CN111961030A - Tetrachlorobithiophene, polymer, synthetic method and application of organic thin film transistor - Google Patents
Tetrachlorobithiophene, polymer, synthetic method and application of organic thin film transistor Download PDFInfo
- Publication number
- CN111961030A CN111961030A CN202010763197.XA CN202010763197A CN111961030A CN 111961030 A CN111961030 A CN 111961030A CN 202010763197 A CN202010763197 A CN 202010763197A CN 111961030 A CN111961030 A CN 111961030A
- Authority
- CN
- China
- Prior art keywords
- tetrachlorobithiophene
- polymer
- compound
- formula
- thin film
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- PVGGJCFWWNCYMP-UHFFFAOYSA-N 2,3,4-trichloro-5-(3-chlorothiophen-2-yl)thiophene Chemical compound ClC1=C(SC=C1)C=1SC(=C(C=1Cl)Cl)Cl PVGGJCFWWNCYMP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000010409 thin film Substances 0.000 title claims abstract description 39
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- -1 tetrachlorobithiophene compound Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 14
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 13
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 12
- QVFXSOFIEKYPOE-UHFFFAOYSA-N 3,4-dichlorothiophene Chemical compound ClC1=CSC=C1Cl QVFXSOFIEKYPOE-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- QSPAEUKIWTXLSC-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li+].CC(C)NC(C)C QSPAEUKIWTXLSC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- QHRVFPPZMPHYHA-UHFFFAOYSA-N bis(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1PC1=CC=CC=C1C QHRVFPPZMPHYHA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000547 conjugated polymer Polymers 0.000 abstract description 18
- 239000000178 monomer Substances 0.000 abstract description 16
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 238000006068 polycondensation reaction Methods 0.000 abstract description 13
- 238000006254 arylation reaction Methods 0.000 abstract description 11
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 238000005227 gel permeation chromatography Methods 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000012546 transfer Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000037230 mobility Effects 0.000 description 14
- 239000012300 argon atmosphere Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000008186 active pharmaceutical agent Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229920001059 synthetic polymer Polymers 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- 229940126214 compound 3 Drugs 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- GMMAPXRGRVJYJY-UHFFFAOYSA-J tetrasodium 4-acetamido-5-hydroxy-6-[[7-sulfonato-4-[(4-sulfonatophenyl)diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].OC1=C2C(NC(=O)C)=CC=C(S([O-])(=O)=O)C2=CC(S([O-])(=O)=O)=C1N=NC(C1=CC(=CC=C11)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 GMMAPXRGRVJYJY-UHFFFAOYSA-J 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- FUTKKEWXZATKHQ-UHFFFAOYSA-N ClC1=C(S(C=C1)(Cl)(Cl)Cl)C=CC=1SC=CC=1 Chemical group ClC1=C(S(C=C1)(Cl)(Cl)Cl)C=CC=1SC=CC=1 FUTKKEWXZATKHQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- AHUQRGHAKJSUKU-UHFFFAOYSA-N 1,4-bis[5-(1-benzofuran-2-yl)thiophen-2-yl]-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound C1=CC=C2OC(C3=CC=C(S3)C3=C4C(=O)N(C(=C4C(=O)N3CC(CC)CCCC)C=3SC(=CC=3)C=3OC4=CC=CC=C4C=3)CC(CC)CCCC)=CC2=C1 AHUQRGHAKJSUKU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- HOCIUAQCKJYCLT-UHFFFAOYSA-N 2-hexyloctan-1-amine Chemical compound CCCCCCC(CN)CCCCCC HOCIUAQCKJYCLT-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 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
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
-
- 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
-
- 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
- C08G61/124—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 nitrogen 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
- 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
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- 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
- 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
- C08G2261/3221—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 nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
-
- 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
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3225—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 Se atoms as the only heteroatom
-
- 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
- C08G2261/92—TFT applications
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to tetrachlorobithiophene, a polymer, a synthetic method and application of an organic thin film transistor. The structural formula of the tetrachlorobithiophene polymer is shown as follows; the tetrachloro bithiophene provided by the invention is a polymerization monomer with high direct arylation polycondensation reaction activity, and is subjected to direct arylation polycondensation reaction with various halogenated aromatic compound monomers to prepare a conjugated polymer. The conjugated polymer obtained by polymerization can be used for preparing organic thin film transistor devices. And the conjugated polymer based on the compound has lower highest unoccupied orbital (LUMO) and highest occupied orbital (HOMO) energy levels, and shows better electron transport (n-type) performance or bipolar transport with the coexistence of electron transport and hole transportThe performance of the filter.
Description
Technical Field
The invention relates to a chlorothiophene compound and synthesis and application of a polymer thereof, belongs to the field of organic semiconductor materials, and particularly relates to tetrachlorobithiophene, a polymer, a synthesis method and application of an organic thin film transistor.
Background
Conjugated polymers are an important class of organic photoelectric functional materials, and can be used for preparing various photoelectric devices, such as Organic Thin Film Transistors (OTFTs), organic photovoltaic devices (OPVs), Organic Light Emitting Diodes (OLEDs), and the like (Mater. chem. front.,2019,3, 1932; Angew. chem. int. Ed.,2019,58, 4442). Among them, research and development of n-type conjugated polymers having electron transport properties and bipolar conjugated polymers having both hole and electron transport properties have been receiving wide attention from researchers, and it is of great importance to develop new n-type and bipolar conjugated polymers and use them in the preparation of OTFTs. n-type and bipolar polymers have lower highest unoccupied orbital (LUMO) and highest occupied orbital (HOMO) energy levels. The introduction of a strong electron-withdrawing group or atom into the main chain of the polymer can effectively reduce the HOMO/LUMO energy level, so that the polymer presents n-type or bipolar characteristics.
The traditional synthetic method of the conjugated polymer is mainly transition metal catalyzed cross coupling polymerization reaction, including Stille coupling polycondensation reaction, Suzuki coupling polycondensation reaction, Kumada coupling polycondensation reaction and the like. The three reactions all need to prepare high-purity aromatic organic metal monomers (aromatic organic tin monomers, aromatic organic boron monomers and Grignard reagents), while the preparation process of the aromatic organic metal reagents is complicated, the stability is poor, the purification is difficult, and the cost is high, particularly the organic tin reagents also have neurotoxicity, so that the defects of multiple steps, high cost, generation of a large amount of harmful byproducts and the like are brought to the cross-coupling polymerization reaction catalyzed by transition metals.
