CN111621003A - D-A type chlorinated conjugated polymer and preparation method and application thereof - Google Patents
D-A type chlorinated conjugated polymer and preparation method and application thereof Download PDFInfo
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- CN111621003A CN111621003A CN202010503371.7A CN202010503371A CN111621003A CN 111621003 A CN111621003 A CN 111621003A CN 202010503371 A CN202010503371 A CN 202010503371A CN 111621003 A CN111621003 A CN 111621003A
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 230000005540 biological transmission Effects 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 6
- XGYRDJVAFZVRTE-UHFFFAOYSA-N 4,7-bis(4-hexylthiophen-2-yl)-2,1,3-benzothiadiazole Chemical compound CCCCCCC1=CSC(C=2C3=NSN=C3C(C=3SC=C(CCCCCC)C=3)=CC=2)=C1 XGYRDJVAFZVRTE-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 3
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 claims description 3
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 3
- -1 4-chloro-5- (2-ethylhexyl) thiophen-2-yl Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- ZYCMDWDFIQDPLP-UHFFFAOYSA-N hbr bromine Chemical compound Br.Br ZYCMDWDFIQDPLP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- GGWHJTJHSJIICG-UHFFFAOYSA-N tributyl-(4-hexylthiophen-2-yl)stannane Chemical compound CCCCCCC1=CSC([Sn](CCCC)(CCCC)CCCC)=C1 GGWHJTJHSJIICG-UHFFFAOYSA-N 0.000 claims description 3
- UKHQRARQNZOXRL-UHFFFAOYSA-N trimethyltin Chemical compound C[SnH](C)C UKHQRARQNZOXRL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000004417 polycarbonate Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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Abstract
The invention provides a D-A type chlorinated conjugated polymer, a preparation method and application thereof, wherein the chlorinated conjugated polymer molecule is prepared by carrying out light-resistant reaction on thiophene unit number, electron-donating monomers, electron-withdrawing monomers and catalysts contained in different repeating units in an organic solvent system under the protection of inert gas, and finally purifying by adopting column chromatography to obtain a target product. The invention has better electron transmission capability and better absorption in the visible light range, is applied to donor materials in organic solar cells, and has good photovoltaic performance.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a D-A type chlorinated conjugated polymer and a preparation method and application thereof.
Background
Energy is an indispensable power in human development and progress so far, development and utilization of energy are a long-standing constant topic, with economic development and social progress, people pursue improvement of material life, more and more energy needs to be consumed, and application of a large amount of petrochemical energy causes irreversible damage to living environment of people, so that seeking of clean energy (such as solar energy, wind energy and the like) is urgent. The active material of the solar cell device occupies the market mainly and mainly comprises crystalline silicon and inorganic semiconductor materials. But the popularization is limited by the disadvantages of high cost, serious environmental pollution and the like. In recent years, it has been found that organic conjugated polymers have good optical, electrochemical and electrical properties, and that the polymers can be processed using solution processes such as spin coating, ink jet printing, screen printing, etc., and have excellent properties such as low cost, simple process, and device sinterability. Is expected to replace inorganic solar cells in the future, is popularized on a large scale and greatly relieves the shortage of energy.
Disclosure of Invention
In order to solve the technical problems, the invention provides a D-A type chlorinated conjugated polymer in a first aspect, wherein the structural formula of the chlorinated polymer is shown as formula I:
the invention provides a preparation method of a D-A conjugated chlorinated polymer, wherein the chlorinated polymer is prepared by a structure shown in a formula II, an electron donor monomer and a catalyst respectively in an organic solvent system under the protection of inert gas, a light-shielding reaction is firstly carried out, and finally, column chromatography purification is adopted to prepare a target product shown in a formula I, wherein the structural formula of the formula II is as follows:
wherein the reaction temperature is 95-135 ℃, and the reaction time is 12-60 h.
