CN110036000A - Conjugated polymer containing alkyl and alkyl ester base side chain - Google Patents
Conjugated polymer containing alkyl and alkyl ester base side chain Download PDFInfo
- Publication number
- CN110036000A CN110036000A CN201780039381.6A CN201780039381A CN110036000A CN 110036000 A CN110036000 A CN 110036000A CN 201780039381 A CN201780039381 A CN 201780039381A CN 110036000 A CN110036000 A CN 110036000A
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- Prior art keywords
- conjugated polymer
- unit
- polymer
- independent choice
- atom
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 72
- 125000000217 alkyl group Chemical group 0.000 title claims description 18
- 125000005907 alkyl ester group Chemical group 0.000 title description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 86
- 239000012188 paraffin wax Substances 0.000 claims abstract description 30
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 61
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 49
- 229910003472 fullerene Inorganic materials 0.000 claims description 22
- 229930192474 thiophene Natural products 0.000 claims description 21
- 238000013086 organic photovoltaic Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 230000005669 field effect Effects 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 8
- QUTGXAIWZAMYEM-UHFFFAOYSA-N 2-cyclopentyloxyethanamine Chemical compound NCCOC1CCCC1 QUTGXAIWZAMYEM-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000003252 repetitive effect Effects 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 40
- 239000007787 solid Substances 0.000 description 30
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 29
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 28
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 description 15
- 235000011152 sodium sulphate Nutrition 0.000 description 15
- CTFNJPHOILFHEL-UHFFFAOYSA-N CC1=C(C=CC=C1)[P] Chemical compound CC1=C(C=CC=C1)[P] CTFNJPHOILFHEL-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 235000003270 potassium fluoride Nutrition 0.000 description 14
- 239000011698 potassium fluoride Substances 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 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 13
- 239000012044 organic layer Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 235000008708 Morus alba Nutrition 0.000 description 9
- 240000000249 Morus alba Species 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- -1 polymer) Chemical class 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical class C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000005693 optoelectronics Effects 0.000 description 7
- 125000003638 stannyl group Chemical group [H][Sn]([H])([H])* 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YNVOMSDITJMNET-UHFFFAOYSA-N thiophene-3-carboxylic acid Chemical compound OC(=O)C=1C=CSC=1 YNVOMSDITJMNET-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N trimethylbenzene Natural products CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 3
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical class C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CRKVMRJSMBQYRV-UHFFFAOYSA-N 3-(2-octyldodecyl)thiophene Chemical compound CCCCCCCCCCC(CCCCCCCC)CC=1C=CSC=1 CRKVMRJSMBQYRV-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229920006126 semicrystalline polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- OQRUVNSOMCBUCK-UHFFFAOYSA-N 2-[4-(2-hexylnonyl)thiophen-2-yl]thiophene-3-carboxylic acid Chemical compound CCCCCCCC(CCCCCC)CC1=CSC(=C1)C2=C(C=CS2)C(=O)O OQRUVNSOMCBUCK-UHFFFAOYSA-N 0.000 description 1
- RVSXMPCELBYUSF-UHFFFAOYSA-N 2-bromothiophene-3-carboxylic acid Chemical compound OC(=O)C=1C=CSC=1Br RVSXMPCELBYUSF-UHFFFAOYSA-N 0.000 description 1
- PSFURMCBWJQCRX-UHFFFAOYSA-N 3-benzyl-4-phenylbut-3-en-2-one Chemical compound C=1C=CC=CC=1C=C(C(=O)C)CC1=CC=CC=C1 PSFURMCBWJQCRX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- IULKOACDRUDJON-UHFFFAOYSA-N S1C(=CC=C1)C=1SC=CC1.S1C=CC=C1 Chemical compound S1C(=CC=C1)C=1SC=CC1.S1C=CC=C1 IULKOACDRUDJON-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical class C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 1
- NRUBUZBAZRTHHX-UHFFFAOYSA-N lithium;propan-2-ylazanide Chemical compound [Li+].CC(C)[NH-] NRUBUZBAZRTHHX-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001894 space-charge-limited current method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical class OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YCIHVFOEJHGEFJ-UHFFFAOYSA-N tributyl-lambda3-chlorane Chemical compound CCCCCl(CCCC)CCCC YCIHVFOEJHGEFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D421/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- 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
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
-
- 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
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
-
- 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
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Abstract
The invention discloses a kind of conjugated polymer, including following two unit, unit (I) and unit (II)In any situation, X is independently selected from Se or S；M1And M2Independently selected from H or F.R1And R2From linear paraffin, branched paraffin or cycloalkane independent choice containing 1-40C.In the polymer chain, the quantitative proportion range of unit (I) and unit (II) is 9: 1 to 1: 9.
Description
The present invention claims U.S. Provisional Patent Application No.62/493,141 priority and rights, on June 24th, 2016
It submits, the disclosure of which is incorporated herein by reference in their entirety.
[technical field]
The present invention relates to Optical Properties of Novel Conjugated, preparation method and used intermediate, which can be used as organic
Semiconductor material in electronics (OE) device, especially in organic solar batteries (OSC) and organic field effect tube
(OFET) devices field, and OE the and OSC device made of these formulas.
[background technique]
In recent years, people increasingly pay close attention to organic semiconductor (including conjugated polymer) in various electronic applications,
Such as organic solar batteries (OSC).One especially important field is organic solar batteries field.Organic semiconductor exists
It is applied in OSC, because they allow to manufacture device by the solution processing technologies such as spin coating and printing.It is inorganic with being used to manufacture
The evaporation technique of thin-film device is compared, and solution processing techniques can be cheaper and be carried out more on a large scale.The prior art it is organic
Solar battery is made of the blend film of conjugated polymer and fullerene derivate.In order to realize efficient OSC device, rationally
It is most important to design high-performance donor polymerization object.
In order to develop high-performance donor polymerization object, most important Consideration is that donor polymerization object should show aggregation
Matter, so that polymer can produce suitable donor: acceptor blend pattern, i.e., it contains crystallization but the fairly small region of size
(< 20nm).
Recently, the new donor polymerization object family with stronger temperature-induced aggregation (TDA) property is developed, and is showed
Advantageous aggregation property out.These polymer depolymerization and are soluble in solution at high temperature mostly, but can send out when cooled to room temperature
Raw strong polymerization.Using this unique TDA property, polymer can be prepared: the hot solution of fullerene mixture.At control
Temperature and other conditions (such as speed of rotation, solution concentration etc.) are managed, the aggregation extent of polymer in solution can be efficiently controlled,
And solid pi-pi accumulation degree is therefore controlled very well, preferable highly crystalline and the sufficiently small BHJ of area size finally can be obtained
Pattern.It is this it is good control and can be used for preparing ten several high efficiency organic solar batteries close to optimal BHJ form, wherein
Active layer is thick close to 300nm but still high FF (70-77%) and energy conversion efficiency (10-11.7%) may be implemented.By grinding
Study carefully the structure-property relationships of donor polymerization object, it has been found that the fluorination in two branched alkyl chains and main polymer chain is to realize
Two crucial structure features of TDA property.
The key structural features of these TDA polymer are the second branched alkyl chains between two thiophene units.
Strong TDA property can be obtained in this second position branched alkyl chain, as shown in Figure 7.When polymer solution is cooled to room temperature from 120 DEG C
When, the absorption peak of polymer solution is mobile more than 50nm
Although seldom report, it is poly- to construct donor that alkyl ester base side chain (as follows) can also be connected on thiophene unit
Close object.However it has been found that the polymer with alkyl ester base side chain does not have strong TDA property.Therefore, building has all carbalkoxy sides
The high-performance polymer of chain has more challenge.
However, lateral chain of ester group has the advantages that, one of them is to adjust highest occupied molecular orbital HOMO and LUMO, because
There is strong electron-withdrawing ability for ester group.For this reason, the open-circuit voltage of OSC device can be enhanced in carbalkoxy group.
Finally, it is important to note that although fullerene derivate in the latest 20 years be always material main selection,
Fullerene shows many disadvantages, such as the absorbent properties of high production cost and difference.In order to overcome these disadvantages, OSC project
Group trying to explore the field non-fullerene OSC always, be considered as it is more more efficient than traditional fullerene device, stablize and cost more
Low next-generation OSC.Constructing non-fullerene OSC has different materials selection.Wherein, polymer donor and small molecule receptor are based on
(SMA) OSC is rapidly developed during the past two years.In order to develop efficient polymer: SMA organic solar batteries have been adopted
Design and synthesis of a lot of research work for novel SMA material are taken, then usually by itself and known donor polymerization object (example
Such as, PTB7-Th) it combines to construct polymer: SMA OSC.However, these known donor polymerization objects are for polymer: fowler
Alkene OSC design.Although they match good with fullerene acceptor and can be realized efficient fullerene photovoltaic device, they
It may not be the best match donor of SMA material.