The direct arylation polycondensation reaction is a new method for preparing conjugated polymers developed in recent years, having advantages of few synthesis steps, economical atoms and no generation of harmful by-products (Acta polymeric ica,2019,2, 109). The reaction does not need to prepare an organic metal reagent, and uses brominated aromatic monomer (C-Br monomer for short) and another aromatic monomer (C-H monomer for short) to directly carry out polymerization reaction to prepare the conjugated polymer. Compared with the traditional cross-coupling polymerization catalyzed by transition metal, the method has great advantages. However, the types of C-H monomers capable of undergoing direct arylation polycondensation are few, so that the types of conjugated polymers prepared by the method are few, and the diversified requirements of devices such as OTFTs (organic thin film transistors) cannot be met. Therefore, it is of great importance to develop new direct arylation polycondensation C-H monomers and to prepare new conjugated polymers.
Research shows that the C-H bond reaction activity can be effectively improved by connecting an electron-withdrawing group to the ortho-position of the C-H bond participating in the reaction. Chlorine atoms have strong electron-withdrawing ability, and chlorine substituted thiophene compounds obtained by introducing chlorine atoms into beta positions of thiophene can be used as C-H monomers to carry out direct arylation polycondensation to prepare conjugated polymers. In addition, the introduction of chlorine atoms can effectively reduce the HOMO/LUMO energy level of the polymer, and an n-type or bipolar transmission type conjugated polymer is obtained. Finally, introducing Cl atoms into the main chain of the polymer also brings about weak interaction of Cl … H or Cl … S and the like, improves the planarity of the structure of the polymer chain, promotes the ordered arrangement of the polymer chain, and improves the transmission of electrons and holes. The monomer tetrachloro dithiophene ethylene (application number 202010325552.5) reported by the subject group can be subjected to direct arylation polycondensation to prepare n-type or bipolar transmission type conjugated polymers, and the electron and hole mobility can reach 1.74cm respectively2V.s and 0.85cm2V.s. However, the synthesis of tetrachlorodithienylethylene requires two reactions with a low overall yield. If the chlorine-containing thiophene monomer can be synthesized more simply and more conveniently with high yield, the synthesis steps of the polymer are greatly simplified, the synthesis cost is reduced, and the method has important significance.
Disclosure of Invention
Aiming at the problems of tetrachloro dithiophene ethylene, the invention provides a chloro bithiophene compound which is simpler and more convenient to synthesize and has higher yield, the chloro bithiophene compound is used as a monomer capable of carrying out direct arylation polycondensation reaction, the monomer is used as a raw material to synthesize an n-type or bipolar conjugated polymer by using a direct arylation polycondensation method, and the synthesized polymer is used as a semiconductor material to prepare an organic thin film transistor device.
In order to achieve the purpose, the following technical scheme is adopted:
the invention provides a compound tetrachlorobithiophene shown as a formula (I):
the invention provides a tetrachlorobithiophene polymer shown in (II):
wherein A represents a second copolymerization unit, n is the number of repeating units, and n is in the range of 5 to 50. The structure of A is one of the structures shown in formulas (III) to (X),
wherein R is an alkyl chain, the structure of R is one of the structures shown in formula (XI) or formula (XII),
wherein R is1And R2Are respectively C6～C18Straight alkyl chain of (A), R1And R2May be equal or unequal in number.
The invention provides a preparation method of a tetrachlorobithiophene compound shown in a formula (I), which comprises the following steps:
reacting 3, 4-dichlorothiophene with lithium diisopropylammonium at-45 to-80 ℃ for 30 to 120 minutes by taking tetrahydrofuran as a solvent, adding anhydrous copper chloride, reacting overnight after returning to room temperature, and purifying by column chromatography to obtain the compound tetrachlorobithiophene shown in the formula (I).
In the above steps, 3, 4-dichlorothiophene is used as 1 time of molar weight, and the molar ratio of the 3, 4-dichlorothiophene, lithium diisopropylammonium and anhydrous copper chloride is 1: 0.9 to 1.0: 0.95 to 1.05. Adding tetrahydrofuran solvent to make the concentration of 3, 4-dichlorothiophene be 0.2-2.0 mol/L. The reaction is carried out under nitrogen or argon atmosphere, and tetrahydrofuran is used as a solvent and is dried by heating, refluxing and drying with sodium metal.
The invention provides a preparation method of a tetrachlorobithiophene polymer shown in a formula (II), which comprises the following steps:
1) selecting a pressure-resistant pipe as a reaction container, and sequentially adding tetrachlorobithiophene, a second comonomer A, Herrmann catalyst (trans-di-mum (M) -bis [2- (di-o-tolylphosphine) benzyl ] dipalladium acetate (II)), tri (o-methoxyphenyl) phosphine, pivalic acid and cesium carbonate under an inert atmosphere;
2) adding toluene as a solvent to ensure that the concentration of the tetrachlorobithiophene is 0.01-0.2 mol/L, sealing a pressure-resistant pipe, reacting at the temperature of 110-125 ℃, and stirring and reacting for 5-30 hours in a dark place;
3) cooling to room temperature, dripping the polymer in the pressure-resistant pipe into methanol for settling, performing suction filtration, washing and extracting the polymer obtained by suction filtration with ethanol, acetone and n-hexane respectively by using a Soxhlet extractor, and decompressing the washed polymer to remove the solvent.
In the step 1), tetrachlorobithiophene is used as a 1-fold molar weight, and the molar ratio of the tetrachlorobithiophene to the catalyst A, Herrmann in the second comonomer, tris (o-methoxyphenyl) phosphine, pivalic acid and cesium carbonate is 1: 1: 0.01-0.08: 0.02-0.16: 0.8-3: 2 to 8. The solvent toluene is dried by heating and refluxing with metallic sodium.
The second comonomer A used in the preparation of the tetrachlorobithiophene polymers of the invention is synthesized according to literature reports.
The invention also provides a polymer semiconductor material formed by the tetrachloro bithiophene polymer in the technical scheme.
The invention also provides an organic thin film transistor which adopts a bottom-gate-top contact configuration and sequentially comprises a substrate, a gate electrode, a dielectric layer, a charge transport layer (a semiconductor layer), a metal source electrode and a drain electrode from bottom to top, wherein the charge transport layer is made of the polymer semiconductor material in the technical scheme.
