CN108727566B - 一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 - Google Patents
一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 Download PDFInfo
- Publication number
- CN108727566B CN108727566B CN201810358163.5A CN201810358163A CN108727566B CN 108727566 B CN108727566 B CN 108727566B CN 201810358163 A CN201810358163 A CN 201810358163A CN 108727566 B CN108727566 B CN 108727566B
- Authority
- CN
- China
- Prior art keywords
- compound
- polymer material
- added
- synthesis
- reaction
- 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.)
- Active
Links
- 239000002861 polymer material Substances 0.000 title claims abstract description 36
- XLXWAFSNXPPDAB-UHFFFAOYSA-N anthracene;9h-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1.C1=CC=CC2=CC3=CC=CC=C3C=C21 XLXWAFSNXPPDAB-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 230000005525 hole transport Effects 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000003860 storage Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical class CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 claims description 2
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 claims description 2
- NJPMFDNZCLKTHE-UHFFFAOYSA-N 2-dodecylthiophene Chemical compound CCCCCCCCCCCCC1=CC=CS1 NJPMFDNZCLKTHE-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- 229940125904 compound 1 Drugs 0.000 claims 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims 2
- 229940125782 compound 2 Drugs 0.000 claims 2
- 229940126214 compound 3 Drugs 0.000 claims 2
- 229940125898 compound 5 Drugs 0.000 claims 2
- 239000012046 mixed solvent Substances 0.000 claims 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 claims 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 claims 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 claims 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims 1
- DRHWBADNSVQEGH-UHFFFAOYSA-L diiodyloxylead Chemical compound O=I(=O)O[Pb]OI(=O)=O DRHWBADNSVQEGH-UHFFFAOYSA-L 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 229920000144 PEDOT:PSS Polymers 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- DJBMGTRWUAMBFN-UHFFFAOYSA-N 1-bromo-9-octylcarbazole Chemical compound BrC1=CC=CC=2C3=CC=CC=C3N(C12)CCCCCCCC DJBMGTRWUAMBFN-UHFFFAOYSA-N 0.000 description 3
- VCDOOGZTWDOHEB-UHFFFAOYSA-N 1-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(Br)=CC=C2 VCDOOGZTWDOHEB-UHFFFAOYSA-N 0.000 description 3
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- BPRGLVVFWRNXEP-UHFFFAOYSA-N 2,6-dibromoanthracene Chemical class C1=C(Br)C=CC2=CC3=CC(Br)=CC=C3C=C21 BPRGLVVFWRNXEP-UHFFFAOYSA-N 0.000 description 2
