、トルエンで抽出し、有機層を減圧濃縮後、化合物Ｂを０．１５ｇ、収率６６％で得た。
Under a nitrogen atmosphere, 2.8 ml (2.8 mmol, 2 eq) of i-PrMgCl·LiCl (1M-THF solution) was added dropwise to 10 ml of a THF solution of 0.3 g (1.4 mmol) of Compound A, and the mixture was stirred at room temperature for 2 hours. At 0 ° C., 0.29 ml (4.2 mmol, 3 eq) of N, N-dimethylformamide was added dropwise. After dropping, the mixture was warmed to room temperature, treated with hydrochloric acid, extracted with toluene, and the organic layer was concentrated under reduced pressure. 0.15 g, 66% yield.
化合物Ｂの１Ｈ−ＮＭＲおよび１３Ｃ−ＮＭＲの測定結果を以下に示す。
１Ｈ―ＮＭＲ（ＣＤＣｌ３， ４００．４ＭＨｚ）δ＝７．４２（１Ｈ，ｄ，Ｊ＝５．５Ｈｚ），７．５６（１Ｈ，ｔ，Ｊ＝７．２Ｈｚ），７．６４（１Ｈ，ｄ，Ｊ＝５．６Ｈｚ），７．８５（１Ｈ，ｄｄｄ，Ｊ＝０．４Ｈｚ，１．１Ｈｚ，７．２Ｈｚ）８．０３（１Ｈ，ｄｄ，Ｊ＝１．１Ｈｚ，７．８Ｈｚ），１０．２３（１Ｈ，ｓ）．１３Ｃ−ＮＭＲ（ＣＤＣｌ３， １００．７ＭＨｚ）δ＝１２２．９，１２４．３，１２９．８，１３０．５，１３０．９，１３１．４，１３７．１，１４１．３，１９１．３．
The measurement results of 1 H-NMR and 13 C-NMR of Compound B are shown below.
1 H-NMR (
窒素雰囲気下、化合物Ｂ０．１５ｇ（０．９３ｍｍｏｌ）のトルエン溶液５ｍｌにＮ，Ｎ−ジメチルホルムアミド０．１ｍｌを加えた。塩化チオニル０．９ｇ（７．４ｍｍｏｌ、８ｅｑ）と硫黄０．０４ｇ（１．１ｍｍｏｌ、１．２ｅｑ）を加え２２０℃に加温し、１時間保った。冷却後、反応液をろ過し、６７ＤＢＴ３を収率１１％で得た Under a nitrogen atmosphere, 0.1 ml of N, N-dimethylformamide was added to 5 ml of a toluene solution of 0.15 g (0.93 mmol) of Compound B. 0.9 g (7.4 mmol, 8 eq) thionyl chloride and 0.04 g (1.1 mmol, 1.2 eq) sulfur were added and heated to 220 ° C. and kept for 1 hour. After cooling, the reaction solution was filtered to obtain 67DBT 3 in a yield of 11%.
以下に、６７ＤＢＴ３のＭＳおよび１Ｈ−ＮＭＲの測定結果を示す。また、６７ＤＢＴ３の１Ｈ−ＮＭＲスペクトルを図４に示す。
ＭＳ（ＡＰＰＩ） ｍ／ｚ＝３５２１Ｈ―ＮＭＲ（Ｃ２Ｄ２Ｃｌ４， ４００．４ＭＨｚ）δ＝７．６２（２Ｈ，ｄ，Ｊ＝５．３Ｈｚ），７．６８（２Ｈ，ｄ，Ｊ＝５．３Ｈｚ），７．９６（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），８．０４（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ）．
The measurement results of MS and 1 H-NMR of 67DBT 3 are shown below. Further, the 1 H-NMR spectrum of 67DBT 3 is shown in FIG.
MS (APPI) m / z = 352 1 H-NMR (C 2 D 2 Cl 4 , 400.4 MHz) δ = 7.62 (2H, d, J = 5.3 Hz), 7.68 (2H, d, J = 5.3 Hz), 7.96 (2H, d, J = 8.5 Hz), 8.04 (2H, d, J = 8.5 Hz).
