WO2023035401A1 - Non-fullerene acceptor having cooperative assembly performance, and preparation method therefor and application thereof - Google Patents
Non-fullerene acceptor having cooperative assembly performance, and preparation method therefor and application thereof Download PDFInfo
- Publication number
- WO2023035401A1 WO2023035401A1 PCT/CN2021/130177 CN2021130177W WO2023035401A1 WO 2023035401 A1 WO2023035401 A1 WO 2023035401A1 CN 2021130177 W CN2021130177 W CN 2021130177W WO 2023035401 A1 WO2023035401 A1 WO 2023035401A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active layer
- assembly performance
- fullerene acceptor
- acceptor
- fullerene
- Prior art date
Links
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims description 85
- 239000000126 substance Substances 0.000 claims description 15
- 230000005525 hole transport Effects 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 230000002195 synergetic effect Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 63
- 238000000137 annealing Methods 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000002425 crystallisation Methods 0.000 abstract description 12
- 230000008025 crystallization Effects 0.000 abstract description 12
- 238000005191 phase separation Methods 0.000 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 6
- 125000003827 glycol group Chemical group 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 94
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 46
- 238000009835 boiling Methods 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000010408 film Substances 0.000 description 30
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 28
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- 239000000243 solution Substances 0.000 description 25
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- -1 12,13-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3,9-diundecyl-12,13- Dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5 ]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole Chemical compound 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000001338 self-assembly Methods 0.000 description 8
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 238000007738 vacuum evaporation Methods 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- IUDNRKGPFWUYIC-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound COCCOCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 IUDNRKGPFWUYIC-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
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- 238000010898 silica gel chromatography Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- NCMQTAQHZHBLOA-UHFFFAOYSA-N C(CCCCCCCCCC)C1=CSC2=C1SC1=C2NC=2C3=C(C=4C(C1=2)=NSN=4)C1=C(N3)C2=C(S1)C(=CS2)CCCCCCCCCCC Chemical compound C(CCCCCCCCCC)C1=CSC2=C1SC1=C2NC=2C3=C(C=4C(C1=2)=NSN=4)C1=C(N3)C2=C(S1)C(=CS2)CCCCCCCCCCC NCMQTAQHZHBLOA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- OSHOYFUNCSYTDD-UHFFFAOYSA-N 4h-thieno[3,2-b]indole Chemical compound N1C2=CC=CC=C2C2=C1C=CS2 OSHOYFUNCSYTDD-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
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- 230000004580 weight loss Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- UXIVXGFGVAWZCH-UHFFFAOYSA-N 2h-triazepine Chemical compound N1N=CC=CC=N1 UXIVXGFGVAWZCH-UHFFFAOYSA-N 0.000 description 1
- AZFHHHGTWOIXMM-UHFFFAOYSA-N CCCCCCCCCCCc1csc2cc(sc12)[Sn](CCCC)(CCCC)CCCC Chemical compound CCCCCCCCCCCc1csc2cc(sc12)[Sn](CCCC)(CCCC)CCCC AZFHHHGTWOIXMM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007713 directional crystallization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 1
- IVEPZFBTLKOZNI-UHFFFAOYSA-N formylsulfinylformaldehyde Chemical compound O=CS(=O)C=O IVEPZFBTLKOZNI-UHFFFAOYSA-N 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- PJSOCBVWZJGTHW-UHFFFAOYSA-N n-(1h-indazol-5-yl)-5-[3-methoxy-4-[2-(2-methoxyethoxy)ethoxy]phenyl]-1,3-oxazol-2-amine Chemical compound C1=C(OC)C(OCCOCCOC)=CC=C1C(O1)=CN=C1NC1=CC=C(NN=C2)C2=C1 PJSOCBVWZJGTHW-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention belongs to the field of photovoltaic materials, and in particular relates to the application of non-fullerene acceptors with cooperative assembly performance in solar cells.
- organic solar cells have many advantages: it requires a wide range of raw materials and low production costs; the preparation process is simple and can be realized by solution spin coating, inkjet printing and other cheap methods; Film forming, easy to carry out physical modification.
- Organic solar cells have become one of the most popular research topics in the field of solar cells due to their characteristics of large-scale preparation, low cost, thinness, rollability, and flexible use.
- the active layers of efficient organic solar cells are usually bulk-heterojunction mixtures of electron donors and Y-series electron acceptors with fused-ring conjugated structures.
- the molecules are prone to excessive aggregation.
- the excessive aggregation of molecules will lead to excessive interfacial tension between different components in the active layer, which will lead to severe phase separation, increase energy loss, and then affect the device voltage.
- the excessive aggregation of molecules can also lead to rapid crystallization of active layer components.
- thermal annealing and solvent annealing post-treatment are usually used to improve the crystallinity of the active layer film to improve carrier transport and reduce recombination.
- the use of the annealing process not only increases the complexity and difficulty of device preparation, but also increases the consumption of solvents and energy, which greatly increases the economic and environmental costs of the industrialization of organic solar cells, and severely limits its industrialization process.
- Liu et al. further confirmed that the thermal annealing process is the key to induce the crystallization of the high-performance active layer system (PM6:Y6) in a controllable orientation that ensures efficient vertical charge transport.
- High-performance organic solar cells based on Y-series non-fullerene acceptors are highly dependent on this optimization process, and no method has been found to reduce its dependence on the annealing process. Therefore, it is urgent and of great significance to find a way to increase the crystallinity and optimize the crystal orientation of Y-series acceptor materials without post-processing.
- the object of the present invention is to provide non-fullerene acceptors with synergistic assembly properties and a preparation method thereof, and to overcome the deficiency that existing non-fullerene acceptors cannot obtain high performance in high boiling point and green solvents , lay the foundation for its large-area preparation, and promote the industrialization process of organic solar cells.
- a non-fullerene acceptor with cooperative assembly performance which has ethylene glycol groups
- its chemical structural formula is one of the following chemical structural formulas.
- X 1 , X 2 , X 3 , and X 4 are independently selected from one of O, S, Se, and Te; terminal group A 1 and terminal group A 2 are independently selected from one of the following structural formulas: Wherein B 1 and B 2 are independently selected from or ; B 3 to B 8 are independently selected from one of H, CH 3 , OCH 3 , F, Cl, Br, CF 3 , CN, Ca H 2a+1 ; a is 1 to 20; R 1 is - (CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , wherein m is 1 to 10, n is 1 to 20; R 2 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , where m is 1-10, n is 1-20; R 3 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , where m is 1-10, and n is 1 ⁇ 20; R 4 is -((CH
- the non-fullerene acceptor with cooperative assembly performance has an ethylene glycol group, which means that in the structural formula of the non-fullerene acceptor with cooperative assembly performance, one substituent is an ethylene glycol group, and the substituent Represented by R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 .
- the ethylene glycol group can be a monoethylene glycol group, such as -(CH 2 CH 2 O)CH 3 , or an oligoethylene glycol group, such as -(CH 2 CH 2 O) m CH 3 , m is 2-10.
- -C n H 2n+1 represents a branched alkane or a straight alkane, n is preferably 3-18, more preferably 5-15.
- R 1 is -(CH 2 CH 2 O) m CH 3 , wherein m is 1-10;
- R 1 and/or R 4 are -(CH 2 CH 2 O) m CH 3 , wherein m is 1-10.
- R 1 is -(CH 2 CH 2 O) m CH 3
- R 2 is -C n H 2n+1
- R 5 is hydrogen or -C n H 2n+1
- R 6 is hydrogen or -C n H 2n+1 , wherein m is 1-10, and n is 1-20.
- R 1 is -(CH 2 CH 2 O) m CH 3 , R 2 is -C n H 2n+1 , and R 4 is -C n H 2n+1 ; or R 4 is -(CH 2 CH 2 O) m CH 3 , R 2 is -C n H 2n+1 , R 1 is -C n H 2n+1 ; wherein m is 1 ⁇ 10, n is 1-20.
- m is 2-8, more preferably 3-6.
- the non-fullerene acceptor with cooperative assembly performance of the present invention includes self-assembling oligoethylene glycol functional groups with different lengths and different substitution positions. It still has good solubility in organic solvents, especially non-halogen solvents, and the molecule has moderate surface energy, which provides a guarantee for regulating the surface energy of the acceptor; in addition, due to the hydrogen bond between the chains, it provides good self-assembly performance , can induce receptor crystallization, improve molecular order, thereby forming a fibrous long-range ordered layered structure, overcoming the existing Y6:PM6 and other active layer materials that require post-annealing treatment to ensure a sufficiently high crystallinity of the active layer Defects have achieved unexpected results.
- the energy conversion efficiency of the solar cell prepared without post-treatment process has reached 16.59%
- the short-circuit current is 26.32 mA/cm 2
- the open-circuit voltage is 0.85 V
- the fill factor is 0.74.
- PC 71 BM is added to expand the absorption spectrum
- the PCE of the p-xylene processed device can be further increased to 17.41%, which is the highest efficiency reported so far for organic solar cell devices processed by green solvents.
- the compatibility and solubility between the host materials can be regulated, and the high
- the large-area module PCE processed by the boiling point green solvent p-xylene can reach 14.26%
- the short-circuit current is 2.01 mA/cm 2
- the open-circuit voltage is 0.71 V
- the fill factor is 0.71. It is currently reported that the effective area of the active layer is greater than 20 cm 2 Highest efficiency for organic solar cell device modules.
- the invention discloses the application of the above-mentioned non-fullerene acceptor with cooperative assembly performance in the preparation of organic solar cells.
- the non-fullerene acceptor with cooperative assembly performance of the present invention is used as a guest to prepare an active layer of an organic solar cell.
- the invention also discloses a method for preparing the non-fullerene acceptor with cooperative assembly performance, which includes the following steps: reacting the DA'D-type conjugated core with an electron-withdrawing terminal group to obtain the non-fullerene with cooperative assembly performance Acceptor; preferably, the reaction is carried out under the protection of nitrogen, in a solvent, and in the presence of a catalyst, the reaction time is 10 to 30 hours, and the temperature is 50 to 80°C; DA'D type conjugated core and electron-withdrawing end group The molar ratio is 1:4.
- the above-mentioned solvent is chloroform, dichloromethane, toluene, etc.;
- the catalyst is an organic small molecule catalyst, such as pyridine.
- the chemical structural formula of the DA'D type conjugated core is one of the following structural formulas: .
- the invention discloses an active layer material for an organic solar cell, which includes the above-mentioned non-fullerene acceptor with cooperative assembly performance; further includes Y series acceptor and donor materials.
- the above-mentioned non-fullerene acceptors with synergistic assembly performance are guest materials, Y series acceptors and donor materials are host materials, which constitute the active layer for solar cells; the donor materials are conjugated polymers or conjugated organic small Molecules, Y series receptors are Y6, Y7, Y11, etc.; for example, Y series receptors are (2,20-((2Z,20Z)-((12,13-bis(2-ethylhexyl)-3,9 -Diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,"30':4',50]thieno[20 ,30:4,5]pyrrolo[3,2-g]thieno[20,30:
- the invention discloses an organic solar cell, which comprises an active layer, an electron transport layer, a hole transport layer and an electrode; the active layer includes the above-mentioned non-fullerene acceptor with cooperative assembly performance.
- the invention discloses a preparation method of the above-mentioned organic solar cell, which comprises the following steps of sequentially preparing an electron transport layer, an active layer, a hole transport layer and an electrode on a conductive substrate to obtain an organic solar cell; properties of non-fullerene acceptors.
- the conjugated polymer or conjugated organic small molecule is used as the donor material, and the Y series conjugated small molecule (such as the star molecule Y6) is used as the acceptor material, wherein the donor material and the acceptor
- the material constitutes the main component; the material uses the above-mentioned non-fullerene acceptor with cooperative assembly performance as the guest material (the third component).
- a green solvent with a high boiling point to prepare a mixed solution containing donor materials, acceptor materials, and guest materials, and then use conventional solution processing methods to prepare the active layer, which is a thin film structure.
- Conventional solution processing methods are spin coating and brush coating , Spray or scrape.
- the green solvent with a high boiling point is toluene, p-xylene, p-xylene or mesitylene; the concentration of the donor material is 10-15 mg/mL; the mass of the donor material, acceptor material, and guest material The ratio is 1:(1-1.5):(0-0.5) excluding 0, preferably 1:(1.1-1.3):(0.1-0.45), more preferably 1:1.2:(0.12-0.25). Further, when preparing the active layer, fullerene acceptors are also included, and the amount thereof is 2-15% of the mass of the donor material, preferably 5-12%, most preferably 8-11%. The content of the guest material of the present invention does not include zero.
- the inventiveness of the present invention lies in that the above-mentioned non-fullerene acceptor with cooperative assembly performance is used as the guest, and the existing light-emitting layer material (composed of the existing donor material and the acceptor material) is used as the main body, and the preparation of the green solvent with a high boiling point is realized. solution, and without annealing, the active layer is prepared, which has excellent photoelectric properties.
- the electron transport layer, the hole transport layer and the electrode are existing products, and the specific preparation method of each layer is also a conventional technology, such as the donor material is PM6, and the electron transport layer material is aluminum-doped Zinc oxide, the material of the hole transport layer is molybdenum trioxide, the electrode is silver or aluminum, and the thickness of the active layer is 100-200 nm.
- the inventiveness of the present invention lies in disclosing a new material as a non-fullerene acceptor with synergistic assembly performance, which can use a green solvent with a high boiling point to prepare a solution without annealing, prepare an active layer, and further prepare a battery with high Performance such as PCE.
- the present invention creatively introduces oligoethylene glycol chains into non-fullerene acceptors to obtain non-fullerene acceptors with cooperative assembly performance.
- it has more effective Induce and regulate the crystallization kinetics of receptor materials, especially prolong the crystallization time of Y series receptors, increase the crystallinity of receptors and the entire active layer, overcome the dependence of directional crystallization of Y series receptors on annealing process, and simplify device preparation process, reducing the cost of preparation.
- the non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is incorporated into the host as a guest component, by regulating the crystallization kinetics of the acceptor in the host component, the crystallization effect of the low boiling point solvent is reduced.
- the active layer components with high regularity are prepared in high boiling point solvents, which solves the problem of non-uniform films caused by the rapid volatilization of low boiling point solvents in the preparation of large-area devices.
- Device preparation laid the foundation.
- the non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is used as a guest molecule to dope the existing host material, which can be dissolved and processed in a non-halogen solvent for the first time, reducing the toxicity and environmental cost of the solvent during device preparation.
- the non-fullerene acceptor with synergistic assembly performance has good compatibility with the acceptor and donor in the main component, and finally realizes the adjustment of the compatibility of the main component, and realizes the high boiling point solvent
- the regulation of the morphology of the active layer during processing avoids the excessive aggregation of donors and acceptors in the main body, and avoids the common phase separation defects in the prior art, thereby reducing the recombination probability of excitons and improving the efficiency of organic solar cells.
- High boiling point The energy conversion efficiency of solar cells prepared by green solvent (p-xylene) processing without post-treatment process has reached 17.41%, which is the highest efficiency of green solvent processed organic solar cell devices reported so far.
- non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is blended with the main active layer, a more stable microstructure and morphology can be obtained, and the obtained device has better working stability.
- the non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is added to the main component as a guest molecule, which solves the problems of toxicity and uneven film caused by halogen-containing and low-boiling solvents, and at the same time realizes no post-processing Processing simplifies the device process, reduces economic and environmental costs, and finally obtains a high-performance, high-stability large-area device module, which promotes the process of industrialization of organic solar cells.
- Fig. 1 is the proton nuclear magnetic resonance spectrum figure of BTO in the embodiment one.
- Fig. 2 is the carbon nuclear magnetic resonance spectrogram of BTO in embodiment one.
- Fig. 3 is the thermal weight loss curve of BTO in Example 1.
- Fig. 4 is the cyclic voltammetry curve of BTO in the first embodiment.
- Fig. 5 is the ultraviolet-visible spectrum of the BTO film processed in chlorobenzene without annealing in Example 1.
- Figure 6 is the H NMR spectrum of BT-2OEG-4F in Example 2.
- Figure 7 is the H NMR spectrum of BT-4OEG-4F in Example 3.
- Figure 8 is the H NMR spectrum of BO1 in Example 4.
- Fig. 9 is the proton nuclear magnetic resonance spectrogram of BO in embodiment five.
- Fig. 10 is the proton nuclear magnetic resonance spectrogram of BO3 in embodiment six.
- Fig. 11 is a physical diagram of the active layer film in the seventh embodiment.
- Fig. 12 is an atomic force microscope image of the active layer thin film in Example 7.
- Fig. 13 is a transmission electron microscope image of the active layer thin film in Example 7.
- Fig. 14 is a J-V curve diagram of the device processed by high boiling point chlorobenzene in the eighth embodiment.
- Fig. 15 is a J-V curve diagram of the device processed with high boiling point chlorobenzene with or without thermal annealing in Example 9.
- Fig. 16 is a J-V curve diagram of the device processed by the high-boiling green solvent p-xylene in Example 10.
- Fig. 17 is a J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 11.
- Fig. 18 is a J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 12.
- Fig. 19 is a J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 13.
- Fig. 20 is the J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 14.
- the raw materials of the present invention are all existing products, and the specific preparation operations and testing methods are conventional methods in this field.
- Example 1 The structural formula of a non-fullerene acceptor material (BTO) with cooperative assembly performance is: .
- the preparation method of the above-mentioned BTO is as follows: add 1 M sodium hydroxide solution (50 mL) into triethylene glycol monomethyl ether (16.41 g, 0.10 mol) in tetrahydrofuran (20 mL), p-toluenesulfonyl chloride (19.64 g, 0.10 mol) of saturated tetrahydrofuran solution was added dropwise to the reaction system, and stirred overnight at room temperature to obtain a colorless liquid 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate ;Under nitrogen protection, 3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'' :4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-
- Figure 1 is the hydrogen nuclear magnetic resonance spectrum of BTO
- Figure 2 is the carbon nuclear magnetic resonance spectrum of BTO, indicating that the present invention has successfully prepared non-fullerene acceptor BTO with self-assembly characteristics.
- Figure 3 is the thermal weight loss curve of BTO, and its decomposition temperature is 317°C, which shows that it has excellent thermal stability.
- Figure 4 is the cyclic voltammetry curve of the BTO thin film, and ferrocene was used as the internal standard during the test.
- the oxidation potential of Fe/Fe+ in 0.1 M TBAPF6 is 0.86 V, and the reduction potential is -0.77 V.
- E LUMO -(4.73- E Ferrocene + E re ).
- E Ferrocene -0.02 V, the corresponding HOMO energy level can be obtained as -5.61eV, and the LUMO energy level is -3.98 eV.
- the BTO film processed without annealing chlorobenzene has obvious shoulder peaks in the range of 600-800 nm, which reflects the orderly stacking of side chains in the BTO molecule, which is mainly attributed to the molecular self-assembly , reflecting the ordered molecular arrangement of BTO molecules in a high boiling point solvent without annealing.
- Example 2 The structural formula of the non-fullerene acceptor material (BT-2OEG-4F) with synergistic assembly performance is: .
- BT-2OEG-4F The preparation method of the above-mentioned BT-2OEG-4F is as follows: under nitrogen protection, 3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e] Thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4, 5] Thieno[3,2-b]indole (747.17 mg, 1 mmol) and tetrabutylammonium bisulfate (86.98 mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50 M sodium hydroxide solution (7 mL) was stirred at room temperature for 15 After min, 2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (603.53 mg, 2.20 mmol) was added to the reaction system, and
- Fig. 6 is the hydrogen nuclear magnetic resonance spectrum of BT-2OEG-4F, indicating that the present invention has successfully prepared the non-fullerene acceptor BT-2OEG-4F with self-assembly characteristics.
- Example 3 The structural formula of the non-fullerene acceptor material (BT-4OEG-4F) with synergistic assembly performance is: .
- BT-4OEG-4F The preparation method of the above-mentioned BT-4OEG-4F is as follows: under the protection of nitrogen, 3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e] Thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4, 5] Thieno[3,2-b]indole (747.17 mg, 1 mmol) and tetrabutylammonium bisulfate (86.98 mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50 M sodium hydroxide solution (7 mL) was stirred at room temperature for 15 After min, 2-[2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (800.80 mg, 2.20 mmol) was
- Fig. 7 is the hydrogen nuclear magnetic resonance spectrum of BT-4OEG-4F, indicating that the present invention has successfully prepared the non-fullerene acceptor BT-4OEG-4F with self-assembly characteristics.
- Example 4 The structural formula of the non-fullerene acceptor material (BO1) is: .
- BO1 was prepared as follows: (1) 4,7-dibromo-2hydro-benzo[d][1,2,3]triazole (609.22 mg, 2.2 mmol), tetrabutylammonium bisulfate (86.98 mg, 0.25 mmol) were dissolved in 20 mL of toluene, 0.5 M sodium hydroxide solution (7 mL) was added and stirred at room temperature for 15 min, then 4-methylbenzenesulfonate Acid 2-[2-(2-methoxyethoxy)ethoxy]ethyl ester (699.84 mg, 2.2 mmol) was added to the reaction system.
- Example 5 The structural formula of the non-fullerene acceptor material (BO2) is: .
- the preparation method of BO2 is as follows: (1) Under nitrogen, 2-(2-ethylhexyl)-5,6-o-dinitrobenzene-4,7-bis(6-undecylthieno[3,2 -b]thiophene-2-yl)-2 hydrogen-benzo[d][1,2,3]triazole (0.91 g, 1.00 mmol) and triethyl phosphate (5 mL) were dissolved in o-dichlorobenzene (2.50 mL), heated and stirred overnight at 180 °C, spin-dried the solvent to obtain a red crude product, added tetrabutylammonium bisulfate (86.98 mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50 M sodium hydroxide solution (7 mL) was stirred at room temperature for 15 After min, 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate
- Example 6 The structural formula of the non-fullerene acceptor material (BO3) is: .
- the preparation method of BO3 includes as follows: (1) under nitrogen, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-5,6-dinitro-4,7 -bis(6-undecylthieno[3,2-b]thiophene-2-yl)-2hydro-benzo[d][1,2,3]triazole (0.94 g, 1.00 mmol) and triethyl phosphate (5 mL) were dissolved in o-dichlorobenzene (2.50 mL), heated and stirred overnight at 180°C, spin-dried the solvent to obtain a red crude product, added tetrabutylammonium bisulfate (86.98 mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50 M sodium hydroxide solution (7 mL) was stirred at room temperature for 15 After min, 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenz
- Embodiment 7 An active layer material for organic solar cells, including the above-mentioned non-fullerene acceptors, other Y series acceptors, and donor materials. Taking Y6 and BTO as the acceptor material and PM6 as the donor material as an example: (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, and spin-coat it at 2000 rpm after drying.
- ITO indium tin oxide
- AZO aluminum-doped zinc oxide
- Embodiment 8 An organic solar cell whose active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials.
- the preparation method of the organic solar cell is as follows: (1) Use ethanol, acetone, and isopropanol to ultrasonically oxidize indium tin (ITO) conductive glass sheet successively, bake After drying, spin-coat a layer of 5 mg/mL AZO with a thickness of 40 nm at 2000 rpm as an electron transport layer, and then heat and dry at 120°C for 15 minutes to remove moisture; (2) use high-boiling point chlorobenzene as a solvent, The preparation PM6 concentration is 12mg/mL, the mixed solution of PM6/Y6:BTO (w/w:w 1/1.2:0, 1/1.2:0.12, 1/1.2:0.36), stirs, then it is with the rotating speed of 2500r
- Embodiment 9 An organic solar cell, the active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials.
- the preparation method of the organic solar cell is as follows: (1) Use ethanol, acetone, and isopropanol to ultrasonically oxidize indium tin (ITO) conductive glass sheet successively, bake After drying, spin-coat a layer of 5 mg/mL AZO with a thickness of 40 nm at 2000 rpm as an electron transport layer, and then heat and dry at 120°C for 15 minutes to remove moisture; (2) use high-boiling point chlorobenzene as a solvent, Prepare a PM6 concentration of 12 mg/mL, a mixed solution of PM6/Y6:BTO (w/w:w 1/1.2:0, 1/1.2:0.24,), stir, and then spin coat it at a speed of 2500rpm On the electron
- the thermal annealing process can further improve the performance of PM6:Y6 devices, and the device PCE can reach 13.98%, the short-circuit current is 25.91 mA/cm 2 , and the open-circuit voltage is 0.86 V , the fill factor is 0.73, because thermal annealing promotes the ordered arrangement of acceptor molecules.
- the thermal annealing treatment led to a slight decrease in device performance, indicating that the phase separation size and morphology of the active layer regulated by the BTO of the present invention have reached a perfect equilibrium state, achieving an excellent battery performance, the thermal annealing treatment degrades the performance instead, which is contrary to the prior art.
- the thermal annealing parameters are conventional thermal annealing parameters of the existing PM6:Y6, which have been reported in the literature.
- Embodiment 11 An organic solar cell whose active layer materials include the above-mentioned non-fullerene acceptors, other Y series acceptors, and donor materials.
- the preparation method of the organic solar cell is as follows: (1) Use ethanol, acetone, and isopropanol to ultrasonically oxidize indium tin (ITO) conductive glass sheet successively, bake After drying, spin-coat a layer of 5 mg/mL AZO with a thickness of 40 nm at 2000 rpm as an electron transport layer, and then heat and dry at 120°C for 15 minutes to remove moisture; (2) Use p-xylene with a high boiling point as a solvent , the prepared PM6 concentration is 12mg/mL, PM6/Y6:BTO:PC 71 BM(w/w:w:w 1/1.2:0:0, 1/1.2:0.24:0, 1/1.2:0:0.1,
- Example 11 Ultrasonic the ITO glass substrate with a size of (10 ⁇ 10 cm 2 ) twice in deionized water, acetone, ethanol and isopropanol, clean it and dry it for later use; (2) Configuration 5mg/mL AZO solution, the electron transport layer was prepared by scraping, the thickness was 40 nm, the height of the scraper from the substrate was 20 ⁇ m, and the scraper speed was 20 mm/s, and then dried on a hot stage at 120°C for 15 min; ( 3) Prepare PM6/Y6:BTO:PC 71 BM (w/w:w:w 1/1.2:0:0, 1/1.2:0.24:0, 1/1.2: 0.24:0.1) mixed solution (PM6 concentration is 12mg/mL), the organic active layer (thickness is 120nm) is prepared by scraping, the height of the scraper from the substrate is 30 ⁇ m, the scraper speed is 25 mm/s, no post-processing is required; ( 4) Using a vacuum
- the PCE of the p-xylene processed device can be further increased to 14.26%, which is the highest efficiency reported so far for the organic solar cell device module with active layer area larger than 20 cm 2 . This proves that the strategy in the present invention effectively improves the efficiency of large-area modules of organic solar cells.
- Embodiment 12 An organic solar cell whose active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials.
- Y6 and BO1 as the acceptor material
- PM6 as the donor material as an example:
- (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, spin-coat at 2000 rpm after drying
- One layer of 5mg/mL AZO layer with a thickness of 40 nm is used as an electron transport layer, and then heated and dried at 120°C for 15 minutes to remove moisture;
- (2) Use high-boiling point chlorobenzene or p-xylene as a solvent to prepare a PM6 concentration of 12mg /mL, the mixed solution of PM6/Y6:BO1 (w/w:w 1/1.2:0, 1/1.2:0.24) was stirred, and then it was spin-coated on the electron transport layer at
- Embodiment 13 An organic solar cell, the active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials.
- Y6 and BO2 as the acceptor material
- PM6 as the donor material as an example:
- (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, spin-coat at 2000 rpm after drying
- One layer of 5mg/mL AZO layer with a thickness of 40 nm is used as an electron transport layer, and then heated and dried at 120°C for 15 minutes to remove moisture; mg/mL, the mixed solution of PM6/Y6:BO2 (w/w:w 1/1.2:0, 1/1.2:0.24) was stirred, and then it was spin-coated on the electron transport layer at a speed of 2500rpm to obtain
- the thickness of the active layer film without annealing treatment is about 120 nm; (3) 10 nm of Mo
- the light intensity is 100mW/cm 2 AM 1.5 under the condition of white light irradiation, and the current-voltage curve is obtained, as shown in Figure 19, and the corresponding performance parameters of the battery are obtained according to the curve, as shown in Table 6.
- Embodiment 14 An organic solar cell, the active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials.
- Y6 and BO3 as the acceptor material
- PM6 as the donor material as an example:
- (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, spin-coat at 2000 rpm after drying
- One layer of 5mg/mL AZO layer with a thickness of 40 nm is used as an electron transport layer, and then heated and dried at 120°C for 15 minutes to remove moisture; mg/mL, the mixed solution of PM6/Y6:BO3 (w/w:w 1/1.2:0, 1/1.2:0.12, 1/1.2:0.24) was stirred, and then it was spin-coated at 2500rpm
- a non-annealed active layer film was obtained, with a film thickness of about 120 nm;
- the light intensity is 100mW/cm 2 AM 1.5 under the condition of white light irradiation, and the current-voltage curve is obtained, as shown in Figure 20, and the corresponding performance parameters of the battery are obtained according to the curve, as shown in Table 7.
- BT-2OEG-4F and BT-4OEG-4F also have improved performance on PM6:Y6, which is lower than the above-mentioned non-fullerene molecules.
- the active layer components have sufficient crystallization time, and the overall order degree is improved, thereby constructing a long-range order, nanoscale phase separation and three-dimensional three-dimensional
- the microstructure of the transmission channel can further improve the short-circuit current and fill factor of the device, which greatly improves the energy conversion efficiency of the device.
- the non-fullerene acceptor with cooperative assembly performance disclosed by the present invention is added as a guest molecule to the main component, which solves the problems of toxicity and film unevenness caused by halogen-containing and low-boiling solvents, and at the same time realizes no post-processing processing,
- the device process is simplified, economic and environmental costs are reduced, and a high-performance, high-stability large-area device module is finally obtained, which promotes the industrialization process of organic solar cells.
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Abstract
Provided are a non-fullerene acceptor having cooperative assembly performance, and a preparation method therefor and an application thereof, the non-fullerene acceptor having cooperative assembly performance comprising oligoethylene glycol side chains having different position substitutions and different lengths. The non-fullerene acceptor as a guest component achieves the dissolution of active layer (host) components in various non-halogen solvents, regulates the compatibility between the active layer components as well as a phase separation size and morphology, and reduce the dependence of an active layer on a low-boiling-point and highly toxic halogen-containing solvent. In addition, the guest non-fullerene acceptor can also regulate the crystallization kinetics of a host in a high-boiling-point solvent by means of self-assembled side chains, prolong the crystallization time of acceptor molecules, improve the overall crystallinity of the active layer, and reduce the dependence of active layer processing on a post-treatment process. By combining the three advantages, the photoelectric conversion efficiency of an organic solar cell obtained by processing with a high-boiling-point and green solvent is greatly improved, and no annealing process is required, thereby simplifying the process of device preparation and reducing the energy consumption of device preparation.
Description
本发明属于光伏材料领域，具体涉及具备协同组装性能的非富勒烯受体在太阳能电池中的应用。The invention belongs to the field of photovoltaic materials, and in particular relates to the application of non-fullerene acceptors with cooperative assembly performance in solar cells.
随着社会的进步，工业产业的发展，人们对于能源的需求不断增加，造成了人们对于能源的过度开采和使用，因此急需寻找一种清洁的、可再生的新型能源，而太阳能就能满足人们的需求，因而如何有效的开发和利用太阳能成为了科学研究的热点。相对于无机太阳能电池而言，有机太阳能电池具有很多优点：它所需要的原料来源广泛，生产成本低；制备工艺简便，可以通过溶液旋涂、喷墨打印等廉价的方式实现；同时可大面积成膜，容易进行物理改性。有机太阳能电池由于具有能大规模制备、低成本、轻薄、可卷曲、可灵活使用等特点，成为了太阳能电池领域最热门的研究课题之一。With the progress of society and the development of industry, people's demand for energy continues to increase, resulting in people's excessive exploitation and use of energy. Therefore, it is urgent to find a clean and renewable new energy source, and solar energy can satisfy people's needs. Therefore, how to effectively develop and utilize solar energy has become a hot spot of scientific research. Compared with inorganic solar cells, organic solar cells have many advantages: it requires a wide range of raw materials and low production costs; the preparation process is simple and can be realized by solution spin coating, inkjet printing and other cheap methods; Film forming, easy to carry out physical modification. Organic solar cells have become one of the most popular research topics in the field of solar cells due to their characteristics of large-scale preparation, low cost, thinness, rollability, and flexible use.
近年来，依靠材料创新、工艺开发和器件架构优化等手段，由低沸点含卤溶剂和各种添加剂加工而成的高性能小面积器件（0.032
cm
2）的光电效率（PCE）达到18%，这也显示了有机光伏产品在柔性、便携能源领域的巨大潜力。但是，卤化试剂（如氯仿）不仅沸点低、易挥发，在制备大面积器件时由于不可控的挥发过程，会导致薄膜形貌难以控制，使得器件PCE较低，而且其毒性巨大，不适用于大规模工业化生产。
In recent years, relying on material innovation, process development, and device architecture optimization, the photoelectric efficiency (PCE) of high-performance small-area devices (0.032 cm 2 ) processed by low-boiling point halogen-containing solvents and various additives has reached 18%. This also shows the great potential of organic photovoltaic products in the field of flexible and portable energy. However, halogenated reagents (such as chloroform) not only have a low boiling point and are volatile, but due to the uncontrollable volatilization process in the preparation of large-area devices, it will lead to difficult control of the film morphology, resulting in low PCE of the device, and its toxicity is huge, so it is not suitable for large-scale industrial production.
目前，高效的有机太阳能电池活性层通常是电子给体和具有稠环共轭结构的Y系列电子受体的体异质结混合物。当使用高沸点、绿色溶剂加工活性层时，由于受体材料分子在溶剂中溶解性差且分子自组装能力弱，分子易出现过度聚集的现象。根据Flory-Huggins模型，分子的过度聚集会导致活性层中不同组分之间的界面张力过大，从而导致严重的相分离，增加能量损失，进而影响器件电压。除此之外，在高沸点溶剂中，分子的过度聚集还会导致活性层组分快速结晶。这种快速的结晶过程会使得晶体结构杂乱无序，从而造成活性层结晶度低且取向混乱，进而影响电荷传输。因此，通过优化分子结构来降低受体材料对低沸点、高毒性卤化试剂的依赖性，最终实现通过高沸点、绿色溶剂制备高性能有机太阳能电池，是实现有机光伏产业化亟待解决的重大问题。Currently, the active layers of efficient organic solar cells are usually bulk-heterojunction mixtures of electron donors and Y-series electron acceptors with fused-ring conjugated structures. When using high boiling point, green solvents to process the active layer, due to the poor solubility of receptor material molecules in the solvent and the weak self-assembly ability of the molecules, the molecules are prone to excessive aggregation. According to the Flory-Huggins model, the excessive aggregation of molecules will lead to excessive interfacial tension between different components in the active layer, which will lead to severe phase separation, increase energy loss, and then affect the device voltage. In addition, in high-boiling point solvents, the excessive aggregation of molecules can also lead to rapid crystallization of active layer components. This rapid crystallization process will make the crystal structure disordered and disordered, resulting in low crystallinity and disordered orientation of the active layer, thereby affecting charge transport. Therefore, reducing the dependence of acceptor materials on low-boiling point and highly toxic halogenated reagents by optimizing molecular structure, and finally realizing the preparation of high-performance organic solar cells through high-boiling point and green solvents, is a major problem to be solved to realize the industrialization of organic photovoltaics.
此外，高性能有机太阳能电池制备过程中通常会依赖于热退火和溶剂退火后处理提高活性层薄膜结晶度，以改善载流子传输，降低复合。然而，退火工艺的使用不仅增加了器件制备的复杂性和难度，而且增加了溶剂和能源的消耗，极大地提高了有机太阳能电池产业化的经济和环境成本，严重限制了其产业化的进程。近期，Liu等人进一步证实了热退火工艺是诱导高性能的活性层体系（PM6:Y6）在可控取向下结晶的关键，该取向确保了电荷高效的垂直传输。基于Y系列非富勒烯受体的高性能有机太阳能电池高度依赖于这一优化工艺，目前还未找到降低其对退火工艺依赖性的方法。因此，寻找一种无需后处理就能提高Y系列受体材料结晶度和优化晶体取向的方法，具有紧迫性和重大意义。In addition, in the preparation process of high-performance organic solar cells, thermal annealing and solvent annealing post-treatment are usually used to improve the crystallinity of the active layer film to improve carrier transport and reduce recombination. However, the use of the annealing process not only increases the complexity and difficulty of device preparation, but also increases the consumption of solvents and energy, which greatly increases the economic and environmental costs of the industrialization of organic solar cells, and severely limits its industrialization process. Recently, Liu et al. further confirmed that the thermal annealing process is the key to induce the crystallization of the high-performance active layer system (PM6:Y6) in a controllable orientation that ensures efficient vertical charge transport. High-performance organic solar cells based on Y-series non-fullerene acceptors are highly dependent on this optimization process, and no method has been found to reduce its dependence on the annealing process. Therefore, it is urgent and of great significance to find a way to increase the crystallinity and optimize the crystal orientation of Y-series acceptor materials without post-processing.
为推进有机太阳能电池的产业化进程，寻找一种能够同时提高高性能Y系列受体在高沸点绿色溶剂中的溶解度，调控给受体相容性，有效控制活性层表面形貌，并提高Y系列受体有序性，降低其对退火工艺的依赖，已经成为有机太阳能电池发展的首要问题。In order to promote the industrialization process of organic solar cells, it is necessary to find a method that can simultaneously improve the solubility of high-performance Y series receptors in high-boiling point green solvents, regulate the compatibility of donors and acceptors, effectively control the surface morphology of the active layer, and improve the Y The ordering of the series receptors and reducing their dependence on the annealing process have become the primary issues for the development of organic solar cells.
为解决上述问题，本发明的目的是提供具备协同组装性能的非富勒烯受体及其制备方法，并克服现有非富勒烯受体无法在高沸点、绿色溶剂中获得高性能的不足，为其大面积制备奠定基础，推进有机太阳能电池的产业化进程。In order to solve the above problems, the object of the present invention is to provide non-fullerene acceptors with synergistic assembly properties and a preparation method thereof, and to overcome the deficiency that existing non-fullerene acceptors cannot obtain high performance in high boiling point and green solvents , lay the foundation for its large-area preparation, and promote the industrialization process of organic solar cells.
为实现上述技术目的，本发明通过以下技术方案实现：一种具备协同组装性能的非富勒烯受体，具有乙二醇基团；其化学结构式为以下化学结构式中的一种。In order to achieve the above technical purpose, the present invention is realized through the following technical solutions: a non-fullerene acceptor with cooperative assembly performance, which has ethylene glycol groups; its chemical structural formula is one of the following chemical structural formulas.
其中，X
1、X
2、X
3、X
4独立的选自O、S、Se、Te中的一种；端基A
1、端基A
2独立的选自以下结构式中的一种：
其中B
1、B
2独立的选自
或者
；B
3～B
8独立的选自H、CH
3、OCH
3、F、Cl、Br、CF
3、CN、C
aH
2a+1中的一种；a为1～20；R
1为-(CH
2CH
2O)
mCH
3或者-C
nH
2n+1，其中m为1～10，n为1～20；R
2为-(CH
2CH
2O)
mCH
3或者-C
nH
2n+1，其中m为1～10，n为1～20；R
3为-(CH
2CH
2O)
mCH
3或者-C
nH
2n+1，其中m为1～10，n为1～20；R
4为-(CH
2CH
2O)
mCH
3或者-C
nH
2n+1，其中m为1～10，n为1～20；R
5为氢、-(CH
2CH
2O)
mCH
3或者-C
nH
2n+1，其中m为1～10，n为1～20；R
6为氢、-(CH
2CH
2O)
mCH
3或者-C
nH
2n+1，其中m为1～10，n为1～20。
Wherein, X 1 , X 2 , X 3 , and X 4 are independently selected from one of O, S, Se, and Te; terminal group A 1 and terminal group A 2 are independently selected from one of the following structural formulas: Wherein B 1 and B 2 are independently selected from or ; B 3 to B 8 are independently selected from one of H, CH 3 , OCH 3 , F, Cl, Br, CF 3 , CN, Ca H 2a+1 ; a is 1 to 20; R 1 is - (CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , wherein m is 1 to 10, n is 1 to 20; R 2 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , where m is 1-10, n is 1-20; R 3 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , where m is 1-10, and n is 1~20; R 4 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , wherein m is 1~10, n is 1~20; R 5 is hydrogen, -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , wherein m is 1 to 10, n is 1 to 20; R 6 is hydrogen, -(CH 2 CH 2 O) m CH 3 or -C n H 2n +1 , where m is 1-10, and n is 1-20.
本发明中，具备协同组装性能的非富勒烯受体具有乙二醇基团是指具备协同组装性能的非富勒烯受体结构式中，有一个取代基为乙二醇基团，取代基以R
1、R
2、R
3、R
4、R
5、R
6表示。乙二醇基团可以是单乙二醇基团，比如-(CH
2CH
2O)CH
3，也可以是低聚乙二醇基团，比如-(CH
2CH
2O)
mCH
3，m为2～10。具备协同组装性能的非富勒烯受体的化学结构式中，具有的乙二醇基团可以为一个也可以为多个。-C
nH
2n+1表示支链烷烃或者直链烷烃，n优选为3～18，再优选为5～15。
In the present invention, the non-fullerene acceptor with cooperative assembly performance has an ethylene glycol group, which means that in the structural formula of the non-fullerene acceptor with cooperative assembly performance, one substituent is an ethylene glycol group, and the substituent Represented by R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 . The ethylene glycol group can be a monoethylene glycol group, such as -(CH 2 CH 2 O)CH 3 , or an oligoethylene glycol group, such as -(CH 2 CH 2 O) m CH 3 , m is 2-10. In the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance, there may be one or more ethylene glycol groups. -C n H 2n+1 represents a branched alkane or a straight alkane, n is preferably 3-18, more preferably 5-15.
优选的，本发明具备协同组装性能的非富勒烯受体的化学结构式为式1或者式3时，R
1为-(CH
2CH
2O)
mCH
3，其中m为1～10；具备协同组装性能的非富勒烯受体的化学结构式为式2时，R
1和/或R
4为-(CH
2CH
2O)
mCH
3，其中m为1～10。进一步优选的，本发明具备协同组装性能的非富勒烯受体的化学结构式为式1或者式3时，R
1为-(CH
2CH
2O)
mCH
3，R
2为-C
nH
2n+1，R
5为氢或者-C
nH
2n+1，R
6为氢或者-C
nH
2n+1，其中m为1～10，n为1～20。具备协同组装性能的非富勒烯受体的化学结构式为式2时，R
1为-(CH
2CH
2O)
mCH
3，R
2为-C
nH
2n+1，R
4为-C
nH
2n+1；或R
4为-(CH
2CH
2O)
mCH
3，R
2为-C
nH
2n+1，R
1为-C
nH
2n+1；其中其中m为1～10，n为1～20。
Preferably, when the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance in the present invention is formula 1 or formula 3, R 1 is -(CH 2 CH 2 O) m CH 3 , wherein m is 1-10; When the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance is Formula 2, R 1 and/or R 4 are -(CH 2 CH 2 O) m CH 3 , wherein m is 1-10. Further preferably, when the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance in the present invention is formula 1 or formula 3, R 1 is -(CH 2 CH 2 O) m CH 3 , and R 2 is -C n H 2n+1 , R 5 is hydrogen or -C n H 2n+1 , R 6 is hydrogen or -C n H 2n+1 , wherein m is 1-10, and n is 1-20. When the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance is Formula 2, R 1 is -(CH 2 CH 2 O) m CH 3 , R 2 is -C n H 2n+1 , and R 4 is -C n H 2n+1 ; or R 4 is -(CH 2 CH 2 O) m CH 3 , R 2 is -C n H 2n+1 , R 1 is -C n H 2n+1 ; wherein m is 1～ 10, n is 1-20.
优选的，本发明中，m为2～8，进一步优选为3～6。Preferably, in the present invention, m is 2-8, more preferably 3-6.
本发明的具备协同组装性能的非富勒烯受体包括不同长度和不同取代位点的具备自组装性的低聚乙二醇功能化基团。在有机溶剂特别是非卤溶剂中仍具有好的溶解性，而且分子具有适中的表面能，为调控给受体表面能提供了保证；另外由于链间的氢键作用，提供了良好的自组装性能，可以诱导受体结晶，提高分子有序性，从而形成纤维状的长程有序的层状结构，克服了现有Y6:PM6等活性层材料需要退火后处理才能保证活性层足够高结晶度的缺陷，取得了意想不到的效果。最终，基于本发明非富勒烯受体为客体，PM6:Y6为主体组分，在高沸点、绿色溶剂（如对二甲苯）加工，无后处理工艺制备的太阳能电池能量转换效率就已经达到了16.59%，短路电流为26.32 mA/cm
2，开路电压为0.85
V，填充因子为0.74。当添加PC
71BM以拓展吸收光谱后，对二甲苯加工的器件PCE能进一步提升至17.41%，是目前报道的绿色溶剂加工有机太阳能电池器件的最高效率。应用本发明中的非富勒烯受体作为客体分子加入主体（PM6:Y6:PC
71BM）中后，可以调控主体材料间的相容性和溶解度，在没有任何后处理的条件下，高沸点绿色溶剂对二甲苯加工的大面积模组PCE可以达到14.26%，短路电流为2.01 mA/cm
2，开路电压为0.71 V，填充因子为0.71，是目前报道活性层有效面积大于20 cm
2的有机太阳能电池器件模组的最高效率。
The non-fullerene acceptor with cooperative assembly performance of the present invention includes self-assembling oligoethylene glycol functional groups with different lengths and different substitution positions. It still has good solubility in organic solvents, especially non-halogen solvents, and the molecule has moderate surface energy, which provides a guarantee for regulating the surface energy of the acceptor; in addition, due to the hydrogen bond between the chains, it provides good self-assembly performance , can induce receptor crystallization, improve molecular order, thereby forming a fibrous long-range ordered layered structure, overcoming the existing Y6:PM6 and other active layer materials that require post-annealing treatment to ensure a sufficiently high crystallinity of the active layer Defects have achieved unexpected results. Finally, based on the non-fullerene acceptor of the present invention as the guest, PM6:Y6 as the main component, processed in a high boiling point, green solvent (such as p-xylene), the energy conversion efficiency of the solar cell prepared without post-treatment process has reached 16.59%, the short-circuit current is 26.32 mA/cm 2 , the open-circuit voltage is 0.85 V, and the fill factor is 0.74. When PC 71 BM is added to expand the absorption spectrum, the PCE of the p-xylene processed device can be further increased to 17.41%, which is the highest efficiency reported so far for organic solar cell devices processed by green solvents. After adding the non-fullerene acceptor in the present invention as a guest molecule into the host (PM6:Y6:PC 71 BM), the compatibility and solubility between the host materials can be regulated, and the high The large-area module PCE processed by the boiling point green solvent p-xylene can reach 14.26%, the short-circuit current is 2.01 mA/cm 2 , the open-circuit voltage is 0.71 V, and the fill factor is 0.71. It is currently reported that the effective area of the active layer is greater than 20 cm 2 Highest efficiency for organic solar cell device modules.
本发明公开了上述具备协同组装性能的非富勒烯受体在制备有机太阳能电池中的应用，具体的，本发明具备协同组装性能的非富勒烯受体作为客体制备有机太阳能电池活性层，尤其是制备无需退火处理的有机太阳能电池活性层；本发明公开的具备协同组装性能的非富勒烯受体与主体活性层共混时可得到更为稳定的微观结构和形貌，同时得到的器件具有较好的工作稳定性。The invention discloses the application of the above-mentioned non-fullerene acceptor with cooperative assembly performance in the preparation of organic solar cells. Specifically, the non-fullerene acceptor with cooperative assembly performance of the present invention is used as a guest to prepare an active layer of an organic solar cell. In particular, the preparation of the active layer of organic solar cells without annealing treatment; when the non-fullerene acceptor with cooperative assembly performance disclosed by the present invention is blended with the active layer of the main body, a more stable microstructure and morphology can be obtained, and the obtained The device has good working stability.
本发明还公开了上述具备协同组装性能的非富勒烯受体的制备方法，包括以下步骤，将DA’D型共轭核与吸电子端基反应，得到具备协同组装性能的非富勒烯受体；优选的，所述反应在氮气保护下、溶剂中、催化剂存在下进行，反应的时间为10～30小时，温度为50～80℃；DA’D型共轭核与吸电子端基的摩尔比为1∶4。上述溶剂为三氯甲烷、二氯甲烷、甲苯等；催化剂为有机小分子催化剂，比如吡啶。The invention also discloses a method for preparing the non-fullerene acceptor with cooperative assembly performance, which includes the following steps: reacting the DA'D-type conjugated core with an electron-withdrawing terminal group to obtain the non-fullerene with cooperative assembly performance Acceptor; preferably, the reaction is carried out under the protection of nitrogen, in a solvent, and in the presence of a catalyst, the reaction time is 10 to 30 hours, and the temperature is 50 to 80°C; DA'D type conjugated core and electron-withdrawing end group The molar ratio is 1:4. The above-mentioned solvent is chloroform, dichloromethane, toluene, etc.; the catalyst is an organic small molecule catalyst, such as pyridine.
上述技术方案中，DA’D型共轭核的化学结构式为以下结构式中的一种：
。
In the above technical scheme, the chemical structural formula of the DA'D type conjugated core is one of the following structural formulas: .
吸电子端基选择以下化合物中的一种：
。
Choose one of the following compounds for the electron-withdrawing end group: .
上述结构式中，取代基（X
1、X
2、X
3、X
4、B
1～B
8、R
1、R
2、R
3、R
4、R
5、R
6）的选择同上文式1、式2、式3取代基的选择。产物端基A1与端基A2可以一样，也可以不一样。
In the above structural formula, the selection of substituents (X 1 , X 2 , X 3 , X 4 , B 1 ~ B 8 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ) is the same as that of the above formula 1, Formula 2, the selection of formula 3 substituents. The end group A1 of the product and the end group A2 may be the same or different.
本发明公开了一种有机太阳能电池用活性层材料，包括上述具备协同组装性能的非富勒烯受体；进一步包括Y系列受体、给体材料。上述具备协同组装性能的非富勒烯受体为客体材料、Y系列受体以及给体材料为主体材料，构成太阳能电池用活性层；所述给体材料为共轭聚合物或共轭有机小分子，Y系列受体为Y6、Y7、Y11等；比如Y系列受体为(2,20-((2Z,20Z)-((12,13-二(2-乙基己基)-3,9-双十一烷基-12,13-二氢-[1,2,5]噻二唑并[3,4-e]噻吩并[2,"30’:4’,50]噻吩并[20,30:4,5]吡咯并[3,2-g]噻吩并[20,30:4,5] 噻吩并[3,2-b]吲哚-2,10-取代基)双(甲酰亚砜))双(5,6-二氟-3-氧-2,3-二氢-1氢-茚-2,1-二亚乙基))二丙二腈（Y6），所述给体材料为聚[(2,6-(4,8-双(5-(2-乙基己基-3-氟代)噻吩-2-yl)-苯并][1,2-b:4,5 - b’]二噻吩))-alt-(5,5-(1’,30-双-2-噻吩-50,7’-双(2-乙基己基)苯并[1’,2’-c:4’,50-c’]二噻吩-4,8-二酮) （PM6）。The invention discloses an active layer material for an organic solar cell, which includes the above-mentioned non-fullerene acceptor with cooperative assembly performance; further includes Y series acceptor and donor materials. The above-mentioned non-fullerene acceptors with synergistic assembly performance are guest materials, Y series acceptors and donor materials are host materials, which constitute the active layer for solar cells; the donor materials are conjugated polymers or conjugated organic small Molecules, Y series receptors are Y6, Y7, Y11, etc.; for example, Y series receptors are (2,20-((2Z,20Z)-((12,13-bis(2-ethylhexyl)-3,9 -Diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,"30':4',50]thieno[20 ,30:4,5]pyrrolo[3,2-g]thieno[20,30:4,5]thieno[3,2-b]indole-2,10-substituent)bis(formyl Sulfoxide)) bis(5,6-difluoro-3-oxo-2,3-dihydro-1 hydrogen-indene-2,1-diethylene)) dimalononitrile (Y6), the given The bulk material is poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophene-2-yl)-benzo][1,2-b:4, 5-b']dithiophene))-alt-(5,5-(1',30-bis-2-thiophene-50,7'-bis(2-ethylhexyl)benzo[1',2' -c:4',50-c']dithiophene-4,8-dione) (PM6).
本发明公开了一种有机太阳能电池，包括活性层、电子传输层、空穴传输层和电极；所述活性层包括上述具备协同组装性能的非富勒烯受体。The invention discloses an organic solar cell, which comprises an active layer, an electron transport layer, a hole transport layer and an electrode; the active layer includes the above-mentioned non-fullerene acceptor with cooperative assembly performance.
本发明公开了上述有机太阳能电池的制备方法，包括以下步骤，在导电基底上依次制备电子传输层、活性层、空穴传输层和电极，得到有机太阳能电池；所述活性层包括上述具备协同组装性能的非富勒烯受体。The invention discloses a preparation method of the above-mentioned organic solar cell, which comprises the following steps of sequentially preparing an electron transport layer, an active layer, a hole transport layer and an electrode on a conductive substrate to obtain an organic solar cell; properties of non-fullerene acceptors.
本发明中，制备活性层时，以共轭聚合物或共轭有机小分子作为给体材料，以Y系列共轭小分子（如明星分子Y6）为受体材料，其中给体材料与受体材料组成主体组分；材料以上述具备协同组装性能的非富勒烯受体作为客体材料（第三组分）。于室温下，利用高沸点的绿色溶剂配制包含给体材料和受体材料、客体材料的混合溶液，再采用常规溶液加工法制备活性层，为薄膜结构，常规溶液加工法为旋涂、刷涂、喷涂或者刮涂。上述混合溶液中，高沸点的绿色溶剂为甲苯、对二甲苯、对二甲苯或均三甲苯；给体材料的浓度为10～15 mg/mL；给体材料和受体材料、客体材料的质量比为1∶（1～1.5）∶（0～0.5）不包括0，优选为1∶（1.1～1.3）∶（0.1～0.45），进一步优选为1∶1.2∶（0.12～0.25）。进一步的，制备活性层时，还包括富勒烯受体，其用量为给体材料质量的2～15%，优选为5～12%，最优选为8～11%。本发明客体材料的含量不包括0。本发明的创造性在于以上述具备协同组装性能的非富勒烯受体作为客体，现有发光层材料（现有给体材料与受体材料组成）为主体，实现了利用高沸点的绿色溶剂配制溶液，且无需退火，制备得到活性层，具有优异的光电性能。In the present invention, when preparing the active layer, the conjugated polymer or conjugated organic small molecule is used as the donor material, and the Y series conjugated small molecule (such as the star molecule Y6) is used as the acceptor material, wherein the donor material and the acceptor The material constitutes the main component; the material uses the above-mentioned non-fullerene acceptor with cooperative assembly performance as the guest material (the third component). At room temperature, use a green solvent with a high boiling point to prepare a mixed solution containing donor materials, acceptor materials, and guest materials, and then use conventional solution processing methods to prepare the active layer, which is a thin film structure. Conventional solution processing methods are spin coating and brush coating , Spray or scrape. In the above mixed solution, the green solvent with a high boiling point is toluene, p-xylene, p-xylene or mesitylene; the concentration of the donor material is 10-15 mg/mL; the mass of the donor material, acceptor material, and guest material The ratio is 1:(1-1.5):(0-0.5) excluding 0, preferably 1:(1.1-1.3):(0.1-0.45), more preferably 1:1.2:(0.12-0.25). Further, when preparing the active layer, fullerene acceptors are also included, and the amount thereof is 2-15% of the mass of the donor material, preferably 5-12%, most preferably 8-11%. The content of the guest material of the present invention does not include zero. The inventiveness of the present invention lies in that the above-mentioned non-fullerene acceptor with cooperative assembly performance is used as the guest, and the existing light-emitting layer material (composed of the existing donor material and the acceptor material) is used as the main body, and the preparation of the green solvent with a high boiling point is realized. solution, and without annealing, the active layer is prepared, which has excellent photoelectric properties.
本发明的有机太阳能电池中，电子传输层、空穴传输层和电极为现有产品，各层的具体制备方法也为常规技术，比如给体材料为PM6，电子传输层材料为铝掺杂的氧化锌，空穴传输层材料为三氧化钼，电极为银或者铝，活性层的厚度为100～200 nm。本发明的创造性在于公开了新的材料作为具备协同组装性能的非富勒烯受体，能够利用高沸点的绿色溶剂配制溶液，且无需退火，制备得到活性层，进一步制备得到电池，具有高的PCE等性能。In the organic solar cell of the present invention, the electron transport layer, the hole transport layer and the electrode are existing products, and the specific preparation method of each layer is also a conventional technology, such as the donor material is PM6, and the electron transport layer material is aluminum-doped Zinc oxide, the material of the hole transport layer is molybdenum trioxide, the electrode is silver or aluminum, and the thickness of the active layer is 100-200 nm. The inventiveness of the present invention lies in disclosing a new material as a non-fullerene acceptor with synergistic assembly performance, which can use a green solvent with a high boiling point to prepare a solution without annealing, prepare an active layer, and further prepare a battery with high Performance such as PCE.
1、本发明创造性地将低聚乙二醇链引入非富勒烯受体中得到具备协同组装性能的非富勒烯受体，相对于现有高效非富勒烯受体，具有更有效地诱导和调控受体材料结晶动力学，特别是延长Y系列受体的结晶时间，提高受体及整个活性层的结晶度，克服了Y系列受体定向结晶对退火工艺的依赖，简化了器件制备工艺，降低了制备的成本。1. The present invention creatively introduces oligoethylene glycol chains into non-fullerene acceptors to obtain non-fullerene acceptors with cooperative assembly performance. Compared with the existing high-efficiency non-fullerene acceptors, it has more effective Induce and regulate the crystallization kinetics of receptor materials, especially prolong the crystallization time of Y series receptors, increase the crystallinity of receptors and the entire active layer, overcome the dependence of directional crystallization of Y series receptors on annealing process, and simplify device preparation process, reducing the cost of preparation.
2、本发明中公开的具备协同组装性能的非富勒烯受体作为客体组分掺入主体中后，通过对主体组分中受体结晶动力学的调控，降低了其结晶对低沸点溶剂快速挥发特性的依赖，实现了在高沸点溶剂中制备了高规整度的活性层组分，解决了低沸点溶剂快速挥发在大面积器件制备时的带来的薄膜不均匀的问题，为大面积器件制备奠定了基础。2. After the non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is incorporated into the host as a guest component, by regulating the crystallization kinetics of the acceptor in the host component, the crystallization effect of the low boiling point solvent is reduced. Relying on the fast volatilization characteristics, the active layer components with high regularity are prepared in high boiling point solvents, which solves the problem of non-uniform films caused by the rapid volatilization of low boiling point solvents in the preparation of large-area devices. Device preparation laid the foundation.
3、本发明公开的具备协同组装性能的非富勒烯受体作为客体分子掺杂现有主体材料，首次实现在非卤溶剂中溶解、加工，降低了器件制备时溶剂的毒性和环境成本。3. The non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is used as a guest molecule to dope the existing host material, which can be dissolved and processed in a non-halogen solvent for the first time, reducing the toxicity and environmental cost of the solvent during device preparation.
4、本发明中具备协同组装性能的非富勒烯受体与主体组分中受体和给体均具有良好的相容性，最终实现对主体成分相容性的调节，实现对高沸点溶剂加工时活性层形貌的调控，避免了主体中给受体的过分聚集，避免现有技术常见的相分离缺陷，从而减少了激子的复合几率，提高了有机太阳能电池的效率，高沸点、绿色溶剂（对二甲苯）加工，无后处理工艺处理制备的太阳能电池能量转换效率就已经达到了17.41%，是目前报道的绿色溶剂加工有机太阳能电池器件的最高效率。4. In the present invention, the non-fullerene acceptor with synergistic assembly performance has good compatibility with the acceptor and donor in the main component, and finally realizes the adjustment of the compatibility of the main component, and realizes the high boiling point solvent The regulation of the morphology of the active layer during processing avoids the excessive aggregation of donors and acceptors in the main body, and avoids the common phase separation defects in the prior art, thereby reducing the recombination probability of excitons and improving the efficiency of organic solar cells. High boiling point, The energy conversion efficiency of solar cells prepared by green solvent (p-xylene) processing without post-treatment process has reached 17.41%, which is the highest efficiency of green solvent processed organic solar cell devices reported so far.
5、本发明公开的具备协同组装性能的非富勒烯受体与主体活性层共混时可得到更为稳定的微观结构和形貌，同时得到的器件具有较好的工作稳定性。5. When the non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is blended with the main active layer, a more stable microstructure and morphology can be obtained, and the obtained device has better working stability.
6、本发明公开的具备协同组装性能的非富勒烯受体作为客体分子添加到主体成分中，解决了含卤、低沸点溶剂带来的毒性、薄膜不均匀问题，同时实现了无后处理加工，简化了器件工艺，降低了经济和环境成本，最终获得了高性能、高稳定性的大面积器件模组，推动了有机太阳能电池的产业化的进程。6. The non-fullerene acceptor with cooperative assembly performance disclosed in the present invention is added to the main component as a guest molecule, which solves the problems of toxicity and uneven film caused by halogen-containing and low-boiling solvents, and at the same time realizes no post-processing Processing simplifies the device process, reduces economic and environmental costs, and finally obtains a high-performance, high-stability large-area device module, which promotes the process of industrialization of organic solar cells.
上述说明仅是本发明技术方案的概述，以下将通过具体实施例对所述非富勒烯受体材料及其制备方法、有机太阳能电池做进一步说明。The above description is only an overview of the technical solution of the present invention, and the non-fullerene acceptor material, its preparation method, and organic solar cell will be further described below through specific examples.
图1为实施例一中BTO的核磁共振氢谱图。Fig. 1 is the proton nuclear magnetic resonance spectrum figure of BTO in the embodiment one.
图2为实施例一中BTO的核磁共振碳谱图。Fig. 2 is the carbon nuclear magnetic resonance spectrogram of BTO in embodiment one.
图3 为实施例一中BTO的热失重曲线。Fig. 3 is the thermal weight loss curve of BTO in Example 1.
图4 为实施例一中BTO的循环伏安曲线。Fig. 4 is the cyclic voltammetry curve of BTO in the first embodiment.
图5为实施例一中BTO的氯苯加工、不退火下薄膜的紫外可见图谱。Fig. 5 is the ultraviolet-visible spectrum of the BTO film processed in chlorobenzene without annealing in Example 1.
图6为实施例二中BT-2OEG-4F的核磁共振氢谱图。Figure 6 is the H NMR spectrum of BT-2OEG-4F in Example 2.
图7为实施例三中BT-4OEG-4F的核磁共振氢谱图。Figure 7 is the H NMR spectrum of BT-4OEG-4F in Example 3.
图8为实施例四中BO1的核磁共振氢谱图。Figure 8 is the H NMR spectrum of BO1 in Example 4.
图9为实施例五中BO2的核磁共振氢谱图。Fig. 9 is the proton nuclear magnetic resonance spectrogram of BO in embodiment five.
图10为实施例六中BO3的核磁共振氢谱图。Fig. 10 is the proton nuclear magnetic resonance spectrogram of BO3 in embodiment six.
图11为实施例七中活性层薄膜的实物图。Fig. 11 is a physical diagram of the active layer film in the seventh embodiment.
图12为实施例七中活性层薄膜原子力显微镜图。Fig. 12 is an atomic force microscope image of the active layer thin film in Example 7.
图13为实施例七中活性层薄膜透射电子显微镜图。Fig. 13 is a transmission electron microscope image of the active layer thin film in Example 7.
图14为实施例八中高沸点氯苯加工的器件J-V曲线图。Fig. 14 is a J-V curve diagram of the device processed by high boiling point chlorobenzene in the eighth embodiment.
图15为实施例九中高沸点氯苯加工有无热退火处理的器件J-V曲线图。Fig. 15 is a J-V curve diagram of the device processed with high boiling point chlorobenzene with or without thermal annealing in Example 9.
图16为实施例十中高沸点绿色溶剂对二甲苯加工的器件J-V曲线图。Fig. 16 is a J-V curve diagram of the device processed by the high-boiling green solvent p-xylene in Example 10.
图17为实施例十一中高沸点绿色溶剂对二甲苯加工的器件J-V曲线图。Fig. 17 is a J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 11.
图18为实施例十二中高沸点绿色溶剂对二甲苯加工的器件J-V曲线图。Fig. 18 is a J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 12.
图19为实施例十三中高沸点绿色溶剂对二甲苯加工的器件J-V曲线图。Fig. 19 is a J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 13.
图20为实施例十四中高沸点绿色溶剂对二甲苯加工的器件J-V曲线图。Fig. 20 is the J-V curve of the device processed by the high-boiling green solvent p-xylene in Example 14.
本发明的原料都为现有产品，具体制备操作以及测试方法都为本领域常规方法。The raw materials of the present invention are all existing products, and the specific preparation operations and testing methods are conventional methods in this field.
实施例一 具备协同组装性能的非富勒烯受体材料（BTO）结构式为：
。
Example 1 The structural formula of a non-fullerene acceptor material (BTO) with cooperative assembly performance is: .
上述BTO的制备方法如下：将1 M的氢氧化钠溶液(50 mL)冰水浴下加入到三乙二醇单甲醚(16.41 g, 0.10
mol)的四氢呋喃(20 mL)溶液中，将对甲苯磺酰氯(19.64
g, 0.10 mol)的饱和四氢呋喃溶液滴加入反应体系，室温搅拌过夜，得到无色液体4-甲基苯磺酸2-[2-(2-甲氧基乙氧基)乙氧基]乙酯；氮气保护下，3,9-双十一烷基-12,13-二氢-[1,2,5]噻二唑并[3,4-e]噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b]吲哚(747.17 mg, 1 mmol)和四丁基硫酸氢铵(86.98
mg, 0.25 mmol)溶解于20 mL甲苯中，加入0.50
M氢氧化钠溶液(7 mL)室温搅拌15
min后，将4-甲基苯磺酸2-[2-(2-甲氧基乙氧基)乙氧基]乙酯(699.84 mg, 2.20 mmol)加入反应体系中，体系在80℃下搅拌12 h后，得到亮黄色固体12,13-二(2-(2-(2-甲氧基乙氧基)乙氧基)乙基)-3,9-双十一基-12,13-二氢-[1,2,5]噻二唑并[3,4-e]噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b]吲哚(BT-OEG)；氮气保护下，BT-OEG (109.56
mg, 0.1 mmol)溶解于15 mL无水四氢呋喃中，冷却至-78℃，向体系中加入正丁基锂溶液(0.20 mL, 1.60 M)后，-78℃下继续搅拌1 h，然后加入无水N,N-二甲基甲酰胺(58 µL, 0.75 mol)，维持温度反应1 h后，体系升至室温搅拌3 h后，加水淬灭反应，得到橙黄色固体BT-OEG-CHO；氮气保护下，BT-OEG-CHO (100.96 mg, 0.1 mmol), 2-(5, 6-二氟-3-氧-2,3-二氢-1氢-茚-1-亚基)丙二腈(92.31mg, 0.4 mmol)溶于20 mL三氯甲烷中，加入吡啶(1 mL)，70℃下反应10 h，旋除溶剂，使用石油醚/乙酸乙酯（体积比10:1）作为淋洗液，硅胶层柱析分离得到深蓝色固体BTO（产率73%）。The preparation method of the above-mentioned BTO is as follows: add 1 M sodium hydroxide solution (50 mL) into triethylene glycol monomethyl ether (16.41 g, 0.10
mol) in tetrahydrofuran (20 mL), p-toluenesulfonyl chloride (19.64
g, 0.10 mol) of saturated tetrahydrofuran solution was added dropwise to the reaction system, and stirred overnight at room temperature to obtain a colorless liquid 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate ;Under nitrogen protection, 3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'' :4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b ]indole (747.17 mg, 1 mmol) and tetrabutylammonium bisulfate (86.98
mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50
M sodium hydroxide solution (7 mL) was stirred at room temperature for 15
After min, 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (699.84 mg, 2.20 mmol) was added to the reaction system, and the system was stirred at 80°C After 12 h, a bright yellow solid 12,13-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3,9-diundecyl-12,13- Dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5 ]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole (BT-OEG); under nitrogen protection, BT-OEG (109.56
mg, 0.1 mmol) was dissolved in 15 mL of anhydrous tetrahydrofuran, cooled to -78°C, and n-butyllithium solution (0.20 mL, 1.60 M) was added to the system, stirred at -78°C for 1 h, and then added without N,N-Dimethylformamide (58 µL, 0.75 mol) in water. After maintaining the temperature for 1 h, the system was raised to room temperature and stirred for 3 h. The reaction was quenched by adding water to obtain orange-yellow solid BT-OEG-CHO; BT-OEG-CHO (100.96 mg, 0.1 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1hydro-indene-1-ylidene)malononitrile under protection (92.31mg, 0.4 mmol) was dissolved in 20 mL of chloroform, added pyridine (1 mL), reacted at 70°C for 10 h, the solvent was removed by spin, and petroleum ether/ethyl acetate (volume ratio 10:1) was used as eluent The washing solution was separated by silica gel chromatography to obtain BTO as a dark blue solid (yield 73%).
图1为BTO的核磁共振氢谱图，图2为BTO的核磁共振碳谱图，说明本发明成功制备得具有自主装特性的非富勒烯受体BTO。Figure 1 is the hydrogen nuclear magnetic resonance spectrum of BTO, and Figure 2 is the carbon nuclear magnetic resonance spectrum of BTO, indicating that the present invention has successfully prepared non-fullerene acceptor BTO with self-assembly characteristics.
图3为BTO的热失重曲线，其分解温度在317℃，说明其具有优异的热稳定性。Figure 3 is the thermal weight loss curve of BTO, and its decomposition temperature is 317°C, which shows that it has excellent thermal stability.
图4为BTO薄膜的循环伏安曲线，测试时以二茂铁做为内标。通过标定可以得到Fe/Fe+在 0.1 M TBAPF6 中的氧化电位为0.86
V，还原电位为 -0.77 V。从图中可以看出BTO的还原电压为-0.98V，通过公式
E
HOMO=-(4.73-
E
Ferrocene+
E
ox).
E
LUMO=-(4.73-
E
Ferrocene+
E
re).
E
Ferrocene= -0.02 V，可以求得对应的HOMO能级为-5.61eV，LUMO能级为-3.98 eV。
Figure 4 is the cyclic voltammetry curve of the BTO thin film, and ferrocene was used as the internal standard during the test. Through calibration, the oxidation potential of Fe/Fe+ in 0.1 M TBAPF6 is 0.86 V, and the reduction potential is -0.77 V. It can be seen from the figure that the reduction voltage of BTO is -0.98V, through the formula E HOMO =-(4.73- E Ferrocene + E ox ). E LUMO =-(4.73- E Ferrocene + E re ). E Ferrocene = -0.02 V, the corresponding HOMO energy level can be obtained as -5.61eV, and the LUMO energy level is -3.98 eV.
将石英玻璃片用乙醇、丙酮、异丙醇超声，然后放到烘箱中150℃加热干燥10分钟，除去异丙醇；室温条件下，以氯仿、氯苯为溶剂，配制BTO（12
mg/mL）的溶液，搅拌，然后将其以1000 rpm的转速，旋涂在石英玻璃片上，得到的薄膜可用于紫外可见吸收测试。参见图5所示，未经退火氯苯加工的BTO薄膜在600-800 nm范围内明显的肩峰存在，这反映了BTO分子中侧链的有序堆积，这主要归因于分子自组装性，体现了BTO分子在高沸点溶剂、不退火条件下的有序分子排列。Ultrasonic the quartz glass sheet with ethanol, acetone, and isopropanol, and then put it in an oven to heat and dry at 150°C for 10 minutes to remove isopropanol; at room temperature, use chloroform and chlorobenzene as solvents to prepare BTO (12
mg/mL) solution, stirred, and then spin-coated on a quartz glass slide at a speed of 1000 rpm, and the obtained film can be used for UV-visible absorption test. As shown in Figure 5, the BTO film processed without annealing chlorobenzene has obvious shoulder peaks in the range of 600-800 nm, which reflects the orderly stacking of side chains in the BTO molecule, which is mainly attributed to the molecular self-assembly , reflecting the ordered molecular arrangement of BTO molecules in a high boiling point solvent without annealing.
实施例二 具备协同组装性能的非富勒烯受体材料（BT-2OEG-4F）结构式为：
。
Example 2 The structural formula of the non-fullerene acceptor material (BT-2OEG-4F) with synergistic assembly performance is: .
上述BT-2OEG-4F的制备方法如下：氮气保护下，3,9-双十一烷基-12,13-二氢-[1,2,5]噻二唑并[3,4-e]噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b]吲哚(747.17 mg, 1 mmol)和四丁基硫酸氢铵(86.98
mg, 0.25 mmol)溶解于20 mL甲苯中，加入0.50
M氢氧化钠溶液(7 mL)室温搅拌15
min后，将4-甲基苯磺酸2-(2-甲氧基乙氧基)乙氧基]乙酯(603.53 mg, 2.20 mmol)加入反应体系中，体系在80℃下搅拌12 h后，得到亮黄色固体12,13-二(2-(2-甲氧基乙氧基)乙氧基)乙基)-3,9-双十一基-12,13-二氢-[1,2,5]噻二唑并[3,4-e]噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b]吲哚(BT-2OEG)；氮气保护下，BT-2OEG (95.14
mg, 0.1 mmol)溶解于15 mL无水四氢呋喃中，冷却至-78℃，向体系中加入正丁基锂溶液(0.20 mL, 1.60 M)后，-78℃下继续搅拌1 h，然后加入无水N,N-二甲基甲酰胺(58 µL, 0.75 mol)，维持温度反应1 h后，体系升至室温搅拌3 h后，加水淬灭反应，得到橙黄色固体BT-2OEG-CHO；氮气保护下，BT-2OEG-CHO (100.75 mg, 0.1 mmol), 2-(5, 6-二氟-3-氧-2,3-二氢-1氢-茚-1-亚基)丙二腈(92.31mg, 0.4 mmol)溶于20 mL三氯甲烷中，加入吡啶(1 mL)，70℃下反应10 h，旋除溶剂，使用石油醚/乙酸乙酯（体积比10:1）作为淋洗液，硅胶层柱析分离得到深蓝色固体BT-2OEG-4F（产率75%）。The preparation method of the above-mentioned BT-2OEG-4F is as follows: under nitrogen protection, 3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e] Thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4, 5] Thieno[3,2-b]indole (747.17 mg, 1 mmol) and tetrabutylammonium bisulfate (86.98
mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50
M sodium hydroxide solution (7 mL) was stirred at room temperature for 15
After min, 2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (603.53 mg, 2.20 mmol) was added to the reaction system, and the system was stirred at 80°C for 12 h , to give bright yellow solid 12,13-bis(2-(2-methoxyethoxy)ethoxy)ethyl)-3,9-diundecyl-12,13-dihydro-[1, 2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3, 2-g]thieno[2',3':4,5]thieno[3,2-b]indole (BT-2OEG); under nitrogen protection, BT-2OEG (95.14
mg, 0.1 mmol) was dissolved in 15 mL of anhydrous tetrahydrofuran, cooled to -78°C, and n-butyllithium solution (0.20 mL, 1.60 M) was added to the system, stirred at -78°C for 1 h, and then added without N,N-Dimethylformamide (58 µL, 0.75 mol) in water, after maintaining the temperature for 1 h, the system was raised to room temperature and stirred for 3 h, then quenched with water to obtain orange-yellow solid BT-2OEG-CHO; Protected, BT-2OEG-CHO (100.75 mg, 0.1 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1hydro-indene-1-ylidene)malononitrile (92.31mg, 0.4 mmol) was dissolved in 20 mL of chloroform, added pyridine (1 mL), reacted at 70°C for 10 h, the solvent was removed by spin, and petroleum ether/ethyl acetate (volume ratio 10:1) was used as eluent The washing solution was separated by silica gel column chromatography to obtain a dark blue solid BT-2OEG-4F (yield 75%).
图6为BT-2OEG-4F的核磁共振氢谱图，说明本发明成功制备得具有自主装特性的非富勒烯受体BT-2OEG-4F。Fig. 6 is the hydrogen nuclear magnetic resonance spectrum of BT-2OEG-4F, indicating that the present invention has successfully prepared the non-fullerene acceptor BT-2OEG-4F with self-assembly characteristics.
实施例三 具备协同组装性能的非富勒烯受体材料（BT-4OEG-4F）结构式为：
。
Example 3 The structural formula of the non-fullerene acceptor material (BT-4OEG-4F) with synergistic assembly performance is: .
上述BT-4OEG-4F的制备方法如下：氮气保护下，3,9-双十一烷基-12,13-二氢-[1,2,5]噻二唑并[3,4-e]噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b]吲哚(747.17 mg, 1 mmol)和四丁基硫酸氢铵(86.98
mg, 0.25 mmol)溶解于20 mL甲苯中，加入0.50
M氢氧化钠溶液(7 mL)室温搅拌15
min后，将4-甲基苯磺酸2-[2-[2-(2-甲氧基乙氧基)乙氧基]乙酯(800.80 mg, 2.20 mmol)加入反应体系中，体系在80℃下搅拌12 h后，得到亮黄色固体12,13-二(2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙基)-3,9-双十一基-12,13-二氢-[1,2,5]噻二唑并[3,4-e]噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b]吲哚(BT-4OEG)；氮气保护下，BT-4OEG (112.77
mg, 0.1 mmol)溶解于15 mL无水四氢呋喃中，冷却至-78℃，向体系中加入正丁基锂溶液(0.20 mL, 1.60 M)后，-78℃下继续搅拌1 h，然后加入无水N,N-二甲基甲酰胺(58 µL, 0.75 mol)，维持温度反应1 h后，体系升至室温搅拌3 h后，加水淬灭反应，得到橙黄色固体BT-4OEG-CHO；氮气保护下，BT-4OEG-CHO (118.37 mg, 0.1 mmol), 2-(5, 6-二氟-3-氧-2,3-二氢-1氢-茚-1-亚基)丙二腈(92.31mg, 0.4 mmol)溶于20 mL三氯甲烷中，加入吡啶(1 mL)，70℃下反应10 h，旋除溶剂，使用石油醚/乙酸乙酯（体积比10:1）作为淋洗液，硅胶层柱析分离得到深蓝色固体BT-4OEG-4F（产率68%）。The preparation method of the above-mentioned BT-4OEG-4F is as follows: under the protection of nitrogen, 3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e] Thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4, 5] Thieno[3,2-b]indole (747.17 mg, 1 mmol) and tetrabutylammonium bisulfate (86.98
mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50
M sodium hydroxide solution (7 mL) was stirred at room temperature for 15
After min, 2-[2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (800.80 mg, 2.20 mmol) was added to the reaction system, and the system was maintained at 80 After stirring at ℃ for 12 h, a bright yellow solid 12,13-bis(2-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3,9-bis-undeca was obtained Base-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2', 3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole (BT-4OEG); under nitrogen protection, BT-4OEG (112.77
mg, 0.1 mmol) was dissolved in 15 mL of anhydrous tetrahydrofuran, cooled to -78°C, and n-butyllithium solution (0.20 mL, 1.60 M) was added to the system, stirred at -78°C for 1 h, and then added without N,N-Dimethylformamide (58 µL, 0.75 mol) in water. After maintaining the temperature for 1 h, the system was raised to room temperature and stirred for 3 h. The reaction was quenched by adding water to obtain orange-yellow solid BT-4OEG-CHO; Protected, BT-4OEG-CHO (118.37 mg, 0.1 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1hydro-indene-1-ylidene)malononitrile (92.31mg, 0.4 mmol) was dissolved in 20 mL of chloroform, added pyridine (1 mL), reacted at 70°C for 10 h, the solvent was removed by spin, and petroleum ether/ethyl acetate (volume ratio 10:1) was used as eluent The washing solution was separated by silica gel column chromatography to obtain dark blue solid BT-4OEG-4F (68% yield).
图7为BT-4OEG-4F的核磁共振氢谱图，说明本发明成功制备得具有自主装特性的非富勒烯受体BT-4OEG-4F。Fig. 7 is the hydrogen nuclear magnetic resonance spectrum of BT-4OEG-4F, indicating that the present invention has successfully prepared the non-fullerene acceptor BT-4OEG-4F with self-assembly characteristics.
实施例四 非富勒烯受体材料（BO1）结构式为：
。
Example 4 The structural formula of the non-fullerene acceptor material (BO1) is: .
BO1的制备方法如下：（1）4,7-二溴-2氢-苯并[d][1,2,3]三氮唑(609.22
mg, 2.2 mmol)，四丁基硫酸氢铵(86.98 mg, 0.25 mmol)溶解于20 mL甲苯中，加入0.5 M氢氧化钠溶液(7 mL)室温搅拌15 min后，将4-甲基苯磺酸2-[2-(2-甲氧基乙氧基)乙氧基]乙酯(699.84 mg, 2.2 mmol)加入反应体系中。体系在90 ℃下搅拌12 h后，得到白色油状液体产物，4,7-二溴-2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-2氢-苯并[d][1,2,3]三氮唑；（2）4,7-二溴-2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-2氢-苯并[d][1,2,3]三氮唑(930.84 mg, 2.20 mmol), 发烟硝酸(10
mL)和浓硫酸(10 mL)搅拌反应4 h后，将反应体系倒入冰水中，过滤得到白色固体产物，4,7-二溴-2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-5,6-二硝基-2氢-苯并[d][1,2,3]三氮唑；（3）4,7-二溴-2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-5,6-二硝基-2氢-苯并[d][1,2,3]三氮唑(1.13
g, 2.20 mmol)，三丁基(6-十一烷基噻吩并[3,2-b]噻吩-2-yl)锡(3.85 g, 6.6
mmol)，二氯二(三苯基磷)合钯(0.03 g, 0.04 mmol)溶于10 mL甲苯中，回流过夜，得到黄色固体产物，2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-5,6-二硝基-4,7-双(6-十一烷基噻吩并[3,2-b]噻吩-2-yl)-2氢-苯并[d][1,2,3]三氮唑；（4） 氮气下，2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-5,6-二硝基-4,7-双(6-十一烷基噻吩并[3,2-b]噻吩-2-yl)-2氢-苯并[d][1,2,3]三氮唑(2.07
g, 2.20 mmol)和磷酸三乙酯(10 mL)溶解于邻二氯苯(5
mL)中，180 ℃下加热搅拌过夜，旋干溶剂得到红色粗产物后，加入溴代异辛烷(0.97
g, 5 mmol)，氢氧化钾(0.50 g, 7.13 mmol)，N,N-二甲基甲酰胺(15 mL), 80 ℃下加热搅拌过夜，得到黄色产物，12,13-双(2-乙基己基)-6-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-3,9-双十一烷基-12,13-二氢-6氢-噻吩并[2'',3'':4',5'] 噻吩并[2',3':4,5] 吡咯并[3,2-g]
噻吩并[2',3':4,5] 噻吩并[3,2-b][1,2,3]均三唑并[4,5-e]吲哚；（5）氮气保护下，12,13-双(2-乙基己基)-6-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-3,9-双十一烷基-12,13-二氢-6氢-噻吩并[2'',3'':4',5'] 噻吩并[2',3':4,5]
吡咯并[3,2-g] 噻吩并[2',3':4,5]
噻吩并[3,2-b][1,2,3]均三唑并[4,5-e]吲哚(1.10 g, 1.00
mmol)溶解于40 mL无水四氢呋喃中，冷却至-78℃，向体系中加正丁基锂溶液(2.00 mL, 1.60 M)后，-78℃下继续搅拌1 h，然后加入无水N,N-二甲基甲酰胺(0.58 mL, 7.50 mol)，维持温度反应1 h后，体系升至室温搅拌3 h后，加水淬灭反应，得到橙黄色固体BO1-CHO；（6）氮气保护下，BO1-CHO (115.67
mg, 0.1 mmol), 2-(5, 6-二氟-3-氧-2,3-二氢-1氢-茚-1-亚基)丙二腈(92.31mg, 0.4
mmol)溶于20 mL三氯甲烷中，加入吡啶(1
mL), 70℃下反应10 h，旋除溶剂，使用石油醚/乙酸乙酯（体积比10:1）作为淋洗液，硅胶层柱析分离得到深蓝色固体BO1（产率72%）。BO1 was prepared as follows: (1) 4,7-dibromo-2hydro-benzo[d][1,2,3]triazole (609.22
mg, 2.2 mmol), tetrabutylammonium bisulfate (86.98 mg, 0.25 mmol) were dissolved in 20 mL of toluene, 0.5 M sodium hydroxide solution (7 mL) was added and stirred at room temperature for 15 min, then 4-methylbenzenesulfonate Acid 2-[2-(2-methoxyethoxy)ethoxy]ethyl ester (699.84 mg, 2.2 mmol) was added to the reaction system. After the system was stirred at 90 °C for 12 h, a white oily liquid product, 4,7-dibromo-2-(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-2 Hydrogen-benzo[d][1,2,3]triazole; (2) 4,7-dibromo-2-(2-(2-(2-methoxyethoxy)ethoxy) ethyl ester)-2H-benzo[d][1,2,3]triazole (930.84 mg, 2.20 mmol), fuming nitric acid (10
mL) and concentrated sulfuric acid (10 mL) were stirred and reacted for 4 h, the reaction system was poured into ice water, and filtered to obtain a white solid product, 4,7-dibromo-2-(2-(2-(2-methoxy (ethoxy)ethoxy)ethyl ester)-5,6-dinitro-2hydro-benzo[d][1,2,3]triazole; (3)4,7-dibromo-2 -(2-(2-(2-Methoxyethoxy)ethoxy)ethyl ester)-5,6-dinitro-2hydro-benzo[d][1,2,3]triazepine Azole (1.13
g, 2.20 mmol), tributyl(6-undecylthieno[3,2-b]thiophene-2-yl)tin (3.85 g, 6.6
mmol), dichlorobis(triphenylphosphine)palladium (0.03 g, 0.04 mmol) was dissolved in 10 mL of toluene and refluxed overnight to obtain a yellow solid product, 2-(2-(2-(2-methoxy Ethoxy)ethoxy)ethyl ester)-5,6-dinitro-4,7-bis(6-undecylthieno[3,2-b]thiophene-2-yl)-2hydro -Benzo[d][1,2,3]triazole; (4) Under nitrogen, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-5 ,6-Dinitro-4,7-bis(6-undecylthieno[3,2-b]thiophene-2-yl)-2hydro-benzo[d][1,2,3] Triazole (2.07
g, 2.20 mmol) and triethyl phosphate (10 mL) were dissolved in o-dichlorobenzene (5
mL), heated and stirred overnight at 180 °C, spin-dried the solvent to obtain a red crude product, added bromoisoctane (0.97
g, 5 mmol), potassium hydroxide (0.50 g, 7.13 mmol), N,N-dimethylformamide (15 mL), heated and stirred at 80 ℃ overnight to obtain a yellow product, 12,13-bis(2- Ethylhexyl)-6-(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-3,9-diundecyl-12,13-dihydro-6hydro -thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]
Thieno[2',3':4,5]thieno[3,2-b][1,2,3]-triazolo[4,5-e]indole; (5) under nitrogen protection, 12,13-bis(2-ethylhexyl)-6-(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-3,9-diundecyl-12 ,13-Dihydro-6hydro-thieno[2'',3'':4',5'] Thieno[2',3':4,5]
Pyrrolo[3,2-g]thieno[2',3':4,5]
Thieno[3,2-b][1,2,3]-triazolo[4,5-e]indole (1.10 g, 1.00
mmol) was dissolved in 40 mL of anhydrous tetrahydrofuran, cooled to -78°C, and n-butyllithium solution (2.00 mL, 1.60 M) was added to the system, and stirred at -78°C for 1 h, then anhydrous N was added, N-Dimethylformamide (0.58 mL, 7.50 mol), after maintaining the temperature for 1 h, the system rose to room temperature and stirred for 3 h, then quenched the reaction with water to obtain orange-yellow solid BO1-CHO; (6) under nitrogen protection , BO1-CHO (115.67
mg, 0.1 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1 hydrogen-inden-1-ylidene)malononitrile (92.31mg, 0.4
mmol) was dissolved in 20 mL of chloroform, adding pyridine (1
mL), react at 70°C for 10 h, spin off the solvent, use petroleum ether/ethyl acetate (volume ratio 10:1) as the eluent, and conduct column chromatography on silica gel to obtain dark blue solid BO1 (yield 72%).
测试BO1的核磁共振氢谱图（图8）、核磁共振碳谱图；说明本发明成功制备得具有自主装特性的非富勒烯受体BO1。Test the H NMR spectrum (Figure 8) and C NMR spectrum of BO1; it shows that the present invention has successfully prepared the non-fullerene acceptor BO1 with self-assembly characteristics.
实施例五 非富勒烯受体材料（BO2）结构式为：
。
Example 5 The structural formula of the non-fullerene acceptor material (BO2) is: .
BO2的制备方法如下：（1） 氮气下，2-(2-乙基己基)-5,6-邻二硝基苯-4,7-双(6-十一烷基噻吩并 [3,2-b]噻吩-2-yl)-2氢-苯并[d][1,2,3]三氮唑(0.91
g, 1.00 mmol)和磷酸三乙酯(5 mL)溶解于邻二氯苯(2.50
mL)中，180 ℃下加热搅拌过夜，旋干溶剂得到红色粗产物后，加入四丁基硫酸氢铵(86.98
mg, 0.25 mmol)溶解于20 mL甲苯中，加入0.50
M氢氧化钠溶液(7 mL)室温搅拌15
min后，将4-甲基苯磺酸2-[2-(2-甲氧基乙氧基)乙氧基]乙酯(699.84 mg, 2.20 mmol)加入反应体系中。体系在80 ℃下搅拌12 h后，得到亮黄色固体产物，6-(2-乙基己基)-12,13-双(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-3,9-双十一烷基-12,13-二氢-6氢-噻吩[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b][1,2,3]均三唑并[4,5-e]吲哚；（2）氮气保护下，6-(2-乙基己基)-12,13-双(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-3,9-双十一烷基-12,13-二氢-6氢-噻吩[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b][1,2,3]均三唑并[4,5-e]吲哚(1.13 g, 1.00 mmol)溶解于40 mL无水四氢呋喃中，冷却至-78℃，向体系中加正丁基锂溶液(2.00 mL, 1.60
M)后，-78 ℃下继续搅拌1 h，然后加入无水N,N-二甲基甲酰胺(0.58 mL, 7.50
mol)，维持温度反应1 h后，体系升至室温搅拌3 h后，加水淬灭反应，得到橙黄色固体BO2-CHO；（3）氮气保护下，BO2-CHO (119.07 mg, 0.1 mmol), 2-(5, 6-二氟-3-氧-2,3-二氢-1氢-茚-1-亚基)丙二腈(92.31mg, 0.4 mmol)溶于20 mL三氯甲烷中，加入吡啶(1 mL), 70℃下反应10 h，旋除溶剂，使用石油醚/乙酸乙酯（体积比10:1）作为淋洗液，硅胶层柱析分离得到深蓝色固体BO2（产率70%）。The preparation method of BO2 is as follows: (1) Under nitrogen, 2-(2-ethylhexyl)-5,6-o-dinitrobenzene-4,7-bis(6-undecylthieno[3,2 -b]thiophene-2-yl)-2 hydrogen-benzo[d][1,2,3]triazole (0.91
g, 1.00 mmol) and triethyl phosphate (5 mL) were dissolved in o-dichlorobenzene (2.50
mL), heated and stirred overnight at 180 °C, spin-dried the solvent to obtain a red crude product, added tetrabutylammonium bisulfate (86.98
mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50
M sodium hydroxide solution (7 mL) was stirred at room temperature for 15
After min, 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (699.84 mg, 2.20 mmol) was added into the reaction system. After the system was stirred at 80 °C for 12 h, a bright yellow solid product, 6-(2-ethylhexyl)-12,13-bis(2-(2-(2-methoxyethoxy)ethoxy ) ethyl ester) -3,9-diundecyl-12,13-dihydro-6 hydrogen-thiophene[2'',3'':4',5']thieno[2',3': 4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b][1,2,3]s-triazolo[4,5 -e] indole; (2) 6-(2-ethylhexyl)-12,13-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester under nitrogen protection )-3,9-Diundecyl-12,13-dihydro-6 hydrogen-thiophene[2'',3'':4',5']thieno[2',3':4,5 ]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b][1,2,3]s-triazolo[4,5-e] Indole (1.13 g, 1.00 mmol) was dissolved in 40 mL of anhydrous tetrahydrofuran, cooled to -78°C, and n-butyllithium solution (2.00 mL, 1.60
After M), stirring was continued at -78°C for 1 h, then anhydrous N,N-dimethylformamide (0.58 mL, 7.50
mol), after maintaining the temperature for 1 h, the system was raised to room temperature and stirred for 3 h, then quenched with water to obtain orange-yellow solid BO2-CHO; (3) under nitrogen protection, BO2-CHO (119.07 mg, 0.1 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1hydro-inden-1-ylidene)malononitrile (92.31mg, 0.4 mmol) was dissolved in 20 mL of chloroform, Add pyridine (1 mL), react at 70°C for 10 h, spin off the solvent, use petroleum ether/ethyl acetate (volume ratio 10:1) as the eluent, and separate by silica gel chromatography to obtain dark blue solid BO2 (yield 70%).
测试BO2的核磁共振氢谱图（图9）、核磁共振碳谱图。说明本发明成功制备得具有自主装特性的非富勒烯受体BO2。Test the H NMR spectrum (Figure 9) and C NMR spectrum of BO2. It shows that the present invention has successfully prepared non-fullerene acceptor BO2 with self-assembly characteristics.
实施例六 非富勒烯受体材料（BO3）结构式为：
。
Example 6 The structural formula of the non-fullerene acceptor material (BO3) is: .
BO3的制备方法包括如下：（1）氮气下，2-(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-5,6-二硝基-4,7-双(6-十一烷基噻吩并[3,2-b]噻吩-2-yl)-2氢-苯并[d][1,2,3]三氮唑(0.94
g, 1.00 mmol)和磷酸三乙酯(5 mL)溶解于邻二氯苯(2.50
mL)中，180℃下加热搅拌过夜，旋干溶剂得到红色粗产物后，加入四丁基硫酸氢铵(86.98
mg, 0.25 mmol)溶解于20 mL甲苯中，加入0.50
M氢氧化钠溶液(7 mL)室温搅拌15
min后，将4-甲基苯磺酸2-[2-(2-甲氧基乙氧基)乙氧基]乙酯(699.84 mg, 2.20 mmol)加入反应体系中。体系在80 ℃下搅拌12 h后，得到亮黄色固体产物，6,12,13-三(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-3,9-双十一烷基-12,13-二氢-6氢-噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b][1,2,3]均三唑并[4,5-e]吲哚；（2）6,12,13-三(2-(2-(2-甲氧基乙氧基)乙氧基)乙酯)-3,9-双十一烷基-12,13-二氢-6氢-噻吩并[2'',3'':4',5']噻吩并[2',3':4,5]吡咯并[3,2-g]噻吩并[2',3':4,5]噻吩并[3,2-b][1,2,3]均三唑并[4,5-e]吲哚(1.17 g, 1.00 mmol)溶解于40 mL无水四氢呋喃中，冷却至-78℃，向体系中加正丁基锂溶液(2.00 mL, 1.60
M)后，-78℃下继续搅拌1 h，然后加入无水N,N-二甲基甲酰胺(0.58 mL, 7.50
mol)，维持温度反应1 h后，体系升至室温搅拌3 h后，加水淬灭反应，得到橙黄色固体BO3-CHO；（3）氮气保护下，BO3-CHO (122.47 mg, 0.1 mmol), 2-(5, 6-二氟-3-氧-2,3-二氢-1氢-茚-1-亚基)丙二腈(92.31mg, 0.4 mmol)溶于20 mL三氯甲烷中，加入吡啶(1 mL), 70℃下反应10 h，旋除溶剂，使用石油醚/乙酸乙酯（体积比10:1）作为淋洗液，硅胶层柱析分离得到深蓝色固体BO3（产率65%）。The preparation method of BO3 includes as follows: (1) under nitrogen, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-5,6-dinitro-4,7 -bis(6-undecylthieno[3,2-b]thiophene-2-yl)-2hydro-benzo[d][1,2,3]triazole (0.94
g, 1.00 mmol) and triethyl phosphate (5 mL) were dissolved in o-dichlorobenzene (2.50
mL), heated and stirred overnight at 180°C, spin-dried the solvent to obtain a red crude product, added tetrabutylammonium bisulfate (86.98
mg, 0.25 mmol) was dissolved in 20 mL toluene, added 0.50
M sodium hydroxide solution (7 mL) was stirred at room temperature for 15
After min, 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (699.84 mg, 2.20 mmol) was added into the reaction system. After the system was stirred at 80 °C for 12 h, a bright yellow solid product, 6,12,13-tris(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-3,9 -Diundecyl-12,13-dihydro-6hydro-thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[ 3,2-g]thieno[2',3':4,5]thieno[3,2-b][1,2,3]s-triazolo[4,5-e]indole;( 2) 6,12,13-tris(2-(2-(2-methoxyethoxy)ethoxy)ethyl ester)-3,9-diundecyl-12,13-dihydro- 6 Hydrogen-thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3' :4,5]thieno[3,2-b][1,2,3]-triazolo[4,5-e]indole (1.17 g, 1.00 mmol) was dissolved in 40 mL of anhydrous THF, Cool to -78°C, add n-butyllithium solution (2.00 mL, 1.60
After M), stirring was continued at -78°C for 1 h, then anhydrous N,N-dimethylformamide (0.58 mL, 7.50
mol), after maintaining the temperature for 1 h, the system was raised to room temperature and stirred for 3 h, then quenched with water to obtain orange-yellow solid BO3-CHO; (3) under nitrogen protection, BO3-CHO (122.47 mg, 0.1 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1hydro-inden-1-ylidene)malononitrile (92.31mg, 0.4 mmol) was dissolved in 20 mL of chloroform, Add pyridine (1 mL), react at 70°C for 10 h, spin off the solvent, use petroleum ether/ethyl acetate (volume ratio 10:1) as the eluent, and separate by silica gel chromatography to obtain dark blue solid BO3 (yield 65%).
测试BO3的核磁共振氢谱图（图10）、核磁共振碳谱图。说明本发明成功制备得具有自主装特性的非富勒烯受体BO3。Test the hydrogen nuclear magnetic resonance spectrum (Figure 10) and the carbon nuclear magnetic resonance spectrum of BO3. It shows that the present invention has successfully prepared the non-fullerene acceptor BO3 with self-assembly characteristics.
实施例七 一种有机太阳能电池用活性层材料，包括上述非富勒烯受体、其他Y系列受体以及给体材料。以Y6和BTO为受体材料、PM6为给体材料为例：(1)先后用乙醇，丙酮、异丙醇超声氧化铟锡（ITO）导电玻璃片，烘干后以2000
rpm转速旋涂一层5 mg/mL的铝掺杂的氧化锌（AZO）层，厚度为40 nm，作为电子传输层，然后120℃加热干燥15 min，除去水分，备用；(2)将Y6、PM6、BTO或者Y6、PM6加入氯苯，制备混合溶液，具体的，以高沸点氯苯为溶剂，配制PM6浓度为12mg/mL，PM6/Y6:BTO(w/w:w
1/1.2:0，1/1.2:0.12，1/1.2:0.24，1/1.2:0.36)的混合溶液，然后将其以2500
rpm的转速，分别旋涂于电子传输层上，得未经退火处理的活性层薄膜，薄膜厚度约120
nm，其实物图见图11，原子力显微镜图见图12，透射电子显微镜图见图13，图中百分比为BTO占Y6质量的百分数；参见图11可见，高沸点氯苯加工的PM6:Y6薄膜呈现出雾状白斑，薄膜表面存在聚集的材料颗粒，随着BTO含量的增加，PM6与Y6之间的相容性得到明显改善，雾状白斑逐渐消失，薄膜变得透明；图12中的活性层薄膜原子力显微镜图显示，PM6:Y6薄膜在高沸点氯苯加工时，表现出较大的粗糙度，均方根表面粗糙度（
R
q）达到了18.58 nm，这是由于Y6的过度聚集和两种材料之间较差的相容性导致的，随着BTO对PM6:Y6相容性的调节，薄膜
R
q逐渐降低至2.28 nm。BTO对PM6:Y6相容性的调节作用在活性层薄膜透射电子显微镜图中也得到了证实，如图13所示，PM6:Y6薄膜的透射电子显微镜图中出现了大块的深色块状区域，这是材料之间相容性差所导致的过大相分离尺寸的体现，而BTO的加入逐渐抑制了这一不良现象，最终块状聚集消失，获得了相分离尺寸适中的三元组分。
Embodiment 7 An active layer material for organic solar cells, including the above-mentioned non-fullerene acceptors, other Y series acceptors, and donor materials. Taking Y6 and BTO as the acceptor material and PM6 as the donor material as an example: (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, and spin-coat it at 2000 rpm after drying. Layer 5 mg/mL aluminum-doped zinc oxide (AZO) layer with a thickness of 40 nm as the electron transport layer, then heat and dry at 120°C for 15 min, remove moisture, and set aside; (2) Y6, PM6, BTO or Add chlorobenzene to Y6 and PM6 to prepare a mixed solution. Specifically, use high-boiling point chlorobenzene as a solvent to prepare a PM6 concentration of 12 mg/mL, PM6/Y6:BTO (w/w:w 1/1.2:0, 1/1.2 :0.12, 1/1.2:0.24, 1/1.2:0.36) mixed solution, and then spin-coat it on the electron transport layer at a speed of 2500 rpm to obtain an active layer film without annealing treatment, and the film thickness is about 120 nm, see Figure 11 for the physical picture, Figure 12 for the atomic force microscope picture, and Figure 13 for the transmission electron microscope picture, and the percentage in the figure is the percentage of BTO in the mass of Y6; see Figure 11, PM6:Y6 processed by high-boiling point chlorobenzene The film showed foggy white spots, and there were aggregated material particles on the surface of the film. With the increase of BTO content, the compatibility between PM6 and Y6 was significantly improved, the foggy white spots disappeared gradually, and the film became transparent; in Figure 12 The atomic force microscope image of the active layer film shows that the PM6:Y6 film exhibits a large roughness when processed with high boiling point chlorobenzene, and the root mean square surface roughness ( R q ) reaches 18.58 nm, which is due to the excessive aggregation of Y6 As a result of the poor compatibility between the two materials, the R q of the film gradually decreased to 2.28 nm with the adjustment of the compatibility of BTO to PM6:Y6. The adjustment effect of BTO on the compatibility of PM6:Y6 has also been confirmed in the transmission electron microscope image of the active layer film. As shown in Figure 13, large dark blocks appear in the transmission electron microscope image of the PM6:Y6 film This is the embodiment of the excessive phase separation size caused by the poor compatibility between materials, and the addition of BTO gradually suppressed this undesirable phenomenon, and finally the massive aggregation disappeared, and a ternary component with a moderate phase separation size was obtained .
实施例八 一种有机太阳能电池，其活性层材料包括上述非富勒烯受体、其他Y系列受体以及给体材料。以Y6和BTO为受体材料、PM6为给体材料为例，有机太阳能电池的制备方法如下：(1)将先后用乙醇，丙酮、异丙醇超声氧化铟锡（ITO）导电玻璃片，烘干后以2000
rpm转速旋涂一层5 mg/mL的AZO层，厚度为40 nm，作为电子传输层，然后120℃加热干燥15分钟，除去水分；(2)以高沸点氯苯为溶剂，配制PM6浓度为12mg/mL，PM6/Y6:BTO (w/w:w 1/1.2:0, 1/1.2:0.12, 1/1.2:0.36)的混合溶液，搅拌，然后将其以2500rpm的转速，旋涂于电子传输层上，得未经退火处理的活性层薄膜，薄膜厚度约120
nm；(3) 利用真空蒸镀机蒸镀10 nm的MoO
3和100
nm的Ag分别作为空穴传输层和电极，器件制备完成。
Embodiment 8 An organic solar cell whose active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials. Taking Y6 and BTO as the acceptor material and PM6 as the donor material as an example, the preparation method of the organic solar cell is as follows: (1) Use ethanol, acetone, and isopropanol to ultrasonically oxidize indium tin (ITO) conductive glass sheet successively, bake After drying, spin-coat a layer of 5 mg/mL AZO with a thickness of 40 nm at 2000 rpm as an electron transport layer, and then heat and dry at 120°C for 15 minutes to remove moisture; (2) use high-boiling point chlorobenzene as a solvent, The preparation PM6 concentration is 12mg/mL, the mixed solution of PM6/Y6:BTO (w/w:w 1/1.2:0, 1/1.2:0.12, 1/1.2:0.36), stirs, then it is with the rotating speed of 2500rpm , spin-coated on the electron transport layer to obtain a non-annealed active layer film with a film thickness of about 120 nm; (3) use a vacuum evaporation machine to evaporate 10 nm of MoO 3 and 100 nm of Ag as hole transport layers and electrodes, and the device is ready.
测试上述不同有机太阳能电池性能，光强为100mW/cm
2AM 1.5白光照射条件下测量，得到电流-电压曲线，如图14所示，得出相对应的电池的性能参数，见表1。
Test the performance of the above-mentioned different organic solar cells under the condition of 100mW/cm 2 AM 1.5 white light irradiation to obtain the current-voltage curve, as shown in Figure 14, and obtain the corresponding performance parameters of the battery, see Table 1.
从表1可知：应用本发明中的非富勒烯受体BTO作为客体分子加入主体（PM6:Y6）中后，可以调控主体材料间的相容性和溶解度，其中当BTO掺杂量为Y6质量的20%时，表现出最优的器件性能。其在没有任何后处理的条件下，高沸点氯苯加工的小面积（活性层有效面积6.28 mm
2）器件PCE可以达到16.39%，短路电流为25.91 mA/cm
2，开路电压为0.86
V，填充因子为0.73。而当掺杂量为10%或者30%时，其性能较PM6:Y6有小幅度提升，但是均低于最优掺杂比例20%。表中百分比为BTO占Y6质量的百分数。
It can be seen from Table 1 that after adding the non-fullerene acceptor BTO in the present invention as a guest molecule into the host (PM6:Y6), the compatibility and solubility between the host materials can be adjusted, wherein when the BTO doping amount is Y6 When 20% of the mass, the best device performance is exhibited. Without any post-treatment, the PCE of the small-area (active layer active layer 6.28 mm 2 ) device processed by high-boiling point chlorobenzene can reach 16.39%, the short-circuit current is 25.91 mA/cm 2 , the open-circuit voltage is 0.86 V, and the filled The factor is 0.73. When the doping amount is 10% or 30%, its performance is slightly improved compared with PM6:Y6, but both are lower than the optimal doping ratio of 20%. The percentages in the table are the percentages of BTO in the mass of Y6.
实施例九 一种有机太阳能电池，其活性层材料包括上述非富勒烯受体、其他Y系列受体以及给体材料。以Y6和BTO为受体材料、PM6为给体材料为例，有机太阳能电池的制备方法如下：(1)将先后用乙醇，丙酮、异丙醇超声氧化铟锡（ITO）导电玻璃片，烘干后以2000
rpm转速旋涂一层5 mg/mL的AZO层，厚度为40 nm，作为电子传输层，然后120℃加热干燥15分钟，除去水分；(2)以高沸点氯苯为溶剂，配制PM6浓度为12 mg/mL，PM6/Y6:BTO (w/w:w 1/1.2:0, 1/1.2:0.24,)的混合溶液，搅拌，然后将其以2500rpm的转速，旋涂于电子传输层上，得未经退火处理和退火处理的活性层薄膜，薄膜厚度约120
nm；(3) 利用真空蒸镀机蒸镀10 nm的MoO
3和100
nm的Ag分别作为空穴传输层和电极，器件制备完成。
Embodiment 9 An organic solar cell, the active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials. Taking Y6 and BTO as the acceptor material and PM6 as the donor material as an example, the preparation method of the organic solar cell is as follows: (1) Use ethanol, acetone, and isopropanol to ultrasonically oxidize indium tin (ITO) conductive glass sheet successively, bake After drying, spin-coat a layer of 5 mg/mL AZO with a thickness of 40 nm at 2000 rpm as an electron transport layer, and then heat and dry at 120°C for 15 minutes to remove moisture; (2) use high-boiling point chlorobenzene as a solvent, Prepare a PM6 concentration of 12 mg/mL, a mixed solution of PM6/Y6:BTO (w/w:w 1/1.2:0, 1/1.2:0.24,), stir, and then spin coat it at a speed of 2500rpm On the electron transport layer, an active layer film without annealing treatment and annealing treatment was obtained, and the film thickness was about 120 nm; (3) 10 nm of MoO 3 and 100 nm of Ag were evaporated by a vacuum evaporation machine as the hole transport layer and electrodes, the device is prepared.
测试上述不同有机太阳能电池性能，光强为100mW/cm
2AM 1.5白光照射条件下测量，得到电流-电压曲线，如图15所示，根据曲线得出相对应的电池的性能参数，见表2。
Test the performance of the above-mentioned different organic solar cells under the condition of light intensity of 100mW/cm 2 AM 1.5 white light irradiation, and obtain the current-voltage curve, as shown in Figure 15, and obtain the corresponding performance parameters of the battery according to the curve, see Table 2 .
从表2可知：相较于为经后处理的器件，热退火工艺能进一步提升PM6:Y6器件的性能，其器件PCE可以达到13.98%，短路电流为25.91 mA/cm
2，开路电压为0.86
V，填充因子为0.73，这是因为热退火促进了给受体分子的有序排列。而在PM6:Y6:20%
BTO器件中，热退火处理反而导致器件性能的略微降低，说明本发明BTO调控的活性层相分离尺寸及形貌已经达到了完美的平衡状态，达到了优异的电池性能，热退火处理反而劣化了该性能，这与现有技术相反。热退火参数为现有PM6:Y6的常规热退火参数，已见于文献报道。
It can be seen from Table 2 that compared with post-processed devices, the thermal annealing process can further improve the performance of PM6:Y6 devices, and the device PCE can reach 13.98%, the short-circuit current is 25.91 mA/cm 2 , and the open-circuit voltage is 0.86 V , the fill factor is 0.73, because thermal annealing promotes the ordered arrangement of acceptor molecules. However, in the PM6:Y6:20% BTO device, the thermal annealing treatment led to a slight decrease in device performance, indicating that the phase separation size and morphology of the active layer regulated by the BTO of the present invention have reached a perfect equilibrium state, achieving an excellent battery performance, the thermal annealing treatment degrades the performance instead, which is contrary to the prior art. The thermal annealing parameters are conventional thermal annealing parameters of the existing PM6:Y6, which have been reported in the literature.
实施例十 一种有机太阳能电池，其活性层材料包括上述非富勒烯受体、其他Y系列受体以及给体材料。以Y6和BTO为受体材料、PM6为给体材料为例，有机太阳能电池的制备方法如下：(1)将先后用乙醇，丙酮、异丙醇超声氧化铟锡（ITO）导电玻璃片，烘干后以2000
rpm转速旋涂一层5 mg/mL的AZO层，厚度为40 nm，作为电子传输层，然后120℃加热干燥15分钟，除去水分；(2)以高沸点对二甲苯为溶剂，配制PM6浓度为12mg/mL，PM6/Y6:BTO:PC
71BM(w/w:w:w 1/1.2:0:0,
1/1.2:0.24:0, 1/1.2:0:0.1, 1/1.2:0.24:0.1)的混合溶液，搅拌，然后将其以2500rpm的转速，旋涂于电子传输层上，得未经退火处理的活性层薄膜，薄膜厚度约120 nm；(3) 利用真空蒸镀机蒸镀10 nm的MoO
3和100
nm的Ag分别作为空穴传输层和电极，器件制备完成。
Embodiment 11 An organic solar cell whose active layer materials include the above-mentioned non-fullerene acceptors, other Y series acceptors, and donor materials. Taking Y6 and BTO as the acceptor material and PM6 as the donor material as an example, the preparation method of the organic solar cell is as follows: (1) Use ethanol, acetone, and isopropanol to ultrasonically oxidize indium tin (ITO) conductive glass sheet successively, bake After drying, spin-coat a layer of 5 mg/mL AZO with a thickness of 40 nm at 2000 rpm as an electron transport layer, and then heat and dry at 120°C for 15 minutes to remove moisture; (2) Use p-xylene with a high boiling point as a solvent , the prepared PM6 concentration is 12mg/mL, PM6/Y6:BTO:PC 71 BM(w/w:w:w 1/1.2:0:0, 1/1.2:0.24:0, 1/1.2:0:0.1, 1/1.2:0.24:0.1) mixed solution, stirred, and then it was spin-coated on the electron transport layer at a speed of 2500rpm to obtain an active layer film without annealing treatment, and the film thickness was about 120 nm; (3) using The vacuum evaporation machine evaporated 10 nm of MoO 3 and 100 nm of Ag as the hole transport layer and electrode, respectively, and the device was prepared.
测试上述不同有机太阳能电池性能，光强为100mW/cm
2AM 1.5白光照射条件下测量，得到电流-电压曲线，如图16所示，根据曲线得出相对应的电池的性能参数，见表3。
Test the performance of the above-mentioned different organic solar cells under the condition of light intensity of 100mW/cm 2 AM 1.5 white light irradiation, and obtain the current-voltage curve, as shown in Figure 16, and obtain the corresponding performance parameters of the battery according to the curve, see Table 3 .
从表3可知：应用本发明中的非富勒烯受体BTO作为客体分子加入主体（PM6:Y6）中后，可以调控主体材料间的相容性和溶解度，在没有任何后处理的条件下，在高沸点、绿色溶剂对二甲苯加工时可以获得高达16.59%的PCE，短路电流为26.32 mA/cm
2，开路电压为0.85 V，填充因子为0.74。当添加PC
71BM以拓展吸收光谱后，对二甲苯加工的器件PCE能进一步提升至17.48%，是目前报道的绿色溶剂加工有机太阳能电池器件的最高效率。
It can be seen from Table 3 that after adding the non-fullerene acceptor BTO in the present invention as a guest molecule into the host (PM6:Y6), the compatibility and solubility between the host materials can be regulated without any post-treatment. , when processed in high-boiling point, green solvent p-xylene, PCE up to 16.59%, short-circuit current of 26.32 mA/cm 2 , open-circuit voltage of 0.85 V and fill factor of 0.74 can be obtained. When PC 71 BM is added to expand the absorption spectrum, the PCE of the p-xylene processed device can be further increased to 17.48%, which is the highest efficiency reported so far for organic solar cell devices processed by green solvents.
实施例十一 （1）将尺寸为（10×10 cm
2）的ITO玻璃基底在去离子水、丙酮、乙醇和异丙醇中各超声两遍，清洗干净以后烘干备用； （2）配置5mg/mL的AZO溶液，以刮涂方式制备电子传输层，厚度为40 nm，刮刀距离基板高度为20 µm，刮刀速度为20 mm/s，随后放在120℃热台上干燥15 min；（3）以高沸点绿色溶剂（对二甲苯）配制PM6/Y6:BTO:PC
71BM (w/w:w:w
1/1.2:0:0，1/1.2:0.24:0, 1/1.2:0.24:0.1)的混合溶液（PM6浓度为12mg/mL），以刮涂方式制备有机活性层（厚度为120nm），刮刀距离基板高度为30µm，刮刀速度为25 mm/s，无需后处理；（4）利用真空蒸镀机蒸镀10 nm的MoO
3和100 nm的Ag分别作为空穴传输层和电极，基底尺寸为10×10 cm
2、活性层有效面积为36 cm
2的大器件制备完成。
Example 11 (1) Ultrasonic the ITO glass substrate with a size of (10×10 cm 2 ) twice in deionized water, acetone, ethanol and isopropanol, clean it and dry it for later use; (2) Configuration 5mg/mL AZO solution, the electron transport layer was prepared by scraping, the thickness was 40 nm, the height of the scraper from the substrate was 20 µm, and the scraper speed was 20 mm/s, and then dried on a hot stage at 120°C for 15 min; ( 3) Prepare PM6/Y6:BTO:PC 71 BM (w/w:w:w 1/1.2:0:0, 1/1.2:0.24:0, 1/1.2: 0.24:0.1) mixed solution (PM6 concentration is 12mg/mL), the organic active layer (thickness is 120nm) is prepared by scraping, the height of the scraper from the substrate is 30µm, the scraper speed is 25 mm/s, no post-processing is required; ( 4) Using a vacuum evaporation machine to evaporate 10 nm of MoO 3 and 100 nm of Ag as the hole transport layer and electrode respectively, a large device with a substrate size of 10×10 cm 2 and an active layer with an effective area of 36 cm 2 was prepared. .
测试上述大面积（活性层有效面积为36 cm
2）有机太阳能电池性能，光强为100mW/cm
2AM 1.5白光照射条件下测量，得到电流-电压曲线，如图17所示，根据曲线得出相对应的电池的性能参数，见表4。
Test the performance of the above-mentioned large-area (effective area of the active layer is 36 cm 2 ) organic solar cell, under the condition of 100mW/cm 2 AM 1.5 white light irradiation, and obtain the current-voltage curve, as shown in Figure 17, according to the curve The performance parameters of the corresponding batteries are shown in Table 4.
从表4可知：应用本发明中的非富勒烯受体BTO作为客体分子加入主体（PM6:Y6）中后，可以调控主体材料间的相容性和溶解度，在没有任何后处理的条件下，高沸点绿色溶剂对二甲苯加工的大面积模组PCE可以达到13.19%，短路电流为1.87 mA/cm
2，开路电压为9.96 V，填充因子为0.70。当添加PC
71BM以拓展吸收光谱后，对二甲苯加工的器件PCE能进一步提升至14.26%，是目前报道活性层有效面积大于20 cm
2的有机太阳能电池器件模组的最高效率。这证明本发明里的策略有效提高了有机太阳能电池大面积模组效率。
It can be seen from Table 4 that after adding the non-fullerene acceptor BTO in the present invention as a guest molecule into the host (PM6:Y6), the compatibility and solubility between the host materials can be regulated without any post-treatment , the PCE of the large-area module processed by the high-boiling point green solvent p-xylene can reach 13.19%, the short-circuit current is 1.87 mA/cm 2 , the open-circuit voltage is 9.96 V, and the fill factor is 0.70. When PC 71 BM is added to expand the absorption spectrum, the PCE of the p-xylene processed device can be further increased to 14.26%, which is the highest efficiency reported so far for the organic solar cell device module with active layer area larger than 20 cm 2 . This proves that the strategy in the present invention effectively improves the efficiency of large-area modules of organic solar cells.
实施例十二 一种有机太阳能电池，其活性层材料包括上述非富勒烯受体、其他Y系列受体以及给体材料。以Y6和BO1为受体材料、PM6为给体材料为例：(1)将先后用乙醇，丙酮、异丙醇超声氧化铟锡（ITO）导电玻璃片，烘干后以2000
rpm转速旋涂一层5mg/mL的AZO层，厚度为40 nm，作为电子传输层，然后120℃加热干燥15分钟，除去水分；(2)以高沸点氯苯或对二甲苯为溶剂，配制PM6浓度为12mg/mL，PM6/Y6:BO1(w/w:w 1/1.2:0，1/1.2:0.24)的混合溶液，搅拌，然后将其以2500 rpm的转速，旋涂于电子传输层上，得未经退火处理的活性层薄膜，薄膜厚度约120
nm；(3) 利用真空蒸镀机蒸镀10 nm的MoO
3和100
nm的Ag分别作为空穴传输层和电极，器件制备完成。
Embodiment 12 An organic solar cell whose active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials. Taking Y6 and BO1 as the acceptor material and PM6 as the donor material as an example: (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, spin-coat at 2000 rpm after drying One layer of 5mg/mL AZO layer with a thickness of 40 nm is used as an electron transport layer, and then heated and dried at 120°C for 15 minutes to remove moisture; (2) Use high-boiling point chlorobenzene or p-xylene as a solvent to prepare a PM6 concentration of 12mg /mL, the mixed solution of PM6/Y6:BO1 (w/w:w 1/1.2:0, 1/1.2:0.24) was stirred, and then it was spin-coated on the electron transport layer at a speed of 2500 rpm to obtain The thickness of the active layer film without annealing treatment is about 120 nm; (3) 10 nm of MoO 3 and 100 nm of Ag were evaporated using a vacuum evaporation machine as the hole transport layer and electrode, respectively, and the device was prepared.
测试上述有机太阳能电池性能，光强为100mW/cm
2AM 1.5白光照射条件下测量，得到电流-电压曲线，如图18所示，根据曲线得出相对应的电池的性能参数，见表5。
To test the performance of the organic solar cell above, measure it under the condition of 100mW/cm 2 AM 1.5 white light irradiation, and obtain the current-voltage curve, as shown in Figure 18, and obtain the corresponding performance parameters of the battery according to the curve, see Table 5.
从表5可知：应用本发明中的非富勒烯受体BO1作为客体分子加入主体（PM6:Y6）中后，可以调控主体材料间的相容性和溶解度，在没有任何后处理的条件下，在高沸点、绿色溶剂对二甲苯加工时可以获得高达16.10%的器件PCE，短路电流为26.85 mA/cm
2，开路电压为0.82 V，填充因子为0.73，相较于PM6:Y6在高沸点、绿色溶剂对二甲苯加工时所获得的11.25%的PCE，性能得到显著提升。
It can be seen from Table 5 that after adding the non-fullerene acceptor BO1 in the present invention as a guest molecule into the host (PM6:Y6), the compatibility and solubility between the host materials can be regulated without any post-treatment , when processed in high-boiling point, green solvent p-xylene, a device PCE of up to 16.10% can be obtained, a short-circuit current of 26.85 mA/cm 2 , an open-circuit voltage of 0.82 V, and a fill factor of 0.73, compared to PM6:Y6 at a high boiling point , The PCE of 11.25% obtained when the green solvent p-xylene is processed, the performance has been significantly improved.
实施例十三：一种有机太阳能电池，其活性层材料包括上述非富勒烯受体、其他Y系列受体以及给体材料。以Y6和BO2为受体材料、PM6为给体材料为例：(1)将先后用乙醇，丙酮、异丙醇超声氧化铟锡（ITO）导电玻璃片，烘干后以2000
rpm转速旋涂一层5mg/mL的AZO层，厚度为40 nm，作为电子传输层，然后120℃加热干燥15分钟，除去水分；(2)以高沸点氯苯或对二甲苯为溶剂，配制PM6浓度为12
mg/mL，PM6/Y6:BO2(w/w:w 1/1.2:0，1/1.2:0.24)的混合溶液，搅拌，然后将其以2500rpm的转速，旋涂于电子传输层上，得未经退火处理的活性层薄膜，薄膜厚度约120 nm；(3) 利用真空蒸镀机蒸镀10 nm的MoO
3和100
nm的Ag分别作为空穴传输层和电极，器件制备完成。
Embodiment 13: An organic solar cell, the active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials. Taking Y6 and BO2 as the acceptor material and PM6 as the donor material as an example: (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, spin-coat at 2000 rpm after drying One layer of 5mg/mL AZO layer with a thickness of 40 nm is used as an electron transport layer, and then heated and dried at 120°C for 15 minutes to remove moisture; mg/mL, the mixed solution of PM6/Y6:BO2 (w/w:w 1/1.2:0, 1/1.2:0.24) was stirred, and then it was spin-coated on the electron transport layer at a speed of 2500rpm to obtain The thickness of the active layer film without annealing treatment is about 120 nm; (3) 10 nm of MoO 3 and 100 nm of Ag were evaporated using a vacuum evaporation machine as the hole transport layer and electrode, respectively, and the device was prepared.
测试上述有机太阳能电池性能，光强为100mW/cm
2AM 1.5白光照射条件下测量，得到电流-电压曲线，如图19所示，根据曲线得出相对应的电池的性能参数，见表6。
To test the performance of the organic solar cell mentioned above, the light intensity is 100mW/cm 2 AM 1.5 under the condition of white light irradiation, and the current-voltage curve is obtained, as shown in Figure 19, and the corresponding performance parameters of the battery are obtained according to the curve, as shown in Table 6.
从表6可知：应用本发明中的非富勒烯受体BO2作为客体分子加入主体（PM6:Y6）中后，可以调控主体材料间的相容性和溶解度，在没有任何后处理的条件下，在高沸点、绿色溶剂对二甲苯加工时可以获得高达15.90%的器件PCE，短路电流为27.11 mA/cm
2，开路电压为0.82 V，填充因子为0.71，相较于PM6:Y6在高沸点、绿色溶剂对二甲苯加工时所获得的11.25%的PCE，性能得到显著提升。
It can be seen from Table 6 that after adding the non-fullerene acceptor BO2 in the present invention as a guest molecule into the host (PM6:Y6), the compatibility and solubility between the host materials can be regulated without any post-treatment , when processed in high-boiling point, green solvent p-xylene, a device PCE of up to 15.90% can be obtained, a short-circuit current of 27.11 mA/cm 2 , an open-circuit voltage of 0.82 V, and a fill factor of 0.71, compared to PM6:Y6 at a high boiling point , The PCE of 11.25% obtained when the green solvent p-xylene is processed, the performance has been significantly improved.
实施例十四：一种有机太阳能电池，其活性层材料包括上述非富勒烯受体、其他Y系列受体以及给体材料。以Y6和BO3为受体材料、PM6为给体材料为例：(1)将先后用乙醇，丙酮、异丙醇超声氧化铟锡（ITO）导电玻璃片，烘干后以2000
rpm转速旋涂一层5mg/mL的AZO层，厚度为40 nm，作为电子传输层，然后120℃加热干燥15分钟，除去水分；(2)以高沸点氯苯或对二甲苯为溶剂，配制PM6浓度为12
mg/mL，PM6/Y6:BO3(w/w:w 1/1.2:0、1/1.2:0.12、1/1.2:0.24)的混合溶液，搅拌，然后将其以2500rpm的转速，旋涂于电子传输层上，得未经退火处理的活性层薄膜，薄膜厚度约120
nm；(3) 利用真空蒸镀机蒸镀10 nm的MoO
3和100
nm的Ag分别作为空穴传输层和电极，器件制备完成。
Embodiment 14: An organic solar cell, the active layer material includes the above-mentioned non-fullerene acceptor, other Y series acceptors and donor materials. Taking Y6 and BO3 as the acceptor material and PM6 as the donor material as an example: (1) Use ethanol, acetone, and isopropanol to ultrasonically indium tin oxide (ITO) conductive glass sheet, spin-coat at 2000 rpm after drying One layer of 5mg/mL AZO layer with a thickness of 40 nm is used as an electron transport layer, and then heated and dried at 120°C for 15 minutes to remove moisture; mg/mL, the mixed solution of PM6/Y6:BO3 (w/w:w 1/1.2:0, 1/1.2:0.12, 1/1.2:0.24) was stirred, and then it was spin-coated at 2500rpm On the electron transport layer, a non-annealed active layer film was obtained, with a film thickness of about 120 nm; (3) 10 nm of MoO3 and 100 nm of Ag were evaporated by a vacuum evaporation machine as the hole transport layer and electrode, respectively, The device preparation is complete.
测试上述有机太阳能电池性能，光强为100mW/cm
2AM 1.5白光照射条件下测量，得到电流-电压曲线，如图20所示，根据曲线得出相对应的电池的性能参数，见表7。
To test the performance of the organic solar cell mentioned above, the light intensity is 100mW/cm 2 AM 1.5 under the condition of white light irradiation, and the current-voltage curve is obtained, as shown in Figure 20, and the corresponding performance parameters of the battery are obtained according to the curve, as shown in Table 7.
从表7可知：应用本发明中的非富勒烯受体BO3作为客体分子加入主体（PM6:Y6）中后，当掺杂量为10%时，器件性能提升到13.20%,短路电流为22.43 mA/cm
2，开路电压为0.80 V，填充因子为0.71，相较于PM6:Y6在高沸点、绿色溶剂对二甲苯加工时所获得的11.25%的PCE，性能得到小幅度提升。而随着BO3比例进一步的增加，器件性能出现降低降低。
It can be seen from Table 7 that after adding the non-fullerene acceptor BO3 in the present invention as a guest molecule into the host (PM6:Y6), when the doping amount is 10%, the device performance is increased to 13.20%, and the short-circuit current is 22.43 mA/cm 2 , the open circuit voltage is 0.80 V, and the fill factor is 0.71. Compared with the PCE of 11.25% obtained when PM6:Y6 is processed in high-boiling point, green solvent p-xylene, the performance has been slightly improved. And with the further increase of BO3 ratio, the performance of the device decreases.
另外，BT-2OEG-4F、BT-4OEG-4F也对PM6:Y6有性能提升，较上述非富勒烯分子改善程度低。In addition, BT-2OEG-4F and BT-4OEG-4F also have improved performance on PM6:Y6, which is lower than the above-mentioned non-fullerene molecules.
研究表明：应用本发明中具备组装性能的非富勒烯受体作为客体组分加入到主体（PM6:Y系列）后，在不通过任何后处理的情况下，能够利用自身和PM6及Y系列较好的相容性，调控主体分子间相容性，从而抑制过大的相分离尺寸。同时，这类客体分子可以利用其与系列受体间的范德瓦尔斯相互作用，提高其在高沸点溶剂（例如氯苯、对二甲苯）中的溶解度，抑制因溶解度带来的过度聚集，抑制了活性层中因不良形貌带来的非辐射符合，进而提高器件开路电压。此外，得益于自主装性客体分子对主体材料结晶过程的延长，活性层组分得到足够的结晶时间，整体有序度得以提高，从而构筑长程有序的，具有纳米尺度相分离以及三维立体传输通道的微观结构，进而提高器件的短路电流，填充因子，使得器件的能量转换效率极大提高。Studies have shown that: after the non-fullerene acceptor with assembly performance in the present invention is added to the host (PM6:Y series) as a guest component, it can use itself and PM6 and Y series without any post-processing. Better compatibility, regulate the compatibility between the host molecules, thereby inhibiting the excessive phase separation size. At the same time, this kind of guest molecules can take advantage of the van der Waals interaction between them and a series of receptors to improve their solubility in high boiling point solvents (such as chlorobenzene, p-xylene), and inhibit excessive aggregation caused by solubility. The non-radiative coincidence caused by the bad shape in the active layer is suppressed, thereby increasing the open circuit voltage of the device. In addition, thanks to the prolongation of the crystallization process of the host material by self-loading guest molecules, the active layer components have sufficient crystallization time, and the overall order degree is improved, thereby constructing a long-range order, nanoscale phase separation and three-dimensional three-dimensional The microstructure of the transmission channel can further improve the short-circuit current and fill factor of the device, which greatly improves the energy conversion efficiency of the device.
本发明公开的具备协同组装性能的非富勒烯受体作为客体分子添加到主体成分中，解决了含卤、低沸点溶剂带来的毒性、薄膜不均匀问题，同时实现了无后处理加工，简化了器件工艺，降低了经济和环境成本，最终获得了高性能、高稳定性的大面积器件模组，推动了有机太阳能电池的产业化的进程。The non-fullerene acceptor with cooperative assembly performance disclosed by the present invention is added as a guest molecule to the main component, which solves the problems of toxicity and film unevenness caused by halogen-containing and low-boiling solvents, and at the same time realizes no post-processing processing, The device process is simplified, economic and environmental costs are reduced, and a high-performance, high-stability large-area device module is finally obtained, which promotes the industrialization process of organic solar cells.
Claims (10)
- 一种具备协同组装性能的非富勒烯受体，其特征在于，具有乙二醇基团；所述具备协同组装性能的非富勒烯受体的化学结构式为以下化学结构式中的一种：A non-fullerene acceptor with cooperative assembly performance is characterized in that it has an ethylene glycol group; the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance is one of the following chemical structural formulas:
其中，X 1、X 2、X 3、X 4独立的选自O、S、Se、Te中的一种；端基A 1、端基A 2独立的选自以下结构式中的一种： Wherein, X 1 , X 2 , X 3 , and X 4 are independently selected from one of O, S, Se, and Te; terminal group A 1 and terminal group A 2 are independently selected from one of the following structural formulas:
其中B 1、B 2独立的选自或者
；B 3～B 8独立的选自H、CH 3、OCH 3、F、Cl、Br、CF 3、CN、C aH 2a+1中的一种；a为1～20； Wherein B 1 and B 2 are independently selected from
or; B 3 to B 8 are independently selected from one of H, CH 3 , OCH 3 , F, Cl, Br, CF 3 , CN, and Ca H 2a+1 ; a is 1 to 20;R 1为-(CH 2CH 2O) mCH 3或者-C nH 2n+1，其中m为1～10，n为1～20；R 2为-(CH 2CH 2O) mCH 3或者-C nH 2n+1，其中m为1～10，n为1～20；R 3为-(CH 2CH 2O) mCH 3或者-C nH 2n+1，其中m为1～10，n为1～20；R 4为-(CH 2CH 2O) mCH 3或者-C nH 2n+1，其中m为1～10，n为1～20；R 5为氢、-(CH 2CH 2O) mCH 3或者-C nH 2n+1，其中m为1～10，n为1～20；R 6为氢、-(CH 2CH 2O) mCH 3或者-C nH 2n+1，其中m为1～10，n为1～20。 R 1 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , wherein m is 1-10, n is 1-20; R 2 is -(CH 2 CH 2 O) m CH 3 Or -C n H 2n+1 , where m is 1 to 10, and n is 1 to 20; R 3 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , where m is 1 to 20 10, n is 1-20; R 4 is -(CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , wherein m is 1-10, n is 1-20; R 5 is hydrogen, - (CH 2 CH 2 O) m CH 3 or -C n H 2n+1 , wherein m is 1 to 10, n is 1 to 20; R 6 is hydrogen, -(CH 2 CH 2 O) m CH 3 or - C n H 2n+1 , wherein m is 1-10, and n is 1-20. - 根据权利要求1所述具备协同组装性能的非富勒烯受体，其特征在于，所述具备协同组装性能的非富勒烯受体的化学结构式为式1或者式3时，R 1为-(CH 2CH 2O) mCH 3，其中m为1～10；所述具备协同组装性能的非富勒烯受体的化学结构式为式2时，R 1和/或R 4为-(CH 2CH 2O) mCH 3，其中m为1～10。 The non-fullerene acceptor with cooperative assembly performance according to claim 1, characterized in that, when the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance is formula 1 or formula 3, R 1 is- (CH 2 CH 2 O) m CH 3 , wherein m is 1 to 10; when the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance is formula 2, R 1 and/or R 4 are -(CH 2 CH 2 O) m CH 3 , wherein m is 1-10.
- 根据权利要求2所述具备协同组装性能的非富勒烯受体，其特征在于，所述具备协同组装性能的非富勒烯受体的化学结构式为式1或者式3时，R 1为-(CH 2CH 2O) mCH 3，R 2为-C nH 2n+1，R 5为氢或者-C nH 2n+1，R 6为氢或者-C nH 2n+1，其中m为1～10，n为1～20。具备协同组装性能的非富勒烯受体的化学结构式为式2时，R 1为-(CH 2CH 2O) mCH 3，R 2为-C nH 2n+1，R 4为-C nH 2n+1；或R 4为-(CH 2CH 2O) mCH 3，R 2为-C nH 2n+1，R 1为-C nH 2n+1；其中m为1～10，n为1～20。 The non-fullerene acceptor with cooperative assembly performance according to claim 2, characterized in that, when the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance is formula 1 or formula 3, R 1 is- (CH 2 CH 2 O) m CH 3 , R 2 is -C n H 2n+1 , R 5 is hydrogen or -C n H 2n+1 , R 6 is hydrogen or -C n H 2n+1 , where m is 1-10, and n is 1-20. When the chemical structural formula of the non-fullerene acceptor with cooperative assembly performance is Formula 2, R 1 is -(CH 2 CH 2 O) m CH 3 , R 2 is -C n H 2n+1 , and R 4 is -C n H 2n+1 ; or R 4 is -(CH 2 CH 2 O) m CH 3 , R 2 is -C n H 2n+1 , R 1 is -C n H 2n+1 ; where m is 1 to 10 , n is 1-20.
- 根据权利要求1所述具备协同组装性能的非富勒烯受体，其特征在于，m为2～8，n为3～18。The non-fullerene acceptor with cooperative assembly performance according to claim 1, characterized in that m is 2-8, and n is 3-18.
- 权利要求1所述具备协同组装性能的非富勒烯受体在制备有机太阳能电池中的应用。The application of the non-fullerene acceptor with cooperative assembly performance described in claim 1 in the preparation of organic solar cells.
- 权利要求1所述具备协同组装性能的非富勒烯受体制备方法，其特征在于，包括以下步骤，将DA’D型共轭核与吸电子端基反应，得到具备协同组装性能的非富勒烯受体；所述DA’D型共轭核的化学结构式为以下结构式中的一种：The method for preparing the non-fullerene acceptor with cooperative assembly performance according to claim 1, characterized in that it comprises the following steps of reacting the DA'D-type conjugated core with the electron-withdrawing terminal group to obtain the non-fullerene acceptor with cooperative assembly performance. Slerene acceptor; the chemical structural formula of the DA'D type conjugated core is one of the following structural formulas:
吸电子端基选择以下化合物中的一种： Choose one of the following compounds for the electron-withdrawing end group:。
. - 一种有机太阳能电池用活性层材料，其特征在于，包括权利要求1所述具备协同组装性能的非富勒烯受体。An active layer material for an organic solar cell, characterized in that it comprises the non-fullerene acceptor with cooperative assembly performance described in claim 1.
- 根据权利要求7所述有机太阳能电池用活性层材料，其特征在于，有机太阳能电池用活性层材料还包括Y系列受体、给体材料。The active layer material for organic solar cells according to claim 7, characterized in that the active layer materials for organic solar cells also include Y series acceptor and donor materials.
- 一种有机太阳能电池，包括活性层、电子传输层、空穴传输层和电极，其特征在于，所述活性层包括权利要求1所述具备协同组装性能的非富勒烯受体。An organic solar cell, comprising an active layer, an electron transport layer, a hole transport layer and an electrode, characterized in that the active layer comprises the non-fullerene acceptor with synergistic assembly performance as claimed in claim 1.
- 一种有机太阳能电池的制备方法，包括以下步骤，在导电基底上依次制备电子传输层、活性层、空穴传输层和电极，得到有机太阳能电池；其特征在于，所述活性层包括权利要求1所述具备协同组装性能的非富勒烯受体。A method for preparing an organic solar cell, comprising the following steps of sequentially preparing an electron transport layer, an active layer, a hole transport layer and an electrode on a conductive substrate to obtain an organic solar cell; it is characterized in that the active layer comprises claim 1 The non-fullerene acceptor with cooperative assembly performance.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948042A (en) * | 2018-09-10 | 2018-12-07 | 中南大学 | Seven yuan of condensed ring class benzotriazole receptors of one kind and its preparation method and application |
| CN109134513A (en) * | 2018-09-10 | 2019-01-04 | 中南大学 | A kind of non-fullerene acceptor material of condensed ring diazosulfide base and its preparation method and application |
| CN110283185A (en) * | 2019-07-01 | 2019-09-27 | 中国科学院化学研究所 | A kind of quinoxaline derivant acceptor material and the preparation method and application thereof |
| CN113072563A (en) * | 2021-03-31 | 2021-07-06 | 广州追光科技有限公司 | Benzotriazole deuterated derivative and application thereof in organic electronic device |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045657B (en) * | 2013-03-14 | 2017-07-21 | 中国科学院化学研究所 | Five-ring heterocycles derivative bridging perylene diimides dimer, its preparation method and its application in organic photovoltaic devices |
| CN106025073B (en) * | 2016-06-14 | 2019-04-05 | 苏州大学 | It is a kind of using ternary component as the organic solar batteries of active layer |
| CN106467547B (en) * | 2016-08-30 | 2018-07-03 | 苏州大学 | A kind of non-fullerene solar cell acceptor material based on multi-fused rings class and its preparation method and application |
| CN110437254A (en) * | 2019-08-27 | 2019-11-12 | 山东师范大学 | The asymmetric non-fullerene small molecule receptor material of one kind and its application |
| CN110690349B (en) * | 2019-10-09 | 2021-04-30 | 浙江大学 | Efficient ternary organic solar cell based on non-fullerene acceptor alloy |
| CN112778327B (en) * | 2019-11-11 | 2022-04-01 | 北京大学深圳研究生院 | Organic non-fullerene electron acceptor material and preparation method and application thereof |
| WO2021118171A1 (en) * | 2019-12-10 | 2021-06-17 | 경상국립대학교산학협력단 | (aryloxy)alkyl group-substituted compound and organic electronic device using same |
| CN111261786B (en) * | 2020-01-19 | 2023-07-28 | 浙江大学 | Efficient organic solar cell based on asymmetric end-capped electron acceptor |
| CN111883659B (en) * | 2020-08-06 | 2024-05-14 | 浙江大学 | Efficient ternary organic solar cell prepared based on gradual deposition method |
| CN112521403B (en) * | 2020-11-18 | 2023-12-12 | 位速科技股份有限公司 | Seven-membered fused ring compound and organic photovoltaic cell |
| CN112802966A (en) * | 2020-12-23 | 2021-05-14 | 中国科学院重庆绿色智能技术研究院 | Full-small-molecule organic solar cell and preparation method thereof |
| CN113173937A (en) * | 2021-04-07 | 2021-07-27 | 香港科技大学深圳研究院 | Non-fullerene acceptor material based on chiral alkane chain and preparation method thereof |
-
2021
- 2021-09-09 CN CN202111058292.0A patent/CN113880862B/en active Active
- 2021-11-11 WO PCT/CN2021/130177 patent/WO2023035401A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948042A (en) * | 2018-09-10 | 2018-12-07 | 中南大学 | Seven yuan of condensed ring class benzotriazole receptors of one kind and its preparation method and application |
| CN109134513A (en) * | 2018-09-10 | 2019-01-04 | 中南大学 | A kind of non-fullerene acceptor material of condensed ring diazosulfide base and its preparation method and application |
| CN110283185A (en) * | 2019-07-01 | 2019-09-27 | 中国科学院化学研究所 | A kind of quinoxaline derivant acceptor material and the preparation method and application thereof |
| CN113072563A (en) * | 2021-03-31 | 2021-07-06 | 广州追光科技有限公司 | Benzotriazole deuterated derivative and application thereof in organic electronic device |
Non-Patent Citations (3)
| Title |
|---|
| CHEN ZHENG, YAN LIANG, RECH JEROMY JAMES, HU JUN, ZHANG QIANQIAN, YOU WEI: "Green-Solvent-Processed Conjugated Polymers for Organic Solar Cells: The Impact of Oligoethylene Glycol Side Chains", ACS APPLIED POLYMER MATERIALS, vol. 1, no. 4, 12 April 2019 (2019-04-12), pages 804 - 814, XP093045541, ISSN: 2637-6105, DOI: 10.1021/acsapm.9b00044 * |
| CHEN, HAIYANG ET AL.: "A Guest-Assisted Molecular-Organization Approach for >17% Efficiency Organic Solar Cells Using Environmentally Friendly Solvents", NATURE ENERGY, vol. 6, 1 November 2021 (2021-11-01), XP037622751, DOI: 10.1038/s41560-021-00923-5 * |
| LI TENGFEI, WANG KANG, CAI GUILONG, LI YAWEN, LIU HENG, JIA YIXIAO, ZHANG ZHENZHEN, LU XINHUI, YANG YE, LIN YUZE: "Asymmetric Glycolated Substitution for Enhanced Permittivity and Ecocompatibility of High-Performance Photovoltaic Electron Acceptor", JACS AU, AMERICAN CHEMICAL SOCIETY ; ACS PUBLICATIONS, vol. 1, no. 10, 25 October 2021 (2021-10-25), pages 1733 - 1742, XP093045540, ISSN: 2691-3704, DOI: 10.1021/jacsau.1c00306 * |
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