CN114605619A - Active layer material of organic photovoltaic device containing star-structure flexible chain segment and preparation and application thereof - Google Patents
Active layer material of organic photovoltaic device containing star-structure flexible chain segment and preparation and application thereof Download PDFInfo
- Publication number
- CN114605619A CN114605619A CN202210053939.9A CN202210053939A CN114605619A CN 114605619 A CN114605619 A CN 114605619A CN 202210053939 A CN202210053939 A CN 202210053939A CN 114605619 A CN114605619 A CN 114605619A
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- group
- star
- active layer
- layer material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 238000013086 organic photovoltaic Methods 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 107
- 125000004432 carbon atom Chemical group C* 0.000 claims description 90
- 239000000178 monomer Substances 0.000 claims description 41
- 238000001914 filtration Methods 0.000 claims description 22
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 17
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000000304 alkynyl group Chemical group 0.000 claims description 15
- 238000004440 column chromatography Methods 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- 125000005108 alkenylthio group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000005114 heteroarylalkoxy group Chemical group 0.000 claims description 4
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 4
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000013087 polymer photovoltaic Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 69
- 238000005160 1H NMR spectroscopy Methods 0.000 description 53
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 52
- -1 1,3, 5-tris (3- (benzyloxy) prop-1-en-1-yl) benzene Chemical compound 0.000 description 51
- 239000000243 solution Substances 0.000 description 46
- 150000001875 compounds Chemical class 0.000 description 37
- 239000000047 product Substances 0.000 description 33
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 238000007867 post-reaction treatment Methods 0.000 description 28
- 238000004458 analytical method Methods 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000012043 crude product Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 229960001701 chloroform Drugs 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003480 eluent Substances 0.000 description 12
- 238000010898 silica gel chromatography Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 239000007983 Tris buffer Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000944 Soxhlet extraction Methods 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 6
- 229920000547 conjugated polymer Polymers 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- BUOKUWQCVSZNCF-UHFFFAOYSA-N selenadiazole Chemical compound C1=C[se]N=N1 BUOKUWQCVSZNCF-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- GHTCEOPJYODOQF-UHFFFAOYSA-N 2-(4-bromobutyl)thiophene Chemical compound BrCCCCC1=CC=CS1 GHTCEOPJYODOQF-UHFFFAOYSA-N 0.000 description 4
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 4
- 238000005406 washing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- YZCRWWDMRZKXNS-UHFFFAOYSA-N pentan-1-imine Chemical compound CCCCC=N YZCRWWDMRZKXNS-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006619 Stille reaction Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- SGDKTJPVCKQTHK-UHFFFAOYSA-N 5-bromo-2-fluoro-3-nitropyridine Chemical compound [O-][N+](=O)C1=CC(Br)=CN=C1F SGDKTJPVCKQTHK-UHFFFAOYSA-N 0.000 description 1
- FPFTWHJPEMPAGE-UHFFFAOYSA-N 6-hydroxy caproaldehyde Chemical compound OCCCCCC=O FPFTWHJPEMPAGE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- HCJWWBBBSCXJMS-UHFFFAOYSA-J copper;dilithium;tetrachloride Chemical compound [Li+].[Li+].[Cl-].[Cl-].[Cl-].[Cl-].[Cu+2] HCJWWBBBSCXJMS-UHFFFAOYSA-J 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- HUGHWHMUUQNACD-UHFFFAOYSA-N prop-2-enoxymethylbenzene Chemical compound C=CCOCC1=CC=CC=C1 HUGHWHMUUQNACD-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical class [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- JUKPJGZUFHCZQI-UHFFFAOYSA-N undecanoyl chloride Chemical compound CCCCCCCCCCC(Cl)=O JUKPJGZUFHCZQI-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
-
- 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
-
- 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
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
-
- 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
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
-
- 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
Abstract
The invention belongs to the technical field of organic photoelectric materials, and discloses an active layer material of an organic photovoltaic device containing a star-shaped structure flexible chain segment, and preparation and application thereof. The structure of the active layer material is shown as the following formula I and is composed of naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Five-membered ring) unit derivative, star-shaped structure flexible chain segment unit and electron donor unit. The preparation method is simple, easy to purify and suitable for large-scale production; the series polymer photovoltaic device active layer material containing the star-structure flexible chain segment can adjust and control the polymer structure and performance by selecting different star-structure flexible units, and meets different scene requirements. The polymer active layer material containing the star-shaped structure flexible chain segment is beneficial to enhancing the deformation performance of the material, thereby obtaining high-performance stretchable materialAn organic photovoltaic device. The polymer active layer material containing the star-shaped structure flexible chain segment is applied to the field of organic photovoltaic devices.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an active layer material of an organic photovoltaic device containing a star-shaped structure flexible chain segment, and preparation and application thereof.
Background
In recent years, as the global demand for energy has been increasing, the problem of energy shortage has been highlighted, and photovoltaic devices have come into the field of vision of people. Compared with an inorganic solar cell, the organic solar cell has the characteristics of flexibility and stretchability, and has great potential and advantages in manufacturing next-generation wearable and stretchable electronic products. This has attracted a great deal of attention, making it the most promising class of materials in various opto-electronic devices during the last decade of development. In practical application, the organic photovoltaic device is exposed to thermal oxygen and tensile stress environments, so that the aging of the device is accelerated, and the photovoltaic performance of the device is reduced.
Active layer cracking caused by strain is one of the most important factors for efficiency degradation. As a key component of flexible and stretchable devices, a polymer active layer with excellent stretchability and electro-optical properties has great advantages in improving strain tolerance and deformability of the devices, but its further development still presents great challenges. Due to the fact that the currently popular conjugated polymer has rigid pi-pi conjugated parts and strong crystallinity of polymer chains, compared with traditional polymers such as rubber and plastics, the conjugated polymer film has limited and volatile tensile property, and strain stability of flexible and stretchable photoelectric devices is limited. Therefore, it is very important to realize stronger strain stability to prepare the ternary random copolymer containing the flexible unit by introducing the flexible chain segment unit into the conjugated polymer system.
Disclosure of Invention
In order to endow the organic photovoltaic device with intrinsic tensile property, a novel active layer material is developed, and the primary object of the invention is to provide an organic photovoltaic device active layer material containing a star-shaped structure flexible chain segment. The active layer material is composed of naphthalene [1,2-c:5,6-c' ] double ([1,2,5] five-membered ring) unit derivatives, star-structure flexible chain segment units and electron donor units, wherein the star-structure flexible chain segment is introduced to enhance the deformation performance of the material, so that the high-performance stretchable organic photovoltaic device is obtained.
The invention further aims to provide a preparation method of the active layer material of the organic photovoltaic device containing the star-structure flexible chain segment.
The invention also aims to provide application of the active layer material of the organic photovoltaic device containing the star-structure flexible chain segment in preparation of the organic photovoltaic device.
The purpose of the invention is realized by the following technical scheme:
an active layer material of an organic photovoltaic device containing a star-shaped structure flexible chain segment has a structure shown in a formula I:
in formula I, m represents the number of star-shaped arms, and m includes but is not limited to 2-10; the polymerization degree n ranges from 5 to 300;
in formula I, Y is relatively independently selected from O, S, Se, or N-R1One of (1);
in formulae I and Y, R1And R2Each occurrence is independently a hydrogen atom, a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a straight chain alkenyl group having 2 to 20 carbon atoms, a branched or cyclic alkenyl group having 3 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkenylthio group having 2 to 20 carbon atoms, a straight chain alkynyl group having 2 to 20 carbon atoms, a branched or cyclic alkynyl group having 3 to 20 carbon atoms, a straight chain alkylcarbonyl group having 2 to 20 carbon atoms, a branched or cyclic alkylcarbonyl group having 3 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an aralkyl group having 4 to 20 carbon atoms, a heteroarylalkyl group having 4 to 20 carbon atoms, an aryloxy group having 4 to 20 carbon atoms, a heteroaryloxy group having 4 to 20 carbon atoms, an arylalkoxy group having 4 to 20 carbon atoms, or a heteroarylalkoxy group having 4 to 20 carbon atomsWherein R is1And R2May be the same or different;
z is, identically or differently on each occurrence, CH or N;
the D unit is an electron donor unit and is one of the following structural formulas:
wherein R is4And R5Relatively independently is one of the following substituted or unsubstituted groups: an alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an aralkyl group having 4 to 20 carbon atoms, a heteroarylalkyl group having 4 to 20 carbon atoms, an aryloxy group having 4 to 20 carbon atoms, a heteroaryloxy group having 4 to 20 carbon atoms, an arylalkoxy group having 4 to 20 carbon atoms, and a heteroarylalkoxy group having 4 to 20 carbon atoms. Wherein substituted means a group formed by substituting one or more hydrogen atoms with at least one of a branched alkyl group, an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, and the like;
in the formula I, the structure of the flexible unit is Ar1(Cn-Ar)mWherein- (Cn-Ar) -is a part of the chain of star structures, m is the same as m in formula I, and each represents the number of chains of star units, and the number of star units m includes but is not limited to 2-10.