Wherein the compound with the structure shown in the formula II is prepared by the following method:
s1, 4, 7-dibromobenzo [ c ]][1,2,5]And (3) synthesis of thiadiazole: a benzene ring [ c ]][1,2,5]Thiadiazole (3.12g, 22.8mmol) was added to a dry three-necked round bottom flask, followed by the addition of hydrobromic acid (HBr) (60mL) to dissolve, and liquid bromine (Br) at 46% concentration was slowly added dropwise after all the material had dissolved2) (2.94mL, 57mmol) and Br was added2Then, the reaction system was heated to 127 ℃ and refluxed for 12 hours, cooled to room temperature after the reaction was completed, and then added with sodium hydrogen sulfite (NaHCO)3) The excess bromine was removed in aqueous solution and chloroform (CHCl)3) Extracting, collecting an organic layer, distilling the organic layer under reduced pressure to obtain a crude product, and purifying the crude product by silica gel column chromatography with a mobile phase of dichloromethane to obtain 2.45g of a target product;
s2, 4, 7-bis (4-hexylthiophen-2-yl) benzo [ c ] [1,2,5] thiadiazole: adding 4, 7-dibromobenzo [ C ] [1,2,5] thiadiazole (582mg, 2mmol), tributyl (4-hexyl-2-thienyl) stannane (2.26g, 5mmol) into a 25mL dry two-necked bottle, dissolving with dry and deoxygenated toluene (15mL), replacing air with nitrogen for three times, adding tris (2-methylphenyl) phosphine, copper oxide, and tris (dibenzylideneacetone) dipalladium into the system, replacing air with nitrogen again for three times, and heating to 115 ℃ for refluxing for 48 hours; after cooling, washing with an appropriate amount of dichloromethane, suction filtration, taking out the filtrate, then carrying out reduced pressure distillation, loading the material onto silica gel, and purifying by silica gel column chromatography using hexane/chloroform (6: 1) as the mobile phase to obtain 0.447g of a yellow solid;
s3, synthesis of compound II: to a tinfoil wrapped 50mL single neck bottle was added 4, 7-bis (4-hexylthiophen-2-yl) benzo [ c ] [1,2,5] thiadiazole (462mg, 0.995mmol), chloroform (20 mL); n-bromosuccinimide (NBS) (328mg, 1.58mmol) was added in portions at 0 ℃ and spotting was performed before each addition until a disubstituted product appeared on the silica gel plate, and the NBS addition was stopped and the product was distilled under reduced pressure to remove the solvent to give a crude product. Purification by column chromatography (15: 1 ratio between petroleum ether and dichloromethane) and drying of the pure product gave 0.365g of a yellow solid.
Wherein the electron-donating monomer is (4, 8-bis (4-chloro-5- (2-ethylhexyl) thiophen-2-yl) benzo [1, 2-b: 4,5-b' ] dithiophene-2, 6-diyl) bis (trimethylstannane).
Wherein the catalyst is tris (2-methylphenyl) phosphine, copper oxide and tris (dibenzylideneacetone) dipalladium serving as a catalyst. Wherein the organic solvent is toluene.
Wherein the molar ratio of the compound with the structure shown in the formula II to the electron-donating monomer is 1: 1-1.5.
Preferably, the molar ratio of the compound with the structure shown in the formula II to the electron-donating monomer is 1: 1-1.2.
The third aspect of the invention provides application of a D-A type chlorinated conjugated polymer, and the D-A type chlorinated conjugated polymer prepared by the method provided by the second aspect of the invention can be applied to an organic solar cell device, and the solar cell device sequentially comprises a glass layer, an indium tin oxide conducting layer, a zinc oxide electron transmission layer, a D-A type chlorinated conjugated polymer and PC (polycarbonate) from bottom to top71BM mixed active layer, molybdenum trioxide hole transport layer and silver electrode layer.
