CN115498108A - Solar cell and preparation method thereof - Google Patents

Solar cell and preparation method thereof Download PDF

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CN115498108A
CN115498108A CN202211014695.XA CN202211014695A CN115498108A CN 115498108 A CN115498108 A CN 115498108A CN 202211014695 A CN202211014695 A CN 202211014695A CN 115498108 A CN115498108 A CN 115498108A
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layer
optionally
active layer
anode
cathode
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陈永胜
孟令贤
万相见
李晨曦
张雅敏
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Nankai University
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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
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present application provides a solar cell comprising a first cell active layer and a second cell active layer, wherein one of the first and second cell active layers comprises an acceptor material F-M and the other of the two active layers comprises an acceptor material selected from the group consisting of: O6T-4F, PC 71 Any one of BM or a combination thereof. The application also provides a preparation method of the solar cell and a solar cell device prepared according to the preparation method.

Description

Solar cell and preparation method thereof
Technical Field
The application belongs to the field of optoelectronics. In particular, the present application relates to solar cells and methods of making the same.
Background
In the current society, the continuous consumption of fossil energy makes people face the crisis of energy shortage, and the development of renewable energy is urgent. Solar energy is used as green, pollution-free and inexhaustible clean energy, and can meet the ever-increasing energy demand of human beings. Therefore, the use of solar energy has attracted worldwide attention. Compared with inorganic silicon crystal solar cells, organic solar cells are one of the most potential photovoltaic devices due to the advantages of low cost, light weight, solution processing, capability of being made into flexible devices, capability of being printed and prepared in large areas and the like.
Through the development of recent years, the energy conversion efficiency of a single junction organic solar cell exceeds 14%, but the absorption spectrum range of a single active layer is narrow, so that most of sunlight is not utilized. The active layer materials with complementary absorption spectra of two or more junctions are connected in series to form the laminated device, so that the absorption spectra of the device on sunlight can be effectively widened, the defects of a single-junction solar cell are overcome, and the energy conversion efficiency of the organic solar cell is further improved. In an ideal case, the connecting layer has no potential loss, and the open-circuit voltage of the tandem structure stacked device is equal to the sum of the open-circuit voltages of the sub-cells; and the short-circuit current density of the whole device depends on the smaller value of the short-circuit current density in the sub-battery. Therefore, for preparing an efficient tandem solar cell, a sub-cell active layer material which has good photoelectric conversion performance and complementary absorption spectrum needs to be selected, so that high short-circuit current density is realized; in addition, it is necessary to select a proper connection layer material to connect the sub-cells, so that electrons and holes are effectively recombined at the connection layer, and ohmic contact between the sub-cells is realized.
The solar cell developed in recent years based on the non-fullerene acceptor has a plurality of unique advantages, and the non-fullerene acceptor material can be well matched with the HOMO and LUMO energy levels of the high-efficiency donor material through the regulation and control of the molecular energy level, so that the separation and transmission of excitons are promoted. Meanwhile, on the premise of ensuring effective separation of excitons, the LUMO energy level of the molecule is improved, and higher open-circuit voltage is expected to be obtained. In addition, the light absorption performance of molecules can be effectively regulated and controlled by further regulating the HOMO energy level of the receptor molecules, so that the absorption spectrum of the receptor material is complementary with the absorption spectrum of the donor material, more solar energy is absorbed, and higher short-circuit current density and energy conversion efficiency are obtained. However, non-fullerene acceptor based tandem solar cell devices are relatively few and lack suitable complementary tandem cell materials.
Disclosure of Invention
In one aspect, the present application provides a solar cell comprising a first cell active layer and a second cell active layer, wherein one of the first cell active layer and the second cell active layer comprises an acceptor material F-M and the other of the two active layers comprises an acceptor material selected from the group consisting of: O6T-4F, PC 71 Any one of BM or a combination thereof.
In some embodiments, the solar cell is a double or multi-junction solar cell.
In some embodiments, the additional active layer comprises O6T-4F and PC 71 BM；
In some embodiments, the first and second battery active layers further comprise at least one donor material.