In the structure of the flexible unit, CnThe flexible chain is a linear alkyl group having 2 to 20 carbon atoms, a branched alkyl group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, an alkylthio group having 2 to 20 carbon atoms, a linear alkenyl group having 3 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, a cyclic alkenyl group having 3 to 20 carbon atoms, an alkenyloxy group having 3 to 20 carbon atoms, an alkenylthio group having 3 to 20 carbon atoms, a linear alkynyl group having 3 to 20 carbon atoms, a branched alkynyl group having 3 to 20 carbon atoms, a cyclic alkynyl group having 3 to 20 carbon atoms, a linear alkylcarbonyl group having 3 to 20 carbon atoms, a branched alkynyl group having 3 to 20 carbon atomsA branched alkylcarbonyl group, a cyclic alkylcarbonyl group having 3 to 20 carbon atoms, and an imino group having 3 to 20 carbon atoms and having one carbon-nitrogen double bond.
In the structure of the flexible unit, Ar is one or more coupling structures in the following structure:
wherein R is3And R6Relatively independently, the substituent is one of a hydrogen atom, a substituted or unsubstituted alkyl group with the carbon number of 1-20, and a substituted or unsubstituted alkoxy group with the carbon number of 1-20, wherein the substitution refers to a group formed by substituting one or more hydrogen atoms by at least one of an oxygen atom, an alkenyl group, an alkynyl group, an aryl group and the like;
in the structure of the flexible unit, Ar1Is one or more coupling structures in the following structures:
the preparation method of the active layer material of the organic photovoltaic device containing the star-shaped flexible chain segment comprises the following steps:
in an inert gas or nitrogen atmosphere and an organic solvent, mixing a monomer containing a star-shaped structure flexible unit, a monomer containing an electron donor unit and a monomer containing a naphthalene [1,2-c:5,6-c' ] bis ([1,2,5] five-membered ring) unit derivative, then carrying out polymerization reaction under the catalysis of a catalyst, and purifying to obtain the polymer active layer material containing the flexible chain segment.
Wherein, the monomer containing naphthalene [1,2-c:5,6-c' ] bis ([1,2,5] five-membered ring) unit derivative is preferably one of the following structural formulas:
wherein R is1、R2As defined above.
The monomer containing the star-structured flexible unit is preferably a monomer in which each chain of the star-structured flexible unit is terminated by trimethyltin, such as
Preferably Ar1(Cn-Ar-(SnMe3))m(ii) a The electron donor unit-containing monomer is preferably a monomer double-terminated with trimethyltin, e.g.
The organic solvent can be one of chlorobenzene, dichlorobenzene, toluene and xylene; the catalyst comprises a palladium catalyst which can be one of palladium tetratriphenylphosphine, palladium acetate and tris (dibenzylideneacetone) dipalladium; the sum of the amount of the substance containing the star-shaped structure flexible unit monomer and the substance containing the electron-donating unit monomer reaction functional group is equal to the amount of the substance containing the naphthalene [1,2-c:5,6-c' ] bis ([1,2,5] five-membered ring) unit monomer reaction functional group.
The reaction temperature of the polymerization reaction is 130-140 ℃, the reaction time is 40-48 h, and the stirring speed is 600-1000 rpm.
The mixing mode is physical mixing; the purification mode comprises more than one of precipitation, filtration, column chromatography and extraction.
The polymer photovoltaic device active layer material containing the star-shaped structure flexible chain segment is prepared by Stille coupling reaction, and the reaction equation is as follows:
the synthesis method has the following characteristics: under the catalysis of a palladium catalyst, naphthalene [1,2-c:5,6-c' ] double ([1,2,5] five-membered ring) unit, star structure flexible chain segment unit, electron donor unit and derivatives thereof carry out ternary random copolymerization reaction through Stille coupling reaction, thereby introducing the star structure flexible unit into a polymer system.
The active layer material of the organic photovoltaic device containing the star-shaped flexible chain segment is applied to the organic photovoltaic device.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polymerized monomer material containing the star-structure flexible chain segment has the advantages of simple preparation method, easy purification and large-scale production;
(2) the polymer structure performance can be regulated and controlled by selecting different star-shaped structure flexible units, so that different scene requirements are met;
(3) the polymer active layer material containing the star-structure flexible chain segment is beneficial to enhancing the deformation performance of the material, so that the high-efficiency stretchable organic photovoltaic device is obtained.
(4) The invention adopts a method of introducing a flexible chain segment unit into a conjugated polymer system to prepare the ternary random copolymer containing the flexible unit, thereby realizing stronger strain stability.
Drawings
FIG. 1 is a UV-VIS absorption curve of a polymer active layer material P1 containing a star-structured soft segment;
FIG. 2 is a cyclic voltammetry characteristic curve of a polymer active layer material P1 containing star-structured soft segments;
FIG. 3 is a voltage-current density curve of polymer active layer materials P2 and P3 containing star-structured flexible segments and a polymer solar cell with N2200 as an active layer respectively;
FIG. 4 is a wavelength-external quantum efficiency curve of polymer active layer materials P2 and P3 containing star-structured soft segments and a polymer solar cell with N2200 as an active layer respectively;
FIG. 5 is the voltage-dark current density curves of the polymer active layer materials P4, P5 and P6 containing the star-structured soft segment and the polymer photodetector with N2200 as the active layer.
FIG. 6 is the stress-strain curves of the polymer active layer materials P1, P2, P3 and P4 containing the star-structured soft segment and N2200 respectively as the active layer materials and the polymers P1-1 and N2200 containing no star-structured soft segment as the active layer materials.
Detailed Description
The present invention will be described in further detail below with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The reagents used in the examples are commercially available without specific reference.
Preparation of Material monomer (M1)
(1) Synthesis of 1,3, 5-tris (3- (benzyloxy) prop-1-en-1-yl) benzene (M1-1): in a 500mL two-necked round bottom flask, 1,3, 5-tribromobenzene (31.18g, 100mmol) was weighed, acetonitrile 150mL and triethylamine 32mL were added, gas was purged 3 times, and palladium acetate (1.12g, 5mmol) and triphenylphosphine (2.24g, 10mmol) were weighed. Under nitrogen protection, the mixture was quickly added to the reaction solution, stirred for 30 minutes, added dropwise with allyl benzyl ether (51.84g, 350mmol) and reacted at 90 ℃ for 20 hours while raising the temperature. And (3) post-reaction treatment: the reaction was quenched by addition of 20mL of hydrochloric acid solution, followed by extraction with dichloromethane, washing with deionized water, repeated extraction 3 times, drying over anhydrous magnesium sulfate, filtration, and removal of the solvent using a reduced pressure rotary evaporator. Further purification was carried out by using a silica gel column chromatography and petroleum ether/ethyl acetate (8: 1) as eluent, and column chromatography gave a brown oily liquid (M1-1).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.34(m,3H),7.31(d,6H),7.28(m,6H),6.65(d,3H),6.55(s,3H),6.25(t,3H),4.88(s,6H),4.04(s, 6H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of 1,3, 5-benzenetriol (M1-2): nitrogen was introduced into a 250mL two-neck round-bottom flask, and lithium aluminum hydride (3.80g, 100mmol) was rapidly weighed and placed in a 0 ℃ cooling circulation apparatusAnd (4) inside. 30mL of anhydrous tetrahydrofuran was added dropwise, and the reaction was stirred for 30 minutes. 1,3, 5-tris (3- (benzyloxy) prop-1-en-1-yl) benzene (M1-1) (1.63g, 30mmol) was weighed, dissolved in 10mL of anhydrous tetrahydrofuran, and was added dropwise to a reaction flask 3 times at 20-minute intervals, followed by 1 hour of reaction after all the addition, and then the mixture was allowed to stand at room temperature for 2 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of 20mL of ice water, followed by extraction with dichloromethane, washing with deionized water, repeated extraction 3 times, drying over anhydrous magnesium sulfate, filtration, and removal of the solvent using a reduced pressure rotary evaporator. The crude product was dissolved in a small amount of tetrahydrofuran, and further purified by recrystallization from n-hexane using a silica gel column chromatography with dichloromethane/methanol (30: 1) as eluent, to give a colorless oily liquid (M1-2) by column chromatography.1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 6.82(s,3H),4.42(t,3H),3.47-3.38(m,6H),2.61-2.49(m,6H),1.73(m, 6H). The chemical reaction equation of the preparation process is as follows.
