WO2022202868A1 - 電荷輸送性組成物 - Google Patents
電荷輸送性組成物 Download PDFInfo
- Publication number
- WO2022202868A1 WO2022202868A1 PCT/JP2022/013373 JP2022013373W WO2022202868A1 WO 2022202868 A1 WO2022202868 A1 WO 2022202868A1 JP 2022013373 W JP2022013373 W JP 2022013373W WO 2022202868 A1 WO2022202868 A1 WO 2022202868A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- charge
- transporting
- carbon atoms
- photoelectric conversion
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 160
- 229920000123 polythiophene Polymers 0.000 claims abstract description 69
- 239000000126 substance Substances 0.000 claims abstract description 56
- 239000010409 thin film Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 239000002019 doping agent Substances 0.000 claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 27
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 18
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 12
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 10
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 5
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 97
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 25
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 238000003475 lamination Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 125000005577 anthracene group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 abstract 2
- -1 —O—[ZO] p —R e Chemical group 0.000 description 216
- 238000000034 method Methods 0.000 description 64
- 239000000243 solution Substances 0.000 description 58
- 239000000463 material Substances 0.000 description 48
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
- 239000000758 substrate Substances 0.000 description 36
- 229910052731 fluorine Inorganic materials 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 150000001412 amines Chemical class 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 20
- 239000011148 porous material Substances 0.000 description 20
- 239000004065 semiconductor Substances 0.000 description 19
- 239000002105 nanoparticle Substances 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- 125000001153 fluoro group Chemical group F* 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 229910044991 metal oxide Inorganic materials 0.000 description 15
- 150000004706 metal oxides Chemical class 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000002736 nonionic surfactant Substances 0.000 description 13
- 229940126062 Compound A Drugs 0.000 description 12
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000903 blocking effect Effects 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 239000010405 anode material Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 4
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Chemical group 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 125000005309 thioalkoxy group Chemical group 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- UWYZHKAOTLEWKK-UHFFFAOYSA-N 1,2,3,4-tetrahydroisoquinoline Chemical compound C1=CC=C2CNCCC2=C1 UWYZHKAOTLEWKK-UHFFFAOYSA-N 0.000 description 2
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 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 description 2
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 2
- ZCSHACFHMFHFKK-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;2,4,6-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)C1NC([N+]([O-])=O)NC([N+]([O-])=O)N1.CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZCSHACFHMFHFKK-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 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 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 2
- 229910006095 SO2F Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910003069 TeO2 Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000002078 anthracen-1-yl 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 description 2
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- LZYIDMKXGSDQMT-UHFFFAOYSA-N arsenic dioxide Inorganic materials [O][As]=O LZYIDMKXGSDQMT-UHFFFAOYSA-N 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MOWNZPNSYMGTMD-UHFFFAOYSA-N boron monoxide Inorganic materials O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000004148 curcumin Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- MMFBQHXDINNBMW-UHFFFAOYSA-N n,n-dipropylaniline Chemical compound CCCN(CCC)C1=CC=CC=C1 MMFBQHXDINNBMW-UHFFFAOYSA-N 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- CXZOCEZMGWOOFD-UHFFFAOYSA-N phenanthren-1-amine Chemical compound C1=CC2=CC=CC=C2C2=C1C(N)=CC=C2 CXZOCEZMGWOOFD-UHFFFAOYSA-N 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical group S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- DCTMXCOHGKSXIZ-UHFFFAOYSA-N (R)-1,3-Octanediol Chemical compound CCCCCC(O)CCO DCTMXCOHGKSXIZ-UHFFFAOYSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical group CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 1
- 125000006013 1,1-difluoroethoxy group Chemical group 0.000 description 1
- 125000006002 1,1-difluoroethyl group Chemical group 0.000 description 1
- 125000004317 1,3,5-triazin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=N1 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- 125000004790 1-fluoroethoxy group Chemical group FC(C)O* 0.000 description 1
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- IUILSTHMSGDSHQ-UHFFFAOYSA-N 13h-dibenzo[a,i]carbazole Chemical compound C1=CC=C2C(NC=3C4=CC=CC=C4C=CC=33)=C3C=CC2=C1 IUILSTHMSGDSHQ-UHFFFAOYSA-N 0.000 description 1
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- FGRJGEWVJCCOJJ-UHFFFAOYSA-N 2,2-dimethylaziridine Chemical compound CC1(C)CN1 FGRJGEWVJCCOJJ-UHFFFAOYSA-N 0.000 description 1
- ZEBFPAXSQXIPNF-UHFFFAOYSA-N 2,5-dimethylpyrrolidine Chemical compound CC1CCC(C)N1 ZEBFPAXSQXIPNF-UHFFFAOYSA-N 0.000 description 1
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- 125000004791 2-fluoroethoxy group Chemical group FCCO* 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- DLBWPRNUXWYLRN-UHFFFAOYSA-N 2-methylazetidine Chemical compound CC1CCN1 DLBWPRNUXWYLRN-UHFFFAOYSA-N 0.000 description 1
- RGHPCLZJAFCTIK-UHFFFAOYSA-N 2-methylpyrrolidine Chemical compound CC1CCCN1 RGHPCLZJAFCTIK-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- IDWRJRPUIXRFRX-UHFFFAOYSA-N 3,5-dimethylpiperidine Chemical compound CC1CNCC(C)C1 IDWRJRPUIXRFRX-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- KYINPWAJIVTFBW-UHFFFAOYSA-N 3-methylpyrrolidine Chemical compound CC1CCNC1 KYINPWAJIVTFBW-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- GZEFZLXJPGMRSP-UHFFFAOYSA-N 37,38,39,40-tetrazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(37),2,4,6,8,10,12(39),13,15,17,19,21,23,25,27,29,31,33,35-nonadecaene Chemical compound c1ccc2c3cc4[nH]c(cc5nc(cc6[nH]c(cc(n3)c2c1)c1ccccc61)c1ccccc51)c1ccccc41 GZEFZLXJPGMRSP-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- STJXCDGCXVZHDU-UHFFFAOYSA-N 7H-Dibenzo[c,g]carbazole Chemical compound N1C2=CC=C3C=CC=CC3=C2C2=C1C=CC1=CC=CC=C12 STJXCDGCXVZHDU-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920003937 Aquivion® Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- AZSFNTBGCTUQFX-UHFFFAOYSA-N C12=C3C(C4=C5C=6C7=C8C9=C(C%10=6)C6=C%11C=%12C%13=C%14C%11=C9C9=C8C8=C%11C%15=C%16C=%17C(C=%18C%19=C4C7=C8C%15=%18)=C4C7=C8C%15=C%18C%20=C(C=%178)C%16=C8C%11=C9C%14=C8C%20=C%13C%18=C8C9=%12)=C%19C4=C2C7=C2C%15=C8C=4C2=C1C12C3=C5C%10=C3C6=C9C=4C32C1(CCCC(=O)OC)C1=CC=CC=C1 Chemical compound C12=C3C(C4=C5C=6C7=C8C9=C(C%10=6)C6=C%11C=%12C%13=C%14C%11=C9C9=C8C8=C%11C%15=C%16C=%17C(C=%18C%19=C4C7=C8C%15=%18)=C4C7=C8C%15=C%18C%20=C(C=%178)C%16=C8C%11=C9C%14=C8C%20=C%13C%18=C8C9=%12)=C%19C4=C2C7=C2C%15=C8C=4C2=C1C12C3=C5C%10=C3C6=C9C=4C32C1(CCCC(=O)OC)C1=CC=CC=C1 AZSFNTBGCTUQFX-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 229920000028 Gradient copolymer Polymers 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- PYFSCIWXNSXGNS-UHFFFAOYSA-N N-methylbutan-2-amine Chemical compound CCC(C)NC PYFSCIWXNSXGNS-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- YUENFNPLGJCNRB-UHFFFAOYSA-N anthracen-1-amine Chemical compound C1=CC=C2C=C3C(N)=CC=CC3=CC2=C1 YUENFNPLGJCNRB-UHFFFAOYSA-N 0.000 description 1
- YCSBALJAGZKWFF-UHFFFAOYSA-N anthracen-2-amine Chemical compound C1=CC=CC2=CC3=CC(N)=CC=C3C=C21 YCSBALJAGZKWFF-UHFFFAOYSA-N 0.000 description 1
- LHNICELDCMPPDE-UHFFFAOYSA-N anthracen-9-amine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=CC2=C1 LHNICELDCMPPDE-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- QXNDZONIWRINJR-UHFFFAOYSA-N azocane Chemical compound C1CCCNCCC1 QXNDZONIWRINJR-UHFFFAOYSA-N 0.000 description 1
- NRHDCQLCSOWVTF-UHFFFAOYSA-N azonane Chemical compound C1CCCCNCCC1 NRHDCQLCSOWVTF-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
- 230000004888 barrier function Effects 0.000 description 1
- 125000002511 behenyl 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])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])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- LJOLGGXHRVADAA-UHFFFAOYSA-N benzo[e][1]benzothiole Chemical compound C1=CC=C2C(C=CS3)=C3C=CC2=C1 LJOLGGXHRVADAA-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 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
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 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
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 150000002240 furans Chemical class 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
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 125000001802 myricyl 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])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])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])[H] 0.000 description 1
- KEEXPDPBIQJVKK-UHFFFAOYSA-N n,2-dimethyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(C)CC(C)C KEEXPDPBIQJVKK-UHFFFAOYSA-N 0.000 description 1
- QKYWADPCTHTJHQ-UHFFFAOYSA-N n,2-dimethylpropan-1-amine Chemical compound CNCC(C)C QKYWADPCTHTJHQ-UHFFFAOYSA-N 0.000 description 1
- ZQGJEUVBUVKZKS-UHFFFAOYSA-N n,2-dimethylpropan-2-amine Chemical compound CNC(C)(C)C ZQGJEUVBUVKZKS-UHFFFAOYSA-N 0.000 description 1
- GDHRQDYGUDOEIZ-UHFFFAOYSA-N n,n,2-trimethylpropan-1-amine Chemical compound CC(C)CN(C)C GDHRQDYGUDOEIZ-UHFFFAOYSA-N 0.000 description 1
- OXQMIXBVXHWDPX-UHFFFAOYSA-N n,n,2-trimethylpropan-2-amine Chemical compound CN(C)C(C)(C)C OXQMIXBVXHWDPX-UHFFFAOYSA-N 0.000 description 1
- ORSUTASIQKBEFU-UHFFFAOYSA-N n,n-diethylbutan-1-amine Chemical compound CCCCN(CC)CC ORSUTASIQKBEFU-UHFFFAOYSA-N 0.000 description 1
- USSPHSVODLAWSA-UHFFFAOYSA-N n,n-dimethylbutan-2-amine Chemical compound CCC(C)N(C)C USSPHSVODLAWSA-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 description 1
- GGARKJIWYNVMBF-UHFFFAOYSA-N n-(2-methylpropyl)aniline Chemical compound CC(C)CNC1=CC=CC=C1 GGARKJIWYNVMBF-UHFFFAOYSA-N 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BBDGYADAMYMJNO-UHFFFAOYSA-N n-butyl-n-ethylbutan-1-amine Chemical compound CCCCN(CC)CCCC BBDGYADAMYMJNO-UHFFFAOYSA-N 0.000 description 1
- MTHFROHDIWGWFD-UHFFFAOYSA-N n-butyl-n-methylbutan-1-amine Chemical compound CCCCN(C)CCCC MTHFROHDIWGWFD-UHFFFAOYSA-N 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- XQOIBQBPAXOVGP-UHFFFAOYSA-N n-ethyl-2-methylpropan-2-amine Chemical compound CCNC(C)(C)C XQOIBQBPAXOVGP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- ITMSSZATZARZCA-UHFFFAOYSA-N n-ethyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CC)C1=CC=CC=C1 ITMSSZATZARZCA-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- KFYKZKISJBGVMR-UHFFFAOYSA-N n-ethylbutan-2-amine Chemical compound CCNC(C)CC KFYKZKISJBGVMR-UHFFFAOYSA-N 0.000 description 1
- KDFFXYVOTKKBDI-UHFFFAOYSA-N n-ethylnaphthalen-1-amine Chemical compound C1=CC=C2C(NCC)=CC=CC2=C1 KDFFXYVOTKKBDI-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004718 n-hexylthio group Chemical group C(CCCCC)S* 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- UVBMZKBIZUWTLV-UHFFFAOYSA-N n-methyl-n-propylpropan-1-amine Chemical compound CCCN(C)CCC UVBMZKBIZUWTLV-UHFFFAOYSA-N 0.000 description 1
- AKEYUWUEAXIBTF-UHFFFAOYSA-N n-methylnaphthalen-1-amine Chemical compound C1=CC=C2C(NC)=CC=CC2=C1 AKEYUWUEAXIBTF-UHFFFAOYSA-N 0.000 description 1
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 1
- VMVGVGMRBKYIGN-UHFFFAOYSA-N n-naphthalen-1-ylnaphthalen-1-amine Chemical compound C1=CC=C2C(NC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 VMVGVGMRBKYIGN-UHFFFAOYSA-N 0.000 description 1
- UNJZLNFHHINVOB-UHFFFAOYSA-N n-naphthalen-1-ylnaphthalen-2-amine Chemical compound C1=CC=C2C(NC=3C=C4C=CC=CC4=CC=3)=CC=CC2=C1 UNJZLNFHHINVOB-UHFFFAOYSA-N 0.000 description 1
- SBMXAWJSNIAHFR-UHFFFAOYSA-N n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(NC=3C=C4C=CC=CC4=CC=3)=CC=C21 SBMXAWJSNIAHFR-UHFFFAOYSA-N 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 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
- 125000004712 n-pentylthio group Chemical group C(CCCC)S* 0.000 description 1
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- PAYSBLPSJQBEJR-UHFFFAOYSA-N naphtho[2,3-e][1]benzothiole Chemical compound C1=CC=C2C=C3C(C=CS4)=C4C=CC3=CC2=C1 PAYSBLPSJQBEJR-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- INAMEDPXUAWNKL-UHFFFAOYSA-N nonadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCN INAMEDPXUAWNKL-UHFFFAOYSA-N 0.000 description 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005804 perfluoroheptyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- ZEAWSFHWVLOENK-UHFFFAOYSA-N phenanthren-2-amine Chemical compound C1=CC=C2C3=CC=C(N)C=C3C=CC2=C1 ZEAWSFHWVLOENK-UHFFFAOYSA-N 0.000 description 1
- HUWRJSZODLRHMY-UHFFFAOYSA-N phenanthren-3-amine Chemical compound C1=CC=C2C3=CC(N)=CC=C3C=CC2=C1 HUWRJSZODLRHMY-UHFFFAOYSA-N 0.000 description 1
- AFPNTTFBCMSLLO-UHFFFAOYSA-N phenanthren-4-amine Chemical compound C1=CC=CC2=C3C(N)=CC=CC3=CC=C21 AFPNTTFBCMSLLO-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- ZVJDFJRDKIADMB-UHFFFAOYSA-N quinolin-8-ol;sodium Chemical compound [Na].C1=CN=C2C(O)=CC=CC2=C1 ZVJDFJRDKIADMB-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 150000005082 selenophenes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920006301 statistical copolymer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000005087 tellurophenes Chemical class 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
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- 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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
-
- 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
Definitions
- the present invention relates to a charge-transporting composition, and more specifically, to a charge-transporting composition for forming a charge-transporting thin film used in combination with a non-fullerene acceptor active layer in a photoelectric conversion device.
