TWI727401B - 共軛聚合物及其應用 - Google Patents
共軛聚合物及其應用 Download PDFInfo
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- TWI727401B TWI727401B TW108129635A TW108129635A TWI727401B TW I727401 B TWI727401 B TW I727401B TW 108129635 A TW108129635 A TW 108129635A TW 108129635 A TW108129635 A TW 108129635A TW I727401 B TWI727401 B TW I727401B
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- Prior art keywords
- alkyl
- group
- following groups
- ring
- alkyne
- Prior art date
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims description 57
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 229910052736 halogen Chemical class 0.000 claims description 11
- 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 description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 150000001345 alkine derivatives Chemical class 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
- 229910003472 fullerene Inorganic materials 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 8
- 229930194542 Keto Chemical group 0.000 claims description 6
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical group 0.000 claims description 2
- 238000013086 organic photovoltaic Methods 0.000 abstract description 6
- 229920005604 random copolymer Polymers 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 78
- 0 CC(C1(C)C(N2*)=O)OC(C)=C1*2=O Chemical compound CC(C1(C)C(N2*)=O)OC(C)=C1*2=O 0.000 description 65
- 238000006243 chemical reaction Methods 0.000 description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 125000003118 aryl group Chemical group 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 18
- -1 polymers) Chemical class 0.000 description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000000746 purification Methods 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 125000001072 heteroaryl group Chemical group 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000370 acceptor Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000944 Soxhlet extraction Methods 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229940078552 o-xylene Drugs 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- 239000002800 charge carrier Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000005669 field effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910004373 