(3) Synthesis of 1,3, 5-tris (3-iodopropyl) benzene (M1-3): triphenylphosphine (23.61g, 90mmol) and iodine (22.83g, 90mmol) were weighed into a 500mL two-necked round-bottomed flask, 200mL of dichloromethane was added, the mixture was stirred at 25 ℃ under a nitrogen atmosphere, and after reaction for 30 minutes, imidazole (7.48g, 110mmol) was added to the mixture, and the reaction was continued for 30 minutes after the addition. Then, 1,3, 5-hydrocinnamatriol (M1-2) (6.30g, 25mmol) was added to the reaction flask, and the temperature was raised to 60 ℃ for reaction for 10 hours. And (3) post-reaction treatment: the reaction was quenched by addition of 90mL of saturated sodium metabisulfite solution, followed by extraction with dichloromethane, washing with deionized water, repeated extraction for 3 times, drying over anhydrous magnesium sulfate, filtration and removal of the solvent using a reduced pressure rotary evaporator. Further purification was carried out by using a silica gel column chromatography and petroleum ether/ethyl acetate (8: 1) as eluent, and column chromatography gave a yellow oily liquid (M1-3).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 6.89(s,3H),3.43(t,6H),2.63(t,6H),2.20(m, 6H). The chemical reaction equation of the preparation process is as follows.
(4) Synthesis of 1,3, 5-tris (3- (thien-2-yl) propyl) benzene (M1-4): to a 100mL round bottom flask was added 20mL of anhydrous tetrahydrofuran followed by magnesium turnings (2.2g, 90mmol) and stirred. 2-bromothiophene (70mmol, 11.4g) was dissolved in 20mL of anhydrous tetrahydrofuran, the temperature was maintained at 60 ℃, and the solution was added dropwise to the tetrahydrofuran mixture of magnesium turnings under a nitrogen atmosphere, and after reacting for 2 hours, the Grignard reagent solution was separated from the remaining Mg using a syringe for use. Compound M1-3(1.16g, 20mmol) and the above reaction mixture, 20mL of anhydrous tetrahydrofuran were charged into a 100mL two-necked round-bottomed flask, and placed in a-10 ℃ cooling circulation apparatus under nitrogen protection, and after cooling for 30 minutes, 0.1M dilithium tetrachlorocuprate (7.5mL, 0.75mmol) was added dropwise to the flask and reacted at that temperature for 5 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of 20mL of saturated ammonium chloride solution, then poured into a beaker containing 200mL of deionized water, extracted with ether, dried over anhydrous magnesium sulfate, filtered and the solvent removed using a reduced pressure rotary evaporator. Further purification was carried out by separating with silica gel column chromatography, eluting with pure petroleum ether, and purifying with column chromatography to obtain colorless oily liquid (M1-4).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1h NMR (400MHz in DMSO), delta (ppm) 7.39(d,3H),7.09-6.85(m,9H),2.83-2.57(m,12H),1.86(m, 6H). The chemical reaction equation of the preparation process is as follows.
(5)1,3, 5-tris (3- (5- (trimethylstannyl) thiophen-2-yl) propyl) benzene (M1)) The synthesis of (2): in a 250mL two-neck round-bottom flask, weighing compound M1-4(2.50g, 5.55mmol), adding 40mL anhydrous tetrahydrofuran, placing the mixture into a cooling circulation device at-78 ℃ under the protection of nitrogen, cooling for 30 minutes, dropwise adding a 2.5M n-butyllithium solution (10.68mL, 26.70mmol) into the reaction flask, reacting at the temperature for 2 hours, dropwise adding a 1.0M trimethyltin chloride solution (35.10mL, 35.10mmol) into the reaction system, returning to the room temperature after the addition is finished, and reacting for 3 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator to give a crude product, which was repeatedly recrystallized three times with ethanol, and the obtained product was dried in a vacuum oven to give a white flaky solid (M1).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.09-7.06(m,6H),6.85(d,3H),2.87-2.74(m,6H),2.63-2.58(m,6H),1.86-1.82(m,6H),0.27(s, 27H). The chemical reaction equation of the preparation process is as follows.
Preparation of Material monomer (M2)
(1) Synthesis of 2- (4-bromobutyl) thiophene (M2-1): thiophene (8.42g, 100mmol) is weighed in a 100mL two-neck round-bottom flask, 40mL anhydrous tetrahydrofuran is added, the mixture is placed in a cooling circulation device at-78 ℃ under the protection of nitrogen, after cooling for 30 minutes, a 2.5M n-butyl lithium solution (36.00mL, 90mmol) is dropwise added into a reaction bottle, reaction is carried out at the temperature for 2 hours, 1, 4-dibromobutane (21.60g, 100mmol) is added into the reaction system, and after the addition is finished, the reaction system is returned to the room temperature and reacts for 6 hours. And (3) post-reaction treatment: adding a small amount of deionized water to quench the reaction, pouring the reaction mixture into a beaker filled with 200mL of deionized water, extracting the reaction mixture with petroleum ether, drying the extraction mixture with anhydrous magnesium sulfate, filtering the extraction mixture, and removing the solvent by using a reduced-pressure rotary evaporator to obtain an initial productThe compound (I) is prepared. Further purification was carried out by using a silica gel column for separation and pure petroleum ether as an eluent, and column chromatography was carried out to obtain a colorless oily liquid (M2-1).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.31(d,1H),6.98(m,1H),6.85(d,1H),3.52(t,2H),2.85(t,2H),1.81(m,2H),1.50(m, 2H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of tris (4- (4- (thiophen-2-yl) butoxy) phenyl) methane (M2-2): in a 250mL two-necked round-bottomed flask, 4' -methylenetrisphenol (5.00g, 10.27mmol) and 2- (4-bromobutyl) thiophene (M2-1) (7.83g, 35.94mmol) and potassium carbonate (5.53g, 40.00mmol) were weighed, 100mL of dimethylformamide was added, and after purging three times, the mixture was heated to 100 ℃ under a nitrogen atmosphere and reacted for 6 hours. And (3) post-reaction treatment: the reaction was quenched by adding a small amount of deionized water, poured into a beaker containing 200mL of a saturated aqueous solution of sodium chloride, then extracted with dichloromethane, washed with deionized water, repeatedly extracted 3 times, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator. Further purification was carried out using a silica gel column chromatography with petroleum ether/dichloromethane (4:1) as eluent, to give a white solid (M2-2) by column chromatography.1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.38(d,3H),7.13(s,6H),7.01-6.85(m,12H),5.41(s,1H),4.11(t,6H),2.81(t,6H),1.73-1.50(m, 12H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of tris (4- (4- (5- (trimethylstannyl) thiophen-2-yl) butoxy) phenyl) methane (M2): sintering in 100mL round bottom with two openingsIn a bottle, weighing compound M2-2(2.50g, 3.54mmol), adding 40mL of anhydrous tetrahydrofuran, placing the mixture into a cooling circulation device at-78 ℃ under the protection of nitrogen, cooling for 30 minutes, dropwise adding a 2.5M n-butyllithium solution (5.10mL, 12.75mmol) into the reaction bottle, reacting at the temperature for 2 hours, dropwise adding a 1M trimethyltin chloride solution (15.20mL, 15.20mmol) into the reaction system, recovering the room temperature after the addition is finished, and reacting overnight. And (3) post-reaction treatment: the reaction was quenched by the addition of a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator to give a crude product, which was repeatedly recrystallized three times with ethanol, and the obtained product was dried in a vacuum oven to give a white solid (M2).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows.1H NMR(400MHz,CDCl3),δ(ppm):7.11(s,6H),7.06-6.85(m,12H),5.41(s,1H),4.15(t,6H),2.82(t,6H),1.73-1.50(m,12H)，0.27(s,27H)。
Preparation of Material monomer (M3)
(1) Synthesis of N, N', N "- (benzene-1, 3, 5-triacyl) tris (6-bromohexane-1-imine) (M3-1): 6-hydroxyhexanal (16.50g, 142.18mmol) is weighed in a 250mL two-neck round-bottom flask, 60mL toluene is added and stirred, 1,3, 5-triaminobenzene (5.04g, 40.62mmol) is added in three times under the protection of nitrogen, stirring is carried out for half an hour at 30 ℃ until complete dissolution, the temperature is raised to 100 ℃, and the reaction is stirred and reacted for 6 hours. And (3) post-reaction treatment: the reaction solution was cooled to room temperature, and 30mL of deionized water was added to quench the reaction, which was then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator. Further purification is carried out by separation using a silica gel column, petroleum ether/dichloromethane: (4:1) as eluent, and obtaining yellow oily liquid (M3-1) by column chromatography.1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 8.52(t,3H),6.65(s,3H),4.73(s,3H),3.65(t,6H),2.21(m,6H),1.58-1.53(m,12H),1.31(m, 6H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of N, N', N "- (benzene-1, 3, 5-triacyl) tris (5- (thiophene-2-oxy) pentane-1-imine) (M3-2): compound M3-1(7.51g, 20mmol), 2-bromothiophene (10.52g, 65mmol) and tetrabutylammonium bromide (0.64g, 2mmol) were weighed into a 250mL round-bottomed flask, 60mL of toluene was added and the reaction was stirred for 6 hours with purging 3 times, increasing the temperature to 100 ℃ under a nitrogen atmosphere. The temperature of the reaction solution was lowered to 60 ℃, and an aqueous NaOH solution (40% by mass, 20mL) was added dropwise to the reaction system, followed by stirring at 80 ℃ for 6 hours. And (3) post-reaction treatment: the reaction solution was cooled to room temperature, and 30mL of deionized water was added to quench the reaction, which was then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator. Further purification was carried out by using a silica gel column chromatography and petroleum ether/dichloromethane (4:1) as eluent, and column chromatography gave a yellow oily liquid (M3-2).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 8.52(t,3H),6.73-6.69(m,6H),6.56(m,3H),6.21(d,3H),4.25(t,6H),2.24(m,6H),1.86(m,6H),1.54(m, 6H). The chemical reaction equation of the preparation process is as follows.