- An electronic device is a device that converts light energy into electrical energy using an organic semiconductor, and examples thereof include organic solar cells.
- An organic solar cell is a solar cell element using an organic material for an active layer and a charge-transporting material.
- An organic thin-film solar cell developed by Tang is well known (Non-Patent Documents 1 and 2). Both are lightweight and thin, flexible, and roll-to-roll production is possible. expected to form.
- organic thin-film solar cells exhibit high photoelectric conversion efficiency even at low illuminance compared to photoelectric conversion elements using existing silicon-based materials. Due to its features such as being able to combine the properties of a filter, it is attracting attention not only for solar cell applications but also for optical sensor applications such as image sensors (Patent Documents 1 and 2, Non-Patent Document 3). .
- organic solar cells die-sensitized solar cells and organic thin-film solar cells
- applications such as optical sensors are collectively referred to as organic photoelectric conversion devices (hereinafter sometimes abbreviated as OPV).
- An organic photoelectric conversion element is composed of an active layer (photoelectric conversion layer), a charge (hole, electron) collection layer, electrodes (anode, cathode), and the like.
- the hole collection layer has the role of extracting the holes generated in the active layer to the electrode, and this can be effectively performed by reducing the energy barrier between the active layer and the hole collection layer. can.
- a conjugated compound as an electron-donating organic material p-type organic semiconductor
- a conjugated compound having n-type semiconductor characteristics as an electron-accepting organic material n-type organic semiconductor
- Active layers using fullerenes such as C 60 and fullerene derivatives (hereinafter abbreviated as FA active layers) have been used.
- NFA Non-Fullerene Acceptor
- the NFA active layer exhibits a higher PCE than the FA active layer due to an increase in photocurrent and an improvement in battery voltage.
- Jianhui Hou et al. reported that the use of the NFA active layer showed a PCE of 18% (Non-Patent Document 5).
- these organic photoelectric conversion elements exhibiting a high PCE widely use MoO 3 , which is a vapor-deposited hole-collecting layer that is disadvantageous for mass production, as the hole-collecting layer.
- MoO 3 is a vapor-deposited hole-collecting layer that is disadvantageous for mass production, as the hole-collecting layer.
- Ip the ionization potential of PEDOT/PSS. Therefore, there is a demand for a coating-type hole-collecting material having a deep Ip (Non-Patent Document 6).
- the present invention has been made in view of the above circumstances, and is suitable for forming a charge-transporting thin film used in combination with an NFA active layer in a photoelectric conversion device.
- a charge-transporting composition which, when used as a layer, further deepens the Ip of the resulting charge-transporting thin film, reduces the energy gap with the NFA active layer, and can realize high-voltage devices. With the goal.
- the inventors of the present invention have extensively studied in order to achieve the above object, and as a result, a charge-transporting composition containing a polythiophene derivative containing a predetermined repeating unit, a specific electron-accepting dopant substance, and a solvent has been developed. , is suitable for forming a charge-transporting thin film in a photoelectric conversion device having an NFA active layer. By deepening, the energy gap with the NFA active layer can be made small, and the inventors have found that the voltage of the device can be increased, and completed the present invention.
- the present invention provides the following charge-transporting composition.
- a charge-transporting composition for forming a charge-transporting thin film in a photoelectric conversion device having a non-fullerene active layer A charge-transporting substance made of a polythiophene derivative containing a repeating unit represented by the following formula (1), an electron-accepting dopant substance, and a solvent, A charge-transporting composition, wherein the electron-accepting dopant substance contains at least one selected from the group consisting of arylsulfonic acids and heteropolyacids represented by the following formula (2).
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or 1 ⁇ 40 fluoroalkoxy group, C6-C20 aryloxy group, -O-[Z-O] p -R e , sulfonic acid group or sulfonic acid group, or formed by combining R 1 and R 2 -O-Y-O-, Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and may be substituted with a sulfonic acid group or a sulfonic acid group, and Z is , an alkylene group having 1 to 40 carbon atoms which may be substituted with a halogen atom, p is an integer of 1 or more, R e is a hydrogen atom,
- a charge-transporting composition wherein the electron-accepting dopant substance contains an arylsulfonic acid represented by formula (2) and a heteropolyacid. 3. 1 or 2 charge-transporting compositions, wherein the heteropolyacid contains at least one selected from the group consisting of phosphotungstic acid and phosphomolybdic acid. 4. 3. The charge-transporting composition of any one of 1 to 3, further comprising a surfactant. 5. 4. The charge-transporting composition of 4, wherein the surfactant is a fluorosurfactant. 6. 6. The charge-transporting composition according to any one of 1 to 5, wherein the solvent contains one or more solvents selected from alcoholic solvents and water. 7. 7. 7.
- the charge-transporting thin film of 9, wherein the charge-transporting thin film is a hole collecting layer of an organic photoelectric conversion device.
- An electronic device comprising 9 or 10 charge-transporting thin films.
- An organic photoelectric conversion device having 10 hole collection layers and a non-fullerene active layer provided in contact therewith. 14. 13 organic photoelectric conversion elements, wherein the non-fullerene active layer contains a polymer having a thiophene skeleton in its main chain. 15. 13 or 14 of the organic photoelectric conversion elements, which are inversely laminated. 16. 16. The organic photoelectric conversion element according to any one of 13 to 15, wherein the organic photoelectric conversion element is an organic thin film solar cell or a photosensor. 17. 16 organic photovoltaic devices with a top anode structure.
- the charge-transporting composition for the organic photoelectric conversion device of the present invention can be produced using a charge-transporting substance composed of a polythiophene derivative that is inexpensively available on the market or can be easily synthesized by a known method.
- the thin film obtained therefrom, particularly when used as a hole-collecting layer of a photoelectric conversion device having an NFA active layer, when used as a hole-collecting layer of an organic photoelectric conversion device, the resulting charge-transporting thin film By further deepening the Ip of the element, the energy gap with the NFA active layer can be reduced, and the voltage of the device can be increased.
- a charge-transporting composition of the present invention is a charge-transporting composition for forming a charge-transporting thin film in a photoelectric conversion device having an NFA active layer, and contains a repeating unit represented by the following formula (1):
- “solid content” is a general term for all components of the charge-transporting composition other than the solvent.
- the NFA active layer means an active layer in which the content of NFA in the n-type semiconductor contained in the active layer is more than 50% by mass.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms.
- Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and may be substituted with a sulfonic acid group or a sulfonate group
- Z is an alkylene group having 1 to 40 carbon atoms which may be substituted with a halogen atom
- p is an integer of 1 or more
- R e is a hydrogen atom, a sulfonic acid group or a sulfonic acid group, even if substituted with an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms optionally substituted with a sulfonic acid group or a sulfonate group
- the alkyl group having 1 to 40 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n- dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, behenyl group
- the fluoroalkyl group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 40 carbon atoms in which at least one hydrogen atom on the carbon atoms is substituted with a fluorine atom.
- the alkyl group therein may be linear, branched or cyclic. Specific examples thereof include methoxy, ethoxy, n-propoxy, i- propoxy group, c-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group , n-heptadecyloxy group, n-octadecyloxy group, n-
- the fluoroalkoxy group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkoxy group having 1 to 40 carbon atoms in which at least one hydrogen atom on the carbon atoms is substituted with a fluorine atom.
- fluoromethoxy group difluoromethoxy group, perfluoromethoxy group, 1-fluoroethoxy group, 2-fluoroethoxy group, 1,2-difluoroethoxy group, 1,1-difluoroethoxy group, 2,2-difluoroethoxy group, 1,1,2-trifluoroethoxy group, 1,2,2-trifluoroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,2, 2,2-tetrafluoroethoxy group, perfluoroethoxy group, 1-fluoropropoxy group, 2-fluoropropoxy group, 3-fluoropropoxy group, 1,1-difluoropropoxy group, 1,2-difluoropropoxy group, 1, 3-difluoropropoxy group, 2,2-difluoropropoxy group, 2,3-difluoropropoxy group, 3,3-difluoropropoxy group, 1,1,2-
- the alkylene group having 1 to 40 carbon atoms may be linear, branched or cyclic, and specific examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentylene, Hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosanylene group and the like.
- aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like, with phenyl group, tolyl group and naphthyl group being preferred.
- aryloxy group having 6 to 20 carbon atoms include phenoxy group, anthracenoxy group, naphthoxy group, phenanthreoxy group, fluorenoxy group and the like.
- Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
- sulfonic acid groups and sulfonic acid groups include groups represented by the following formula (S).
- M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH(R S ) 3 or HNC 5 H 5 .
- R S independently represents a hydrogen atom, or represents an optionally substituted alkyl group having 1 to 6 carbon atoms.
- R S is an alkyl group having a substituent
- substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydroxy group. , an amino group, a carboxy group, and the like.
- alkyl group having 1 to 6 carbon atoms include the same groups as those exemplified for the above alkyl group.
- Specific examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, etc.
- aryl groups having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl groups and the like.
- a hydroxy group is preferable as the substituent, and specific examples of the alkyl group having a hydroxy group include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group and the like. mentioned.
- R S is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
- R 1 and R 2 are each independently a hydrogen atom, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, —O[C(R a R b )—C(R c R d )—O] p —R e , —OR f , a sulfonate group or a sulfonate group, or —O—Y— formed by combining R 1 and R 2 O- is preferred.
- R a to R d each independently represent a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Specific examples of these groups are the same as those listed above. Among them, R a to R d are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group.
- R e represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Specific examples of these groups are the same as those listed above. Among them, R e is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group, and more preferably a hydrogen atom, a methyl group, a propyl group, or a butyl group. Also, p is preferably 1 to 5, more preferably 1, 2 or 3.
- R f is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 20 carbon atoms, but a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, A fluoroalkyl group having 1 to 8 carbon atoms or a phenyl group is preferred, and -CH 2 CF 3 is more preferred.
- R 1 is preferably a hydrogen atom, a sulfonic acid group or a sulfonic acid group, more preferably a sulfonic acid group or a sulfonic acid group, and R 2 is preferably an alkoxy group having 1 to 40 carbon atoms.
- a group or -O-[Z-O] p -R e more preferably -O[C(R a R b )-C(R c R d )-O] p -R e or -OR f , more preferably preferably -O[C(R a R b )-C(R c R d )-O] p -R e , -O-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 3 , -O -CH 2 CH 2 -O-CH 2 CH 2 -OH or -O-CH 2 CH 2 -OH, or -O-Y-O- formed by combining R 1 and R 2 together is.
- the polythiophene derivative according to a preferred embodiment of the present invention comprises a repeating unit in which R 1 is a sulfonic acid group or a sulfonate group and R 2 is other than a sulfonic acid group or a sulfonate group, or R 1 and R 2 are combined to form --O--Y--O--.
- R 1 is a sulfonic acid group or a sulfonic acid group
- R 2 is an alkoxy group having 1 to 40 carbon atoms or —O—[ZO] p —R e or repeat units wherein R 1 and R 2 are joined to form -O-Y-O-.
- R 1 is a sulfonic acid group or a sulfonic acid group
- R 2 is —O[C(R a R b )–C(R c R d )–O] p — It contains repeating units that are R e or —OR f .
- R 1 is a sulfonic acid group or a sulfonic acid group
- R 2 is —O[C(R a R b )–C(R c R d )–O] p It includes repeating units that are —R e or —O—Y—O— formed by combining R 1 and R 2 .
- R 1 is a sulfonic acid group or a sulfonic acid group
- R 2 is --O--CH 2 CH 2 --O--CH 2 CH 2 --O--CH 3 , --O-- It contains a repeating unit that is CH 2 CH 2 —O—CH 2 CH 2 —OH or —O—CH 2 CH 2 —OH, or R 1 and R 2 are bonded to each other, and the following formulas (Y1) and /or a repeating unit that is a group represented by (Y2) is included.
- polythiophene derivative examples include polythiophene containing at least one repeating unit represented by the following formulas (1-1) to (1-5).
- examples of suitable structures of the above polythiophene derivatives include polythiophene derivatives having a structure represented by the following formula (1a).
- each unit may be combined randomly or may be combined as a block polymer.
- M is the same as above.
- polythiophene derivatives may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers).
- block copolymers include, for example, AB diblock copolymers, ABA triblock copolymers, and (AB) m -multiblock copolymers.
- Polythiophenes contain repeat units derived from other types of monomers such as thienothiophenes, selenophenes, pyrroles, furans, tellurophenes, anilines, arylamines, and arylenes such as phenylenes, phenylene vinylenes, and fluorenes. may contain.
- the content of the repeating unit represented by formula (1) in the polythiophene derivative is preferably more than 50 mol%, more preferably 80 mol% or more, more preferably 90 mol% of all repeating units contained in the polythiophene derivative.
- the above is more preferable, 95 mol % or more is more preferable, and 100 mol % is most preferable.
- the content of repeating units having a sulfonic acid group or a sulfonate group is 10% of the repeating units represented by formula (1) in the polythiophene derivative.
- mol % or more is preferred, 30 mol % or more is more preferred, 50 mol % or more is even more preferred, and 100 mol % is even more preferred.