In order to obtain efficient non-fullerene OSC, donor polymerization object plays crucial work in control bulk heterojunction (BHJ) pattern
With.A kind of successful methods that suitable pattern (containing highly crystalline and small phase size of separation) is obtained in fullerene OSC are to make
With the donor polymerization object family with strong temperature induced aggregation (TDA) property, it can be used for making a variety of high efficiency and (be higher than
10%) polymer: fullerene OSC.The crystallinity of these TDA polymer is significantly larger than traditional PTB7 race polymer, this can be with
It is proved by their bigger (010) and (100) crystalline size and higher hole mobility.Key characteristic is polymer
Strong TDA behavior, this causes the polymerization process in film cooling and drying process that can be well controlled, at the same generate height tie
Brilliant but small region (< 20nm).However it has been found that the TDA polymer of the prior art is performed poor in SMA OSC.Though for example,
Right PffBT4T-2OD can prepare 10.8% fullerene battery, but it only generates lower than 4% with SMA device.
In summary, it is evident that the donor polymerization object of all alkyl side chains does not work to non-fullerene OSC.
[invention brief introduction]
In order to overcome the prior art poly- for the polymer with all alkyl side chains and with all alkyl ester base side chains
The shortcomings that closing object, the present invention provides following various embodiments.
In one embodiment, surprisingly it has been found that the polymer containing alkylthrophene and carbalkoxy thiophene unit is [as follows
Show unit (I) and unit (II)] in conjunction with non-fullerene small molecule receptor when can show extraordinary performance.
In other words, such polymer (has some alkyl side chains and some carbalkoxy sides on the position β of thiophene unit
Chain) surprisingly it is better than the polymer with 100% alkyl side chain and the polymer with 100% alkyl ester base side chain.Alkyl
With alkyl ester base side chain be applied in combination produce it is very astonishing and effective as a result, as follows:
In another embodiment, the polymer table containing part alkylthrophene and part carbalkoxy thiophene unit is found
Reveal the TDA property similar with previous polymer (when solution is mobile more than 50nm from absorption peak when being cooled to room temperature for 100 DEG C),
And the polymer with 100% carbalkoxy thiophene does not have such TDA property, pattern is controlled for this and solar energy in large area
The renewable product of battery is important.
In another embodiment, when polymer is in conjunction with the non-fullerene acceptor based on PDI, it is surprised to find tool
Have three thiophen polymers of 50% alkylthrophene and 50% carbalkoxy thiophene unit show unprecedented high open circuit voltage and
Energy conversion efficiency, a wide range of interior better than the polymer with 100% alkyl side chain.
In one embodiment of the invention, discovery introduces alkyl ester base side chain on the position β of thiophene unit and can be enhanced
The crystallinity of polymer, this is advantageously possible for OSC production.However, it was also surprising that its all side chain is alkyl ester base side chain
Polymer does not have TDA property, this is the critical nature for controlling OSC pattern.
In another embodiment, in fact it has surprisingly been found that there is 50% alkyl side chain on the position β of thiophene unit
Show two attracting features in identical position with the polymer of 50% alkyl ester base side chain: 1) it shows strong TDA
Matter controls pattern most important；2) with the polymer phase ratio with 100% alkyl side chain, it has preferable crystallinity.
In another embodiment, it has therefore been surprisingly found that on the position β of thiophene unit have 50% alkyl side chain and
The polymer of 50% alkyl ester base side chain is shown close to perfect blend pattern, the area size with about 10nm and simultaneously
With high-crystallinity.
[Detailed description of the invention]
Figure 1A illustrates donor polymerization object P3TEA and SMA SF-PDI2Chemical structure.
Figure 1B illustrates P3TEA:SF-PDI2The J-V curve of-based solar battery.Set figure: P3TEA:SF-PDl2-
The device parameters of based solar battery.
Fig. 1 C illustrates the EQE curve of P3TEA:SF-PD12-based solar battery.
Fig. 2 shows that the UV of polymer P 3TEA absorbs.
Fig. 3 shows cyclic voltammetry curve of the polymer P 3TEA in 0.1M (n-Bu) 4N+PF6- acetonitrile solution.
Fig. 4 A is P3TEA:SF-PDl2The afm image (1 1 μm of μ m, left) of-based blend film.
Fig. 4 B shows P3TEA:SF-PDl2The TEM image (right side) of-based blend film.
Fig. 5 is pure PffBT4T-20D (Y5), pure PffBT4T-E (G5), PffBT4T-20D:SF-PDI2(Y5/Js1),
PffBT4T-E:SF-PDI2(G5/Jsl), pure PffBT3T-1,2 (S26), pure P3TEA (G17), PffBT3T-1,2:SP-PDI2
(S26/Jsl) and P3TEA:SP-PDI2(G17/JsI) the GIWAXS map of film.
Fig. 6 illustrates PffBT4T-2OD:SF-PDI2(Y5/Jsl), PffBT4T-E:SF-PDI2(G5/Jsl),
PffBT3T-1,2:SP-PDI2(S26/Jsl) and P3TEA:SP-PDI2(G17/Jsl) the R-SoXS spectrum of four kinds of blend films.
[summary of the invention]
The formula of this introduction can show semiconductor behavior, such as light absorption/charge point of the optimization in photovoltaic device
From；Charge transmission in luminescent device is/compound/to shine；And/or high carrier mobility in fieldtron and/or good
Current modulation characteristic.In addition, this formula can have certain processing advantages under natural environmental condition, such as solution can be handled
Property and/or good stability (such as air stability).The formula of this introduction can be used for preparing p-type, and (donor or hole pass
It is defeated), N-shaped (receptor or electron-transport) or bipolar semiconductor material can be used for manufacturing various organic matters or mixed electrical optical again
Product, structure and device, including organic electro-optic device and organic light-emitting transistor.
In the application, wherein element or component be referred to as include in the list of cited component or component and/or from
It is selected in the list of cited component or component, it should be understood that the component or component can be in the component or component
Any one or component or component can be selected from the group being made of component described in two or more or component.In addition, answering
Work as understanding, compositions described herein, the component and/or feature of device or method can be combined in various ways without departing from this
The spirit and scope of introduction, it is either specific or implicit.
Unless stated otherwise, otherwise term " includes ", or " having " use usually should be understood it is open and
It is unrestricted.
Unless stated otherwise, otherwise the use of odd number herein includes plural (vice versa).In addition, term " about "
Use be before quantitative values, unless stated otherwise, otherwise this introduction further includes specific quantitative values itself.As herein
Used, term " about " refers to ± 10% variation with standard value, unless otherwise indicated or infers.
As long as it should be appreciated that this introduction be still it is operable, the sequence of step or the sequence for executing certain processing are not
Important.Furthermore, it is possible to carry out two or more steps or processing simultaneously.
As used herein, " p-type semiconductor material " or " alms giver " material refers to semiconductor material, for example, organic semiconductor
Material has the hole as main electrical current or electric charge carrier.In some embodiments, when p-type semiconductor material is heavy
Product can provide when on substrate more than about 10-5The hole mobility of cm/Vs.In the case where scene effect device, p-type is partly led
Body also may be implemented electric current on/off ratio and be approximately more than 10.
As used herein, " n-type semiconductor " or " acceptor " material refers to semiconductor material, for example, organic semiconductor
Material, with electronics as main electrical current or electric charge carrier.In some embodiments, when n-type semiconductor deposits
When on substrate, it is more than about 10 that it, which can be provided,-5The electron mobility of cm/Vs.In the case where scene effect device, N-shaped half
Conductor also may be implemented electric current on/off ratio and be approximately more than 10.
As used herein, " mobility " is the measurement of carrier velocity, for example, being that hole is (or single in p-type semiconductor material
Position positive charge), it is electronics (or unit negative charge) to pass through material under the influence of electric fields in the case where n-type semiconductor.
The parameter depends on device architecture, and fieldtron or space charge limited current measurement method can be used to measure.
As used herein, the guarantor when mixing compound and showing as the transistor of its semiconductor material when compound exposure
When holding the carrier mobility near its initial measurement, compound can be considered as " ambient stable " or " in environment item
Stablize under part ".Such as whithin a period of time, environmental condition, such as air, environment temperature and humidity.For example, if containing the change
The transistor for closing object is being exposed to environmental condition (including air, humidity and temperature) 3 days, 5 days or 10 days in, and display carrier moves
The variation of shifting rate is no more than 20% or variation is no more than 10% comparing with intial value, then compound can be described as ambient stable.
