CN117255574A - Efficient stable organic solar cell containing fluorescence conversion agent and preparation method thereof - Google Patents
Efficient stable organic solar cell containing fluorescence conversion agent and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 239000011787 zinc oxide Substances 0.000 claims abstract description 31
- 239000006081 fluorescent whitening agent Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 11
- 229910003472 fullerene Inorganic materials 0.000 claims description 11
- 230000005525 hole transport Effects 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- IBMVRGMZLQWAJY-SLZAGEDMSA-N 2-[(2Z)-2-[[20-[(Z)-[1-(dicyanomethylidene)-3-oxoinden-2-ylidene]methyl]-12,12,24,24-tetrakis(5-hexylthiophen-2-yl)-5,9,17,21-tetrathiaheptacyclo[13.9.0.03,13.04,11.06,10.016,23.018,22]tetracosa-1(15),2,4(11),6(10),7,13,16(23),18(22),19-nonaen-8-yl]methylidene]-3-oxoinden-1-ylidene]propanedinitrile Chemical compound CCCCCCc1ccc(s1)C1(c2ccc(CCCCCC)s2)c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c4ccc(CCCCCC)s4)(c4ccc(CCCCCC)s4)c3cc2-c2sc3cc(\C=C4/C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12 IBMVRGMZLQWAJY-SLZAGEDMSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- 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
Abstract
The invention discloses a high-efficiency stable organic solar cell containing a fluorescence conversion agent and a preparation method thereof. When the electron transport layer coated with the fluorescent converting agent or the electron transport layer doped with the fluorescent whitening agent reaches 170nm in thickness, the device efficiency of the battery is significantly higher than that of a battery prepared from pure zinc oxide of 170 nm.
Description
Technical Field
The invention relates to the technical field of organic photoelectric devices, in particular to a high-efficiency stable organic solar cell containing a fluorescence conversion agent and a preparation method thereof.
Background
With the rapid development of economy in the world, the energy problem is getting more and more attention. The solar energy is widely distributed, green, pollution-free and sustainable, and is favored by a plurality of scientists, so that the solar energy plays a key role in solving serious environmental problems and solar energy challenges facing the world today, and the rapid development of photovoltaic technology is promoted. The organic solar cell polymer bulk heterojunction photovoltaic device is a novel semiconductor device which is only appeared in modern times, integrates various excellent characteristics, and can be prepared into a flexible, portable and cheaper photoelectric device through a simple solution processing method.
Organic photovoltaic cells based on non-fullerenes have been rapidly developed in recent years. Organic photovoltaic cells have reached the point of commercial intersections. However, the organic solar cell still has the problems of too short service life of the cell and too low energy conversion efficiency of the cell after the effective area of the cell is enlarged. In order to further improve the efficiency and the service life of the organic solar cell, the cathode interface layer can be used for improving the efficiency and the service life of the organic solar cell.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-efficiency stable organic solar cell containing a fluorescence conversion agent and a preparation method thereof.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the organic solar cell containing the fluorescence conversion agent comprises the steps of sequentially forming a cathode, an electron transport layer containing the fluorescence conversion agent, an active layer, a hole transport layer and an anode by the photovoltaic cell element;
in the electron transport layer containing the fluorescent converting agent, the fluorescent converting agent is present in the electron transport layer in a cover form;
the fluorescent conversion agent is a material with an absorption peak value of 300-450 nm, and emits fluorescent light with an emission peak value of 300-450 nm again after ultraviolet light and/or deep blue light are irradiated.
Preferably, the fluorescent converting agent is a fluorescent whitening agent,
selected from organic semiconductors based on the following specific units, or by incorporating groups in the following specific unit structure that facilitate the dissolution of the material in hydroalcoholic solvents:
preferably, the group which facilitates the dissolution of the material in the hydroalcoholic solvent is one or more of a sulfonic acid group, a carboxyl group, a quaternary ammonium salt and a hydroxyl group.
Preferably, the method comprises the steps of:
(1) Cleaning the substrate with the cathode electrode and drying;
(2) Firstly, preparing an electron transmission layer, and then spin-coating a fluorescence conversion agent on the electron transmission layer;
(3) Spin-coating an organic solar cell active layer on the fluorescent converter layer;
(4) Evaporating a hole transport layer on the active layer;
(5) And evaporating an anode on the hole transport layer.