- the polymer formed may contain repeating units derived from impurities, depending on the purity of the starting monomers used for polymerization.
- the term "homopolymer” means a polymer containing repeating units derived from one type of monomer, but may contain repeating units derived from impurities.
- the polythiophene derivative is preferably a polymer in which basically all the repeating units are the repeating units represented by the above formula (1). ) is more preferably a polymer containing at least one repeating unit.
- the polythiophene derivative contains a repeating unit having a sulfonic acid group
- at least part of the sulfonic acid group contained in the polythiophene derivative is an amine compound. is preferably an amine adduct to which is added.
- Amine compounds that can be used to form amine adducts include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, n-hexylamine.
- n-heptylamine, n-octylamine 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-penta Monoalkylamine compounds such as decylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosanylamine; aniline, tolylamine, 1-naphthylamine, 2-naphthylamine, 1- anthrylamine, 2-anthrylamine, 9-anthrylamine, 1-phenanthrylamine, 2-phenanthrylamine, 3-phenanthrylamine, 4-phenanthrylamine, 9-phenanthrylamine Primary
- the above polythiophene derivative or its amine adduct may be treated with a reducing agent.
- some of the repeating units constituting them may have an oxidized chemical structure called a "quinoid structure".
- the term "quinoid structure” is used for the term “benzenoid structure”, the latter being a structure containing an aromatic ring, whereas the former is a structure in which the double bond within the aromatic ring moves out of the ring (the As a result, the aromatic ring disappears), meaning a structure in which two exocyclic double bonds conjugated with other double bonds remaining in the ring are formed.
- R 1 and R 2 are as defined in formula (1) above.
- This quinoid structure is generated by a process in which the polythiophene derivative containing the repeating unit represented by the above formula (1) undergoes an oxidation reaction by a dopant, a so-called doping reaction, and imparts charge transport properties to the polythiophene derivative. It forms part of a structure called "bipolaron structure". These structures are known. Introduction of a “polaron structure” and/or a “bipolaron structure” is essential in the production of an organic solar cell element, and in fact, when producing an organic solar cell element, the thin film formed from the charge-transporting composition is baked. Sometimes the doping reaction described above is deliberately induced to achieve this.
- the reason why the quinoid structure is included in the polythiophene derivative before the doping reaction is that the polythiophene derivative undergoes an unintended oxidation reaction equivalent to the doping reaction during the manufacturing process (especially the sulfonation step therein). This is thought to be due to the
- the polythiophene derivative when the polythiophene derivative is subjected to a reduction treatment using a reducing agent, even if the quinoid structure is excessively introduced into the polythiophene derivative, the quinoid structure is reduced by the reduction, and the solubility and dispersibility of the polythiophene derivative in an organic solvent are improved. is improved, it becomes possible to stably produce a good charge-transporting composition that gives a thin film with excellent uniformity.
- the conditions for the reduction treatment are such that the quinoid structure is reduced to appropriately convert to the non-oxidized structure, that is, the benzenoid structure (for example, in the polythiophene derivative containing the repeating unit represented by the above formula (1),
- the quinoid structure represented by the above formula (1′) is not particularly limited as long as it can be converted to the structure represented by the above formula (1), for example, in the presence of a suitable solvent or
- This treatment can be carried out simply by contacting the polythiophene derivative or amine adduct with a reducing agent in the absence thereof.
- a reducing agent is not particularly limited as long as the reduction is performed properly, but suitable examples include aqueous ammonia, hydrazine, etc., which are readily available on the market.
- the amount of the reducing agent varies depending on the amount of the reducing agent to be used, and cannot be categorically defined. It is 0.1 parts by mass or more and 10 parts by mass or less from the viewpoint of preventing excess reducing
- a polythiophene derivative or an amine adduct is stirred overnight at room temperature in 28% ammonia water.
- the reduction treatment under such relatively mild conditions sufficiently improves the solubility and dispersibility of the polythiophene derivatives and amine adducts in organic solvents.
- the reduction treatment may be performed before or after forming the amine adduct.
- the solubility and dispersibility of the polythiophene derivative or its amine adduct in the solvent change, and as a result, the polythiophene derivative or its amine adduct, which was not dissolved in the reaction system at the start of the treatment, will be removed after the treatment is completed. Sometimes dissolved. In such a case, an organic solvent (acetone, isopropyl alcohol, etc. in the case of sulfonated polythiophene) incompatible with the polythiophene derivative or its amine adduct is added to the reaction system to obtain the polythiophene derivative or its amine adduct.
- the polythiophene derivative or its amine adduct can be recovered by a method such as causing precipitation and filtering.
- the weight-average molecular weight of the polythiophene derivative containing the repeating unit represented by formula (1) or its amine adduct is preferably from about 1,000 to about 1,000,000, more preferably from about 5,000 to about 100,000. Preferably, from about 10,000 to about 50,000 is even more preferred.
- a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography.
- the polythiophene derivative or its amine adduct contained in the charge-transporting composition of the present invention may be only one kind of polythiophene derivative or its amine adduct containing a repeating unit represented by formula (1), or two kinds. or more.
- a commercially available product or a product obtained by polymerizing a thiophene derivative or the like as a starting material by a known method may be used. It is also preferable to use those purified by methods such as reprecipitation and ion exchange. By using the purified one, the characteristics of the organic solar cell element provided with the thin film obtained from the charge-transporting composition of the present invention can be further enhanced. Examples of commercially available products include SELFTRON (registered trademark) manufactured by Tosoh Corporation.
- conjugated polymers and sulfonated conjugated polymers are described in US Pat. No. 8,017,241 to Seshadri et al. Sulfonated polythiophenes are also described in WO2008/073149 and WO2016/171935.
- At least part of the polythiophene derivative containing the repeating unit represented by formula (1) or its amine adduct contained in the charge-transporting composition is dissolved in an organic solvent.
- a polythiophene derivative containing a repeating unit represented by formula (1) or an amine adduct thereof and a charge-transporting substance other than the polythiophene derivative containing the repeating unit may be used in combination.
- the ionization potential of the hole collection layer is preferably close to the ionization potential of the p-type semiconductor material in the active layer.
- the absolute value of the difference is preferably 0 to 1 eV, more preferably 0 to 0.5 eV, and even more preferably 0 to 0.2 eV. Therefore, the charge-transporting composition of the present invention contains an arylsulfonic acid compound represented by the following formula (2) and a heteropolyacid for the purpose of adjusting the ionization potential of the charge-transporting thin film obtained using the composition.
- A represents a naphthalene ring or anthracene ring
- B represents a divalent to tetravalent perfluorobiphenyl group
- l represents the number of sulfonic acid groups bonded to A, satisfying 1 ⁇ l ⁇ 4 is an integer
- q indicates the number of bonds between B and X, and is an integer satisfying 2 to 4.
- the arylsulfonic acid compound represented by formula (2) can be synthesized by a known method, for example, by the method described in International Publication No. 2006/025342.
- heteropolyacids include heteropolyacid compounds such as phosphomolybdic acid, phosphotungstic acid, phosphotungstomolybdic acid, silicotungstic acid, sodium phosphomolybdate, and phosphovanadomolybdic acid described in International Publication No. 2010/058777. Inorganic oxidizing agents can be mentioned. Phosphomolybdic acid and phosphotungstic acid are preferred in the present invention.
- the content of the electron-accepting dopant substance is appropriately set in consideration of the type of the charge-transporting substance and the charge-transporting substance to be expressed. 0.05 to 10, preferably 0.1 to 3.0, more preferably 0.2 to 2.0.
- the mixing ratio of the arylsulfonic acid compound represented by the formula (2) and the heteropolyacid is 10:90 to 90:10 is preferred, and 20:80 to 80:20 is more preferred.
- the charge-transporting composition of the present invention may contain an electron-accepting dopant substance other than the arylsulfonic acid compound represented by formula (2) and the heteropolyacid.
- electron-accepting dopant substances include strong inorganic acids such as hydrogen chloride, sulfuric acid , nitric acid, phosphoric acid; boron chloride (BBr 3 ), boron trifluoride etherate (BF 3 OEt 2 ), iron chloride (III) (FeCl 3 ), copper chloride (II) (CuCl 2 ), antimony pentachloride (V) (SbCl 5 ), arsenic pentafluoride (V) (AsF 5 ), phosphorus pentafluoride (PF 5 ), tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); Lewis acids such as benzenesulfonic acid, tosylic acid, hydroxyl Benzenes
- the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably not contained, based on the total electron-accepting dopant substances.
- the charge-transporting composition of the present invention may contain a surfactant.
- the surfactant is not particularly limited, and fluorine-based surfactants, silicone-based surfactants, and the like can be used. In the present invention, it is preferable to use fluorine-based surfactants.
- the fluorosurfactant used in the present invention is available as a commercial product.
- Such commercial products include DuPont Capstone® FS-10, FS-22, FS-30, FS-31, FS-34, FS-35, FS-50, FS-51 , FS-60, FS-61, FS-63, FS-64, FS-65, FS-66, FS-81, FS-83, FS-3100; Daiichi Kogyo Seiyaku Co., Ltd.
- Neugen FN-1287 Examples include, but are not limited to, Megafac F-444, F-477, F-559 manufactured by DIC Corporation.
- Capstone FS-30, 31, 34, 35 and 3100, Neugen FN-1287 and Megafac F-559, which are nonionic surfactants, are preferred.
- the fluorine-based surfactant is not particularly limited as long as it contains a fluorine atom, and may be cationic, anionic, or nonionic, but fluorine-based nonionic surfactants are preferred. At least one fluorine-based nonionic surfactant selected from the following formulas (A1) and (B1) is particularly preferred.
- R represents a monovalent organic group containing a fluorine atom
- n represents an integer of 1-20.
- organic groups include alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms.
- aralkyl groups having 7 to 20 carbon atoms include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group and p-ethylphenylmethyl. group, 2-propylphenylmethyl group, 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, ⁇ -naphthylmethyl group and the like.
- heteroaryl groups include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4 -isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4-imidazolyl group, 2 -pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 3-pyrazyl group, 5-pyrazyl group, 6-pyrazyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 6 -pyrimidyl group, 3-pyridazyl group, 4-pyridazyl group, 5-pyridazyl group
- n is not particularly limited as long as it is an integer of 1-20, but an integer of 1-10 is more preferable.
- n has the same meaning as above.
- a specific example of the perfluoroalkyl group having 1 to 40 carbon atoms is a group in which all the hydrogen atoms of the alkyl group having 1 to 40 carbon atoms are substituted with fluorine atoms.
- a surfactant When a surfactant is included, its content is not particularly limited. About 0.01 to 0.1% by mass of the whole is preferable, 0.02 to 0.08% by mass is more preferable, and 0.03 to 0.06% by mass is most preferable.
- compositions of the present invention may contain one or more metal oxide nanoparticles.
- a nanoparticle means a fine particle having an average primary particle size of the order of nanometers (typically 500 nm or less).
- Metal oxide nanoparticles refer to metal oxides shaped into nanoparticles.
- a nanoparticle means a fine particle having an average primary particle size of the order of nanometers (typically 500 nm or less).
- Metal oxide nanoparticles refer to metal oxides shaped into nanoparticles.
- the primary particle size of the metal oxide nanoparticles used in the present invention is not particularly limited as long as it is nano-sized. 100 nm is more preferred, and 5 to 50 nm is even more preferred.
- the particle size is a measured value using a nitrogen adsorption isotherm by the BET method.
- Metals constituting metal oxide nanoparticles in the present invention include not only metals in the usual sense, but also semimetals.
- Metals in the usual sense include, but are not limited to, tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum ( It is preferable to use one or more selected from the group consisting of Ta) and W (tungsten).
- metalloids refer to elements whose chemical and/or physical properties are intermediate between those of metals and nonmetals. A universal definition of metalloids has not been established, but in the present invention, a total of six Let the elements be semimetals. These semimetals may be used alone or in combination of two or more, and may also be used in combination with metals in the usual sense.
- Metal oxide nanoparticles used in the present invention include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti) , aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (tungsten).
- the metal oxide may be a mixture of oxides of individual single metals, or a composite oxide containing a plurality of metals.
- metal oxides include B2O3 , B2O , SiO2 , SiO, GeO2 , GeO , As2O4 , As2O3 , As2O5 , Sb2O3 , Sb2 . O5, TeO2, SnO2 , ZrO2 , Al2O3 , ZnO and the like, but also B2O3 , B2O , SiO2 , SiO , GeO2 , GeO , As2O4 , As2 . O3 , As2O5 , SnO2 , SnO, Sb2O3, TeO2 , and mixtures thereof are preferred, with SiO2 being more preferred.
- the metal oxide nanoparticles may contain one or more organic capping groups.
- This organic capping group may be reactive or non-reactive.
- Examples of reactive organic capping groups include organic capping groups that can be crosslinked by UV light or radical initiators.
- silica sol in which SiO 2 nanoparticles are dispersed in a dispersion medium as the metal oxide nanoparticles.
- the silica sol is not particularly limited, and can be appropriately selected from known silica sols and used. Commercially available silica sols are usually in the form of dispersions.
- SiO2 nanoparticles are mixed with various solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, acetic acid.
- solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, acetic acid.
- solvent water-soluble alcohols are preferable, and methanol, 2-propanol and ethylene glycol are more preferable.
- silica sols include Snowtex (registered trademark) ST-O, ST-OS, ST-O-40 and ST-OL manufactured by Nissan Chemical Industries, Ltd., and Silidol 20 manufactured by Nippon Chemical Industries Co., Ltd. , 30, 40, etc.; methanol silica sol manufactured by Nissan Chemical Co., Ltd., MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, EG- Examples include, but are not limited to, organosilica sols such as ST.
- the solid content concentration of the silica sol is also not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 30% by mass.
- the content is not particularly limited, but in consideration of sufficient adhesion to the active layer, 50 parts per 100 parts by mass of the charge-transporting substance. ⁇ 95 parts by mass is preferable, 60 to 95 parts by mass is more preferable, and 80 to 95 parts by mass is even more preferable.
- the charge-transporting substance is used as a solution or dispersion, the amount of metal oxide nanoparticles to be added is based on the solid content of the charge-transporting substance.
- the composition of the present invention may contain an alkoxysilane.
