CN105175691B - 一类基于噻吩并芳基吲哚单元的共轭聚合物半导体材料、制备及其高效聚合物太阳电池应用 - Google Patents
一类基于噻吩并芳基吲哚单元的共轭聚合物半导体材料、制备及其高效聚合物太阳电池应用 Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 30
- 239000004065 semiconductor Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000005842 heteroatom Chemical group 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- KWQMJXZUGBNSOY-UHFFFAOYSA-N 1h-thieno[2,3-g]indole Chemical class C1=C2SC=CC2=C2NC=CC2=C1 KWQMJXZUGBNSOY-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- -1 benzothiadiazole bis-boronate Chemical compound 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 7
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 claims description 4
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims 1
- 238000010898 silica gel chromatography Methods 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 15
- 230000005693 optoelectronics Effects 0.000 abstract description 6
- 230000002950 deficient Effects 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 230000005669 field effect Effects 0.000 abstract description 3
- 125000003107 substituted aryl group Chemical group 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 abstract 1
- 230000007812 deficiency Effects 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 19
- 239000003960 organic solvent Substances 0.000 description 13
- 238000010992 reflux Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 3
- WRGKKASJBOREMB-UHFFFAOYSA-N 1,4-dibromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Br)=CC=C1Br WRGKKASJBOREMB-UHFFFAOYSA-N 0.000 description 3
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 238000006619 Stille reaction Methods 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-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