Preferably, the substrate is one of transparent glass, polyimide PI substrate and polyester PET substrate; the cathode is an Indium Tin Oxide (ITO) layer and is arranged on the substrate, and the thickness of the cathode is 30-200 nm;
the electron transport layer is made of an organic electron transport material or an organic-inorganic hybrid electron transport material, and the thickness of the electron transport layer is 20-200nm;
the thickness of the active layer is 120-150nm;
the hole transport layer is MoO 3 The thickness is 8-15nm;
the anode is Ag and has a thickness of 80-120 nm.
Preferably, the thickness of the electron transport layer is 30-170nm, and the electron transport layer comprises one or more than two of the following materials: there are otherZinc oxide ZnO doped and/or undoped with metal, tin oxide SnO doped and/or undoped with other metals, titanium dioxide TiO 2 。
Preferably, when the fluorescence conversion agent is present in the electron transport layer in a coating form, the concentration of the fluorescence conversion agent is 2-8mg/mL, and the spin-coating thickness of the fluorescence conversion agent is 2-30nm, between the electron transport layer and the active layer.
Preferably, in step (3), the active layer is prepared as follows: dissolving a polymer donor material and a non-fullerene acceptor material in an organic solvent, and reacting for 6+/-2 hours at 50-60 ℃;
the polymer donor material is more than one of PBDB-T-F, PTB7-Th, the non-fullerene acceptor material is more than one of BTP-eC9 and Y6-BO-4F, ITIC-Th, and the organic solvent is more than one of chlorobenzene, o-xylene, thiophene and o-dichlorobenzene;
the structure of the polymer donor material and the non-fullerene acceptor material is as follows:
preferably, the concentration of the polymer donor material in the organic solvent is 8-10mg/mL, and the mass ratio of the polymer donor material to the non-fullerene acceptor material is 1:1.2-1.3.
An organic solar cell containing a fluorescence conversion agent, which is prepared by the method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The present invention provides a method of improving the efficiency of an organic solar cell by introducing a fluorescent converting agent between the electron transport layer and the active layer.
(2) The invention is characterized in that after the fluorescent conversion agent is irradiated by ultraviolet light or deep blue light, charge transfer exists between the fluorescent conversion agent and the metal oxide electron transport layer.
(3) The invention is innovative in that the fluorescence conversion agent is introduced into the organic solar cell structure, and the efficiency of the cell prepared by the thick film of the electron transport layer is improved.
(4) The fluorescent conversion agent introduced by the invention can absorb ultraviolet light and deep blue light and weaken the damage of high-energy photons to the active layer of the organic solar cell.
(5) When the fluorescence conversion agent is positioned between the electron transmission layer and the active layer, under the irradiation of ultraviolet light, fluorescence emitted by the fluorescence conversion agent can be absorbed by the electron transmission layer and the active layer of the organic solar cell, so that the cell efficiency is improved, and the cell efficiency is kept above 89%.
Drawings
Fig. 1 is a schematic view of an organic solar cell device in example 1. Wherein 1 is a substrate, 2 is a cathode transparent electrode, 3 is an electron transport layer, 4 is a fluorescent conversion agent layer, 5 is an active layer, 6 is a hole transport layer, and 7 is an anode metal electrode.
Fig. 2 is a normalized thin film absorption diagram of the fluorescence converter layer CBS.
FIG. 3 is a photoluminescence plot of a CBS-coated ZnO bilayer film of example 1.
FIG. 4 shows the optical transmittance of ITO/ZnO and ITO/ZnO/CBS of example 1 at different thicknesses.
Fig. 5 shows the phenomenon that fluorescence representing CBS is absorbed by the active layer in example 1.
FIG. 6 is a PBDB-T-F based embodiment 1: the active layer of the BTP-eC9 combination has a voltammetric characteristic curve and an efficiency profile of the organic solar cell device under electron transport layers with different thicknesses.
FIG. 7 is a PBDB-T-F based embodiment 1: current-voltage characteristics of a battery device of pure zinc oxide combined with BTP-eC9 active layer and a battery device of zinc oxide covered with a fluorescence conversion agent.
FIG. 8 is a PBDB-T-F based embodiment 1: the External Quantum Efficiency (EQE) of a battery device of pure zinc oxide combined with BTP-eC9 active layer and zinc oxide covered with fluorescence conversion agent CBS.
Fig. 9 is the stability under light of the battery prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but embodiments of the present invention are not limited thereto.