As used herein, fill factor (FF) is that practical maximum available power (Pm or Vmp*Jmp) (can not be real with theory
Border obtain, (Jsc*Voc)) power ratio (being given as percentages).Therefore, it is possible to use following equation determines FF:
FF=(Vmp*Jmp)/(Jsc*Voc)
Wherein Jmp and Vmp respectively indicates current density and voltage at peak power output (Pm), which is to pass through change
Resistance in circuit is obtained until J*V is in its maximum value；Jsc and Voc respectively represent short circuit current and open-circuit voltage.It fills out
Filling the factor is to assess the key parameter of solar cell properties.Commercial solar cell usually has about 60% or higher filling
The factor.
As used herein, open-circuit voltage (Voc) be when do not have connect external loading when device anode and cathode between
Potential difference.
As it is used herein, the energy conversion efficiency (PCE) of solar battery is to be converted into electric energy from the luminous energy of absorption
Percentage.The PCE of solar battery can by by peak power output (Pm) divided by defeated under standard test condition (STC)
Enter light irradiance (E, W/M2) and solar battery surface area (Ac, M2) calculate.STC typically refer to 25 DEG C temperature and
The irradiation level of 1000W/m2, air quality are 1.5 (AM 1.5) spectrum.
As used herein, as fruit component (such as film layer) containing it is one or more can absorb photon with generate exciton into
And generating the compound of photoelectric current, then it can be considered as " photoactive ".
As used herein, " solution processable " refer to can be used for various solution phase processors compound (such as polymer),
Material or composition, including spin coating, printing (such as ink jet printing, intaglio printing, hectographic printing etc.), spraying, electrospray, drop
Painting, dip-coating and blade coating.
As used herein, " semi-crystalline polymer " refers to when being subjected to dynamic advantage such as Slow cooling, or works as
When depositing from molten condition cooling or from solution, polymer or solvent the evaporation speed of the partially crystallizable with tropism
Rate is low.By using several analysis methods, such as differential scanning calorimetry (DSC) and/or X-ray diffraction (XRD), Ke Yirong
It changes places and identifies its crystallization degree.
As used herein, " annealing " refers in the environment or sinks after carrying out under buck/boost to semi-crystalline polymer film
Accumulated heat duration of the processing more than 100 seconds, and " annealing temperature " refers to maximum value.Polymer film is sudden and violent in the annealing process
At least 60 seconds temperature of dew.It is not intended to be any particular theory, annealing can lead to polymer in the conceived case
The increase of crystallinity in film, to increase field-effect mobility.The increase of crystallinity can be monitored by several method, for example,
It is measured by comparing the differential scanning calorimetry (DSC) or X-ray diffraction (XRD) of deposition and annealing film.
As used herein, " polymerizable compound " (or " polymer ") refer to comprising be keyed by covalent chemical one or
The molecule of multiple repetitive units.Polymerizable compound can be indicated by general formula:
Throughout the specification, structure can have or not have chemical name.If there is any about nomenclature
Problem, then be subject to structure.
In first embodiment of the invention, containing unit (I) [Unit (I)] and unit (II) [Unit (II)]
Conjugated polymer is as follows:
Wherein:
In any situation, X independent choice from Se or S；
M1And M2The independent choice from H or F；
R1And R2From linear paraffin, branched paraffin or cycloalkane independent choice containing 1-40C；
In the polymer chain, the quantitative proportion range of unit (I) and unit (II) is 9: 1 to 1: 9.
In one example, M1And M2For H atom, X is S atom.
In another example, R1And R2It is the independent choice from the position the 2- branched-alkyl group with 4-40 C atom.
In some instances, the average molecular weight of conjugated polymer is at least 20, and 000 gram/mol, more excellent is 40,000
Gram/mol.
In yet another example, a kind of composition is provided.The composition includes to be dissolved or dispersed in liquid medium
Conjugated polymer, when the composition is from when being cooled to room temperature for 120 DEG C, the composition shows the optical absorption peak of at least 50nm
Red shift.
In another example, a kind of organic photovoltaic devices are disclosed.Organic photovoltaic devices include the confession of conjugated polymer
Body and one or more non-fullerene small molecule receptors (SMA), wherein in donor: forming phase separation region in acceptor blend pattern
Domain.Phase size of separation is more preferably less than 20nm.Small molecule receptor (SMA) includes the structure based on imidodicarbonic diamide (PDI).
In yet another example, a kind of optics, electronics or opto-electronic device are disclosed.The device includes conjugated polymer,
In general, the device is selected from organic field effect tube, organic light-emitting transistor or organic photovoltaic devices.
In having an example, conjugated polymer tends to following below formula:
Wherein:
Any position, R are the independent choices from the position the 2- branched-alkyl group with 4-40 C atom.
In second embodiment of the invention, conjugated polymer is disclosed.Conjugated polymer contains one or more
The repetitive unit of chemical formula (I) contains at least one unit (I) and at least one unit (II):
Wherein:
Ar is the aromatic unit for not being thiophene；
The X independent choice from S or Se in each case；
M1、M2、M3And M4The independent choice from H or F；
R1And R2From linear paraffin, branched paraffin or cycloalkane independent choice containing 1-40C；
In the polymer chain, the quantitative proportion range of unit (I) and unit (II) is 9: 1 to 1: 9.
In one example, conjugated polymer is selected from the group being made of following polymer:
In another example, with chemical formula (IA) [Formula (IA)] and chemical formula (IB) [Formula (IB)]
Conjugated polymer is as follows:
Wherein:
Arl and Ar2 is the aromatic unit for not being thiophene, AR1And AR2Can it is identical can also be different；
M5, M6, M7, M8, M8, M10, M11, M12, M13, M14, M15, M16, M17, M18, M19And M20The independent choice from H or F.Still
It is old in another example, Ar is selected from:
In yet another example, wherein M1, M2, M3And M4It is H atom, and X is S.
In yet another example, wherein R1And R2Independently selected from the position the 2- branched-alkyl with 4-40 C atom.
In another example, wherein the number-average molecular weight of conjugated polymer is at least 20,000 gram/mol, it is intended to be
40,000 grams/mol.
In yet another example, a kind of composition is provided.The composition includes to be dissolved or dispersed in liquid medium
Conjugated polymer, when the composition is from when being cooled to room temperature for 120 DEG C, the composition shows the optical absorption peak of at least 50nm
Red shift.
In yet another example, a kind of organic photovoltaic devices are disclosed.Organic photovoltaic devices include the confession of conjugated polymer
Body and one or more non-fullerene small molecule receptors (SMA), wherein in donor: forming farmland in acceptor blend form.Region
Size is preferably smaller than 20nm.Small molecule receptor (SMA) includes the structure based on imidodicarbonic diamide (PDI).
In yet another example, a kind of optics, electronics or opto-electronic device are disclosed.The device includes conjugated polymer,
And generally, which is selected from organic field effect tube, organic light-emitting transistor or organic photovoltaic devices.
In third embodiment of the invention, conjugated polymer is disclosed.Conjugated polymer has chemical formula (II)
[Formula (II)] contains at least one unit (I) and at least one unit (II):
Wherein:
Ar is the aromatic unit for not being thiophene；
The X independent choice from S or Se in each case；
M1、M2、M3And M4The independent choice from H or F；
R1And R2From linear paraffin, branched paraffin or cycloalkane independent choice containing 1-40C；
In the polymer chain, the quantitative proportion range of unit 1 and unit 2 is 9: 1 to 1: 9.
In one example, conjugated polymer is selected from the group being made of following polymer:
Wherein:
M1' selected from H or F；
R1' from linear paraffin, branched paraffin or cycloalkane independent choice containing 2-40C；
M1And M1' can be identical or different；
R1And R1' can be identical or different.
In another example, the conjugated polymer with chemical formula (IIA) [Formula IIA] is as follows:
Wherein:
R1' from linear paraffin, branched paraffin or cycloalkane independent choice containing 2-40C；
R1And R1' can be identical or different
Still in another example, Ar is selected from:
In yet another example, M1, M2, M3, M4, M5And M6It is H atom, and X is S.
In another example, R1And R2Independently selected from the position the 2- branched-alkyl with 4-40 C atom.
In this embodiment, optics, electronics or opto-electronic device include above-mentioned conjugated polymer.
In this embodiment, above-mentioned device is selected from organic field effect tube, organic light-emitting transistor and organic photovoltaic
Device.