(3) N, N ', N' - (benzene-1, 3, 5-triacyl) tris (5- ((5- (trimethylstannyl) thiophen-2-yl) oxy)) Synthesis of pentane-1-imine) (M3): compound M3-2(2.48g, 4.00mmol) was weighed in a 100mL two-necked round-bottomed flask, 30mL of anhydrous tetrahydrofuran was added, the mixture was placed in a cooling circulation device at-78 ℃ under a nitrogen atmosphere, after cooling for 30 minutes, a 2.5M n-butyllithium solution (5.40mL, 13.50mmol) was added dropwise to the reaction flask, and the mixture was reacted at this temperature for 2 hours, a 1.0M trimethyltin chloride solution (15.60mL, 15.60mmol) was further added dropwise to the reaction system, and after completion of the addition, the reaction was returned to room temperature and reacted for 3 hours. And (3) post-reaction treatment: the reaction was quenched by addition of a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator to give a primary product, which was repeatedly recrystallized three times with ethanol, and the resulting product was dried in a vacuum oven to give a yellow solid (M3).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 8.50(t,3H),6.73-6.69(m,6H),6.24(d,3H),4.25(t,6H),2.24(m,6H),1.86(m,6H),1.54(m,6H),0.27(s, 27H). The chemical reaction equation of the preparation process is as follows.
Preparation of Material monomer (M4)
(1) Synthesis of 1, 5-heneicosylnaphthalene (M4-1): naphthalene (6.4g, 50mmol) and undecanoyl chloride (20.5g, 100mmol) were weighed into a 250mL two-necked round-bottomed flask, dissolved in 70mL dichloromethane, purged 2 times, and aluminum trichloride (14.6g, 110mmol) was added to the reaction solution 3 times in 30 minutes, and the temperature was raised to 65 ℃ for 6 hours. And (3) post-reaction treatment: and slowly adding 50mL of ice water into the reaction solution to quench the reaction, extracting with dichloromethane, washing with deionized water, repeatedly extracting for 3 times, drying with anhydrous magnesium sulfate, filtering, and removing the solvent by using a reduced-pressure rotary evaporator for later use. The colorless oily substance was dissolved in concentrated hydrochloric acid, and zinc powder (6.5g, 100mmol) was added thereto, followed by stirring at 65 ℃ for 4 hours.And (3) post-reaction treatment: the reaction was quenched by the addition of 100mL of saturated sodium bicarbonate solution and the unreacted zinc dust was removed by filtration. The filtrate was repeatedly extracted with dichloromethane three times, then dried over anhydrous magnesium sulfate, filtered, and the solvent was removed using a reduced pressure rotary evaporator to obtain a crude product. Further purification was carried out by using a silica gel column chromatography and petroleum ether/dichloromethane (5:1) as eluent, and column chromatography gave a colorless oily liquid (M4-1).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.95(d,2H),7.61(t,2H),6.96(d,2H),3.21(t,4H),1.63(m,4H),1.28-1.24(m,32H),0.86(m, 6H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of 2, 6-dibromo-4, 8-heneicosyl naphthalene (M4-2): compound M4-1(6.50g, 14.89mmol) and N-bromosuccinimide (5.83g, 32.74mmol) were weighed into a 250mL two-necked round bottom flask, 60mL of chloroform was added, the temperature was raised to 65 ℃ under nitrogen, and the reaction was stirred for 8 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and the solvent removed using a reduced pressure rotary evaporator to give the crude product. Further purification was carried out using a silica gel column chromatography with petroleum ether/dichloromethane (6:1) as eluent, and column chromatography gave a white solid powder (M4-2).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 8.15(d,2H), 6.85(d,2H),3.21(t,4H),1.63(m,4H),1.28-1.24(m,32H),0.86(m, 6H). The chemical reaction equation of the preparation process is as follows.
(3) Synthesis of 2, 6-dibromo-1, 5-dinitro-4, 8-heneicosyl naphthalene (M4-3): compound M4-2(3.76g, 10.00mmol) was weighed into a 250mL two-necked round-bottomed flask, 50mL of glacial acetic acid was added, dissolved with stirring under nitrogen, concentrated nitric acid (10.22mL, 23.00mmol) was added dropwise to raise the temperature to 65 ℃ and the reaction was stirred for 8 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of 50mL of saturated sodium bicarbonate solution, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and the solvent removed using a reduced pressure rotary evaporator to give the crude product. Further purification was carried out using a silica gel column chromatography with petroleum ether/dichloromethane (6:1) as eluent, and column chromatography gave a brown solid powder (M4-3).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.67(s,2H),3.11(t,4H),1.63(m,4H),1.28-1.24(m,32H),0.87(m, 6H). The chemical reaction equation of the preparation process is as follows.
(4) Synthesis of N, N' - (1, 5-dinitro-4, 8-heneicosyl naphthalene-2, 6-diacyl) bis (1, 1-diphenylmethanimine) (M4-4): sodium tert-butoxide (1.92g, 20.00mmol) was weighed in a 100mL two-necked round-bottomed flask, dissolved in 30mL toluene, purged 3 times, and tripropanedione dipalladium tris (0.17g, 0.18mmol) and 2 '-bis (diphenylphosphino) -1,1' -binaphthyl (0.23g, 0.36mmol) were rapidly added to the reaction mixture. After stirring at room temperature for 10 minutes, the reaction solution turned into a dark red solution. Then 2, 6-dibromo-1, 5-dinitro-4, 8-heneicosyl naphthalene (M4-3) (2.50g, 3.67mmol) was added to the reaction mixture in 3 portions, the reaction temperature was raised to 85 ℃ and the reaction solution was stirred for further 30 minutes. To the reaction solution was added dropwise diphenylmethanimine (1.85mL, 11.05mmol) to produce a brown solid, and the reaction was continued for 2 hours. And (3) post-reaction treatment: the heating was stopped, and after the reaction mixture was cooled to room temperature, the mixture was filtered to obtain a black solid as a crude product (M4-4).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) Delta. (ppm) 7.95(d,4H), 7.64-7.58(m,10H),7.41-7.38(m,8H), 3.13(t,4H), 1.61(m,4H), 1.28-1.24(m,32H), 0.85(m, 6H). The chemical reaction equation of the preparation process is as follows.
(5) Synthesis of 4, 8-heneicosyl-1, 2,5, 6-tetrahydronaphthalene-1, 2,5, 6-tetramine (M4-5): in a 100mL two-necked round-bottomed flask, N' - (1, 5-dinitro-4, 8-heneicosylnaphthalene-2, 6-diacyl) bis (1, 1-diphenylmethanimine) (M4-4) (2.10g, 2.37mmol) and stannous dichloride (1.35g, 7.11mmol) were weighed and dissolved in 35mL hydrochloric acid. The temperature was raised to 70 ℃ and the reaction was carried out for 5 hours. Then, the heating was stopped, and after cooling to room temperature, the mixture was transferred to a cold trap at 0 ℃ and stirred for 30 minutes, and reddish brown solid matters appeared. And (3) post-reaction treatment: filtration gave a reddish brown solid, which was washed with anhydrous ethanol until the filtrate became colorless, and the obtained solid was a crude product (M4-5).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 6.85(s,2H), 4.83(d,8H), 3.13(t,4H), 1.59(m,4H), 1.28-1.26(m,32H), 0.85(m, 6H). The chemical reaction equation of the preparation process is as follows.