同様の合成法を用いて８−６７ＤＢＴ３を合成した。８−６７ＤＢＴ３としたのは、端末のチオフェン環にオクチル基であるＣ８Ｈ１７が付加しているためである。８−６７ＤＢＴ３の反応式を［化７］に示す。
［化７］
[Chemical 7]
８−６７ＤＢＴ３のＭＳ、１Ｈ−ＮＭＲおよび１３Ｃ−ＮＭＲの測定結果を以下に示す。また、８−６７ＤＢＴ３の１Ｈ−ＮＭＲスペクトルを図５に、１３Ｃ−ＮＭＲスペクトルを図６に示す。
ＭＳ（ＡＰＰＩ） ｍ／ｚ＝５７６
１ Ｈ−ＮＭＲ（Ｃ２Ｄ２Ｃｌ４， ４００．４ＭＨｚ）δ＝０．９１（６Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．３１（２０Ｈ，ｍ），１．８５（４Ｈ，ｍ），３．０４（４Ｈ，ｔ，Ｊ＝７．４Ｈｚ），７．２５（２Ｈ，ｓ），７．７６（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ），７．９４（2Ｈ，ｄ，Ｊ＝８．６Ｈｚ）．
１３Ｃ−ＮＭＲ（Ｃ２Ｄ２Ｃｌ４， １００．７ＭＨｚ）δ＝１４．３，２２．７，２９．２，２９．３，２９．４，３０．９，３１．５，３１．９，１２０．１，１２０．２，１２１．２，１２７．０，１３１．８，１３２．１，１３７．７，１３９．０，１４６．７
The measurement results of MS, 1 H-NMR and 13 C-NMR of 8-67DBT 3 are shown below. Further, the 1 H-NMR spectrum of 8-67DBT 3 is shown in FIG. 5, and the 13 C-NMR spectrum is shown in FIG.
MS (APPI) m / z = 576
1 H- NMR (C 2 D 2 C l4, 400.4MHz) δ = 0.91 (6H, t, J = 7.1Hz), 1.31 (20H, m), 1.85 (4H, m) 3.04 (4H, t, J = 7.4 Hz), 7.25 (2H, s), 7.76 (2H, d, J = 8.6 Hz), 7.94 (2H, d, J = 8.6 Hz).
13 C-NMR (C 2 D 2 Cl 4 , 100.7 MHz) δ = 14.3, 22.7, 29.2, 29.3, 29.4, 30.9, 31.5, 31.9, 120.1, 120.2, 121.2, 127.0, 131.8, 132.1, 137.7, 139.0, 146.7
同様の合成法を用いて５４ＤＢＴ３を合成した。５４ＤＢＴ３の合成は、前記の反応式［化５］に示されている。
５４ＤＢＴ３のＭＳおよび１Ｈ−ＮＭＲの測定結果を以下に示す。また、５４ＤＢＴ３の１Ｈ−ＮＭＲスペクトルを図７に示す。
ＭＳ（ＡＰＰＩ） ｍ／ｚ＝３５２
１Ｈ―ＮＭＲ（Ｃ２Ｄ２Ｃｌ４， ４００．４ＭＨｚ）δ＝７．７６（２Ｈ，ｄ，Ｊ＝５．３Ｈｚ），７．９６（６Ｈ，ｍ）．
54DBT 3 was synthesized using a similar synthesis method. The synthesis of 54DBT 3 is shown in the above reaction formula [Chem. 5].
The measurement results of MS and 1 H-NMR of 54DBT 3 are shown below. The 1 H-NMR spectrum of 54DBT 3 is shown in FIG.
MS (APPI) m / z = 352
1H-NMR (C 2 D 2 Cl 4 , 400.4 MHz) δ = 7.76 (2H, d, J = 5.3 Hz), 7.96 (6H, m).
図８、図９、図１０に、有機溶媒１，１，２，２−Ｔｅｔｒａｃｈｌｏｒｏｅｔｈａｎｅに溶解させたペンタセン、５４ＤＢＴ３及び８−６７ＤＢＴ３の０時間、２４時間及び４８時間後の経時変化におけＵＶスペクトルを示す。これらの図より、５４ＤＢＴ３及び８−６７ＤＢＴ３は、溶液中で４８時間放置しても、スペクトルの変化が全く無く、非常に安定しているということがいえる。一方、ペンタセンは２４時間後でスペクトルが大きく変化し、溶液中で不安定で、分解してしまっていることがわかる。
8, FIG. 9, FIG. 10, UV put pentacene dissolved in an
溶解度は、２，３―ＤＮＴＴがジクロロメタン中３．４ｍｇ／Ｌ（文献値）、４５ＤＢＴ３は、４５．５ｍｇ／Ｌであるのに対し、５４ＤＢＴ３は、１６６．７ｍｇ／Ｌという結果となり、５４ＤＢＴ３は、４５ＤＢＴ３、２，３―ＤＮＴＴよりも溶解性が高いことが分かる。
また、アルキル基を有する８−６７ＤＢＴ３の溶解度は、ジクロロメタン中１１２５ｍｇ／Ｌであり、８０℃トルエン中６６ｇ／Ｌと溶解性が非常に高い。
Solubility, 2,3-DNTT is dichloromethane 3.4 mg / L (literature value), is 45DBT3, whereas a 45.5mg / L, 54DBT 3 becomes a result of 166.7mg / L, 54DBT 3 Is more soluble than 45DBT 3 , 2,3-DNTT.