- JVAQVYKSURQMBE-UHFFFAOYSA-N 11-(bromomethyl)tricosane Chemical compound CCCCCCCCCCCCC(CBr)CCCCCCCCCC JVAQVYKSURQMBE-UHFFFAOYSA-N 0.000 description 2
- ZURZUPKWSBYZKB-UHFFFAOYSA-N 2-(2-nitrophenyl)thiophene Chemical compound [O-][N+](=O)C1=CC=CC=C1C1=CC=CS1 ZURZUPKWSBYZKB-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- FASQVICVMDAZLR-UHFFFAOYSA-N 1,2,3-benzothiadiazole;thiophene Chemical compound C=1C=CSC=1.C=1C=CSC=1.C1=CC=C2SN=NC2=C1 FASQVICVMDAZLR-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical class [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- ODDBHAGNNBEBEY-UHFFFAOYSA-N boric acid;thiophene Chemical compound OB(O)O.C=1C=CSC=1 ODDBHAGNNBEBEY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- JCZMXVGQBBATMY-UHFFFAOYSA-N nitro acetate Chemical compound CC(=O)O[N+]([O-])=O JCZMXVGQBBATMY-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- SSDDBKANEGGSRG-UHFFFAOYSA-N thiophene;tin Chemical compound [Sn].C=1C=CSC=1 SSDDBKANEGGSRG-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明公开了一类基于噻吩并芳基吲哚单元的共轭聚合物半导体材料、制备方法及其有机聚合物太阳电池器件应用。其结构如通式(I)所示:其中Ar表示芳基、取代芳基、杂环芳基及取代杂环芳基;R可以是直链烷基或支链烷基;E表示碳原子、氮原子、硅原子等;A表示缺电子的受体单元,一般为缺电子共轭芳香基团。本发明所及的半导体材料具有良好的溶解性、热稳定性和成膜性,较高的迁移率以及高达5.83%的聚合物太阳电池光电转换效率;本发明提供的制备方法所获得的噻吩并芳基吲哚共轭单元及其衍生材料有望在有机太阳能电池、有机场效应晶体管等光电半导体器件领域获得广泛应用。
Description
技术领域
本发明涉及一类有机共轭半导体材料设计、合成及其在聚合物太阳电池器件中的应用领域,具体涉及一类基于噻吩并芳基吲哚单元的共轭聚合物半导体材料、制备及其高效聚合物太阳电池应用领域。
背景技术
有机共轭聚合物作为一种新型的功能材料,人们已逐渐认识到其丰富的功能特性。从小分子到高分子,其电磁光等特性越来越明显。早在20世纪70年代,有机共轭聚合物材料就引起人们的广泛关注,作为一种新型的功能材料,既具有金属和半导体的电子性质,又具有聚合物的一些优点,比如质轻、价廉、可溶液加工和柔韧性好等,这些优点使其在构筑低成本、大面积、全柔性光电器件方面显示了潜在的应用前景。同时,有机共轭聚合物材料的来源丰富、种类繁多,还可以通过对聚合物材料的结构进行优化,以此方便对其物理性能和成膜特性进行调控,共轭聚合物光电材料在有机发光二极管、场效应晶体管、太阳能电池、生物与化学传感等领域的应用研究方兴未艾。各种不同结构、不同发光波长的共轭聚合物正在被源源不断地开发出来。
调控共轭聚合物的光电特性对于构建共轭聚合的光电器件具有重要的意义,在共轭聚合物链中引入电子给体和电子受体(D–A),并优化D–A化学结构和拓扑结构,能够有效地调控共轭聚合物分子内的电荷转移,提高载流子迁移率,调节分子的HOMO和LUMO能级,降低禁带宽度。这一策略在有机太阳能电池中应用较为广泛,D–A交替排列的共轭聚合物应用在有机太阳能电池上其光电转换效率达到了10%以上。