In some embodiments, the donor material in the first cell active layer and the donor material in the second cell active layer are each independently selected from any one of PBDB-T, PBDB-TF, PTB7-Th, J52-2F, PDBT-T1, or any combination thereof.
In some embodiments, the donor material in the F-M containing active layer in both the first and second cell active layers is selected from any one of PBDB-T, PBDB-TF, J52-2F, PDBT-T1, or a combination thereof, and the donor material in the other active layer is selected from PTB7-Th.
In some embodiments, the donor material in the F-M containing active layer in both the first and second cell active layers is selected from PBDB-T and the donor material in the other active layer is selected from PTB7-Th.
In some embodiments, in the active layer comprising F-M, the donor material: the mass ratio of F to M is 1.
In some embodiments, in the further active layer, the donor material: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 1:0-1.5:0-1.5.
In some embodiments, the active layer comprising F-M in both the first and second battery active layers serves as a front battery active layer, and the other active layer serves as a rear battery active layer.
In some embodiments, the solar cell further comprises one or more of a cathode, a cathode modification layer, an interface modification layer, a hole collection layer, an electron collection layer, an anode modification layer, and an anode.
In some embodiments, the cathode serves as a conductive substrate. In some embodiments, the anode serves as a conductive substrate.
In some embodiments, when the cathode is the conductive substrate, the anode comprises a metal.
In some embodiments, when the anode is the conductive substrate, the cathode comprises a metal.
In some embodiments, the metal is selected from any one of silver, gold, aluminum, or any combination thereof.
In some embodiments, the material of the conductive substrate is selected from any one of Indium Tin Oxide (ITO), fluorine-doped tin oxide (FTO), or a combination thereof.
In some embodiments, the cathode modification layer comprises a metal oxide. In some embodiments, the metal oxide is selected from ZnO, tiO 2 And SnO 2 Any one of them or any combination thereof.
In some embodiments, the interface-modifying layer comprises a conductive polymer. In some embodiments, the conductive polymer is selected from any one or combination of PFN-Br and PFN.
In some embodiments, the hole-collecting layer comprises MoO 3 、WO 3 Neutral PDEOT, and poly 3, 4-ethylenedioxythiophene: PSS or any combination thereof.
In some embodiments, the electron collection layer comprises zinc oxide nanoparticles, PFN, tiO 2 Any one of them or any combination thereof.
In some embodiments, the anode modification layer comprises MoO 3 、V 2 O 5 Or WO 3 Any one of them or any combination thereof.
In some embodiments, the solar cell comprises the following structures stacked in sequence: the battery comprises a conductive cathode substrate, a cathode modification layer, an interface modification layer, an active layer containing F-M, a hole collection layer, an electron collection layer, another active layer, an anode modification layer and an anode, wherein the first battery active layer and the second battery active layer comprise the active layer containing F-M, the hole collection layer, the electron collection layer, the another active layer, the anode modification layer and the anode.
In some embodiments, the solar cell comprises the following structures stacked in sequence: the battery comprises a conductive cathode substrate, a cathode modification layer, an interface modification layer, a front battery active layer, a hole collection layer, an electron collection layer, a rear battery active layer, an anode modification layer and an anode.
In some embodiments, the conductive cathode substrate is made of a material selected from Indium Tin Oxide (ITO).
In some embodiments, the cathode modification layer comprises ZnO nanoparticles.
In some embodiments, the interface-modifying layer comprises PFN-Br.
In some embodiments, the front cell active layer comprises PBDB-T and F-M. In some embodiments, the PBDB-T: the mass ratio of F to M is 1;
in some embodiments, the hole-collecting layer comprises poly 3, 4-ethylenedioxythiophene: PSS, namely polystyrene sulfonate PEDOT.
In some embodiments, the electron collection layer comprises zinc oxide nanoparticles.
In some embodiments, the rear battery active layer comprises PTB7-Th, O6T-4F and PC 71 And (4) BM. In some embodiments, PTB7-Th: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 1:0-1.5:0-1.5.