HOAc Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HDZULVYGCRXVNQ-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthieno[3,2-b]thiophen-2-yl)stannane Chemical compound S1C([Sn](C)(C)C)=CC2=C1C=C([Sn](C)(C)C)S2 HDZULVYGCRXVNQ-UHFFFAOYSA-N 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- 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 1
- 125000005955 1H-indazolyl group Chemical group 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- ISRPCLCPFYVEHU-UHFFFAOYSA-N 7-(iodomethyl)pentadecane Chemical compound CCCCCCCCC(CI)CCCCCC ISRPCLCPFYVEHU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- ARWITRDGJQOWKR-XLEKPZQQSA-O CC(C(/C1=N\S)=N)=CC(C2=N)=C1N=C(C)/C2=N/[SH2+] Chemical compound CC(C(/C1=N\S)=N)=CC(C2=N)=C1N=C(C)/C2=N/[SH2+] ARWITRDGJQOWKR-XLEKPZQQSA-O 0.000 description 1
- HCNGGFBATUNZJC-UHFFFAOYSA-N CC(C(N=C(C)C1=N)=C(C)C1=N)=C Chemical compound CC(C(N=C(C)C1=N)=C(C)C1=N)=C HCNGGFBATUNZJC-UHFFFAOYSA-N 0.000 description 1
- IZBZURUEJPODJK-UHFFFAOYSA-N CC(C)=Cc1c(C)c([s]c(C)c2)c2[s]1 Chemical compound CC(C)=Cc1c(C)c([s]c(C)c2)c2[s]1 IZBZURUEJPODJK-UHFFFAOYSA-N 0.000 description 1
- ZRDXMJDANVTQOW-QUKXEYFDSA-N CC(C1=C)=CC(/C(/C(C(C)=C2)=N)=N/S)=C2C1=N Chemical compound CC(C1=C)=CC(/C(/C(C(C)=C2)=N)=N/S)=C2C1=N ZRDXMJDANVTQOW-QUKXEYFDSA-N 0.000 description 1
- WNUWVWHLYLRGHC-IXIGIJJYSA-N CC1c2n[s]nc2C(CCC(C(C(C(C)C2=N)NC)N=S)/C2=N/S)C2N=S=NC12 Chemical compound CC1c2n[s]nc2C(CCC(C(C(C(C)C2=N)NC)N=S)/C2=N/S)C2N=S=NC12 WNUWVWHLYLRGHC-IXIGIJJYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ITZAJJPFJXBVKY-UHFFFAOYSA-N Cc(c(C)nc(C)c1N)c1SN Chemical compound Cc(c(C)nc(C)c1N)c1SN ITZAJJPFJXBVKY-UHFFFAOYSA-N 0.000 description 1
- FSGZNQMXKRHFDG-UHFFFAOYSA-N Cc(c1c2[s]nn1)cc1c2nc(CCc2cc3c4ONN(C)c4c(C)nc3c3c2nn[o]3)c2c1[s]nn2 Chemical compound Cc(c1c2[s]nn1)cc1c2nc(CCc2cc3c4ONN(C)c4c(C)nc3c3c2nn[o]3)c2c1[s]nn2 FSGZNQMXKRHFDG-UHFFFAOYSA-N 0.000 description 1
- LUEQYYWRCOQSCP-UHFFFAOYSA-N Cc(c1n[o]nc11)cc2c1nc(C)c1n[o]nc21 Chemical compound Cc(c1n[o]nc11)cc2c1nc(C)c1n[o]nc21 LUEQYYWRCOQSCP-UHFFFAOYSA-N 0.000 description 1
- HLEPBLSDJZCKBT-UHFFFAOYSA-O Cc1c(CC([SH2+])=C(C(C)=C2)N=N)cc2c2c1nn[s]2 Chemical compound Cc1c(CC([SH2+])=C(C(C)=C2)N=N)cc2c2c1nn[s]2 HLEPBLSDJZCKBT-UHFFFAOYSA-O 0.000 description 1