(6)4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Synthesis of thiadiazole) (M4-6): in a 250mL two-neck round-bottom flask, 4, 8-heneicosyl-1, 2,5, 6-tetrahydronaphthalene-1, 2,5, 6-tetramine (M4-5) (5.00g, 10.00mmol) was weighed and dissolved in 100mL of anhydrous pyridine, after purging three times, thionyl chloride (3.27mL, 45.00mmol) was added dropwise under nitrogen atmosphere, and the mixture was heated to 80 ℃ for reaction for 3 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of 20mL of saturated aqueous sodium bicarbonate solution and poured into a container containing 200mL of saturated chlorideIn a beaker of an aqueous sodium solution, the mixture was extracted with dichloromethane, washed with deionized water, repeatedly extracted 3 times, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator. Recrystallization from a hot dioxane solution gave an orange solid (M4-6).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 8.22(d,2H),3.07(t,4H),1.64(m,4H),1.29-1.15(m,32H),0.88(m, 6H). The chemical reaction equation of the preparation process is as follows.
(7)5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Synthesis of thiadiazole) (M4): compound M4-6(2.50g, 4.53mmol) and N-bromosuccinimide (1.73g, 9.96mmol) were weighed into a 100mL two-necked round bottom flask, 30mL of chloroform was added, the temperature was raised to 65 ℃ under nitrogen, glacial acetic acid (2mL) was added dropwise, and the reaction was stirred for 5 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and the solvent removed using a reduced pressure rotary evaporator to give the crude product. Further purification was carried out using a silica gel column chromatography with petroleum ether/dichloromethane (6:1) as eluent, which gave an orange solid (M4) by column chromatography.1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) Delta (ppm) 3.07(t,4H),1.64(m,4H),1.29-1.15(m,32H),0.88(m, 6H). The chemical reaction equation of the preparation process is as follows.
Fifthly, preparation of material monomer (M5)
(1)4, 9-heneicosylnaphthalene [1,2-c:5,6-c']bis ([1,2, 5)]Synthesis of selenadiazole) (M5-1): 4, 8-heneicosyl-1, 2,5, 6-tetrahydronaphthalene-1, 2,5, 6-tetramine (5.00g, 10.00mmol) is weighed in a 250mL two-neck round-bottom flask and dissolved in 100mL anhydrous pyridine, after the gas is pumped and exchanged for three times, the reaction solution is cooled to 0 ℃ under the protection of nitrogen atmosphere, selenium oxychloride (7.46g, 45.00mmol) is added dropwise, and the reaction is heated to 80 ℃ for 3 hours. And (3) post-reaction treatment: the reaction was quenched by adding 20mL of saturated aqueous sodium bicarbonate solution, poured into a beaker containing 200mL of saturated aqueous sodium chloride solution, extracted with dichloromethane, washed with deionized water, extracted 3 times repeatedly, dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed using a reduced pressure rotary evaporator. Recrystallization from hot dioxane solution gave a brown solid (M5-1).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) Delta (ppm) 5.98(d,2H),2.41(t,4H),1.64(m,4H),1.29-1.15(m,32H),0.88(m, 6H). The chemical reaction equation of the preparation process is as follows.
(2)5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Synthesis of selenadiazole) (M5): compound M5-1(3.00g, 4.62mmol) and N-bromosuccinimide (1.81g, 10.18mmol) were weighed into a 100mL two-necked round-bottomed flask, 40mL of chloroform was added, the temperature was raised to 65 ℃ under nitrogen, glacial acetic acid (2.10mL) was added dropwise, and the reaction was stirred for 5 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and the solvent removed using a reduced pressure rotary evaporator to give the crude product. Further purification was carried out using a silica gel column chromatography with petroleum ether/dichloromethane (5:1) as eluent, to give a brown solid (M5) by column chromatography.1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 2.43(t,4H),1.62(m,4H),1.29-1.15(m,32H),0.88(m, 6H). The chemical reaction equation of the preparation process is as follows.
Example 1 Synthesis of Polymer active layer Material P1 containing Flexible segment of Star-shaped Structure
Weighing M4 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Thiadiazole) (70.82mg, 0.10mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thiophen-2-) -benzodithiophene (77.02mg, 0.085mmol) and M1 monomer 1,3, 5-tris (3- (5- (trimethyltin) thiophen-2-yl) propyl) benzene (9.42mg, 0.01mmol) and Pd (PPh)3)4(6.9mg) in a 15mL pressure tube, 1.20mL of ultra-dry chlorobenzene was added under a nitrogen atmosphere. The reaction system was heated to 140 ℃ and maintained at this temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction liquid was dropped into anhydrous methanol, and a crude product was obtained by filtration. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using anhydrous methanol, acetone, n-hexane and trichloromethane, finally concentrating the solution of the trichloromethane component, then settling the solution into the anhydrous methanol again, filtering and drying to finally obtain a purple black solid (P1).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.74(s,3H),7.36(s,3H),7.31(s,9H),7.24(s,3H),6.78(d,9H),3.32(s,6H),3.07(s,6H),2.97(s,9H),2.77(s,3H),2.63(s,3H),2.44(s,9H),2.27(s,18H),2.01(s,3H),1.90(s,3H),1.61(s,12H),1.55(s,6H),1.38(s,6H), 1.35-1.13 (m,123H),0.91(d, 48H). High temperature GPC: mn ═ 37.6 kDa; mw 56.5 kDa. The chemical reaction equation of the preparation process is as follows:
corresponding to P1, not containing star-structured soft segmentsSynthesis of Polymer active layer Material P1-1: weighing M4 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Thiadiazole) (70.82mg, 0.10mmol) and 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thiophenyl-2-) -benzodithiophene (90.61mg, 0.10mmol) and Pd (PPh)3)4(6.9mg) in a 15mL pressure tube, 1.20mL of ultra-dry chlorobenzene was added under a nitrogen atmosphere. The reaction system was heated to 140 ℃ and maintained at this temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction liquid was dropped into anhydrous methanol, and a crude product was obtained by filtration. Treating the crude product by using a Soxhlet extraction device, sequentially extracting by using anhydrous methanol, acetone, n-hexane and trichloromethane, finally concentrating the solution of the trichloromethane component, then settling the solution into the anhydrous methanol again, filtering and drying to finally obtain a purple brown solid (P1-1).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.76(s,2H),7.42(s,2H),7.31(d,6H),6.80(s,4H),3.60(s,3H),3.07(s,4H),2.77(s,3H),1.77(s,2H),1.58(d,11H),1.38(s,4H), 1.32-1.23 (m,81H),0.93(s,12H),0.89(s, 19H). High temperature GPC: mn ═ 31.5 kDa; mw 49.3 kDa.
The ultraviolet-visible light absorption curve of the polymer active layer material P1 containing the star-structured soft segment is shown in FIG. 1, and the main absorption peak of the polymer is at about 593nm, and the absorption edge is at about 684 nm. Compared with the system polymer without the flexible chain segment, the absorption peak generates a certain degree of red shift, and the intramolecular charge transfer effect is enhanced.
The cyclic voltammetry characteristic curve of the polymer active layer material P1 containing the star-structured flexible segment is shown in FIG. 2, the initial oxidation potential of the polymer is 1.09V, and the initial reduction potential is-0.77V. By the formula EHOMO＝-e[Eox-E(Fc/Fc+)+4.80](eV)；ELUMO＝-e[Ered-E(Fc/Fc+)+4.80](eV) the LUMO and HOMO energy levels of the polymer were calculated to be-3.63 eV/-5.48 eV.
Example 2 Synthesis of Polymer active layer Material P2 containing Flexible segment of Star-shaped Structure
Weighing M4 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6c']Bis ([1,2, 5)]Thiadiazole) (70.82mg, 0.10mmol), 5 '-bis (trimethylstannyl) -2,2' -bithiophene (41.98mg, 0.085mmol) and M2 monomers tris (4- (4- (5- (trimethylstannyl) thiophen-2-yl) butoxy) phenyl) methane (11.99mg, 0.01mmol) and Pd (PPh)3)4(6.90mg) in a 15mL pressure tube, 1.2mL of ultra-dry chlorobenzene was added under a nitrogen atmosphere. The reaction system was heated to 140 ℃ and maintained at this temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction liquid was dropped into anhydrous methanol, and a crude product was obtained by filtration. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using anhydrous methanol, acetone, n-hexane and trichloromethane, finally concentrating the solution of the trichloromethane component, then settling the solution into the anhydrous methanol again, filtering and drying to finally obtain a blue-black solid (P2).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm):7.50(s,3H),7.50(s,3H),7.39(dd,12H),7.11(s,12H),6.94(s,6H),6.77(dd,24H),6.72(d,15H),6.72(d,45H),5.41(s,1H),4.11(s,3H),3.07(s,6H),2.81(s,3H),2.44(s,9H),1.80(s,3H),1.61(s,6H),1.50(s,3H),1.26(s,93H),0.89(s, 15H). High temperature GPC: mn 43.0 kDa; mw 68.7 kDa.