The solubility of 8-67DBT 3 having an alkyl group is 1125 mg / L in dichloromethane, and the solubility is very high at 66 g / L in 80 ° C. toluene.
また、図１１、図１２に示すように、ＤＳＣ（示差走査熱量計）の測定結果より、２，１−ＤＮＴＴの融点が３０６．３−３０７．０℃、５４ＤＢＴ３の融点が３５７．６−３５８．０℃となり、５４ＤＢＴ３は２，１−ＤＮＴＴよりも融点が高く、低温での相転移点もないことから、耐熱性に優れているといえる。 Further, as shown in FIGS. 11 and 12, from the measurement results of DSC (differential scanning calorimeter), the melting point of 2,1-DNTT is 306.3-307.0 ° C., and the melting point of 54DBT3 is 357.6-358. The temperature is 0.0 ° C., and 54DBT 3 has a higher melting point than 2,1-DNTT and has no phase transition point at a low temperature.
４５ＤＢＴ３、５４ＤＢＴ３、６７ＤＢＴ３、５４ＤＢＴ３および８−６７ＤＢＴ３のＨＯＭＯ−ＬＵＭＯの計算を目的として、分子軌道計算プログラムＧａｕｓｓｉａｎ０９を用いて、密度汎関数理論（ＤＦＴ）に基づく計算により構造最適化計算を行った。ＤＦＴ計算を行うにあたり、密度汎関数にＢ３ＬＹＰを、基底関数に６−３１Ｇ（ｄ）を選択した。 For the purpose of calculating HOMO-LUMO of 45DBT 3 , 54DBT 3 , 67DBT 3 , 54DBT 3 and 8-67DBT 3, a structure optimization calculation is performed by calculation based on density functional theory (DFT) using a molecular orbital calculation program Gaussian09. Went. In performing the DFT calculation, B3LYP was selected as the density functional and 6-31G (d) as the basis function.
ここで、Ｇａｕｓｓｉａｎ及び密度汎関数理論について概説する。
Ｇａｕｓｓｉａｎは、多種多様な分子・化学反応を解析・設計するための量子化学計算ソフトウェアであり、有名で利用者数の多い量子化学計算ソフトウェアである。分子設計・構造解析・化学反応解析などで多くの成果を上げている。Ｇａｕｓｓｉａｎは、様々な半経験的・非経験的量子化学計算法に関する機能を有しており、密度汎関数理論に基づく計算にも対応している。また、分子構造・基準振動などの基礎物性や、ＮＭＲ化学シフトや紫外・可視吸収スペクトルなどの分子の同定や材料設計に役立つ物性値などを算出することが可能である。
密度汎関数理論（Ｄｅｎｓｉｔｙ Ｆｕｎｃｔｉｏｎａｌ Ｔｈｅｏｒｙ, ＤＦＴ）とは、物理や化学の分野に於いて、原子、分子、凝集系などの多体電子系の電子状態を調べるために用いられる量子力学の理論である。この理論では、多体系の全ての物理量は空間的に変化する電子密度の汎関数として表され、密度汎関数理論という名前はそれに由来している。汎関数理論を用いた計算は実験結果と十分に一致し、また計算コストもハートリー-フォック法などの多体の波動関数を用いる手法と比べて低為、最も広く使われている手法である。
Here, an overview of Gaussian and density functional theory will be given.
Gaussian is quantum chemistry calculation software for analyzing and designing a wide variety of molecules and chemical reactions, and is a well-known and widely used quantum chemistry calculation software. Has achieved many achievements in molecular design, structural analysis, chemical reaction analysis and so on. Gaussian has functions related to various semi-empirical and ab initio quantum chemical calculation methods, and also supports calculations based on density functional theory. It is also possible to calculate basic physical properties such as molecular structure and reference vibration, physical properties useful for molecular identification and material design such as NMR chemical shift and ultraviolet / visible absorption spectrum.