In the 4th embodiment of the invention, provide containing one or more chemical formula (III) [Formula
III] repetitive unit conjugated polymer:
Wherein:
Ar1 and Ar2 is the aromatic unit for not being thiophene, and Ar1 and Ar2 can identical can also be different；
M13, M14, M15, M16, M17, M18, M19And M20The independent choice from H or F.
In this embodiment, in above-mentioned conjugated polymer: R7 and R8 can be independently selected from 4-40 C atom
2- branched-alkyls.
In this embodiment, in above-mentioned conjugated polymer: M13, M14, M15, M16, M17, M18, M19And M20For H atom.
In this embodiment, Arl and Ar2 can be selected from above-mentioned conjugated polymer:
In this embodiment, a kind of optics, electronics or opto-electronic device include above-mentioned conjugated polymer.
In this embodiment, above-mentioned device is selected from organic field effect tube, organic light-emitting transistor and organic photovoltaic
Device.
In fifth embodiment of the invention, conjugated polymer contains one or more with lower chemical formula (IV)
The repetitive unit of [Formula IV]:
Wherein:
Ar1 and Ar2 is the aromatic unit for not being thiophene, and Arl and Ar2 can identical can also be different；
X is S or Se atom；
M21, M22, M23, M24、M25、M26、M27And M28The independent choice from H or F；
R9And R10From linear paraffin, branched paraffin or cycloalkane independent choice containing 2-40C.
In this embodiment, in above-mentioned conjugated polymer: R9 and R10 can be independently selected from 4-40 C atom
The position 2- branched-alkyl.
In this embodiment, in above-mentioned conjugated polymer: M21, M22, M23, M24、M25、M26、M27And M28It can be H original
Son.
In this embodiment, above-mentioned conjugated polymer, wherein Arl and Ar2 can be selected from:
In this embodiment, a kind of optics, electronics or opto-electronic device include above-mentioned conjugated polymer.
In this embodiment, above-mentioned device is selected from organic field effect tube, organic light-emitting transistor and organic photovoltaic
Device.
In sixth embodiment of the invention, three kinds are provided containing one or more chemical formula (V) [Formula
V], the conjugated polymer of the repetitive unit of chemical formula (VI) [Formula VI] and chemical formula (VII) [Formula VII]:
Wherein:
Ar1 and Ar2 is the aromatic unit for not being thiophene, and Ar1 and Ar2 can identical can also be different；
R11, R12, R13, R14 R15, R16, R17, R18 and R19From containing 2-40C linear paraffin, branched paraffin or cycloalkane it is only
Vertical selection.
In this embodiment, in above-mentioned conjugated polymer: R11, R12, R13, R14, R15, R16, R17, R18And R19It can be from
Independent choice in the position 2- branched-alkyl with 4-40 C atom.
In this embodiment, above-mentioned conjugated polymer, wherein Arl and Ar2 can be selected from:
In this embodiment, a kind of optics, electronics or opto-electronic device include above-mentioned conjugated polymer.
In this embodiment, above-mentioned device is selected from organic field effect tube, organic light-emitting transistor and organic photovoltaic
Device.
In the 7th embodiment of the invention, two kinds of monomer-types for being used to form above-mentioned conjugated polymer are provided
(VIII) [Formula VIII] and monomer formula (IX) [Formula IX]:
Wherein:
Ar is the aromatic unit for not being thiophene；
Y is Br or I；
M1、M2、M3And M4The independent choice from H or F；
R21、R22、R23And R24From linear paraffin, branched paraffin or cycloalkane independent choice containing 4-40C；
Ar is selected from:
In the 8th embodiment of the invention, three kinds of monomer-types for being used to form above-mentioned conjugated polymer are provided
(X) [Formula X], monomer-type (XI) [Formula XI] and monomer-type (XII) [Formula XII].
Wherein:
Ar is the aromatic unit for not being thiophene；
Y is Br or I；
M1、M2、M3And M4The independent choice from H or F；
R24、R25、R26、R27、R28And R24From linear paraffin, branched paraffin or cycloalkane independent choice containing 4-40C；
Ar is selected from:
In the 9th embodiment of the invention, several conjugated polymers containing one or more repetitive units are provided
Object:
Wherein:
R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47And R48Independently selected from 4-
The position the 2- branched-alkyl of 40 C atoms.R49Selected from the straight chain with 2-40 C atom, branch or cyclic alkyl.
In one example, above-mentioned first conjugated polymer, wherein R33It is 2- branchings C8C12, R34It is 2- branchings
C6C9。
In this embodiment, a kind of optics, electronics or opto-electronic device include above-mentioned conjugated polymer.
In this embodiment, above-mentioned device is selected from organic field effect tube, organic light-emitting transistor and organic photovoltaic
Device.
In the tenth embodiment of the invention, several conjugated polymers are provided:
Wherein:
R is at each occurrence independently selected from the position the 2- branched-alkyl with 4-40 C atom.
It was surprisingly found that due to the strong electron-withdrawing ability of ester group on thiophene, the polymer containing above structure unit
LUMO and HOMO energy level can be substantially reduced.Therefore, blend (polymer/fullerene or polymer/small molecule) is usually shown
High open circuit voltage, for example, P3TEA:SF-PDl2Show the high open circuit voltage of 1.11V.The band gap of P3TEA polymer is
1.66eV, this is calculated from ABSORPTION EDGE.While with high open circuit voltage, which loses with the low-voltage of 0.55eV.
Therefore, the polymer based on thiophene carboxylic acid's salt is used to be likely to show high open circuit voltage as the blend of donor, because poly-
The HOMO energy level for closing object is deeper.
It is astonishing and it is advantageous that tend to be formed with small molecule receptor most preferably with the polymer of this structural unit
Pattern, being proved such as AFM and TEM image.Therefore, it can be realized simultaneously high Voc and Jsc, final PCE efficiency is up to 9.5%.
Our OSC system has fundamental significance to more efficient solar battery is developed, because it efficiently solves Voc and Jsc
Between trade-off problem.
[specific embodiment]
Example 1- synthon DibromoffBT-E, A and polymer P 3TEA
2- octyldodecyl thiophene -3- carboxylic acid (S1).
It is dissolved in thiophene 3 carboxylic acid (1,5.126g, 40mmol) solution room temperature under the protection of nitrogen atmosphere of 150ml DCM
Stirring.Then by 4-dimethylaminopyridine (1.466g, 12mmol), N, N '-dicyclohexylcarbodiimide (9904mg, 48mmol)
In 2- chlorine hexamethylene -1- alcohol (2,23.88g, 80mmol) addition system, it is stirred to react mixture 12 hours.After reaction, will
Quenching reaction is added in 50ml distilled water, is filtered with n-hexane, diluted reaction mixture, and cleaned with water and salt water.Organic layer quilt
After sodium sulphate is dry, filters and be concentrated.Reaction residual is purified with silica gel chromatographic column, with the pure products of output clear solution
(17.25g, yield 92%).
1H NMR (400MHz, CDCl3) δ 8.08 (d, J=1.7Hz, 1H), 7.54-7.51 (m, 1H), 7.31-7.28 (m,
1H), 4.18 (d, J=5.6Hz, 2H), 1.74 (d, J=4.4Hz, 1H), 1.41-1.22 (m, 32H), 0.88 (t, J=6.3Hz,
6H).13C NMR (101MHz, CDCl3) δ 163.13,134.27,132.57,128.09,126.07,67.68,37.63,
32.12,32.11,31.64,30.15,29.85,29.80,29.76,29.55,29.51,26.96,22.89,22.88,
14.31.HRMS(MALDI+)Calcd for C25H44O2S (M+): 408.3062, Found:408.3080.
2- octyldodecyl 2- (trimethylsilyl) thiophene -3- carboxylic acid (S2).
3- (2- octyldodecyl) thiophene is dissolved in the tetrahydrofuran solution of 40ml, and cold under nitrogen atmosphere protection
But subzero 78 degrees Celsius are arrived.Diisopropylamino lithium (2M, 4.2mL, 8.4mmol) solution is added dropwise and is stirred under subzero 78 degrees Celsius
Mixture 1 hour.Trim,ethylchlorosilane (1.1mL, 8.4mmol) is then added drop-wise to the reaction mixture of recovered room temperature
In, it is stirred overnight.After reaction, 30mL distilled water quenching reaction is added, and reactant n-hexane is filtered, diluting reaction
Mixture is successively cleaned with water and salt water.After organic layer is dried by sodium sulphate, filters and be concentrated.Reaction residual silica gel color
Column purification is composed, with the pure products (1.28g, yield 43%) of output clear solution.