The chemical reaction equation of the preparation process is as follows:
example 3 Synthesis of Polymer active layer Material P3 containing Flexible segment of Star-shaped Structure
Weighing M5 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6c']Bis ([1,2, 5)]Selenadiazole) (80.40mg, 0.10mmol), 5 '-bis (trimethylstannyl) -2,2' -bithiophene (41.98mg, 0.085mmol) and M2 monomer tris (4- (4- (5- (trimethylstannyl) thiophen-2-yl) butoxy) phenyl) methane (11.99mg, 0.01mmol) and Pd (PPh)3)4(6.90mg) into a 15mL pressure tube, 1.2mL of extra dry chlorine was added under a nitrogen atmosphereBenzene. The reaction system was heated to 140 ℃ and maintained at this temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction liquid was dropped into anhydrous methanol, and a crude product was obtained by filtration. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using anhydrous methanol, acetone, normal hexane and trichloromethane, finally concentrating the solution of the trichloromethane component, then settling the solution into the anhydrous methanol again, filtering and drying to finally obtain a purple black solid (P3).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm):7.50(s,3H),7.50(s,3H),7.39(dd,12H),7.11(s,12H),6.94(s,6H),6.77(dd,24H),6.72(d,15H),6.72(d,45H),5.41(s,1H),4.11(s,3H),3.07(s,6H),2.81(s,3H),2.44(s,9H),1.80(s,3H),1.61(s,6H),1.50(s,3H),1.26(s,93H),0.89(s, 15H). High temperature GPC: mn 38.7 kDa; mw 62.8 kDa.
The chemical reaction equation of the preparation process is as follows:
example 4 Synthesis of Polymer active layer Material P4 containing Flexible segments of Star configuration
Weighing M4 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Thiadiazole) (70.82mg, 0.10mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thiophen-2-) -benzodithiophene (63.43mg, 0.07mmol) and M3 monomer N, N ', N' - (benzene-1, 3, 5-triacyl) tris (5- ((5- (trimethyltin) thiophen-2-yl) oxy) pentane-1-imine) (22.26mg, 0.02mmol) and Pd (PPh)3)4(6.9mg) in a 15mL pressure tube, 1.20mL of ultra-dry chlorobenzene was added under a nitrogen atmosphere. The reaction system was heated to 140 ℃ and maintained at this temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction liquid was dropped into anhydrous methanol, and a crude product was obtained by filtration. Treating the crude product with Soxhlet extraction device, sequentially extracting with anhydrous methanol, acetone, n-hexane and chloroform, and dissolving chloroform componentThe solution was concentrated and then again settled into anhydrous methanol, filtered and dried to give a black solid (P4).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm) 7.78(s,6H),7.65(s,3H),7.56(d,9H),7.33(d,6H),6.87(s,6H),6.80(s,12H),6.70(s,12H),6.25(s,6H),4.11(s,6H),3.38(s,9H),3.07(s,12H),2.94(s,9H),2.44(s,18H),2.25(d,21H),2.15(d,3H),1.82(t,42H),1.75-1.68(m,3H),1.64-1.48(m,54H),1.52-1.48(m,6H),1.38(s,12H),1.31-1.23(m,210H),1.01(s,9H),0.93(s, 36H). High temperature GPC: mn ═ 35.5 kDa; mw 51.7 kDa.
The chemical reaction equation of the preparation process is as follows:
example 5 Synthesis of Polymer active layer Material P5 containing Flexible segments of Star configuration
Weighing M5 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Selenadiazole) (80.40mg, 0.10mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thiophen-2-) -benzodithiophene (77.02mg, 0.085mmol) and M1 monomer 1,3, 5-tris (3- (5- (trimethyltin) thiophen-2-yl) propyl) benzene (9.42mg, 0.01mmol) and Pd (PPh)3)4(6.9mg) in a 15mL pressure tube, 1.20mL of ultra-dry chlorobenzene was added under a nitrogen atmosphere. The reaction system was heated to 140 ℃ and maintained at this temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction liquid was dropped into anhydrous methanol, and a crude product was obtained by filtration. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using anhydrous methanol, acetone, normal hexane and trichloromethane, finally concentrating a solution containing the trichloromethane, then settling the solution into the anhydrous methanol again, filtering, and drying to finally obtain a black solid (P5).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3),δ(ppm):7.78(s,3H),7.31(d,15H),6.75(d,15H) 3.70(s,6H),3.06(s,6H),2.74(d,9H),2.62(s,3H),2.43(s,9H),2.26(s,18H),1.97(d,9H),1.39(s,6H),1.30(s,6H),1.28-1.23(m,114H),0.91(d, 42H). High temperature GPC: mn ═ 37.2 kDa; mw 48.8 kDa.
The chemical reaction equation of the preparation process is as follows:
example 6 Synthesis of Polymer active layer Material P6 containing Flexible segment of Star configuration
Weighing M5 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c']Bis ([1,2, 5)]Selenadiazole) (81.40mg, 0.10mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thiophen-2-) -benzodithiophene (77.02mg, 0.085mmol) and the M3 monomer N, N ', N' - (benzene-1, 3, 5-triacyl) tris (5- ((5- (trimethyltin) thiophen-2-yl) oxy) pentane-1-imine) (11.13mg, 0.01mmol) and Pd (PPh)3)4(6.9mg) in a 15mL pressure tube, 1.20mL of ultra-dry chlorobenzene was added under a nitrogen atmosphere. The reaction system was heated to 140 ℃ and maintained at this temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction liquid was dropped into anhydrous methanol, and a crude product was obtained by filtration. And (2) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using anhydrous methanol, acetone, n-hexane and trichloromethane, finally concentrating the solution of the trichloromethane component, then settling the solution into the anhydrous methanol again, filtering and drying to finally obtain a black solid (P6).1HNMR、13The results of CNMR, MS and element analysis show that the obtained compound is a target product,1H NMR(400MHz,CDCl3) δ (ppm):7.78(s,9H),7.55(s,3H),7.49(d,18H),7.41(dd,36H),6.87(s,6H),6.80(s,12H),6.70(s,18H),6.23(s,6H),4.11(s,6H),3.38(s,9H),3.07(s,12H),2.94(s,9H),2.44(s,18H),2.21(d,45H),1.79(d,15H),1.63-1.53(m,42H),1.53-1.52(m,6H),1.38(s,12H),1.31-1.23(m,204H),0.93(s,36H),0.89(s, 57H). High temperature GPC: mn is 35.8 kDa; mw 51.6 kDa.
The chemical reaction equation of the preparation process is as follows:
example 7 preparation of organic photovoltaic device
The organic photovoltaic device was prepared by using the polymer active layer material P1 containing the star-structured soft segment in the above-mentioned example 1, the polymer active layer material P2 containing the star-structured soft segment in the above-mentioned example 2, the polymer active layer material P3 containing the star-structured soft segment in the above-mentioned example 3, the polymer active layer material P4 containing the star-structured soft segment in the above-mentioned example 4, the polymer active layer material P5 containing the star-structured soft segment in the above-mentioned example 5, and the polymer active layer material P6 containing the star-structured soft segment in the above-mentioned example 6 as donor materials and N2200 as acceptor materials, respectively, and the device structure was ITO/PEDOT: PSS/active layer/PFN-Br (methanol 0.5mg mL)-1) and/Ag. The structure of N2200 is formula III:
the steps for preparing the organic photovoltaic device are as follows:
(1) cleaning a conductive glass ITO substrate: sequentially placing the ITO glass substrate in acetone, isopropanol, cleaning liquid, deionized water and isopropanol for ultrasonic cleaning, removing possible residual stains (such as photoresist and the like) on the surface of the ITO glass substrate and improving interface contact, and after cleaning, placing the ITO glass substrate in a vacuum oven for drying;
(2) placing the ITO in an oxygen plasma etching instrument, and bombarding the ITO for twenty minutes by using oxygen plasma to thoroughly remove possible residual organic matters on the surface of the ITO glass substrate;
(3) PSS, a hole transport interface, PEDOT, about 30nm thick was spin coated on ITO, then thermally annealed at 100 ℃ for 20 minutes;
(4) in a glove box under nitrogen atmosphere, the polymer active layer materials containing the soft segment, P1, P2, P3, P4, P5 and P6, were mixed with N2200 at a ratio of 2: 1, dissolving the mixture in methyltetrahydrofuran, preparing a solution with the concentration of 5mg/mL, spin-coating an active layer with the thickness of 120nm on a PEDOT (PSS) layer, and then heating and annealing the active layer on a heating table at 120 ℃ for 20 minutes to remove residual solvent and improve the appearance of the active layer film;
(5) in a glove box under nitrogen atmosphere, an electron transport material was spin-coated onto the active layer material in a thickness of 20nm using 0.5mg/mL of poly [ (9, 9-bis (3' - (N, N-dimethylamino) propyl) fluorenyl-2, 7-diyl) -ALT- [ (9, 9-di-N-octylfluorenyl 2, 7-diyl) -bromo (PFN-Br);
(6) and finally, placing the prepared device in an evaporation chamber, and evaporating an electrode with the thickness of 100nmAg in a vacuum environment.