The organic thin film transistor device is coated with silicon dioxide (SiO)2) Of a layerHeavily doped n-type silicon wafer as substrate, gate electrode and dielectric layer, and lower silicon wafer as substrate and gate electrode simultaneously, SiO2The layer is used as a dielectric layer, and the thickness of the dielectric layer is selected from 100nm, 200nm and 300nm, preferably 300 nm; the charge transport layer is made of the polymer semiconductor material, and the thickness of the charge transport layer is 20-120 nm, preferably 30-60 nm; the source electrode and the drain electrode are made of gold and aluminum, preferably gold, and have the thickness of 15-50 nm, preferably 35 nm.
The organic thin film transistor based on the tetrachloro bithiophene polymer has better n-type or bipolar transmission characteristics. Wherein the highest electron and hole mobility of the bipolar organic thin film transistor are respectively 1.79cm2V.s and 0.79cm2The highest electron mobility of the/V.s, n-type organic thin film transistor is 0.90cm2/V·s。
The tetrachlorobithiophene compound provided by the invention has a plurality of chlorine atoms with strong electron-withdrawing property, so that the compound has high direct arylation reaction activity, and is subjected to direct arylation polycondensation with a plurality of second copolymerization units to obtain a conjugated polymer based on tetrachlorobithiophene with higher molecular weight. Also, since the conjugated polymer contains a chlorine atom with strong electron withdrawing property, the polymer has a lower HOMO/LUMO energy level, is favorable for the injection and the transmission of electrons, and shows bipolar or n-type transmission characteristics.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectra of compounds of formula (I).
Fig. 2 is a schematic structural diagram of a bottom-gate top-contact configuration (BGTC) organic thin film transistor provided in the present invention.
FIG. 3(a) shows the gate voltage (V) of the organic thin film transistor according to example 13 of the present inventionGS) A transfer curve graph with the range of-20-80V; FIG. 3(b) is a graph showing the gate voltage (V) of the organic thin film transistor according to example 13 of the present inventionGS) A transfer curve graph with the range of-80-20V; FIG. 3(c) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 13 of the present inventionDS) An output curve chart with the range of 0-80V; FIG. 3(d) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 13 of the present inventionDS) An output profile in the range of 0 to-80V.
FIG. 4(a) is a graph showing the gate voltage (V) of an organic thin film transistor according to example 14 of the present inventionGS) A transfer curve graph with the range of-20-80V; FIG. 4(b) is a graph showing the gate voltage (V) of the organic thin film transistor according to example 14 of the present inventionGS) A transfer curve graph with the range of-80-20V; FIG. 4(c) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 14 of the present inventionDS) An output curve chart with the range of 0-80V; FIG. 4(d) is the drain voltage (V) of the organic thin film transistor according to example 14 of the present inventionDS) An output profile in the range of 0 to-80V.
FIG. 5(a) is a graph showing the gate voltage (V) of an organic thin film transistor according to example 15 of the present inventionGS) A transfer curve graph with the range of-20-80V; FIG. 5(b) is a graph showing the gate voltage (V) of the organic thin film transistor according to example 15 of the present inventionGS) A transfer curve graph with the range of-80-20V; FIG. 5(c) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 15 of the present inventionDS) An output curve chart with the range of 0-80V; FIG. 5(d) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 15 of the present inventionDS) An output profile in the range of 0 to-80V.
FIG. 6(a) is a graph showing the gate voltage (V) of an organic thin film transistor according to example 16 of the present inventionGS) A transfer curve graph with the range of-20-80V; FIG. 6(b) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 16 of the present inventionDS) And the output curve chart is in the range of 0-80V.
FIG. 7(a) is a graph showing the gate voltage (V) of an organic thin film transistor according to example 17 of the present inventionGS) A transfer curve graph with the range of-20-80V; FIG. 7(b) is a graph showing the gate voltage (V) of the organic thin film transistor according to example 17 of the present inventionGS) A transfer curve graph with the range of-80-20V; FIG. 7(c) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 17 of the present inventionDS) An output curve chart with the range of 0-80V; FIG. 7(d) is a graph showing the drain voltage (V) of the organic thin film transistor according to example 17 of the present inventionDS) An output profile in the range of 0 to-80V.
FIG. 8(a) is a graph showing the gate voltage (V) of an organic thin film transistor according to example 18 of the present inventionGS) In the range of-20 to 80V transition profile; FIG. 18 is a graph showing the drain voltage (V) of the organic thin film transistor according to example 18 of the present inventionDS) And the output curve chart is in the range of 0-80V.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail below with reference to the accompanying drawings and examples.
The invention provides a compound tetrachlorobithiophene (shown in a formula (I)) and a synthesis method thereof.
The invention provides a polymer containing tetrachlorobithiophene (shown in a formula (II)) and a synthesis method thereof.
Wherein A represents a second copolymerization unit, n is the number of repeating units, and n is in the range of 5 to 50. The structure of A is one of the structures shown in formulas (III) to (X),
wherein R is an alkyl chain, the structure of R is one of the structures shown in formula (XI) or formula (XII),
wherein R is1And R2Are respectively C6～C18Straight alkyl chain of (A), R1And R2May be equal or unequal in number.
The organic thin film transistor device based on the tetrachloro bithiophene polymer has the structure of Bottom Gate Top Contact (BGTC) and the channel width-length ratio of112. FIG. 2 is a schematic view of a BGTC device construction. 1 is a substrate and a gate electrode, and the material is a heavily doped n-type silicon wafer; 2 is a dielectric layer, which is a silicon dioxide layer attached on the silicon wafer, the thickness is selected from 100nm, 200nm and 300nm, preferably 300nm, the capacitance is 10nF/cm2(ii) a 3 is a charge transport layer, also called a semiconductor layer, which is a film prepared by the tetrachloro bithiophene polymer provided by the invention, and the thickness of the film is 20-120 nm, preferably 30-60 nm; 4, a source electrode is made of gold and aluminum, preferably gold, and has the thickness of 15-50 nm, preferably 35 nm; 5 is a drain electrode, the material is selected from gold and aluminum, preferably gold, and the thickness is 15-50 nm, preferably 35 nm. The source and drain electrodes (4, 5) are deposited by thermal evaporation.