在D–A交替排列的共轭聚合物中引入杂原子可以增强分子的结晶性和分子间的相互作用,提高载流子迁移率,另外还可以降低分子的HOMO和LUMO能级。
发明内容
本发明通过硝化、Suzuki偶联反应和Stille偶联反应、关环反应、卤化反应、Suzuki或 Stille偶联聚合反应合成一类基于噻吩并芳基吲哚单元的共轭聚合物半导体材料。制备简单,成本低廉,提纯方便,并且很容易引入功能单元、柔性烷基链等,从而改善材料的稳定性和溶解性,能级和光电活性。此外,所述材料在聚合物太阳电池器件中表现较高的光电转换效率。
本发明的噻吩并芳基吲哚单元的共轭聚合物半导体材料,结构如式(Ⅰ):
其中,R是直链烷基或支链烷基;Ar是芳基或取代芳基是苯、噻吩、萘、芴、咔唑、苯并噻吩等中的一种;此外,这种芳基或杂环芳基可含有烷基、烷氧基等取代基以改善其溶解性等。Ar可以是以下结构式(1)~(7)中的一种:
其中,R1,R2为C6或更长碳链的直链或支链烷基,R3为C12或更长碳链的直链或支链烷基,R4,R5为C8或更长碳链的直链或支链烷基或烷氧基。
通式(I)所示的聚合物,其特征在于在式(Ⅰ)中,受体基团A可以是苯并噻二唑(BT)、 4,7–二噻吩苯并噻二唑(DTBT)、二酮吡咯并吡咯(DPP)及其衍生物等常见于有机半导体材料的缺电子受体单元。A可以是以下结构式(8)~(13)中的一种:
其中,R6为H,F中的一种或者两种;R7或R11为C6或更长碳链的直链或支链烷基,;R8为C8或更长碳链的直链或支链烷基或烷氧基;R9,R10为C8或更长碳链的直链或支链烷基。
噻吩并芳基吲哚单元的共轭聚合物半导体材料的制备方法,包括以下的步骤:
噻吩并芳基吲哚单元的共轭聚合物半导体材料的制备方法,包括以下合成步骤:
1.合成方案通式(I)中,
(1)Ar所代表的基团为权利要求1的一种;X为硝基,Y可以为碘或溴,Z可以为锡试剂或硼酸,或硼酸酯;Acceptor units(受体单元)可具有权利要求3中所述的母体结构之一,并具有双溴或双硼酯或双锡试剂结构;若X为硝基,在冰水浴或加热条件下,二溴代物溶于有机溶剂,缓慢滴加硝化试剂,反应得到一类如式I-1所示的硝基化合物;
(2)式I-1所示硝基化合物,与噻吩硼酸酯、噻吩锡试剂经Suzuki或Stille偶联反应得到中间体,分离之后,加入关环试剂,注入有机溶剂,在氮气保护下加热回流,柱色谱分离得到如式I-2所示的杂环化合物;
(3)式I-2所示的杂环化合物,在碱和相转移催化剂的作用下,加入烷基试剂,氮气保护下在有机溶剂中回流反应16~24小时,经柱色谱分离后溶于有机溶剂,经卤化试剂卤化,得一类如式I-3所表示的卤代噻吩并吲哚化合物;
(4)式I-3所表示的卤代噻吩并芳基吲哚化合物,在低温条件下,无水有机溶剂中缓慢滴加锂试剂后制备其锡试剂或者硼酸酯I-4;
(5)式I-4所示双硼酸酯,在有机溶剂中,钯催化剂和碱溶液的作用下加热回流,与缺电子基团即受体A的双溴或双碘试剂,通过Suzuki偶联聚合反应,得到聚合物通式(I)所表示的基于噻吩并芳基吲哚单元的共轭聚合物。式I-4所示的双锡试剂在有机溶剂中,钯催化剂作用下加热,与缺电子基团即受体A的双溴或双碘试剂经过Stille聚合反应得到聚合物通式(I)所表示的基于噻吩并芳基吲哚单元的共轭聚合物;式I-4所示的卤代噻吩并吲哚化合物,在有机溶剂中,钯催化剂作用下加热,与缺电子基团即受体A的双锡试剂或双硼酸酯,经过Stille或Suzuki聚合反应得到聚合物通式(I)所表示的基于噻吩并芳基吲哚单元的共轭聚合物。
步骤(1)所述的硝化试剂是硝酸和硫酸、硝酸钠和硫酸、硝酸铝、乙酰基硝酸酯中任一种,所用的有机溶剂是二氯甲烷、氯仿、1,2-二氯乙烷或1,4-二氧六环中任一种;
步骤(2)所述的关环试剂是三苯基膦或三乙氧基膦,所用的有机溶剂是氯苯、邻二氯苯;
步骤(3)所使用的碱是碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钾、氢氧化钠中任一种;所述的相转移催化剂为碘化钾、四丁基碘化铵、四丁基溴化铵中任一种;所述的烷基试剂为直链卤代烷烃或支链卤代烷烃,直链烷基磺酸酯或支链烷基磺酸酯;所述的卤代试剂是液溴、 N-溴代丁二酰亚胺,N-碘代丁二酰亚胺、高碘酸、碘化钾、碘酸钾中任一种,所述的有机溶剂为四氢呋喃、N,N-二甲基甲酰胺、二氯甲烷、氯仿、1,4-二氧六环、二甲亚砜和50%氢氧化钠溶液中任一种。
步骤(4)所述的有机溶剂为四氢呋喃、乙醚等;所述的锂试剂为正丁基锂、叔丁基锂、二异丙基氨基锂中任一种;
步骤(5)所述的碱是碳酸钾、碳酸氢钾、碳酸钠或碳酸氢钠;所述的催化剂是四(三苯基膦)钯、醋酸钯、二氯二三苯基膦钯、三(二亚苄基丙酮)二钯和三(邻甲苯基)膦中任一种;所述的有机溶剂为四氢呋喃、甲苯、苯、氯苯中任一种;
基于噻吩并芳基吲哚单元的共轭聚合物半导体材料的纯化方法为甲醇沉降之后,经正己烷、二氯甲烷、氯仿或氯苯抽提,取最终抽提产物在正己烷中沉降得到的固体为目标产物;
基于噻吩并芳基吲哚单元的共轭聚合物半导体材料,应用到有机太阳能电池中,其制备的聚合物太阳电池器件结构为:ITO/PEDOT:PSS/聚合物:PC61BM/Ca/Al或ITO/PEDOT:PSS/ 聚合物:PC71BM/Ca/Al,器件均为常规溶液法制备。
与现有技术相比,本发明具有以下有益效果:
本发明的噻吩并芳基吲哚单元的共轭聚合物半导体材料,杂原子的引入不仅有利于分子的结晶,还可以增强分子内的作用力,提高载流子的迁移率,同时也降低了分子的HOMO和 LUMO能级,另外烷基链的引入可以产生一定的空间效应,调控分子的形貌,提高材料的溶解性。与此同时,这类噻吩并芳基吲哚单元的共轭聚合物半导体材料合成工艺简单,产率高,而且易纯化,通过本发明所提供的制备方法和所获得的噻吩并芳基吲哚单元的共轭聚合物半导体材料有着良好的溶解性、合适的分子能级、较高的稳定性和迁移率。本发明的噻吩并芳基吲哚单元的共轭聚合物半导体材料,在有机太阳能电池或有机场效应晶体管等光电领域存在着潜在的应用价值。
附图说明
图1-1为聚合物PTiDBT薄膜的紫外可见吸收(Uv-vis)光谱;
图1-2为聚合物PTiDBT薄膜的循环伏安(CV)曲线;
图1-3为聚合物PTiDBT的热重曲线;
图1-4为聚合物PTiDBT的J-V曲线;
图2-1为聚合物PTiDDTBT薄膜的紫外可见吸收(Uv-vis)光谱;
图2-2为聚合物PTiDDTBT薄膜的循环伏安(CV)曲线;
图2-3为聚合物PTiDDTBT的热重曲线;
图2-4为聚合物PTiDDTBT的J-V曲线;
图3-1为聚合物PTiDTBT薄膜的紫外可见吸收(Uv-vis)光谱;
图3-2为聚合物PTiDTBT薄膜的循环伏安(CV)曲线;
图3-3为聚合物PTiDTBT的热重曲线;
图3-4为聚合物PTiDTBT的J-V曲线;;
图4为三种聚合物PTiDBT,PTiDTBT和PTiDDTBT应用到有机太阳能电池中的器件结构示意图;
表1为三种聚合物PTiDBT,PTiDTBT和PTiDDTBT分别与富勒烯混合应用于太阳能电池的光伏参数和效率。
具体实施例
为了更清楚的阐述本发明,下面通过具体实施例子来对本发明做进一步说明,不是对本发明的限制。
实施例1
聚合物PTiDBT(I)的制备
在单口圆底烧瓶(250mL)中,加入对二溴苯(11.8g,50mmol),二氯甲烷(50mL),冰水浴下,滴加硝酸(10mL)和硫酸(27.5mL),0℃条件下,搅拌反应2小时,然后加水猝灭反应,二氯甲烷萃取,有机相用水、饱和碳酸氢钠、饱和氯化钠溶液洗涤,无水硫酸镁干燥,浓缩,乙醇重结晶得12.6g 2-硝基-对二溴苯,产率90%。
在两口瓶(100mL)中,将2-硝基-对二溴苯(2.80g,10mmol),2-噻吩硼酸(1.53g,12mmol) 溶解在20mL甲苯中,注入2M碳酸钾溶液15mL.抽换气三次,氮气保护下,加入四(三苯基膦)钯(150mg,0.14mmol),加热至75℃,反应24小时。自然冷至室温,二氯甲烷萃取,干燥,浓缩,柱层析分离得到亮黄色液体2.35g,产率83%。1H NMR(400MHz,CDCl3)δ(ppm) 7.95(d,J=1.9Hz,1H),7.77(dd,J=8.1,1.9Hz,1H),7.56(d,J=8.1Hz,1H),7.42(d,J=1.0Hz,1H),7.39(dd,J=5.1,1.1Hz,1H),7.11(d,J=1.4Hz,1H).13C NMR(100MHz,CDCl3)δ(ppm)141.03,132.68,128.69,128.53,127.94,127.50,127.24,127.21,126.71,124.88,120.74.
在两口圆底烧瓶(250mL)中加入2-硝基-苯联噻吩(9.37g,33mmol),三苯基膦(3.89g, 14.85mmol)和1,2-邻二氯苯(50mL),氮气保护,加热至180℃搅拌反应36小时,冷至室温,二氯甲烷萃取,浓缩,经柱层析分离得噻吩并吲哚化合物,米白色粉末4.83g,产率58.1%。1H NMR(400MHz,CDCl3)δ(ppm)8.21(d,1H),7.60(d,J=6.7Hz,2H),7.39(d,J=5.2Hz,1H), 7.29(dd,J=8.4,1.7Hz,1H),7.07(d,J=5.2Hz,1H).13C NMR(100MHz,CDCl3)δ(ppm) 143.37,141.83,127.73,123.02,121.07,119.98,117.88,116.02,114.81,111.51.
在两口瓶(250mL)中加入上述噻吩并吲哚(4.54g,18mmol)、碳酸钾(4g,37.8mmol)、 2-葵基-1-溴十四烷(8.35g,20.0mmol)和N,N-二甲基甲酰胺(100mL),氮气保护下,135℃搅拌24h。二氯甲烷萃取,无水硫酸钠干燥。浓缩,硅胶色谱柱分离得烷基化的噻吩并吲哚 8.00g淡黄色液体,产率96%。1H NMR(400MHz,CDCl3)δ(ppm)7.59(d,J=8.4Hz,1H),7.50 (d,J=1.6Hz,1H),7.39(d,J=5.2Hz,1H),7.27-7.24(dd,J=1.7Hz,1H),7.02(d,J=5.2Hz, 1H),4.06(d,J=7.5Hz,2H),2.04(m,1H),1.28(m,24H),0.84-0.89(m,6H).13C NMR(100MHz, CDCl3)δ(ppm)146.16,142.42,127.29,122.03,121.30,119.97,115.84,115.73,113.02,110.56, 49.79,38.37,31.88,31.78,31.68,31.6,29.90,29.58,29.50,29.27,26.4,26.40,22.68,22.63,14.14, 14.10.
在单口瓶100mL)中加入烷基化的噻吩并吲哚(4.62g,10mmol),加入四氢呋喃(50mL),0℃条件下,分批加入N-溴代丁二酰亚胺(1.96g,11mmol),搅拌反应2h。二氯甲烷萃取,无水硫酸钠干燥。浓缩,硅胶色谱柱分离得4.98g无色蜡状固体,产率92%。1H NMR(400MHz,CDCl3)δ(ppm)7.50(d,J=8.4Hz,1H),7.47(d,J=1.6Hz,1H),7.25(dd,J=8.4,1.6 Hz,1H),7.05(s,1H),3.98(d,J=7.5Hz,2H),1.99(m,1H),1.44-1.17(m,26H),0.94-0.82(m, 6H).13C NMR(100MHz,CDCl3)δ(ppm)143.69,141.18,122.51,120.29,119.75,115.90,115.75, 114.06,113.97,113.17,49.79,38.33,31.91,31.80,31.59,31.58,29.91,29.60,29.53,29.31,26.38, 22.71,22.61,14.19,14.15.
在单口瓶(50mL)中,将苯并噻二唑的双硼酯(0.1552g,0.40mmol)和上述无色蜡状固体 (0.2669g,0.40mmol)溶解在甲苯(25mL)溶液中,注入2M碳酸钾溶液10mL,抽换气20分钟,氮气保护下加入四(三苯基膦)钯(12mg,0.01mmol),加热至90℃,反应24小时。自然冷至室温,将反应液缓慢滴加到500mL甲醇中沉降,室温搅拌12小时,抽滤得到黑色粉末,丙酮回流抽提24h,石油醚回流抽提24h,最终得到PTiDBT黑色粉末0.22g,产率78%。结构式为:
图1-1为聚合物PTiDBT薄膜的紫外可见吸收(Uv-vis)光谱;图1-2为聚合物PTiDBT薄膜的循环伏安(CV)
曲线;图1-3为聚合物PTiDBT的热重曲线;图1-4为聚合物PTiDBT的J-V曲线。
实施例2
聚合物PTiDDTBT(II)的制备
在单口圆底烧瓶(250mL)中,加入对二溴苯(12.0g,50mmol),二氯甲烷(50mL),冰水浴下,滴加硝酸(10mL)和硫酸(25mL),0℃条件下,搅拌反应2小时,然后加水猝灭反应,二氯甲烷萃取,有机相用水、饱和碳酸氢钠、饱和氯化钠溶液洗涤,无水硫酸镁干燥,浓缩,乙醇重结晶得12.5g 2-硝基-对二溴苯,产率90%。
在两口瓶(100mL)中,将2-硝基-对二溴苯(2.80g,10mmol),2-噻吩硼酸(1.42g,11mmol) 溶解在30mL甲苯中,注入2M碳酸钾溶液20mL.抽换气三次,氮气保护下,加入四(三苯基膦)钯(150mg,0.14mmol),加热至90℃,反应24小时。自然冷至室温,二氯甲烷萃取,干燥,浓缩,柱层析分离得到亮黄色液体2.35g,产率83%。1H NMR(400MHz,CDCl3)δ(ppm) 7.95(d,J=1.9Hz,1H),7.77(dd,J=8.1,1.9Hz,1H),7.56(d,J=8.1Hz,1H),7.42(d,J=1.0Hz,1H),7.39(dd,J=5.1,1.1Hz,1H),7.11(d,J=1.4Hz,1H).13C NMR(100MHz,CDCl3)δ(ppm)141.03,132.68,128.69,128.53,127.94,127.50,127.24,127.21,126.71,124.88,120.74.
在两口圆底烧瓶(250mL)中加入2-硝基-苯联噻吩(9.37g,33mmol),三苯基膦(3.89g, 14.85mmol)和1,2-邻二氯苯(100mL),氮气保护,加热至180℃搅拌反应36小时,冷至室温,二氯甲烷萃取,浓缩,经柱层析分离得噻吩吲哚化合物,米白色粉末4.83g,产率58.1%。1H NMR(400MHz,CDCl3)δ(ppm)8.21(br,1H),7.60(d,J=6.7Hz,2H),7.39(d,J=5.2Hz, 1H),7.29(dd,J=8.4,1.7Hz,1H),7.07(d,J=5.2Hz,1H).13C NMR(100MHz,CDCl3)δ(ppm) 143.37,141.83,127.73,123.02,121.07,119.98,117.88,116.02,114.81,111.51.
在两口瓶(250mL)中加入上述噻吩并吲哚(4.54g,18mmol)、碳酸钾(4g,37.8mmol)、 2-葵基-1-溴十四烷(8.35g,20.0mmol)和N,N-二甲基甲酰胺(100mL),氮气保护下,135℃搅拌24h。二氯甲烷萃取,无水硫酸钠干燥。浓缩,硅胶色谱柱分离得烷基化的噻吩并吲哚 8.00g淡黄色液体,产率96%。1H NMR(400MHz,CDCl3)δ(ppm)7.59(d,J=8.4Hz,1H),7.50 (d,J=1.6Hz,1H),7.39(d,J=5.2Hz,1H),7.27-7.24(dd,J=1.7Hz,1H),7.02(d,J=5.2Hz, 1H),4.06(d,J=7.5Hz,2H),2.04(m,1H),1.28(m,24H),0.84-0.89(m,6H).13C NMR(100MHz, CDCl3)δ(ppm)146.16,142.42,127.29,122.03,121.30,119.97,115.84,115.73,113.02,110.56, 49.79,38.37,31.88,31.78,31.68,31.6,29.90,29.58,29.50,29.27,26.4,26.40,22.68,22.63,14.14, 14.10.