- GOGCCGZWMJDIMX-UHFFFAOYSA-N Cc1c(ccnc2C)c2ncc1 Chemical compound Cc1c(ccnc2C)c2ncc1 GOGCCGZWMJDIMX-UHFFFAOYSA-N 0.000 description 1
- AUZMMOQXEVKJIK-UHFFFAOYSA-N Cc1c2[o]nnc2c(cc(CCc2c3[s]nnc3c(cc(CCc3cc(c4c(c(C)c5)[s]nn4)c5c(N=N)c3S)c3c4nn[s]3)c4c2)c2c3nn[o]2)c3c1 Chemical compound Cc1c2[o]nnc2c(cc(CCc2c3[s]nnc3c(cc(CCc3cc(c4c(c(C)c5)[s]nn4)c5c(N=N)c3S)c3c4nn[s]3)c4c2)c2c3nn[o]2)c3c1 AUZMMOQXEVKJIK-UHFFFAOYSA-N 0.000 description 1
- NREQPSOCYMEHRE-UHFFFAOYSA-N Cc1c2nn[o]c2c(cc(CCc2cc(c3c(c(C)c4)nn[s]3)c4c3c2nn[s]3)c2c3[o]nn2)c3c1 Chemical compound Cc1c2nn[o]c2c(cc(CCc2cc(c3c(c(C)c4)nn[s]3)c4c3c2nn[s]3)c2c3[o]nn2)c3c1 NREQPSOCYMEHRE-UHFFFAOYSA-N 0.000 description 1
- YHOAEJWGYWSPAZ-UHFFFAOYSA-N Cc1c2nn[s]c2c(C)cc1 Chemical compound Cc1c2nn[s]c2c(C)cc1 YHOAEJWGYWSPAZ-UHFFFAOYSA-N 0.000 description 1
- HXTOFHAPBHUOFP-UHFFFAOYSA-N Cc1cc(c2n[s]nc2c(C)c2)c2c2n[s]nc12 Chemical compound Cc1cc(c2n[s]nc2c(C)c2)c2c2n[s]nc12 HXTOFHAPBHUOFP-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N Cc1ccc(C)nc1 Chemical compound Cc1ccc(C)nc1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- KUTCUGTVOQEDFB-UHFFFAOYSA-N Cc1ccnc2c(C)ccnc12 Chemical compound Cc1ccnc2c(C)ccnc12 KUTCUGTVOQEDFB-UHFFFAOYSA-N 0.000 description 1
- CAIGRHPYOPDUCR-UHFFFAOYSA-N Cc1ccnc2c(C)cncc12 Chemical compound Cc1ccnc2c(C)cncc12 CAIGRHPYOPDUCR-UHFFFAOYSA-N 0.000 description 1
- LCZUOKDVTBMCMX-UHFFFAOYSA-N Cc1cnc(C)cn1 Chemical compound Cc1cnc(C)cn1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000003016 chromanyl group Chemical group O1C(CCC2=CC=CC=C12)* 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
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Abstract
Description
本案主張2018年10月30日申請之美國臨時專利申請案第62/752,791號的優先權,其揭露的全部內容引用併入本案。
本發明係關於一種新的共軛聚合物、其製備方法以及其應用,特別是由前述共軛聚合物所製作的有機光伏裝置。
與過去的矽太陽能電池相比,具有較低成本、可撓曲性、毒性較低,以及可大面積生產的這些優點,加強了有機光伏裝置(亦可稱作高分子太陽能電池或是聚合物太陽能電池)在於太陽能領域的競爭優勢,進而解決能源與環境危機。
主動層材料的改良在高效率聚合物太陽能電池中,扮演重要的角色。主動層材料分為給體與受體兩個部份,對於受體材料,早期大多是以富勒烯衍生物PCBM為主,近年來則是以非富勒烯材料(以IC為主的梯型分子)為主(IC是1,1-dicyanomethylene-3-indanone的縮寫)。
對於給體材料,以發展D-A型的共軛聚合物為主流,其聚合物中的多電子單元與缺電子單元所進行的推-拉電子效應,可用來調控聚合物的能階與能隙。對應於不同受體,會使用不同D-A型的共軛聚合物來搭配。PCBM其吸光範圍位於400nm-600nm,適合搭配低能隙共軛聚合物,而以IC為主的梯型分子因為吸光範圍為700nm-900nm,適合搭配中能隙共軛聚合物,這兩種組合皆可達到10%以上的光電轉換效率。
目前技術發展的狀況是低能隙共軛聚合物的研究成果甚多,然而,中能隙共軛聚合物材料仍然稀少,需要學界與業界大力投入開發,以便於搭配非富勒烯受體使用,達到10%以上的光電轉換效率。
