WO2011094950A1 - 含芴共轭聚合物、其制备方法和太阳能电池器件 - Google Patents
含芴共轭聚合物、其制备方法和太阳能电池器件 Download PDFInfo
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- WO2011094950A1 WO2011094950A1 PCT/CN2010/070551 CN2010070551W WO2011094950A1 WO 2011094950 A1 WO2011094950 A1 WO 2011094950A1 CN 2010070551 W CN2010070551 W CN 2010070551W WO 2011094950 A1 WO2011094950 A1 WO 2011094950A1
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- WIPO (PCT)
- Prior art keywords
- conjugated polymer
- ruthenium
- containing conjugated
- represented
- polymer
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 15
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229930192474 thiophene Natural products 0.000 claims abstract description 19
- 229920000547 conjugated polymer Polymers 0.000 claims description 45
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 37
- 229910052707 ruthenium Inorganic materials 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 230000001568 sexual effect Effects 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 11
- 230000003595 spectral effect Effects 0.000 abstract description 8
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- 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 5
- -1 n-octyl Chemical group 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 3
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical group BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 2
- 0 C*(C)C(C)(C)c(cc1)cc(C(*)(*)c2c3)c1-c2ccc3[Al] Chemical compound C*(C)C(C)(C)c(cc1)cc(C(*)(*)c2c3)c1-c2ccc3[Al] 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
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- IXADHCVQNVXURI-UHFFFAOYSA-N 1,1-dichlorodecane Chemical compound CCCCCCCCCC(Cl)Cl IXADHCVQNVXURI-UHFFFAOYSA-N 0.000 description 1
- FTBODWYOSACVAV-UHFFFAOYSA-N 1,2-dioctylhydrazine Chemical compound CCCCCCCCNNCCCCCCCC FTBODWYOSACVAV-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RSNPEOGYTFIJBE-UHFFFAOYSA-N C(C)(C)OB1OC(C(O1)(CCCCCCCCCC)CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC Chemical compound C(C)(C)OB1OC(C(O1)(CCCCCCCCCC)CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC RSNPEOGYTFIJBE-UHFFFAOYSA-N 0.000 description 1
- QQTPMQLDWKPLFO-UHFFFAOYSA-N CCCCCCCCC1(C)c2cc(B3OC(C)(C)C(C)(C)O3)ccc2-c2c1cc(B1OC(C)(C)C(C)(C)O1)cc2 Chemical compound CCCCCCCCC1(C)c2cc(B3OC(C)(C)C(C)(C)O3)ccc2-c2c1cc(B1OC(C)(C)C(C)(C)O1)cc2 QQTPMQLDWKPLFO-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 239000012267 brine Substances 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
- 239000013590 bulk material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 150000004141 diterpene derivatives Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WABAEEDHTRIFPM-UHFFFAOYSA-N hydroxy-sulfanyl-sulfanylidene-$l^{4}-sulfane Chemical compound SS(S)=O WABAEEDHTRIFPM-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ZYSDERHSJJEJDS-UHFFFAOYSA-M tetrakis-decylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC ZYSDERHSJJEJDS-UHFFFAOYSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
-
- 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
-
- 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
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- 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
- H10K85/115—Polyfluorene; Derivatives thereof
-
- 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
- H10K85/151—Copolymers
-
- 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
- C08G2261/10—Definition of the polymer structure
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Definitions
- the present invention relates to the field of organic materials, and in particular to a cerium-containing conjugated polymer, a method for preparing the same, and a solar cell device.
- Organic solar cells are a new type of solar cells. Compared with inorganic semiconductor materials, which are limited in source, expensive, toxic, complicated in preparation process and high in cost, they have some advantages that inorganic solar cells cannot match, such as a wide range of materials. Structure diversity and controllability, low cost, safety and environmental protection, simple production process, light weight, large area flexible preparation, etc., can be widely used in various fields such as construction, lighting and power generation, with important development and application. prospect. However, to the eyes Until now, the photoelectric conversion efficiency of organic solar cells has been lower than that of inorganic solar cells. Therefore, the development of new organic materials is of great significance for improving the efficiency of organic solar cells and other semiconductor devices or optoelectronic devices. Summary of the invention
- a ruthenium-containing conjugated polymer having a broad response to light and stability and a preparation method of a ruthenium-containing conjugated polymer having a simple synthesis route and low cost are provided.