- JUFYHUWBLXKCJM-UHFFFAOYSA-N 2,6-dibromoanthracene-9,10-dione Chemical class BrC1=CC=C2C(=O)C3=CC(Br)=CC=C3C(=O)C2=C1 JUFYHUWBLXKCJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- GVRVHDUHAVNFOW-UHFFFAOYSA-N 2,7-dibromo-9-octylcarbazole Chemical class C1=C(Br)C=C2N(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 GVRVHDUHAVNFOW-UHFFFAOYSA-N 0.000 description 1
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9h-carbazole Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 1
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- 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
-
- 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
- C08G2261/14—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
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
-
- 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
-
- 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
- C08G2261/95—Use in organic luminescent diodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明开发一类基于咔唑‑蒽结构的空穴传输聚合物材料：其化学结构式为：其中n的值为1‑100；A为具有π共轭结构的单元，选自下列单元中的一种：R1为下列基团中的一种：R2为下列基团中的一种：
Description
技术领域
本发明涉及有机电子领域，具体来说涉及一类基于咔唑-蒽结构的空穴传输聚合物材料的开发及在有机电子领域中的应用。
背景技术
在有机电子发展过程中，利用有机材料代替传统半导体材料制备有机电子器件是现代电子工业发展的一个巨大变革；有机电子器件重量轻、成本低、可弯曲、适于大面积制备，与无机半导体器件，具有明显的优势，在曲面显示、无线射频识别、光检测、新能源获取与存储等领域有已经有了广阔的应用。有机电子器件包括有机发光二极管、有机薄膜晶体管、有机太阳能电池、有机存储等。这些器件由各种功能材料构成，空穴传输材料具有空穴传输性能，是将空穴载流子向电极传入或从电极传出，是制约电子器件性能的关键材料之一。
尽管国内外已开发不同类型的空穴传输材料，但是，稳定性好、溶解性能好、高载流子迁移率、能级易调控的空穴传输材料仍需要大力开发。
发明内容
解决的技术问题：针对现有的空穴传输材料存在稳定性差、溶解性差、载流子迁移率低、能级不易调的缺点，本发明设计了一类基于咔唑-蒽结构的空穴传输聚合物材料，该材料具有稳定性好、溶解性能好、高载流子迁移率、能级易调控等优点。
技术方案：一类基于咔唑-蒽结构的空穴传输聚合物材料，所述材料的化学结构式为：
其中n的值为1-100；A为具有π共轭结构的单元，选自下列单元中的一种：
R1为下列基团中的一种：
R2为下列基团中的一种：
上面所述的A为R1为R2为空穴传输聚合物材料为Cbz-Ant，其结构式为：
其中n的值为1-100。
本发明提供上述聚合物材料Cbz-Ant的合成方法。
本发明提供上述聚合物材料Cbz-Ant作为空穴传输材料在钙钛矿太阳能电池中的应用。
有益效果：本发明提供的一类基于咔唑-蒽结构的空穴传输聚合物材料，具有以下有益效果：
(1)本发明基于咔唑-蒽结构的聚合物材料具有很好的稳定性，咔唑结构单元控制HOMO能级，蒽单元提供较高载流子迁移率，保证这类材料具有能级匹配、高载流子迁移率优异性能；
(2)调控π共轭结构单元A，进而调控聚合物链的共轭程度与链间堆积；侧链上引入多个柔性直链或支链，保证材料具有好的溶液加工性能；这样的空穴传输材料在钙钛矿太阳能电池、有机太阳能电池、有机发光二极管、有机存储、有机薄膜晶体管等电子领域，具有潜在而广泛的应用前景。
附图说明
结合如下附图及详细描述将会更清楚地理解本上述发明内容和其它特征及优点，其中：
图1是4，4′-二溴-2-硝基-1，1′-联苯(1)的核磁共振氢谱图；
图2是2，7-二溴-9H-咔唑(2)的核磁共振氢谱图；
图3是2，7-二溴-9-辛基-9H-咔唑(3)的核磁共振氢谱图；
图4是9-辛基-2，7-二噻吩-9H-咔唑(4)的核磁共振氢谱图；
图5是单体M1的核磁共振氢谱图；
图6是2，6-二溴-9，10-蒽醌(5)的核磁共振氢谱图；
图7是5，5′-[9，10-(2，6-二溴蒽)]-双十二烷基噻吩(6)的核磁共振氢谱图；
图8是单体M2的核磁共振氢谱图；
图9是聚合物材料Cbz-Ant的核磁共振氢谱图；
图10是聚合物材料Cbz-Ant的UV-vis吸收光谱图；
图11是聚合物材料Cbz-Ant的UPS曲线图；
图12是聚合物材料Cbz-Ant的热分析TGA图；
图13是钙钛矿太阳能电池器件的添加剂m-MTDATA化学结构式；
图14是钙钛矿太阳能电池器件的结构示意图；
图15是聚合物材料Cbz-Ant作为空穴传输材料的钙钛矿太阳能电池器件的J-V曲线图。
优选实施方案的详细说明
下面对本发明的优选实施例进行详细阐述，以使本发明的优点和特征能更易于被本领域技术人员理解。
实例1：
(1)单体M1的合成
4，4′-二溴-2-硝基-1，1′-联苯(1)
在4，4′-二溴-1，1′-联苯(10.00g，32.00mmol)溶于醋酸中(300ml)，100℃时缓慢加入HNO3和水(7.5ml)的混合物。100℃加热30分钟后，一开始形成的沉淀溶解。反应结束后待溶液冷却，过滤后得到黄色粉末。在乙醇中重结晶得到目标产物(9.30g，81％)。1H NMR(400MHz，CDCl3)：δ8.03(d，J＝1.3Hz，1H)，7.75(m，1H)，7.56(d，J＝7.9Hz，2H)，7.28(m，1H)，7.16(d，J＝7.9Hz，2H).
