CN110452363A - A kind of organic solar batteries and preparation method thereof - Google Patents
A kind of organic solar batteries and preparation method thereof Download PDFInfo
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- CN110452363A CN110452363A CN201810428556.9A CN201810428556A CN110452363A CN 110452363 A CN110452363 A CN 110452363A CN 201810428556 A CN201810428556 A CN 201810428556A CN 110452363 A CN110452363 A CN 110452363A
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- -1 and using CV method Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000002484 cyclic voltammetry Methods 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000003115 supporting electrolyte Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- XFJQZJBQLJFFRR-UHFFFAOYSA-N 2,3,4-trichloro-5,6-dihydrobenzo[b][1]benzoxepine Chemical compound ClC=1C(=C(C2=C(C1)OC1=C(C=CC=C1)CC2)Cl)Cl XFJQZJBQLJFFRR-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 abstract description 10
- 230000007935 neutral effect Effects 0.000 abstract description 6
- 229920000144 PEDOT:PSS Polymers 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000010669 acid-base reaction Methods 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 150000002220 fluorenes Chemical class 0.000 abstract 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- 238000013086 organic photovoltaic Methods 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 239000013317 conjugated microporous polymer Substances 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 3
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 125000006708 (C5-C14) heteroaryl group Chemical group 0.000 description 1
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- 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
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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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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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Abstract
The invention belongs to organic solar batteries fields, and in particular to a kind of organic solar batteries and preparation method thereof.The present invention provides the purposes of two fluorenes polymer of a kind of spiral shell, can be used for organic solar batteries anodic interface material.The material can be by polymer monomer, and using CV method, film forming in situ is on electro-conductive glass.And in film forming procedure, the thickness of film forming can be regulated and controled.Polymer of the present invention is applied in organic solar batteries as anode interface layer, compared with PEDOT:PSS, can get higher electric current, it is compound to show more dominant bimolecular.And polymer monomer of the invention forms neutral thin polymer film after electrochemical method forms a film.Neutral boundary layer, relative to acid PEDOT:PSS, there are two advantages: 1, reducing the acid corrosion to electrode;If 2, active layer material contains basic group, to avoid with it interface acid-base reaction can occur for neutral boundary layer.Moreover, of the invention, preparation method is simple.
Description
Technical Field
The invention belongs to the field of organic solar cells, and particularly relates to an organic solar cell and a preparation method thereof.
Background
As a clean and cheap sustainable energy source, Organic Photovoltaic (OPVs) cells have been developed greatly and have achieved a series of remarkable results for decades since their development.
OPVs use the photovoltaic effect as a basic principle, generate hole-electron pairs by using solar radiation, and then separate the hole-electron pairs into carriers which respectively enter the positive electrode and the negative electrode, thereby achieving the purpose of converting solar energy into electric energy. Among them, the interface material plays an important role in battery performance. Because the interface material plays roles of carrier transmission, counter exciton blocking and the like in the battery, the interface material has the following characteristics: (1) forming ohmic contact with the electrode and the active layer; (2) having appropriate energy levels to select exciton transport; (3) the conductivity is excellent; (4) the physical stability is good.
In the existing research on OPVs, an aqueous solution of a conductive polymer (Poly (3,4-ethylenedioxythiophene): Poly (phenylenesulfinate), abbreviated as PEDOT: PSS) is often used as an anode interface material for transporting holes. The PEDOT and PSS have the advantages of conductivity controllability, good work function matching, simple process and the like, so that the PEDOT and PSS become a relatively common anode interface material. But the ITO film has the characteristics of acidity and water absorption, and is easy to cause the corrosion of an ITO electrode. In addition, it has been reported that the electron blocking material can be used as an electrode to collect electrons, so the ability of blocking electrons is not questioned.
In addition, P-type Transition Metal Oxides (TMOs) are also commonly used as anode interface materials, such as MoO3、V2O5NiO, etc. TMOs have good light transmission in visible and infrared regions, so that photons can reach the active layer to generate excitons. In addition, the conduction band is higher than the LUMO energy level of most donor and acceptor materials, and electrons are effectively blocked. However, the formation of TMOs films typically requires completion by a vacuum thermal evaporation process. Not only the cost is sharply increased, but also it cannot be applied to a printing process in mass production. In recent years, some scholars report the process of spin-coating TMOs film by solution-gel method, so that the TMOs film can be further applied. However, light absorption in the visible region still limits its popularity.
Conjugated Microporous Polymers (CMPs) are a class of Polymers with a wide range of pi-conjugation. The unique structure of the molecule enables the molecule to show a series of excellent properties, such as fluorescence, neutrality, work function controllability, electron transfer and the like. It is these advantages that CMPs are receiving more and more attention and research, and are applied to anode interface materials of OPVs, and a series of remarkable results are obtained.
Therefore, there is a need to develop a new anode interface material for organic solar cells to overcome the disadvantages of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and an electrochemically synthesized polymer film is used as a hole transport layer and applied to an organic solar cell to improve the current situation that an ITO electrode is corroded due to the acidity of PEDOT (Poly ethylene styrene) PSS. The bimolecular complexation is enhanced while maintaining equivalent performance.
In order to achieve the purpose, the invention provides the following technical scheme:
the polymer is used as an anode interface material of an organic solar cell, wherein the polymer is obtained by polymerizing one or more compounds shown in the following formula I,
wherein,
R1-R8, which may be the same or different, are independently selected from H, heteroaryl;
the heteroaryl group is a monovalent monocyclic, bicyclic or tricyclic aromatic ring system: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The "5-to 14-membered heteroaryl" is a monovalent monocyclic, bicyclic or tricyclic aromatic ring system having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contains 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S, and, in addition, may be benzo-fused in each case. In particular, the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, indazolyl, indolyl, isoindolyl, pyridyl, carbazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like.
The heteroaryl group is preferably a pyridyl group, a carbazolyl group, a thienyl group, a pyrrolyl group, a furyl group.
Preferably, the formula I is 2,2 ', 7, 7' -tetracarbazolyl-9, 9-spirobifluorene.
According to the invention, the polymer is prepared by Cyclic Voltammetry (CV method for short).
The invention also provides an organic solar cell, which comprises an anode and an anode interface layer, wherein the anode interface layer is the polymer.
According to the invention, the thickness of the polymer may be 10-100nm, for example 30-90 nm.
According to the present invention, the solar cell includes: the anode comprises a substrate, an anode interface layer, a photoactive layer and a cathode.
According to the invention, the substrate may be a glass substrate, the anode, photoactive layer, cathode may be any known to those skilled in the art, for example, the anode is ITO and the photoactive layer may be PTB7-Th: PC71BM, the cathode may be aluminum.
The invention also provides a preparation method for preparing the organic solar cell, which comprises the following steps:
(1) dissolving a compound shown in a formula I and a supporting electrolyte in a solvent to prepare a mixed solution;
(2) the compound of formula I is polymerized in situ on the anode by Cyclic Voltammetry (hereinafter abbreviated CV).
According to the present invention, in the step (1),
the supporting electrolyte may be any electrolyte that does not participate in this electrochemical reaction, such as one or more of tetraethylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium perchlorate, such as tetrabutylammonium perchlorate;
the solvent may be an organic solvent, preferably a polar organic solvent, and may be selected from one or more of acetonitrile, N-dimethylformamide, hexamethylphosphoramide, methanol, ethanol, acetic acid, isopropanol, pyridine, tetramethylethylenediamine, acetone, triethylamine, N-butanol, dioxane, tetrahydrofuran, methyl formate, tributylamine, methyl ethyl ketone, chloroform, ethyl acetate, trioctylamine, dimethyl carbonate, diethyl ether, isopropyl ether, N-butyl ether, trichloroethylene, diphenyl ether, and dichloromethane;
for example, the solvent may be selected from a mixed solution of dichloromethane and acetonitrile; the volume ratio of the dichloromethane to the acetonitrile in the mixed solution can be 1: 1-10: 1, and preferably 2: 1-9: 1;
the concentration of the compound of formula I in the solution may be 0.01-2mmol/L, preferably 0.1-1 mmol/L;
the concentration of the supporting electrolyte in the solution can be 0.01-2mmol/L, preferably 0.1-1 mmol/L;
according to the present invention, in the step (2),
the cyclic voltammetry uses a three-electrode system of an electrochemical workstation, and the reference electrode of the three-electrode system can be Ag+Ag electrode, Hg2+an/Hg electrode or a hydrogen electrode, preferably Ag+an/Ag electrode;
the sweep cut-off voltage of the cyclic voltammetry may be 0.4-1.8V, preferably 0.7-1.5V;
the number of scans of the cyclic voltammetry may be 1-4, e.g. 1, 2, 3, 4;
the invention has the beneficial effects that:
the invention provides application of a spirobifluorene polymer, which can be used as an organic solar cell anode interface material. The material can be formed on conductive glass in situ by a polymer monomer by adopting a CV method. And in the film forming process, the thickness of the formed film can be regulated and controlled by controlling the solution concentration, the scanning cut-off voltage, the scanning times and other factors.
The polymer provided by the invention is used as an anode interface layer to be applied to an organic solar cell, and can obtain higher current and show more dominant bimolecular recombination compared with PEDOT/PSS. And the polymer monomer of the invention forms a neutral polymer film after forming a film by an electrochemical method. Neutral interface layer, relative to acidic PEDOT: PSS has two advantages: 1. the corrosion of the acid to the electrode is reduced; 2. if the active layer material contains basic groups, the neutral interface layer can avoid interface acid-base reaction with the active layer material.
The preparation method is simple and feasible.
Drawings
FIG. 1 is a graph of data obtained from successive CV scans of electrodeposition in example 1.
FIG. 2 is a graph showing the final film thickness as fitted to different scanning times in example 1.
Fig. 3 is a data image obtained by measuring the energy level of the CMP film by the CV method in example 1.
Fig. 4 is a J-V characteristic curve obtained when CMP films of different thicknesses are used in an organic solar cell in example 1.
FIG. 5 shows J measured at different light intensities in the examplesscFitting image to light intensity.
Detailed Description
The invention is described in further detail below with reference to the figures and examples. It will be appreciated by those skilled in the art that the scope of the present invention is not limited to the following examples. In light of the above disclosure, it is within the scope of the present invention to provide several variations and modifications of the above examples without departing from the technical features and scope of the present invention. The drugs referred to in the following examples are commercially available unless otherwise specified.
Example 1
Organic compound monomer 2,2 ', 7, 7' -tetracarbazolyl-9, 9-spirobifluorene (abbreviated as SpCz) is prepared into a film poly (2,2 ', 7, 7' -tetracarbazolyl-9, 9-spirobifluorene) (abbreviated as PSpCz) by a CV method.
(1) Dissolving 2,2 ', 7, 7' -tetracarbazolyl-9, 9-spirobifluorene (abbreviated as SpCz) and tetrabutylammonium perchlorate (abbreviated as TBAP) serving as a supporting electrolyte in dichloromethane and acetonitrile (volume ratio is 7:3) to form a mixed solution, wherein the concentration of the SpCz is 0.1mmol/L, and the concentration of the TBAP is 0.1 mol/L;
(2) the polymer film was prepared by CV method using three-electrode system. Wherein the parameters are set as follows:
scanning range: 0-1.4V; scanning rate: 0.05V/s;
the scanning times are as follows: 1, 2, 3; precision: 1E-5 (A/V);
removing small molecules remained on the surface of the polymer film by spin coating dichloromethane, and constructing PTB7-Th PC by subsequent processes of spin coating, thermal evaporation and the like71BM organic solar cells.
The results and descriptions of the related experiments are as follows:
FIG. 1 is a graph obtained by the CV method. During the first scan, a distinct peak appears at 1.29V, indicating that the carbazolyl group is oxidized to form a film, and thereafter the carbazolyl group continues to polymerize on the already formed polymer film, so that no peak is shown here.
FIG. 2 is a graph showing the relationship between the film thickness and the number of scans, and the relationship between the film thickness and the number of scans was approximately in a direct proportional relationship by data fitting, and the proportionality coefficient was 30 nm/cycle. The results show that the method achieves film thickness control.