The tetrachloro bithiophene polymer provided by the invention is deposited to form a film as a charge transport layer 3 by a solution method, and the specific method adopts a solution spin coating method, and comprises the following operation steps: 1) preparing a polymer solution: the polymer semiconductor material prepared by the method is dissolved in chloroform, chlorobenzene and o-dichlorobenzene as solvents, wherein o-dichlorobenzene is preferably selected, and the concentration of the o-dichlorobenzene is 2-8 mg/mL, and 4mg/mL is preferably selected; 2) preparing a film by a spin-coating method: coating the surface with silicon dioxide (SiO)2) And fixing the heavily doped n-type silicon wafer substrate on a spin coater, coating the polymer solution on the silicon wafer, and starting spin coating at the spin coating speed of 600-3000 rpm, preferably 1000rpm, for 60-200 seconds, preferably 90 seconds. 3) After the spin coating is finished, the silicon wafer with the polymer semiconductor layer attached to the surface is subjected to thermal annealing treatment to remove residual solvent molecules, promote the thermal motion of polymer molecules and enhance the ordering of molecular arrangement, so that the charge transport capability of the film is improved. The thermal annealing temperature is 80-280 ℃, preferably 150-230 ℃, and the annealing time is 5-20 minutes, preferably 10 minutes. The above processes are all carried out under an inert atmosphere.
The invention will be further illustrated with reference to specific examples.
Example 1: synthesis of the Compound Tetrachlorobithiophene (formula (I))
3, 4-dichlorothiophene (2.0g, 13.1mmol) was dissolved in 12mL of tetrahydrofuran, and a diisopropylammoniumbithium solution (12.4mL, 12.4mmol, 1.0mol/L) was added dropwise at-65 ℃ for reaction for 75 minutes, followed by addition of copper chloride (1.76g, 13.1mmol), warmed to room temperature, and reacted overnight. The reaction mixture was quenched with water, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and then separated with a silica gel column (eluent: petroleum ether), and the obtained solid was recrystallized from n-hexane to give a white solid (compound represented by formula (I)) (0.60g, yield: 30%).1H NMR(CDCl3400MHz, ppm): 7.35(s, 2H). The nuclear magnetic hydrogen spectrum is shown in FIG. 1.
Example 2: synthesis of the Compound Tetrachlorobithiophene (formula (I))
3, 4-dichlorothiophene (2.0g, 13.1mmol) was dissolved in 65mL of tetrahydrofuran, and a diisopropylammoniumbithium solution (11.8mL, 11.8mmol, 1.0mol/L) was added dropwise at-45 ℃ for reaction for 30 minutes, followed by addition of copper chloride (1.67g, 12.4mmol), warming to room temperature, and reaction overnight. The reaction mixture was quenched with water, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and then separated with a silica gel column (eluent: petroleum ether), and the obtained solid was recrystallized from n-hexane to give a white solid (compound represented by formula (I)) (0.54g, yield: 27%).1H NMR(CDCl3400MHz, ppm): 7.35(s, 2H). The nuclear magnetic hydrogen spectrum is shown in FIG. 1.
Example 3: synthesis of the Compound Tetrachlorobithiophene (formula (I))
3, 4-Dichlorothiophene (2.0g, 13.1mmol) was dissolved in 6.5mL of tetrahydrofuran, and a diisopropylammoniumbithium solution (13.1mL, 13.1mmol, 1.0mol/L) was added dropwise at-80 deg.C for 120 minutes, followed by addition of copper chloride(1.85g, 13.7mmol), warmed to room temperature and reacted overnight. The reaction mixture was quenched with water, extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and then separated with a silica gel column (eluent: petroleum ether), and the obtained solid was recrystallized from n-hexane to give a white solid (compound represented by formula (I)) (0.56g, yield: 28%).1H NMR(CDCl3400MHz, ppm): 7.35(s, 2H). The nuclear magnetic hydrogen spectrum is shown in FIG. 1.
Example 4: synthetic Polymer P1
In a 50mL pressure-resistant polymerization tube, the compound 3, 6-bis (5-bromothien-2-yl) -2, 5-bis (4-hexyldodecyl) pyrrolo [3,4-c ] was added in sequence]Pyrrole-1, 4- (2H,5H) -dione (158.4mg,1eq, 164.5 μmol) (synthesis methods refer to literature reports adv.sci.,2019,6,1902412), tetrachlorobithiophene (compound of formula (I)) (50.0mg,1eq, 164.5 μmol), Herrmann catalyst (1.5mg,0.01eq, 1.6 μmol), tris (o-methoxyphenyl) phosphine (1.2mg,0.02eq,3.3 μmol), pivalic acid (13.4mg,0.8eq, 131.6 μmol), and cesium carbonate (107.2mg,2eq, 328.9 μmol). 16.4mL of toluene (0.01mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was heated at 110 ℃ for 5 hours with stirring. After cooling to room temperature, the polymer in the pressure-resistant tube was dropped into methanol for settling, suction filtration was performed, the polymer obtained by suction filtration was washed and extracted with ethanol, acetone, and n-hexane, respectively, using a Soxhlet extractor, and the solvent was removed under reduced pressure to obtain 167.5mg of a brilliant black polymer film with a yield of 92%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝32kDa,
Example 5: synthetic Polymer P2
In a 50mL pressure-resistant polymerization tubeIn the reaction solution, the compound 3, 6-di (5-bromothiophene-2-yl) -2, 5-di (4-tetradecyl octadecyl) pyrrolo [3,4-c ] is added in sequence]Pyrrole-1, 4- (2H,5H) -dione (223.0mg,1eq., 164.5. mu. mol) (synthetic methods refer to literature reports: Macromolecules,2018,51,8752), tetrachlorobithiophene (compound of formula (I)) (50.0mg,1eq., 164.5. mu. mol), Herrmann catalyst (3.1mg,0.02eq, 3.3. mu. mol), tris (o-methoxyphenyl) phosphine (2.3mg,0.04eq, 6.6. mu. mol), pivalic acid (16.8mg,1eq., 164.5. mu. mol) and cesium carbonate (160.8mg,3eq., 493.4. mu. mol). 8.2mL of toluene (0.02mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was stirred and heated at 120 ℃ for 12 hours. After cooling to room temperature, the polymer in the pressure-resistant tube was dropped into methanol for settling, suction filtration was performed, the polymer obtained by suction filtration was washed and extracted with ethanol, acetone, and n-hexane, respectively, using a Soxhlet extractor, and the solvent was removed under reduced pressure to obtain 234.4mg of a brilliant black polymer film with a yield of 95%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝39kDa,