- Embodiments of the present invention also provide a solar cell device having the above ruthenium-containing conjugated polymer.
- a ruthenium-containing conjugated polymer comprising the polymer represented by the following structural formula (1):
- a method for preparing a ruthenium containing conjugated polymer comprising the steps of:
- the compound A, B, and C are subjected to a Suzuki reaction in the presence of a catalyst, a solvent, and an alkaline solution to obtain a polymer represented by the following structural formula (1):
- n in the structural formula (1) is a natural number between 1 and 1000.
- a solar cell device comprising a glass substrate, a transparent anode, an intermediate auxiliary layer, an active layer and a cathode which are sequentially laminated, the active layer comprising an electron donor material and an electron acceptor material, wherein the electron donor material is The above ruthenium-containing conjugated polymer.
- ruthenium-containing conjugated polymer ruthenium or a derivative thereof contained has excellent photostability and thermal stability, and thiophene is introduced into the polymer main chain. Subgroup, due to thiophene.
- the fraction is a five-membered ring structure, conforming to the Hugh's rule, with a moderate energy band gap, a wide spectral response, good thermal stability and environmental stability, which helps to broaden the optical response range of the polymer.
- the benzothiadiazole group is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
- the spectral response range of a wide polymer is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
- these introduced groups have a macrocyclic ring and/or a fused ring structure, which can increase the electron cloud density of the polymer skeleton, so that the absorption spectrum of the ruthenium-containing conjugated polymer can be adjusted over a wide range, which makes These materials can have a wider spectral response range, and when used as a photovoltaic material, they can better match the solar emission spectrum and make full use of solar energy.
- a relatively simple synthesis route is adopted, which is basically a one-step synthesis, thereby reducing the process flow and reducing the manufacturing cost.
- the above solar cell device can not only improve its photoelectric conversion efficiency but also reduce the quality of the solar cell device by using a ruthenium-containing conjugated polymer, thereby facilitating mass production.
- FIG. 1 is a schematic view showing the structural formula of a ruthenium-containing conjugated polymer according to an embodiment of the present invention
- FIG. 2 is a flow chart showing a preparation method of a ruthenium-containing conjugated polymer according to an embodiment of the present invention
- FIG. 3 is a schematic view showing the structure of a solar cell device containing a ruthenium-containing conjugated polymer according to an embodiment of the present invention
- a structural formula of a ruthenium-containing conjugated polymer of an embodiment of the present invention i.e., a polymer represented by the following structural formula (1):
- ⁇ ⁇ is selected from at least one of the groups represented by the structural formula:
- R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are the same or different alkyl groups represented by H or dC ⁇ , and R u , R 12 , R 13 , R 14 and R 15 are the same Or a different alkyl group represented by C C20 , m is a natural number between 1 and 20.
- R 5 , R 6 , R 7 , R 8 , R 9 , R 1 () are the same or different alkyl groups represented by H or dC 6
- R u , R 12 , R 13 , R 14 , R 15 is preferably the same or different alkyl group represented by C Qs
- m is preferably a natural number between 2 and 10.
- the group represented by the formula (c), R 7 and R 8 are preferably H, that is, the ⁇ ⁇ formula is represented by -C 6 H 2 S 2 -.
- the preparation method of the above ruthenium-containing conjugated polymer comprises the following steps:
- R 2 , R 3 , and R 4 are the same or different alkyl groups represented by H or dC ⁇ , and the molar fractions of the reaction amounts of the compounds B and C are X and y, respectively.
- y l , x ⁇ 0, y ⁇ 0, the group containing a thiophene;
- n in the structural formula (1) A natural number between 1 and 1000.
- the compounds A, B, and C can be directly obtained from the market or prepared by an existing synthesis method.
- x and y are both 50%.