1NMR (400MHz, CDCl3) δ 7.63 (d, J=4.8Hz, 1H), 7.47 (d, J=4.8Hz, 1H), 4.19 (d, J=
5.8Hz, 2H), 1.11 (d, J=5.3Hz, 1H), 1.43-1.23 (m, 32H), 0.89 (t, J=6.6Hz, 6H), 0.41 (s,
9H).13C NMR (101MHz, CDCl3) δ 164.05,150.07,139.27,130.85,129.65,67.61,37.68,
32.15,32.13,31.61,30.20,29.88,29.82,29.78,29.58,29.54,26.94,22.92,22.90,
14.33, -0.23.HRMS (MALDI+) Calcd for C28H52O2SSi (M+): 480.3457, Found:480.3477.
2- octyldodecyl 5- (tributyl tin alkyl) -2 (trimethyl silicon substrate) thiophene -3- carboxylic acid (S3).
2- octyldodecyl 2- (trimethylsilyl) -3- carboxylic acid group 3- (2 octyldodecyl) thiophene (S2,
2.124g, 5mmol) it is dissolved in 30mL tetrahydrofuran solution, and it is cooled to subzero 78 degrees Celsius under nitrogen atmosphere.It is added dropwise two
Isopropylamino lithium (2M, 2.8mL, 5.5mmol) solution simultaneously stirs mixture 1 hour at -78 degrees Celsius.Then by tributyl chlorine
Change tin (1.6mL, 6mmol) to be added drop-wise in the reaction mixture of recovered room temperature, be stirred overnight.After reaction, mixture
The middle aqueous solution that potassium fluoride is added is quenched, and is cleaned, diluted with n-hexane, successively clear with potassium fluoride solution, water and salt water
It washes.Organic layer finally is dried, filtered with sodium sulphate, evaporation solvent obtains yellow oil product, directly uses, do not need further
Purification.
Bis- (2- octyldodecyls) -5,5 '-(5,6- difluoro benzo [c] [1,2,5] thiadiazoles -4,7- diyl) bis- (2-
Bromothiophene -3- carboxylic acid)) DibromoffBT-E).
By -2 (trimethyl silicon substrate) thiophene -3- carboxylic acid of 2- octyldodecyl 5- (tributyl tin alkyl) (S3,3.388g,
~4.4mmol), bromo- 5, the 6- bis- fluoro- 2 of 4,7- bis-, 1,3- diazosulfide (3,607mg, 2mmol), three (dibenzalacetones)
Two palladiums (92mg, 0.1mmol) and three (o-methyl-phenyl) phosphorus (122mg, 0.4mmol) mixtures are dissolved in 20mL toluene solution,
And it is refluxed overnight under 100 degrees Celsius under the protection of nitrogen atmosphere.After reaction, mixture be added potassium fluoride aqueous solution into
Row is quenched, and is cleaned, diluted with n-hexane, is successively cleaned with potassium fluoride solution, water and salt water.Organic layer is dried by sodium sulphate
Afterwards, it filters and is concentrated.Reaction residual is purified with silica gel chromatographic column, obtains yellow oil product, is directly used, is not needed into one
Step purification.
Under zero degrees celsius, N- bromo-succinimide (784mg, 4.4mmol) is added, dissolved with silicon in yellow oil product
The 30mL chloroform and the trifluoroacetic mixture solution of 6mL of glue (10mg).Then reaction mixture is warming up to room temperature, and stirred
Overnight.After washing organic phase, and solvent is dried and evaporated with sodium sulphate.Reaction residual is purified with silica gel chromatographic column, obtains orange
Solid pure products (1.715g, yield 75%).
1NMR (400MHz, CDCl3) δ 8.44 (s, 2H), 4.26 (d, J=5.6Hz, 4H), 1.80 (dd, J=11.1,
5.5Hz, 2H), 1.52-1.21 (m, 64H), 0.90-0.83 (m, 12H)13C NMR (101MHz, CDCl3) δ 162.00,
151.51,151.30,148.90,148.70,148.27,148.23,148.20,132.96,132.90,132.86,132.03,
131.80,123.74,123.71,111.07,111.03,110.98,110.94,68.31,37.62,32.14,32.13,
31.67,30.23,29.90,29.88,29.85,29.80,29.58,29.56,27.01,22.89,14.31.19F NMR
(376MHz, CDCl3) 5-126.87.HRMS (MALDI+) Calcd for C56H84Br2F2N2O4S3(M+): 1142.3908,
Found:1142.4729.
Bis- (2- octyldodecyls) -5,5 "-(5,6 difluoroanilines [c] [1,2,5] thiadiazoles -4,7- diyl) bis- (4 ' -
(2 hexyl nonyl)-[2,2 '-bithiophene] -3- carboxylic acid) (S4).
DibromoffBT-E (1.144g, 1mmol), tributyl (4- (2- hexyl nonyl) thiophene -2- base) tin (4,
1.343g, 2.3mmol), tris(dibenzylideneacetone) dipalladium (46mg, 0.05mmol) and three (o-methyl-phenyl) phosphorus (61mg,
Mixture 0.2mmol) is dissolved in tetrahydrofuran solution, and under nitrogen atmosphere protection, and the heating of 80 degree celsius temperatures flowed back
Night.After reaction, the aqueous solution that potassium fluoride is added in mixture is quenched, and is cleaned, diluted with n-hexane, molten with potassium fluoride
Liquid, water and salt water successively clean.Reaction residual is purified with silica gel chromatographic column, obtains Red oil product (1.429g, yield
91%).
1NMR (400MHz, CDCl3) δ 8.64 (s, 2H), 7.42 (d, J=1.1Hz, 2H), 7.03 (s, 2H), 4.22 (d, J
=5.8Hz, 4H), 2.58 (d, J=6.7Hz, 4H), 1.76 (s, 2H), 1.66 (s, 2H), 1.28 (dd, J=24.6,14.4Hz,
108H), 0.93-0.82 (m, 24H)13C NMR (101MHz, CDCl3) δ 163.41,151.63,151.43,149.03,
148.80,148.76,148.72,146.35,142.59,142.12,134.38,132.85,131.86,129.19,129.01,
127.90,124.96,124.54,120.83,111.34,111.25,111.21,68.07,39.12,37.61,35.16,
33.55,32.15,31.65,30.26,30.24,29.95,29.93,29.89,29.87,29.83,29.60,29.58,
27.01,26.87,26.83,22.92,22.90,14.33,14.31.19F NMR (376 MHz, CDC13)5-127.21.HRMS
(MALDI+)Calcd for C94H150F2N2O4S5(M+): 1570.0201, Found:1570.0461.
Bis- (2- octyldodecyls) -5,5 "-(5,6- difluoroanilines [c] [1,2,5] thiadiazoles -4,7- diyl) bis- (5 ' -
Bromo- 4 '-(2- hexyl nonyls)-[2,2 "-bithiophene] -3- carboxylic acid).(referred to as: DibromoffBT-E, A).
N- bromo-succinimide is added under zero degrees celsius to S4 (1.414g, 0.9mmol) and silica gel (10mg) mixture
10mL chloroformic solution in.Reaction mixture stirs 15 minutes.After washing, organic phase is dried over sodium sulfate, re-evaporation solvent.It is surplus
Excess is cleaned to obtain orange solid product (1.540g, yield 99%) by fast column chromatography.
1NMR (400MHz, CDCl3) δ 8.61 (s, 2H), 7.28 (s, 2H), 4.23 (d, J=5.8Hz, 4H), 2.53 (d, J
=7.1Hz, 4H), 1.78 (d, J=4.4Hz, 2H), 1.71 (s, 2H), 1.30 (t, J=23.5Hz, 108H), 0.92-0.81
(m, 24H)13C NMR (101MHz, CDCl3) δ 163.27,151.66,151.46,149.06,148.86,148.71,
148.67,145.45,141.74,134.35,132.77,131.18,129.23,127.85,114.26,111.27,111.19,
111.15,68.25,38.79,37.62,34.38,33.58,32.15,31.67,30.28,30.23,29.93,29.89,
29.88,29.83,29.59,27.02,26.78,26.74,22.92,22.90,14.34,14.32.19F NMR (376MHz,
CDCl3)δ-126.97.HRMS(MALDI+)Calcd for C94H148Br2F2N2O4S5(M+): 1726.8357, Found:
1726.8539.