2，7-二溴-9H-咔唑(2)
1(10.00g，28.00mmol)和磷酸三乙酯(50ml)的混合物加热回流18小时，多余的磷酸三乙酯蒸馏除去，柱层析法纯化产物(淋洗剂：乙酸乙酯∶正己烷＝5∶95)，得到目标产物(4.66g，87％)。1H NMR(400MHz，CDCl3)：δ8.03(s，1H)，7.87(d，J＝8.3Hz，2H)，7.56(d，J＝1.6Hz，2H)，7.35(dd，J＝1.6Hz，1.6Hz，2H)。
2，7-二溴-9-辛基-9H-咔唑(3)
2(4.00g，12.31mmol)溶于DMF(200ml)中，加入NaOH(0.49g，12.31mmol)和1-溴辛烷(2.31ml，13.29mmol)。反应物在N2保护下室温下搅拌过夜。反应结束后加水淬灭反应。反应物用氯仿萃取，用MgSO4干燥。除去溶剂后柱层析法纯化产物(淋洗剂：正己烷)，得到化合物3(4.73g，88％)。1H NMR(400MHz，CDCl3)：δ7.88(d，J＝8.3Hz，2H)，7.52(d，J＝1.6Hz，2H)，7.35(dd，J＝1.6Hz，1.6Hz，2H)，4.18(t，J＝7.4Hz，2H)，1.83(m，2H)，1.31(m，10H)，0.88(t，J＝6.8Hz，3H)。
9-辛基-2，7-二噻吩-9H-咔唑(4)
3(3.99g，12.16mmol)和三丁基(2-噻吩基)锡(9.95g，26.74mmol)在N2保护下溶于无水甲苯(56ml)和DMF(14ml)中。加入四(三苯基膦)钯(0)(1.70g，1.49mmol)，然后加热至100℃。反应在黑暗中反应回流过夜。除去大部分溶剂后，加入二氯甲烷与水，进行萃取；有机相用稀盐酸、饱和NaHCO3与盐水洗，然后用MgSO4干燥，在正己烷中重结晶两次得到产物(2.82g，70％)。1H NMR(400MHz，CDCl3)：δ8.04(d，J＝7.8Hz，2H)，7.59(d，J＝0.6Hz，2H)，7.52(dd，J＝1.8，1.2Hz，2H)，7.42(dd，J＝0.6，1.1Hz，2H)，7.31(dd，J＝0.6，1.1Hz，2H)，7.14(dd，J＝3.6，3.6Hz，2H)，4.35(t，J＝7.3Hz，2H)，1.93(m，2H)，1.46(m，2H)，1.38(m，2H)，1.26(m，6H)，0.86(t，J＝7.0Hz，3H)。
单体M1的制备
4(2.50g，5.63mmol)、NBS(4.11g，23.10mmol)和氯仿(体积：250ml)在黑暗中0℃下搅拌过夜。反应结束后加入水与二氯甲烷进行萃取，有机相经MgSO4干燥。用柱层析法进行纯化(淋洗液：二氯甲烷∶正己烷＝1∶4)得到产物(1.25g，34％)。1H NMR(400MHz，CDCl3)：δ8.02(d，J＝8.4Hz，2H)，7.47(d，J＝1.1Hz，2H)，7.41(dd，J＝1.2，1.8Hz，2H)，7.15(d，J＝3.8Hz，2H)，7.08(d，J＝4.2Hz，2H)，4.31(t，J＝7.2Hz，2H)，1.90(m，2H)，1.39(m，4H)，1.26(m，6H)，0.87(t，J＝7.2Hz，3H)。
(2)单体M2的合成
2，6-二溴-9，10-蒽醌(5)
2，6-二氨基-9，10-蒽醌(5g，20.99mmol)、亚硝酸特丁酯(6.20ml，52.00mmol)、溴化铜(11.72g，52.50mmol)与乙腈(300ml)加到反应瓶中，在65℃反应2h。加入20％盐酸进行淬灭，沉淀过滤，用二氯甲烷与盐水进行洗涤。用1，4-二氧六环进行重结晶，得到产物(2.44g，30％)。1H NMR(400MHz，CDCl3)：δ8.44(d，J＝1.2Hz，2H)，8.17(d，J＝5.2Hz，2H)，7.94(dd，J＝1.2，1.6Hz，2H)。
5，5′-[9，10-(2，6-二溴蒽)]-双十二烷基噻吩(6)