Example 6: synthetic Polymer P3
The compound 3, 6-di (5-bromoselenophen-2-yl) -2, 5-di (4-tetradecyl octadecyl) pyrrolo [3,4-c ] is sequentially added into a 50mL pressure-resistant polymerization tube]Pyrrole-1, 4- (2H,5H) -dione (238.4mg,1eq.,164.5 μmol), tetrachlorobithiophene (compound of formula (I)) (50.0mg,1eq.,164.5 μmol), Herrmann catalyst (12.3mg,0.08eq, 13.1 μmol), tris (o-methoxyphenyl) phosphine (9.3mg,0.16eq,26.3 μmol), pivalic acid (50.4mg,3eq.,493.4 μmol) and cesium carbonate (428.7mg,8eq.,1.32 mmol). 8.2mL of toluene (0.02mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was stirred and heated at 125 ℃ for 30 hours. Cooling to room temperature, dripping the polymer in a pressure-resistant tube into methanol for settling, performing suction filtration, washing and extracting the polymer obtained by suction filtration with ethanol, acetone and n-hexane respectively by using a Soxhlet extractor, and removing the solvent under reduced pressure to obtain the productThe black polymer film was 251.6mg, 96% yield. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝42kDa,
The compound 3, 6-bis (5-bromoselenophen-2-yl) -2, 5-bis (4-tetradecanooctadecyloxy) pyrrolo [3,4-c ] pyrrole-1, 4- (2H,5H) -dione used in this example was synthesized according to the reaction conditions reported in the literature (Macromolecules,2018,51,8752), and the specific steps are as follows, and are divided into steps 1) and 2):
step 1):
under inert atmosphere, the compound 3, 6-di (selenophen-2-yl) -pyrrolo [3,4-c]Pyrrole-1, 4- (2H,5H) -dione (788.3mg,2.0mmol), 1-iodo-4-tetradecanoyl octadecyl (2.88g,5.0mmol), potassium carbonate (829.2mg,6.0mmol) and 18-crown-6 (10mg, 37.8. mu. mol) were dissolved in dry N, N-Dimethylformamide (DMF) (20mL) and reacted at 120 ℃ for 48 hours. After cooling to room temperature, DMF was removed under reduced pressure, and the solid residue was extracted with chloroform, dried over anhydrous magnesium sulfate, filtered and spin-dried. Purifying the crude product by silica gel column chromatography (eluent is petroleum ether: dichloromethane: 1:2, volume ratio) to obtain deep red solid 3, 6-di (selenophen-2-yl) -2, 5-di (4-tetradecyl octadecyl) pyrrolo [3, 4-c)]Pyrrole-1, 4- (2H,5H) -dione (1.11g, yield: 43%).1H NMR(CDCl3400MHz, ppm): 8.88(dd,2H),8.39(dd,2H),7.50(dd,2H),3.98(t,4H), 1.72(s,4H),1.40-1.11(m,110H), 0.88(t, 12H). Step 2):
under inert atmosphere, the compound 3, 6-di (selenophen-2-yl) -2, 5-di (4-tetradecyl octadecyl) pyrrolo [3,4-c]Pyrrole-1, 4- (2H,5H) -dione (516.7mg,0.4mmol), N-bromosuccinimide (145.9mg,0.82mmol) was dissolved in chloroform (30mL) at 0 deg.C, returned to room temperature, and stirred overnight. The reaction was quenched with water, extracted with chloroform, dried over anhydrous magnesium sulfate, filtered and spin-dried. Subjecting the crude product to silica gel column chromatography (eluent is petroleum ether: dichloromethane: 1)Volume ratio) to obtain the mauve solid 3, 6-di (5-bromoselenophen-2-yl) -2, 5-di (4-tetradecyl octadecyl) pyrrolo [3, 4-c)]Pyrrole-1, 4- (2H,5H) -dione (394.3mg, yield: 68%).1H NMR(CDCl3，400MHz，ppm)：8.47(d,J＝4.4Hz,2H),7.42(d,J＝4.4Hz,2H),3.98(t,4H)，1.72(s,4H),1.40-1.11(m,110H)，0.88(t,12H)。
Example 7: synthetic Polymer P4
In a 50mL pressure-resistant polymerization tube, the compound 3, 6-bis (5-bromopyridin-2-yl) -2, 5-bis (4-tetradecanooctadecyl) pyrrolo [3,4-c ] was added in this order]Pyrrole-1, 4- (2H,5H) -dione (221.3mg,1eq., 164.5. mu. mol) (synthesis methods are reported: adv. Funct. Mater.,2018,1801097), tetrachlorobithiophene (compound of formula (I)) (50.0mg,1eq., 164.5. mu. mol), Herrmann catalyst (3.1mg,0.02 eq., 3.3. mu. mol), tris (o-methoxyphenyl) phosphine (2.3mg,0.04 eq., 6.6. mu. mol), pivalic acid (16.8mg,1eq., 164.5. mu. mol) and cesium carbonate (160.8mg,3eq., 493.4. mu. mol). 8.2mL of toluene (0.02mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was heated with stirring at 120 ℃ for 24 hours. After cooling to room temperature, the polymer in the pressure-resistant tube was dropped into methanol for settling, suction filtration was carried out, the polymer obtained by suction filtration was washed and extracted with ethanol, acetone and n-hexane respectively by a Soxhlet extractor, and the solvent was removed under reduced pressure to obtain 231.3mg of a brilliant black polymer film with a yield of 94%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝51kDa,
Example 8: synthetic Polymer P5
In a 50mL pressure-resistant polymerization tube, the compound 1, 1' -bis (4-octadecyldialkyl) was added in this order) -6, 6' -dibromoisoindigo (253.6mg,1eq.,164.5 μmol) (synthetic methods refer to patent reports: pelamidol, a branched alkyl chain and its preparation and use in organic conjugated molecules, CN102775273A), tetrachlorobithiophene (compound of formula (I) (50.0mg,1eq., 164.5. mu. mol), Herrmann catalyst (3.1mg,0.02eq, 3.3. mu. mol), tris (o-methoxyphenyl) phosphine (2.3mg,0.04eq, 6.6. mu. mol), pivalic acid (16.8mg,1eq., 164.5. mu. mol) and caesium carbonate (160.8mg,3eq., 493.4. mu. mol). 8.2mL of toluene (0.02mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was heated with stirring at 120 ℃ for 24 hours. After cooling to room temperature, the polymer in the pressure-resistant tube was dropped into methanol for settling, suction filtration was performed, the polymer obtained by suction filtration was washed and extracted with ethanol, acetone, and n-hexane, respectively, using a Soxhlet extractor, and the solvent was removed under reduced pressure to obtain 257.4mg of a brilliant black polymer film with a yield of 93%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝52kDa,
Example 9: synthetic Polymer P6