Microwave-assisted polymerization
Bis- (5 trimethyl stannyl) thiophenes of monomer DibromoffBT-E (25.9mg, 0.015mmol), fluoro- 4, the 7- of 5,6- bis-
Pheno -2- base) benzo [c] [1,2,5] thiadiazoles (6,10.0mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium (0.6mg,
It 0.0007mmol) is placed in microwave tube with three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar, in glove box
Nitrogen atmosphere protection lower 0.2mL chlorobenzene is added.Reaction mixture is heated to 140 degrees Celsius by microwave reactor, and Shi Changwei 2 is small
When.Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.It is collected by filtration to obtain solid, then uses chlorine
It is imitative to carry out special extraction in Suo Gesi.Solution is by being concentrated by evaporation and settling in methyl alcohol.Solid is through being obtained by filtration, and in a vacuum
It is dry, finally obtain the polymer (13.4g, yield 37%) of mulberry solid.
1NMR (400MHz, CDCl3) δ 8.71 (s, 1H), 8.37 (d, J=3.6Hz, 1H), 7.56 (s, 1H), 7.43 (d, J
=3.8Hz, 1H), 4.34 (d, J=5.8Hz, 2H), 2.93 (d, J=6.2Hz, 2H), 1.89 (s, 2H), 1.55-1.25 (m,
54H), 1.00-0.86 (m, 12H) .GPC:Mn:48.4kDa；Mw:100.2kDa；PDI=2.07.Anal.Calcd for
C108H152F4N4O4S8:C, 68.17；H, 8.05；N, 2.94.Found C, 68.20；H, 7.90；N, 2.84.
Example two-synthesizes to obtain P3TEA with different alkyl chains
Microwave-assisted polymerization
Bis- (5- trimethyl stannyl) thiophenes of monomer DibromoffBT-E (29.3mg, 0.015mmol), fluoro- 4, the 7- of 5,6- bis-
Pheno -2- base) benzo [c] [1,2,5] thiadiazoles (10.0mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium (0.6mg,
It 0.0007mmol) is placed in microwave tube with three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar, in glove box
Under nitrogen atmosphere protection, 0.2mL chlorobenzene is added.Reaction mixture is heated to 140 degrees Celsius, duration 2 hours by microwave reactor.
Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.Be collected by filtration to obtain solid, then with chloroform into
Special extraction in row Suo Gesi.Solution is by being concentrated by evaporation and settling in methyl alcohol.Solid is done through being obtained by filtration, and in a vacuum
It is dry, finally obtain the polymer (20.1mg, yield 61%) of mulberry solid.
Example three-synthesizes DibromoffBT-A, E monomer and corresponding polymer P ffBT3T-A, E
Microwave-assisted polymerization
Monomer DibromoffBT-A, E (24.7mg, 0.015mmol), fluoro- 4, the 7- of 5,6- bis- bis- (5- trimethyl stannyls)
Thiophene -2- base) benzo [c] [1,2,5] thiadiazoles (10.0mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium (0.6mg,
It 0.0007mmol) is placed in microwave tube with three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar, in glove box
Nitrogen atmosphere protection is lower to be added 0.2mL chlorobenzene.Reaction mixture is heated to 140 degrees Celsius, duration 2 hours by microwave reactor.
Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.Be collected by filtration to obtain solid, then with chloroform into
Special extraction in row Suo Gesi.Solution is by being concentrated by evaporation and settling in methyl alcohol.Solid is done through being obtained by filtration, and in a vacuum
It is dry, finally obtain the polymer (15.3mg, yield 52%) of mulberry solid.
Four-DibromoffBT-EAA of example and corresponding polymer P ffBT4T-EAA
Microwave-assisted polymerization
Monomer DibromoffBT-EAA (35.5mg, 0.015mmol), fluoro- 4, the 7- of 5,6- bis- bis- (5- trimethyl stannyls)
Thiophene -2- base) benzo [c] [1,2,5] thiadiazoles (10.0mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium (0.6mg,
It 0.0007mmol) is placed in microwave tube with three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar, in glove box
Nitrogen atmosphere protection is lower to be added 0.2mL chlorobenzene.Reaction mixture is heated to 140 degrees Celsius, duration 2 hours by microwave reactor.
Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.Be collected by filtration to obtain solid, then with chloroform into
Special extraction in row Suo Gesi.Solution is by being concentrated by evaporation and settling in methyl alcohol.Solid is done through being obtained by filtration, and in a vacuum
It is dry, finally obtain the polymer (17.8mg, yield 47%) of mulberry solid.
Five-synthon of example DibromoffBT-AEA and corresponding polymer P ffBT4T-AEA
Microwave-assisted polymerization
Monomer DibromoffBT-AEA (35.5mg, 0.015mmol), fluoro- 4, the 7- of 5,6- bis- bis- (5- trimethyl stannyls)
Thiophene -2- base) benzo [c] [1,2,5] thiadiazoles (10.0mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium (0.6mg,
It 0.0007mmol) is placed in microwave bottle with three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar, in glove box
Nitrogen atmosphere protection is lower to be added 0.2mL chlorobenzene.Reaction mixture is heated to 140 degrees Celsius, duration 2 hours by microwave reactor.
Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.Be collected by filtration to obtain solid, then with chloroform into
Special extraction in row Suo Gesi.Solution is by being concentrated by evaporation and settling in methyl alcohol.Solid is done through being obtained by filtration, and in a vacuum
It is dry, finally obtain the polymer (14.6mg, yield 38%) of mulberry solid.
Six-synthon of example DibromoffBT-AAE and corresponding polymer P ffBT4T-AAE
Microwave-assisted polymerization
Monomer DibromoffBT-AAE (35.5mg, 0.015mmol), fluoro- 4, the 7- of 5,6- bis- bis- (5- trimethyl stannyls)
Thiophene -2- base) benzo [c] [1,2,5] thiadiazoles (10.0mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium (0.6mg,
It 0.0007mmol) is placed in microwave bottle with three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar, in glove box
Nitrogen atmosphere protection is lower to be added 0.2mL chlorobenzene.Reaction mixture is heated to 140 degrees Celsius, duration 2 hours by microwave reactor.
Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.Be collected by filtration to obtain solid, then with chloroform into
Special extraction in row Suo Gesi.Solution is by being concentrated by evaporation and settling in methyl alcohol.Solid is done through being obtained by filtration, and in a vacuum
It is dry, finally obtain the polymer (16.5mg, yield 43%) of mulberry solid.
Seven-synthon of example DibromoffBTSe-E, A and corresponding polymer P ffBT4TSe-E, A
Microwave-assisted polymerization
Bis- (the 5- trimethyl first tin of monomer DibromoffBTSe-E, A (26.3mg, 0.015mmol), fluoro- 4, the 7- of 5,6- bis-
Alkane) thiophene -2- base) benzo [c] [1,2,5] thiadiazoles (10.0mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium
(0.6mg, 0.0007mmol) and three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar are placed in microwave tube,
0.2mL chlorobenzene is added under the protection of glove box nitrogen atmosphere.Reaction mixture is heated to 140 degrees Celsius by microwave reactor, when
It is 2 hours long.Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.It is collected by filtration to obtain solid, then
Special extraction in Suo Gesi is carried out with chloroform.Solution is by being concentrated by evaporation and settling in methyl alcohol.Solid is through being obtained by filtration, and true
It is aerial dry, finally obtain the polymer (13.9mg, yield 49%) of mulberry solid.
Example eight-synthesizes related polymer S9 and S17
Synthesize S9
By solution S 1 (406mg, 0.352mmol), tris(dibenzylideneacetone) dipalladium (10mg, 0.02mmol)
It is dissolved in 20mL toluene solution with three (o-methyl-phenyl) phosphorus (22mg, 0.07mmol), and adds in nitrogen atmosphere
Enter S2, is refluxed overnight.The aqueous solution that potassium fluoride is added in mixture is quenched, and is cleaned, diluted with n-hexane, molten with potassium fluoride
Liquid, water and salt water successively clean.After organic layer is dried by sodium sulphate, filters and be concentrated.Reaction residual is mentioned with silica gel chromatographic column
It is pure, red product is obtained, directly uses, does not need further to purify.
After solution S 33 (485mg, 0.267mmol) solution 20mL chloroform, the N- bromo succinyl of zero degrees celsius is added
Imines (178mg, 0.90mmol), reaction is stirred overnight.Organic layer is dry by sodium sulphate after washing, filtering, is concentrated.Reaction is remaining
Object is purified by silica gel chromatographic column, obtains kermesinus S4 product.
