CN118165470A - Conjugated polymer film and preparation method and application thereof - Google Patents
Conjugated polymer film and preparation method and application thereof Download PDFInfo
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 125000000524 functional group Chemical group 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 13
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical group OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 12
- -1 amino, carboxyl Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 230000003993 interaction Effects 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920006132 styrene block copolymer Polymers 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 9
- 239000003607 modifier Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 3
- 230000005622 photoelectricity Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000002042 Silver nanowire Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920006254 polymer film Polymers 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
- 239000004593 Epoxy Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FNKCOUREFBNNHG-UHFFFAOYSA-N 1,3-dibromo-5-chlorobenzene Chemical compound ClC1=CC(Br)=CC(Br)=C1 FNKCOUREFBNNHG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Health & Medical Sciences (AREA)
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Abstract
The invention relates to the technical field of photoelectricity and discloses a conjugated polymer film and a preparation method and application thereof. The film includes a conjugated polymer and a functional group-modified insulating polymer blended with the conjugated polymer. And forming a blend solution of the conjugated polymer and the insulating polymer modified by the functional group, and then forming a film to obtain the conjugated polymer film. The conjugated polymer film provided by the invention has improved mechanical properties, and can maintain and even optimize electrical properties when used for electronic devices, and simultaneously, the conjugated polymer film endows the flexible devices with higher mechanical bending stability. In addition, the source of the selectable insulating polymer and the functional compound modifier is wide, and the selectable insulating polymer and the functional compound modifier can be flexibly adjusted according to the requirements of the target conjugated polymer, so that the selectable insulating polymer and the functional compound modifier exhibit excellent customized design capability.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to a conjugated polymer film and a preparation method and application thereof.
Background
Conjugated polymers have become key materials for development of advanced flexible electronic products, such as electronic skin, wearable devices and implantable medical devices, due to their characteristics of light weight, flexibility, strong functional adjustability, solution processing and the like. However, the rigid backbone of these polymers is susceptible to self-aggregation or crystallization in films upon stretching due to strong pi-pi interactions, resulting in a strain at break of typically less than 10%, limiting its application in the flexible electronics field. For this reason, researchers have tried various solutions to improve the mechanical properties of conjugated polymers, including the application of chemical strategies through molecular design, such as main chain and side chain engineering, and crosslinking strategies, among others. However, these synthetic processes are costly and time consuming.
Another effective solution is to physically blend a rigid conjugated polymer with commercial insulating polymers such as polydimethylsiloxane, styrene-ethylene-butylene-styrene block copolymers, styrene-butadiene-styrene block copolymers, polystyrene, polyarylether, polyvinylchloride, and butyl rubber. These insulating polymers generally improve the overall tensile properties of the hybrid film to some extent due to their excellent tensile properties, but greatly reduce the electrical properties of the device when the hybrid film is used in an electronic device.
Accordingly, there is a need to develop a conjugated polymer film that further enhances mechanical properties while ensuring that the electrical properties of the device are not degraded.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a conjugated polymer film, and a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a conjugated polymer film, wherein the film comprises a conjugated polymer and an insulating polymer modified with a functional group blended with the conjugated polymer;
Wherein the functional groups are derived from a compound containing both an a group and a B group; the A group is a group which can react with the insulating polymer; the B group is a group that can form a hydrogen bond interaction force with the conjugated polymer.
In a second aspect, the present invention provides a method for preparing a conjugated polymer film according to the first aspect, wherein the method comprises: and forming a blend solution of the conjugated polymer and the insulating polymer modified by the functional group, and then forming a film to obtain the conjugated polymer film.
A third aspect of the present invention provides the use of a conjugated polymer film according to the first aspect or a conjugated polymer film obtained by the production method according to the second aspect in the production of an organic electronic device.
A fourth aspect of the present invention provides a rigid organic solar cell comprising the conjugated polymer film of the first aspect or the conjugated polymer film obtained by the production method of the second aspect as a light absorbing layer.
A fifth aspect of the present invention provides a flexible organic solar cell comprising the conjugated polymer film of the first aspect or the conjugated polymer film obtained by the production method of the second aspect as a light absorbing layer.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
The conjugated polymer film provided by the invention has improved mechanical properties, and can maintain and even optimize electrical properties when used for electronic devices, and simultaneously, the conjugated polymer film endows the flexible devices with higher mechanical bending stability. In addition, the source of the selectable insulating polymer and the functional compound modifier is wide, and the selectable insulating polymer and the functional compound modifier can be flexibly adjusted according to the requirements of the target conjugated polymer, so that the selectable insulating polymer and the functional compound modifier exhibit excellent customized design capability.
Drawings
FIG. 1 is a reaction process of SBS-COOH in preparation example 1 of the present invention;
FIG. 2 is a chemical formula of PM 6;
FIG. 3 is a schematic illustration of a water borne film tensile test performed in accordance with the present invention; wherein, (a) is an image of a "film over water" tensile test system and (b) is an image of a film in a tensile test;
FIG. 4 is a stress-strain curve of the conjugated polymer films prepared in example 1 and comparative examples 1-2 of the present invention;
FIG. 5 is a stress-strain curve of a conjugated polymer film prepared in example 2 of the present invention;
FIG. 6 is a stress-strain curve of a conjugated polymer film prepared in example 3 of the present invention;
FIG. 7 is the chemical structural formula of L8-BO;
FIG. 8 is a current density-voltage curve of the rigid organic solar cells prepared in example 4, comparative example 3 and comparative example 4 of the present invention;
Fig. 9 is a change in photoelectric conversion efficiency during repeated bending of 4 ten thousand times under the condition that the bending radius is 1mm of the flexible organic solar cell prepared in example 7 and comparative example 5 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a conjugated polymer film, wherein the film comprises a conjugated polymer and an insulating polymer modified with functional groups blended with the conjugated polymer;
Wherein the functional groups are derived from a compound containing both an a group and a B group; the A group is a group which can react with the insulating polymer; the B group is a group that can form a hydrogen bond interaction force with the conjugated polymer.
The invention improves the mechanical property of the conjugated polymer film by adding the insulating polymer modified by specific functional groups into the conjugated polymer, and maintains or even improves the electrical property of the device when the film is used for electronic devices.
In the invention, the preparation method of the functional group modified insulating polymer comprises the following steps:
(1) Quantitatively dissolving an insulating polymer;
(2) Adding a functional compound modifier in a metered molar ratio;
(3) Introducing functional groups on the insulating polymer by a specific chemical reaction;
(4) Separating, purifying and drying to obtain the functional group modified insulating polymer.
In some embodiments of the invention, the a group is selected from at least one of hydroxyl, epoxy, carboxyl, isocyanate, and mercapto groups.
In some embodiments of the invention, the B group is selected from at least one of amino, carboxyl, hydroxyl, amido, ureido, and thiourea groups.
In some embodiments of the invention, the compound containing both a and B groups is thioglycolic acid.
In some embodiments of the invention, the insulating polymer includes an R group selected from at least one of epoxy, double bond, amino, carboxyl, and hydroxyl.
In some embodiments of the present invention, the insulating polymer is selected from at least one of polydimethylsiloxane, styrene-ethylene-butylene-styrene block copolymer, styrene-butadiene-styrene block copolymer, polystyrene, polyarylether, polyvinylchloride, and butyl rubber, preferably styrene-butadiene-styrene block copolymer (SBS).
In some embodiments of the invention, the molar ratio of A groups to R groups is from 0.1 to 1.5:1, preferably from 0.19 to 0.38:1, and more preferably 0.38:1. In the invention, the excessively high molar ratio can lead to the difficulty in dissolving the functional group modified insulating polymer in a common solvent of the conjugated polymer, and can not be used for the subsequent device preparation; the molar ratio is too low, which results in too small amount of modified functional groups, and it is difficult to achieve the goal of improving the mechanical properties of the conjugated polymer film while maintaining or even improving the electrical properties of the device. When the compound containing both the a group and the B group is thioglycolic acid and the insulating polymer is a styrene-butadiene-styrene block copolymer, the above molar ratio refers to the molar ratio of the mercapto group in the thioglycolic acid to the double bond in the styrene-butadiene-styrene block copolymer.
In some embodiments of the invention, the conjugated polymer is selected from at least one of PM6, D18-Cl, and PTQ 10.
In some embodiments of the invention, the functional group modified insulating polymer comprises 5-30%, preferably 5-20%, more preferably 5% by weight of the conjugated polymer.
In a second aspect, the present invention provides a method for preparing a conjugated polymer film according to the first aspect, wherein the method comprises: and forming a blend solution of the conjugated polymer and the insulating polymer modified by the functional group, and then forming a film to obtain the conjugated polymer film.
In the present invention, the film formation can be performed according to the methods disclosed in the prior art, for example: spin-coating the blend solution on a clean glass sheet to form a film by using a spin coater, and annealing at 80 ℃ for 10min to obtain the conjugated polymer film.
A third aspect of the present invention provides the use of a conjugated polymer film according to the first aspect or a conjugated polymer film obtained by the production method according to the second aspect in the production of an organic electronic device.
In some embodiments of the invention, the conjugated polymer film acts as a light absorbing layer.
In some embodiments of the invention, the organic electronic device is a rigid organic solar cell or a flexible organic solar cell.
A fourth aspect of the present invention provides a rigid organic solar cell comprising the conjugated polymer film of the first aspect or the conjugated polymer film obtained by the production method of the second aspect as a light absorbing layer.
A fifth aspect of the present invention provides a flexible organic solar cell comprising the conjugated polymer film of the first aspect or the conjugated polymer film obtained by the production method of the second aspect as a light absorbing layer.
The present invention will be described in detail by examples.
The following examples and comparative examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
Material description: SBS (styrene butadiene styrene)Purchased from Sigma-Aldrich company (number average molecular weight M n =153 kg/mol, styrene mass fraction 30%).
PM6Supplied by solarmer company (number average molecular weight M n =67 kg/mol).
Preparation example 1
The preparation example is used for explaining the preparation method of the functional group modified insulating polymer with thioglycollic acid as a functional group source, and the reaction process is shown in figure 1:
(1) 2g of styrene-butadiene-styrene block copolymer (SBS) was dissolved in 20mL of cyclohexane to obtain SBS solution;
(2) Transferring the SBS solution into a 100mL polymerization tube, adding 40mg of Azodiisoheptanenitrile (ABVN) free radical initiator and thioglycollic acid, wherein the molar ratio of the mercapto group to the double bond in SBS is 0.38:1;
(3) Stirring thoroughly for dissolving, and stirring in low temperature bath at 0deg.C for 10min;
(4) Pumping and filling nitrogen for 5 times, and transferring to 60 ℃ oil bath for reaction for 4 hours;
(5) Terminating the reaction in a stirring bath at low temperature of 0 ℃;
(6) Settling the product in ethanol to remove redundant thioglycollic acid;
(7) Dissolving the product in a small amount of tetrahydrofuran, and settling in deionized water;
(8) Repeating the step (7) for three times, and carrying out suction filtration;
(9) Vacuum drying at room temperature to constant mass, to obtain carboxyl modified SBS (marked as SBS-COOH).
Preparation example 2
SBS-COOH was prepared according to the method of preparation example 1, except that the molar ratio of mercapto groups in thioglycolic acid to double bonds in SBS was 0.19:1.
Example 1
This example illustrates the preparation of a conjugated polymer film.
PM6 (chemical structural formula shown in FIG. 2) and SBS-COOH prepared in preparation example 1 were dissolved in chloroform to form a blend solution, wherein the concentration of PM6 was 20mg/mL and SBS-COOH accounted for 20% by weight of PM 6. Spin-coating the film on a clean glass sheet by using a spin coater, and annealing at 80 ℃ for 10min to obtain the polymer film with the thickness of about 100 nm.
Example 2
A conjugated polymer film was prepared in the same manner as in example 1, except that SBS-COOH prepared in preparation example 2 was used.
Example 3
A conjugated polymer film was prepared as in example 1, except that SBS-COOH was 5% by weight of PM 6.
Comparative example 1
A conjugated polymer film was prepared as in example 1, except that PM6 was used directly to prepare the film.
Comparative example 2
A conjugated polymer film was prepared as in example 1, except that SBS was blended with PM6 directly to prepare the film.
Test example 1
The conjugated polymer films prepared in examples 1-3 and comparative examples 1-2 were subjected to a water film tensile test.
Test device: the M-110 linear displacement table (PI, germany) is connected with a clamp as a stretching end of a stretching test, so that the displacement of a sample during stretching can be monitored, and the sample stretching strain data can be obtained; meanwhile, se:Sup>A DPM-900 series dynamic strain amplifier (KYOWA, japan) is combined with se:Sup>A micro-load sensor VS-A (KYOWA, japan), se:Sup>A clamp is arranged on the micro-load sensor to serve as se:Sup>A fixed end of se:Sup>A tensile test, and tensile stress datse:Sup>A can be obtained through the load sensor and the amplifier. Finally, integrating the stretching displacement end and the load fixing end into the groove containing water, and finally connecting test software to start the stretching test of the water film as shown in fig. 3 (a).
Preparation of bone rod sample test membranes: the bone rod-shaped sample film is etched by a laser etching or plasma etching machine, the etched sample film is placed in water, water-soluble substances on a glass sheet are dissolved to obtain a polymer film floating on the water surface, and the bone rod-shaped polymer film is adhered to a stretching displacement end and a loading fixed end by PDMS (polydimethylsiloxane) respectively, so that the test can be performed as shown in fig. 3 (b).
The addition of SBS-COOH was found to significantly improve the mechanical properties of PM6 films by water tensile testing.
FIG. 4 shows the stress-strain curves of the pure PM6 film of comparative example 1, the PM6:20% SBS-COOH conjugated polymer film of example 1, and the PM6:SBS conjugated polymer film of comparative example 2. The fracture initiation strain (COS) and toughness of the pure PM6 film were 8.32% and 2.02MJ/m 3, respectively, and the addition of unmodified SBS resulted in a decrease in mechanical properties of the film, COS to 5.93%, and toughness to 0.08MJ/m 3. The results of example 1 show that COS and toughness of the conjugated polymer film prepared after mixing 20% SBS-COOH into PM6 are improved to 21.48% and 7.10MJ/m 3, respectively.
Fig. 5 shows the stress-strain curve of the conjugated polymer film prepared in example 2. In example 2, the conjugated polymer film prepared after 20% SBS-COOH was mixed into PM6 had COS and toughness of 18.08% and 4.92MJ/m 3, respectively, and the mechanical properties were inferior to those of the conjugated polymer film prepared in example 1. Fig. 6 shows stress-strain curves of the conjugated polymer film prepared in example 3. In example 3, when SBS-COOH was 5% by weight of PM6, the prepared conjugated polymer film had COS and toughness of 16.25% and 5.67MJ/m 3, respectively, and mechanical properties were inferior to those of the conjugated polymer film prepared in example 1.
Example 4
This example is for illustrating the preparation of a rigid organic solar cell using SBS-COOH as a light absorbing layer additive in preparation example 1, and specifically comprises the following steps:
the first step: preparation of hole transport layer: diluting PEDOT to PSS (AI 4083) with deionized water at a volume ratio of 3:1, uniformly mixing the solutions, spin-coating the solution on an ITO/glass bottom electrode by using a spin coater to form a film, and then annealing at 150 ℃ for 15min to obtain a hole transport layer with a thickness of about 30 nm;
And a second step of: preparation of the light absorbing layer: PM6 (chemical structural formula shown in figure 2) and L8-BO (chemical structural formula shown in figure 7) are added into a chloroform solution of 1, 3-dibromo-5-chlorobenzene with the mass ratio of 1:1.2 to form a mixed solution with the total concentration of PM6 and L8-BO of 16mg/mL, SBS-COOH (5% of the mass of PM 6) is added into the mixed solution, stirred, dissolved and uniformly mixed to obtain a light absorption layer solution, spin-coated on a hole transmission layer by using a spin coater to form a film, and then annealed at 80 ℃ for 5min to obtain a light absorption layer with the thickness of about 100 nm;
And a third step of: preparation of an electron transport layer: PDINN is dissolved in a mixed solvent of ethanol and trifluoroethanol in a volume ratio of 7:3, the concentration is 1mg/mL, and an electron transport layer with the thickness of about 5nm is formed on the light absorption layer by spin coating through a spin coater;
fourth step: preparation of the top electrode: and (3) carrying out vacuum evaporation on the metallic silver on the electron transport layer to form a top electrode with the thickness of about 80nm, thereby completing the preparation of the organic solar cell (PM 6:L8-BO:5% SBS-COOH).
Example 5
A rigid organic solar cell (labeled PM6:L 8-BO) was prepared as in example 4, except that SBS-COOHS was added to 10% of the mass of PM6 in the preparation of the light-absorbing layer.
Example 6
A rigid organic solar cell (labeled PM6:L 8-BO) was prepared as in example 4, except that SBS-COOHS added in the preparation of the light-absorbing layer was 20% of the mass of PM 6.
Comparative example 3
A rigid organic solar cell (labeled PM6:L 8-BO) was prepared as in example 4, except that no insulating polymer was added in the preparation of the light absorbing layer.
Comparative example 4
A rigid organic solar cell (labeled PM6:L8-BO:5% SBS) was prepared as in example 4, except that unmodified SBS was added as a light absorbing layer additive in the preparation of the light absorbing layer.
Test example 2
The organic solar cell prepared with SBS-COOH as the light absorbing layer additive in example 4 has significant advantages over the organic solar cells of comparative examples 3 and 4. Fig. 8 is a current density-voltage curve of the rigid organic solar cell of example 4, comparative example 3 and comparative example 4. The organic solar cell prepared in example 4 had a higher photoelectric conversion efficiency of 19.04%, the photoelectric conversion efficiency of the organic solar cell prepared in comparative example 3 was 18.17%, and the photoelectric conversion efficiency of the organic solar cell prepared in comparative example 4 was only 17.21%. The organic solar cell prepared in example 5 had a photoelectric conversion efficiency of 18.08%, the organic solar cell prepared in example 6 had a higher photoelectric conversion efficiency of 17.04%,
Example 7
This example is for illustrating the preparation of a flexible organic solar cell using SBS-COOH as a light absorbing layer additive in preparation example 1, and specifically comprises the following steps:
the first step: preparation of silver nanowires/glass electrodes: the silver nanowire ethanol dispersion (concentration 3.3 mg/mL) was first coated on a clean glass sheet, and then annealed at 150 ℃ for 15min. Then repeating the steps once to obtain a silver nanowire/glass electrode covered with two layers of silver nanowires;
And a second step of: preparation of semi-embedded silver nanowire/polyimide flexible electrode: firstly, dripping N, N-dimethylacetamide solution of polyimide with 5% of solid content on the surface of a silver nanowire/glass electrode; then gradually volatilizing the solvent by adopting a gradient heating mode, wherein the heating gradient is set to be 30 ℃, 60 ℃, 90 ℃, 120 ℃, 150 ℃ and 180 ℃, and the annealing time of each temperature gradient is 30min; finally, stripping from the glass substrate to obtain a semi-embedded silver nanowire/polyimide flexible electrode;
and a third step of: preparation of a flexible organic solar cell: hole transport layer, light absorption layer, electron transport layer and top electrode were prepared stepwise on silver nanowires/polyimide flexible electrode in the same manner as in example 7, with cell labeled F-PM6:l8-BO 5% SBS-COOH.
Comparative example 5
A flexible organic solar cell (labeled F-PM6: L8-BO) was fabricated as in example 7, except that no insulating polymer was added in the fabrication of the light absorbing layer.
Test example 3
The organic solar cell prepared with SBS-COOH as the light absorbing layer additive in example 7 has significant advantages over the organic solar cell of comparative example 5. Fig. 9 is a change in photoelectric conversion efficiency during repeated bending of the flexible organic solar cells of example 7 and comparative example 5 for 4 ten thousand times under the condition of a bending radius of 1 mm. The flexible organic solar cell prepared in example 7 has higher mechanical bending stability, and can still maintain 88.9% of the initial efficiency after repeated bending for 4 ten thousand times, while the flexible organic solar cell prepared in comparative example 5 can only maintain 83.5% of the initial efficiency.
The results show that the blending of the insulating polymer modified by the functional group and the conjugated polymer can not only improve the mechanical property of the conjugated polymer film, but also maintain and even optimize the electrical property when used for an electronic device, and simultaneously endow the flexible device with higher mechanical bending stability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A conjugated polymer film, characterized in that the film comprises a conjugated polymer and an insulating polymer modified with functional groups blended with the conjugated polymer;
Wherein the functional groups are derived from a compound containing both an a group and a B group; the A group is a group which can react with the insulating polymer; the B group is a group that can form a hydrogen bond interaction force with the conjugated polymer.
2. The conjugated polymer film according to claim 1, wherein the a group is selected from at least one of a hydroxyl group, an epoxy group, a carboxyl group, an isocyanate group, and a mercapto group;
Preferably, the B group is selected from at least one of amino, carboxyl, hydroxyl, amido, ureido, and thiourea groups;
Preferably, the compound containing both a group and a group B is thioglycollic acid.
3. The conjugated polymer film according to claim 1 or 2, wherein the insulating polymer comprises an R group selected from at least one of an epoxy group, a double bond, an amino group, a carboxyl group, and a hydroxyl group;
Preferably, the insulating polymer is selected from at least one of polydimethylsiloxane, styrene-ethylene-butylene-styrene block copolymer, styrene-butadiene-styrene block copolymer, polystyrene, polyarylether, polyvinyl chloride, and butyl rubber, preferably styrene-butadiene-styrene block copolymer.
4. A conjugated polymer film according to claim 3, wherein the molar ratio of a groups to R groups is 0.1-1.5:1, preferably 0.19-0.38:1, further preferably 0.38:1.
5. The conjugated polymer film of any of claims 1-4, wherein the conjugated polymer is selected from at least one of PM6, D18-Cl, and PTQ 10.
6. The conjugated polymer film according to any of claims 1-5, wherein the functional group modified insulating polymer comprises 5-30%, preferably 5-20%, further preferably 5% by weight of the conjugated polymer.
7. A method of preparing a conjugated polymer film according to any one of claims 1 to 6, comprising: and forming a blend solution of the conjugated polymer and the insulating polymer modified by the functional group, and then forming a film to obtain the conjugated polymer film.
8. Use of the conjugated polymer film according to any one of claims 1 to 6 or the conjugated polymer film obtained by the production method of claim 7 for the production of an organic electronic device;
Preferably, the conjugated polymer film serves as a light absorbing layer;
Preferably, the organic electronic device is a rigid organic solar cell or a flexible organic solar cell.
9. A rigid organic solar cell comprising the conjugated polymer film according to any one of claims 1 to 6 or the conjugated polymer film obtained by the production method according to claim 7 as a light absorbing layer.
10. A flexible organic solar cell comprising the conjugated polymer film according to any one of claims 1 to 6 or the conjugated polymer film obtained by the production method according to claim 7 as a light absorbing layer.
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