CN103168044B - 有机半导体材料及其制备方法和应用 - Google Patents
有机半导体材料及其制备方法和应用 Download PDFInfo
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- CN103168044B CN103168044B CN201080069676.6A CN201080069676A CN103168044B CN 103168044 B CN103168044 B CN 103168044B CN 201080069676 A CN201080069676 A CN 201080069676A CN 103168044 B CN103168044 B CN 103168044B
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- organic semiconductor
- semiconductor material
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- bis
- alkyl
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000004065 semiconductor Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- 239000002585 base Substances 0.000 claims description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- BFRDBSBKJUVSNP-UHFFFAOYSA-N 9h-fluorene;silicon Chemical class [Si].C1=CC=C2CC3=CC=CC=C3C2=C1 BFRDBSBKJUVSNP-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical group BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 238000005401 electroluminescence Methods 0.000 claims description 5
- 230000005669 field effect Effects 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- -1 thiophene-thiophene pyrrole dione unit Chemical group 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012265 solid product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000010025 steaming Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- MFAXBTKOLOJEHX-UHFFFAOYSA-N 2,3-dihydro-2-methylthiophene Chemical compound CC1CC=CS1 MFAXBTKOLOJEHX-UHFFFAOYSA-N 0.000 description 3
- VUUIFTOEHZDVDO-UHFFFAOYSA-N 2-decyl-2,3-dihydrothiophene Chemical compound CCCCCCCCCCC1CC=CS1 VUUIFTOEHZDVDO-UHFFFAOYSA-N 0.000 description 3
- 0 CC(C)(C)*(cc1)cc(*2*C=CC)c1-c1c2cc(C2OC(c([n]c(C(*C3C(C)(C)*C33)=C3I)c3C(*4*)O)c3C4=O)=C(*)C2NC=CC)cc1 Chemical compound CC(C)(C)*(cc1)cc(*2*C=CC)c1-c1c2cc(C2OC(c([n]c(C(*C3C(C)(C)*C33)=C3I)c3C(*4*)O)c3C4=O)=C(*)C2NC=CC)cc1 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002220 fluorenes Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- XMJORWORGGVBDT-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCCCC)C1CC=CS1 Chemical compound C(CCCCCCCCCCCCCCCCCCC)C1CC=CS1 XMJORWORGGVBDT-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- IACUBCVQZQWLQM-UHFFFAOYSA-N CC1C=C(C2(C)C)C2=CC1C(CC1)=C(C)C=C1c1c(C)c(C)c(-c2c(C(N(C)C3=O)O)c3c(-c3c(C)c(CC4(C)C)c4[s]3)[s]2)[s]1 Chemical compound CC1C=C(C2(C)C)C2=CC1C(CC1)=C(C)C=C1c1c(C)c(C)c(-c2c(C(N(C)C3=O)O)c3c(-c3c(C)c(CC4(C)C)c4[s]3)[s]2)[s]1 IACUBCVQZQWLQM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- 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