- alkoxysilane By containing alkoxysilane, it is possible to improve the solvent resistance and water resistance of the obtained thin film, improve the electron blocking property, and optimize the HOMO level and LUMO level for the active layer.
- the alkoxysilane may be a siloxane-based material.
- any one or more alkoxysilanes selected from tetraalkoxysilane, trialkoxysilane and dialkoxysilane can be used.
- Methoxysilane, methyltriethoxysilane, methyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethyldiethoxysilane and dimethyldimethoxysilane are preferred, and tetraethoxysilane is more preferred.
- siloxane-based materials include polysiloxanes such as poly(tetraethoxysilane) and poly(phenylethoxysilane) obtained by reactions such as hydrolysis of the alkoxysilanes.
- alkoxysilane When alkoxysilane is used, its content is not particularly limited as long as it exhibits the above effects. 0.01 to 50 times is more preferred, and 0.05 to 10 times is even more preferred.
- the charge-transporting composition of the present invention may further contain a matrix polymer, if necessary.
- a matrix polymer include matrix polymers containing repeating units represented by the following formula (I) and repeating units represented by the following formula (II).
- R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a halogen atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a a perfluoroalkyl group of 1 to 20,
- Q is -[OC(R h R i )-C(R j R k )] y -O-[CR l R m ] z -SO 3 H
- R h , R i , R j , R k , R l and R m are each independently a hydrogen atom, a halogen atom, a C 1-20 fluoroalkyl group, or a C 1-20 perfluoroalkyl group, y is 0-10, and z is 1-5.
- halogen atom the fluoroalkyl group having 1 to 20 carbon atoms
- perfluoroalkyl group having 1 to 20 carbon atoms are the same as those described above.
- R 3 , R 4 , R 5 and R 6 are preferably a fluorine atom or a chlorine atom, R 3 , R 5 and R 6 are a fluorine atom and R 4 is a chlorine atom is more preferred, and it is even more preferred that all of R 3 , R 4 , R 5 and R 6 are fluorine atoms.
- R 7 , R 8 and R 9 are preferably fluorine atoms.
- R h , R i , R j , R k , R l and R m are preferably a fluorine atom, a C 1-8 fluoroalkyl group, or a C 1-8 perfluoroalkyl group.
- R l and R m are fluorine atoms.
- y is preferably 0, and z is preferably 2.
- R 3 , R 5 and R 6 above are a fluorine atom
- R 4 is a chlorine atom
- each of R 1 and R m is a fluorine atom
- y is 0
- z is preferably two.
- each R3 , R4 , R5 , and R6 is a fluorine atom; and each R1 and Rm is a fluorine atom; y is 0; and z is preferably two.
- the ratio (s:t ratio) between the number "s" of repeating units represented by formula (I) and the number "t” of repeating units represented by formula (II) is not particularly limited.
- the s:t ratio is preferably 9:1 to 1:9, more preferably 8:2 to 2:8.
- the matrix polymer that can be suitably used in the present invention may be synthesized using a known method or may be a commercially available product.
- the polymer containing the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) is represented by the monomer represented by the following formula (Ia) and the following formula (IIa)
- Monomers can be prepared by copolymerization by known polymerization methods, followed by hydrolysis of the sulfonyl fluoride groups to convert them to sulfonic acid groups.
- TFE tetrafluoroethylene
- CFE chlorotrifluoroethylene
- F 2 C fluorinated monomers
- SO2F CF-[O-CF2 - CR12FO ] y - CF2 - CF2 - SO2F where R12 is F or CF3 and y is 1 to 10
- F 2 C CF-O-CF 2 -CF 2 -CF 2 -SO 2 F
- F 2 C CF-OCF 2 -CF 2 -CF 2 -CF 2 -SO 2 F, etc.).
- the matrix polymer means the mass (g/mol) of the matrix polymer per 1 mol of acid groups present in the matrix polymer.
- the equivalent weight of the matrix polymer is preferably from about 400 to about 15,000 g/mol, more preferably from about 500 to about 10,000 g/mol, even more preferably from about 500 to about 8,000 g/mol, even more preferably about 500 to about 2,000 g/mol, most preferably about 600 to about 1,700 g/mol.
- Such matrix polymers are commercially available.
- Commercially available products include, for example, NAFION (registered trademark) manufactured by DuPont, AQUIVION (registered trademark) manufactured by Solvay Specialty Polymers, and FLEMION (registered trademark) manufactured by Asahi Glass Co., Ltd., and the like.
- the matrix polymer is preferably polyethersulfone containing at least one repeating unit containing at least one sulfonic acid residue (--SO 3 H).
- composition of the present invention may contain other additives as long as the object of the present invention can be achieved.
- the type of additive can be appropriately selected from known additives depending on the desired effect.
- a highly soluble solvent that can dissolve the polythiophene derivative and the electron-accepting dopant substance well can be used as the solvent for preparing the charge-transporting composition.
- the highly soluble solvent can be used alone or in combination of two or more, and the amount used can be 5 to 100% by mass of the total solvent used in the composition.
- Examples of such highly soluble solvents include water; alcohol solvents such as ethanol, 2-propanol, 1-butanol, 2-butanol, s-butanol, t-butanol, 1-methoxy-2-propanol; - amides such as methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone
- Organic solvents such as solvents can be mentioned.
- at least one selected from water and alcoholic solvents is preferable, and water, ethanol and 2-propanol are more preferable.
- both the charge-transporting substance and the electron-accepting dopant substance are completely dissolved in the solvent or are in a state of being uniformly dispersed. Considering obtaining a pore-collecting layer with good reproducibility, it is more preferable that these substances are completely dissolved in the solvent.
- the charge-transporting composition of the present invention has a viscosity of 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25° C. in order to improve film-forming properties and ejection properties from a coating apparatus.
- the high-viscosity organic solvent is not particularly limited, and examples include cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and 1,3-butane. diol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol and the like.
- the addition ratio is preferably within a range in which solids do not precipitate, and as long as solids do not precipitate, it is 1 to 80% by mass of the total solvent used in the composition. preferable.
- solvents examples include butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl carbitol, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, n-hexyl acetate and the like.
- the addition ratio is preferably 1 to 90% by mass, more preferably 1 to 50% by mass, of the total solvent used in the composition.
- the solid content concentration of the composition of the present invention is appropriately set in consideration of the viscosity and surface tension of the composition, the thickness of the thin film to be produced, etc., but is usually 0.1 to 10.0 mass. %, preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass.
- the viscosity of the charge-transporting composition used in the present invention may be appropriately adjusted depending on the coating method, taking into consideration the thickness of the thin film to be produced and the solid content concentration. ⁇ 50 mPa ⁇ s.
- a charge-transporting substance, a surfactant, a metal oxide nanoparticle, an electron-accepting dopant substance, a solvent, and the like are used as long as the solid content is uniformly dissolved or dispersed in the solvent. They can be mixed in any order.
- a method of dissolving a polythiophene derivative in a solvent and then dissolving an electron-accepting dopant substance in the solution a method of dissolving an electron-accepting dopant substance in a solvent and then dissolving a polythiophene derivative in the solution
- Any method of mixing a polythiophene derivative and an electron-accepting dopant substance and then dissolving the mixture in a solvent can be employed as long as the solid content is uniformly dissolved or dispersed in the solvent.
- the order of adding the matrix polymer and the alkoxysilane is also arbitrary.
- the preparation of the composition is carried out under an inert gas atmosphere at normal temperature and normal pressure. bottom) or while heating.
- the composition described above is coated on the anode in the case of a forward stacking type organic thin film solar cell, or on the active layer in the case of a reverse stacking type organic thin film solar cell, and then sintered to obtain the hole collection of the present invention. It can form layers.
- the viscosity and surface tension of the composition, the thickness of the desired thin film, etc. are taken into consideration, and the drop casting method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, An optimum wet process method such as an inkjet method, a printing method (letterpress, intaglio, lithography, screen printing, etc.) may be adopted. Further, coating is usually carried out in an inert gas atmosphere at normal temperature and pressure. You may carry out, and you may carry out while heating.
- the film thickness is not particularly limited, it is preferably about 0.1 to 800 nm, more preferably about 30 to 500 nm in any case.
- a method for changing the film thickness there are methods such as changing the solid content concentration in the composition and changing the amount of the solution at the time of coating.
- a method for producing an organic thin-film solar cell using the charge-transporting composition of the present invention as a composition for forming a hole-collecting layer will be described below, but the present invention is not limited thereto.
- Laminated organic thin film solar cell A process of forming a layer of anode material on the surface of a transparent substrate to manufacture a transparent electrode.
- Inorganic oxides such as zinc oxide (IZO), metals such as gold, silver and aluminum, and highly charge-transporting organic compounds such as polythiophene derivatives and polyaniline derivatives can be used. Among these, ITO is most preferred.
- the transparent substrate a substrate made of glass or transparent resin can be used as the transparent substrate. The method for forming the anode material layer (anode layer) is appropriately selected according to the properties of the anode material.
- a dry process such as a vacuum deposition method or a sputtering method is selected. Considering the thickness of the thin film, etc., the optimum one is adopted from among the various wet process methods described above.
- a commercially available transparent anode substrate can also be used, and in this case, from the viewpoint of improving the yield of the device, it is preferable to use a substrate that has been smoothed.
- the method for producing an organic thin film solar cell of the present invention does not include the step of forming an anode layer.
- an inorganic oxide such as ITO
- surface treatment such as UV ozone treatment and oxygen-plasma treatment immediately before use.
- the anode material is mainly composed of an organic substance, surface treatment may not be performed.
- a step of forming an active layer on the formed hole collection layer It may be a laminate of layers or a non-laminate thin film made of a mixture of these materials.
- an NFA active layer is formed as the active layer.
- the NFA active layer means an active layer in which the content of NFA in the n-type semiconductor contained in the active layer is more than 50% by mass in the present invention, and the content is preferably 70% by mass. % or more, more preferably 80 mass % or more, and still more preferably 90 mass % or more.
- n-type semiconductor materials include compounds represented by the following formulas (3-1) to (3-4).
- Examples of p-type semiconductor materials include regioregular poly(3-hexylthiophene) (P3HT), PTB7 represented by the following formula (4-1), PM6 represented by the following formula (4-2) (also known as PBDB- T-2F), polymers containing a thiophene skeleton in the main chain, such as thienothiophene unit-containing polymers as described in JP-A-2009-158921 and WO 2010/008672, CuPC, ZnPC, etc. porphyrins such as phthalocyanines and tetrabenzoporphyrin;
- the compound represented by the formula (3-1) is preferred as the n-type semiconductor material, and among these, ITIC-4F in which both X 1 and X 2 are F is more preferred.
- the p-type semiconductor material polymers containing a thiophene skeleton in the main chain, such as PM6 and PTB7, are preferable.
- thiophene skeleton in the main chain refers to a divalent aromatic ring consisting only of thiophene, or thienothiophene, benzothiophene, dibenzothiophene, benzodithiophene, naphthothiophene, naphthodithiophene, anthrathiophene, anthradithiophene.
- alkyl group having 1 to 20 carbon atoms alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon It may be substituted with an aralkyl group having 7 to 20 carbon atoms or an acyl group having 1 to 20 carbon atoms.
- the halogen atom, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms are the same as those exemplified above. is mentioned.
- thioalkoxy group having 1 to 20 carbon atoms include groups obtained by substituting the oxygen atom of the above alkoxy group with a sulfur atom.
- thioalkoxy (alkylthio) groups having 1 to 20 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio and t-butylthio.
- n-pentylthio group n-hexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetra decylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group, n-nonadecylthio group, n-eicosanylthio group and the like.
- alkenyl groups having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- 1-pentenyl group, n-1-decenyl group, n-1-eicosenyl group and the like.
- alkynyl groups having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl and n-3-butynyl.
- haloalkyl groups having 1 to 20 carbon atoms include groups obtained by substituting at least one hydrogen atom in the above alkyl group with a halogen atom.
- Halogen atoms may be chlorine, bromine, iodine or fluorine atoms. Among them, a fluoroalkyl group is preferred, and a perfluoroalkyl group is more preferred.
- Specific examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,3- pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, nonafluorobutyl group, 4,4,4-trifluoro butyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoro pentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4,4,5 , 5,6,6-
- acyl groups having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
- the n-type semiconductor material corresponding to FA may be included as the remainder in the range of less than 50 mass % of the n-type semiconductor material contained in the active layer.
- Specific examples of such n-type semiconductor materials include fullerene, [6,6]-phenyl-C 61 -butyric acid methyl ester (PC 61 BM), [6,6]-phenyl-C 71 -butyric acid methyl ester ( PC 71 BM) and the like.
- the active layer composition used for the NFA active layer can also be obtained as a commercial product.
- Examples of commercially available products include PV-X Plus (manufactured by Raynergy tek) and PV-ATL-D1A1 (manufactured by Raynergy tek).
- the same dry process as described above is selected when the active layer material is a poorly soluble sublimable material, and when the active layer material is a solution material or a dispersion liquid material, the viscosity and surface of the composition are selected.
- the most suitable wet process method is adopted from among the various wet process methods described above.
- An electron collecting layer may be formed.
- Materials for forming the electron collection layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride (NaF), and magnesium fluoride.
- the various dry processes described above are selected. Considering the viscosity, surface tension, desired thickness of the thin film, etc., the optimum wet process method is adopted from among the various wet process methods described above.
- a step of forming a cathode layer on the formed electron collection layer metals such as barium, silver, and gold; inorganic oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO); and highly charge-transporting organic compounds such as polythiophene derivatives and polyaniline derivatives. can be used by laminating or mixing the cathode materials.
- metals such as barium, silver, and gold
- inorganic oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO)
- highly charge-transporting organic compounds such as polythiophene derivatives and polyaniline derivatives.
- the various dry processes described above are selected. Considering the viscosity and surface tension of the film, the desired thickness of the thin film, etc., the optimum one is adopted from among the various wet process methods described above.
- a carrier block layer may be provided between arbitrary layers for the purpose of controlling the rectification of photocurrent.
- a carrier blocking layer When a carrier blocking layer is provided, an electron blocking layer is usually inserted between the active layer and the hole collecting layer or the anode, and a hole blocking layer is inserted between the active layer and the electron collecting layer or the cathode.