Density Functional Theory (DFT) is a quantum mechanics theory used to investigate the electronic states of many-body electronic systems such as atoms, molecules, and aggregates in the fields of physics and chemistry. . In this theory, all physical quantities of many-body systems are expressed as spatially varying electron density functionals, and the name density functional theory is derived from it. Calculations using functional theory agree well with experimental results, and are also the most widely used method because the calculation cost is low compared to methods using many-body wave functions such as the Hartley-Fock method. .
上記のように計算した結果を図３に示す。４５ＤＢＴ３のＨＯＭＯレベルが、−５．５０ｅＶで、５４ＤＢＴ３のほうが、ＨＯＭＯレベルのＡｕ電極の仕事関数に近いため、正孔の注入障壁が小さく、Ａｕ電極から半導体層へ正孔が注入しやすくなり、より低電圧で駆動するようになり、トランジスタ性能が向上すると推察される。 The results calculated as described above are shown in FIG. The HOMO level of 45DBT 3 is −5.50 eV, and 54DBT 3 is closer to the work function of the Au electrode at the HOMO level, so the hole injection barrier is small and holes can be easily injected from the Au electrode into the semiconductor layer. Thus, it is assumed that the transistor is driven at a lower voltage and the transistor performance is improved.
また、同様な方法で計算した各種ＤＢＴ３の分子起動計算結果を以下の表１に示す。
前述のごとく、５４ＤＢＴ３はウェットプロセスに利用するため溶液中で安定であり、かつ溶解性の高いことが特徴である。しかし、有機トランジスタの半導体層に使用して、その基本的な特性を評価する場合、多結晶やアモルファス状態の薄膜として使用するよりも、単結晶の薄膜を用いて評価するほうが、欠陥が少ないために、材料本来のポテンシャルを評価できると考えられている。 As described above, 54DBT 3 is characterized by being stable in a solution and having high solubility because it is used in a wet process. However, when evaluating the basic characteristics of a semiconductor layer used in an organic transistor, it is less likely to evaluate using a single crystal thin film than to use it as a polycrystalline or amorphous thin film. In addition, it is thought that the original potential of the material can be evaluated.
そこで、本発明では、Ｐｈｙｓｉｃａｌ Ｖａｐｏｒ Ｔｒａｎｓｐｏｒｔ（ＰＶＴ）法およびキャスト法を用いて、５４ＤＢＴ３誘導体の少なくとも一種の単結晶を含有してなる有機トランジスタを試作し、その性能を評価した。次いで、真空蒸着装置を用いて、５４ＤＢＴ３誘導体を半導体層として使用した有機薄膜トランジスタを作成し、その性能を評価した。なお、トランジスタ性能を調べるため、各素子は以下のように作成した。 Therefore, in the present invention, an organic transistor containing at least one single crystal of 54DBT 3 derivative was prototyped using the Physical Vapor Transport (PVT) method and the cast method, and the performance was evaluated. Next, an organic thin film transistor using a 54DBT 3 derivative as a semiconductor layer was prepared using a vacuum deposition apparatus, and the performance was evaluated. In addition, in order to investigate transistor performance, each element was created as follows.
５４ＤＢＴ３の単結晶トランジスタの作成（ＰＶＴ法）
５４ＤＢＴ３を１７０℃に加熱しながら、アルゴンガスをキャリアガスとして、１００ｍｌ／ｍｉｎの流速で流し、結晶の析出部分を１２０℃にすることで５４ＤＢＴ３の単結晶サンプルを作成した。
54DBT 3 single crystal transistor fabrication (PVT method)
While heating 54DBT 3 to 170 ° C., an argon gas as a carrier gas, at a flow rate of 100 ml / min, to create a single-crystal sample of 54DBT3 by precipitation portion of the crystal to 120 ° C..