傳統上,給體材料的共軛聚合物係以交替(alternating)的共軛聚合物為主。與習知技術不同,本發明揭示一種無規律(random)共軛聚合物,其係為無規共聚物(random copolymer),優點在於可以加入不同的多電子或缺電子單元於聚合物中,依添加不同的比例可以微調其吸光範圍,電子能階,更可改善溶解度、增加載子遷移率,還可保有原來交替共軛聚合物的優勢,使得與受體材料有良好的匹配性,進而獲得更高的光電轉換效率。
在眾多材料中,N-alkylthieno[3,4-c]pyrrole-4,6-dione(TPD)為一種結構對稱且平面的材料,因為結構中含有imide的官能基,可作為一種具有強拉電子能力的受體單元,廣泛被應用在光電材料領域中。含有TPD單元的聚合物具有高的電子遷移率,優異的電化學還原性質等。同時TPD的氮原子具有化學可修飾性,可引入不同的烷基,有效地改善溶解度,可以用於給體材料的建構單元,在太陽能電池中有良好的表現。另外其合成簡易,利於大量生產,對於商業化也有很大的幫助。
本發明之一目的在於提供一種含有TPD的無規律共軛聚合物與其製備方法。
本發明之另一目的在於提供一種中能隙共軛聚合物材料,一種光學能隙範圍為1.85~2.5eV的共軛聚合物給體,以便於搭配非富勒烯受體使用,達到10%以上的光電轉換效率,改善聚合物太陽能電池的轉換效率過低的問題。
20‧‧‧基板
22‧‧‧陽極
24‧‧‧主動層
26‧‧‧陰極
第一圖係為M3材料的 1 H NMR光譜。
第二圖係為M6材料的 1 H NMR光譜。
第三圖係為M9材料的 1 H NMR光譜。
第四圖顯示有機光伏裝置的代表構造,使用本發明的共軛聚合物作為主動層材料。
定義
本文所用之「給體」材料,係指一半導體材料,例如有機半導體材料,具備電洞作為主要電流或電荷載子。於某些實施例,當p型半導體材料被沈積於一基板,其可提供超過約10-5cm2/Vs之電洞移動率。於場效元件的例,一p型半導體材料可顯示超過約10之電流開/關比。
本文所用之「受體」材料,係指一半導體材料,例如有機半導體材料,具備電子作為主要電流或電荷載子。於某些實施例,當n型半導體材料被沈積於一基板,其可提供超過約10-5cm2/Vs之電子移動率。於場效元件的例,一n型半導體材料可顯示超過約10之電流開/關比。
本文所用之「遷移率」,係指電荷載子在電場的影響下移動穿過該材料的速率之測量,例如電荷載子在p型半導體材料中為電洞(正電荷),在n型半導體材料中為電子(負電荷)。該參數取決於元件的架構,可利用場效元件或空間電荷限制電流量測。
本文所用之化合物被視為「環境安定」或「環境條件下安定」,係指當結合化合物作為其半導體材料之電晶體,在該化合物暴露於環境條件下,例如空氣、環境溫度及濕度一段時間後,顯示載子遷移率維持在其初始值。例如一化合物可視為環境安定,若是結合該化合物之電晶體,在暴露於包括空氣、濕度及溫度之環境條件3天、5天或10天後,顯示載子遷移率之變化不超過20%或不超過10%之初始值。
本文所用之填充因子(FF),係指實際最大可獲得功率(Pm或Vmp*Jmp)與理論(非實際可獲得)功率之比值((Jsc*Voc)。因此,填充因子可由下式決定:FF=(Vmp*Jmp)/(Jsc*Voc)其中Jmp及Vmp分別表示在最大功率點(Pm)之電流密度及電壓,該點係藉由變化電路中的電阻直到J*V為最大值而得;Jsc及Voc分別表示開路電流及開路電壓。填充因子是評價太陽電池的關鍵參數。商業用太陽電池通常具有約0.60%以上的填充因子。
本文所用之開路電壓(Voc),係在無連接外部負載下元件的陽極與陰極之間的電位差。
本文所用之太陽電池的功率轉換效率(PCE),係指從入射光轉變為電力的功率百分比。太陽電池的功率轉換效率(PCE)可藉由最大功率點(Pm)除以標準測試條件下(STC)入射光輻射照度(E;W/m2)及太陽電池的表面積(Ac;m2)而算出。STC通常指在溫度25℃、輻射照度1000W/m2、空氣質量1.5(AM 1.5)光譜。
本文所用之構件(例如一薄膜層),若其包含一個或一個以上的可吸收光子而產生用以產生光電流的激子之化合物,可被視為「光活性」。
本文所用之「溶液加工」,係指化合物(例如聚合物)、材料或組成物可用於溶液態的製程,例如旋轉塗佈、印刷法(例如噴墨印刷、凹版印刷、平版印刷等)、噴塗法、電噴塗法、滴鑄法、浸塗法及刮刀塗佈法。
如本文所用之「退火」,係指在環境中或在減壓或加壓下,對半結晶聚合物膜進行超過100秒的持續時間的沉積後熱處理,「退火溫度」,係指該退火過程中該聚合物膜暴露至少60秒的最高溫度。不受任何特定理論束縛,據信退火可在可能的情況下導致聚合物膜中的結晶度的增加,從而增加場效應遷移率。結晶度的增加,可以藉由數種方法檢測,例如藉由比較沉積及退火過的膜的差示掃描量熱(DSC)或X射線繞射分析(XRD)的測量。
如本文所用之「聚合物化合物」(或「聚合物」),係指包含複數的一種或一種以上的共價鍵結連接之重複單元之分子。一聚合物化合物(聚合物)可由以下一般式(I)表示。
*-(-(Ma) x -(Mb) y -) z *一般式(I)其中每個Ma及Mb是重複單元或單體。聚合物可以僅具有一種類型的重複