The invention has the beneficial effects that:
the D-A type chlorinated conjugated polymer provided by the invention can be dissolved in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene and the like, and can be processed by adopting a solution processing mode (such as spin coating); has better absorption in the visible light range and proper energy level, and is suitable for being used as a donor material in an organic solar cell. The matching degree of the absorption spectrum of the solar cell material and the solar spectrum, the carrier mobility and the appropriate energy level are crucial to obtaining high device efficiency, and the benzothiadiazole adopted by the invention is used as an acceptor to form a donor-acceptor (D-A) conjugated structure with a chlorinated electron-donating group, so that the energy level can be effectively regulated and controlled, thereby obtaining a lower energy band gap, widening and enhancing the spectral absorption of the material, and being applied to constructing a high-efficiency organic solar cell material.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows the chlorinated conjugated polymer D-A in CHCl as provided in example 1 of the present invention3Ultraviolet-visible absorption spectrum of (1);
FIG. 2 is a graph showing an ultraviolet-visible absorption spectrum of a D-A type chlorinated conjugated polymer in a film, provided in example 1 of the present invention;
FIG. 3 is a J-V curve diagram of a D-A type chlorinated conjugated polymer solar cell device provided in example 1 of the present invention;
fig. 4 is a schematic structural diagram of a D-a type chlorinated conjugated polymer solar cell device provided in embodiment 1 of the present invention.
Detailed Description
The following is a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention.
The invention provides a D-A type chlorinated conjugated polymer, the structural formula of which is shown in formula I as follows:
the D-A type chlorinated conjugated polymer provided in this example is prepared by the following method:
1mmol of the compound with the structure shown in the formula II and 1mmol (4, 8-bis (4-chloro-5- (2-ethylhexyl) thiophen-2-yl) benzo [1, 2-b: 4,5-b']Putting dithiophene-2, 6-diyl) bis (trimethylstannane) in a toluene solvent, adopting tris (dibenzylideneacetone) dipalladium as a catalyst, controlling the temperature to be 115 ℃ under the protection of inert gas, carrying out a light-shielding reaction for 48 hours, and carrying out column chromatography purification to obtain a target product shown in a formula I;1H NMR(CDCl3,500MHz,/ppm):8.31(s,1H),7.59(s,2H),741(s,2H),7.24(s,2H),7.09(s,1H),4.31(t,4H),2.89(t,2H),2.39(t,2H),1.72(m,10H),1.48(m,10H),1.27(m,110H).13C NMR(CDCl3,125MHz,/ppm):159.1,155.2,147.2,143.9,131.1,128.7,128.3,117.1,86.2,68.4,42.5,38.3,36.5,35.1,34.3,32.8,30.3,28.5,27.4,25.6,24.1,15.3。
the synthetic route of the formula I is as follows:
the synthesized chlorinated polymer is applied to an organic solar cell device, and as shown in fig. 4, the solar cell device sequentially comprises a Glass (Glass) layer, an Indium Tin Oxide (ITO) conducting layer, a zinc oxide (ZnO) electronic transmission layer, a D-A conjugated polymer and a C from bottom to top71Hybrid (D-A conjugated Polymer/PC71BM), molybdenum trioxide (MoO)3) A hole transport layer and a silver (Ag) electrode layer, wherein the structural formula of the D-A conjugated polymer is a compound shown in formula I, and the hole transport layer and the silver (Ag) electrode layer are prepared by the method provided in example 1.
The preparation method of the solar cell device is not particularly limited, and may be implemented by using a technical scheme for solar cell preparation well known to those skilled in the art, and in the embodiment of the present invention, the preparation method of the solar cell device preferably includes the following steps:
s1: firstly, sequentially cleaning and carrying out ultraviolet ozone treatment on glass with ITO sputtered on the surface to obtain a clean ITO glass layer;
s2: then, the ITO treated in step S1ZnO and D-A conjugated polymer/PC are sequentially spin-coated on the glass layer71BM and then sequentially evaporating MoO3And an Ag electrode, wherein a ZnO electron transmission layer and a D-A conjugated polymer/PC are sequentially formed on the ITO glass layer71BM active layer, MoO3And preparing the hole transport layer and the Ag electrode layer to obtain the solar cell device.
The compound of formula II described in example 1 was prepared by the following method:
s1, 4, 7-dibromobenzo [ c ]][1,2,5]And (3) synthesis of thiadiazole: a benzene ring [ c ]][1,2,5]Thiadiazole (3.12g, 22.8mmol) was added to a dry three-necked round bottom flask, followed by the addition of hydrobromic acid (HBr) (60mL) to dissolve, and liquid bromine (Br) at 46% concentration was slowly added dropwise after all the material had dissolved2) (2.94mL, 57mmol) and Br was added2Then, the reaction system was heated to 127 ℃ and refluxed for 12 hours, cooled to room temperature after the reaction was completed, and then added with sodium hydrogen sulfite (NaHCO)3) The excess bromine was removed in aqueous solution and chloroform (CHCl)3) Extracting, collecting an organic layer, distilling the organic layer under reduced pressure to obtain a crude product, and purifying the crude product by silica gel column chromatography with a mobile phase of dichloromethane to obtain 2.45g of a target product;
s2, 4, 7-bis (4-hexylthiophen-2-yl) benzo [ c ] [1,2,5] thiadiazole: adding 4, 7-dibromobenzo [ C ] [1,2,5] thiadiazole (582mg, 2mmol), tributyl (4-hexyl-2-thienyl) stannane (2.26g, 5mmol) into a 25mL dry two-necked bottle, dissolving with dry and deoxygenated toluene (15mL), replacing air with nitrogen for three times, adding tris (2-methylphenyl) phosphine, copper oxide, and tris (dibenzylideneacetone) dipalladium into the system, replacing air with nitrogen again for three times, and heating to 115 ℃ for refluxing for 48 hours; after cooling, washing with an appropriate amount of dichloromethane, suction filtration, taking out the filtrate, then carrying out reduced pressure distillation, loading the material onto silica gel, and purifying by silica gel column chromatography using hexane/chloroform (6: 1) as the mobile phase to obtain 0.447g of a yellow solid;
s3, synthesis of compound II: to a tinfoil wrapped 50mL single neck bottle was added 4, 7-bis (4-hexylthiophen-2-yl) benzo [ c ] [1,2,5] thiadiazole (462mg, 0.995mmol), chloroform (20 mL); n-bromosuccinimide (NBS) (328mg, 1.58mmol) was added in portions at 0 ℃ and spotting was performed before each addition until a disubstituted product appeared on the silica gel plate, and the NBS addition was stopped and the product was distilled under reduced pressure to remove the solvent to give a crude product. Purification by column chromatography (15: 1 ratio between petroleum ether and dichloromethane) and drying of the pure product gave 0.365g of a yellow solid.
The synthetic route of the compound of formula II is as follows:
the above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the spirit of the present invention, and these changes and modifications are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A D-A type chlorinated conjugated polymer, characterized in that the structural formula of the polymer is formula I:
2. a preparation method of D-A type chlorinated conjugated polymer is characterized in that: the chlorinated polymer is prepared by respectively carrying out a light-shielding reaction on a compound with a structure shown in a formula II, an electron donor monomer and a catalyst in an organic solvent system under the protection of inert gas, and finally purifying by adopting column chromatography to obtain a target product shown in a formula I, wherein the structural formula of the formula II is as follows:
3. the process for preparing a chlorinated conjugated polymer of D-A type according to claim 2, characterized in that: the reaction temperature is 95-135 ℃, and the reaction time is 12-60 h.
4. The method for preparing the D-A type chlorinated conjugated polymer according to claim 2, wherein the compound of the structure shown in the formula II is prepared by the following method:
s1, 4, 7-dibromobenzo [ c ]][1,2,5]And (3) synthesis of thiadiazole: a benzene ring [ c ]][1,2,5]Thiadiazole (3.12g, 22.8mmol) was added to a dry three-necked round bottom flask, followed by the addition of hydrobromic acid (HBr) (60mL) to dissolve, and liquid bromine (Br) at 46% concentration was slowly added dropwise after all the material had dissolved2) (2.94mL, 57mmol) and Br was added2Then, the reaction system was heated to 127 ℃ and refluxed for 12 hours, cooled to room temperature after the reaction was completed, and then added with sodium hydrogen sulfite (NaHCO)3) The excess bromine was removed in aqueous solution and chloroform (CHCl)3) Extracting, collecting an organic layer, distilling the organic layer under reduced pressure to obtain a crude product, and purifying the crude product by silica gel column chromatography with a mobile phase of dichloromethane to obtain 2.45g of a target product;
s2, 4, 7-bis (4-hexylthiophen-2-yl) benzo [ c ] [1,2,5] thiadiazole: adding 4, 7-dibromobenzo [ C ] [1,2,5] thiadiazole (582mg, 2mmol), tributyl (4-hexyl-2-thienyl) stannane (2.26g, 5mmol) into a 25mL dry two-necked bottle, dissolving with dry and deoxygenated toluene (15mL), replacing air with nitrogen for three times, adding tris (2-methylphenyl) phosphine, copper oxide, and tris (dibenzylideneacetone) dipalladium into the system, replacing air with nitrogen again for three times, and heating to 115 ℃ for refluxing for 48 hours; after cooling, washing with an appropriate amount of dichloromethane, suction filtration, taking out the filtrate, then carrying out reduced pressure distillation, loading the material onto silica gel, and purifying by silica gel column chromatography using hexane/chloroform (6: 1) as the mobile phase to obtain 0.447g of a yellow solid;
s3, synthesis of compound II: to a tinfoil wrapped 50mL single neck bottle was added 4, 7-bis (4-hexylthiophen-2-yl) benzo [ c ] [1,2,5] thiadiazole (462mg, 0.995mmol), chloroform (20 mL); n-bromosuccinimide (NBS) (328mg, 1.58mmol) was added in portions at 0 deg.C, spotting was performed before each addition, and NBS addition was stopped until disubstituted product appeared on the silica gel plate. And carrying out reduced pressure distillation on the product to remove the solvent to obtain a crude product. Purification by column chromatography (15: 1 ratio between petroleum ether and dichloromethane) and drying of the pure product gave 0.365g of a yellow solid.
5. The process for preparing a chlorinated conjugated polymer of D-A type according to claim 2, characterized in that: the electron-donating monomer is (4, 8-bis (4-chloro-5- (2-ethylhexyl) thiophen-2-yl) benzo [1, 2-b: 4,5-b' ] dithiophene-2, 6-diyl) bis (trimethylstannane).
6. The process for preparing a chlorinated conjugated polymer of D-A type according to claim 2, characterized in that: the catalyst is tris (2-methylphenyl) phosphine, copper oxide and tris (dibenzylideneacetone) dipalladium.
7. The process for preparing a chlorinated conjugated polymer of D-A type according to claim 2, characterized in that: the organic solvent is toluene.
8. The process for preparing a chlorinated conjugated polymer of D-A type according to any one of claims 2 to 7, wherein: the molar ratio of the compound with the structure shown in the formula II to the electron-donating monomer is 1: 1-1.5.
9. The application of a D-A type chlorinated conjugated polymer is characterized in that: the D-A type chlorinated conjugated polymer prepared according to the claims 1-8 can be applied to organic solar cell devices.
10. Use of a chlorinated conjugated polymer of type D-a according to claim 9, characterized in that: the solar cell device is composed ofComprises a glass layer, an indium tin oxide conducting layer, a zinc oxide electron transmission layer, a D-A type chlorinated conjugated polymer and PC in sequence from bottom to top71BM mixed active layer, molybdenum trioxide hole transport layer and silver electrode layer.
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