在三颈圆底烧瓶中2-十二烷基噻吩(11.06g，44.00mmol)溶解在无水THF(100ml)，用N2置换空气。将体系降到0℃，缓慢加入n-BuLi(1.6M in hexane，27.50ml，44.00mmol)。溶液自然升高到室温，搅拌30min后开始加热到50℃。两小时后，加入5(4.00g，11.00mmol)在50℃搅拌1.5h。混合物降温到0℃，加入SnCl2·2H2O(22.40g，99.00mmol)的盐酸溶液(10％，50ml)，搅拌1.5h。反应结束后，将混合物倒入冰水中，用乙醚进行萃取。除去溶剂，粗品用柱层析法(淋洗液：正己烷)、重结晶法纯化，得到黄色针状纯品(5.02g，58％)。1H NMR(400MHz，CDCl3)：δ8.07(d，J＝1.8Hz，2H)，7.79(d，J＝9.0Hz，2H)，7.45(dd，J＝1.8，1.8Hz，2H)，6.97(m，4H)，2.96(t，J＝7.5Hz，4H)，1.82(m，4H)，1.48(m，4H)，1.34(m，32H)，0.88(t，J＝6.9Hz，6H)。
单体M2的制备
6(1.00g，1.12mmol)、联硼酸频那醇酯(1.21g，4.78mmol)、Pd(pddf)Cl2(0.04g，0.06mmol)、碳酸钾(0.74g，5.38mmol)与1，4-二氧六环(80ml)加入到圆底烧瓶中，N2保护下，在80℃搅拌过夜。冷却至室温，将混合物倒入水中，用二氯甲烷萃取。除去溶剂，粗品用柱层析法(淋洗液：正己烷)进行提纯，得到产品M2(0.78g，70％)。1H NMR(400MHz，CDCl3)：δ8.49(s，2H)，7.91(dd，J＝0.8，0.8Hz，2H)，7.71(dd，J＝1.2，1.2Hz，2H)，7.00(dd，J＝3.6，3.2Hz，4H)，2.99(t，J＝7.5Hz，4H)，1.83(m，4H)，1.48(m，4H)，1.31(m，56H)，0.89(t，J＝6.9Hz，6H)。
(3)聚合物材料Cbz-Ant的合成
M1(0.50g，0.83mmol)、M2(0.77g，0.83mmol)和Pd2(dba)3(0.05g，0.05mmol)一起放置于微波反应管中。然后整个体系注入N2半小时。脱气的水(5ml)和无水THF(15ml)加入反应管中，在微波反应器中120℃反应20分钟。粗产物用索式提取器提纯，依次使用甲醇、丙酮、乙酸乙酯、正己烷、二氯甲烷和氯仿。最后将氯仿除去得到聚合物材料Cbz-Ant(0.28g，56％)。1H NMR(400MHz，C2D2Cl4)：δ7.63(br，2H)，7.42(br，4H)，7.11(br，2H)，7.00(br，2H)，6.89(br，2H)，6.77(br，4H)，6.51(br，2H)，6.44(br，2H)，3.73(br，2H)，2.41(br，4H)，1.30(br，6H)，0.83(br，52H)，0.25(br，9H)。数均分子量为30400g/mol，重均分子量为61900g/mol，聚合物分散性指数为2.04。
(4)材料的性能与表征
图10为聚合物材料Cbz-Ant的UV-vis吸收光谱，最大吸收峰为397nm。
图11是聚合物材料Cbz-Ant的UPS曲线，测得HOMO能级为-5.15eV，根据图10所得到的能级差为2.59eV，算出Cbz-Ant的LUMO能级为-2.56eV。
图12是聚合物材料Cbz-Ant的热分析TGA，聚合物材料Cbz-Ant的分解温度为435℃。
使用结构为ITO/PEDOT：PSS/聚合物膜/MoO3/Ag测得，聚合物材料Cbz-Ant的空穴迁移率为1.31×10-4cm2V-1s-1，含有30wt％m-MTDATA的聚合物材料Cbz-Ant的空穴迁移率为7.15×10-3cm2V-1s-1。
(5)器件性能的表征
(a)器件制备
图14是钙钛矿太阳能电池ITO/HTM/perovskite/PC61BM/C60/BCP/Al的结构示意图。ITO基片清洗后臭氧处理15min，接着在基片上旋涂含有30wt％m-MTDATA的聚合物材料Cbz-Ant的1，2-二氯苯溶液(4500rpm，30S)，100℃的条件下退火20min；之后将其转移到氮气气氛手套箱中。将1M的碘化铅(PbI2)溶液旋涂到ITO/HTM上(3000rpm，40S)，随即立刻旋涂一层甲基碘化铵(3000rpm，40S)，紧接着在100℃的条件下退火5min左右；接下来将2wt％的PC61BM的1，2-二氯苯溶液旋涂到钙钛矿层上(6000rpm，30S)；最后将C60(20nm)、BCP(8nm)缓冲层以及Al(100nm)电极蒸镀上去。对照电池结构为ITO/PEDOT：PSS/perovskite/PC61BM/C60/BCP/Al。