單元以及兩種或兩種以上的不同重複單元。當聚合物化合物僅具有一種類型的重複單元時,其可以稱為同元聚合物。當高分子化合物具有兩種以上不同的重複單元時,可以使用術語「共聚物」或「共聚化合物」。例如,共聚化合物可以包括重複單元,其中Ma及Mb表示兩種不同的重複單元。除非另有說明,重複單元在共聚物中的組裝可以是頭對尾、頭對頭或尾對尾。此外,除非另有說明,共聚物可以是無規共聚物、交替共聚物或嵌段共聚物。例如,一般式(I)可用於表示共聚物中具有x莫耳分率Ma及y莫耳分率Mb的Ma與Mb的共聚物,其中共聚單體Ma及Mb的重複方式可以是交替、無規則、區域性無規則(regiorandom)、區域規則或嵌段,存在至多z個共聚單體。除了其組成之外,一聚合化合物,根據量測技術,可由聚合度(n)、莫耳質量(例如數量平均分子量(Mn)及/或重量平均分子量(Mw))描繪。
本文所用之「鹵基」或「鹵素」係指氟、氯、溴及碘。
本文所用的「烷基」,係指直鏈或支鏈狀飽和烴基。烷基的例,包括甲基(Me),乙基(Et),丙基(例如正丙基及異丙基),丁基(例如正丁基、異丁基、第2丁基、第3丁基),戊基(例如正戊基、異戊基),己基等。於各種實施例,烷基可具有1至40個碳原子(亦即C1-40烷基),例如1-30個碳原子(亦即C1-30烷基)。於一些實施例,烷基可具有1至6個碳原子,且可被稱為「低級烷基」。低級烷基的例,包括甲基、乙基、丙基(例如正丙基及異丙基)及丁基(例如正丁基、異丁基、第2丁基、第3丁基)。於一些實施例,烷基可以如本文所述被取代。烷基通常不被另一烷基、烯基或炔基取代。
本文所用的「烯基」,係指具有一個或一個以上碳-碳雙鍵的直鏈或支鏈狀烷基。烯基的例,包括乙烯基、丙烯基、丁烯基、戊烯基、己烯基、丁二烯基、戊二烯基、己二烯基等。一個或一個以上碳-碳雙鍵可以是內部(例如在2-丁烯中)或末端(例如在1-丁烯中)。於各種實施例,烯基可具有2至40個碳原子(亦即C2-40烯基),例如2至20個碳原子(亦即C2-20烯基)。於一些實施例,烯基可以如本文所述被取代。烯基通常不被另一個烯基、烷基或炔基取代。
本文所用之「稠合(fused)環」或「稠合(fused)環基團」,係指具有至少兩個環的多環系統,其中至少一個環為芳香族的,且如此的芳香族環(碳環或雜環),與至少一個芳香族或非芳香族的其它環以及碳環或雜環共有一鍵結。該等多環系統可如本文所述的高度地p-共軛及選擇性地任選如本文所述地被取代。
本文所用之「雜原子」,係指除碳或氫以外的任意元素的原子,包括例如氮、氧、矽、硫、磷及硒。
本文所用之「芳香基」係指芳香性的單環烴環系統或一個或一個以上的芳香性烴環稠合在一起或至少一個芳香性單環烴環與一個或一個以上的環烷基環及/或雜環稠合的多環系統。芳香基可包含6~24個碳原子(例如C6-24芳香基),可包含複數稠合環。於一些實施例,多環芳香基可具有8~24個碳原子。任一適合的芳香基的環位置,可共價鍵結於定義的化學結構。只具有芳香性碳環的芳香基之例,包括苯基、1-萘基(雙環)、2-萘基(雙環)、蒽基(三環)、菲基(三環)、並五苯基(五環)等。至少一個芳香性單環烴環與一個或一個以上的環烷基環及/或雜環稠合的多環系統之例,包括環戊烷的苯衍生物(亦即茚基,5,6-雙環烷基/芳香環系統)、包括環己烷的苯衍生物(亦即四氫萘基,6,6-雙環烷基/芳香環系統)、包括咪唑啉的苯衍生物(亦即苯並咪唑啉基,5,6-雙環雜環基/芳香環系統)及包括吡喃的苯衍生物(亦即苯並吡喃基,6,6-雙環雜環基/芳香環系統)。芳香基的其他例,包括苯並二噁烷基、苯並二氧呃基(benzodioxolyl)、苯並二氫吡喃基、吲哚啉基等。於一些實施例,芳香基可以如本文所述地被取代。於一些實施例,芳香基可具有一個或其以上的鹵素取代基,可稱為鹵芳香基。全鹵芳香基,亦即芳香基中所有的氫原子皆被鹵原子取代(例如-C6F5),包含於鹵芳香基之定義。於某些實施例,芳香基被另一芳香基取代,可稱為雙芳香基。雙芳香基的各芳香基可以如本文揭露的被取代。
本文所用之「雜芳香基」係指含有至少一個選自氧(O)、氮(N)、硫(S)、矽(Si)及硒(Se)群組之一環雜原子之芳香性單環系統或至少一環為芳香性及含有至少一個環雜原子之多環系統。多環雜芳香基包含一個或一個以上的芳香性碳環、非芳香性碳環及/或非芳香性雜環。
雜芳香基整體,可具有例如5~24個環原子,含有1~5個環雜原子(例如5~20員的雜芳香基)。雜芳香基在任一雜原子或碳原子處,可連接至定義的化學結構,成為穩定的結構。通常雜芳香基環,不含有O-O、S-S或S-O鍵結。然而,雜芳香基中的一個或其以上的N或S原子,可被氧化(例如吡啶N-氧化物、噻吩S-氧化物、噻吩S,S-二氧化物)。雜芳香基之例,包括例如5或6員單環及5-6雙環系統:其中T為O、S、NH、N-烷基、N-芳香基、N-(芳香基烷基)(例如N-苯甲基)、SiH2、SiH(烷基)、Si(烷基)2、SiH(芳香基烷基)、Si(芳香基烷基)2或Si(烷基)(芳香基烷基)。如此的雜芳香基環之例,包括吡咯基、呋喃基、噻吩基、吡啶基、嘧啶基、噠嗪基(pyridazinyl)、吡嗪基(pyrazinyl)、三唑基、四唑基、吡唑基、咪唑基、異噻唑基、噻唑基、噻二唑基、異噁唑基、噁唑基、噁二唑基、吲哚基、異吲哚基、苯並呋喃基、苯並噻吩基、喹啉基、2-甲基喹啉基、異喹啉基、喹喔啉基(quinoxalyl)、喹唑啉基(quinazolyl)、苯並三唑基、苯並咪唑基、苯並噻唑基、苯並異噻唑基、苯並異噁唑基、苯並噁二唑基、苯並噁唑基、噌啉基(cinnolinyl)、1H-吲唑基、2H-吲唑基、吲哚嗪基(indolizinyl)、異苯並呋喃基、萘啶基(naphthyridinyl)、酞嗪基(phthalazinyl)、蝶啶基(pteridinyl)、嘌呤基(purinyl)、噁唑並吡啶基(oxazolopyridinyl)、噻唑並吡啶基、咪唑並吡啶基、呋喃並吡啶基、噻吩並吡啶基、吡啶並嘧啶基、吡啶並吡嗪基、吡啶並噠嗪基、噻吩並噻唑基、噻吩並噁唑基、噻吩並咪唑基等。再者,雜芳香基之例,包括4,5,6,7-四氫吲哚基、四氫喹啉基、苯並噻吩並吡啶基、苯並呋喃並吡啶基等。於一些實施例,雜芳香基可以如本文揭露的被取代。