In some embodiments, the anode modification layer comprises MoO 3 。
In some embodiments, the anode comprises silver.
In some embodiments, the cathode modification layer has a thickness of from about 10nm to about 40nm, or from about 15nm to about 30nm.
In some embodiments, the interface-modifying layer has a thickness of from about 5nm to about 15nm, or from about 8nm to about 12nm.
In some embodiments, the active layer comprising F-M of the first and second battery active layers has a thickness of about 120nm to about 200nm, or about 140nm to about 160nm.
In some embodiments, the hole-collecting layer has a thickness of about 40nm to about 65nm, or about 45nm to about 55nm.
In some embodiments, the electron-collecting layer has a thickness of from about 15nm to about 50nm, or from about 15nm to about 30nm.
In some embodiments, the thickness of the further active layer is from about 90nm to about 120nm, or from about 100nm to about 115nm.
In some embodiments, the thickness of the anode modification layer is from about 3nm to about 15nm, or from about 5nm to about 10nm.
In some embodiments, the anode has a thickness of about 65nm to about 120nm, or about 70nm to about 100nm.
In another aspect, the present application provides a method of making a solar cell comprising a first cell active layer and a second cell active layer, wherein one of the first cell active layer and the second cell active layer comprises an acceptor material F-M and the other of the two active layers comprises an acceptor material selected from the group consisting of: O6T-4F, PC 71 Any one of or a combination of BMs; the preparation method comprises the following stepsThe method comprises the following steps:
and respectively mixing the receptor materials respectively used for the first battery active layer and the second battery active layer with a solvent to form two mixed solutions, and respectively carrying out spin coating on the two mixed solutions to obtain the first battery active layer and the second battery active layer.
In some embodiments of the preparation method, the solvent is selected from any one of chlorobenzene, chloroform, o-dichlorobenzene, and dichloromethane, or any combination thereof.
In some embodiments of the method of making, the mixed liquor further comprises an additive selected from the group consisting of: any one of 1, 8-diiodooctane, chloronaphthalene, methylnaphthalene, mercaptonaphthalene, 1, 8-octanedithiol, phenylnaphthalene or any combination thereof.
In some embodiments of the method of making, the additive is present in a volume fraction of 0.1% to 2% or 0.2% to 1% relative to the solvent.
In some embodiments of the method of making, when the first cell-active layer and the second cell-active layer further comprise at least one donor material, the total concentration of donor material and acceptor material in the mixed liquor is 16mg/mL to 25mg/mL or 18mg/mL to 22mg/mL.
In some embodiments of the method of making, the solar cell further comprises one or more of a cathode, a cathode modification layer, an interface modification layer, a hole collection layer, an electron collection layer, an anode modification layer, and an anode, wherein optionally the cathode is the conductive substrate or the anode is the conductive substrate; and wherein:
when the cathode is used as a conductive substrate, all the layers except the anode modification layer and the anode are prepared by evaporation, and all the other layers are prepared by adopting a spin-coating method;
when the anode is used as a conductive substrate, all the layers except the cathode modification layer and the cathode are prepared by evaporation, and all the other layers are prepared by adopting a spin-coating method.
In some embodiments of the method of making, the method of making comprises the steps of:
carrying out surface pretreatment on the conductive cathode substrate;
forming a cathode modification layer on the surface of the conductive cathode substrate through spin coating;
forming an interface modification layer on the cathode modification layer through spin coating;
forming an F-M-containing active layer of the first and second battery active layers by spin coating on the interface-modifying layer, in some embodiments, as a pre-battery active layer;
forming a hole collecting layer on the active layer including F-M by spin coating;
forming an electron collection layer on the hole collection layer by spin coating;
forming the further active layer on the electron collection layer by spin coating, in some embodiments as a post-cell active layer;
forming an anode modification layer on the other active layer by evaporation;
and forming an anode layer on the anode modifying layer by evaporation.