In a 50mL pressure resistant polymerization tube, the compound 1,1 ' -bis (4-tetradecanooctadecyl) -6,6 ' -dibromo-7, 7 ' -difluoroisoindigo (222.6mg,1eq., 164.5. mu. mol) (synthesis method reported in Adv. Mater.,2017,29,1606217), tetrachlorobithiophene (compound represented by formula (I)) (50.0mg,1eq., 164.5. mu. mol), Herrman catalyst (3.1mg,0.02eq, 3.3. mu. mol), tris (o-methoxyphenyl) phosphine (2.3mg,0.04eq, 6.6. mu. mol), pivalic acid (16.8mg,1eq., 164.5. mu. mol), and cesium carbonate (160.8mg,3eq., 493.4. mu. mol) were sequentially added. 8.2mL of toluene (0.02mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was heated with stirring at 120 ℃ for 24 hours. Cooling to room temperature, dripping the polymer in a pressure-resistant tube into methanol for settling, performing suction filtration, washing and extracting the polymer obtained by suction filtration with ethanol, acetone and n-hexane respectively by using a Soxhlet extractor, and removing the solvent under reduced pressure to obtain brilliant blackPolymer film 225.5mg, yield 92%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝77kDa,
Example 10: synthetic Polymer P7
In a 50mL pressure resistant polymerization tube, the compound N, N' -bis (2-octyldodecyl) -2, 6-dibromo-1, 4,5, 8-naphthalene diimide (162.0mg,1eq., 164.5. mu. mol) (synthesis method reported in J.Am.Chem.Soc.,2009,131,8), tetrachlorobithiophene (compound represented by formula (I)) (50.0mg,1eq., 164.5. mu. mol), Herrmann catalyst (3.1mg,0.02eq, 3.3. mu. mol), tris (o-methoxyphenyl) phosphine (2.3mg,0.04eq, 6.6. mu. mol), pivalic acid (16.8mg,1eq., 164.5. mu. mol), and cesium carbonate (160.8mg,3eq., 493.4. mu. mol) were sequentially added. 8.2mL of toluene (0.02mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was heated with stirring at 120 ℃ for 24 hours. After cooling to room temperature, the polymer in the pressure-resistant tube was dropped into methanol for settling, suction filtration was performed, the polymer obtained by suction filtration was washed and extracted with ethanol, acetone, and n-hexane, respectively, using a Soxhlet extractor, and the solvent was removed under reduced pressure to obtain a brilliant black polymer film 171.4mg, with a yield of 92%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝40kDa,
Example 11: synthetic Polymer P8
The compound N, N' -bis (2-decyltetradecyl) -1, 7-dibromo-3, 4: 9.10-perylene diimide (200.9mg,1eq., 164.5. mu. mol) (the synthesis method is reported in the literature: Macromolecules,2012,45,4115) and tetrakis-shell are sequentially added into a 50mL pressure-resistant polymerization tubeChlorobithiophene (compound of formula (I)) (50.0mg,1eq.,164.5 μmol), Herrmann catalyst (3.1mg,0.02eq, 3.3 μmol), tris (o-methoxyphenyl) phosphine (2.3mg,0.04eq,6.6 μmol), pivalic acid (16.8mg,1eq.,164.5 μmol) and cesium carbonate (160.8mg,3eq.,493.4 μmol). 8.2mL of toluene (0.02mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was heated with stirring at 120 ℃ for 24 hours. After cooling to room temperature, the polymer in the pressure-resistant tube was dropped into methanol for settling, suction filtration was performed, the polymer obtained by suction filtration was washed and extracted with ethanol, acetone, and n-hexane, respectively, using a Soxhlet extractor, and the solvent was removed under reduced pressure to obtain 215.6mg of a brilliant black polymer film with a yield of 96%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝39kDa,
Example 12: synthetic Polymer P9
In a 10mL pressure-resistant polymerization tube, the compound 2, 8-dibromo-5- (2-hexyloctylalkyl) thieno [3,4-c ] was added in this order]Pyrrole-4, 6-dione (83.4mg,1eq.,164.5 μmol), tetrachlorobithiophene (compound of formula (I)) (50.0mg,1eq.,164.5 μmol), Herrmann catalyst (3.1mg,0.02eq, 3.3 μmol), tris (o-methoxyphenyl) phosphine (2.3mg,0.04eq,6.6 μmol), pivalic acid (16.8mg,1eq.,164.5 μmol) and cesium carbonate (160.8mg,3eq.,493.4 μmol). 0.8mL of toluene (0.2mol/L) was added under an argon atmosphere, the reaction tube was closed, and the mixture was heated with stirring at 120 ℃ for 24 hours. After cooling to room temperature, the polymer in the pressure-resistant tube was dropped into methanol for settling, suction filtration was performed, the polymer obtained by suction filtration was washed and extracted with ethanol, acetone, and n-hexane, respectively, using a Soxhlet extractor, and the solvent was removed under reduced pressure to obtain a brilliant black polymer film of 99.6mg in a yield of 93%. The structural characterization data is as follows: gel Permeation Chromatography (GPC): mn＝35kDa,
The compound 2, 8-dibromo-5- (2-hexyloctylalkyl) thieno [3,4-c ] pyrrole-4, 6-dione used in this example was synthesized according to the reaction conditions reported in the literature (angew. chem. int. ed.,2016,55,12996) by the following specific steps:
under inert atmosphere, the compound 2, 5-dibromo thieno [3,4-c]Furan-4, 6-dione (1.46g,4.68mmol) and 2-hexyl-1-octylamine (1.05g,4.91mmol) were dissolved in 25mL of dry tetrahydrofuran, and the mixture was stirred at 50 ℃ for 3 hours, and after recovering substances were removed under reduced pressure, 8mL of thionyl chloride was added and the mixture was stirred at 50 ℃ for 4 hours. The reaction solution was dropped into water and methanol to quench and settle, and the solid was filtered and purified by silica gel column chromatography (eluent n-hexane: ethyl acetate 10: 1, volume ratio) to give the product (1.40g, yield: 59%).1H NMR(CDCl3，400MHz，ppm)：3.49(d,2H),1.82(m,1H),1.30-1.20(m,20H),0.88(t,6H)。
Examples 13 to 18:
the substrate is a heavily doped n-type silicon wafer with 300nm silicon dioxide attached to the surface, the silicon wafer is used as a gate electrode, a silicon dioxide layer is used as a dielectric layer, the polymers P1-P6 described in the embodiments 4-9 are used as semiconductor materials, an o-dichlorobenzene solution with the concentration of 4mg/mL is prepared from the polymers P1-P6, spin coating operation is carried out in an argon atmosphere glove box, the rotating speed of a spin coater is 1000rpm, the spin coating time is 90 seconds, and the thickness of a film prepared by spin coating is 30-60 nm. And then carrying out thermal annealing treatment on the semiconductor layer, wherein the annealing temperature is 200 ℃, and the annealing time is 10 minutes. And preparing gold (Au) with the thickness of 35nm as a source/drain electrode of the OTFT device by adopting a vacuum evaporation method. The carrier mobilities of the OTFT devices are listed in table 1:
TABLE 1 measurement results of the Properties of thin film transistors prepared based on polymers P1 to P6
In the inventive example 13, the polymer P1 in example 4 is used as a charge transport layer material, and the prepared OTFT device shows bipolar transport performance, and the hole and electron mobilities are respectively 0.50 and 1.12cm2The transfer curves of the devices are shown in FIGS. 3(a) and 3(b), and the output curves are shown in FIGS. 3(c) and 3 (d). In example 14 of the invention, the polymer P2 in example 5 is used as a charge transport layer material, and the prepared OTFT device shows bipolar transport performance, and the hole and electron mobilities are respectively 0.79 and 1.75cm2The transfer curves of the devices are shown in FIGS. 4(a) and 4(b), and the output curves are shown in FIGS. 4(c) and 4 (d). In example 15 of the invention, the polymer P3 in example 6 is used as a charge transport layer material, and the prepared OTFT device shows bipolar transport performance, and the hole mobility and the electron mobility of the OTFT device are respectively 0.71 cm and 1.79cm2The transfer curves of the devices are shown in FIGS. 5(a) and 5(b), and the output curves are shown in FIGS. 5(c) and 5 (d). In the embodiment 16 of the invention, the polymer P4 in the embodiment 7 is used as a charge transport layer material, and the prepared OTFT device shows n-type transport performance, and the electron mobility of the OTFT device is 0.90cm2The transfer curve of the device is shown in FIG. 6(a), and the output curve is shown in FIG. 6 (b). In the inventive example 17, the polymer P5 in example 8 was used as the charge transport layer material, and the prepared OTFT device showed bipolar transport performance, with hole and electron mobilities of 0.21 and 0.77cm respectively2The transfer curves of the devices are shown in FIGS. 7(a) and 7(b), and the output curves are shown in FIGS. 7(c) and 7 (d). In the embodiment 18 of the invention, the polymer P6 in the embodiment 9 is used as a charge transport layer material, and the prepared OTFT device shows n-type transport performance, and the electron mobility of the OTFT device is 0.62cm2The transfer curve of the device is shown in FIG. 8(a), and the output curve is shown in FIG. 8 (b).
Compared with the tetrachloro bithiophene ethylene compound reported in the patent application No. 202010325552.5, the synthesis steps of the compound tetrachloro bithiophene provided by the invention are simpler. Compared with tetrachloro dithiophene ethylene polymer, the tetrachloro dithiophene polymer provided by the invention has slightly improved performance of an organic thin film transistor. The mobility of the organic thin film transistors described in examples 14 and 15 above is higher than that of the corresponding tetrachlorodithienylethylene polymer having the same second copolymerization unit (application No. 202010325552.5). The mobility values described in examples 16, 18 are essentially the same as the mobility of the corresponding tetrachlorodithienylethylene polymer in the patent application No. 202010325552.5.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A tetrachlorobithiophene compound; the structure is characterized in that:
the tetrachlorobithiophene is shown as (I):
2. a tetrachlorobithiophene polymer obtained by polymerizing the compound of claim 1, characterized in that the tetrachlorobithiophene polymer is represented by the formula (II):
wherein A represents a second copolymerization unit, n is the number of repeating units, and n is a natural number of 5 to 50.
3. The polymer of claim 2, wherein A is one of the structures of formula (III) to formula (X),
wherein R is alkanyl, and the structure of R is shown in one of formula (XI) or formula (XII):
wherein R is1And R2Are respectively C6～C18Straight alkyl chain of (A), R1And R2Equal or unequal in number of carbon atoms.
4. A process for the preparation of the compound tetrachlorobithiophene according to claim 1, characterized by comprising the steps of:
reacting 3, 4-dichlorothiophene with lithium diisopropylammonium at-45 to-80 ℃ for 30 to 120 minutes by taking tetrahydrofuran as a solvent, adding anhydrous copper chloride, reacting overnight after returning to room temperature, and purifying by column chromatography to obtain the compound tetrachlorobithiophene shown in the formula (I).
5. The method according to claim 4, wherein the molar ratio of 3, 4-dichlorothiophene to lithium diisopropylammonium to anhydrous copper chloride in the step of using 3, 4-dichlorothiophene as a 1-fold molar amount is 1: 0.9 to 1.0: 0.95 to 1.05. Adding tetrahydrofuran solvent to make the concentration of 3, 4-dichlorothiophene be 0.2-2.0 mol/L.
6. A process for the preparation of tetrachlorobithiophene polymers according to claim 2, characterized by comprising the steps of:
1) the reaction vessel is a pressure-resistant pipe, and tetrachlorobithiophene, a second comonomer A, Herrmann catalyst (trans-di-mum (M) -bis [2- (di-o-tolylphosphine) benzyl ] dipalladium (II) acetate), tri (o-methoxyphenyl) phosphine, pivalic acid and cesium carbonate are sequentially added under inert atmosphere;
2) adding toluene as a solvent to ensure that the concentration of the tetrachlorobithiophene is 0.01-0.2 mol/L, sealing a pressure-resistant pipe, reacting at the temperature of 110-125 ℃, and stirring and reacting for 5-30 hours in a dark place;
3) cooling to room temperature, dripping the polymer in the pressure-resistant pipe into methanol for settling, performing suction filtration, washing and extracting the polymer obtained by suction filtration with ethanol, acetone and n-hexane respectively by using a Soxhlet extractor, and decompressing the washed polymer to remove the solvent.