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- 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
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- 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
- C08G2261/3244—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing only one kind of heteroatoms other than N, O, S
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- 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
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electroluminescent Light Sources (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Thin Film Transistor (AREA)
- Photovoltaic Devices (AREA)
Abstract
公开了具有通式(I)的有机半导体材料,其中R1、R2、R3、R4、R5、R6、R7为C1-C20的烷基;n为大于1小于等于100的整数。还公开了该有机半导体材料的制备方法和应用。该有机半导体材料具有提高的稳定性和光电转化效率。
Description
技术领域
本发明涉及一种有机半导体材料,更具体的涉及为一种含硅芴和噻吩-噻吩吡咯二酮单元的有机半导体材料。本发明还涉及一种有机半导体材料的制备方法及其应用。
背景技术
当今世界经济主要是建立在以化石能源,如煤炭、石油和天然气等基础之上的经济。然而,这些不可再生的化石能源都在不断的枯竭。进入21世纪以来,全球性的能源问题以及随之而来的环境污染和气候变暖等问题日益凸现和逐渐加剧。由于太阳能具有分布普遍和广阔,资源数量多,无污染,清洁,安全以及获取方便等突出优点,被认为是最有希望的可再生能源之一。太阳能电池直接把太阳光能转化成电能,是利用太阳能切实可行的有效方法。然而,目前商品化的太阳能电池还局限于硅基等无机太阳能电池,但它们的价格过于昂贵,超出了目前人们普遍可以接受的程度,这大大限制了它们的使用范围。为了降低电池成本,拓展应用范围,长期以来,人们一直在寻找新型的太阳能电池材料。
有机太阳能电池是一种新型的太阳能电池,相对于无机半导体材料来源有限,价格昂贵,有毒,制备工艺复杂,成本太高等而言,它具有无机太阳能电池无法比拟的一些优点,如材料来源广泛,结构多样性和可调控性,成本低廉,安全环保,制作工艺简单,产品重量轻,可大面积柔性制备等等,可以广泛应用在建筑、照明和发电等多种领域,具有重要的发展和应用前景。因此,国内外众多的研究机构和企业等都给予了相当的关注和投入。然而,到目前为止,有机太阳能电池的光电转换效率比无机太阳能电池还是要低很多。因此,开发新型的有机半导体材料对于提高有机太阳能电池的效率具有重要意义。
发明内容
基于上述问题,本发明的目的在于提供一种含硅芴和噻吩-噻吩吡咯二酮单元的有机半导体材料。
本发明的目的还在于提供一种有机半导体材料的制备方法及其应用。
本发明提供的一种有机半导体材料,具有以下通式(I):
式中:R1、R2、R3、R4、R5、R6、R7相同或不同地表示为C1-C20的烷基;n的取值范围为大于1小于等于100的整数,优选n的取值范围为大于等于20小于等于80的整数。
上述有机半导体材料的制备方法,其包括如下步骤:
步骤S1、将2,7-二溴-9,9-二烷基硅芴和正丁基锂在-100℃~-25℃下,以摩尔比1:2.0~1.0:4.0加入至第一溶剂中溶解,然后加入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,反应24~48小时,得到2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴;
步骤S2、将1,3-双(3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮和溴化剂在0℃~30℃下,以摩尔比1:2~1:3加入至第二溶剂中,溶解、反应12~48小时,得到1,3-双(5-溴-3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮;
步骤S3、无氧环境中,将S1步骤中制得的所述2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴和S2步骤中制得的所述1,3-双(5-溴-3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮,以摩尔比1:a,加入到含有催化剂、碱溶液的第三溶剂中,在65℃~120℃下进行Suzuki反应24~72小时,得到所述有机半导体材料;其中,a的取值范围为大于等于0.95小于等于1.05。