- Materials for forming the hole blocking layer include titanium oxide, zinc oxide, tin oxide, bathocuproine (BCP), 4,7-diphenyl-1,10-phenanthroline (BPhen), and the like.
- Materials for forming the electron blocking layer include N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine ( ⁇ -NPD) and triarylamine-based materials such as poly(triarylamine) (PTAA). materials and the like.
- the various dry processes described above are selected. Considering the viscosity and surface tension of the composition, the desired thickness of the thin film, and the like, the most suitable one is adopted from among the various wet process methods described above.
- the dry process described above is selected in the case of the poorly soluble and difficultly dispersible sublimable material, and in the case of the solution material or dispersion liquid material, the viscosity of the composition and the Considering the surface tension, the desired thickness of the thin film, etc., the most suitable wet process method is adopted from among the various wet process methods described above.
- a commercially available transparent cathode substrate can be suitably used, and from the viewpoint of improving the yield of the device, it is preferable to use a substrate that has been smoothed.
- the method for producing an organic thin-film solar cell of the present invention does not include the step of forming a cathode layer.
- an inorganic oxide is used as a cathode material to form a transparent cathode substrate, it may be subjected to the same cleaning treatment and surface treatment as those for the sequentially laminated anode material.
- a trapping layer may be formed.
- Materials for forming the electron collection layer include zinc oxide (ZnO), titanium oxide (TiO), tin oxide (SnO), etc., in addition to the materials exemplified in the above-mentioned forward stacking type materials.
- the above-described dry process is selected in the case of a poorly soluble or difficultly dispersible sublimation material, and in the case of a solution material or a dispersion liquid material, the viscosity and surface tension of the composition are adjusted to the desired value.
- the optimum one is adopted from among the various wet process methods described above.
- a method of forming an inorganic oxide precursor layer on the cathode using a wet process (particularly spin coating or slit coating) and firing to form an inorganic oxide layer can also be employed.
- the active layer consists of an n-layer, which is a thin film made of an n-type semiconductor material, and a p-layer, which is a thin film made of a p-type semiconductor material. or a non-laminated thin film made of a mixture of these materials.
- the n-type and p-type semiconductor materials include the same materials as those exemplified in the above-mentioned forwardly laminated semiconductor materials. Polymers containing a thiophene skeleton in the main chain, such as PTB7, are preferred.
- the method for forming the active layer is also the same as the method described for the forward lamination type active layer.
- a step of forming an anode layer on the formed hole collection layer. is the same as that of the positively laminated cathode layer.
- a carrier block layer may be provided between arbitrary layers for the purpose of controlling the rectification of photocurrent.
- Materials for forming the hole blocking layer and materials for forming the electron blocking layer are the same as those described above, and the method for forming the carrier blocking layer is also the same as described above.
- the OPV element manufactured by the method exemplified above is introduced into the glove box again and sealed in an inert gas atmosphere such as nitrogen. It is possible to exhibit the function as a solar cell and to measure the solar cell characteristics.
- a sealing method a concave glass substrate having a UV curable resin attached to the edge is attached to the film forming surface side of the organic thin film solar cell element in an inert gas atmosphere, and the resin is cured by UV irradiation.
- a film-sealing type sealing method using a method such as sputtering under vacuum is a method such as sputtering under vacuum.
- Example 1-2 2.50 g of isopropanol was added to 2.53 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution), and the above formula (2) synthesized based on the description of International Publication No. 2006/025342 25.3 mg of the arylsulfonic acid compound A represented by -1) was added to prepare a dark blue solution having a concentration of 1.5% by mass. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B2.
- Example 1-3 To a solution of 2.49 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution) and 2.45 g of isopropanol, the above formula (2) synthesized based on the description of WO 2006/025342 50.2 mg of the arylsulfonic acid compound A represented by -1) was added to prepare a dark blue solution having a concentration of 2.0% by mass. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B3.
- SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution) 2.54 g of isopropanol was added to a solution of 2.48 g of 12 molybdo (IV) phosphoric acid n-hydrate (Fujifilm Wako Pure Chemical ( Co., Ltd.) was added to prepare a dark blue solution with a concentration of 1.1% by mass. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B4.
- SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution) and 2.47 g of isopropanol were added to a solution containing 2.53 g of 12 molybdo (IV) phosphoric acid n-hydrate (Fujifilm Wako Pure Chemical Industries, Ltd. ( Co., Ltd.) was added to prepare a dark blue solution with a concentration of 1.5% by mass. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B5.
- SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution) 2.52 g of isopropanol 2.46 g was added to a solution, 12 molybdo (IV) phosphate n-hydrate (Fujifilm Wako Pure Chemical ( Co., Ltd.) was added to prepare a dark blue solution with a concentration of 2.0% by mass. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B6.
- Example 1-7 2.64 g of isopropanol was added to 2.68 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution), and the above formula (2) synthesized based on the description of International Publication No. 2006/025342 26.9 mg of the arylsulfonic acid compound A represented by -1) and 26.9 mg of 12 molybdo (IV) phosphate n-hydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added, and the concentration was 2.0 mass. % dark blue solution was prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B7.
- SELFTRON SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution
- PEDOT PSS aqueous solution (HTL Solar, manufactured by Heraeus, 1.0% by mass aqueous dispersion) 3.6 g, synthesized based on the description of International Publication No. 2006/025342, represented by the above formula (2-1) 18.7 mg of arylsulfonic acid compound A and 18.9 mg of 12-molybdo(IV) phosphate n-hydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) dissolved in 3.6 g of pure water was added, and the concentration was adjusted to A 1.0% by weight dark blue solution was prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 1.00 ⁇ m to obtain a hole-collecting layer composition B8.
- HTL Solar manufactured by Heraeus, 1.0% by mass aqueous dispersion
- Example 1-9 2.48 g of isopropanol and 1.5 mg of fluorine-based nonionic surfactant (F-559, manufactured by DIC Corporation) were added to 2.52 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution). To the solution obtained, 5.05 mg of the arylsulfonic acid compound A represented by the above formula (2-1) synthesized according to the description of WO 2006/025342 was added to obtain a dark blue solution with a concentration of 1.1% by mass. was prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B9.
- F-559 fluorine-based nonionic surfactant
- Example 1-10 2.46 g of isopropanol and 1.5 mg of fluorine-based nonionic surfactant (F-559, manufactured by DIC Corporation) were added to 2.51 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution). To the solution obtained, 25.05 mg of the arylsulfonic acid compound A represented by the above formula (2-1) synthesized according to the description of WO 2006/025342 was added to obtain a dark blue solution having a concentration of 1.5% by mass. was prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B10.
- Example 1-11 2.47 g of isopropanol and 1.5 mg of fluorine-based nonionic surfactant (F-559, manufactured by DIC Corporation) were added to 2.48 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution). To the solution obtained, 49.05 mg of the arylsulfonic acid compound A represented by the above formula (2-1) synthesized according to the description of WO 2006/025342 was added to obtain a dark blue solution having a concentration of 2.0% by mass. was prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B11.
- Example 1-12 2.46 g of isopropanol and 1.5 mg of fluorine-based nonionic surfactant (F-559, manufactured by DIC Corporation) were added to 2.53 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution). To the solution, 25.05 mg of the arylsulfonic acid compound A represented by the above formula (2-1) synthesized based on the description of WO 2006/025342, 12 molybdo (IV) phosphate n-hydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added in an amount of 25.05 mg to prepare a dark blue solution having a concentration of 2.0% by mass. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B12.
- SELFTRON fluorine-based nonionic surfactant
- Example 1-13 1.25 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution), 3.71 g of pure water, fluorine-based nonionic surfactant (FN-1287, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5.00 mg of the above formula ( 25.0 mg of arylsulfonic acid compound A represented by 2-1) and 7.50 mg of silicomolybdic acid n-hydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to obtain a dark blue color having a concentration of 1.15% by mass. A solution was prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B13.
- SELFTRON SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution
- Example 1-14 1.25 g of SELFTRON (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution), 3.71 g of pure water, fluorine-based nonionic surfactant (FN-1287, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5.00 mg of the above formula ( 25.0 mg of the arylsulfonic acid compound A represented by 2-1) and 7.50 mg of silicotungstic acid n-hydrate (manufactured by Alfa Aesar Co., Ltd.) were added to obtain a dark blue solution having a concentration of 1.15% by mass. prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a hole-collecting layer composition B14.
- SELFTRON SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution
- fluorine-based nonionic surfactant FN-1287, manufactured
- PEDOT PSS aqueous solution (HTL Solar, manufactured by Heraeus, 1.0% by mass aqueous dispersion) 2.99 g, synthesized based on the description of International Publication No. 2006/025342, represented by the above formula (2-1) 3.0 mg of arylsulfonic acid compound A and 3.0 mg of 12 molybdo (IV) phosphate n-hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to obtain a dark blue solution with a concentration of 1.2% by mass. was prepared. The resulting dark blue solution was filtered through a syringe filter with a pore size of 1.00 ⁇ m to obtain a hole-collecting layer composition B15.
- Example 2-1 Fabrication of hole-collecting layer composition film-coated substrate for ionization potential measurement
- a glass substrate with an ITO transparent conductive layer of 20 mm ⁇ 20 mm was treated with UV/ozone for 15 minutes.
- the hole-collecting layer composition B1 prepared in Example 1-1 was applied to this substrate by a spin coating method, and then annealed by heating at 100° C. for 5 minutes to form a hole-collecting layer.
- a composition film-coated substrate was prepared.
- Example 2-2 A hole-collecting layer composition-coated substrate was prepared in the same manner as in Example 2-1, except that the hole-collecting layer composition B2 was used instead of the hole-collecting layer composition B1. did.
- Example 2-3 A hole-collecting layer composition-coated substrate was produced in the same manner as in Example 2-1, except that the hole-collecting layer composition B3 was used instead of the hole-collecting layer composition B1. did.
- Example 2-4 A hole-collecting layer composition-coated substrate was prepared in the same manner as in Example 2-1, except that the hole-collecting layer composition B4 was used instead of the hole-collecting layer composition B1. did.
- Example 2-5 A hole-collecting layer composition-coated substrate was produced in the same manner as in Example 2-1, except that the hole-collecting layer composition B5 was used instead of the hole-collecting layer composition B1. did.
- Example 2-6 A hole-collecting layer composition-coated substrate was produced in the same manner as in Example 2-1, except that the hole-collecting layer composition B6 was used instead of the hole-collecting layer composition B1. did.
- Example 2-7 A hole-collecting layer composition-coated substrate was produced in the same manner as in Example 2-1, except that the hole-collecting layer composition B7 was used instead of the hole-collecting layer composition B1. did.
- Example 2-8 A hole-collecting layer composition-coated substrate was prepared in the same manner as in Example 2-1, except that the hole-collecting layer composition B13 was used instead of the hole-collecting layer composition B1. did.
- Example 2-9 A hole-collecting layer composition-coated substrate was produced in the same manner as in Example 2-1, except that the hole-collecting layer composition B14 was used instead of the hole-collecting layer composition B1. did.
- Example 2-10 A hole-collecting layer composition-coated substrate was produced in the same manner as in Example 2-1, except that the hole-collecting layer composition B8 was used instead of the hole-collecting layer composition B1. did.
- Example 2-1 A hole-collecting layer composition-coated substrate was produced in the same manner as in Example 2-1, except that the hole-collecting layer composition C1 was used instead of the hole-collecting layer composition B1. did.
- Example 2-2 A hole-collecting layer composition-coated substrate was prepared in the same manner as in Example 2-1, except that the hole-collecting layer composition C2 was used instead of the hole-collecting layer composition B1. did.
- Example 2-3 A hole-collecting layer composition-coated substrate was prepared in the same manner as in Example 2-1, except that the hole-collecting layer composition C3 was used instead of the hole-collecting layer composition B1. did.
- the hole-collecting layer composition B9 prepared in Example 1-9 was applied onto the active layer by spin coating, and then annealed by heating at 100° C. for 5 minutes to obtain a positive electrode. A pore trapping layer was formed. The film thickness of the hole collection layer was about 150 nm.
- the laminated substrate is placed in a vacuum deposition apparatus, the apparatus is evacuated to a degree of vacuum of 1 ⁇ 10 ⁇ 3 Pa or less, and a silver layer serving as an anode is formed to a thickness of 100 nm by resistance heating.
- a reverse lamination type OPV element having an area of 10 mm ⁇ 10 mm at the intersection of the striped ITO layer and the silver layer was fabricated.
- Example 3-2 A reverse laminated OPV element was fabricated in the same manner as in Example 3-1, except that the hole-collecting layer composition B10 was used instead of the hole-collecting layer composition B9.
- Example 3-3 A reverse laminated OPV element was fabricated in the same manner as in Example 3-1, except that the hole-collecting layer composition B11 was used instead of the hole-collecting layer composition B9.
- Example 3-4 A reverse laminated OPV element was fabricated in the same manner as in Example 3-1, except that the hole-collecting layer composition B12 was used instead of the hole-collecting layer composition B9.
- Example 3-5 A reverse laminated OPV element was fabricated in the same manner as in Example 3-1, except that the hole-collecting layer composition B15 was used instead of the hole-collecting layer composition B9.
- Example 3-6 Except that NFA active layer PV-X Plus (manufactured by Raynergy tek) was used instead of active layer product A1, and hole-collecting layer composition B13 was used instead of hole-collecting layer composition B9.
- a reverse lamination type OPV element was produced in the same manner as in Example 3-1.
- Example 3-7 A reverse laminated OPV element was fabricated in the same manner as in Example 3-6, except that the hole-collecting layer composition B14 was used instead of the hole-collecting layer composition B13.
- Example 3-1 A reverse laminated OPV element was produced in the same manner as in Example 3-1, except that the hole-collecting layer composition C1 was used instead of the hole-collecting layer composition B9.
- Example 3-2 A reverse laminated OPV element was fabricated in the same manner as in Example 3-1, except that the hole-collecting layer composition C3 was used instead of the hole-collecting layer composition B9.
- Example 3-3 A reverse laminated OPV element was fabricated in the same manner as in Example 3-6, except that the hole-collecting layer composition C2 was used instead of the hole-collecting layer composition B9.
- Example 3-4 A reverse lamination type OPV element was fabricated in the same manner as in Example 3-5, except that the active layer composition A2 was used instead of the active layer composition A1.