In some embodiments of the method of making, the step of forming a cathode modification layer comprises: will be selected from ZnO, tiO 2 And SnO 2 A precursor solution of a metal oxide (e.g., znO nanoparticles) of any one or any combination thereof is spin-coated on a conductive cathode substrate to obtain the cathode modification layer. In some embodiments, the spin coating is followed by a thermal annealing treatment. In some embodiments, the thermal annealing treatment step comprises heating at 150 ℃ to 200 ℃ for 30min to 60min.
In some embodiments of the method of making, the step of forming an interface-modifying layer comprises: and spin-coating a solution of a conductive polymer (such as PFN-Br) selected from any one of PFN-Br and PFN or a combination thereof in a solvent (such as methanol) selected from any one of methanol, isopropanol and ethanol or a combination thereof on the cathode modification layer. In some embodiments, the concentration of the conducting polymer in the solution is from 0.5mg/mL to 1.5mg/mL.
In some embodiments of the method of making, the step of forming the active layer comprising F-M comprises: and mixing a mixture of a donor material (such as PBDB-T) selected from any one of PBDB-T, PBDB-TF, J52-2F and PDBT-T1 or a combination thereof and F-M with a solvent to form a mixed solution, and spin-coating the mixed solution on the interface modification layer to obtain the active layer containing F-M. In some embodiments, the donor material in the mixed liquor: the mass ratio of F to M is 1.6-1.4, or 1.
In some embodiments of the method of making, the step of making the hole-collecting layer comprises: will be selected from MoO 3 、WO 3 Neutral PDEOT, and poly 3, 4-ethylenedioxythiophene: and a mixed solution of a hole collection layer material (such as PEDOT: PSS) of any one or any combination of PEDOT: PSS serving as polystyrene sulfonate and a solvent (such as isopropanol) selected from isopropanol, methanol and ethanol or any combination of isopropanol and the like is spin-coated on the surface of the active layer containing the F-M to obtain the hole collection layer. In some embodiments, the spin coating is followed by a thermal annealing treatment. In some embodiments, the thermal annealing treatment step comprises heating at 80 ℃ to 150 ℃ for 5min to 30min. In some embodiments, the volume ratio of the hole collection layer material (e.g., PEDOT: PSS) to the solvent is 1.
In some embodiments of the method of making, the step of making the electron collecting layer comprises: selected from zinc oxide nano particles, PFN, tiO 2 A solution of an electron collecting layer material (e.g., zinc oxide nanoparticles) in a solvent (e.g., n-butanol) selected from any one of n-butanol, methanol, isopropanol, or any combination thereof is spin coated on the surface of the hole collecting layer to obtain the electron collecting layer. In some embodiments, the spin coating is followed by a thermal annealing treatment. In some embodiments, the thermal annealing step comprises heating at 80 ℃ to 150 ℃ for 5min to 30min. In some embodiments, the electron collection layer has a thickness of about 15nm to about 50nm.
In some embodiments of the method of making, the step of forming the additional active layer comprisesComprises the following steps: and mixing a donor material selected from PTB7-Th and an acceptor material selected from any one of O6T-4F and PC71BM or a combination thereof with a solvent to form a mixed solution, and spin-coating the mixed solution on the electron collection layer to form the other active layer. In some embodiments, the donor material PTB7-Th in the mixed liquor: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 1:0-1.5:0-1.5.
In some embodiments of the method of making, the step of forming an anode modification layer comprises: depositing a material selected from the group consisting of: moO 3 、V 2 O 5 Or WO 3 Any one of them or any combination of them, to obtain the anode modification layer.
In some embodiments of the method of making, the step of forming the anode comprises: and (2) evaporating and plating a metal material selected from the following metal materials on the surface of the anode modification layer: any one of silver, gold, aluminum or any combination thereof to obtain the anode.
In yet another aspect, the present application provides a solar cell fabricated according to the fabrication method of the present disclosure.
Drawings
Fig. 1 is a schematic diagram of an exemplary tandem solar cell in example 1.
FIG. 2 is PBDB-T: F-M and PTB7-Th: O6T-4F 71 Ultraviolet-visible absorption spectrum of BM in the thin film state.