上述有机半导体材料可以被广泛应用于有机太阳能电池,有机场效应晶体管,有机电致发光器件,有机光存储,有机非线性材料和有机激光器件中。
与现有技术相比,本发明的主要优点在于:
1、合成硅芴类单体、噻吩-噻吩吡咯二酮类单体的路线比较简单且成熟,易通过引入烷基提高产物的溶解性和分子量,以实现可旋涂的聚合物或可旋涂的寡聚物;
2、硅芴类单体具有较好的光稳定性和热稳定性,是一种非常优异的给体材料,噻吩-噻吩吡咯二酮类单体是一种非常优异的受体材料,由硅芴类单体、噻吩-噻吩吡咯二酮类单体构成的聚合物能够形成一种很强的给体-受体结构,一方面有利于提高了材料的稳定性,另一方面有利于降低材料的能带隙,从而扩大太阳光吸收范围,提高光电转化效率;
3、Suzuki反应是一种非常成熟的聚合反应,产率高,且条件温和,易于控制。
附图说明
图1是实施例5以本发明有机半导体材料为活性层的有机太阳能电池器件的结构示意图;
图2是实施例5以本发明有机半导体材料为活性层的有机太阳能电池器件的I-V曲线图;
图3是实施例6以本发明有机半导体材料为发光层的有机电致发光器件的结构示意图;
图4是实施例7以本发明有机半导体材料为有机半导体层的有机场效应晶体管器件的结构示意图。
具体实施方式
本发明提供的一种含硅芴和噻吩-噻吩吡咯二酮单元的有机半导体材料,具有以下通式(I):
式中:R1、R2、R3、R4、R5、R6、R7相同或不同地表示为C1-C20的烷基,优选R1与R2为相同的C1-C20的烷基,或者R3与R4为相同的C1-C20的烷基,或者R6与R7为相同的C1-C20的烷基;n的取值范围为大于1小于等于100的整数,优选n的取值范围为大于等于20小于等于80的整数。
本发明还提供了一种上述有机半导体材料的制备方法,包括如下步骤:
步骤S1、将2,7-二溴-9,9-二烷基硅芴(A1)和正丁基锂(n-BuLi)在-100℃~-25℃下以摩尔比1:2~1:4加入至第一溶剂中,然后加入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷(C1),或者为结构式为的双频哪醇合二硼,继续反应24~48小时,得到产物,即2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴(B1);其中,第一溶剂为四氢呋喃、乙醚、二氯甲烷、三氯甲烷或乙酸乙酯等,C1的摩尔用量为A1摩尔量的2~4倍;其反应式如下:
或
式中,R1、R2相同或不同地表示为C1-C20的烷基;
步骤S2、将噻吩-噻吩吡咯二酮类原料,如1,3-双(3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮(A2)和溴化剂,如N-溴代丁二酰亚胺(NBS,下同),在10℃~30℃下以摩尔比1:2~1:4加入至第二溶剂中,反应12~48小时,得到产物,即1,3-双(5-溴-3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮(B2);其中,第二溶剂为N,N-二甲基甲酰胺(DMF)、四氢呋喃(THF)、乙醚、二氯甲烷、三氯甲烷、乙酸乙酯或醋酸中的至少一种;其反应式如下:
式中,R3、R4、R5、R6、R7相同或不同地表示为C1-C20的烷基;
步骤S3、无氧环境中,将步骤S1中制得的B1和步骤S2中制得的B2以摩尔比1.0:a(其中,0.95≤a≤1.05)添加到含有催化剂、碱溶液的第三溶剂中,在65℃~120℃下进行Suzuki反应24~72小时,得到产物,即有机半导体材料(I);其中,催化剂为有机钯或有机钯和有机膦的配体混合物,(该混合物中,有机钯与有机膦配体的摩尔比为1:1~20);有机钯可以选自Pd(PPh3)4、Pd2(dba)3或Pd(PPh3)2Cl2,有机膦配体为P(o-Tol)3,有机钯和有机膦的配体混合物可以为Pd2(dba)3/P(o-Tol)3;催化剂的摩尔用量为2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴(B1)摩尔用量的0.005-0.10倍;碱溶液为NaOH水溶液、Na2CO3水溶液、NaHCO3水溶液或四乙基氢氧化铵水溶液,碱溶液中相应碱的摩尔用量为2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴(B1)摩尔用量的2-20倍,第三溶剂为四氢呋喃、甲苯、三氯甲烷或乙酸乙酯中的至少一种,其反应式如下:
式中,n的取值范围为大于1小于等于100的整数,优选n的取值范围为大于等于20小于等于80的整数。
为了更好地理解本发明专利的内容,下面通过具体的实例和图例来进一步说明本发明的技术案,具体包括材料制备和器件制备,但这些实施实例并不限制本发明。
本实施例中,无氧环境中所形成的无氧气氛主要为氮气气氛,也可以是其它的惰性气体气氛;在此对其不进行限制。
实施例1、本实施例公开一种结构如下的有机半导体材料:
n=20;
上述有机半导体材料的制备步骤如下:
一、2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二甲基硅芴的制备:
在-100℃、氮气条件下,将40.00mL(1.00M)正丁基锂溶液加入至盛有3.68g 2,7-二溴-9,9-二甲基硅芴和120mL四氢呋喃的反应瓶中,搅拌2小时后慢慢滴加4.33mL 2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,恢复至室温,继续搅拌48小时。反应结束,将反应液倒入水中,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):462.3(M+).