上記の方法で作成した５４ＤＢＴ３の単結晶を用いて、図１に示す構造の薄膜デバイスを作成した。具体的には未処理の熱酸化膜を形成したシリコンウェハー（Ｓｉ／ＳｉＯ２基板（ｂａｒｅ））、０．３ｗｔ％のポリスチレン（ＰＳ）溶液を２０００ｒｐｍで３０秒間スピンコートし、９０℃で１時間アニールを行ったＳｉ／ＳｉＯ２基板（膜厚１３ｎｍ）、ＣＹＴＯＰ：薄め液＝１：９の溶液を２０００ｒｐｍで３０秒間の条件でスピンコート法により成膜し、９０℃で１０分間、２００℃で１時間アニールを行ったＳｉ／ＳｉＯ２基板を用いた（膜厚２７．８ｎｍ）。ソース・ドレイン電極は単結晶の両端にカーボンペーストを塗布することで形成、トップコンタクト型のＦＥＴ素子を作製し、減圧条件下でＦＥＴ測定を行った。 A thin film device having a structure shown in FIG. 1 was prepared using a single crystal of 54DBT 3 prepared by the above method. Specifically, a silicon wafer (Si / SiO 2 substrate (bare)) on which an unprocessed thermal oxide film is formed, a 0.3 wt% polystyrene (PS) solution is spin-coated at 2000 rpm for 30 seconds, and 90 ° C. for 1 hour. An annealed Si / SiO 2 substrate (film thickness: 13 nm), a solution of CYTOP: thinning solution = 1: 9 was formed by spin coating at 2000 rpm for 30 seconds, 90 ° C. for 10 minutes, 200 ° C. A Si / SiO 2 substrate annealed for 1 hour was used (film thickness 27.8 nm). The source / drain electrodes were formed by applying carbon paste to both ends of a single crystal to produce a top contact type FET element, and FET measurement was performed under reduced pressure conditions.
５４ＤＢＴ３の単結晶トランジスタの作成（キャスト法）
５４ＤＢＴ３の０．０１ｗｔ％メシチレン溶液を基板へキャストした。調整の際、室温でサンプルが溶解しなかったため、ヒートガンを使用した。基板は０．７ｗｔ％のポリメチルメタクリレート（ＰＭＭＡ）溶液を２０００ｒｐｍで３０秒間の条件でスピンコート法により成膜し、１２０℃で４時間アニールしたＳｉ／ＳｉＯ２基板（膜厚３０ｎｍ）を使用した。ソース・ドレイン電極は単結晶の両端にカーボンペーストを塗布することで形成し、減圧条件下でＦＥＴ測定を行った。
54DBT 3 single crystal transistor fabrication (cast method)
A 0.01 wt% mesitylene solution of 54DBT 3 was cast onto the substrate. At the time of adjustment, since the sample did not dissolve at room temperature, a heat gun was used. The substrate used was a Si / SiO 2 substrate (
５４ＤＢＴ３の有機薄膜トランジスタの作成(蒸着)
５４ＤＢＴ３を真空蒸着装置を用いて基板上に５０ｎｍ蒸着し、さらにその上にソース、ドレイン電極となる金を電子ビーム法を用いて８０ｎｍ蒸着（Ｌ＝５０μｍ、Ｗ＝１．５ｍｍ）し、トップコンタクト型素子を作成した。なお、用いた基板はＳｉ／ＳｉＯ２基板にＰＳとＣＹＴＯＰでそれぞれ表面処理したものと未処理（ｂａｒｅ）のものを用い、有機膜の作製条件として、基板温度は室温で作製を行った。ＡＦＭ測定によりＰＳの膜厚は１３ｎｍ、ＣＹＴＯＰの膜厚は２７．８ｎｍであった。
54DBT 3 organic thin film transistor fabrication (vapor deposition)
54DBT 3 was deposited on a substrate by 50 nm using a vacuum deposition apparatus, and gold used as a source and drain electrode was further deposited by 80 nm using an electron beam method (L = 50 μm, W = 1.5 mm). A contact-type element was created. The substrate used was a Si / SiO 2 substrate surface-treated with PS and CYTOP and untreated (bare), and the substrate temperature was room temperature as the organic film preparation conditions. The film thickness of PS was 13 nm and the film thickness of CYTOP was 27.8 nm by AFM measurement.
８−６７ＤＢＴ３についても同様に有機トランジスタを試作し、その性能を評価した。 For 8-67DBT 3 , an organic transistor was also made in the same manner and its performance was evaluated.
