CN115594828A - Halogenated cyclopentadithiophene polymer, preparation method thereof and application thereof in photovoltaic devices - Google Patents
Halogenated cyclopentadithiophene polymer, preparation method thereof and application thereof in photovoltaic devices Download PDFInfo
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- CN115594828A CN115594828A CN202211231780.1A CN202211231780A CN115594828A CN 115594828 A CN115594828 A CN 115594828A CN 202211231780 A CN202211231780 A CN 202211231780A CN 115594828 A CN115594828 A CN 115594828A
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- cyclopentadithiophene
- polymer
- halogenated
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- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000002861 polymer material Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 15
- 230000002950 deficient Effects 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007256 debromination reaction Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
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- 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 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
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- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000006467 substitution reaction Methods 0.000 abstract description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 9
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- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 6
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
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- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 2
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical group BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 229940125782 compound 2 Drugs 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
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- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
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- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
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- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
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Abstract
The invention discloses a halogenated cyclopentadithiophene polymer material, which takes halogenated cyclopentadithiophene as an electron-donating unit and has the following structural formula:
Description
Technical Field
The invention belongs to the technical field of photoelectric materials and devices thereof, and particularly relates to a halogenated cyclopentadithiophene polymer, a preparation method thereof and application thereof in a photovoltaic device.
Background
The energy problem is the first problem of economic development of all countries in the world nowadays, solar energy is one of the most promising energy sources in the future, and is an inexhaustible pollution-free clean energy source, and the conversion of solar energy into electric energy is a target which is always pursued by scientists (nat. Energy 2016,1, 16089). The organic solar cell as a novel solar cell device has the characteristics of flexibility, light weight, adjustable color, solution-soluble processing, large-area printing preparation and the like (adv. Energy mater.2016,6, 1601325), and is a hotspot in the solar cell research field. At present, the energy conversion efficiency (PCE) of the organic solar cell breaks through 18% (J.Mater.Chem.A. 2021,9, 5711), but because the synthesis of an active layer is complex and the cost is high, the commercialization is difficult to realize, and the PCE is good for the public.
The active layer is used as a core part of the organic solar cell and is composed of an acceptor material and a donor material. In recent years, non-fullerene small molecules rise rapidly, the design space of a polymer donor material matched with the non-fullerene small molecules is greatly expanded, and in the existing high-performance polymer donor material, a copolymer with a D-A structure can effectively regulate and control the molecular energy level, so that the D-A structure copolymer is widely used for constructing organic conjugated materials. Cyclopentadithiophene (CPDT) is an electron-rich thiophene ring fused to extend the planar backbone and enhance intermolecular π - π interactions. At present, photovoltaic materials prepared based on Cyclopentadithiophene (CPDT) and derivatives thereof generally exhibit small short-circuit current (J) sc ) So that the energy conversion efficiency (PCE) is not high, and the problems of high synthesis difficulty, high cost and the like generally exist; further exploration and optimization of thienyl electron donor unitsAnd the preparation process is optimized, so that the method has important research and application significance. .
Disclosure of Invention
The invention mainly aims to solve the problems and the defects in the prior art, and provides a halogenated cyclopentadithiophene polymer material which is easy to stack molecules, low in synthesis difficulty, low in cost and good in photovoltaic property.
In order to achieve the purpose, the invention adopts the technical scheme that:
a halogenated cyclopentadithiophene polymer material takes halogenated cyclopentadithiophene as an electron donor unit, and the structural formula is shown as formula I:
wherein X is selected from Cl or F,
is an electron deficient unit.
In the scheme, the molecular weight of the halogenated cyclopentadithiophene polymer is 1-8 ten thousand.
Further, the structural formula of the electron donating unit (D unit) is shown in formula II;
wherein X is selected from Cl or F.
Further, the electron-deficient unit (a unit) specifically includes one or more of the following structural formulas:
wherein R is 1 Is C 1 ～C 20 One carbon atom of the alkyl group or the alkyl group is substituted with an oxygen atom or a sulfur atom; r 2 Is selected from C 1 ～C 30 Y is selected from F, cl and CH 3 、OCH 3 CN, ester group or alkylthiophene.
The preparation method of the halogenated cyclopentadithiophene polymer comprises the following steps: adding an electron-donating unit monomer, an electron-deficient unit monomer and a catalyst into an organic solvent, uniformly mixing, carrying out debromination coupling reaction at 100-120 ℃ under a protective atmosphere, and then carrying out sedimentation and extraction to obtain the halogenated cyclopentadithiophene polymer.
In the scheme, the debromination coupling reaction temperature is 100-150 ℃, and the time is 12-96 h.
In the scheme, the molar ratio of the electron donor unit monomer to the electron deficient unit monomer to the catalyst is 1 (0.03-0.15).
In the above scheme, the structural formula of the electron donor unit monomer is shown in formula III, and the structural formula of the electron deficient unit monomer is shown in formula IV (taking the second electron deficient unit structure as an example);
in the formula, R 1 Is selected from C 1 ～C 30 An alkyl chain of (a); y is selected from F, cl, CH 3 、OCH 3 CN, ester group or alkylthiophene; x is Cl or F.
In the scheme, the catalyst is tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium and the like; the organic solvent is toluene or chlorobenzene, etc.
In the above scheme, the protective atmosphere may be nitrogen or argon.
In the above scheme, the preparation method of the electron donor unit monomer comprises the following steps:
firstly, carrying out lithiation on the 2-position of 3-bromothiophene by using LDA (lithium diisopropylamide), and then carrying out coupling reaction by using copper chloride to obtain a compound 1; further using dimethylcarbamoyl chloride to carry out cyclization reaction to obtain a compound 2; reacting the compound 2 with ethanedithiol to protect carbonyl to obtain a compound 3; chlorocyclopentadithiophene monomers (CPDTs-Cl) and fluorocyclopentadithiophene monomers (CPDTs-F) are prepared by one-step reaction of a pyridine solution with HF or HCl and a mixed solution of NBS.
In the scheme, the coupling reaction is carried out at the temperature of 0-78 ℃ for 1-12 h; the temperature adopted by the cyclization reaction is-40 to-78 ℃, and the time is 1 to 12 hours; the reaction temperature of the ethanedithiol is 0-80 ℃, and the reaction time is 5-24 h; the temperature of the reaction of the mixed solution of HF or HCl pyridine solution and NBS is 0-80 ℃ and the time is 1-24 h.
The invention also comprises the application of the polymer taking the molecules containing the halogenated cyclopentadithiophene as electron donor units as an active layer material or a transmission layer material in photoelectric devices.
Specifically, the polymer material can be used for organic solar cells, perovskite solar cells, organic light emitting diodes, organic detectors and the like.
The invention is from the green and economic perspective, and aims at the problems that the preparation process of the existing polymer donor (D) unit and the existing polymer acceptor (A) unit is complex, the synthesis difficulty is high, the existing polymer donor (D) unit and the existing polymer acceptor (A) unit are not suitable for large-scale production, and the like.
Compared with the prior art, the invention has the following beneficial effects:
1) The synthesized halogenated cyclopentadithiophene derivatives (CPDTs), F, cl and other atoms are introduced to adjust the space electron cloud distribution of the Cyclopentadithiophene (CPDT), so that the energy level optimization is realized, the substitution on the thiophene ring is facilitated, the synthesis difficulty is reduced, and the compound yield is improved; in addition, the halogen with high electronegativity represents an atom F/Cl, can further form F \8230, H or Cl \8230, H non-covalent interaction, improves the rigid skeleton of molecules, regulates pi-pi accumulation among molecules, improves the crystallization performance of the molecules and is beneficial to charge transmission;
2) The halogenated Cyclopentadithiophene (CPDTs) disclosed by the invention is simple in synthesis process, low in cost and easy to obtain raw materials; the organic silicon/carbon composite material is applied to a donor polymer material of an organic solar cell, can greatly reduce the synthesis cost, and is a promising organic photovoltaic material.
Drawings
FIG. 1 is a structural formula of the polymers CPDTs-Tz and Y6 obtained by the invention;
FIG. 2 shows the UV-VIS absorption spectra of the polymer CPDTs-Tz obtained by the present invention in the states of ortho-dichlorobenzene solution (room temperature) and thin film respectively;
FIG. 3 is an electrochemical cyclic voltammetry curve of the polymer CPDTs-Tz obtained by the present invention, using 0.1M anhydrous acetonitrile solution of tetrabutylammonium hexafluorophosphate as an electrolyte solution, and the scanning rate is 0.1V/s;
FIG. 4 is a diagram showing the energy level distribution of CPDTs-Tz and Y6 of the polymer obtained by the present invention;
FIG. 5 is a J-V curve of an organic solar cell prepared from CPDTs-Tz prepared from the polymer donor and the small molecule acceptor Y6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A polymer with fluorinated cyclopentadithiophene as a D unit and 3, 5-di (2-ethylhexane) thiophene substituted-s-trichlorooxazine as an A unit is prepared by the following steps:
(1) The preparation of the fluorinated cyclopentadithiophene electron donor unit monomer comprises the following synthetic route:
the preparation method comprises the following specific steps:
1) Slowly adding LDA (60mmol, 30mL) into a two-neck flask containing tetrahydrofuran (80 mL) solution of 3-bromothiophene (60mmol, 9.78g) at 0 ℃ under the nitrogen atmosphere, keeping the temperature at 0 ℃ for reacting for 2h, moving to-78 ℃, reducing the temperature for 10min, adding anhydrous copper chloride (120mmol, 16.13g), moving to room temperature after reacting for 2h, and stirring overnight; after the reaction was complete, the reaction was quenched by addition of deionized water, extracted with dichloromethane, the organic phase was retained by petroleum ether: dichloromethane 10 through the column. Compound 1.1 was obtained in 80% yield; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):7.44(d,J＝3.6Hz,2H),7.02(d,J＝3.6Hz,2H)
2) Dissolving compound 1.1 (0.48g, 1.5mmol) in a 100mL two-necked flask under a nitrogen atmosphere, dropwise adding n-BuLi (1.32mL, 3.3mmol) at-78 ℃ to react for 1h, then slowly dropwise adding dimethylcarbamoyl chloride (0.19g, 1.2mmol), and continuing to react at-78 ℃ for 1h; and after the reaction is finished, adding deionized water to quench the reaction, adding dichloromethane to extract, drying by using anhydrous sodium sulfate, and spin-drying the organic phase to obtain a solid matter. Using petroleum ether: dichloro 1; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):7.57(d,J＝3.6Hz,2H),7.45(d,J＝3.6Hz,2H)；
3) Compound 1.2 (0.96g, 5.0 mmol), alCl were sequentially added 3 (2.0g, 15.0mmol), 1, 2-ethanedithiol (0.65mL, 7.5mmol,. Rho =1.12g mL) -1 ) Adding into a 100mL double-neck bottle, injecting 15mL ClCH into the bottle under the protection of nitrogen 2 CH 2 Cl, reacting for 2 hours at normal temperature; after the reaction is finished, adding distilled water into the system to quench the reaction, extracting with dichloromethane, collecting an organic phase, drying with anhydrous sodium sulfate, desolventizing, and reacting a crude product with petroleum ether: performing column chromatography with dichloromethane =1 and 2 to obtain compound 1.3 with a yield of 76%; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):7.50(d,J＝3.6Hz,2H),7.02(d,J＝3.6Hz,2H),2.81(s,4H)；
4) Pyridine hydrofluoric acid solution (2.3 mL,25mmol,. Rho =1.1g mL) was added under nitrogen blanket -1 ) Slow downDropwise adding into 20mL of dichloromethane solution dissolved with NBS (1.1g, 6.25mmol), allowing to react for 30min, and then adding 8mL of dichloromethane solution dissolved with compound 1.3 (0.67g, 2.5 mmol), reacting at room temperature for 5h; after the reaction is finished, adding distilled water into the system for quenching reaction, extracting by dichloromethane, collecting an organic phase, drying by anhydrous sodium sulfate, desolventizing, and using petroleum ether: column chromatography with dichloromethane =8 to give compound 1.4 in 72% yield; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):6.86(s,2H)；
5) Compound 1.4 (0.37g, 1mmol) was dissolved in a 10mL two-necked flask under a nitrogen atmosphere, n-BuLi (1.87mL, 4.5 mmol) was added dropwise at-78 ℃ for 1 hour, and after reaction, tributyltin chloride (4 mL,4mmol, c =1.0mol L) was slowly added dropwise -1 ) Continuously reacting for 1h at-78 ℃; and after the reaction is finished, adding deionized water to quench the reaction, adding dichloromethane to extract, drying by using anhydrous sodium sulfate, and spin-drying the organic phase to obtain a solid matter. Recrystallizing with methanol to obtain compound 1.5 with yield of 80%; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):7.05(s,2H),0.27(s,18H)；
(2) The preparation of the triazine electron-deficient unit monomer comprises the following synthetic route:
1) Under nitrogen atmosphere, the compound 3-alkylthiophene (25.24g, 100mmol) and tetrahydrofuran (120 mL) were placed in a two-necked flask, n-butyllithium (40mL, 100mmol) was added dropwise at-78 ℃, and the mixture was stirred for 1 hour; liquid bromine (16.85g, 106mmol) was added slowly. After the reaction was completed, an aqueous solution of sodium thiosulfate was added. Extracting with dichloromethane, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing solvent, and distilling under reduced pressure to obtain compound 2.1 with yield of 70%; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):6.85(s,1H),6.78(s,1H),2.48(d,J＝6.8Hz,2H),1.50(m,1H),1.27(m,8H),0.88(m,6H)；
2) Compound 2.1 (10.60g, 32mmol) and dry THF (10 mL) were placed in a constant pressure dropping funnel under nitrogen to aSlowly dripping the magnesium chips (1.55g, 64mmol), iodine (1-3 granules) and tetrahydrofuran (15 mL) into a 100mL three-neck flask, and refluxing for 2h after dripping is finished to obtain a compound 2.2; subsequently, compound 2.2 was slowly added dropwise to a solution of 2,4, 6-trichloro-1, 3, 5-triazine (2.21g, 12mmol) in tetrahydrofuran (50 mL); refluxing overnight after the dropwise addition, quenching with deionized water after the reaction is finished, extracting with dichloromethane, and extracting the organic phase with anhydrous NaSO 4 After drying, removing the solvent; purification by column chromatography on silica gel eluting with petroleum ether/dichloromethane (3; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):8.04(s,2H),7.26(s,2H),2.60(d,J＝6.8Hz,4H),1.61(m,2H),1.28(m,16H),0.89(m,12H)；
3) Dissolving compound 2.3 (0.61g, 1mmol) in chloroform, adding NBS (0.356g, 2mmol) after dissolving, and reacting overnight; quenching with deionized water, adding dichloromethane for extraction, and extracting with anhydrous NaSO 4 After drying, the solvent was removed and purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane (volume ratio 4; 1 HNMR(400MHz，CDCl 3 )，δ(ppm):7.87(s,2H),2.55(d,J＝6.8Hz,4H),1.67(m,2H),1.31(m,16H),0.90(m,12H)；
(3) The preparation of the halogenated cyclopentadithiophene compound has the following synthetic route:
the preparation method comprises the following specific steps: under the protection of nitrogen, compound 2.4 (0.1542g, 0.2mmol) and compound 1.5 (0.1084g, 0.2mmol) were added in sequence, and catalyst Pd (PPh) 3 ) 4 (0.0138g, 0.012mmol) and 5mL of anhydrous toluene, and reacting at 100 ℃ for 48h; settling the crude product by using methanol, and then sequentially extracting by using acetone, normal hexane, dichloromethane and trichloromethane; and (3) performing rotary evaporation on the trichloromethane, adding methanol for sedimentation, and performing suction filtration to obtain a final polymer product CPDTs-Tz (yield is 80%).
The polymer CPDTs-Tz obtained in the embodiment is respectively subjected to tests of optical performance, electrochemical performance and the like, and the results are respectively shown in the following figures 2 and 3.
As shown in FIG. 2, the concentration is 10 -2 In mg/mL o-dichlorobenzene solution, the absorption peak of the obtained polymer CPDTs-Tz is positioned at 533nm, which is attributed to the electron transition of the main structure in the compound, and the absorption peak positioned at 567nm is an obvious shoulder peak, which shows that the polymer still shows good intermolecular pi-pi stacking effect in a solution state, because halogen atoms are easy to form X-H non-covalent bond interaction with H atoms; dissolving the obtained CPDTs-Tz in chloroform to prepare a solution with the concentration of 0.1g/mL, and then coating a film by rotary evaporation to obtain a film with the thickness of 80-160 nm, wherein the polymer CPDTs-Tz does not show obvious red shift in the film state, which shows that the stacking state of molecules is not obviously changed in the solution or film state, and the high carrier mobility is favorably obtained. The absorption at the edge of the polymer CPDTs-Tz film is 673nm, and forms a complementary absorption spectrum with the receptor Y6 molecule, which is favorable for improving the photon utilization rate, and according to the formula E g Can be calculated by = 1240/lambda, and the band gap E g The difference is 1.84 eV.
The redox process of the polymer CPDTs-Tz is tested by utilizing an electrochemical cyclic voltammetry to obtain an initial redox potential relative to ferrocene, and then the front line orbital energy levels (HUMO energy level and LUMO energy level) of the corresponding material can be estimated: a three-electrode system is adopted, a synthesized polymer CPDTs-Tz is dissolved in chloroform to prepare a solution with the concentration of 10mg/mL, the solution is dripped on a glassy carbon electrode to prepare a film, then the film is placed in an acetonitrile electrolyte solution containing 0.1M tetrabutylammonium hexafluorophosphate for testing, the whole testing process needs nitrogen protection, the scanning speed is 0.1V/s, and the result is shown in figure 3. As can be seen from fig. 3: the polymer CPDTs-Tz has an irreversible redox process only at the anode, corresponding to an initial oxidation potential of 0.69eV. According to the formula HOMO = - (E) Ox,onset + 4.8) eV, the HOMO energy level of the polymer CPDTs-Tz is calculated to be-5.49eV, the difference between the HOMO energy levels of the CPDTs-Tz polymer and the receptor Y6 molecule is not large, so that the energy offset between the two materials is small, and the voltage loss (V) of the organic solar cell is further reduced loss ) The loss is small; the LUMO energy level is obtained according to the optical bandgap and HUMO of the material as-3.65eV(LUMO＝HUMO+Eg)。
As can be seen from FIG. 4, the CPDTs-Tz and the Y6 polymer have good energy level matching, and meanwhile, the CPDTs-Tz polymer shows a high absorption coefficient in a range of 410-630nm, and forms good complementary absorption with the receptor Y6 molecules, so that more photons can be captured, and the short-circuit current of the device can be further improved. The polymer CPDTs-Tz prepared by the invention is used as a donor material to be applied to an organic solar cell, can obtain higher photoelectric conversion efficiency, and is a good organic photovoltaic material.
The solar cell was fabricated with a conventional device configuration of ITO/PEDOT: PSS/CPDTs-Tz: Y6/PDINN/Ag, polyethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS weight ratio 1), spin-coated onto an ITO substrate at 4000r/min for 30s, and then dried at 150 ℃ for 15 minutes. The donor: the acceptor mixture (1.05 by weight) was dissolved in chloroform (total concentration of mixture solution of all mixtures was 10-20mg mL _ -1 DIO was chosen as an additive at 0.25% by volume) and stirred at room temperature overnight. The blended solution was spin coated at 1800r/min for 30s. After coating, the active layer was annealed on a hot plate at 100 ℃ for 3 minutes. And coating a PDNN layer on the active layer, and then performing vacuum evaporation on the active layer to form metal silver with the thickness of about 50-200nm as a cathode of the photovoltaic device. From the resulting J-V curve (FIG. 5), we can measure the short-circuit current J of the device sc The magnetic flux density was 21.028mA cm -2 Open circuit voltage V oc 0.877V, a fill factor FF of 71.27% and an energy conversion efficiency PCE of 13.15%, compared with the current cyclopentadithiophene polymer donor material, the energy conversion efficiency is obviously improved (J.Mater.chem.C., 2018,6,500-511 polymer 137 (2018) 303-311.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (9)
1. A halogenated cyclopentadithiophene polymer material is characterized in that halogenated cyclopentadithiophene is used as an electron donor unit, and the structural formula is shown as formula I:
2. The halogenated cyclopentadithiophene polymeric material of claim 1, wherein said halogenated cyclopentadithiophene polymer has a molecular weight of from 1 to 8 million.
3. The halogenated cyclopentadithiophene polymeric material of claim 1, wherein said electron donating unit has a structural formula shown in formula II;
4. The halogenated cyclopentadithiophene polymer material of claim 1, wherein said electron-deficient units comprise one or more of the following structural formulas:
wherein R is 1 Is C 1 ～C 20 One carbon atom of the alkyl group or the alkyl group is substituted with an oxygen atom or a sulfur atom; r is 2 Is selected from C 1 ～C 30 Y is selected from F, cl, CH 3 、OCH 3 CN, ester group or alkylthiophene.
5. A process for producing a halogenated cyclopentadithiophene polymer according to any one of claims 1 to 4, comprising the steps of: adding an electron donor unit monomer, an electron deficient unit monomer and a catalyst into an organic solvent, uniformly mixing, carrying out debromination coupling reaction under a protective atmosphere, and then carrying out sedimentation and extraction to obtain the halogenated cyclopentadithiophene polymer.
6. The preparation method according to claim 5, wherein the temperature of the debromination coupling reaction is 100-120 ℃ and the time is 12-96 h.
7. The method according to claim 5, wherein the molar ratio of the electron donor unit monomer, the electron deficient unit monomer and the catalyst is 1.
8. The production method according to claim 5, wherein the catalyst is tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium; the organic solvent is toluene or chlorobenzene.
9. An application of a polymer taking halogenated cyclopentadithiophene polymer material as an electron donor unit as an active layer material or a transmission layer material in photoelectric devices.
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