二、1,3-双(5-溴-3,4-二甲基噻吩-2-基)5-甲基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮的制备:
在0℃、避光条件下,将0.36g NBS分批加入至盛有0.39g 1,3-双(3,4-二甲基噻吩-2-基)5-甲基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮和20mLDMF的反应瓶中,搅拌48小时。反应结束,将反应液倒入冰水中淬灭,二氯甲烷萃取,无水硫酸镁干燥,抽虑,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):545.33(M+).
三、有机半导体材料的制备:
在氮气保护下,往含有0.462g 2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二甲基硅芴、0.544g 1,3-双(5-溴-3,4-二甲基噻吩-2-基)5-甲基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮、0.082g Pd(PPh3)4的反应瓶中加入7mL 20%Wt四乙基氢氧化铵水溶液和甲苯(20mL)。氮气置换1小时后,加热至65℃,反应72小时。反应结束,甲醇沉降三次,抽滤,真空干燥得到固体产物。
GPC:Mn=12198,PDI=2.4.
实施例2、本实施例公开一种结构如下的有机半导体材料:
n=43;
上述有机半导体材料的制备步骤如下:
一、2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二辛基硅芴的制备:
在-78℃、氮气条件下,用注射器将10.00mL(2.00M)正丁基锂溶液加入至盛有5.65g 2,7-二溴-9,9-二辛基硅芴和100.00mL乙醚的两口烧瓶中,搅拌2小时后慢慢滴加4.90mL 2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,恢复至室温,继续搅拌33小时。反应结束,将反应液倒入水中,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):658.6(M+).
二、1,3-双(5-溴-3,4-二辛基噻吩-2-基)5-辛基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮的制备:
在10℃、避光条件下,将0.42g NBS分批加入至盛有1.04g 1,3-双(3,4-二辛基噻吩-2-基)5-辛基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮和30mL四氢呋喃的反应瓶中,搅拌38小时。反应结束,将反应液倒入冰水中淬灭,二氯甲烷萃取,无水硫酸镁干燥,抽虑,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):1036.3(M+).
三、有机半导体材料的制备:
在氮气保护下,往含有0.659g 2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二辛基硅芴、1.036g 1,3-双(5-溴-3,4-二辛基噻吩-2-基)5-辛基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮、0.084g Pd(PPh3)2Cl2的反应瓶中加入8mL 20%Wt NaHCO3水溶液和四氢呋喃(30mL)。氮气置换1小时后,加热至85℃,反应64小时。反应结束,甲醇沉降三次,抽滤,真空干燥得到固体产物。
GPC:Mn=55176,PDI=2.0.
实施例3、本实施例公开一种结构如下的有机半导体材料:
n=80;
上述有机半导体材料的制备步骤如下:
一、2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二癸基硅芴的制备:
在-45℃、氮气条件下,用注射器将25.00mL(2.00M)正丁基锂溶液加入至盛有12.40g 2,7-二溴-9,9-二癸基硅芴和200.00mL三氯甲烷的两口烧瓶中,搅拌1小时后慢慢滴加9.89mL 2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,恢复至室温,继续搅拌26小时。反应结束,将反应液倒入水中,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):714.7(M+).
二、1,3-双(5-溴-3,4-二癸基噻吩-2-基)5-癸基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮的制备:
在20℃、避光条件下,将0.55g NBS分批加入至盛有1.02g 1,3-双(3,4-二癸基噻吩-2-基)5-癸基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮和30mL乙醚的反应瓶中,搅拌24小时。反应结束,将反应液倒入冰水中淬灭,二氯甲烷萃取,无水硫酸镁干燥,抽虑,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):1176.5(M+).
三、有机半导体材料的制备:
在氮气保护下,往含有0.715g 2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二辛基硅芴、1.177g 1,3-双(5-溴-3,4-二癸基噻吩-2-基)5-癸基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮、0.133g Pd(PPh3)4的反应瓶中加入9mL 2M碳酸钠水溶液、0.101g季铵盐336和三氯甲烷(40mL)。氮气置换2小时后,加热至100℃,反应45小时。反应结束,甲醇沉降三次,抽滤,真空干燥得到固体产物。GPC:Mn=118363,PDI=1.9.