８−６７ＤＢＴ３の単結晶トランジスタの作成（キャスト法）
８−６７ＤＢＴ３のメシチレン溶液を０．２ｗｔ％、０．１ｗｔ％、０．０５ｗｔ％の濃度で調整し、基板へキャストした。調整の際、室温でサンプルが溶解しなかったため、ヒートガンを使用した。基板は０．７ｗｔ％のＰＭＭＡ溶液を２０００ｒｐｍで３０秒間の条件でスピンコート法により成膜し、１２０℃で４時間アニールしたＳｉ／ＳｉＯ２基板（膜厚３０ｎｍ）を使用した。ソース・ドレイン電極は単結晶の両端にカーボンペーストを塗布することで形成し、減圧条件下でＦＥＴ測定を行った。
8-67DBT 3 single crystal transistor fabrication (cast method)
A mesitylene solution of 8-67DBT 3 was prepared at concentrations of 0.2 wt%, 0.1 wt%, and 0.05 wt% and cast onto a substrate. At the time of adjustment, since the sample did not dissolve at room temperature, a heat gun was used. The substrate used was a Si /
８−６７ＤＢＴ３の有機薄膜トランジスタの作成(蒸着)
８−６７ＤＢＴ３を真空蒸着装置を用いて基板上に５０ｎｍ蒸着し、さらにその上にソース、ドレイン電極となる金を電子ビーム法を用いて８０ｎｍ蒸着（Ｌ＝５０μｍ、Ｗ＝１．５ｍｍ）し、トップコンタクト型素子を作成した。なお、用いた基板はＳｉ／ＳｉＯ２基板にＰＳとＣＹＴＯＰでそれぞれ表面処理したものと未処理（ｂａｒｅ）のものを用い、有機膜の作製条件として、基板温度は室温で作製を行った。
Preparation of 8-67DBT 3 organic thin film transistor (vapor deposition)
8-67DBT 3 is deposited on a substrate by 50 nm using a vacuum deposition apparatus, and further, gold serving as a source and drain electrode is deposited by 80 nm using an electron beam method (L = 50 μm, W = 1.5 mm). A top contact type element was prepared. The substrate used was a Si / SiO 2 substrate surface-treated with PS and CYTOP and untreated (bare), and the substrate temperature was room temperature as the organic film preparation conditions.
上記のように作製した各素子についてその性能を測定した結果を表２に示す。
本願に係わる発明は、末端にチオフェンを有する屈曲型のチエノチオフェン骨格を特徴とする有機半導体材料を有機半導体層に使用した有機トランジスタである。この有機半導体材料は、上記のように有機溶媒に対する溶解度が高く、安定性もあり、特に安価とされるウェットプロセスで有機トランジスタを作製することが可能である。そのため、今後、広くこの分野での需要使用が期待される。 The invention according to the present application is an organic transistor in which an organic semiconductor material characterized by a bent thienothiophene skeleton having a thiophene at a terminal is used for an organic semiconductor layer. As described above, this organic semiconductor material has high solubility in an organic solvent, is stable, and can produce an organic transistor by a wet process that is particularly inexpensive. Therefore, it is expected that demand will be widely used in this field in the future.
１ トップコンタクト型ＦＥＴ
２ ボトムコンタクト型ＦＥＴ
３ ソース
４ ドレイン
５ 有機半導体
６ 絶縁膜
７ 基板（ゲート）
1 Top contact FET
2 Bottom contact FET
3
Claims (4)
［化１］
置換基Ｒ１からＲ８における、ハロゲン原子はフッ素、塩素、臭素、ヨウ素であり、好ましい例はフッ素原子である。
置換基Ｒ１からＲ８における、アリール基は炭素数が３から６０の芳香環基で、例えば、フェニル基、１−ナフチル基、２−ナフチル基、ビフェニル基、ターフェニル基、アントリル基、フェナントリル基、クリセンなどが挙げられ、これらの各基は置換基を有していてもよい。
置換基Ｒ１からＲ８における、複素環基は炭素数が３から６０の複素環基で、ピリジン、ピラジン、トリアジン、ピロール、キノリン、チオフェン、ベンゾチオフェン、ジベンゾチオフェン、チエノチオフェン、フラン、ベンゾフラン、ジベンゾフラン、チアゾール、ベンゾチアゾールなどが挙げられ、これらの各基は置換基を有していてもよい。
置換基Ｒ１からＲ８における、アルキル基は炭素数が１から３０の直鎖型、分岐型、環状型のアルキル基であり、例えば、メチル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、イソプロピル基、ｔ-ブチル基、シクロプロピル基、シクロヘキシル基、アダマンチル基、ｎ−トリフルオロメチル基などが挙げられ、これらの各基は置換基を有していてもよい。
置換基Ｒ１からＲ８における、アルケニル基は炭素数が２から３０のアルケニル基で、例えば、エテニル基、メチルエテニル基、（ｎ−オクチル）エテニル基、フェニルエテニル基、ナフチルエテニル基、ビフェニルエテニル基、ターフェニルエテニル基、パーフルオロフェニルエテニル基などが挙げられ、これらの各基は置換基を有していてもよい。
置換基Ｒ1からＲ８における、アルキニル基は炭素数が２から３０のアルキニル基で、例えば、エチニル基、メチルエチニル基、（ｎ−オクチル）エチニル基、フェニルエチニル基、ナフチルエチニル基、ビフェニルエチニル基、ターフェニルエチニル基、パーフルオロフェニルエチニル基などが挙げられ、これらの各基は置換基を有していてもよい。
置換基Ｒ１からＲ８における、アミノ基は炭素数が１から６０のアミノ基で、例えば、ジフェニルアミノ基、ジナフチルアミノ基、ジチエニルアミノ基、ジピリジルアミノ基などが挙げられ、これらの各基は置換基を有していてもよい。