(7) And testing the photoelectric conversion efficiency, the current-voltage characteristic curve and the dark current-voltage characteristic curve of the polymer solar cell device on an AM 1.5G simulated solar lamp.
The prepared organic solar cell devices were subjected to photoelectric property tests, and the test results are shown in table 1.
TABLE 1 device parameters of organic solar cells
As can be seen from the data in table 1, the organic solar cell device using P1 as the donor material of the active layer and N2200 as the acceptor material of the active layer has excellent photoelectric properties. The short-circuit current density of the device is 18.53 milliampere/square centimeter, the open-circuit voltage is 0.87 volt, the filling factor is 68.52%, and the final device efficiency is 10.06%; the organic solar cell device with P2 as an active layer donor material and N2200 as an active layer acceptor material has excellent photoelectric properties. The short-circuit current density of the device is 18.04 milliamperes per square centimeter, the open-circuit voltage is 0.93 volts, the filling factor is 65.43 percent, and the final device efficiency is 10.92 percent; the organic solar cell device with P3 as an active layer donor material and N2200 as an active layer acceptor material has excellent photoelectric properties. The short circuit current density of the device was 19.56 milliamps/cm, the open circuit voltage was 0.91 volts, the fill factor was 71.40%, and the final device efficiency was 12.64%. Wherein, fig. 3 and fig. 4 are respectively a voltage-current density curve and a wavelength-external quantum efficiency curve of the organic solar cell with P2 and P3 as donors and N2200 as an acceptor, and the corresponding currents are respectively 17.23 milliamperes/square centimeter and 18.55 milliamperes/square centimeter. Fig. 5 is a dark state voltage-current density curve obtained by testing an organic photovoltaic device prepared by respectively using polymer active layer materials P4, P5 and P6 containing star-shaped structure flexible chain segments as donors and N2200 as acceptors, and the device shows obvious diode characteristics, namely unidirectional current conduction, and forward dark current is obviously higher than reverse dark current, which plays an important role in improving the detectivity of a detector and improving the detectivity of the detector to weak light.
FIG. 6 is the stress-strain curves of the polymer active layer materials P1, P2, P3 and P4 containing the star-structured soft segment and N2200 respectively as the active layer and the polymers P1-1 and N2200 containing no star-structured soft segment as the active layer materials. As can be seen from FIG. 6, the polymer P1-1 containing no star-structured soft segment: the elongation at break of the N2200 active layer is only 1.6%, and the material P1 of the polymer active layer containing the star-shaped flexible chain segment has the following structure: n2200, P2: n2200, P3: n2200, P4: the elongation at break of the N2200 active layer is respectively 10.7%, 13.0%, 21.9% and 23.1%, which are all higher than that of the polymer active layer without the star-shaped flexible segment. Thus, the introduction of the soft segment into the conjugated polymer backbone can improve the stretchability of the device without decreasing the device efficiency.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention and are intended to be equivalent to the above embodiments are included in the scope of the present invention.
Claims (10)
1. Active layer materials of organic photovoltaic devices containing star-structure flexible chain segments are characterized in that the structures are shown as the following formula I:
in formula I, m represents the number of star-shaped arms, and m includes but is not limited to 2-10; the polymerization degree n ranges from 5 to 300;
in formula I, Y is relatively independently selected from O, S, Se, or N-R1One of (1);
in formulae I and Y, R1And R2Each occurrence is independently a hydrogen atom, a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a straight chain alkenyl group having 2 to 20 carbon atoms, a branched or cyclic alkenyl group having 3 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkenylthio group having 2 to 20 carbon atoms, a straight chain alkynyl group having 2 to 20 carbon atoms, a branched or cyclic alkynyl group having 3 to 20 carbon atoms, a straight chain alkylcarbonyl group having 2 to 20 carbon atoms, a branched or cyclic alkylcarbonyl group having 3 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an aralkyl group having 4 to 20 carbon atoms, a heteroarylalkyl group having 4 to 20 carbon atoms, an aryloxy group having 4 to 20 carbon atoms, a heteroaryloxy group having 4 to 20 carbon atoms, an arylalkoxy group having 4 to 20 carbon atoms, or a heteroarylalkoxy group having 4 to 20 carbon atoms;
in formula I, Z is, identically or differently at each occurrence, CH or N;
in formula I, the D unit is an electron donor unit and is one of the following structural formulas:
wherein R is4And R5Relatively independently is one of the following substituted or unsubstituted groups: alkyl having 1-20 carbon atoms, aryl having 4-20 carbon atoms, heteroaryl having 4-20 carbon atoms, EAn aralkyl group of 20 carbon atoms, a heteroarylalkyl group of 4 to 20 carbon atoms, an aryloxy group of 4 to 20 carbon atoms, a heteroaryloxy group of 4 to 20 carbon atoms, an arylalkoxy group of 4 to 20 carbon atoms, and a heteroarylalkoxy group of 4 to 20 carbon atoms; wherein substituted refers to a group formed by substituting one or more hydrogen atoms by at least one of branched alkyl, oxygen atom, alkenyl, alkynyl and aryl;
in the formula I, the structure of the flexible unit is Ar1(Cn-Ar)mWherein- (Cn-Ar) -is a part of a chain of star structures, m is the same as the definition of m in the formula I and represents the number of the chain of star units, and the number m of the star units comprises but is not limited to 2-10;
in the structure of the flexible unit, CnThe flexible chain is a linear alkyl group having 2 to 20 carbon atoms, a branched alkyl group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, an alkylthio group having 2 to 20 carbon atoms, a linear alkenyl group having 3 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, a cyclic alkenyl group having 3 to 20 carbon atoms, an alkenyloxy group having 3 to 20 carbon atoms, an alkenylthio group having 3 to 20 carbon atoms, a linear alkynyl group having 3 to 20 carbon atoms, a branched alkynyl group having 3 to 20 carbon atoms, a cyclic alkynyl group having 3 to 20 carbon atoms, one of a linear alkylcarbonyl group having 3 to 20 carbon atoms, a branched alkylcarbonyl group having 3 to 20 carbon atoms, a cyclic alkylcarbonyl group having 3 to 20 carbon atoms, and an imino group having 3 to 20 carbon atoms and having one carbon-nitrogen double bond;
in the structure of the flexible unit, Ar is one or more coupling structures in the following structures:
wherein R is3And R6Relatively independently is one of hydrogen atom, substituted or unsubstituted alkyl with 1-20 carbon atoms, and substituted or unsubstituted alkoxy with 1-20 carbon atoms, whereinSubstituted refers to a group formed by substituting one or more hydrogen atoms by at least one of oxygen atoms, alkenyl groups, alkynyl groups and aryl groups;
structure of flexible unit Ar1Is one or more coupling structures in the following structures:
2. the active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 1, wherein the structure is one of the following structures:
wherein n ranges from 5 to 300.
3. A method for preparing an active layer material of an organic photovoltaic device containing a star-structured flexible segment according to any one of claims 1 to 2, characterized by comprising the following steps:
in an inert gas or nitrogen atmosphere and an organic solvent, mixing a monomer containing a star-shaped structure flexible unit, a monomer containing an electron donor unit and a monomer containing a naphthalene [1,2-c:5,6-c' ] bis ([1,2,5] five-membered ring) unit derivative, then carrying out polymerization reaction under the catalysis of a catalyst, and purifying to obtain the polymer active layer material containing the flexible chain segment.