- the Voc of Comparative Examples 3-3 and 3-4 were 0.74 V and 0.76 V, respectively, and when the FA active layer was used, it was confirmed that the Voc was improved as the Ip depth of the hole collection layer was increased. I didn't. This suggests that the HOMO level of the FA active layer and the Ip of the hole collection layer match even without adding an electron-accepting dopant, and that further improvement of Voc cannot be expected by deepening the Ip. That is, the present invention is suitable for obtaining a high Voc by reducing the energy gap between the HOMO level of the active layer and the Ip of the hole-collecting layer in the NFA active layer that provides a higher Voc than the FA active layer. It can be said that it is a composition for a hole collection layer.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- General Chemical & Material Sciences (AREA)
- Photovoltaic Devices (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
有機太陽電池は、活性層や電荷輸送性物質に有機物を使用した太陽電池素子であり、M.グレッツェルによって開発された色素増感太陽電池と、C.W.タンによって開発された有機薄膜太陽電池とがよく知られている(非特許文献1、2)。
いずれも軽量・薄膜で、フレキシブル化可能である点、ロール・トゥ・ロールでの生産が可能である点など、現在主流の無機系太陽電池とは異なる特長を持っていることから、新たな市場形成が期待されている。
1. 非フラーレン活性層を備える光電変換素子における電荷輸送性薄膜を形成するための電荷輸送性組成物であって、
下記式(1)で表される繰り返し単位を含むポリチオフェン誘導体からなる電荷輸送性物質と、電子受容性ドーパント物質と、溶媒とを含み、
上記電子受容性ドーパント物質が、下記式(2)で表されるアリールスルホン酸およびヘテロポリ酸からなる群より選ばれる少なくとも1種を含む電荷輸送性組成物。
2. 上記電子受容性ドーパント物質が、上記式(2)で表されるアリールスルホン酸およびヘテロポリ酸を含む1の電荷輸送性組成物。
3. 上記ヘテロポリ酸が、リンタングステン酸およびリンモリブデン酸からなる群より選ばれる少なくとも1種を含む1または2の電荷輸送性組成物。
4. さらに、界面活性剤を含む1~3のいずれかの電荷輸送性組成物。
5. 上記界面活性剤が、フッ素系界面活性剤である4の電荷輸送性組成物。
6. 上記溶媒が、アルコール系溶媒および水から選ばれる1種または2種以上の溶媒を含む1~5のいずれかの電荷輸送性組成物。
7. 有機光電変換素子の正孔捕集層用である1~6のいずれかの電荷輸送性組成物。
8. 上記有機光電変換素子が、有機薄膜太陽電池、色素増感太陽電池または光センサーである7の電荷輸送性組成物。
9. 1~6のいずれかの電荷輸送性組成物から得られる電荷輸送性薄膜。
10. 上記電荷輸送性薄膜が、有機光電変換素子の正孔捕集層である9の電荷輸送性薄膜。
11. 9または10の電荷輸送性薄膜を備える電子素子。
12. 上記電子素子が、有機光電変換素子である11の電子素子。
13. 10の正孔捕集層と、それに接するように設けられた非フラーレン活性層とを有する有機光電変換素子。
14. 上記非フラーレン活性層が、主鎖にチオフェン骨格を含むポリマーを含む13の有機光電変換素子。
15. 逆積層型である13または14の有機光電変換素子。
16. 上記有機光電変換素子が、有機薄膜太陽電池または光センサーである13~15のいずれかの有機光電変換素子。
17. トップ陽極構造を有する16の有機光電変換素子。
本発明の電荷輸送性組成物は、NFA活性層を備える光電変換素子における電荷輸送性薄膜を形成するための電荷輸送性組成物であって、下記式(1)で表される繰り返し単位を含むポリチオフェン誘導体からなる電荷輸送性物質と、界面活性剤と、溶媒とを含み、上記電子受容性ドーパント物質が、下記式(2)で表されるアリールスルホン酸およびヘテロポリ酸からなる群より選ばれる少なくとも1種を含むことを特徴とする。なお、本発明において、「固形分」とは電荷輸送性組成物の全成分のうち、溶剤以外のものの総称である。また、本発明において、NFA活性層とは、NFAの含有量が活性層に含まれるn型半導体のうち50質量%超である活性層を意味する。
炭素数1~6のアルキル基としては、上記アルキル基において例示した基と同じものが挙げられる。
炭素数1~6のアルコキシ基の具体例としては、メトキシ、エトキシ、n-プロポキシ、i-プロポキシ、n-ブトキシ等が挙げられ、炭素数6~20のアリール基の具体例としては、フェニル、トリル、1-ナフチル、2-ナフチル、1-アントリル、2-アントリル、9-アントリル、1-フェナントリル、2-フェナントリル、3-フェナントリル、4-フェナントリル、9-フェナントリル基等が挙げられる。
特に、置換基としてはヒドロキシ基が好ましく、ヒドロキシ基を有するアルキル基の具体例としては、2-ヒドロキシエチル基、3-ヒドロキシプロピル基、2-ヒドロキシプロピル基、2,3-ジヒドロキシプロピル基等が挙げられる。
これらの中でも、RSとしては、水素原子、炭素数1~3の直鎖状または分岐鎖状のアルキル基が好ましく、水素原子、メチル基がより好ましい。
中でも、Ra~Rdは、互いに独立して、水素原子、炭素数1~8のアルキル基、炭素数1~8のフルオロアルキル基、またはフェニル基が好ましい。
中でも、Reは、水素原子、炭素数1~8のアルキル基、炭素数1~8のフルオロアルキル基、またはフェニル基が好ましく、水素原子、メチル基、プロピル基、またはブチル基がより好ましい。
また、pは、1~5が好ましく、1、2または3がより好ましい。
好ましくは、上記ポリチオフェン誘導体は、R1が、スルホン酸基またはスルホン酸塩基であり、R2が、炭素数1~40のアルコキシ基もしくは-O-[Z-O]p-Reである繰り返し単位を含むか、またはR1およびR2が結合して形成される-O-Y-O-である繰り返し単位を含む。
より好ましくは、上記ポリチオフェン誘導体は、R1が、スルホン酸基またはスルホン酸塩基であり、R2が、-O[C(RaRb)-C(RcRd)-O]p-Reまたは-ORfである繰り返し単位を含む。
より一層好ましくは、上記ポリチオフェン誘導体は、R1が、スルホン酸基またはスルホン酸塩基であり、R2が、-O[C(RaRb)-C(RcRd)-O]p-Reである繰り返し単位を含むか、またはR1およびR2が結合して形成される-O-Y-O-である繰り返し単位を含む。
更に好ましくは、上記ポリチオフェン誘導体は、R1が、スルホン酸基またはスルホン酸塩基であり、R2が、-O-CH2CH2-O-CH2CH2-O-CH3、-O-CH2CH2-O-CH2CH2-OH、もしくは-O-CH2CH2-OHである繰り返し単位を含むか、またはR1およびR2が互いに結合して、下記式(Y1)および/または(Y2)で表される基である繰り返し単位を含む。
アミン付加体は、アミン自体またはその溶液にポリチオフェン誘導体を投入し、よく撹拌することで得ることができる。
ポリチオフェン誘導体またはそのアミン付加体では、それらを構成する繰り返し単位の一部において、その化学構造が「キノイド構造」と呼ばれる酸化型の構造となっている場合がある。用語「キノイド構造」は、用語「ベンゼノイド構造」に対して用いられるもので、芳香環を含む構造である後者に対し、前者は、その芳香環内の二重結合が環外に移動し(その結果、芳香環は消失する)、環内に残る他の二重結合と共役する2つの環外二重結合が形成された構造を意味する。当業者にとって、これらの両構造の関係は、ベンゾキノンとヒドロキノンの構造の関係から容易に理解できるものである。種々の共役ポリマーの繰り返し単位についてのキノイド構造は、当業者にとって周知である。一例として、上記式(1)で表される繰り返し単位を含むポリチオフェン誘導体の繰り返し単位に対応するキノイド構造を、下記式(1’)に示す。
そこで、上記ポリチオフェン誘導体を、還元剤を用いる還元処理に付すと、ポリチオフェン誘導体にキノイド構造が過剰に導入されていても、還元によりキノイド構造が減少し、ポリチオフェン誘導体の有機溶媒に対する溶解性や分散性が向上するため、均質性に優れた薄膜を与える良好な電荷輸送性組成物を、安定的に製造することが可能になる。
このような還元剤も還元が適切にされる限り特に制限はないが、例えば、市販品で入手が容易であるアンモニア水、ヒドラジン等が適当である。
また、還元剤の量は、用いる還元剤の量に応じて異なるため一概に規定できないが、処理すべきポリチオフェン誘導体やアミン付加体100質量部に対し、通常、還元が適切にされる観点から、0.1質量部以上であり、過剰な還元剤が残存しないようにする観点から、10質量部以下である。
また、式(1)で表される繰り返し単位を含むポリチオフェン誘導体は、市販品を用いても、チオフェン誘導体などを出発原料とした公知の方法によって重合したものを用いてもよいが、いずれの場合も再沈殿やイオン交換等の方法により精製されたものを用いることが好ましい。精製したものを用いることで、本発明の電荷輸送性組成物から得られる薄膜を備えた有機太陽電池素子の特性をより高めることができる。市販品としては、例えば、東ソー(株)製のセルフトロン(SELFTRON,登録商標)等が挙げられる。
したがって、本発明の電荷輸送性組成物には、これを用いて得られる電荷輸送性薄膜のイオン化ポテンシャルを調節することを目的として、下記式(2)で表されるアリールスルホン酸化合物およびヘテロポリ酸からなる群より選ばれる少なくとも1種の電子受容性ドーパント物質を含む。
また、式(2)で表されるアリールスルホン酸化合物およびヘテロポリ酸を併用することが好ましく、この場合、式(2)で表されるアリールスルホン酸化合物とヘテロポリ酸の混合比率は、質量比で10:90~90:10が好ましく、20:80~80:20がより好ましい。
そのような市販品としては、デュポン社製キャップストーン(Capstone,登録商標)FS-10、FS-22、FS-30、FS-31、FS-34、FS-35、FS-50、FS-51、FS-60、FS-61、FS-63、FS-64、FS-65、FS-66、FS-81、FS-83、FS-3100;第一工業製薬(株)製ノイゲンFN-1287;DIC社製メガファックF-444、F-477、F-559等が挙げられるが、これらに限定されるものではない。
特に、ノニオン性界面活性剤である、キャップストーンFS-30、31、34、35、3100、ノイゲンFN-1287、メガファックF-559が好適である。
有機基の具体例としては、炭素数1~40のアルキル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、炭素数2~20のヘテロアリール基等が挙げられる。
上記nは、1~20の整数であれば、特に限定されるものではないが、1~10の整数がより好ましい。
ナノ粒子とは、一次粒子についての平均粒子径がナノメートルのオーダー(典型的には500nm以下)である微粒子を意味する。金属酸化物ナノ粒子とは、ナノ粒子に成形された金属酸化物を意味する。
本発明で用いる金属酸化物ナノ粒子の一次粒子径は、ナノサイズであれば特に限定されるものではないが、活性層に対する密着性をより高めることを考慮すると、2~150nmが好ましく、3~100nmがより好ましく、5~50nmがより一層好ましい。なお、粒子径は、BET法による窒素吸着等温線を用いた測定値である。
通常の意味での金属としては、特に限定されるものではないが、スズ(Sn)、チタン(Ti)、アルミニウム(Al)、ジルコニウム(Zr)、亜鉛(Zn)、ニオブ(Nb)、タンタル(Ta)およびW(タングステン)からなる群より選択される1種または2種以上を用いることが好ましい。
一方、半金属とは、化学的および/または物理的性質が金属と非金属の中間である元素を意味する。半金属の普遍的な定義は確立されていないが、本発明では、ホウ素(B)、ケイ素(Si)、ゲルマニウム(Ge)、ヒ素(As)、アンチモン(Sb)およびテルル(Te)の計6元素を半金属とする。これらの半金属は、単独で用いても、2種以上を組み合わせて用いてもよく、また通常の意味での金属と組み合わせて用いてもよい。
シリカゾルとしては、特に限定されるものではなく、公知のシリカゾルから適宜選択して用いることができる。
市販のシリカゾルは通常、分散液の形態にある。市販のシリカゾルとしては、SiO2ナノ粒子が種々の溶媒、例えば、水、メタノール、メチルエチルケトン、メチルイソブチルケトン、N,N-ジメチルアセトアミド、エチレングリコール、イソプロパノール、メタノール、エチレングリコールモノプロピルエーテル、シクロヘキサノン、酢酸エチル、トルエン、プロピレングリコールモノメチルエーテルアセタート等に分散したものが挙げられる。
特に、本発明においては、分散媒がアルコール溶媒または水であるシリカゾルが好ましく、分散媒がアルコール溶媒であるシリカゾルがより好ましい。アルコール溶媒としては、水溶性のアルコールが好ましく、メタノール、2-プロパノール、エチレングリコールがより好ましい。
また、シリカゾルの固形分濃度も特に限定されるものではないが、5~60質量%が好ましく、10~50質量%がより好ましく、15~30質量%がより一層好ましい。
なお、電荷輸送性物質を溶液や分散液として用いる場合、金属酸化物ナノ粒子の添加量は、電荷輸送性物質の固形分量を基準とする。
アルコキシシランとしては、テトラアルコキシシラン、トリアルコキシシラン、ジアルコキシシランの中から任意の1種以上のアルコキシシランを用いることができるが、特にテトラエトキシシラン、テトラメトキシシラン、フェニルトリエトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、メチルトリメトキシシラン、3,3,3-トリフルオロプロピルトリメトキシシラン、ジメチルジエトキシシラン、ジメチルジメトキシシランが好ましく、テトラエトキシシランがより好ましい。
シロキサン系材料としては、上記アルコキシシランに対して加水分解等の反応により得られる、ポリ(テトラエトキシシラン)、ポリ(フェニルエトキシシラン)等のポリシロキサンが挙げられる。
アルコキシシランを使用する場合、その含有量は、上記の効果が発揮される量であれば特に限定されないが、本発明で用いるポリチオフェン誘導体に対し、質量比で0.0001~100倍が好ましく、0.01~50倍がより好ましく、0.05~10倍がより一層好ましい。
上記マトリックス高分子の具体例としては、下記式(I)で表される繰り返し単位および下記式(II)で表される繰り返し単位を含むマトリックス高分子を挙げることができる。
市販品としては、例えば、デュポン製のナフィオン(NAFION,登録商標)、Solvay Specialty Polymers製のアクイヴィオン(AQUIVION,登録商標)、および旭硝子(株)製のフレミオン(FLEMION,登録商標)等が挙げられる。
添加剤の種類としては、所望の効果に応じて公知のものから適宜選択して用いることができる。
これらの中でも、水およびアルコール系溶媒から選ばれる少なくとも1種が好ましく、水、エタノール、2-プロパノールがより好ましい。
高粘度有機溶媒としては、特に限定されるものではなく、例えば、シクロヘキサノール、エチレングリコール、1,3-オクチレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール、1,3-ブタンジオール、2,3-ブタンジオール、1,4-ブタンジオール、プロピレングリコール、へキシレングリコール等が挙げられる。
そして、本発明において用いる電荷輸送性組成物の粘度は、作製する薄膜の厚み等や固形分濃度を考慮し、塗布方法に応じて適宜調節されるものではあるが、通常25℃で0.1~50mPa・s程度である。
なお、マトリックス高分子、アルコキシシランの添加順序も任意である。
塗布にあたっては、組成物の粘度と表面張力、所望する薄膜の厚さ等を考慮し、ドロップキャスト法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法(凸版、凹版、平版、スクリーン印刷等)等といった各種ウェットプロセス法の中から最適なものを採用すればよい。
また、通常、塗布は、常温、常圧の不活性ガス雰囲気下で行われるが、組成物中の化合物が分解したり、組成が大きく変化したりしない限り、大気雰囲気下(酸素存在下)で行ってもよく、加熱しながら行ってもよい。
[陽極層の形成]:透明基板の表面に陽極材料の層を形成し、透明電極を製造する工程
陽極材料としては、インジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)等の無機酸化物や、金、銀、アルミニウム等の金属、ポリチオフェン誘導体、ポリアニリン誘導体等の高電荷輸送性有機化合物を用いることができる。これらの中ではITOが最も好ましい。また、透明基板としては、ガラスあるいは透明樹脂からなる基板を用いることができる。