其中,
其中,R係選自下列群組之一,C1~C30的烷基、支鏈烷基、矽烷基、酯基、烷氧基、烷硫基、鹵代烷基、含有烯或炔之烷基、含有氰基或硝基或羥基或酮基取代之烷鏈及鹵素;D1與D2係獨立地選自下列群組之一,
其中,R為C1~C30的烷基、支鏈烷基、矽烷基、酯基、烷氧基、烷硫基、鹵代烷基、含有烯或炔之烷基、含有氰基或硝基或羥基或酮基取代之烷鏈及鹵素;其中,Ar係選自下列群組之一,C1~C30的稠環芳香烴、C1~C30的苯稠雜環化合物、C1~C30的稠雜環化合物、含有C1~C30的烷基、支鏈烷基、矽烷基、酯基、烷氧基、烷硫基、鹵代烷基、含有烯或炔之烷基、含有氰基或硝基或羥基或酮基取代之烷鏈、鹵素之苯環、五元雜環及六元雜環;以及m與n各為2~200的任意整數。
於一實施態樣中,A2係選自下列群組之一,
其中,R為C1~C30的烷基、支鏈烷基、矽烷基、酯基、烷氧基、烷硫基、鹵代烷基、含有烯或炔之烷基、含有氰基或硝基或羥基或酮基取代之烷鏈及鹵素;以及其中,Ar係選自下列群組之一,C1~C30的稠環芳香烴、C1~C30的苯稠雜環化合物、C1~C30的稠雜環化合物、含有C1~C30的烷基、支鏈烷基、矽烷基、酯基、烷氧基、烷硫基、鹵代烷基、含有烯或炔之烷基、含有氰基或硝基或羥基或酮基取代之烷鏈、鹵素之苯環、五元雜環及六元雜環。
於又一實施態樣中,前述之共軛聚合物的光學能隙範圍為1.85~2.5eV。
於本實施例中,其中下列條件至少一者會成立,A1≠A2以及D1≠D2。較佳者,A1≠A2且D1=D2。
本發明之第二實施例揭示一有機光伏裝置,其包含一第一電極、一第二電極以及一主動層材料,前述主動層材料位於第一電極與第二電極之間,其中,主動層材料包含一非富勒烯受體以及一給體,前述給體係如第一實施例中所述之共軛聚合物。
於一實施態樣中,前述非富勒烯受體的光學能隙範圍小於或等於1.7eV。
於另一實施態樣中,前述給體的光學能隙範圍為1.85~2.5eV。
範例
範例1:材料合成(M3)
合成M1:
氬氣下,Thiophene(8.4g,100.00mmol)置於500mL四頸反應瓶中,攪拌下加入40mL anhydrous THF溶解並降溫至15℃。緩慢滴入40mL n-BuLi,並持續攪拌1小時。滴入7-(iodomethyl)pentadecane(23.49g,66.67mmol),緩慢回溫至室溫攪拌隔夜。冰浴下,加入5mL水中止反應,加入100mL Heptane,以20mL水萃取三次。取有機層除水,旋濃除去有機溶劑。以減壓蒸餾方式除去雜質(0.25torr,80-100℃)。釜殘以20g silica gel過色,沖提液為Heptane。收集主要段,除去有機溶劑,真空乾燥後,得淡黃色油狀物M1,產率:13.37g,65%。
合成M2:
氬氣下,M1(13.37g,43.33mmol)置於500mL三頸瓶。攪拌下加入134mL anhydrous THF溶解,並降溫至8℃。緩慢滴入17.33mL n-BuLi,8℃下攪拌反應1小時。8℃下,一次性投入BTD(4.66g,21.13
mmol),攪拌3小時。緩慢加入溶解於35mL 10% HCl(aq)的SnCl2 2H2O(11.65g,51.63mmol),溫度不超過20℃。滴加完畢後,緩慢回溫到室溫,攪拌隔夜。加入200mL Heptane後,以50mL水萃取三次,並確保水溶液為中性。取有機層除水,過濾取溶液,旋濃去除有機溶劑。管柱層析,沖提液為Heptane,收集主要片段,除去有機溶劑,真空下加熱50℃乾燥,得淡黃色油狀物M2,產率:11.88g,70%。
合成M3:
氬氣下,M2(11.88g,14.79mmol)置於500mL三頸瓶,以120mL anhydrous THF溶解,並降溫至-60℃,緩慢滴入14.8mL n-BuLi,-60℃攪拌反應0.5小時。緩慢滴入溶於8mL anhydrous THF的Me3SnCl(8.25g,41.41mmol),緩慢回溫至10℃,攪拌2小時。加入10mL水中止反應,加100mL Heptane,以20mL水萃取三次。有機層除水,旋濃除去有機溶劑得到粗產物,真空乾燥得黃色油狀物M3,產率:15.86g,95%。M3材料的 1 H NMR光譜請參考第一圖所示。
範例2:材料合成(M6)
合成M5:
取M4(5.00g,11.81mmol)及TBS(9.03g,24.19mmol)加入100毫升反應瓶,再加入10V THF(50mL),於室溫下以除氧30分鐘。加入Pd2(dba)3(0.43g,0.46mmol)及P(o-tol)3(0.57g,1.87mmol)在氬氣系統下,置於油浴加熱至反應溫度達67℃回流反應1小時。反應結束後降回室溫,以Celite過濾後,濃縮後以120g silica gel管柱純化,沖提液為DCM:Heptane=4:6,收集主要片段。濃縮,真空乾燥得螢光黃色粉末M5,產率:4.15g,81%。
合成M6:
取M5(1.20g,2.79mmol)加入100毫升三頸反應瓶,再加入