Example 1
Ultrasonically cleaning a glass substrate coated with an ITO layer sequentially by using acetone, a micron-sized semiconductor special-purpose detergent, deionized water and isopropanol, drying by using dry nitrogen, and placing the dried glass substrate in a culture dish for standby (a cathode in the embodiment);
(1) Preparation of zinc oxide electron transport layers with different thicknesses:
the formula of the 30nm zinc oxide electron transport layer comprises: 1g of zinc acetate dihydrate was weighed and dissolved in 10mL of ethylene glycol methyl ether, 300. Mu.L of ethanolamine was added, stirred at 60℃for 2 hours for dissolution, filtered with a 0.22 μm PTFE filter, spin-coated on an ITO substrate at 2600rpm, and annealed at 200℃for 30 minutes to prepare a 30nm zinc oxide electron transport layer.
90nm zinc oxide formulation: 2.5g of zinc acetate dihydrate was weighed and dissolved in 10mL of ethylene glycol methyl ether, 500. Mu.L of ethanolamine was added, stirred at 60℃for 2 hours for dissolution, filtered with a 0.22. Mu.M PTFE filter, spin-coated on an ITO substrate at 3000rpm, and annealed at 200℃for 30 minutes to prepare a 90nm zinc oxide electron transport layer.
170nm zinc oxide electron transport layer formulation: 4g of zinc acetate dihydrate was weighed and dissolved in 10mL of ethylene glycol methyl ether, 700. Mu.L of ethanolamine was added, stirred at 60℃for 2 hours for dissolution, filtered with a 0.22 μm PTFE filter, spin-coated on an ITO substrate at 2600rpm, and annealed at 200℃for 30 minutes to prepare a 170nm single-component zinc oxide electron transport layer.
(2) The fluorescence conversion agent CBS is dissolved in methanol solvent to prepare solutions with different concentrations of 2mg/mL,4mg/mL,6mg/mL and 8mg/mL, and the solutions are spin-coated on zinc oxide at 2000 rpm. The concentration of CBS used was 2mg/mL for 30nm zinc oxide and 4mg/mL for 90nm zinc oxide. For 170nm zinc oxide, the concentration of CBS used was 6mg/mL.
(3) Dissolving a polymer donor material PBDB-T-F and a non-fullerene acceptor material BTP-eC9 in a chlorobenzene solvent, wherein the concentration of the PBDB-T-F is 8mg.mL -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of PBDB-T-F to BTP-eC9 is 1:1.2, and the solution is stirred for 6 hours at 50 ℃. Then spin coating the solution over the fluorescent converting agent at 3000rpm to prepare the fluorescent converting agentObtaining an active layer of 120 nm;
(4) Vapor deposition of 12nm MoO on active layer 3 As a hole transport layer;
(5) In MoO 3 Silver with the thickness of 100nm is vacuum thermal evaporated on the hole transport layer to be used as a metal electrode.
The chemical structural formula of the polymer donor and the non-fullerene acceptor in this example is as follows:
the chemical structural formula of the fluorescence conversion agent CBS in this example is as follows:
the organic solar cell device structure obtained in this example is shown in fig. 1. In order to test the photovoltaic performance of the organic solar cell prepared with the fluorescent brightening agent described in the examples, an active layer combination was selected, which is PBDB-T-F: BTP-eC9 combination with ITO/ZnO/fluorescent converter/active layer/MoO device structure x The cell device performance results are shown in Table 1 for Ag and the current-voltage curve for the device is shown in FIG. 7.
Comparative example 1
The preparation method was the same as in example 1, except that the fluorescent converting agent layer was not present.
TABLE 1 organic solar cell device Performance parameters under different thickness of electron transport layers based on PBDB-T-F BTP-eC9 combinations
Labeling: v (V) oc Is the open circuit voltage, J sc Is short-circuit current, FF is filling factor, PCE is energy conversion efficiency, J SC,EQE And calculating the obtained short-circuit current according to the external quantum efficiency.