陽極材料の層(陽極層)の形成方法は、陽極材料の性質に応じて適宜選択される。通常、難溶性、難分散性昇華性材料の場合には真空蒸着法やスパッタ法等のドライプロセスが選択され、溶液材料あるいは分散液材料の場合には、組成物の粘度と表面張力、所望する薄膜の厚さ等を考慮し、上述した各種ウェットプロセス法の中から最適なものが採用される。
ITO等の無機酸化物を陽極材料として用いて透明陽極基板を形成する場合、上層を積層する前に、洗剤、アルコール、純水等で洗浄してから使用することが好ましい。更に、使用直前にUVオゾン処理、酸素-プラズマ処理等の表面処理を施すことが好ましい。陽極材料が有機物を主成分とする場合、表面処理を行わなくともよい。
上記方法に従い、陽極材料の層上に、本発明の組成物を用いて正孔捕集層を形成する。
活性層は、n型半導体材料からなる薄膜であるn層と、p型半導体材料からなる薄膜であるp層とを積層したものであっても、これら材料の混合物からなる非積層薄膜であってもよい。なお、本発明では、活性層として、NFA活性層が形成される。ここで、NFA活性層とは、本発明においてはNFAの含有量が活性層に含まれるn型半導体のうち50質量%超である活性層を意味するが、その含有量は、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは90質量%以上である。
なお、ここでいう「主鎖にチオフェン骨格」とはチオフェンのみからなる2価の芳香環、またはチエノチオフェン、ベンゾチオフェン、ジベンゾチオフェン、ベンゾジチオフェン、ナフトチオフェン、ナフトジチオフェン、アントラチオフェン、アントラジチオフェン等のような1以上のチオフェンを含む2価の縮合芳香環を表し、これらはハロゲン原子、ニトロ基、シアノ基、スルホン酸基、炭素数1~20のアルコキシ基、炭素数1~20のチオアルコキシ基、炭素数1~20のアルキル基、炭素数2~20のアルケニル基、炭素数2~20のアルキニル基、炭素数1~20のハロアルキル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、または炭素数1~20のアシル基で置換されていてもよい。
炭素数1~20のチオアルコキシ(アルキルチオ)基の具体例としては、メチルチオ基、エチルチオ基、n-プロピルチオ基、イソプロピルチオ基、n-ブチルチオ基、イソブチルチオ基、s-ブチルチオ基、t-ブチルチオ基、n-ペンチルチオ基、n-ヘキシルチオ基、n-ヘプチルチオ基、n-オクチルチオ基、n-ノニルチオ基、n-デシルチオ基、n-ウンデシルチオ基、n-ドデシルチオ基、n-トリデシルチオ基、n-テトラデシルチオ基、n-ペンタデシルチオ基、n-ヘキサデシルチオ基、n-ヘプタデシルチオ基、n-オクタデシルチオ基、n-ノナデシルチオ基、n-エイコサニルチオ基等が挙げられる。
その具体例としては、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基、2,2,2-トリフルオロエチル基、ヘプタフルオロプロピル基、2,2,3,3,3-ペンタフルオロプロピル基、2,2,3,3-テトラフルオロプロピル基、2,2,2-トリフルオロ-1-(トリフルオロメチル)エチル基、ノナフルオロブチル基、4,4,4-トリフルオロブチル基、ウンデカフルオロペンチル基、2,2,3,3,4,4,5,5,5-ノナフルオロペンチル基、2,2,3,3,4,4,5,5-オクタフルオロペンチル基、トリデカフルオロヘキシル基、2,2,3,3,4,4,5,5,6,6,6-ウンデカフルオロヘキシル基、2,2,3,3,4,4,5,5,6,6-デカフルオロヘキシル基、3,3,4,4,5,5,6,6,6-ノナフルオロヘキシル基等が挙げられる。
市販品としては、例えば、PV-X Plus(Raynergy tek製)、PV-ATL-D1A1(Raynergy tek製)等が挙げられる。
必要に応じて、電荷の移動を効率化すること等を目的として、活性層と陰極層の間に電子捕集層を形成してもよい。
電子捕集層を形成する材料としては、酸化リチウム(Li2O)、酸化マグネシウム(MgO)、アルミナ(Al2O3)、フッ化リチウム(LiF)、フッ化ナトリウム(NaF)、フッ化マグネシウム(MgF2)、フッ化ストロンチウム(SrF2)、炭酸セシウム(Cs2CO3)、8-キノリノールリチウム塩(Liq)、8-キノリノールナトリウム塩(Naq)、バソクプロイン(BCP)、4,7-ジフェニル-1,10-フェナントロリン(BPhen)、ポリエチレンイミン(PEI)、エトキシ化ポリエチレンイミン(PEIE)等が挙げられる。
陰極材料としては、アルミニウム、マグネシウム-銀合金、アルミニウム-リチウム合金、リチウム、ナトリウム、カリウム、セシウム、カルシウム、バリウム、銀、金等の金属や、インジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)等の無機酸化物や、ポリチオフェン誘導体、ポリアニリン誘導体等の高電荷輸送性有機化合物が挙げられ、複数の陰極材料を積層したり、混合したりして使用することができる。
陰極層の形成方法も、上記と同様、陰極層材料が難溶性、難分散性昇華性材料の場合には上述した各種ドライプロセスが選択され、溶液材料あるいは分散液材料の場合には、組成物の粘度と表面張力、所望する薄膜の厚さ等を考慮し、上述した各種ウェットプロセス法の中から最適なものが採用される。
必要に応じて、光電流の整流性をコントロールすること等を目的として、任意の層間にキャリアブロック層を設けてもよい。キャリアブロック層を設ける場合、通常、活性層と、正孔捕集層または陽極との間に電子ブロック層を、活性層と、電子捕集層または陰極との間に正孔ブロック層を挿入する場合が多いが、この限りではない。
正孔ブロック層を形成する材料としては、酸化チタン、酸化亜鉛、酸化スズ、バソクプロイン(BCP)、4,7-ジフェニル1,10-フェナントロリン(BPhen)等が挙げられる。
電子ブロック層を形成する材料としては、N,N′-ジ(1-ナフチル)-N,N′-ジフェニルベンジジン(α-NPD)、ポリ(トリアリールアミン)(PTAA)等のトリアリールアミン系材料等が挙げられる。
[陰極層の形成]:透明基板の表面に陰極材料の層を形成し、透明陰極基板を製造する工程
陰極材料としては、上記順積層型の陽極材料で例示したものに加え、フッ素ドープ酸化錫(FTO)が挙げられ、透明基板としては、上記順積層型の陽極材料で例示したものが挙げられる。
陰極材料の層(陰極層)の形成方法も、難溶性、難分散性昇華性材料の場合には上述したドライプロセスが選択され、溶液材料あるいは分散液材料の場合には、組成物の粘度と表面張力、所望する薄膜の厚さ等を考慮し、上述した各種ウェットプロセス法の中から最適なものが採用される。
また、この場合も市販の透明陰極基板を好適に用いることができ、素子の歩留を向上させる観点からは、平滑化処理がされている基板を用いることが好ましい。市販の透明陰極基板を用いる場合、本発明の有機薄膜太陽電池の製造方法は、陰極層を形成する工程を含まない。
無機酸化物を陰極材料として使用して透明陰極基板を形成する場合、順積層型の陽極材料と同様の洗浄処理や、表面処理を施してもよい。
必要に応じて、電荷の移動を効率化すること等を目的として、活性層と陰極層の間に電子捕集層を形成してもよい。
電子捕集層を形成する材料としては、上記順積層型の材料で例示したものに加え、酸化亜鉛(ZnO)、酸化チタン(TiO)、酸化スズ(SnO)等が挙げられる。
電子捕集層の形成方法も、難溶性、難分散性昇華性材料の場合には上述したドライプロセスが選択され、溶液材料あるいは分散液材料の場合には、組成物の粘度と表面張力、所望する薄膜の厚さ等を考慮し、上述した各種ウェットプロセス法の中から最適なものが採用される。また、無機酸化物の前駆体層をウェットプロセス(特にスピンコート法かスリットコート法)を用いて陰極上に形成し、焼成して無機酸化物の層を形成する方法を採用することもできる。
活性層は、n型半導体材料からなる薄膜であるn層と、p型半導体材料からなる薄膜であるp層とを積層したものであっても、これら材料の混合物からなる非積層薄膜であってもよい。
n型およびp型半導体材料としては、上記順積層型の半導体材料で例示したものと同様のものが挙げられるが、n型半導体材料としては、ITIC-4F、p型半導体材料としては、PM6およびPTB7等の主鎖にチオフェン骨格を含むポリマー類が好ましい。
活性層の形成方法も、上記順積層型の活性層で説明した方法と同様である。
上記方法に従い、活性層材料の層上に、本発明の組成物を用いて正孔捕集層を形成する。
陽極材料としては、上記順積層型の陽極材料と同様のものが挙げられ、陽極層の形成方法としても、順積層型の陰極層と同様である。
順積層型の素子と同様、必要に応じて、光電流の整流性をコントロールすること等を目的として、任意の層間にキャリアブロック層を設けてもよい。
正孔ブロック層を形成する材料および電子ブロック層を形成する材料としては、上記と同様のものが挙げられ、キャリアブロック層の形成方法も上記と同様である。
封止法としては、端部にUV硬化樹脂を付着させた凹型ガラス基板を、不活性ガス雰囲気下、有機薄膜太陽電池素子の成膜面側に付着させ、UV照射によって樹脂を硬化させる方法や、真空下、スパッタリング等の手法によって膜封止タイプの封止を行う方法などが挙げられる。
(1)グローブボックス:山八物産(株)製、VACグローブボックスシステム
(2)蒸着装置:アオヤマエンジニアリング(株)製、真空蒸着装置
(3)ソーラーシミュレータ:分光計器(株)製、OTENTOSUN-III、AM1.5Gフィルター、放射強度:100mW/cm2
(4)ソースメジャーユニット:ケースレーインスツルメンツ(株)製、2612A
(5)イオン化ポテンシャル測定装置:理研計器(株)製、AC-3
[調製例1]
PBDB-T-2F(Sigma-Aldrich社製)25mgおよびITIC-4F(Sigma-Aldrich社製)25mgが入ったサンプル瓶の中にクロロベンゼン2.5mLと1,8-ジヨードオクタン(東京化成工業(株)製)12.5μLを加え、70℃のホットプレート上で15時間撹拌した。この溶液を室温まで放冷し、溶液A1(活性層組成物)を得た。
PTB7(1-Material社製)20mgおよびPC61BM(フロンティアカーボン社製、製品名:nanom spectra E100)30mgが入ったサンプル瓶の中にクロロベンゼン2.0mLを加え、80℃のホットプレート上で15時間撹拌した。この溶液を室温まで放冷した後、1,8-ジヨードオクタン(東京化成工業(株)製)10μLを加えて撹拌し、溶液A2(活性層組成物)を得た。
PTB7(1-Material社製)20mgおよびPC61BM(フロンティアカーボン社製、製品名:nanom spectra E100)30mgが入ったサンプル瓶の中にクロロベンゼン2.0mLを加え、80℃のホットプレート上で15時間撹拌した。この溶液を室温まで放冷した後、1,8-ジヨードオクタン(東京化成工業(株)製)60μLを加えて撹拌し、溶液A3(活性層組成物)を得た。
[実施例1-1]
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.53gにイソプロパノール2.47gを加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを5.05mg加え、濃度1.1質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B1を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.53gにイソプロパノール2.50gを加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを25.3mg加え、濃度1.5質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B2を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.49gにイソプロパノール2.45gを加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを50.2mg加え、濃度2.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B3を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.54gにイソプロパノール2.48gを加えた溶液に、12モリブド(IV)りん酸n水和物(富士フイルム和光純薬(株)製)を5.03mg加え、濃度1.1質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B4を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.53gにイソプロパノール2.47gを加えた溶液に、12モリブド(IV)りん酸n水和物(富士フイルム和光純薬(株)製)を24.9mg加え、濃度1.5質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B5を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.52gにイソプロパノール2.46gを加えた溶液に、12モリブド(IV)りん酸n水和物(富士フイルム和光純薬(株)製)を50.0mg加え、濃度2.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B6を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.68gにイソプロパノール2.64gを加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを26.9mg、12モリブド(IV)りん酸n水和物(富士フイルム和光純薬(株)製)を26.9mg加え、濃度2.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B7を得た。
PEDOT:PSS水溶液(HTL Solar、へレウス社製、1.0質量%水分散液)3.6gに、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物A18.7mgと12モリブド(IV)りん酸n水和物(富士フイルム和光純薬(株)製)18.9mgを純水3.6gに溶解させた水溶液を加え、濃度1.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径1.00μmのシリンジフィルターでろ過して、正孔捕集層用組成物B8を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.52gにイソプロパノール2.48g、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)1.5mgを加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを5.05mg加え、濃度1.1質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B9を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.51gにイソプロパノール2.46g、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)1.5mgを加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを25.05mg加え、濃度1.5質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B10を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.48gにイソプロパノール2.47g、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)1.5mgを加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを49.05mg加え、濃度2.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B11を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.53gにイソプロパノール2.46g、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)を1.5mg加えた溶液に、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを25.05mg、12モリブド(IV)りん酸n水和物(富士フイルム和光純薬(株)製)を25.05mg加え、濃度2.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B12を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)1.25gに純水を3.71g、フッ素系ノニオン性界面活性剤(FN-1287、第一工業製薬(株)製)を5.00mg、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)を1.00mg加えた溶液に、国際公開第2006/025342号の記載に基づて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを25.0mg、ケイモリブド酸n水和物(富士フイルム和光純薬(株)製)を7.50mg加え、濃度1.15質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B13を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)1.25gに純水を3.71g、フッ素系ノニオン性界面活性剤(FN-1287、第一工業製薬(株)製)を5.00mg、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)を1.00mg加えた溶液に、国際公開第2006/025342号の記載に基づて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを25.0mg、ケイタングステン酸n水和物(Alfa Aesar(株)製)を7.50mg加え、濃度1.15質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物B14を得た。