Solution S 4 (724mg, 0.62mmol), tris(dibenzylideneacetone) dipalladium (18mg, 0.031mmol) and three are (adjacent
Aminomethyl phenyl) phosphorus (37mg, 0.124mmol) is dissolved in 20mL toluene solution, under nitrogen atmosphere protection, be added S5 (578mg,
1.55mmol), it is refluxed overnight.After reaction, the aqueous solution that potassium fluoride is added in mixture is quenched, and clear with n-hexane
It washes, dilute, successively cleaned with potassium fluoride solution, water and salt water.After organic layer is dried by sodium sulphate, filters and be concentrated.Reaction is surplus
Excess is purified with silica gel chromatographic column, obtains dark red oil S6 product, is directly used, is not needed further to purify.
After solution S 6 (343mg, 0.172mmol) solution 20mL chloroform, it is cooled to zero degrees celsius, and N- bromo fourth is added
Imidodicarbonic diamide (58mg, 0.33mmol), reaction is stirred overnight.After washing, after organic layer is dried by sodium sulphate, filters and be concentrated.
Reaction residual is purified with silica gel chromatographic column, obtains dark red oil S7 product.
Microwave-assisted polymerization
Monomer S7 (79.1mg, 0.037mmol), 4,7- it is bis- (5 "-bromo- 3,4 '-bis- (2- decyl alkyl)-[2,2 ':
5 ', 2 "-thiophene] -5- base) -5,6- difluoro benzo thiophene [c] [1,2,5] oxadiazoles (24.3mg, 0.037mmol), three (two benzal
Benzylacetone) two palladiums (0.6mg, 0.0007mmol) and three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar
It is placed in microwave tube, under the protection of glove box nitrogen atmosphere, 0.2mL chlorobenzene is added.Reaction mixture is heated to by microwave reactor
140 degrees Celsius, duration 2 hours.Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.Solid is with third
Ketone, chloroform and toluene carry out special extraction in Suo Gesi.Polymer finally obtains mulberry solid product after toluene fractionation.
Synthesize S17
By solution S 11 (396mg, 0.347mmol), tris(dibenzylideneacetone) dipalladium (20mg, 0.047mmol) and three
(o-methyl-phenyl) phosphorus (42mg, 0.14mmol) is dissolved in 20mL toluene solution, in nitrogen atmosphere, addition S12 (1250mg,
2.2mmol), it is refluxed overnight.The water-soluble of potassium fluoride is added in mixture to be quenched, and cleaned, diluted with n-hexane, it is molten with potassium fluoride
Liquid, water and salt water successively clean.After organic layer is dried by sodium sulphate, filters and be concentrated.Reaction residual is mentioned with silica gel chromatographic column
It is pure, red S13 product is obtained, directly uses, does not need further to purify.
After solution S 13 (373mg, 0.218mmol) solution 20mL chloroform, it is cooled to zero degrees celsius, and N- bromo is added
Succimide (166mg, 0.93mmol), reaction is stirred overnight.After washing, organic layer is dried, filtered and concentrated by sodium sulphate.
Reaction residual is purified with silica gel chromatographic column, obtains red solid S14 product.
By solution S 14 (364mg, 0.195mmol), tris(dibenzylideneacetone) dipalladium (5.6mg, 0.01mmol) and three
(o-methyl-phenyl) phosphorus (12.0mg, 0.04mmol) is dissolved in 20mL toluene solution, and under nitrogen atmosphere protection, S5 is added
(217mg, 0.584mmol), is refluxed overnight.The aqueous solution that potassium fluoride is added in mixture is quenched, and is cleaned with n-hexane, is dilute
It releases, is successively cleaned with potassium fluoride solution, water and salt water.Organic layer is dry by sodium sulphate, filtering, is concentrated.Organic layer is by sodium sulphate
It is dried, filtered and concentrated.Reaction residual is purified with silica gel chromatographic column, obtains kermesinus S15 product, is directly used, is not needed
Further purification.
After solution S 15 (214mg, 0.114mmol) solution 15mL chloroform, it is cooled to zero degrees celsius, and N- bromo is added
Succimide (38.1mg, 0.38mmol), reaction is stirred overnight.After washing, organic layer is dried, filtered and dense by sodium sulphate
Contracting.Reaction residual is purified with silica gel chromatographic column, obtains dark red solid S16 product.
Microwave-assisted polymerization
Monomer S16 (53mg, 0.026mmol), 4,7- it is bis- (5 "-bromo- 3,4 '-bis- (2- decyl alkyl)-[2,2 ':
5 ', 2 "-thiophene] -5- base) -5,6- difluoro benzo thiophene [c] [2,5] oxadiazoles (12mg, 0.004mmol), three (dibenzylidenes third
Ketone) two palladiums (0.6mg, 0.0007mmol) and three (o-methyl-phenyl) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar be placed in
0.2mL chlorobenzene is added under the protection of glove box nitrogen atmosphere in microwave tube.Reaction mixture is heated to 140 by microwave reactor and takes the photograph
Family name's degree, duration 2 hours.Mixture is cooled to room temperature, and 10ml chlorobenzene is added before settling using methanol.Solid acetone, chlorine
Imitative and toluene carries out special extraction in Suo Gesi.Polymer finally obtains dark blue solid product after toluene fractionation.
Example 9- synthesizes comparative polymer PffBT4T-E
Microwave-assisted polymerization
Monomer DibromoffBT-E (17.2mg, 0.015mmol), 5,5 '-bis- (5- trimethyl stannyl) thiophene -2,2 ' -
Bithiophene (5,7.4mg, 0.015mmol), tris(dibenzylideneacetone) dipalladium (0.6mg, 0.0007mmol) and three (o-methyl-benzenes
Base) phosphorus (1.2mg, 0.004mmol) and magnetic stir bar be placed in microwave tube, 0.2mL is added under the protection of glove box nitrogen atmosphere
Chlorobenzene.Reaction mixture is heated to 140 degrees Celsius, duration 2 hours by microwave reactor.Mixture is cooled to room temperature, makes
10ml chlorobenzene is added before being settled with methanol.Solid then carries out rope with the chloroform of different volumes ratio and acetone by being collected by filtration
Special extraction in Gus.Polymer is finally collected from 100% chloroform and is obtained.The solution of this ratio then passes through distillation and in first
Sedimentation is concentrated in alcohol.Solid is dried in a vacuum through being obtained by filtration, and finally obtains the polymer of mulberry solid
(8.7mg, yield 35%).
1H NMR (400MHz, CDCl3) 68.70 (s, 1H), 7.65 (s, 1H), 7.30 (s, 1H), 4.33 (d, J=5.8Hz,
2H), 1.87 (s, 1H), 1.53-1.24 (m, 32H), 0.96-0.88 (m, 6H) .GPC:Mn:89.4kDa；Mw:181.7kDa；
PDI=2.03.Anal.Calcd for C64H88F2N2O4S5: C, 66.98；H, 7.73；N, 2.44.Found C, 67.02；H,
7.56；N, 2.45.
Example 10- device preparation
Photovoltaic device preparation and measurement
Using about 15 ohm of sheet resistance of ito glass as substrate.Successively in soap deionized water, deionized water, acetone
30 minutes are handled with continuous ultrasound in isopropanol to clean it.After sixty minutes with UV/ ozone treatment, by from ZnO precursor solution
(diethyl zinc) prepares ZnO electron transfer layer with 5000rpm spin coating.Containing the 1,2 of pungent two mercaptan (ODT) of 2.5%1,8-,
Active layer solution (D/A ratio 1:1.5, polymer concentration 9mg/ml) is prepared in 4- trimethylbenzene (TMB).In order to be completely dissolved polymerization
Object should stir active layer solution at least 1 hour on hot plate at 100 DEG C.Before spin coating, by polymer solution and ITO
Substrate all preheats in about 90 DEG C of thermal station.With 1500rpm from the warm polymer on the substrate of preheating in nitrogen glove box
Solution spin coating active layer, with acquisition~120nm thickness.Then by polymer: small molecule receptor blend membrane heat transfer, then
It is transferred in the vacuum chamber of the hot vaporizer in same glove box.3 × 10-6Under the vacuum level of Torr, stringer
The V of (20nm)2O5As anode interlayer, the Al of 100nm is then deposited as top electrodes.All batteries use in glove box
Epoxy resin encapsulation.At room temperature using Newport solar simulator in AM1.5G (100mW/cm2) under positive measurement device J-
V characteristic curve, residence time 2s, speed 0.8V/s.We have also carried out forward and backward scanning and have generated identical result.
Using standard Si diode (using KG5 filter, be purchased from PV Measurement) calibration luminous intensity, reach spectrum mismatch
Unanimously.J-V characteristic is recorded using 236 source instrument pack of Keithley.Device area is 5.9 square millimeters, is determined by metal mask
Justice, aperture are aligned with device area, and the cellar area by certification is 4.18 square millimeters.EQE uses two pole of outfit standard silicon
The Newport EQE system of pipe is characterized.Monochromatic light is generated by Newport 300W lamp source.It provides from 300nm to 850nm
EQE data, calculated Jsc(12.79mA/cm2) suitable with J-V map.In our experiment, it has tested more than 30
Kind device, average efficiency 0.4%.We have also carried out stability analysis, this shows our organic solar batteries two
Quite stable after week, efficiency declines 0.2-0.3%).