18mL CHCl3及1.8mL HOAc,於氮氣下進行反應。室溫下緩慢加入NBS(1.09g,6.12mmol),置於油浴加熱至反應溫度達40℃,1小時後反應結束,降溫後加入54mL MeOH,固體析出後進行抽氣過濾。取固體以36mL THF溶解,在室溫下滴加72mL IPA做再結晶。抽氣過濾,真空乾燥得螢光黃色粉末M6,產率:1.41g,85%。M6材料的 1 H NMR光譜請參考第二圖所示。
範例3:材料合成(M9)
合成M8:
取M7(6.00g,14.17mmol)及TBS(13.22g,35.42mmol)加入250毫升反應瓶,再加入60mL THF(60mL),於室溫下以氬氣除氧30分鐘。加入Pd2(dba)3(0.52g,0.56mmol)及P(o-tol)3(0.69g,2.26mmol)在氬氣系統下,加熱至反應溫度達66℃回流反應2小時。反應結束降回室溫,以Celite及silica gel過濾。濃縮後配置300g silica gel管柱純化,沖提液為DCM:Heptane=4:6,收集主要片段。濃縮,真空乾燥得螢光黃色粉末M8,產率:4.86g,80%。
合成M9:
取M8(4.86g,11.31mmol)加入100毫升三頸反應瓶,再加入72mL CHCl3及7.2mL HOAc,於氮氣下進行反應。室溫下緩慢加入NBS(4.42g,24.83mmol),置於油浴加熱至反應溫度達40℃,1小時後反應結束,降溫後加入145mL MeOH,固體析出後進行抽氣過濾。取固體以30mL THF溶解,在室溫下滴加60mL IPA做再結晶。抽氣過濾,真空乾燥得螢光黃色粉末M9,產率:5.8g,87.3%。M9材料的 1 H NMR光譜請參考第三圖所示。
範例4:材料合成(P1,P2)
合成40-033(P1):m:n=9:1
將M3(0.63g,0.56mmol)、M6(0.30g,0.51mmol)和BDD(0.043g,0.056mmol)放入100毫升三頸瓶。倒入22毫升鄰-二甲苯。通入氬氣並攪拌30分鐘。通氬氣下,加入Pd2(dba)3(0.021g,0.0225mmol)和P(o-tol)3(0.027g,0.090mmol)。反應加熱到130℃,反應17小時。冷卻,將反應物倒入甲醇中析出。索式萃取純化材料,使用甲醇和二氯甲烷作為純化溶劑。最後使用氯苯將產物溶出並在甲醇中析出。收集固體並用甲醇沖洗。用真空烘箱乾燥隔夜。產率:0.62g,87.7%。
合成40-033(P2):m:n=8:2
將M3(0.72g,0.64mmol)、M6(0.30g,0.51mmol)和BDD(0.098g,0.13mmol)放入100毫升三頸瓶。倒入25毫升鄰-二甲苯。通入氬氣並攪拌30分鐘。通氬氣下,加入Pd2(dba)3(0.023g,0.0255mmol)和P(o-tol)3(0.031g,0.102mmol)。反應加熱到130℃,反應18小時。冷卻,將反應物倒入甲醇中析出。索式萃取純化材料,使用甲醇和二氯甲烷作為純化溶劑。最後使用氯苯將產物溶出並在甲醇中析出。收集固體並用甲醇沖洗。用真空烘箱乾燥隔夜。產率:0.69g,85.5%。
範例5:材料合成(P3)
合成40-073(P3):m:n=5:5
將M3(0.54g,0.48mmol)、M6(0.14g,0.24mmol)和M9(0.14g,0.24mmol)放入100毫升三頸瓶。倒入19毫升鄰-二甲苯。通入氬氣
並攪拌30分鐘。通氬氣下,加入Pd2(dba)3(0.017g,0.0192mmol)和P(o-tol)3(0.0233g,0.0767mmol)。反應加熱到130℃,反應19小時。冷卻,將反應物倒入甲醇中析出。索式萃取純化材料,使用甲醇和二氯甲烷作為純化溶劑。最後使用氯苯將產物溶出並在甲醇中析出。收集固體並用甲醇沖洗。用真空烘箱乾燥隔夜。產率:0.41g,69.9%。
範例6:材料合成(P4)
合成40-082(P4):m:n=9:1
將M3(0.73g,0.65mmol)、M6(0.34g,0.58mmol)和BTZ(0.045g,0.065mmol)放入100毫升三頸瓶。倒入25毫升鄰-二甲苯。通入氬氣並攪拌30分鐘。通氬氣下,加入Pd2(dba)3(0.024g,0.026mmol)和P(o-tol)3(0.032g,0.104mmol)。反應加熱到130℃,反應22小時。冷卻,將反應物倒入甲醇中析出。索式萃取純化材料,使用甲醇和二氯甲烷作為純化溶劑。最後使用氯苯將產物溶出並在甲醇中析出。收集固體並用甲醇沖洗。用真空烘箱乾燥隔夜。產率:0.60g,75.2%。
範例7:材料合成(P5)
合成26-145(P5):m:n=0.95:0.05
將M3(0.57g,0.51mmol)、M6(0.31g,0.53mmol)和2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene(0.0125g,0.027mmol)放入100毫升三頸瓶。倒入40毫升氯苯。通入氬氣並攪拌30分鐘。通氬氣下,加入Pd2(dba)3(0.020g,0.021mmol)和P(o-tol)3(0.026g,0.086mmol)。反應
加熱到130℃,反應22小時。冷卻,將反應物倒入甲醇中析出。索式萃取純化材料,使用甲醇和二氯甲烷作為純化溶劑。最後使用氯苯將產物溶出並在甲醇中析出。收集固體並用甲醇沖洗。用真空烘箱乾燥隔夜。產率:0.41g,64.8%。