PEDOT:PSS水溶液(HTL Solar、へレウス社製、1.0質量%水分散液)2.99gに、国際公開第2006/025342号の記載に基づいて合成した上記式(2-1)で表されるアリールスルホン酸化合物Aを3.0mg、12モリブド(IV)りん酸n水和物(富士フイルム和光純薬(株)製)を3.0mg加え、濃度1.2質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径1.00μmのシリンジフィルターでろ過して、正孔捕集層用組成物B15を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)2.52gにイソプロパノール2.47g、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)1.5mgを加え、濃度1.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物C1を得た。
SELFTRON(SELFTRON S、東ソー(株)製、2.0質量%水溶液)1.25gに純水を3.71g、フッ素系ノニオン性界面活性剤(FN-1287、第一工業製薬(株)製)を5.00mg、フッ素系ノニオン性界面活性剤(F-559、DIC(株)製)を1.00mg加え、濃度1.0質量%の濃青色溶液を調製した。得られた濃青色溶液を、孔径0.45μmのシリンジフィルターでろ過して、正孔捕集層用組成物C2を得た。
PEDOT:PSS水溶液(HTL Solar、へレウス社製、1.0質量%水分散液)を、孔径1.00μmのシリンジフィルターでろ過して、正孔捕集層用組成物C3を得た。
[実施例2-1]
20mm×20mmのITO透明導電層付ガラス基板を15分間UV/オゾン処理した。この基板に、実施例1-1で調製した正孔捕集層用組成物B1をスピンコート法により塗布した後、100℃で5分加熱してアニール処理を行うことで、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B2を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B3を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B4を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B5を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B6を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B7を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B13を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B14を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物B8を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物C1を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物C2を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
正孔捕集層用組成物B1の代わりに正孔捕集層用組成物C3を用いた以外は実施例2-1と同様の方法で、正孔捕集層用組成物成膜基板を作製した。
上記実施例2-1~2-10および比較例2-1~2-3で作製した正孔捕集層用組成物成膜基板について、イオン化ポテンシャル測定装置を用いてイオン化ポテンシャル(Ip)測定を行った。設定光量は20.0nW、4.00-6.00eVの範囲を0.1eVごとに測定し、光電子放出の閾値エネルギーからIpを求めた。結果を表1に示す。
このように、2種類の添加物を有することで、より効果的にIpを深化できることが分かる。
[実施例3-1]
陰極となるITO透明導電層を10mm×25mmのストライプ状にパターニングした25mm×25mmのガラス基板を15分間UV/オゾン処理した。この基板に、電子捕集層となる酸化亜鉛の溶液(Genes’ Ink製)を滴下し、スピンコート法により成膜した。電子捕集層の膜厚は約30nmであった。その後、不活性ガスにより置換されたグローブボックス中で、形成した電子捕集層上に調製例1で得られた溶液A1を滴下してスピンコート法により成膜し、活性層を形成した。
次に、この活性層上に実施例1-9で調製した正孔捕集層用組成物B9をスピンコート法により塗布した後、100℃で5分加熱してアニール処理を行うことで、正孔捕集層を形成した。正孔捕集層の膜厚は約150nmであった。
最後に、積層した基板を真空蒸着装置内に設置して、装置内の真空度が1×10-3Pa以下になるまで排気し、抵抗加熱法によって、陽極となる銀層を100nmの厚さに蒸着することで、ストライプ状のITO層と銀層とが交差する部分の面積が10mm×10mmである逆積層型OPV素子を作製した。
正孔捕集層用組成物B9の代わりに正孔捕集層用組成物B10を用いた以外は実施例3-1と同様の方法で、逆積層型OPV素子を作製した。
正孔捕集層用組成物B9の代わりに正孔捕集層用組成物B11を用いた以外は実施例3-1と同様の方法で、逆積層型OPV素子を作製した。
正孔捕集層用組成物B9の代わりに正孔捕集層用組成物B12を用いた以外は実施例3-1と同様の方法で、逆積層型OPV素子を作製した。
正孔捕集層用組成物B9の代わりに正孔捕集層用組成物B15を用いた以外は実施例3-1と同様の方法で、逆積層型OPV素子を作製した。
活性層生成物A1の代わりに、NFA活性層PV-X Plus(Raynergy tek製)を用い、正孔捕集層用組成物B9の代わりに正孔捕集層用組成物B13を用いた以外は実施例3-1と同様の方法で、逆積層型OPV素子を作製した。
正孔捕集層用組成物B13の代わりに正孔捕集層用組成物B14を用いた以外は実施例3-6と同様の方法で、逆積層型OPV素子を作製した。
正孔捕集層用組成物B9の代わりに正孔捕集層用組成物C1を用いた以外は実施例3-1と同様の方法で、逆積層型OPV素子を作製した。
正孔捕集層用組成物B9の代わりに正孔捕集層用組成物C3を用いた以外は実施例3-1と同様の方法で、逆積層型OPV素子を作製した。
正孔捕集層用組成物B9の代わりに正孔捕集層用組成物C2を用いた以外は実施例3-6と同様の方法で、逆積層型OPV素子を作製した。
活性層組成物A1の代わりに活性層組成物A2を用いた以外は実施例3-5と同様の方法で、逆積層型OPV素子を作製した。
活性層組成物A1の代わりに活性層組成物A3を用いた以外は比較例3-2と同様の方法で、逆積層型OPV素子を作製した。
上記実施例3-1~3-7および比較例3-1~3-3で作製した各OPV素子について、短絡電流密度(Jsc〔mA/cm2〕)、開放電圧(Voc〔V〕)、曲線因子(FF)、およびPCE〔%〕の評価を行った。結果を表2に示す。
なおPCE〔%〕は、下式により算出した。
PCE〔%〕=Jsc〔mA/cm2〕×Voc〔V〕×FF÷入射光強度(100〔mW/cm2〕)×100
Claims (17)
- 非フラーレン活性層を備える光電変換素子における電荷輸送性薄膜を形成するための電荷輸送性組成物であって、
下記式(1)で表される繰り返し単位を含むポリチオフェン誘導体からなる電荷輸送性物質と、電子受容性ドーパント物質と、溶媒とを含み、
上記電子受容性ドーパント物質が、下記式(2)で表されるアリールスルホン酸およびヘテロポリ酸からなる群より選ばれる少なくとも1種を含む電荷輸送性組成物。
- 上記電子受容性ドーパント物質が、上記式(2)で表されるアリールスルホン酸およびヘテロポリ酸を含む請求項1記載の電荷輸送性組成物。
- 上記ヘテロポリ酸が、リンタングステン酸およびリンモリブデン酸からなる群より選ばれる少なくとも1種を含む請求項1または2記載の電荷輸送性組成物。
- さらに、界面活性剤を含む請求項1~3のいずれか1項記載の電荷輸送性組成物。
- 上記界面活性剤が、フッ素系界面活性剤である請求項4記載の電荷輸送性組成物。
- 上記溶媒が、アルコール系溶媒および水から選ばれる1種または2種以上の溶媒を含む請求項1~5のいずれか1項記載の電荷輸送性組成物。
- 有機光電変換素子の正孔捕集層用である請求項1~6のいずれか1項記載の電荷輸送性組成物。
- 上記有機光電変換素子が、有機薄膜太陽電池、色素増感太陽電池または光センサーである請求項7記載の電荷輸送性組成物。
- 請求項1~6のいずれか1項記載の電荷輸送性組成物から得られる電荷輸送性薄膜。
- 上記電荷輸送性薄膜が、有機光電変換素子の正孔捕集層である請求項9記載の電荷輸送性薄膜。
- 請求項9または10記載の電荷輸送性薄膜を備える電子素子。
- 上記電子素子が、有機光電変換素子である請求項11記載の電子素子。
- 請求項10記載の正孔捕集層と、それに接するように設けられた非フラーレン活性層とを有する有機光電変換素子。
- 上記非フラーレン活性層が、主鎖にチオフェン骨格を含むポリマーを含む請求項13記載の有機光電変換素子。
- 逆積層型である請求項13または14記載の有機光電変換素子。
- 上記有機光電変換素子が、有機薄膜太陽電池または光センサーである請求項13~15のいずれか1項記載の有機光電変換素子。
- トップ陽極構造を有する請求項16記載の有機光電変換素子。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023509231A JPWO2022202868A1 (ja) | 2021-03-26 | 2022-03-23 | |
US18/279,323 US20240172550A1 (en) | 2021-03-26 | 2022-03-23 | Charge-transporting composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021053355 | 2021-03-26 | ||
JP2021-053355 | 2021-03-26 | ||
JP2021086174 | 2021-05-21 | ||
JP2021-086174 | 2021-05-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022202868A1 true WO2022202868A1 (ja) | 2022-09-29 |
Family
ID=83397323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/013373 WO2022202868A1 (ja) | 2021-03-26 | 2022-03-23 | 電荷輸送性組成物 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20240172550A1 (ja) |
JP (1) | JPWO2022202868A1 (ja) |
TW (1) | TW202305028A (ja) |
WO (1) | WO2022202868A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023080024A1 (ja) * | 2021-11-02 | 2023-05-11 | 日産化学株式会社 | 電荷輸送性組成物 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016003302A (ja) * | 2014-06-18 | 2016-01-12 | 三菱化学株式会社 | 組成物、電子デバイス及び電子デバイスの製造方法 |
WO2020009138A1 (ja) * | 2018-07-04 | 2020-01-09 | 日産化学株式会社 | 電荷輸送性組成物 |
JP2020516706A (ja) * | 2018-03-12 | 2020-06-11 | エルジー・ケム・リミテッド | 重合体およびこれを含む有機太陽電池 |
CN112574623A (zh) * | 2020-11-30 | 2021-03-30 | 位速科技股份有限公司 | 高分子金属配合物涂布液与有机光伏元件 |
-
2022
- 2022-03-23 JP JP2023509231A patent/JPWO2022202868A1/ja active Pending
- 2022-03-23 US US18/279,323 patent/US20240172550A1/en active Pending
- 2022-03-23 WO PCT/JP2022/013373 patent/WO2022202868A1/ja active Application Filing
- 2022-03-24 TW TW111111067A patent/TW202305028A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016003302A (ja) * | 2014-06-18 | 2016-01-12 | 三菱化学株式会社 | 組成物、電子デバイス及び電子デバイスの製造方法 |
JP2020516706A (ja) * | 2018-03-12 | 2020-06-11 | エルジー・ケム・リミテッド | 重合体およびこれを含む有機太陽電池 |
WO2020009138A1 (ja) * | 2018-07-04 | 2020-01-09 | 日産化学株式会社 | 電荷輸送性組成物 |
CN112574623A (zh) * | 2020-11-30 | 2021-03-30 | 位速科技股份有限公司 | 高分子金属配合物涂布液与有机光伏元件 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023080024A1 (ja) * | 2021-11-02 | 2023-05-11 | 日産化学株式会社 | 電荷輸送性組成物 |
Also Published As
Publication number | Publication date |
---|---|
TW202305028A (zh) | 2023-02-01 |
JPWO2022202868A1 (ja) | 2022-09-29 |
US20240172550A1 (en) | 2024-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7276314B2 (ja) | 電荷輸送性組成物 | |
EP3373354B1 (en) | Composition for hole trapping layer of organic photoelectric conversion element | |
JP7180379B2 (ja) | 有機光電変換素子の正孔捕集層用組成物 | |
JP7243636B2 (ja) | 有機光電変換素子の正孔捕集層用組成物 | |
WO2022202868A1 (ja) | 電荷輸送性組成物 | |
WO2023080024A1 (ja) | 電荷輸送性組成物 | |
WO2022202872A1 (ja) | 電荷輸送性組成物 | |
WO2024071060A1 (ja) | 電荷輸送性組成物 | |
JP2023149746A (ja) | 電荷輸送性組成物およびその製造方法 | |
EP4159800A1 (en) | Composition for hole collecting layer of organic photoelectric conversion element | |
BR112020018774B1 (pt) | Composição de transporte de carga, filme fino, elemento eletrônico e elemento de conversão fotoelétrica orgânica | |
KR20230147645A (ko) | 전하 수송성 잉크 조성물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22775650 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2023509231 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18279323 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22775650 Country of ref document: EP Kind code of ref document: A1 |