(b)器件的表征
图15是Cbz-Ant作为空穴传输材料的钙钛矿太阳能电池器件的J-V曲线图。在AM1.5太阳辐照光模拟光源下，电池显示短路电流Jsc和开路电压Voc都有提高，最大功率转换效率为15.50％，与PEDOT：PSS空穴传输材料构建电池的转化效率11.38％相比，提高36％。
综上所述，聚合物材料Cbz-Ant具有高稳定性、好的溶解性、高载流子迁移率、能级匹配等优点，显著提高钙钛矿太阳能电池转化效率。展示出基于咔唑-蒽结构的一类空穴传输聚合物材料，在电子领域具有潜在而广泛的应用前景。
Claims (5)
1.一类基于咔唑-蒽结构的空穴传输聚合物材料，其化学结构如下：
其中n的值为1-100；A为具有π共轭结构的单元，选自下列单元中的一种：
R1为下列基团中的一种：
R2为下列基团中的一种：
。
2.根据权利要求1中所述的咔唑-蒽结构的空穴传输聚合物材料，其特征在于：A为
，R1为，R2为，空穴传
输聚合物材料为Cbz-Ant，其结构式为：
，其中n的值为1-100。
3.根据权利要求2所述聚合物材料Cbz-Ant的合成方法，其合成路线如下：
其合成步骤如下：
（1）化合物1的合成：将10.00克4,4'-二溴-1,1'-联苯溶于300 ml醋酸中，100 ℃时缓慢加入7.5 ml HNO3和水的混合液；加热30 min后，开始形成的沉淀全部溶解；反应结束后待溶液冷却，过滤得到黄色粉末，在乙醇中重结晶得到化合物1，产率81%；
（2）化合物2的合成：10.00克化合物1和50 ml磷酸三乙酯的混合物加热回流18 h，多余的磷酸三乙酯蒸馏除去，用乙酸乙酯与正己烷的混合溶剂作为淋洗剂通过柱层析法纯化产物，得到化合物2，产率87%；
（3）化合物3的合成：4.00克化合物2溶于200 ml DMF中，加入0.49克NaOH和2.31 ml的1-溴辛烷，在N2保护下室温搅拌过夜；反应结束后加水淬灭，用氯仿萃取，用MgSO4干燥；除去溶剂后用正己烷作为淋洗剂通过柱层析法纯化，得到化合物3，产率88%；
（4）化合物4的合成：3.99克化合物3和9.95克的三丁基（2-噻吩基）锡在N2保护下溶于56ml无水甲苯和14 ml的DMF中，加入1.70克的四（三苯基膦）钯（0），升温至100 ℃，回流过夜；除去大部分溶剂后，加入二氯甲烷与水进行萃取；有机相用稀盐酸、饱和NaHCO3与盐水洗，用MgSO4干燥，在正己烷中重结晶两次得到化合物4，产率70%；
（5）单体M1的合成：2.50克的化合物4、4.11克的NBS和250 ml的氯仿在黑暗中0 ℃下搅拌过夜，反应结束后加入水与二氯甲烷进行萃取，有机相经MgSO4干燥；用二氯甲烷与正己烷的混合溶剂作为淋洗剂通过柱层析法进行纯化，得到单体M1，产率34%；
（6）化合物5的合成：5克的2,6-二氨基-9,10-蒽醌、6.20 ml的亚硝酸特丁酯、11.72克的溴化铜与300 ml乙腈加到反应瓶中，在65 ℃反应2 h；加入20%盐酸进行淬灭，沉淀过滤，用二氯甲烷与盐水进行洗涤；用1,4-二氧六环进行重结晶，得到化合物5，产率30%；
（7）化合物6的合成：在三颈圆底烧瓶中11.06克的2-十二烷基噻吩溶解在100 ml无水THF，用N2置换空气；将体系降到0 ℃，缓慢加入27.50 ml浓度为1.6 M的n-BuLi；溶液自然升至室温，搅拌30 min后开始加热到50 ℃；两小时后，加入4.00克化合物5，在50 ℃搅拌1.5 h；混合物降温到0 ℃，加入50 ml浓度为10% SnCl2·2H2O的盐酸溶液，搅拌1.5 h；反应结束后，将混合物倒入冰水中，用乙醚进行萃取；除去溶剂，粗品用柱层析法、重结晶法纯化，得到黄色针状化合物6，产率58%；
（8）单体M2的合成：1.00克的化合物6、1.21克的联硼酸频哪醇酯、0.04克的Pd(pddf)Cl2、0.74克的碳酸钾与80 ml的1,4-二氧六环加入到圆底烧瓶中，N2保护下，在80 ℃搅拌过夜；冷却至室温，将混合物倒入水中，用二氯甲烷萃取；除去溶剂，粗品用正己烷作为淋洗剂通过柱层析法进行提纯，得到单体M2，产率70%；
（9）聚合物材料Cbz-Ant的合成：0.50克的单体M1、0.77克的单体M2和0.05克的Pd2(dba)3一起放置于微波反应管中，整个体系注入N2半小时；5 ml脱气的水和15 ml无水THF加入反应管中，在微波反应器中120 ℃ 反应20 min；粗产物用索式提取器提纯，依次使用甲醇、丙酮、乙酸乙酯、正己烷、二氯甲烷和氯仿，最后将氯仿除去得到聚合物材料Cbz-Ant，产率56%。