Fig. 3 is a current density-voltage curve of the solar cell device in example 1.
Detailed Description
Definition of
The following definitions and methods are provided to better define the present application and to guide those of ordinary skill in the art in the practice of the present application. Unless otherwise indicated, terms are to be understood in accordance with their ordinary usage by those of ordinary skill in the relevant art. All patent documents, academic papers, and other publications cited herein are incorporated by reference in their entirety.
The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
Unless specifically stated otherwise, the terms "first," "second," and the like, as used herein, do not denote any particular quantity or order, but rather are used to distinguish one element from another.
The term "double-junction solar cell" used herein refers to two solar subcells made of semiconductor materials with different bandwidths selected in different wave bands according to the solar spectrum, and finally the subcells are connected in series to form the double-junction solar cell.
The term "multijunction solar cell" used herein refers to a plurality (more than two) solar sub-cells made of semiconductor materials with different bandwidths selected in different bands according to the solar spectrum, and finally the sub-cells are connected in series to form a multijunction solar cell.
The term "front cell" as used herein refers to a sub-cell in a tandem cell that utilizes light of a shorter wavelength. The term "front cell active layer" refers to the active layer of the front cell as defined above.
The term "back cell" as used herein refers to a sub-cell in a stacked cell that utilizes light of a longer wavelength. The term "rear cell active layer" refers to the active layer of the rear cell as defined above.
The term "chlorobenzene" as used herein is a compound formed by the replacement of one hydrogen of benzene by a chlorine atom.
The term "poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS) "is a mixture containing poly (3, 4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonate (PSS), and aqueous solutions having different conductivities can be obtained according to different formulations, and includes PEDOT: PSS 4083, PH1000, PH500 (trade name), and the like.
The term "F-M" as used herein refers to a compound having the structure shown below, which can be prepared by reference (Y. Zhang, et al, nonfullene random organic solar cells with a high performance of 14.11%. Adv Mater 30,1707508 (2018)) or by other known methods.
Figure BDA0003812054710000091
The term "O6T-4F" as used herein refers to a compound having the structure shown below, which is referenced (Z. Xiao, et al,26mA cm) -2 Jsc from organic solar cells with a low-band gap nonfullerene aceptor. Sci. Bull.62,1494-1496 (2017)) or by other known methods.
Figure BDA0003812054710000092
The term "PC" as used herein 71 BM "refers to a compound having the structure, which is commercially available or prepared by known methods.
Figure BDA0003812054710000093
The term "PBDB-T" as used herein refers to a compound having the structure, which is commercially available or prepared by known methods.
Figure BDA0003812054710000101
The term "PTB7-Th" as used herein refers to a compound having the structure (where R is 2-ethylhexyl) which may be prepared by reference to (S.Zhang, et al, side Chain Selection for Designing high efficiency polymeric Polymers with 2D-Conjugated structures. Macromolecules 47,4653-4659 (2014)) or by other known methods.
Figure BDA0003812054710000102
The term "PDBT-T1" as used herein refers to a compound having the structure, which is commercially available or prepared by known methods.
Figure BDA0003812054710000103
The term "PDBT-TF" as used herein refers to a compound having the structure, which is commercially available or prepared by known methods.
Figure BDA0003812054710000104
The term "J52-2F" as used herein refers to a compound having the structure, which is commercially available or prepared by known methods.
Figure BDA0003812054710000111
Where a range of numerical values is recited herein, the range includes the endpoints thereof, and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values within the stated range to the same extent as if each of those narrower ranges was explicitly recited. For example, a thickness of the electron collecting layer of about 15nm to about 50nm means that the thickness may be 15nm, 169m, 17nm,18nm,19nm,20nm,21nm,22nm,23nm,24nm,25nm,26nm,27nm,28nm,29nm,30nm,31nm,32nm,33nm,34nm,35nm,36nm,37nm,38nm,39nm,40nm,41nm,42nm,43nm,44nm,45nm,46nm,47nm,48nm,49nm,50nm, ranges formed therefrom, or the like.