Figure 3 is a CV scan image of the polymer. This result was obtained by immersing the formed polymer film in a pure electrolyte (TBAP) solution and performing CV scanning. From this result, the energy level of the polymer film obtained was: HOMO is-5.18 eV, and LUMO is-3.79 eV.
FIG. 4 is a graph of J-V parameters obtained after applying polymer films of different thicknesses to OPVs. It can be seen that at a thickness of 60nm, comparable levels to PEDOT: PSS are achieved, and V isocAnd JscAll are slightly improved. Specific values are shown in table 1.
TABLE 1 detailed parameter table of J-V characteristic curve
FIG. 5 shows the variation light intensity test JscAnd (4) data. Fitting this set of data, it can be seen that when the polymer film is used as an anode interface material, JscPSS, which is linear in light intensity and has a slope closer to 1 than PEDOT, indicates that it exhibits slightly more dominant bimolecular complexation.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The polymer is used as an anode interface material of an organic solar cell and is characterized in that the polymer is obtained by polymerizing one or more compounds shown as the following formula I,
wherein,
R1-R8, which may be the same or different, are independently selected from H, heteroaryl;
the heteroaryl can be pyridyl, carbazolyl, thienyl, pyrrolyl, furyl;
preferably, the polymer is prepared by cyclic voltammetry.
2. An organic solar cell comprising an anode, an anode interface layer, wherein the anode interface layer is the polymer of claim 1;
preferably, the thickness of the polymer may be 10-100nm, for example 30-90 nm;
preferably, the solar cell includes: the device comprises a substrate, an anode interface layer, a photoactive layer and a cathode;
preferably, theThe substrate may be a glass substrate, the anode may be ITO, and the photoactive layer may be PTB7-Th PC71BM, the cathode may be aluminum.
3. A method for preparing the organic solar cell of claim 2, comprising the steps of:
(1) dissolving a compound of formula I according to claim 1 and a supporting electrolyte in a solvent to prepare a mixed solution;
(2) the compound of formula I is polymerized in situ on the anode by cyclic voltammetry.
4. The production method according to claim 3, wherein in the step (1), the supporting electrolyte is one or more of tetraethylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium perchlorate, such as tetrabutylammonium perchlorate.
5. The method according to claim 3 or 4, wherein in the step (1), the solvent may be an organic solvent, preferably a polar organic solvent, and the solvent may be selected from a mixture of one or more of acetonitrile, N-dimethylformamide, hexamethylphosphoramide, methanol, ethanol, acetic acid, isopropanol, pyridine, tetramethylethylenediamine, acetone, triethylamine, N-butanol, dioxane, tetrahydrofuran, methyl formate, tributylamine, methyl ethyl ketone, chloroform, ethyl acetate, trioctylamine, dimethyl carbonate, diethyl ether, isopropyl ether, N-butyl ether, trichloroethylene, diphenyl ether, and dichloromethane.
6. The production method according to any one of claims 3 to 5, wherein in the step (1), the solvent may be selected from a mixed solution of dichloromethane and acetonitrile; the volume ratio of dichloromethane to acetonitrile in the mixed solution can be 1: 1-10: 1, and preferably 2: 1-9: 1.
7. The process according to any one of claims 3 to 6, wherein in step (1), the concentration of the compound of formula I in the solution is from 0.01 to 2mmol/L, preferably from 0.1 to 1 mmol/L.
8. The production method according to any one of claims 3 to 7, wherein in the step (1), the concentration of the supporting electrolyte in the solution may be 0.01 to 2mmol/L, preferably 0.1 to 1 mmol/L.
9. The method for preparing a silver solution according to any one of claims 3 to 8, wherein the cyclic voltammetry in step (2) uses a three-electrode system of an electrochemical workstation, and a reference electrode of the three-electrode system is Ag+Ag electrode, Hg2+an/Hg electrode or a hydrogen electrode, preferably Ag+an/Ag electrode.
10. The method according to any one of claims 3 to 9, wherein in step (2), the sweep cut-off voltage of the cyclic voltammetry may be 0.4 to 1.8V, preferably 0.7 to 1.5V;
the number of scans of the cyclic voltammetry may be 1-4, e.g. 1, 2, 3, 4.
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