4.根据权利要求3所述聚合物材料Cbz-Ant作为空穴传输材料HTM在钙钛矿太阳能电池ITO/HTM/perovskite/PC61BM/C60/BCP/Al中的应用，其特征在于：ITO基片清洗后臭氧处理15 min，接着在基片上以转速4500 rpm旋涂含有30 wt% m-MTDATA的聚合物材料Cbz-Ant的1,2-二氯苯溶液，100 ℃的条件下退火20 min；之后将其转移到氮气气氛手套箱中；将1M的碘化铅溶液以转速3000 rpm旋涂到ITO/HTM上，随即立刻旋涂一层甲基碘化铵，紧接着在100 ℃的条件下退火5 min左右；接下来将2 wt%的PC61BM的1,2-二氯苯溶液旋涂到钙钛矿层上，最后将20 nm的C60、8 nm的BCP缓冲层以及100 nm的Al电极蒸镀上去。
5.根据权利要求1所述一类咔唑-蒽结构的空穴传输聚合物材料在有机发光二极管、有机薄膜晶体管、有机太阳能电池、有机存储领域中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810358163.5A CN108727566B (zh) | 2018-04-10 | 2018-04-10 | 一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810358163.5A CN108727566B (zh) | 2018-04-10 | 2018-04-10 | 一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108727566A CN108727566A (zh) | 2018-11-02 |
| CN108727566B true CN108727566B (zh) | 2019-06-14 |
Family
ID=63939680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810358163.5A Active CN108727566B (zh) | 2018-04-10 | 2018-04-10 | 一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108727566B (zh) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2291469A1 (en) * | 2008-06-23 | 2011-03-09 | Basf Se | Novel polymers |
| WO2011002927A2 (en) * | 2009-06-30 | 2011-01-06 | Plextronics, Inc. | Novel compositions, methods and polymers |
| CN102295750B (zh) * | 2010-06-24 | 2012-10-31 | 海洋王照明科技股份有限公司 | 含咔唑卟啉-蒽共聚物、制备方法及其应用 |
| JP5667704B2 (ja) * | 2010-12-20 | 2015-02-12 | オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー | 有機半導体材料の作製方法、及び、有機半導体材料 |
| CN103772651A (zh) * | 2012-10-17 | 2014-05-07 | 海洋王照明科技股份有限公司 | 含亚烷基芴与咔唑的有机聚合物半导体材料及其制备方法和应用 |
| CN104292429A (zh) * | 2013-07-19 | 2015-01-21 | 海洋王照明科技股份有限公司 | 一种含蒽醌基的聚合物及其制备方法和有机太阳能电池器件 |
-
2018
- 2018-04-10 CN CN201810358163.5A patent/CN108727566B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108727566A (zh) | 2018-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107275490B (zh) | 一种以环戊双噻吩衍生物为电子受体的有机太阳电池 | |