FIG. 2 showsThe absorption characteristics of the newly introduced fluorescence enhancer are mainly distributed in ultraviolet and deep blue light, the photodecomposition of high-energy light photons on the active layer is effectively shielded, and fig. 3 shows that fluorescence quenching occurs from the photoluminescence spectrum, and the transmittance of ultraviolet light is obviously reduced after the CBS is covered with zinc oxide to form a blend film from fig. 5. As can be seen from table 1, the performance of the organic solar cell prepared by covering the electron transport material with the fluorescent brightening agent and the pure zinc oxide electron transport layer can significantly improve the cell efficiency, especially after the electron transport layer thickness reaches 170nm, the cell efficiency prepared by the modified zinc oxide is maintained at 89% or more, while the efficiency of the organic solar device prepared by the pure zinc oxide is greatly reduced, mainly due to the difference of short-circuit currents. From fig. 6, zinc oxide with a fluorescent converter coating shows good thickness resistance. FIG. 8 measured in PBDB-T-F using external quantum efficiency method: BTP-eC9 is the external quantum effect of the cell of the active layer. FIG. 9 compares the stability of CBS coated 170nm ZnO/CBS with 170nm ZnO prepared cells under light. After being covered with ZnO by CBS, T 80 The lifetime is increased from 1.8h to 1448h of ZnO at 170 nm.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The preparation method of the organic solar cell containing the fluorescence conversion agent is characterized in that the organic solar cell comprises a substrate and a photovoltaic cell element, wherein the photovoltaic cell element sequentially comprises a cathode, an electron transport layer containing the fluorescence conversion agent, an active layer, a hole transport layer and an anode;
in the electron transport layer containing the fluorescent converting agent, the fluorescent converting agent is present in the electron transport layer in a cover form;
the fluorescent conversion agent is a material with an absorption peak value of 300-450 nm, and emits fluorescent light with an emission peak value of 300-450 nm again after ultraviolet light and/or deep blue light are irradiated.
2. The method according to claim 1, wherein the fluorescent converting agent is a fluorescent whitening agent,
selected from organic semiconductors based on the following specific units, or by incorporating groups in the following specific unit structure that facilitate the dissolution of the material in hydroalcoholic solvents:
3. the preparation method according to claim 2, wherein the group which facilitates the dissolution of the material in the hydroalcoholic solvent is one or more of a sulfonic acid group, a carboxyl group, a quaternary ammonium salt, and a hydroxyl group.
4. The method of manufacturing according to claim 1, comprising the steps of:
(1) Cleaning the substrate with the cathode electrode and drying;
(2) Firstly, preparing an electron transmission layer, and then spin-coating a fluorescence conversion agent on the electron transmission layer;
(3) Spin-coating an organic solar cell active layer on the fluorescent converter layer;
(4) Evaporating a hole transport layer on the active layer;
(5) And evaporating an anode on the hole transport layer.
5. The method according to claim 4, wherein the substrate is one of transparent glass, polyimide PI substrate, and polyester PET substrate; the cathode is an Indium Tin Oxide (ITO) layer and is arranged on the substrate, and the thickness of the cathode is 30-200 nm;
the electron transport layer is made of an organic electron transport material or an organic-inorganic hybrid electron transport material, and the thickness of the electron transport layer is 20-200nm;
the thickness of the active layer is 120-150nm;
the hole transport layer is MoO 3 The thickness is 8-15nm;
the anode is Ag and has a thickness of 80-120 nm.
6. The method according to claim 5, wherein the electron transport layer has a thickness of 30-170nm and comprises one or more of the following materials: zinc oxide ZnO doped and/or undoped with other metals, tin oxide SnO doped and/or undoped with other metals, titanium oxide TiO 2 。
7. The method according to claim 4, wherein when the fluorescent converting agent is present in the electron transport layer in a coating form, the concentration of the fluorescent converting agent is 2 to 8mg/mL, and the spin-coating thickness of the fluorescent converting agent is 2 to 30nm, between the electron transport layer and the active layer.
8. The method of claim 4, wherein in step (3), the active layer is prepared by: dissolving a polymer donor material and a non-fullerene acceptor material in an organic solvent, and reacting for 6+/-2 hours at 50-60 ℃;
the polymer donor material is more than one of PBDB-T-F, PTB7-Th, the non-fullerene acceptor material is more than one of BTP-eC9 and Y6-BO-4F, ITIC-Th, and the organic solvent is more than one of chlorobenzene, o-xylene, thiophene and o-dichlorobenzene;
the structure of the polymer donor material and the non-fullerene acceptor material is as follows:
9. the method of claim 8, wherein the concentration of the polymeric donor material in the organic solvent is 8-10mg/mL, and the mass ratio of the polymeric donor material to the non-fullerene acceptor material is 1:1.2-1.3.
10. An organic solar cell containing a fluorescence conversion agent prepared according to any one of claims 1 to 9.
Priority Applications (1)
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