4. The preparation method of the active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 3, wherein the preparation method comprises the following steps:
the monomer containing naphthalene [1,2-c:5,6-c' ] bis ([1,2,5] five-membered ring) unit is one of the following structural formulas:
wherein R1 and R2 are as defined in claim 1 or 2.
5. The preparation method of the active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 3, wherein the preparation method comprises the following steps:
the monomer containing the star-shaped structure flexible unit is a monomer of which each star-shaped unit chain is terminated by trimethyltin; the monomer containing the electron donor unit is a monomer double-terminated by trimethyl tin.
6. The preparation method of the active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 3, wherein the preparation method comprises the following steps:
the organic solvent is one of chlorobenzene, dichlorobenzene, toluene and xylene;
the catalyst comprises a palladium catalyst.
7. The preparation method of the active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 3, wherein the preparation method comprises the following steps:
the sum of the amount of the substance containing the reactive functional group of the monomer containing the star-structure flexible unit and the monomer containing the electron donor unit is equal to the amount of the substance containing the reactive functional group of the monomer containing the naphthalene [1,2-c:5,6-c' ] bis ([1,2,5] five-membered ring) unit.
8. The preparation method of the active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 3, wherein the preparation method comprises the following steps:
the reaction temperature of the polymerization reaction is 130-140 ℃, and the reaction time is 40-48 h.
9. The preparation method of the active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 3, wherein the preparation method comprises the following steps:
the mixing mode is physical mixing;
the purification mode comprises more than one of precipitation, filtration, column chromatography and extraction.
10. The active layer material of the organic photovoltaic device containing the star-structured flexible segment according to claim 1 or 2 is applied to the organic photovoltaic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210053939.9A CN114605619B (en) | 2022-01-18 | 2022-01-18 | Organic photovoltaic device active layer material containing star-structure flexible chain segments, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210053939.9A CN114605619B (en) | 2022-01-18 | 2022-01-18 | Organic photovoltaic device active layer material containing star-structure flexible chain segments, and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114605619A true CN114605619A (en) | 2022-06-10 |
| CN114605619B CN114605619B (en) | 2023-12-29 |
Family
ID=81858066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210053939.9A Active CN114605619B (en) | 2022-01-18 | 2022-01-18 | Organic photovoltaic device active layer material containing star-structure flexible chain segments, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114605619B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130014115A (en) * | 2011-07-29 | 2013-02-07 | 중앙대학교 산학협력단 | Dendrimer compound having tin core and organic electronic diodes comprising of the same |
| US20140011973A1 (en) * | 2012-07-05 | 2014-01-09 | Boe Technology Group Co., Ltd. | Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device |
| JP2014047139A (en) * | 2012-08-29 | 2014-03-17 | Hiroshima Univ | Naphthobisthiadiazole derivative and method of producing the same |
| KR101799562B1 (en) * | 2016-09-26 | 2017-11-20 | 한국과학기술연구원 | Conjugated polymer for organic solar cells and Organic solar cells comprising the same |
| WO2018076247A1 (en) * | 2016-10-27 | 2018-05-03 | South University Of Science And Technology Of China | A weak electron-donating building block, copolymers thereof and their preparation methods as well as their applications |
| US20190233578A1 (en) * | 2018-01-29 | 2019-08-01 | Phillips 66 Company | Polymers for organic photovoltaics |
| CN111153858A (en) * | 2020-01-16 | 2020-05-15 | 华南理工大学 | Star-shaped electroluminescent material based on phenanthroimidazole unit and preparation method and application thereof |
| CN111788704A (en) * | 2018-09-19 | 2020-10-16 | 科学与工业研究委员会 | Thermoelectric material and method for producing same |
| CN112521934A (en) * | 2019-12-31 | 2021-03-19 | 华南理工大学 | Hyperbranched electroluminescent polymer, and polymerized monomer, preparation method and application thereof |
-
2022
- 2022-01-18 CN CN202210053939.9A patent/CN114605619B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130014115A (en) * | 2011-07-29 | 2013-02-07 | 중앙대학교 산학협력단 | Dendrimer compound having tin core and organic electronic diodes comprising of the same |
| US20140011973A1 (en) * | 2012-07-05 | 2014-01-09 | Boe Technology Group Co., Ltd. | Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device |
| JP2014047139A (en) * | 2012-08-29 | 2014-03-17 | Hiroshima Univ | Naphthobisthiadiazole derivative and method of producing the same |
| KR101799562B1 (en) * | 2016-09-26 | 2017-11-20 | 한국과학기술연구원 | Conjugated polymer for organic solar cells and Organic solar cells comprising the same |
| WO2018076247A1 (en) * | 2016-10-27 | 2018-05-03 | South University Of Science And Technology Of China | A weak electron-donating building block, copolymers thereof and their preparation methods as well as their applications |
| US20190233578A1 (en) * | 2018-01-29 | 2019-08-01 | Phillips 66 Company | Polymers for organic photovoltaics |
| CN111788704A (en) * | 2018-09-19 | 2020-10-16 | 科学与工业研究委员会 | Thermoelectric material and method for producing same |
| CN112521934A (en) * | 2019-12-31 | 2021-03-19 | 华南理工大学 | Hyperbranched electroluminescent polymer, and polymerized monomer, preparation method and application thereof |
| CN111153858A (en) * | 2020-01-16 | 2020-05-15 | 华南理工大学 | Star-shaped electroluminescent material based on phenanthroimidazole unit and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| BAITIAN HE ET AL.: ""Star-like n-type conjugated polymers based on naphthalenediimide for all-polymer solar cells"", vol. 159, pages 85 - 91, XP085442465, DOI: 10.1016/j.dyepig.2018.06.004 * |
| PENG LIU ET AL.: ""Optimizing Light-Harvesting Polymers via Side Chain Engineering"", vol. 25, pages 6458, XP055421297, DOI: 10.1002/adfm.201501878 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114605619B (en) | 2023-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10290809B2 (en) | Macromolecular compound | |
| US9209404B2 (en) | Macromolecular compound | |
| JP5954814B2 (en) | Nitrogen-containing condensed ring compound, nitrogen-containing condensed ring polymer, organic thin film and organic thin film element | |
| JP2008109114A (en) | Organic photoelectric conversion element | |
| CN112608309B (en) | Non-condensed ring organic small molecular material containing fluorene ring group and preparation method and application thereof | |
| Gupta et al. | Band-gap tuning of pendant polymers for organic light-emitting devices and photovoltaic applications | |
| EP2927259B1 (en) | Benzodithiophene based copolymer containing thiophene pyrroledione units and preparing method and applications thereof | |
| Gao et al. | Efficient polymer solar cells based on poly (thieno [2, 3-f] benzofuran-co-thienopyrroledione) with a high open circuit voltage exceeding 1 V | |
| JP6247581B2 (en) | Polymer compound and electronic device using the same | |
| KR102439270B1 (en) | Novel polymer and organic electronic device using them | |
| KR101828012B1 (en) | Conjugated polymer for organic solar cell and manufacturing method thereof | |
| JP6004848B2 (en) | Polymer, organic thin film and organic thin film element using the polymer | |
| CN106832231B (en) | Containing 1,2,3 triazol iso-indoles -5,7 (2H, 6H)-diketone conjugated polymer and its preparation method and application | |
| CN114605619A (en) | Active layer material of organic photovoltaic device containing star-structure flexible chain segment and preparation and application thereof | |
| Santos et al. | Synthesis of novel low bandgap random and block terpolymers with improved performance in organic solar cells | |
| CN112961326A (en) | Naphtho-difurane conjugated polymer and preparation method and application thereof | |
| KR101317912B1 (en) | Polymer with phenanthrothiadiazole thereof and photovoltaic device using same | |
| WO2012118128A1 (en) | Polymer and organic thin film and organic thin film element using same | |
| KR102519331B1 (en) | Polymers based on bi-halogen atoms-substituted heterocyclic compounds, an organic solar cell comprising the same and manufacturing method of the polymers and the solar cell | |
| KR101922974B1 (en) | Conducting polymer comprising acceptor monomer substituted with side chain and perovskite solar cells comprising the same | |
| EP2566857B1 (en) | Aromatic monomers deriving from glycerol units, process for their preparation and use thereof for the preparation of water-soluble conjugated polymers | |
| CN110790772A (en) | Hydroxyquinoline-based metal organic micromolecule complex material grafted with perylene diimide and aromatic group and preparation method and application thereof | |
| WO2012090972A1 (en) | Reactive compound, and method for producing polymer using same | |
| CN115724873A (en) | Fused ring monomer based on benzodithiophene, polymer thereof, preparation method and application | |
| JP2009256594A (en) | Fluorene-based polymer compound and organic thin film element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |