CN108794504B - Multi-fused ring conjugated macromolecule and preparation method and application thereof - Google Patents
Multi-fused ring conjugated macromolecule and preparation method and application thereof Download PDFInfo
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- 229920002521 macromolecule Polymers 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 73
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- -1 methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio Chemical group 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 125000003367 polycyclic group Chemical group 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 150000007514 bases Chemical class 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 125000004708 n-butylthio group Chemical group C(CCC)S* 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 26
- 239000000741 silica gel Substances 0.000 description 26
- 229910002027 silica gel Inorganic materials 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- 239000003480 eluent Substances 0.000 description 11
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 238000004770 highest occupied molecular orbital Methods 0.000 description 9
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000008033 biological extinction Effects 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
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- 239000011259 mixed solution Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- VOWZMDUIGSNERP-UHFFFAOYSA-N carbamimidoyl iodide Chemical compound NC(I)=N VOWZMDUIGSNERP-UHFFFAOYSA-N 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- JAHFQMBRFYOPNR-UHFFFAOYSA-N iodomethanamine Chemical compound NCI JAHFQMBRFYOPNR-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- OTNMXNJAYRIKQO-UHFFFAOYSA-N 5-fluoroindene-1,3-dione Chemical compound FC1=CC=C2C(=O)CC(=O)C2=C1 OTNMXNJAYRIKQO-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S50/00—Monitoring or testing of PV systems, e.g. load balancing or fault identification
- H02S50/10—Testing of PV devices, e.g. of PV modules or single PV cells
- H02S50/15—Testing of PV devices, e.g. of PV modules or single PV cells using optical means, e.g. using electroluminescence
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- 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
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to the field of organic and perovskite solar cells and photodetectors, in particular to a multi-fused ring conjugated macromolecule and a preparation method and application thereof. The poly-fused ring conjugated macromolecule is a compound shown in the following formula (1). The poly-fused ring conjugated macromolecule provided by the invention has stronger light absorption, higher charge transmission performance and proper electronic energy level, and is suitable for being used as a photovoltaic material or a light detection material to be applied to the preparation of a solar cell or a light detector.
Description
Technical Field
The invention relates to the field of organic and perovskite solar cells and photodetectors, in particular to a poly-fused ring conjugated macromolecule and a preparation method and application thereof.
Background
In recent years, organic solar cells have been rapidly developed, and have received much attention from academia and industry due to their advantages of light weight, good flexibility, simple processing method, large-area preparation, and low cost. Perovskite solar cells have received great attention in academia and industry in recent years due to the rapid increase in efficiency. Organic photodetectors as a new type of photodetector are also an important direction of organic electronics research. At present, the photoelectric conversion efficiency of organic solar cells prepared based on blending of polymer donors and fullerene receptors has broken through by 11%. This shows a great application prospect for organic solar cells. The polymer material has higher molar extinction coefficient and wider solar spectrum absorption, so that the photoelectric conversion efficiency of the photovoltaic device is higher. However, polymers also have deficiencies such as: uncertain molecular structure, polydispersity molecular weight distribution, difficult batch repeatability, difficult purification and the like. Different from polymers, organic condensed ring micromolecules and macromolecular semiconductor materials have the advantages of determined molecular structures and molecular weights, stable batches, simplicity in purification, high purity and the like, so that the research of organic condensed ring micromolecules and macromolecular solar cells tends to be hot.
Due to the advantages of sufficient electron affinity, isotropic electron transmission performance, relatively matched electron energy level and the like of the fullerene derivative (PC), the fullerene derivative 61 BM and PC 71 BM) has been the dominant star molecule in the receptor material. However, PCBM also has many disadvantages, such as weak visible light absorption, difficult energy level regulation, complicated purification process, etc. The novel organic multi-fused ring macromolecules have strong visible region absorption characteristics, are particularly suitable for organic solar cells and photodetectors as photovoltaic materials, and can also be used as doping components of a modification layer, an electron transmission layer or a light capture layer of the perovskite solar cell because the energy level of the novel organic multi-fused ring macromolecules is easy to regulate and control. Therefore, the synthesis of novel receptor materials is still necessary.
Disclosure of Invention
The invention aims to provide a novel multi-fused ring conjugated macromolecule which can be used for a solar cell as an electron donor or electron acceptor material and has stronger light absorption, higher charge transmission performance and proper electron energy level, and a preparation method and application thereof.
In order to achieve the above object, an aspect of the present invention provides a multiple-fused ring conjugated macromolecule, which is a compound represented by the following formula (1), and which is not a compound represented by the following formula (GK):
formula (1)
Formula (GK)
Wherein the two groups a are each independently selected from the following structures:
each group B independently represents 1-10 thiophene conjugated condensed ring structures or 1-10 furan conjugated condensed ring structures;
each R is 1 And R 2 Each independently selected from the group consisting of
A group shown; each R is 3 Are each independently selected from the group consisting of>
A group shown;
each Z is independently selected from C, N, si and Ge;
each X, each X', and each Y is independently selected from O, S or Se;
m is an integer of 0 to 6; n is an integer of 0 to 6; p is an integer of 0 to 6;
each R is 4 -R 10 Each independently selected from H, halogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio and C6-C30 aryl.
In a second aspect, the present invention provides a method for preparing the above-mentioned polycyclic conjugated macromolecule, which comprises:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a) to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1); wherein,
formula (2)
Formula (a) is selected from one or more of the following compounds:
in a third aspect, the present invention provides a photovoltaic material or a photodetection material containing one or more of the above-mentioned multiple-fused ring conjugated macromolecules.
In a fourth aspect, the invention provides a solar cell in which the photovoltaic material contains the above-described polycyclic and fused ring conjugated macromolecule.
The fifth aspect of the present invention provides a method for manufacturing the above solar cell, including: disposing the multiple fused ring conjugated macromolecules in a layer comprising a photovoltaic material.
In a sixth aspect, the present invention provides a photodetector comprising a light trapping active layer, wherein an electron donor material and/or an electron acceptor material in the light trapping active layer comprises one or more of the above-mentioned polya-fused ring conjugated macromolecules.
The seventh aspect of the present invention provides a method for preparing a photodetector, wherein the method comprises using an electron donor material and/or an electron acceptor material containing one or more of the above-mentioned polycyclic conjugated macromolecules for forming a light-trapping active layer.
The poly-fused ring conjugated macromolecule provided by the invention has stronger light absorption, higher charge transmission performance and proper electronic energy level, and is suitable for being used as a photovoltaic material or a light detection material to be applied to the preparation of a solar cell or a light detector.
Drawings
FIG. 1 shows an ultraviolet-visible absorption spectrum of a polycyclic conjugated macromolecule represented by the formula (1-7-1) obtained in example 1 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent -6 mol/L) of the film is a film (100 nm in thickness) formed by spin coating of a chloroform solution.
FIG. 2 is a cyclic voltammogram of a polycyclic conjugated macromolecule represented by formula (1-7-1) obtained in example 1 of the present invention.
Fig. 3 is an I-V curve (current-voltage curve) of the solar cell obtained in example 9.
FIG. 4 is an I-V curve of the solar cell obtained in example 10.
FIG. 5 is an I-V curve of the solar cell obtained in example 11.
FIG. 6 is an I-V curve of the solar cell obtained in example 12.
FIG. 7 is an I-V curve of the solar cell obtained in example 13.
FIG. 8 is an I-V curve of the solar cell obtained in example 14.
FIG. 9 is an I-V curve of the solar cell obtained in example 15.
FIG. 10 is an I-V curve of the solar cell obtained in comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, each group is independently selected from the group represented, and when each group occurs simultaneously and at multiple positions in the compound, they are independently selected, may be the same, or may be different, for example, although
Having 4R in the group shown 8 However, these 4 Rs 8 Are independently selectable, and may be the same or different.
In the present invention, the first and second liquid crystal display panels,
the dotted lines in the structures with dotted connecting bonds indicate the connecting sites and indicate the connecting bonds;
The solid lines other than parentheses to which any group or atom is not attached in the structures with solid line bonds also indicate the attachment sites, indicating bonds.
In the present invention, the composition contains
The group represents that both the left and right sides of the bond through which the group-F intervenes are substituted with F, respectively, and for example, the following formula (1-7-F1) actually means a mixture of compounds represented by formula (1-7-2) in which both A groups are the group A-2, formula (1-7-3) in which both A groups are the group A-3, and formula (1-7-4) in which one of the A groups is the group A-2 and the other is the group A-3.
The present invention provides a polycyclic fused ring conjugated macromolecule, which is a compound represented by the following formula (1), and the conjugated macromolecule is not a compound represented by the following formula (GK):
formula (1)
Formula (GK)
The individual radicals in formula (1) are as defined in the summary of the invention.
According to the present invention, in order to obtain a conjugated molecule having stronger light absorption, higher charge transport performance, and more suitable electron energy level, it is preferable that each group B independently represents 1 to 5 thiophene conjugated condensed ring structures or 1 to 5 furan conjugated condensed ring structures; each Z is independently selected from C, N and Si; each X, each X' and each Y is independently selected from O and S; m is an integer of 0 to 4; n is an integer of 0 to 4; p is an integer of 0 to 4; each R is 4 -R 10 Each independently selected from H, halogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C24 aryl.
More preferably, each group B independently represents 1 to 4 thiophene conjugated fused ring structures or 1 to 4 furan conjugated fused ring structures; each of R 4 -R 5 Each R 7 -R 8 And each R 10 Each independently selected from H, halogen, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio and C6-C12 aryl; each R is 6 And each R 9 Each independently selected from H,Halogen, C4-C15 alkyl, C4-C15 alkoxy, C4-C15 alkylthio and C6-C12 aryl.
Even more preferably, each Z is selected from C; each R is 4 -R 5 Each R 7 -R 8 And each R 10 Each independently selected from H, F, cl, br, I, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio and n-butylthio; each R is 6 And each R 9 Each independently selected from the group consisting of H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octoxy, 2-ethylhexoxy, n-butylthio, n-pentoxy, n-hexoxy, n-octoxy, and 2-ethylhexoxy.
Where n is 0, R can be considered to be 3 When the substituent is absent, the group A is directly bonded to the fused ring unit main body of the compound represented by the formula (1) to form a conjugated structure.
Specific examples of the C1-C30 alkyl group may be, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl, and the like. Alkyl groups within other ranges of the invention may also be selected from this specific example as appropriate.
Among them, specific examples of the alkoxy group having 1 to 30 carbon atoms may be, for example: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, 2-ethylhexoxy, and the like. The alkoxy group in the other ranges of the present invention can be selected from the specific examples as appropriate.
Among them, specific examples of the alkylthio group of C1 to C30 may be, for example: methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, 2-ethylhexylthio and the like. Alkylthio groups in other ranges of the present invention may be selected from the specific examples as appropriate.
Specific examples of the aryl group having 6 to 30 carbon atoms may include: phenyl, benzyl, p-tolyl, and the like. Aryl groups within other ranges of the invention may also be selected from this specific example as appropriate.
Wherein, two groups B located at both sides of the structure of the compound (1) are understood to constitute a conjugated structure together with the middle and both end structures of the compound (1), wherein each independently represents 1-10 thiophene conjugated condensed-ring structures or 1-10 furan conjugated condensed-ring structures, and when the group B is 1 thiophene conjugated condensed-ring structure or 1 furan conjugated condensed-ring structure, actually, 1 thiophene or furan group forms a basic structure of a conjugated macromolecule with the middle structure and both end structures at both sides; for example, when the group B has 2 or more thiophene conjugated condensed ring structures, it can be understood as an n-thiophene structure 1
And the anti-thiophene structure 2->
In alternating conjugated connection, as shown in formula>
The two carbon atoms joined by the dotted line are shared between the two rings to form: ->
If the fused ring structure is 2 thiophene conjugated fused ring structures and is 3 thiophene rings, a structure No. 2 can be connected to the left side of the structure No. 1 in the same manner, or a structure No. 1 can be connected to the right side of the structure No. 2 to form positive and negative alternating thiophene conjugated fused ring structures such as 1-2-1 and the like. Multiple furan conjugated fused ring structures are similarly understood.
Preferably, the conjugated macromolecule is one of the compounds shown in the following formula:
formula (1-7)
Formula (1-9)
In a preferred embodiment of the invention, R is 1 Are not all H.
According to the invention, the group A has a strong electron pulling effect, and the group A is positioned at two ends of the condensed ring unit, so that the obtained conjugated macromolecule has strong visible light absorption capacity, high charge transmission performance and proper electronic energy level, and is suitable for being used as a photovoltaic material to be applied to the preparation of an organic solar cell; the material is also suitable for being used as a light detection material in a light detector.
Preferably, the group a is selected from one or more of the following groups:
the group A-1 is
Group A-2 is->
Group A-3 is->
Group A-4 is>
Group A-5 is->
Group A-6 is>
According to the present invention, preferably, the multiple-fused ring conjugated macromolecule is one of compounds represented by the following formulae:
formula (1-7-1): in the formula (1-7), Z is C, A is the group A-1,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-7-2): in the formula (1-7), Z is C, A is the group A-2,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-7-3): in the formula (1-7), Z is C, A is the group A-3,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-7-4): in the formula (1-7), Z is C, one A is a group A-2, and the other A is a group A-3,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-7-5): in the formula (1-7), Z is C, A is a group A-4,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-7-6): in the formula (1-7), Z is C, A is a group A-5,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-7-7): in the formula (1-7), Z is C, A is a group A-6,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-1): in the formula (1-9), Z is C, A is group A-1,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-2): in the formula (1-9), Z is C, A is group A-2,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-3): in the formula (1-9), Z is C, A is group A-3,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-4): in the formula (1-9), Z is C, one A is a group A-2, and the other A is a group A-3,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-5): in the formula (1-9), Z is C, A is group A-4,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl.
Formula (1-9-6): in the formula (1-9), Z is C, A is group A-5,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-7): in the formula (1-9), Z is C, A is group A-6,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl.
In a second aspect, the present invention provides a method for preparing the above-mentioned polycyclic conjugated macromolecule, which comprises:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a) to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1); wherein,
formula (2)
Formula (a) is selected from one or more of the following compounds:
in this method, the group A-B, R 1 -R 10 As described above, the present invention is not described in detail herein.
Wherein, the compound shown in the formula (2) can be selected according to the structure of the poly-fused ring conjugated macromolecule, preferably, the compound shown in the formula (2) is one or more of the following formulas:
formula (2-7)
Formula (2-9)
Specific examples of the compound represented by the formula (2) may be, for example, one or more of the following formulae:
formula (2-7-1): in the formula (2-7), Z is C or R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (2-9-1): in the formula (2-9), Z is C or R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl.
According to the present invention, the compound represented by the formula (2) may be a commercially available product, or may be prepared by a method conventional in the art, for example, by reacting an aldehyde group with butyllithium (for example, by a method described in adv. Mater.,2015,27,1170-1174, j.am. Chem. Soc.,2016,138,4955-4961, etc..
According to the present invention, the compound represented by the formula (a) may be appropriately selected according to the group a, and for example, specific examples of the compound represented by the formula (a) may include:
formula (a-2-1):
formula (a-2-2):
Formula (a-2-3):
Formula (a-2-4):
Formula (a-2-5):
Formula (a-2-6):
Formula (a-2-7):
Formula (a-2-8):
Formula (a-2-9):
formula (a-2-10):
Formula (a-2-11):
Formula (a-2-12):
Is based on the formula (a-4-1)>
Is based on the formula (a-5-1)>
Formula (a-6-1)>
According to the present invention, the compound represented by formula (a) may be a commercially available product or may be prepared by a method conventional in the art, and will not be described herein again.
According to the present invention, aldehyde groups connected to both ends of the compound represented by formula (2) can be subjected to dehydration condensation with the compound represented by formula (a) to form the compound represented by formula (1), wherein the amount of the compound represented by formula (2) and the compound represented by formula (a) used is not particularly limited as long as the compound represented by formula (1) can be obtained, and preferably, the molar ratio of the compound represented by formula (2) to the compound represented by formula (a) is 1:2-100, more preferably 1:4-10.
According to the present invention, the reaction is carried out in the presence of a basic compound, which may be, for example, one or more of piperidine, pyridine and triethylamine, thereby making it possible to provide a basic environment to the reaction system. The amount of the basic compound to be used is not particularly limited as long as it can provide a basic environment and contribute to the progress of the dehydration condensation reaction, and is, for example, 0.1 to 1000mmol, more preferably 1 to 50mmol, relative to 1mmol of the compound represented by formula (2).
According to the invention, the organic solvent is, for example, chloroform and/or dichloromethane. The amount of the organic solvent to be used may be, for example, 20 to 500mL (preferably 40 to 400 mL) per 1mmol of the compound represented by the formula (2).
According to the present invention, preferably, the dehydration condensation reaction conditions include: the temperature is 20-100 deg.C (such as 50-100 deg.C), and the time is 10min-48h (such as 10-20 h). More preferably, the conditions of the dehydration condensation reaction include: the temperature is 60-80 ℃ and the time is 10-15h.
In order to ensure the smooth progress of the reaction, the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after all the raw materials are added, the inert gas is introduced into the reaction system for 20-40min to remove air. The inert gas may be, for example, argon, helium, nitrogen, or the like.
According to the present invention, in order to extract the compound represented by formula (1) from the reaction solution, the method further comprises a post-treatment step of, for example, mixing the dehydration condensation reaction product with methanol (the amount of methanol may be 200 to 1000mL, for example, relative to the total volume of 100mL of the reaction solution), followed by solid-liquid separation, and subjecting the resulting solid phase to chromatographic separation using a silica gel column (200 to 300 mesh silica gel may be used, and the eluent may be a mixture of petroleum ether and dichloromethane in a volume ratio of 1.2 to 3).
In a third aspect, the present invention provides a photovoltaic material or a photodetection material containing one or more of the above-mentioned multiple-fused ring conjugated macromolecules.
According to the present invention, the photovoltaic material is not particularly limited as long as it contains the above-mentioned multiple-fused ring conjugated macromolecule of the present invention, and preferably refers to an electron donor material and/or an electron acceptor material in a light trapping active layer in a solar cell; or photovoltaic materials in the electron transport layer and/or the modification layer (for example for perovskite solar cells).
For example, the electron donor polymer material PBnDT-FTAZ may be mixed with the conjugated molecule provided by the present invention in a weight ratio of 0.5 to 4:1 as a material for the photovoltaic material, in particular as a material for a light-trapping active layer of a solar cell, wherein in particular the polyatomic fused ring conjugated macromolecule provided by the invention is preferred as an electron acceptor material.
The structural unit of the polymer material PBnDT-FTAZ is shown as follows:
wherein-C 6 H 13 Represents n-hexyl, -C 4 H 9 Represents a n-butyl group. The preparation of the polymer material PBnDT-FTAZ can be carried out, for example, by a method in reference (j.am. Chem. Soc.2011,133, 4625), and the present invention is not described herein again.
According to the present invention, the photodetecting material is not particularly limited as long as it contains the above-mentioned multiple-fused-ring conjugated macromolecule of the present invention.
In a fourth aspect, the invention provides a solar cell in which the photovoltaic material comprises the above polycyclic and fused ring conjugated macromolecule.
According to the present invention, the structure of the solar cell is not particularly limited as long as the photovoltaic material used therein contains the polyacene ring conjugated macromolecule of the present invention, so that the photoelectric conversion efficiency of the solar cell can be effectively improved. For example, the solar cell is an organic solar cell, a perovskite solar cell, or the like.
Wherein, when the cell is an organic solar cell comprising a light-trapping active layer, the electron donor material and/or the electron acceptor material in the light-trapping active layer contain one or more of the multiple fused ring conjugated macromolecules.
When the cell is a perovskite solar cell comprising an electron transport layer, a perovskite light trapping layer and a modification layer, one or more of the poly-fused ring conjugated macromolecules are contained in the light trapping layer and/or the electron transport layer and/or the modification layer.
In particular, the conjugated molecules of the present invention are preferably used as electron acceptor materials in combination with other electron donor materials to form a light-trapping active layer of a solar cell. As such an electron donor material there may be mentioned, for example, the polymeric material PBnDT-FTAZ, as defined above.
Wherein, the polymer material PBnDT-FTAZ can be mixed with the conjugated macromolecule provided by the invention in a weight ratio of 0.5-4:1 are combined to form a light trapping active layer.
The fifth aspect of the present invention provides a method for manufacturing the above solar cell, the method including: disposing the multiple fused ring conjugated macromolecules in a layer comprising a photovoltaic material.
According to the present invention, the process of manufacturing the solar cell is not particularly limited, and may be performed by a method that is conventional in the art.
Wherein, for organic solar cells, the layer comprising the photovoltaic material may be an active layer for light trapping.
For perovskite solar cells, the photovoltaic material-containing layer may be a light-trapping layer and/or an electron-transporting layer and/or a modifying layer.
According to the present invention, the process of manufacturing the organic solar cell may include, for example: for a device with an inverted structure: coating a ZnO layer as a cathode modification layer (with the thickness of 20-50nm for example) on conductive glass (such as indium tin oxide glass and ITO) as a cathode, drying, coating a mixture of a polymer material PBnDT-FTAZ and the conjugated macromolecules provided by the invention as an active layer on the ZnO layer, drying, and performing vacuum evaporation on molybdenum oxide (with the thickness of 5-10nm for example) and Ag (with the thickness of 50-100nm for example) as an anode. For a forward structure device: unlike the inverted structure devices, which use a polymer layer formed from a polymer combination such as poly 3,4-ethylenedioxythiophene-polystyrene sulfonate, poly 3,4-ethylenedioxythiophene-polystyrene sulfonate also stands for PEDOT: PSS; metal calcium replaces molybdenum oxide; al replaces Ag.
According to the present invention, the process of manufacturing a perovskite solar cell may for example comprise: cleaning Indium Tin Oxide (ITO) glass as cathode with detergent, sequentially ultrasonic cleaning with deionized water, acetone and isopropanol, drying, and spin-coating an electron transport layer (such as SnO) with thickness of about 30nm 2 ) And annealing for 30 minutes for standby. Dissolving the above poly-fused ring conjugated macromolecule in DMF (e.g. 0.25 mg/mL), adding appropriate amount of PbI 2 Then spin-coating the uniformly mixed solution on the electron transport layer, annealing for 20 minutes at 70 ℃, cooling, spin-coating the iodoformamidine (FAI)/iodomethylamine (MAI) 2:1) mixed solution on the electron transport layer, annealing for 15 minutes at 150 ℃ to obtain the conjugated macromolecule doped perovskite layer provided by the invention, and finally spin-coating 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] with the concentration of 80mg/mL]-9,9' -spirobifluorene (spiro-OMeTAD) solution as hole transport layer. Vacuum (absolute pressure 2X 10) on the active layer -5 Pa) and depositing metal Ag with the thickness of about 150nm as an anode of the solar cell.
The conjugated molecule provided by the invention has stronger absorption peaks in visible light and near infrared regions, for example, the conjugated molecule has a strong absorption peak in a wavelength range of 600-800 nm; the conjugated molecule has good thermal stability, can resist the temperature of about 340 ℃ without decomposition; the test result of the cyclic voltammetry shows that the HOMO energy level and the LUMO energy level of the material can be matched with the energy level of most universal electron donor materials, and the material has better electron or hole accepting capability, and is very favorable for being used as a photovoltaic material of a solar cell, particularly an electron acceptor and/or an electron donor material, and particularly as an electron acceptor material.
In a sixth aspect, the present invention provides a photodetector comprising a light trapping active layer, wherein an electron donor material and/or an electron acceptor material in the light trapping active layer comprises one or more of the above-mentioned polya-fused ring conjugated macromolecules.
The present invention is not particularly limited in the configuration of the photodetector, and a conventional configuration in the art may be employed as long as it includes the above-mentioned multiple-fused ring conjugated macromolecule of the present invention, so that an excellent photodetection effect can be obtained.
The seventh aspect of the present invention provides a method for preparing a photodetector, wherein the method comprises using an electron donor material and/or an electron acceptor material containing one or more of the above-mentioned multiple-fused-ring conjugated macromolecules for forming a light-trapping active layer.
The present invention is not particularly limited in the process for preparing the photodetector, and the process for preparing the photodetector in the art can be employed as long as it includes the above-mentioned multiple fused ring conjugated macromolecule of the present invention, so that an excellent photodetection effect can be obtained.
The present invention will be described in detail below by way of examples.
In the following examples: molecular structural formula of-C 6 H 13 Are each n-hexyl, -C 4 H 9 Are all n-butyl, -C 2 H 5 Are all ethyl groups. 1 H NMR was measured using a Bruker AVANCE model 400/300 NMR spectrometer. MS (MALDI) was measured using a Bruker Daltonics Biflex III MALDI-TOF Analyzer model mass spectrometer. The UV-visible absorption spectrum and the visible light transmittance spectrum were measured using a Jasco V-570spectrophotometer model UV-visible spectrophotometer. The cyclic voltammetry curve is cyclic voltammetry measurement adopting CHI660C electrochemical work modelThe tester is used for measurement. The I-V curve is measured by B2912A Precision Source/measurement Unit (Agilent Technologies), from which parameters such as short-circuit current, open-circuit voltage, fill factor, and photoelectric conversion efficiency can be obtained. The preparation of the polymeric material PBnDT-FTAZ can be carried out, for example, by the methods in the literature (for example, j.am. Chem. Soc.2011,133, 4625). The compound represented by the formula (a-2-6) was prepared according to the method described in "J.Am.chem.Soc.2017,139, 1336-1343". The compound represented by the formula (a-5-1) was prepared according to the method in "adv.mater.2017,29,1700254".
Preparation example 1
This preparation example is illustrative of the method for producing the compound represented by the formula (2-7-1).
As shown in the above reaction scheme, a compound represented by the formula IT1 (141mg, 0.1mmol; available from Technology Ltd, nakay, suzhou), tetrahydrofuran (20 mL) was charged into a reaction vessel, and the mixture was stirred at-78 ℃ for 1 hour under argon gas. N-butyllithium (0.19mL, 0.3mmol, 1.6M) was slowly added dropwise, stirring was carried out at-78 deg.C for 2h, N-dimethylformamide (36.6mg, 0.5mmol) was added, and the reaction product was slowly returned to room temperature (about 25 deg.C), stirring was carried out overnight (about 12 h). Then, water (0.2 mL) was added for quenching, saturated brine and dichloromethane were used for extraction, the mixture was dried over magnesium sulfate and spin-dried, and the obtained precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel, eluent petroleum ether/dichloromethane at a volume ratio of 2:1) to obtain a bright yellow solid (111 mg, yield 75.8%), which was the compound represented by formula (2-7-1). 1 H NMR(400MHz,CDCl 3 ):δ9.65(s,2H),7.41(s,2H),6.98(m,8H),6.95(m,8H),6.41(d,J＝3.2Hz,2H),6.07(d,J＝3.2Hz,2H),2.72(m,12H),1.60(m,14H),1.33(m,36H),0.97(m,24H).MS(MALDI):m/z1464(M+).
Preparation example 2
This preparation example is illustrative of the method for producing the compound represented by the formula (2-9-1).
As shown in the above reaction scheme, a compound represented by the formula IT3 (152mg, 0.1mmol; available from Technology Ltd, nakay, suzhou), tetrahydrofuran (20 mL) was charged into a reaction vessel, and the mixture was stirred at-78 ℃ for 1 hour under argon gas. N-butyllithium (0.19mL, 0.3mmol, 1.6M) was slowly added dropwise, stirred at-78 deg.C for 2h, N-dimethylformamide (36.6mg, 0.5mmol) was added, and the reaction product was slowly returned to room temperature (about 25 deg.C) and stirred overnight (about 12 h). Then, water (0.2 mL) was added for quenching, extraction was performed with saturated brine and dichloromethane, drying was performed with magnesium sulfate, and spin-drying was performed to obtain a precipitate, which was chromatographed on a silica gel column (using 200-300 mesh silica gel, eluent petroleum ether/dichloromethane at a volume ratio of 2:1) to obtain a bright yellow solid (118 mg, yield 74.9%), which was the compound represented by formula (2-9-1). 1 H NMR(400MHz,CDCl 3 ):δ9.84(s,2H),8.15(s,2H),7.22(d,J＝3.2Hz,2H),6.98(m,8H),6.89(m,8H),6.81(d,J＝3.2Hz,2H),2.75(m,12H),1.62(m,14H),1.30(m,36H),0.99(m,24H).MS(MALDI):m/z1518(M+).
Preparation example 3
This preparation example is illustrative of the method for producing the compound represented by the formula (a-4-1).
As shown in the above reaction scheme, compound T1 (200mg, 1.3mmol; synthesized according to the method of the document Dyes and Pigments 2016,134,129), malononitrile (171mg, 2.6 mmol), ethanol (20 mL) were added to the reaction vessel, argon was passed through, and stirring was carried out at 25 ℃ for 30 minutes. Sodium acetate (132mg, 1.6 mmol) was added slowly and stirred at 25 ℃ for 2h, water (30 mL) was added and stirred for 1.5h. Then, concentrated hydrochloric acid was added to adjust PH =2, and the precipitate was filtered through filter paper and washed with water (400 mL), and the resulting precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel and chloroform as an eluent) to obtain an orange solid (85 mg, yield 32%), which was the compound represented by the formula (a-4-1). 1 H NMR(400MHz,CDCl 3 ):δ8.64(d,J＝2.4Hz,1H),8.07(d,J＝2.4Hz,1H),4.00(s,2H).MS(EI):m/z 200(M + ).
Preparation example 4
This preparation example is intended to illustrate the preparation of the compounds represented by the formulae (a-2-3) and (a-2-4).
As shown in the above reaction scheme, 5-fluoro-1,3-indandione (820mg, 5mmol; from Ark Co.), malononitrile (660mg, 10mmol), and ethanol (30 mL) were charged into a reaction vessel, and stirred at 25 ℃ for 30 minutes under argon gas. Sodium acetate (492mg, 6 mmol) was added slowly and stirred at 25 ℃ for 2h, water (40 mL) was added and stirred for 1.5h. Then, concentrated hydrochloric acid was added to adjust pH =2, and the precipitate was filtered through a filter paper, washed with water (300 mL), and subjected to chromatographic separation on a silica gel column (using 200 to 300 mesh silica gel, and an eluent was methanol/chloroform at a volume ratio of 1:5) to obtain an off-white solid (610 mg, yield 57.5%) which was a mixture of the compound represented by formula (a-2-3) (71 mol%) and the compound represented by formula (a-2-4) (29 mol%). Of mixtures 1 H NMR(400MHz,CDCl 3 ):δ8.68(dd,J＝8.8Hz,0.28H),7.61(dd,J＝8.2Hz,0.72H),8.01(m,0.76H),7.61(m,0.36H),7.55(m,1H),3.76(d,2H).MS(EI):m/z 212(M + ).
Example 1
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, the compound represented by the formula (2-7-1) (146.2 mg, 0.1mmol) obtained in production example 1, the compound represented by the formula (a-2-1) (78mg, 0.4mmol; available from TCI Co., ltd.), pyridine (0.8 mL, 0.96mmol) and chloroform (30 mL) were charged into a reaction vessel, and argon gas was introduced for 25min, followed by refluxing at 65 ℃ for 15h. After cooling to room temperature (about 25 ℃ C.), the reaction product was poured into 200mL of methanolAnd filtering, and separating the obtained precipitate by chromatography with silica gel chromatographic column (200-300 mesh silica gel, and eluting with 1:2 petroleum ether/dichloromethane) to obtain blue solid (168.7 mg, yield 92.9%), which is the poly-fused ring conjugated macromolecule represented by formula (1-7-1). 1 H NMR(400MHz,CDCl 3 ):δ8.69(s,2H),8.62(d,J＝7.6Hz,2H),7.86(d,J＝6.8Hz,2H),7.75(m,4H),7.44(s,2H),7.01(m,16H),6.43(d,J＝3.2Hz,2H),6.10(d,J＝3.2Hz,2H),2.61(m,12H),2.12(m,2H),1.61(m,12H),1.37(m,36H),1.00(m,24H).MS(MALDI):m/z 1814(M+).
The ultraviolet-visible absorption spectrum of the polycyclic conjugated macromolecule represented by the formula (1-7-1) is shown in FIG. 1, wherein the ultraviolet-visible absorption spectrum has a strong absorption peak in a wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.7 × 10 5 M –1 ·cm –1 The film has the strongest absorption at about 738 nm; the maximum absorption peak of the film is shifted 24nm from the red in solution.
The cyclic voltammogram is shown in FIG. 2, the HOMO energy level is-5.45eV, the LUMO energy level is-3.84 eV, and the band gap is 1.61eV, which indicates that the poly-fused ring conjugated macromolecule shown in the formula (1-7-1) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 2
This example illustrates the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, the compound represented by the formula (2-7-1) obtained in production example 1 (146.2mg, 0.1mmol), the mixture represented by the formulae (a-2-3) and (a-2-4) obtained in production example 4 (85mg, 0.4 mmol), pyridine (0.8mL, 0.96mmol), and chloroform (30 mL) were charged into a reaction vessel, purged with argon for 25min, and refluxed at 65 ℃ for 15h. Cooling to room temperature (about 25 deg.C), pouring the reaction product into 200mL of methanol and filtering to obtain a precipitate, and separating with silica gel column (using 200-300 mesh silica gel, eluting with petroleum ether/dichloromethane at a volume ratio of 1:2) to obtain a productTo a blue solid (172.2 mg, yield 93.1%), which was a poly-fused ring conjugated macromolecule represented by formula (1-7-F1) which was a mixture of compounds represented by formula (1-7-2), formula (1-7-3) and formula (1-7-4). 1 H NMR(400MHz,CDCl 3 ):δ8.85(s,2H),8.73(dd,J＝4.0Hz,0.5H),8.38(dd,J＝1.6Hz,1.5H),7.94(dd,J＝5.2Hz,1.5H),7.57(dd,J＝2.8Hz,0.5H),7.50(m,2H),7.44(s,2H),7.01(m,16H),6.43(d,J＝3.2Hz,2H),6.10(d,J＝3.2Hz,2H),2.61(m,12H),2.12(m,2H),1.61(m,12H),1.37(m,36H),1.00(m,24H).MS(MALDI):m/z 1851(M+).
The ultraviolet-visible absorption spectrum of the mixture of the three poly-fused ring conjugated macromolecules shown in the formula (1-7-F1) shows that the mixture has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.9 multiplied by 10 5 M –1 ·cm –1 The film absorbs most strongly at about 743 nm; the maximum absorption peak of the film is shifted 20nm from the red in solution.
The HOMO energy level is-5.49eV, the LUMO energy level is-3.89 eV and the band gap is 1.60eV according to cyclic voltammetry, and the result shows that the mixture of the three multi-fused ring conjugated macromolecules shown in the formula (1-7-F1) has good electron accepting capacity and can be matched with most of universal electron donor materials in energy level.
Example 3
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, the compound represented by the formula (2-7-1) (146.2mg, 0.1mmol) obtained in the above production example 1, the compound represented by the formula (a-2-6) (92mg, 0.4 mmol), pyridine (0.8mL, 0.96mmol) and chloroform (30 mL) were charged into a reaction vessel, and argon gas was introduced for 25min, followed by refluxing at 65 ℃ for 15h. After cooling to room temperature (about 25 deg.C), the reaction product was poured into 200mL of methanol and filtered, and the resulting precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel, eluent petroleum ether/dichloromethane at a volume ratio of 1:2) to give a blue solid (168.1 mg, yield89.1 percent), namely the poly-fused ring conjugated macromolecule shown as the formula (1-7-5). 1 H NMR(400MHz,CDCl 3 ):δ8.83(s,2H),8.69(s,2H),8.51(s,2H),8.32(s,2H),7.11(m,16H),6.58(d,J＝3.2Hz,2H),6.32(d,J＝3.2Hz,2H),2.59(m,12H),2.15(m,2H),1.63(m,12H),1.39(m,36H),1.03(m,24H).MS(MALDI):m/z 1887(M+).
The ultraviolet-visible absorption spectrum of the poly-fused ring conjugated macromolecule shown in the formula (1-7-5) shows that the poly-fused ring conjugated macromolecule has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.9 multiplied by 10 5 M –1 ·cm –1 The film has strongest absorption at the position of 746nm or so; the maximum absorption peak of the film is shifted 20nm from the red in solution.
The HOMO energy level is-5.50eV, the LUMO energy level is-3.93 eV and the band gap is 1.57eV through cyclic voltammetry, which shows that the poly-fused ring conjugated macromolecule shown in the formula (1-7-5) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 4
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, the compound represented by the formula (2-7-1) (146.2mg, 0.1mmol) obtained in production example 1, the compound represented by the formula (a-4-1) (80mg, 0.4 mmol) obtained in production example 3, pyridine (0.8 mL, 0.96mmol) and chloroform (30 mL) were charged into a reaction vessel, and argon gas was introduced for 25min, followed by refluxing at 65 ℃ for 15h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel with an eluent of petroleum ether/dichloromethane at a volume ratio of 1:2) to obtain a blue solid (162.1 mg, yield 88.8%) which was the poly-fused ring conjugated macromolecule represented by formula (1-7-6). 1 H NMR(400MHz,CDCl 3 ):δ8.65(s,2H),8.36(s,2H),7.97(s,2H),7.40(s,2H),7.00(m,16H),6.40(d,J＝3.2Hz,2H),6.12(d,J＝3.2Hz,2H),2.59(m,12H),2.10(m,2H),1.63(m,12H),1.37(m,36H),1.00(m,24H).MS(MALDI):m/z 1826(M+).
The ultraviolet-visible absorption spectrum of the poly-fused ring conjugated macromolecule shown in the formula (1-7-6) shows that the poly-fused ring conjugated macromolecule has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.8 multiplied by 10 5 M –1 ·cm –1 The film has the strongest absorption at the position of about 752 nm; the maximum absorption peak of the film is 30nm red-shifted from the solution.
The HOMO energy level is-5.50eV, the LUMO energy level is-3.94 eV and the band gap is 1.56eV through cyclic voltammetry, which shows that the poly-fused ring conjugated macromolecule shown in the formula (1-7-6) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 5
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, the compound represented by the formula (2-7-1) (146.2mg, 0.1mmol) obtained in the above production example 1, the compound represented by the formula (a-5-1) (80mg, 0.4 mmol), pyridine (0.8mL, 0.96mmol) and chloroform (30 mL) were charged into a reaction vessel, and argon gas was introduced for 25min, followed by refluxing at 65 ℃ for 15h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by using a silica gel column (using 200-300 mesh silica gel, eluent being petroleum ether/dichloromethane at a volume ratio of 1:2) to obtain a blue solid (165.8 mg, yield 90.8%), which was the poly-fused ring conjugated macromolecule represented by formula (1-7-7). 1 H NMR(400MHz,CDCl 3 ):δ8.65(s,2H),8.00(m,4H),7.40(s,2H),7.00(m,16H),6.40(d,J＝3.2Hz,2H),6.12(d,J＝3.2Hz,2H),2.59(m,12H),2.10(m,2H),1.63(m,12H),1.37(m,36H),1.00(m,24H).MS(MALDI):m/z 1826(M+).
The ultraviolet-visible absorption spectrum of the poly-fused ring conjugated macromolecule shown in the formula (1-7-7) shows that the poly-fused ring conjugated macromolecule has a strong absorption peak in the wavelength range of 600-800nm and has the maximum molar extinctionCoefficient of 1.8X 10 5 M –1 ·cm –1 The film has the strongest absorption at the position of about 695 nm; the maximum absorption peak of the film is 30nm shifted from the red in solution.
The HOMO energy level is-5.40eV, the LUMO energy level is-3.70 eV and the band gap is 1.70eV, which show that the poly-fused ring conjugated macromolecule shown in the formula (1-7-7) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 6
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, the compound represented by the formula (2-9-1) (157.4 mg, 0.1mmol) obtained in the above production example 2, the compound represented by the formula (a-2-1) (78mg, 0.4mmol; available from TCI Co., ltd.), pyridine (0.8 mL, 0.96mmol) and chloroform (30 mL) were charged into a reaction vessel, passed through argon for 25min, and refluxed at 65 ℃ for 15h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by using a silica gel column (using 200-300 mesh silica gel, eluent being petroleum ether/dichloromethane at a volume ratio of 1:2) to obtain a blue solid (173.6 mg, yield 90.1%) which was the poly-fused ring conjugated macromolecule represented by formula (1-9-1). 1 H NMR(400MHz,CDCl 3 ):δ8.72(s,2H),8.68(d,J＝7.6Hz,2H),7.89(d,J＝6.8Hz,2H),7.74(m,4H),7.49(s,2H),6.99(m,16H),6.45(d,J＝3.2Hz,2H),6.12(d,J＝3.2Hz,2H),2.60(m,12H),2.09(m,2H),1.58(m,12H),1.35(m,36H),0.98(m,24H).MS(MALDI):m/z 1927(M+).
The ultraviolet-visible absorption spectrum of the poly-fused ring conjugated macromolecule shown in the formula (1-9-1) shows that the poly-fused ring conjugated macromolecule has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.7 multiplied by 10 5 M –1 ·cm –1 The film has strongest absorption at the position of about 758 nm; the maximum absorption peak of the film is 25nm red-shifted from the solution.
The HOMO energy level is-5.40eV, the LUMO energy level is-3.84 eV and the band gap is 1.56eV, which show that the poly-fused ring conjugated macromolecule shown in the formula (1-9-1) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 7
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction formula, the compound represented by the formula (2-9-1) obtained in production example 2 (157.4 mg, 0.1mmol), the mixture represented by the formulae (a-2-3) and (a-2-4) obtained in production example 4 (85mg, 0.4 mmol), pyridine (0.8 mL, 0.96mmol) and chloroform (30 mL) were charged into a reaction vessel, and argon was introduced for 25min, followed by refluxing at 65 ℃ for 15h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel, eluent petroleum ether/dichloromethane at a volume ratio of 1:2) to give a blue solid (169.7 mg, yield 86.5%) which is a mixture of the poly-fused ring conjugated macromolecules represented by formula (1-9-F1) which are compounds represented by formula (1-9-2), formula (1-9-3) and formula (1-9-4). 1 H NMR(400MHz,CDCl 3 ):δ8.83(s,2H),8.70(dd,J＝4.0Hz,0.5H),8.32(dd,J＝1.6Hz,1.5H),7.90(dd,J＝5.2Hz,1.5H),7.75(dd,J＝2.8Hz,0.5H),7.50(m,2H),7.32(s,2H),7.11(m,16H),6.53(d,J＝3.2Hz,2H),6.30(d,J＝3.2Hz,2H),2.56(m,12H),2.12(m,2H),1.59(m,12H),1.32(m,36H),0.96(m,24H).MS(MALDI):m/z 1851(M+).
The ultraviolet-visible absorption spectrum of the mixture of the three poly-fused ring conjugated macromolecules shown in the formula (1-9-F1) shows that the mixture has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.9 multiplied by 10 5 M –1 ·cm –1 The film has strongest absorption at the position of 768nm or so; the maximum absorption peak of the film is 30nm shifted from the red in solution.
The HOMO energy level of the polymer is-5.42eV, the LUMO energy level of the polymer is-3.89 eV, and the band gap of the polymer is 1.53eV through cyclic voltammetry, which shows that the mixture of the three multi-fused ring conjugated macromolecules shown in the formula (1-9-F1) has good electron accepting capacity and can be matched with most of universal electron donor materials in energy level.
Example 8
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, the compound represented by the formula (2-9-1) (157.4 mg, 0.1mmol) obtained in production example 2 above, the compound represented by the formula (a-2-6) (92mg, 0.4 mmol), pyridine (0.8 mL, 0.96mmol) and chloroform (30 mL) were charged into a reaction vessel, purged with argon for 25min, and then refluxed at 65 ℃ for 15h. After cooling to room temperature (about 25 ℃), the reaction product is poured into 200mL of methanol and filtered, and the obtained precipitate is chromatographically separated by using a silica gel chromatographic column (200-300 meshes of silica gel is adopted, and the eluent is petroleum ether/dichloromethane with the volume ratio of 1:2) to obtain a blue solid (181.9 mg, the yield is 91.0 percent), namely the poly-fused ring conjugated macromolecule shown in the formula (1-9-5). 1 H NMR(400MHz,CDCl 3 ):δ8.84(s,2H),8.70(s,2H),8.61(s,2H),8.42(s,2H),7.07(m,16H),6.60(d,J＝3.2Hz,2H),6.30(d,J＝3.2Hz,2H),2.53(m,12H),2.11(m,2H),1.69(m,12H),1.40(m,36H),1.05(m,24H).MS(MALDI):m/z 1999(M+).
The ultraviolet-visible absorption spectrum of the poly-fused ring conjugated macromolecule shown in the formula (1-9-5) shows that the poly-fused ring conjugated macromolecule has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 3.0 multiplied by 10 5 M –1 ·cm –1 The film absorbs most strongly at about 772 nm; the maximum absorption peak of the film is 30nm red-shifted from the solution.
The HOMO energy level of the conjugated macromolecule is-5.44eV, the LUMO energy level of the conjugated macromolecule is-3.96 eV, and the band gap of the conjugated macromolecule is 1.48eV through cyclic voltammetry, so that the conjugated macromolecule with multiple fused rings shown in the formula (1-9-5) has good electron accepting capacity and can be matched with most of universal electron donor materials in energy level.
Example 9
This example is for illustrating the solar cell of the present invention.
Indium Tin Oxide (ITO) glass (purchased from Shenzhen glass float glass Co., ltd.) as a cathode is cleaned by a detergent, then sequentially cleaned by deionized water, acetone and isopropanol in an ultrasonic mode, a ZnO cathode modification layer with the thickness of 30nm is coated in a spin mode after drying, and the ZnO cathode modification layer is dried for 30 minutes at the temperature of 200 ℃ for later use.
1.5mg of the poly-fused ring conjugated macromolecule represented by the above formula (1-7-1) and 1mg of the polymer donor material PBnDT-FTAZ were mixed in 0.1mL of chloroform to obtain a mixed solution, which was then spin-coated on the above ZnO layer, and dried to obtain a light trapping active layer (effective area 4 mm) 2 ). Vacuum (absolute pressure 2X 10- 5 Pa) vapor deposition thickness of about 5nm of MoO 3 (available from carbofuran technologies, inc.) and about 80nm of metallic Ag as the anode of the solar cell.
A solar light source was simulated with an AM1.5 filter (model XES-70S1, SAN-EI ELECTRIC Co., ltd.) at 100mW/cm 2 The devices were tested for photovoltaic performance at light intensity calibrated by standard single crystal silicon solar cells (available from VLSI Standards Inc). The resulting I-V curve was measured using B2912A Precision Source/Measure Unit (Agilent Technologies) and controlled by computer using Labview software.
The resulting I-V curve is shown in FIG. 3. The open-circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 3 OC 0.92V, short-circuit current J SC Is 20.85 mA-cm -2 The fill factor FF is 61% and the photoelectric conversion efficiency PCE is 11.70%.
Example 10
A solar cell was finally prepared and tested according to the method described in example 9, except that 1.5mg of a mixture of three polyacondensed ring conjugated macromolecules represented by formula (1-7-F1) was used instead of the polyacondensed ring conjugated macromolecule represented by formula (1-7-1).
The resulting I-V curve is shown in FIG. 4. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 4 OC Is 0.84V, short-circuit current J SC Is 19.04mA · cm -2 The fill factor FF is 62% and the photoelectric conversion efficiency PCE is 9.92%.
Example 11
According to the method described in example 9, except that 1.5mg of the multiple-and condensed-ring conjugated macromolecule represented by the formula (1-7-5) was used instead of the multiple-and condensed-ring conjugated macromolecule represented by the formula (1-7-1), a solar cell was finally prepared and tested.
The resulting I-V curve is shown in FIG. 5. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 5 OC 0.80V, short-circuit current J SC Is 20.46mA cm -2 The fill factor FF is 66% and the photoelectric conversion efficiency PCE is 10.80%.
Example 12
A solar cell was finally prepared and tested according to the method described in example 9, except that 1.5mg of the multiple fused ring conjugated macromolecule represented by formula (1-7-6) was used instead of the multiple fused ring conjugated macromolecule represented by formula (1-7-1).
The resulting I-V curve is shown in FIG. 6. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 6 OC 0.87V, short-circuit current J SC Is 21.26mA · cm -2 The fill factor FF is 68% and the photoelectric conversion efficiency PCE is 12.58%.
Example 13
A solar cell was finally prepared and tested according to the method described in example 9, except that 1.5mg of the multiple fused ring conjugated macromolecule represented by formula (1-7-7) was used instead of the multiple fused ring conjugated macromolecule represented by formula (1-7-1).
The resulting I-V curve is shown in FIG. 7. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 7 OC 1.00V, short-circuit current J SC Is 19.64mA · cm -2 The fill factor FF is 67% and the photoelectric conversion efficiency PCE is 13.16%.
Example 14
According to the method described in example 9, except that 1.5mg of the multiple-and condensed-ring conjugated macromolecule represented by the formula (1-9-5) was used instead of the multiple-and condensed-ring conjugated macromolecule represented by the formula (1-7-1), a solar cell was finally prepared and tested.
The resulting I-V curve is shown in FIG. 8. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 8 OC 0.94V, short-circuit current J SC Is 17.06mA · cm -2 The fill factor FF is 66% and the photoelectric conversion efficiency PCE is 10.58%.
Example 15
This example serves to illustrate a perovskite solar cell of the present invention.
Indium Tin Oxide (ITO) glass (purchased from Shenzhen glass float glass Co., ltd.) as a cathode is cleaned by a detergent, then sequentially cleaned by deionized water, acetone and isopropanol in an ultrasonic manner, and then dried and coated with a 30 nm-thick SnO layer in a spin coating manner 2 And annealing the electron transport layer at 150 ℃ for 30 minutes for later use.
0.25mg of the poly-fused ring conjugated macromolecule represented by the above formula (1-7-5) was dissolved in 1mL of DMF, and 500mg of PbI was added 2 Then spin-coating the uniformly mixed solution on the electron transport layer, annealing at 70 ℃ for 20 minutes, cooling, spin-coating the iodoformamidine (FAI)/iodomethylamine (MAI) 2:1) mixed solution on the electron transport layer, annealing at 150 ℃ for 15 minutes to obtain the multi-fused ring conjugated macromolecule (1-7-5) doped perovskite layer, and finally spin-coating 80mg/mL 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]-9,9' -spirobifluorene (spiro-OMeTAD) solution as hole transport layer. Vacuum (absolute pressure 2X 10) on the active layer -5 Pa) and depositing metal Ag with the thickness of about 150nm as an anode of the solar cell.
A solar light source was simulated with an AM1.5 filter (model SAN-EI ELECTRIC Co., ltd., XES-70S 1) at 100mW/cm 2 The devices were tested for photovoltaic performance at light intensity calibrated by standard single crystal silicon solar cells (available from VLSI Standards Inc). The resulting I-V curve was measured using B2912A Precision Source/Measure Unit (Agilent Technologies) and controlled by computer using Labview software.
The resulting I-V curve is shown in FIG. 9. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 9 OC 1.07V, short circuitStream J SC Is 23.70 mA.cm -2 The fill factor FF is 79% and the photoelectric conversion efficiency PCE is 20.13%.
Comparative example 1
A solar cell was finally prepared and tested according to the method described in example 9, except that 1.5mg of the compound represented by formula (GK) (prepared by the method described in reference j.am.chem.soc.2017,139, 4929) was used instead of the poly-fused ring conjugated macromolecule represented by formula (1-7-1).