11-relevant device parameters of example
Photovoltaic device parameter of the table 1. based on four kinds of polymer: SF-PDI2Blend
The crystallinity of several only polymer of example 12-compares
Fig. 5 is pure PffBT4T-2OD (in figure, referred to as Y5), pure PffBT4T-E (in figure, referred to as G5), PffBT4T-
2OD:SF-PDI2(Y5) GIWAXS map./ .Jsl), PffBT4T-E:SF-PDI2(G5/Jsl), pure PffBT3T-1,2 (
In figure, referred to as S26), pure P3TEA (being referred to as G17 in the figure), PfEBT3T-1,2:SP-PDI2 (S26/Jsl), P3TEA:
SP-PDI2 (G17/Jsl) film, wherein Jsl is the short name of the non-fullerene acceptor SF-PDI2 based on PDI.It may be seen that
(010) peak ratio PffBT4T-20D of PffBT4T-E is more sharp (higher FWHM value), and in pure film and hybrid films peak q
Position is all bigger.As a result, PffBT4T-E shows pi-pi accumulation and crystallinity than PffBT4T-20D enhancing, PffBT4T-20D
There is no carbalkoxy group along polymer chain.For three thiophen polymer P3TEA, the alkyl of half is replaced by carbalkoxy group.?
It in pure/blend film, is compared with PffBT3T-1,2, P3TEA shows more sharp (010) peak and the bigger position q, shows
Stronger crystallinity.These show to have the polymer of alkyl ester base side chain to have higher crystallinity.
Example 13-several polymer base blends object form compares
Fig. 6 shows the R-SoXS spectrum of PffBT4T-20D: SF-PDI2(Y5/Jsl), PffBT4T-E:SF-PDI2G5/
Jsl), PffBT3T-1,2:SP-PDI2 (S26/Jsl) and P3TEA:SP-PDI2(G17/Jsl) four kinds of blend films.For
PffBT4T-20D:SF-PDI2 blend film, average domain size 15.15nm, relative domain purity are 0.3368.Work as steering
When PffBT4T-E:SF-PDI2, the domain sizes of blend membrane increase to 44.48nm, and relative domain purity increases to 0.5699.Four points
One of thiophene system PffBT3T-1,2 and P3TEA the case where be also such.The two systems give such conclusion: esterification
Polymer can form bigger and purer region with small molecule receptor.However, for having 50% alkyl and 50% carbalkoxy
The optimal G17/Jsl mixture of the performance of chain, domain sizes are minimum, and < 10nm, this is unprecedented value for OSC.
Claims (31)
1. a kind of conjugated polymer includes following two unit, unit (I) and unit (II), in which:
In any situation, X is independently selected from Se or S；
M1And M2Independently selected from H or F；
R1And R2From linear paraffin, branched paraffin or cycloalkane independent choice containing 1-40C；
In the polymer chain, the quantitative proportion range of unit (I) and unit (II) is 9:1 to 1:9.
2. conjugated polymer as described in claim 1, it is characterised in that:
M1And M2For H atom；
X is S.
3. conjugated polymer as claimed in claim 2, it is characterised in that: R1And R2It is from the 2- position branching with 4-40C atom
Independent choice in alkyl group.
4. conjugated polymer as claimed in claim 3, it is characterised in that: the average molecular weight of conjugated polymer is minimum
20000 grams every mole.
5. a kind of composition of the conjugated polymer comprising the claim 3, is dissolved or dispersed in liquid medium, when this
For composition from when being cooled to room temperature for 120 DEG C, the composition shows the red shift of at least optical absorption peak of 50nm.
6. a kind of organic photovoltaic devices, comprising the conjugated polymer in the claim 1 as its donor and one or more
Non- fullerene small molecule receptor (SMA) is formed for acceptor blend pattern.
7. organic photovoltaic devices as claimed in claim 6, aforementioned small molecule receptor (SMA) includes to be based on imidodicarbonic diamide
(PDI) structure.
8. organic photovoltaic devices as claimed in claim 6, interior zone size is less than 20nm.
9. a kind of optics comprising the conjugated polymer in claim 1, electronics or photoelectric device.
10. optics as claimed in claim 9, electronics or photoelectric device are organic field effect tube, organic light-emitting transistor
Or organic photovoltaic devices.
11. conjugated polymer as described in claim 1, is selected from:
Wherein, in all of above polymer, R is the independent choice from the position the 2- branched-alkyl group with 4-40C atom.
12. conjugated polymer as described in claim 1, chemical formula are as follows:
Wherein, R is the independent choice from the position the 2- branched-alkyl group with 4-40C atom.
13. a kind of conjugated polymer includes the repetitive unit of one or more chemical formula (I)s, which is contained at least one
Unit (I) and a unit (II):
Wherein:
Ar is the aromatic unit for not being thiophene；
The X independent choice from S or Se in each case；
M1、M2、M3And M4The independent choice from H or F；
R1And R2From linear paraffin, branched paraffin or cycloalkane independent choice containing 1-40C；
In the polymer chain, the quantitative proportion range of unit (I) and unit (II) is 9:1 to 1:9.
14. conjugated polymer as claimed in claim 13, is selected from:
15. conjugated polymer as claimed in claim 12, the conjugated polymer with chemical formula (IA) and chemical formula (IB)
It is as follows:
Wherein:
Ar1 and Ar2 is the aromatic unit for not being thiophene, and Ar1 and Ar2 can identical can also be different；
M5,M6,M7,M8,M8,M10,M11,M12,M13,M14,M15,M16,M17,M18,M19And M20The independent choice from H or F.
16. conjugated polymer as claimed in claim 13, Ar are selected from:
17. conjugated polymer as claimed in claim 13, M1、M2、M3And M4For H atom, X is S atom.
18. conjugated polymer as claimed in claim 13, R1And R2It is from the position the 2- branched-alkyl group with 4-40C atom
Independent choice.
19. conjugated polymer as claimed in claim 18, minimum 20000 grams every mole of average molecular weight.
20. a kind of composition of the conjugated polymer comprising the claim 18, is dissolved or dispersed in liquid medium, when
For the composition from when being cooled to room temperature for 120 DEG C, the composition shows the red shift of at least optical absorption peak of 50nm.
21. a kind of organic photovoltaic devices, comprising the conjugated polymer in the claim 18 as its donor and a kind of or more
The non-fullerene small molecule receptor (SMA) of kind, forms for acceptor blend pattern.
22. organic photovoltaic devices as claimed in claim 21, aforementioned small molecule receptor (SMA) includes to be based on imidodicarbonic diamide
(PDI) structure.
23. organic photovoltaic devices as claimed in claim 21, interior zone size is less than 20nm.
24. a kind of optics comprising the conjugated polymer in claim 18, electronics or photoelectric device.
25. optics as claimed in claim 24, electronics or photoelectric device are organic field effect tube, organic light emission crystal
Pipe or organic photovoltaic devices.
26. a kind of conjugated polymer with chemical formula (II) contains at least one unit (I) and a unit (II):
Wherein:
Ar is the aromatic unit for not being thiophene；
The X independent choice from S or Se in each case；
M1、M2、M3、M4, M5 and the M6 independent choice from H or F；
R1And R2From linear paraffin, branched paraffin or cycloalkane independent choice containing 1-40C；
In the polymer chain, the quantitative proportion range of unit (I) and unit (II) is 9:1 to 1:9.
27. conjugated polymer as claimed in claim 26, is selected from:
Wherein:
M1' selected from H or F；
R1' from linear paraffin, branched paraffin or cycloalkane independent choice containing 2-40C；
M1And M1' can be identical or different；
R1And R1' can be identical or different.
28. conjugated polymer as claimed in claim 26, the conjugated polymer with chemical formula (IIA) is as follows:
Wherein:
R1' from linear paraffin, branched paraffin or cycloalkane independent choice containing 2-40C；
R1And R1' can be identical or different.
29. conjugated polymer as claimed in claim 26, Ar are selected from:
30. such as the conjugated polymer in claim 25, M therein1、M2、M3、M4、M5And M6For H atom, X is S atom.
31. such as the conjugated polymer in claim 25, R therein1And R2It is from the position the 2- branched-alkyl with 4-40C atom
Independent choice in group.
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