- 1 and may be the same linear alkyl group, preferably C 8 H 17 , that is, an isomer of n-octyl or octyl group, more preferably an n-octyl group.
- R 3 and R 4 are each preferably hydrogen.
- n is preferably from 30 to 800, more preferably from 50 to 500.
- ⁇ ⁇ is selected from at least one of the groups represented by the above structural formulae (a) - (g), preferably, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same Or a different alkyl group represented by 11 or dC 6 , R u , R 12 , R 13 , R 14 , R 15 are preferably the same or different alkyl group represented by -C 6 , and m is preferably between 2 and 10 Natural number.
- A is a group represented by the formula (c), and R 7 and R 8 are preferably H, that is, the formula A is represented by -C 6 H 2 S 2 -.
- the catalyst may be an organic palladium catalyst in an amount of from 0.1 to 20% by mole based on the amount of the compound A.
- the organic palladium catalyst may be, for example but not limited to, Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 .
- the alkaline solution may be an inorganic alkali solution or an organic alkali solution, and the inorganic alkali solution may be an aqueous solution of an alkali metal hydroxide or an alkali metal carbonate, and may be, for example, but not limited to, a sodium hydroxide solution, a potassium hydroxide solution, or a sodium carbonate.
- the solution, the potassium carbonate solution or the like is preferably a sodium carbonate solution
- the organic alkali solution may be an aqueous solution of an alkyl ammonium hydroxide, such as, but not limited to, tetradecyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl hydroxide.
- the above alkaline solution may be used in an amount of from 1 to 10 times the molar amount of the compound A.
- the solvent is a weakly polar or polar aprotic organic solvent or a mixed solvent thereof, and may be, for example but not limited to, chloroform, dichlorodecane, dimercaptosulfoxide (DMSO), tetrahydrofuran (THF), toluene, diterpene Benzene or a similar compound thereof is preferably anthracene.
- the solvent is used in an amount sufficient to dissolve the respective reactants and sufficiently react.
- step S02 The reaction carried out in step S02 can be expressed by the following reaction equation (i):
- step S02 is carried out under the protection of nitrogen. After adding each raw material and reagent, it is first replaced with nitrogen for 0.5-3 hours, then heated to reflux, reacted for 1-5 days, and then reacted with bromobenzene under reflux. After 24 hours, the reaction was continued for a further 6-24 hours by the addition of phenylboronic acid to give the product.
- reaction product may be further subjected to the following purification step: the solvent is removed under reduced pressure, extracted with chloroform/water, washed, dried, and the chloroform is removed under reduced pressure, precipitated with decyl alcohol, suction filtered, and the precipitate is filtered off with chloroform.
- the washing agent was separated by alumina column chromatography, rotary-scrayed, sedimented with methanol, and suction filtered.
- the obtained solid was subjected to Soxhlet extraction with acetone for three days, sedimented with decyl alcohol, suction filtered, and the precipitate was filtered off under vacuum to obtain a solid. ⁇ Conjugated polymer.
- the solvent is distilled off under reduced pressure, extracted with chloroform/water, washed with saturated brine, and dried over anhydrous sodium sulfate. Then, the dried product was evaporated to dryness under reduced pressure to a large amount of chloroform, which was precipitated with methanol and filtered. The precipitate was filtered off and separated by alumina column chromatography with chloroform as the eluent. The mixture was subjected to rotary distillation, and the mixture was filtered with decyl alcohol. The obtained solid was subjected to Soxhlet extraction with acetone for three days, and then decyl alcohol was precipitated, suction filtered, vacuum. The precipitate was filtered off to give a solid product in a yield of about 60-85%.
- the synthesis routes of the three monomers of the compounds A, B and C are relatively simple and mature, and are basically one-step synthesis, thereby reducing the process flow and reducing the manufacturing cost.
- the Suzuki reaction is a very mature polymerization reaction with high yield, mild conditions, easy control, and easy introduction of an alkyl group to increase the solubility and molecular weight of the product to achieve a spin-coatable polymer.
- a solar cell device using the ruthenium-containing conjugated polymer in the above embodiment comprises a glass base layer 11 , a transparent anode 12 , an intermediate auxiliary layer 13 , an active layer 14 , and a cathode 15 which are sequentially laminated.
- the intermediate auxiliary layer 13 is made of polyethylene dioxythiophene: polystyrene-cross-acid composite (referred to as PEDOT: PSS), the active layer 14 comprises an electron donor material and an electron acceptor material, the electron donor material adopts the above-mentioned ruthenium-containing conjugated polymer, and the electron acceptor material may be [6,6]phenyl-C 61 -butyrate Ester (abbreviated as PCBM).
- the transparent anode 12 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
- the cathode 15 may be an aluminum electrode or a bimetal electrode such as Ca/Al or Ba/Al.
- the glass base layer 11 can be used as a bottom layer.
- ITO glass is selected, and after ultrasonic cleaning, treated with oxygen-Plasma, the intermediate auxiliary layer 13 is coated on the ITO glass, and the ytterbium-containing conjugated polymer and electrons are subjected to
- the bulk material is applied to the intermediate auxiliary layer 13 by blending to form the active layer 14, and then the cathode 15 is deposited on the active layer 14 by a vacuum evaporation technique to obtain the above solar cell device.
- the transparent anode 12, the intermediate auxiliary layer 13, the active layer 14, the bimetal layer Ca, and the A1 layer have thicknesses of 160 nm, 40 nm, 150 nm, 20 nm, and 70 nm, respectively.
- the ytterbium-containing conjugated polymer in the active layer 14 absorbs light energy and generates excitons, which then migrate to the electron donor/ At the interface of the acceptor material, electrons are transferred to an electron acceptor material, such as PCBM, to separate the charge, thereby forming free carriers, ie free electrons and holes. These free electrons are transported along the electron acceptor material to the metal cathode and collected by the cathode. Free holes are transported along the electron donor material to the ITO anode and collected by the anode, thereby forming photocurrent and photovoltage for photoelectric conversion, external connection. When the load is 16, it can be powered.
- the polymer Since the polymer has thiophene.
- these introduced groups have a macrocyclic ring and/or a fused ring structure, which can increase the electron cloud density of the polymer skeleton, so that the absorption spectrum of the ruthenium-containing conjugated polymer can be adjusted within a wide range. So that these materials can have a wider spectral response range, used as In the case of optoelectronic materials, it can better match the solar emission language, make full use of solar energy, and increase the power generation capacity of solar cell devices.
- the organic material can also reduce the quality of the solar cell device, and can be fabricated by techniques such as spin coating, which is convenient for mass production.
- the ytterbium-containing conjugated polymer can be applied not only to solar cell devices but also to electroluminescent devices, organic field effect transistors, organic optical memory devices, organic nonlinear materials or organic laser devices.
- the preparation of the ruthenium-containing conjugated polymer and its properties and the like are exemplified below by way of a preferred embodiment.
- the eighth, B, and C in the following embodiments are directly prepared, and of course, they may be directly purchased from the market in other embodiments, and are not limited thereto.
- Compound A is prepared, wherein Compound A is 2,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolanyl)-9, 9- Take Dixinji as an example, its structural formula is as follows:
- the specific preparation process was as follows: 1.44 mL (4.20 mmol) of n-butyllithium solution was added to a solution containing 1.10 g (2.00 mmol) of 2,7-dibromo-9, 9- under a nitrogen atmosphere at -78 °C. The two-necked flask of dioctylhydrazine and 20 mL of tetrahydrofuran was stirred for 10 minutes, then warmed to 0 ° C and stirring was continued for 20 minutes.
- test results were: MALDI-TOF-MS (m/z): 642.5 (M + ).
- a compound B is prepared in which the compound B is 2, 5-dibromothiophene [3, 2-b] thiophene. Divided into examples, its structural formula is:
- the specific preparation process was as follows: 2.15 g (12.10 mmol) of NBS and 10 mL of DMF were added to an ice bath and protected from light to contain 0.84 g (6.00 mmol) of thiophene [3, 2-b] thiophene and 20 mL of DMF. Stir in the two-necked flask for 4 hours. After the reaction was completed, the reaction solution was poured into ice water and quenched, extracted with dichloromethane, washed once with deionized water, dried over anhydrous magnesium sulfate, and the filtrate was collected and then evaporated, and then separated by a neutral alumina column. The product was obtained as a pale yellow solid with a yield of 81%.
- compound C is prepared, wherein compound C is exemplified by 4,7-dibromo-2,1-3-benzothiadiazole, and its structural formula is:
- the specific preparation process is as follows: 13.6 g (100.00 mmol) of benzothiadiazole is weighed, dissolved in 20 mL of 45% hydrobromic acid, stirred under heating to reflux, and 48 g (300.00 mmol) of bromine is added dropwise. After the addition was completed, 10 mL of hydrobromic acid was added and reflux was continued for 3 hours. The reaction mixture was filtered while hot, cooled, filtered, washed with water, dried, chloroform, and crystals.
- the third step the formation of the ruthenium-containing conjugated polymer, the structural formula of the ruthenium-containing conjugated polymer of the present embodiment is:
- the specific formation process is as follows: Under nitrogen protection, it contains 0.321 g (0.50 mmol) of 2,7-bis(4 4,5,5-tetradecyl-1,3,2-dioxaborolanyl)- 9, 9-dioctylhydrazine, 0.0745 g (0.25 mmol) 2, 5-dibromothiophene [3, 2-b] thiophene, 0.0735 g (0.25 mmol) 4, 7-dibromo-2, 1, 3-benzothiadiazole, 0.00416 g (0.0036 mmol) Pd ( To the reactor of PPh 3 ) 4 was added 10 mL of a Na 2 C0 3 ( 2 M ) aqueous solution and toluene (20 mL).
- Alumina column chromatography was carried out using chloroform as a eluent, and the mixture was subjected to rotary distillation, decyl alcohol, and suction filtration, and the obtained solid was subjected to Soxhlet extraction with acetone for three days. The decyl alcohol was precipitated, suction filtered, and dried in vacuo to give a solid material.
- ruthenium-containing conjugated polymer ruthenium or a derivative thereof contained has excellent photostability and thermal stability, and thiophene is introduced into the polymer main chain. Subgroup, due to thiophene.
- the fraction is a five-membered ring structure, conforming to the Hugh's rule, with a moderate energy band gap, a wide spectral response, good thermal stability and environmental stability, which helps to broaden the optical response range of the polymer.
- the benzothiadiazole group is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
- the spectral response range of a wide polymer is also introduced into the main chain of the polymer, and has a five-membered ring structure and a conjugated diene structure, which not only produces a similar action to the thiophene, but also functions as a conjugated diene.
- these introduced groups have a macrocyclic ring and/or a fused ring structure, which can increase the electron cloud density of the polymer skeleton, so that the absorption spectrum of the ruthenium-containing conjugated polymer can be adjusted over a wide range, which makes These materials can have a wider spectral response range, and when used as a photovoltaic material, they can better match the solar emission spectrum and make full use of solar energy.
- a relatively simple synthesis route is adopted, which is basically a one-step synthesis, thereby reducing the process flow and reducing the manufacturing cost.
- the above solar cell device adopts a ruthenium-containing conjugated polymer, which not only can improve its photoelectric conversion efficiency, but also can reduce the quality of the solar cell device, and is convenient for mass production.
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US20060174937A1 (en) * | 2005-02-09 | 2006-08-10 | Zhang-Lin Zhou | High performance organic materials for solar cells |
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RU2789133C2 (ru) * | 2021-02-26 | 2023-01-30 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) | Сопряженный полимер на основе замещенного флуорена, бензотиадиазола и тиофена и его применение в перовскитных солнечных батареях |
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EP2532696A1 (en) | 2012-12-12 |
US20120312374A1 (en) | 2012-12-13 |
CN102686636B (zh) | 2014-05-07 |
JP5599903B2 (ja) | 2014-10-01 |
EP2532696A4 (en) | 2016-12-28 |
CN102686636A (zh) | 2012-09-19 |
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