在单口瓶100mL)中加入烷基化的噻吩并吲哚(4.62g,10mmol),加入四氢呋喃(50mL),0℃条件下,分批加入N-溴代丁二酰亚胺(1.96g,11mmol),搅拌反应2h。二氯甲烷萃取,无水硫酸钠干燥。浓缩,硅胶色谱柱分离得4.98g无色蜡状固体,产率92%。1H NMR(400MHz,CDCl3)δ(ppm)7.50(d,J=8.4Hz,1H),7.47(d,J=1.6Hz,1H),7.25(dd,J=8.4,1.6 Hz,1H),7.05(s,1H),3.98(d,J=7.5Hz,2H),1.99(m,1H),1.44-1.17(m,26H),0.94-0.82(m, 6H).13C NMR(100MHz,CDCl3)δ(ppm)143.69,141.18,122.51,120.29,119.75,115.90,115.75, 114.06,113.97,113.17,49.79,38.33,31.91,31.80,31.59,31.58,29.91,29.60,29.53,29.31,26.38, 22.71,22.61,14.19,14.15.
在单口瓶(50mL)中,将苯并噻二唑的二联噻吩的三丁基锡试剂(0.1377g,0.22mmol)和上述无色蜡状固体(0.1191g,0.22mmol)溶解在甲苯(25mL)溶液中,抽换气20分钟,氮气保护下加入四(三苯基膦)钯(12mg,0.01mmol),加热至90℃,反应24小时。自然冷至室温,将反应液缓慢滴加到500mL甲醇中沉降,室温搅拌12小时,抽滤得到黑色粉末,丙酮回流抽提24h,石油醚回流抽提24h,最终得到PTiDDTBT黑色粉末0.12g,产率78%。结构式为:
图2-1为聚合物PTiDDTBT薄膜的紫外可见吸收(Uv-vis)光谱;图2-2为聚合物PTiDDTBT薄膜的循环伏安(CV)曲线;图2-3为聚合物PTiDDTBT的热重曲线;图2-4为聚合物PTiDDTBT的J-V曲线。
实施例3
聚合物PTiDTBT(II)的制备
在两口瓶(150mL)中,将烷基化的噻吩并吲哚(4.62g,10mmol),2-噻吩硼酸(1.42g, 11mmol)溶解在50mL甲苯中,注入2M碳酸钾溶液30mL.抽换气三次,氮气保护下,加入四(三苯基膦)钯(150mg,0.14mmol),加热至90℃,反应24小时。自然冷至室温,二氯甲烷萃取,干燥,浓缩,柱层析分离得到无色液体3.75g,产率78%。
1H NMR(400MHz,CDCl3)δ(ppm)7.73(d,J=8.2Hz,1H),7.59(d,J=1.2Hz,1H),7.45(dd,J= 8.2,1.5Hz,1H),7.40–7.33(m,2H),7.28(d,J=1.1Hz,1H),7.11(dd,J=5.1,3.5Hz,1H),7.04 (d,J=5.2Hz,1H),4.14(d,J=7.3Hz,2H),2.39-1.95(m,1H),1.43-1.19(m,24H),0.86(m, 6H).13C NMR(100MHz,CDCl3)δ(ppm)146.57,146.03,142.08,128.84,128.00,126.92,124.03, 122.43,121.25,119.19,117.76,115.95,110.68,107.37,49.67,38.53,31.99,31.98,31.82,29.97, 29.74,29.73,29.72,29.68,29.67,29.65,29.43,29.40,26.57,22.76,14.20.