前記置換基とは、水素原子及びハロゲン原子、アリール基、複素環基、アルキル基、フルオロアルキル基、アルケニル基、フルオロアルケニル基、アルキニル基、フルオロアルキニル基、アルコキシル基、フルオロアルコキシル基、アミノ基、アミド基、イミノ基、カルボキシル基、ヒドロキシル基、エステル基、ニトロ基、ニトリル基、スルフィド基、メルカプト基、スルホニル基、シリル基が挙げられる。 An organic transistor in which a compound characterized by a bent thienothiophene skeleton having a thiophene at a terminal represented by the chemical formula [Chemical Formula 1] is used for an organic semiconductor layer.
[Chemical 1]
In the substituents R 1 to R 8 , the halogen atom is fluorine, chlorine, bromine or iodine, and a preferred example is a fluorine atom.
In the substituents R 1 to R 8 , the aryl group is an aromatic ring group having 3 to 60 carbon atoms, such as a phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl group, terphenyl group, anthryl group, phenanthryl. Group, chrysene and the like, and each of these groups may have a substituent.
The heterocyclic group in the substituents R 1 to R 8 is a heterocyclic group having 3 to 60 carbon atoms, such as pyridine, pyrazine, triazine, pyrrole, quinoline, thiophene, benzothiophene, dibenzothiophene, thienothiophene, furan, benzofuran, Dibenzofuran, thiazole, benzothiazole and the like can be mentioned, and each of these groups may have a substituent.
In the substituents R 1 to R 8 , the alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, such as a methyl group, n-butyl group, n-pentyl group, n -Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, isopropyl, t-butyl, cyclopropyl , A cyclohexyl group, an adamantyl group, an n-trifluoromethyl group, and the like, and each of these groups may have a substituent.
In the substituents R 1 to R 8 , the alkenyl group is an alkenyl group having 2 to 30 carbon atoms such as ethenyl group, methylethenyl group, (n-octyl) ethenyl group, phenylethenyl group, naphthylethenyl group, biphenylethenyl group. Group, terphenyl ethenyl group, perfluorophenyl ethenyl group and the like, and each of these groups may have a substituent.
In the substituents R 1 to R 8 , the alkynyl group is an alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, methylethynyl group, (n-octyl) ethynyl group, phenylethynyl group, naphthylethynyl group, biphenylethynyl group. Group, terphenylethynyl group, perfluorophenylethynyl group and the like, and each of these groups may have a substituent.
In the substituents R 1 to R 8 , the amino group is an amino group having 1 to 60 carbon atoms, and examples thereof include a diphenylamino group, a dinaphthylamino group, a dithienylamino group, and a dipyridylamino group. The group may have a substituent.
Examples of the substituent include a hydrogen atom and a halogen atom, an aryl group, a heterocyclic group, an alkyl group, a fluoroalkyl group, an alkenyl group, a fluoroalkenyl group, an alkynyl group, a fluoroalkynyl group, an alkoxyl group, a fluoroalkoxyl group, an amino group, Examples include amide group, imino group, carboxyl group, hydroxyl group, ester group, nitro group, nitrile group, sulfide group, mercapto group, sulfonyl group, and silyl group.
［化２］
[Chemical formula 2]
［化３］
[Chemical formula 3]
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