实施例4、本实施例公开一种结构如下的有机半导体材料:
n=100;
上述有机半导体材料的制备步骤如下:
一、2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-双二十烷基硅芴的制备:
在-25℃、氮气条件下,将10.00mL(2.00M)正丁基锂溶液加入至盛有9.01g 2,7-二溴-9,9-双二十烷基硅芴和150mL四氢呋喃的反应瓶中,搅拌2小时后慢慢滴加5.30mL 2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,恢复至室温,继续搅拌47小时。反应结束,将反应液倒入水中,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):995.3(M+).
二、1,3-双(5-溴-3,4-双二十烷基噻吩-2-基)5-二十烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮的制备:
在30℃、避光条件下,将0.71g NBS分批加入至盛有1.72g 1,3-双(3,4-双二十烷基噻吩-2-基)5-二十烷基基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮和40mL四氢呋喃的反应瓶中,搅拌12小时。反应结束,将反应液倒入冰水中淬灭,二氯甲烷萃取,无水硫酸镁干燥,抽虑,旋蒸,柱层析分离得到固体产物。
MALDI-TOF-MS(m/z):1877.9(M+).
三、有机半导体材料的制备:
在氮气保护下,往含有0.995g 2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-双二十烷基硅芴、1.878g 1,3-双(5-溴-3,4-双二十烷基噻吩-2-基)5-二十烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮、0.112gPd2(dba)3,0.052g P(o-Tol)3的反应瓶中加入11mL 20%Wt四乙基氢氧化铵水溶液和甲苯(40mL)。氮气置换1小时后,加热至120℃,反应24小时。反应结束,甲醇沉降三次,抽滤,真空干燥得到固体产物。
GPC:Mn=246140,PDI=1.7.
实施例5、对以本发明的有机半导体材料为活性层的有机太阳能电池器件,其结构如图1所示。
一个有机太阳能电池器件,其结构设置为:玻璃11/ITO层12/PEDOT:PSS层13/活性层14/Al层15;其中,活性层14的材料包含有电子给体材料和电子受体材料,电子给体材料为本发明中的有机半导体材料,[6,6]苯基-C61-丁酸甲酯(简称PCBM)作为电子受体材料,ITO是方块电阻为10-20Ω/口的氧化铟锡,PEDOT为聚(3,4-亚乙二氧基噻吩),PSS为聚(苯乙烯磺酸);ITO玻璃经过超声波清洗后,用氧-Plasma处理,在ITO上旋涂PEDOT:PSS,本发明中的半导体材料作为电子给体材料和PCBM作为电子受体材料采用旋涂技术,金属铝电极通过真空蒸镀技术制备,得到有机太阳能电池器件。ITO、PEDOT:PSS、活性层、Al层的厚度分别为110nm、40nm、110nm、110nm。
以实施例3中的材料为例,制备好的电池的有效面积为9平方毫米,测量是在太阳光模拟器下进行的,光的强度用硅标准电池进行校验,I-V曲线用Keithley 2400进行测量。该器件在100毫瓦每平方厘米的模拟光照条件下的I-V曲线如图2所示。开路电压为0.34伏,短路电流为0.053毫安,填充因子为0.45,能量转换效率为0.091%。
实施例6、对含本发明的有机半导体材料的有机电致发光器件,其结构如图3所示:
一种有机电致发光器件,其结构设置为:在一个玻璃基片21上沉积一层方块电阻为10-20Ω/口的氧化铟锡(ITO)层22,作为透明阳极,通过旋涂技术在ITO层22上制备一层以本发明中的有机半导体材料为材质的发光层23,再在此发光层23上真空蒸镀LiF,作为缓冲层24,最后蒸镀金属Al层25,作为器件的阴极。
实施例7、对含本发明的有机半导体材料的有机场效应晶体管,其结构如图4所示:
一种有机场效应晶体管,采用硅片(Si)作为衬底31,500nm厚的SiO2作为绝缘层32,将本发明中的有机半导体材料为为材质的有机半导体层34旋涂到用于修饰SiO2层32的十八烷基三氯硅烷(OTS)层33上,采用金(也可以采用其他金属材质,铝、铂、银)作为电极源电极(S)35和漏电极(D)36设置在有机半导体层34上。