範例8:材料合成(P6)
合成26-147(P6):m:n=0.9:0.1
將M3(0.70g,0.62mmol)、M6(0.40g,0.69mmol)和2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene(0.0322g,0.069mmol)放入100毫升三頸瓶。倒入54毫升氯苯。通入氬氣並攪拌30分鐘。通氬氣下,加入Pd2(dba)3(0.025g,0.027mmol)和P(o-tol)3(0.034g,0.110mmol)。反應加熱到130℃,反應18小時。冷卻,將反應物倒入甲醇中析出。索式萃取純化材料,使用甲醇和二氯甲烷作為純化溶劑。最後使用氯苯將產物溶出並在甲醇中析出。收集固體並用甲醇沖洗。用真空烘箱乾燥隔夜。產率:0.62g,77.4%。
範例9:聚合物太陽能電池的製造及測試
使用具有~11Ω/□的薄層電阻的預圖案化的ITO塗覆的玻璃作為基板。依順序在中性清潔劑、去離子水、丙酮及異丙醇中超音波震盪處理,在每個步驟中清洗15分鐘。用UV-O3清潔器進一步處理洗滌過的基材15分鐘。將ZnO(二乙基鋅溶液,在甲苯中15wt%,用四氫呋喃稀釋)的頂塗層,以5000rpm的旋轉速率30秒旋轉塗佈在ITO基板上,然後在空氣中在120℃下烘烤20分鐘。在o-xylene或CB中製備活性層溶液,並加入0.5%(v/v)1,8-diiodoocatne(DIO)作為添加劑以調整薄膜形態(聚合物:℃梯形分子重量比為1:1~1:1.25)。IC梯形分子更包含IDTT衍生物,例如:
聚合物濃度為8~10mg ml-1。為了完全溶解聚合物,活性層溶液應在加熱板上在100℃下攪拌至少3小時。隨後將高分子溶液置於室溫冷卻後進行塗佈,以塗佈轉速控制膜厚範圍於100nm上下。之後混合膜在120℃下退火5分鐘,然後傳送至熱蒸鍍機中。在3×10-6Torr的真空度下,沉積MoO3的薄層(8nm)作為陽極中間層,隨後沉積100nm厚度的銀作為上電極。並使用環氧樹脂在手套箱內封裝所有電池。使用太陽光模擬器(具有AM1.5G濾光器的氙燈)在空氣中及室溫下AM1.5G(100mW cm-2)下測量元件J-V特性。此處使用具有KG5濾光片的標準矽二極體作為參考電池來校準光強度,以使光譜不匹配的部分達到一致。使用Keithley 2400source meter儀器記錄J-V特性。典型的電池具有4mm2的元件面積,其由具有孔徑的金屬遮罩對準元件面積所定義。每片元件有4個有效點,我們將這4個點結果取平均值為PCEAVE。每片元件中有4個有效點,數值最高的就是PCEBEST。
範例10:聚合物太陽能電池的效能分析
第四圖顯示有機光伏裝置的代表構造,通常包括基板20(例如玻璃)、陽極22(例如ITO)、陰極26(例如鋁或鈣)以及在陽極和陰極之間的主動層24,其使用本發明的共軛聚合物作為主動層材料。
P5與P6的結構相同,只是m與n的比例不同,P5的比例為m:n=0.95:0.05,而P6的比例為m:n=0.9:0.1。P5和P6是屬於A1=A2且D1≠D2的結構,請參考表一的數據,使用P5和P6所製備元件的最佳功率轉換效率(PCEBEST)分別為9.58%以及8.55%。
P1與P2的結構相同,只是m與n的比例不同,P1的比例為m:n=0.9:0.1,而P2的比例為m:n=0.8:0.2。P1和P2是屬於A1≠A2且D1=D2的結構,請參考表二的數據,使用P1和P2所製備元件的最佳功率轉換效率(PCEBEST)分別為12.5%以及12.45%。
P3和P4是屬於A1≠A2且D1=D2的結構,P3的比例為m:n=0.5:0.5,而P4的比例為m:n=0.9:0.1。請參考表二的數據,使用P3和P4所製備元件的最佳功率轉換效率(PCEBEST)分別為12.45%以及10.88%。
綜合上述數據可以發現,使用D1≠D2的結構(P5和P6)所製備元件的最佳功率轉換效率(PCEBEST)落在10%以下,相對地,使用D1=D2的結構(P1、P2、P3和P4)所製備元件的最佳功率轉換效率(PCEBEST)落在10%以上,由此可以得知D1=D2的結構有利於提高功率轉換效率(PCE)。
另外,前案所揭示的低能隙共聚物中的m與n的比例通常會巨幅影響功率轉換效率(PCE)的高低,也就是m與n的比例調配要非常精準,造成製程難度偏高,也不利於工業化大量製造。相反的,請參考本發明的表二,m與n的摻雜比例由0.9:0.1至0.5:0.5,所製備元件的最佳功率轉換效率(PCEBEST)都能維持在10%以上,因此製程彈性,利於工業化大量生產。
20‧‧‧基板
22‧‧‧陽極
24‧‧‧主動層
26‧‧‧陰極
Claims (4)
- 一包含一第一電極、一第二電極與一主動層材料之裝置,該主動層材料位於該第一電極與該第二電極之間,該主動層材料包含:一非富勒烯受體,其光學能隙範圍小於或等於1.7eV;以及一給體,其光學能隙範圍為1.85~2.5eV,該給體係為一共軛聚合物(conjugated polymer),且該共軛聚合物具有下式(式一):
- 如申請專利範圍第1項所述之裝置,其中該非富勒烯受體係為1,1-dicyanomethylene-3-indanone衍生物。
- 如申請專利範圍第2項所述之裝置,其中該非富勒烯受體係為IDTT衍生物。
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