The resulting I-V curve is shown in FIG. 10. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 10 OC 0.92V, short-circuit current J SC Is 16.45mA · cm -2 The fill factor FF is 56% and the photoelectric conversion efficiency PCE is 8.54%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (20)
1. A multiple-fused ring conjugated macromolecule, wherein the conjugated macromolecule is a compound represented by the following formula (1):
the compound shown in the formula (1) is selected from compounds shown in formulas (1-7);
wherein the two groups a are each independently selected from the following structures:
the radical A-5 is
Group A-6 is->
Each R is 2 Each independently selected from the group consisting of
A group shown; each R is 3 Are each independently selected from the group consisting of>
A group shown; each R is 1 Are each independently selected from the group consisting of>
A group shown;
each Z is independently selected from C, N, si and Ge;
each X and each Y is independently selected from O, S or Se; j is 1; k is 1;
m is an integer of 0 to 6; n is an integer of 0 to 6; p is an integer of 0 to 6;
each R is 6 -R 10 Each independently selected from H, halogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio and C6-C30 aryl.
2. The polya-fused ring conjugated macromolecule of claim 1, wherein each Z is independently selected from C, N and Si; each X and each Y is independently selected from O and S; m is an integer of 0 to 4; n is an integer of 0 to 4; p is an integer of 0 to 4; each R is 6 -R 10 Each independently selected from H, halogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C24 aryl.
3. The polya-fused ring conjugated macromolecule of claim 2, wherein each R is 7 -R 8 And each R 10 Each independently selected from H, halogen, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio and C6-C12 aryl; each R is 6 And each R 9 Each independently selected from H, halogen, C4-C15 alkyl, C4-C15 alkoxy, C4-C15 alkylthio and C6-C12 aryl.
4. The multiple fused ring conjugated macromolecule of claim 3, wherein each Z is selected from C; each R is 7 -R 8 And each R 10 Each independently selected from H, F, cl, br, I, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio and n-butylthio; each R is 6 And each R 9 Each independently selected from the group consisting of H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octoxy, 2-ethylhexoxy, n-butylthio, n-pentoxy, n-hexoxy, n-octoxy, and 2-ethylhexoxy.
5. The multiple fused ring conjugated macromolecule of claim 1, wherein the multiple fused ring conjugated macromolecule is one of the compounds shown in the following formulae:
formula (1-7-6): in the formula (1-7), Z is C, A is a group A-5,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-7-7): in the formula (1-7), Z is C, A is a group A-6,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
6. a multiple fused ring conjugated macromolecule, wherein the conjugated macromolecule is a compound represented by the following formula (1-9):
formula (1-9)
Wherein the two groups a are each independently selected from the following structures:
each R is 2 Each independently selected from the group consisting of
A group shown; each R is 3 Are each independently selected from the group consisting of>
A group shown; each R is 1 Are each independently selected from the group consisting of>
A group shown;
each Z is independently selected from C, N, si and Ge;
each X, each X', and each Y is independently selected from O, S or Se;
j is 0 to 6; k is 0 to 6;
m is an integer of 0 to 6; n is an integer of 0 to 6; p is an integer of 0 to 6;
each R is 4 -R 10 Each independently selected from H, halogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio and C6-C30 aryl.
7. The polya-fused ring conjugated macromolecule of claim 6, wherein: the group A-1 is
Group A-2 is>
Group A-3 is->
Group A-4 is->
Group A-5 is->
Group A-6 is>
The polycyclic and fused ring conjugated macromolecule is one of the compounds shown in the following formula:
formula (1-9-1): in the formula (1-9), Z is C, A is group A-1,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-2): in the formula (1-9), Z is C, A is the group A-2,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-3): in the formula (1-9), Z is C, A is group A-3,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-4): in the formula (1-9), Z is C, one A is a group A-2, and the other A is a group A-3,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-5): in the formula (1-9), Z is C, A is group A-4,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-6): in the formula (1-9), Z is C, A is group A-5,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl;
formula (1-9-7): in the formula (1-9), Z is C, A is group A-6,R 3 Is absent, R 1 Are all made of
And R is 6 Is 2-ethylhexyl, R 2 Are all->
And R is 9 Is n-hexyl.
8. A method of preparing a poly-fused ring conjugated macromolecule of any one of claims 1-7, comprising:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a) to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1); wherein,
formula (2)
Formula (a) is selected from one or more of the following compounds:
9. the method of claim 8, wherein the molar ratio of the compound of formula (2) to the compound of formula (a) is 1:2-100.
10. The method of claim 8 or 9, wherein the conditions of the dehydration condensation reaction comprise: the temperature is 20-100 deg.C, and the time is 10min-48h.
11. The method of claim 8, wherein the basic compound is one or more of piperidine, pyridine, and triethylamine.
12. The method according to claim 11, wherein the basic compound is used in an amount of 0.1 to 1000mmol relative to 1mmol of the compound represented by formula (2).
13. The method of claim 11, wherein the organic solvent is chloroform and/or dichloromethane.
14. A photovoltaic material or a photodetecting material comprising one or more of the multiple fused ring conjugated macromolecules of any one of claims 1-7.
15. A solar cell in which the photovoltaic material comprises a poly-fused ring conjugated macromolecule as claimed in any one of claims 1 to 7.
16. The solar cell of claim 15, wherein, when the cell is an organic solar cell comprising a light-trapping active layer, the electron donor material and/or the electron acceptor material in the light-trapping active layer comprises one or more of the multiple fused-ring conjugated macromolecules;
when the cell is a perovskite solar cell comprising an electron transport layer, a perovskite light trapping layer and a modification layer, the light trapping layer and/or the electron transport layer and/or the modification layer contain one or more of the multiple fused ring conjugated macromolecules.
17. A method of manufacturing a solar cell according to claim 15 or 16, the method comprising: and configuring the poly-condensed ring conjugated macromolecule in the light trapping layer and/or the electron transport layer and/or the modification layer.
18. The method of claim 17, wherein, for organic solar cells, the photovoltaic material-containing layer is a light-trapping active layer;
for perovskite solar cells, the photovoltaic material containing layer is a light trapping layer and/or an electron transporting layer and/or a modifying layer.
19. A photodetector comprising a light trapping active layer, wherein an electron donor material and/or an electron acceptor material in the light trapping active layer comprises one or more of the multiple fused ring conjugated macromolecules of any one of claims 1-7.
20. A method of making a photodetector, comprising using an electron donor material and/or an electron acceptor material comprising one or more of the polya-fused ring conjugated macromolecules of any of claims 1-7 to form a light trapping active layer.
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| CN110818725B (en) * | 2019-10-30 | 2022-06-14 | 华南理工大学 | Conjugated micromolecule based on multi-nitrogen heterocyclic ring and application of conjugated micromolecule in organic photoelectric device |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107011361A (en) * | 2017-03-13 | 2017-08-04 | 南开大学 | Organic photoelectric acceptor material and its preparation method and application |
-
2017
- 2017-04-27 CN CN201710286150.7A patent/CN108794504B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467547A (en) * | 2016-08-30 | 2017-03-01 | 苏州大学 | Polycyclic-based non-fullerene solar cell receptor material and preparation method and application thereof |
| CN107011361A (en) * | 2017-03-13 | 2017-08-04 | 南开大学 | Organic photoelectric acceptor material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| A fused thieno[3,2-b]thiophene-dithiophene based donor molecule for organic photovoltaics: a structural comparative study with indacenodithiophene;Yuichiro Abe et al.;《Journal of Materials Chemistry C》;20160914;第4卷;9656-9663 * |
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