在单口瓶(100mL)中,加入上述无色液体(2.40g,5mmol),加入四氢呋喃(30mL),0℃条件下,分批加入N-溴代丁二酰亚胺(1.86g,10.5mmol),搅拌反应2h。二氯甲烷萃取,无水硫酸钠干燥。浓缩,硅胶色谱柱分离得2.75g无色蜡状固体,产率86%。
1H NMR(400MHz,CDCl3)δ(ppm)7.61(d,J=8.2Hz,1H),7.41(d,J=1.2Hz,1H),7.32(dd,J =8.3,1.5Hz,1H),7.06(d,J=3.9Hz,1H),7.04(d,J=4.4Hz,2H),4.00(d,J=7.4Hz,2H),2.26 –1.88(m,1H),1.56-1.15(m,24H),0.88(m,6H).13C NMR(100MHz,CDCl3)δ(ppm)147.20, 144.29,140.75,130.85,128.22,122.60,121.17,119.15,117.71,115.89,114.09,113.96,110.49, 107.26,49.70,38.43,31.96,31.94,31.69,29.92,29.71,29.69,29.65,29.61,29.40,29.36,26.43, 22.73,14.16.
在单口瓶(50mL)中,将苯并噻二唑双硼酯(0.1552g,0.40mmol)和上述无色蜡状固体 (0.266g,0.40mmol)溶解在甲苯(25mL)溶液中,抽换气20分钟,氮气保护下加入四(三苯基膦)钯(14mg,0.01mmol),加热至90℃,反应24小时。自然冷至室温,将反应液缓慢滴加到500mL甲醇中沉降,室温搅拌12小时,抽滤得到黑色粉末,丙酮回流抽提24h,石油醚回流抽提24h,最终得到PTiDTBT黑色粉末0.24g,产率73%。结构式为:
图3-1为聚合物PTiDTBT薄膜的紫外可见吸收(Uv-vis)光谱;图3-2为聚合物PTiDTBT薄膜的循环伏安 (CV)曲线;图3-3为聚合物PTiDTBT的热重曲线;图3-4为聚合物PTiDTBT的J-V曲线。
图4为三种聚合物PTiDBT,PTiDTBT和PTiDDTBT应用到有机太阳能电池中的器件结构示意图;
下表为三种聚合物PTiDBT,PTiDTBT和PTiDDTBT分别与富勒烯混合应用于太阳能电池的光伏参数和效率。
Claims (3)
1.一种基于噻吩并芳基吲哚单元的共轭聚合物半导体材料,其结构特征如式I所示:
2.权利要求1所述噻吩并芳基吲哚单元的共轭聚合物半导体材料的制备方法,其特征是包括以下合成步骤:
(1)在150mL两口瓶中,将4.62g烷基化的噻吩并吲哚,1.42g的2-噻吩硼酸溶解在50mL甲苯中,注入2mol/L碳酸钾溶液30mL,抽换气三次,氮气保护下,加入150mg四(三苯基膦)钯,加热至90℃,反应24小时,自然冷至室温,二氯甲烷萃取,干燥,浓缩,柱层析分离得到无色液体3.75g,产率78%;
(2)在100mL单口瓶中,加入2.40g上述无色液体,加入30mL四氢呋喃,0℃条件下,分批加入1.86g N-溴代丁二酰亚胺,搅拌反应2h,二氯甲烷萃取,无水硫酸钠干燥,浓缩,硅胶色谱柱分离得2.75g无色蜡状固体,产率86%;
(3)在50mL单口瓶中,将0.1552g苯并噻二唑双硼酯和0.266g上述无色蜡状固体溶解在25mL甲苯溶液中,抽换气20分钟,氮气保护下加入14mg四(三苯基膦)钯,加热至90℃,反应24小时,自然冷至室温,将反应液缓慢滴加到500mL甲醇中沉降,室温搅拌12小时,抽滤得到黑色粉末,丙酮回流抽提24h,石油醚回流抽提24h,最终得到PTiDTBT黑色粉末0.24g,产率73%。
3.权利要求1所述的基于噻吩并芳基吲哚单元的共轭聚合物半导体材料的应用,其特征在于,应用到有机太阳能电池中,其制备的聚合物太阳电池器件结构为:ITO/PEDOT:PSS/聚合物:PC61BM/Ca/Al或ITO/PEDOT:PSS/聚合物:PC71BM/Ca/Al,器件均为常规溶液法制备。
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