| CN109666033A (zh) | 基于九并稠杂环类共轭小分子及其制备方法与应用 | |
| CN107586379A (zh) | 含氯代苯并噻二唑的共轭聚合物及其制备方法和有机太阳能电池器件 | |
| CN103483560B (zh) | 一种2,1,3-苯并噻二唑并二噻吩衍生溴代物与咔唑的共轭聚合物及其合成方法 | |
| CN113429383A (zh) | 一种非富勒烯受体材料、其制备方法和应用 | |
| JP5688164B2 (ja) | 光起電重合体材料、その調製方法及び応用 | |
| CN109400853A (zh) | 基于3’-氟苯基取代喹喔啉结构单元的共轭聚合物及其制备方法和应用 | |
| CN109912621B (zh) | 一种不对称的萘核小分子受体材料及其制备方法和应用 | |
| CN108727566B (zh) | 一类基于咔唑-蒽结构的空穴传输聚合物材料的开发与应用 | |
| CN110343235A (zh) | 一种萘并二噻吩共轭聚合物及其制备方法与应用 | |
| CN103408732A (zh) | 含苯并二噻吩的聚芳基乙炔撑半导体材料 | |
| CN103265687A (zh) | 含有大体积支化烷氧基侧链的聚合物材料、制备方法及应用 | |
| CN107778280A (zh) | 基于三聚茚的星形对称有机太阳能电池小分子受体材料及其制备方法与一种有机太阳能电池 | |
| CN110964040B (zh) | 基于苯并氧族二唑的受体材料及其制备方法和应用 | |
| CN106589325A (zh) | 一种含有苯并[c]噌啉的共轭聚合物及其合成方法与应用 | |
| CN111807992B (zh) | 一类d-a型四氰基蒽醌二甲烷光电功能材料及其制备方法和应用 | |
| CN113637023B (zh) | 一种不对称的吲哚衍生物核小分子受体材料及其制备方法 | |
| CN109293887B (zh) | 一类基于三苯胺-蒽结构空穴传输聚合物材料的开发及其在钙钛矿太阳能电池中的应用 | |
| CN103865044A (zh) | 含环戊二烯二噻吩和苯并二(苯并硒二唑)单元的共聚物及其制备方法和应用 | |
| CN109651599B (zh) | 一种p型聚合物半导体材料及其制备方法和应用 | |
| CN106565753A (zh) | 一种富勒烯衍生物、制备方法和应用 | |
| CN110790772B (zh) | 接枝苝二酰亚胺并芳香基团的羟基喹啉基金属有机小分子配合物材料及其制备方法与应用 | |
| CN102532491A (zh) | 含Ladder型芳香稠杂环的聚合物材料 | |
| Gayathri et al. | Pentyl side chain-based benzoditiophene π-conjugated polymer for non-halogenated solvent processed organic solar cells | |
| CN111019097A (zh) | 一种烯基侧链共轭的引达省并二呋喃基聚合物材料、其制备方法及应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211028 Address after: No. 606, ningliu Road, Changlu street, Jiangbei new district, Nanjing City, Jiangsu Province, 211500 Patentee after: Nanjing Hesong Material Technology Co., Ltd Address before: 215200 No. 8, pangyang Road, Wujiang, Suzhou, Jiangsu Patentee before: SUZHOU HESONG BIOCHEMISTRY TECHNOLOGY Co.,Ltd. |