7. The method as set forth in claim 6, characterized in that in the step 1), tetrachlorobithiophene is used in a 1-fold molar amount, and tetrachlorobithiophene, the second comonomer A, Herrmann catalyst, tris (o-methoxyphenyl) phosphine, pivalic acid and cesium carbonate are used in a molar ratio of 1: 1: 0.01-0.08: 0.02-0.16: 0.8-3: 2 to 8.
8. Use of the tetrachlorobithiophene polymers according to claim 2 in semiconductor materials.
9. The tetrachlorobithiophene polymer of claim 2, which is used as a bipolar transport or n-type transport material for organic thin film transistor devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010763197.XA CN111961030A (en) | 2020-07-31 | 2020-07-31 | Tetrachlorobithiophene, polymer, synthetic method and application of organic thin film transistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010763197.XA CN111961030A (en) | 2020-07-31 | 2020-07-31 | Tetrachlorobithiophene, polymer, synthetic method and application of organic thin film transistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111961030A true CN111961030A (en) | 2020-11-20 |
Family
ID=73363234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010763197.XA Pending CN111961030A (en) | 2020-07-31 | 2020-07-31 | Tetrachlorobithiophene, polymer, synthetic method and application of organic thin film transistor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111961030A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940228A (en) * | 2021-01-14 | 2021-06-11 | 中国科学院长春应用化学研究所 | Polythiophene conjugated polymer containing electron withdrawing substituent, preparation method and application |
| CN113881019A (en) * | 2021-10-18 | 2022-01-04 | 福州大学 | 2-indolone-based polymer donor material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750196A (en) * | 2017-01-06 | 2017-05-31 | 天津大学 | Electron-transporting type polymer and organic field effect tube based on bioxindol derivative |
| CN108690183A (en) * | 2018-05-10 | 2018-10-23 | 天津大学 | The electron-transporting type polymer semiconducting material based on pyridine substituted azole and pyrroledione applied to organic field effect tube |
-
2020
- 2020-07-31 CN CN202010763197.XA patent/CN111961030A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750196A (en) * | 2017-01-06 | 2017-05-31 | 天津大学 | Electron-transporting type polymer and organic field effect tube based on bioxindol derivative |
| CN108690183A (en) * | 2018-05-10 | 2018-10-23 | 天津大学 | The electron-transporting type polymer semiconducting material based on pyridine substituted azole and pyrroledione applied to organic field effect tube |
Non-Patent Citations (5)
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940228A (en) * | 2021-01-14 | 2021-06-11 | 中国科学院长春应用化学研究所 | Polythiophene conjugated polymer containing electron withdrawing substituent, preparation method and application |
| WO2022151675A1 (en) * | 2021-01-14 | 2022-07-21 | 中国科学院长春应用化学研究所 | Polythiophene conjugated polymer containing electron-withdrawing substituent, preparation method therefor and use thereof |
| CN112940228B (en) * | 2021-01-14 | 2023-11-28 | 中国科学院长春应用化学研究所 | Polythiophene conjugated polymer containing electron-withdrawing substituent, preparation method and application |
| CN113881019A (en) * | 2021-10-18 | 2022-01-04 | 福州大学 | 2-indolone-based polymer donor material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001233B (en) | Double S, S dioxydibenze bithiophene and five-membered ring monomer and preparation method thereof and polymer | |
| KR101601362B1 (en) | Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device | |
| KR101340737B1 (en) | Copolymer, organic solar cell using the same and manufacturing method thereof | |
| Qian et al. | Synthesis and study of low-bandgap polymers containing the diazapentalene and diketopyrrolopyrrole chromophores for potential use in solar cells and near-infrared photodetectors | |
| EP2774940A1 (en) | Method for producing conjugated polymer, conjugated polymer, photoelectric conversion element, solar cell, and solar cell module | |
| Donaghey et al. | Pyrroloindacenodithiophene containing polymers for organic field effect transistors and organic photovoltaics | |
| Ashraf et al. | Fused ring thiophene-based poly (heteroarylene ethynylene) s for organic solar cells | |
| EP2581399B1 (en) | Conjugated polymer based on perylene tetracarboxylic acid diimide and benzodithiophene and its preparation method and application | |
| CA2844439C (en) | Process for the preparation of polymers containing benzohetero[1,3]diazole units | |
| Wu et al. | Star-Shaped Fused-Ring Electron Acceptors with a C 3 h-Symmetric and Electron-Rich Benzotri (cyclopentadithiophene) Core for Efficient Nonfullerene Organic Solar Cells | |
| Wu et al. | (Z)-(Thienylmethylene) oxindole-based polymers for high-performance solar cells | |
| CN111961030A (en) | Tetrachlorobithiophene, polymer, synthetic method and application of organic thin film transistor | |
| WO2017212961A1 (en) | Boron-containing polymer and use thereof | |
| Zhan et al. | Synthesis, characterization and photovoltaic properties of platinum-containing poly (aryleneethynylene) polymers with electron-deficient diketopyrrolopyrrole unit | |
| CN110041508B (en) | Star-shaped conjugated structure polymer and preparation method and application thereof | |
| Kim et al. | Molecular design and ordering effects of alkoxy aromatic donor in a DPP copolymer on OTFTs and OPVs | |
| Agneeswari et al. | Effects of the incorporation of an additional pyrrolo [3, 4-c] pyrrole-1, 3-dione unit on the repeating unit of highly efficient large band gap polymers containing benzodithiophene and pyrrolo [3, 4-c] pyrrole-1, 3-dione derivatives | |
| Chen et al. | Donor–acceptor photovoltaic polymers based on 1, 4‐dithienyl‐2, 5‐dialkoxybenzene with intramolecular noncovalent interactions | |
| CN111518074A (en) | Tetrachlorodithiophene ethylene, polymer, synthetic method and application of organic thin film transistor | |
| JP2017119805A (en) | Method for producing conjugated polymer having specific thienothiophene-benzodithiophene as unit segment | |
| CN110872376B (en) | Cyclized indigo receptor and polymer as well as preparation method and application thereof | |
| CN114621251B (en) | Condensed ring unit based on quinoxaline derivative, small molecule and polymer containing same, and preparation methods and applications thereof | |
| Liu et al. | Tuning terminal units to improve the photovoltaic performance of small molecules based on a large planar fused-ring core in solution-processed organic solar cells | |
| Sharma et al. | Direct arylation polymerization approach for the synthesis of narrow band gap cyclopentadithiophene based conjugated polymer and its application in solar cell devices | |
| CN109749058B (en) | Anthracene bithiophene imide polymer and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201120 |
|
| RJ01 | Rejection of invention patent application after publication |