应当理解的是,上述针对本发明较佳实施例的表述较为详细,并不能因此而认为是对本发明专利保护范围的限制,本发明的专利保护范围应以所附权利要求为准。
Claims (10)
1.下述通式(I)的有机半导体材料:
式中:R1、R2、R3、R4、R5、R6、R7为C1-C20的烷基;n的取值范围为大于1小于等于100的整数。
2.根据权利要求1所述的有机半导体材料,其特征在于,R1与R2为相同的C1-C20的烷基;或者R3与R4为相同的C1-C20的烷基;或者R6与R7为相同的C1-C20的烷基。
3.根据权利要求1所述的有机半导体材料,其特征在于,R1、R2、R3、R4、R5、R6、R7为相同的C1-C20的烷基。
4.根据权利要求1所述的有机半导体材料,其特征在于,所述n的取值范围为大于等于20小于等于80的整数。
5.一种如权利要求1至4任一所述的有机半导体材料的制备方法,其特征在于,该制备方法包括如下步骤:
S1、将2,7-二溴-9,9-二烷基硅芴和正丁基锂在-100℃~-25℃下,以摩尔比1:2.0~1.0:4.0加入至第一溶剂中溶解,然后加入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,反应24~48小时,得到2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴;
S2、将1,3-双(3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮和溴化剂在0℃~30℃下,以摩尔比1:2~1:3加入至第二溶剂中,溶解、反应12~48小时,得到1,3-双(5-溴-3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮;
S3、无氧环境中,将S1步骤中制得的所述2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴和S2步骤中制得的所述1,3-双(5-溴-3,4-二烷基噻吩-2-基)5-烷基-4H-噻吩[3,4-c]并吡咯-4,6(5H)-二酮,以摩尔比1:a,加入到含有催化剂、碱溶液的第三溶剂中,在65℃~120℃下进行Suzuki反应24~72小时,得到所述有机半导体材料;其中,a的取值范围为大于等于0.95小于等于1.05。
6.根据权利要求5所述的有机半导体材料的制备方法,其特征在于,S1步骤中,所述第一溶剂为四氢呋喃、乙醚、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种;所述2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷的摩尔用量为所述2,7-二溴-9,9-二烷基硅芴摩尔量的2~4倍。
7.根据权利要求5所述的有机半导体材料的制备方法,其特征在于,所述S2步骤中,所述溴化剂为N-溴代丁二酰亚胺;所述第二溶剂为N,N-二甲基甲酰胺、四氢呋喃、乙醚、二氯甲烷、三氯甲烷、乙酸乙酯或醋酸中的至少一种。
8.根据权利要求5所述的有机半导体材料的制备方法,其特征在于,S3步骤中,所述第三溶剂为四氢呋喃、甲苯、三氯甲烷或乙酸乙酯中的至少一种;
所述催化剂为有机钯或有机钯与有机膦配体的混合物;所述催化剂的用量为所述2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴摩尔用量的0.005~0.1倍;
所述碱溶液为NaOH水溶液、Na2CO3水溶液、NaHCO3水溶液或四乙基氢氧化铵水溶液中的至少一种;所述碱溶液中碱的摩尔用量为所述2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基硅芴摩尔用量的2-20倍。
9.根据权利要求8所述的有机半导体材料的制备方法,其特征在于,所述有机钯为Pd(PPh3)4、Pd2(dba)3或Pd(PPh3)2Cl2;所述有机膦配体为P(o-Tol)3。
10.一种如权利要求1至4任一所述的有机半导体材料在有机太阳能电池,有机场效应晶体管,有机电致发光器件,有机光存储或有机激光器件领域中的应用。
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