As used herein, the term "about" means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact values, but may be approximate and/or greater or less than exact values to reflect tolerances, conversion factors, numerical rounding off, measurement error and the like, and other factors known to those of skill in the art. Generally, an amount, size, formulation, parameter, or other quantity or characteristic is "about" or "approximately" whether or not expressly stated to be such.
Detailed description of the embodiments
In one aspect, the present application provides a solar cell comprising a first cell active layer and a second cell active layer, wherein one of the first cell active layer and the second cell active layer comprises an acceptor material F-M and the other of the two active layers comprises an acceptor material selected from the group consisting of: O6T-4F, PC 71 Any one of BMs or combinations thereof.
In some embodiments, the solar cell is a double or multi-junction solar cell.
In some embodiments, the first and second battery active layers further comprise at least one donor material.
In some embodiments, the donor material in the first cell active layer and the donor material in the second cell active layer are each independently selected from any one of PBDB-T, PBDB-TF, PTB7-Th, J52-2F, PDBT-T1, or any combination thereof.
In some embodiments, the donor material in the F-M containing active layer in both the first and second cell active layers is selected from any one of PBDB-T, PBDB-TF, J52-2F, PDBT-T1, or a combination thereof, and the donor material in the other active layer is selected from PTB7-Th.
In some embodiments, the donor material in the F-M containing active layer in both the first and second cell active layers is PBDB-T and the donor material in the other active layer is PTB7-Th.
In some embodiments, the additional active layer comprises O6T-4F and PC 71 BM。
In some embodiments, in the active layer comprising F-M, a donor material (e.g., PBDB-T, PBDB-TF, etc.): the mass ratio of F-M is 1.6-1.4 (1.
In some embodiments, in the further active layer, a donor material (e.g., PTB 7-Th): O6T-4F: PC (personal computer) 71 The mass ratio of BM is 1:0-1.5:0-1.5 (e.g. 1.5.
In some embodiments, the active layer comprising F-M in both the first and second battery active layers serves as a front battery active layer, and the other active layer serves as a rear battery active layer.
In some embodiments, the solar cell further comprises one or more of a cathode, a cathode modification layer, an interface modification layer, a hole collection layer, an electron collection layer, an anode modification layer, and an anode.
In some embodiments, the cathode serves as a conductive substrate. In some embodiments, the anode serves as a conductive substrate.
In some embodiments, when the cathode is the conductive substrate, the anode comprises a metal.
In some embodiments, when the anode is the conductive substrate, the cathode comprises a metal.
In some embodiments, the metal is selected from any one of silver, gold, aluminum, or any combination thereof.
In some embodiments, the material of the conductive substrate is selected from any one of Indium Tin Oxide (ITO), fluorine-doped tin oxide (FTO), or a combination thereof.
In some embodiments, the cathode modification layer comprises a metal oxide. In some embodiments, the metal oxide is selected from ZnO, tiO 2 And SnO 2 Any one of them or any combination thereof.
In some embodiments, the interface-modifying layer comprises a conductive polymer. In some embodiments, the conductive polymer is selected from any one or combination of PFN-Br and PFN.
In some embodiments, theThe hole collecting layer comprises MoO 3 、WO 3 Neutral PDEOT, and poly 3, 4-ethylenedioxythiophene: PSS, or any combination thereof.
In some embodiments, the electron collection layer comprises zinc oxide nanoparticles, PFN, tiO 2 Any one of them or any combination thereof.
In some embodiments, the anode modification layer comprises MoO 3 、V 2 O 5 Or WO 3 Any one of them or any combination thereof.
In some embodiments, the solar cell comprises the following structure stacked in sequence: the battery comprises a conductive cathode substrate, a cathode modification layer, an interface modification layer, an active layer containing F-M, a hole collection layer, an electron collection layer, the other active layer, an anode modification layer and an anode, wherein the first battery active layer and the second battery active layer comprise the active layer containing F-M, the hole collection layer, the electron collection layer, the other active layer, the anode modification layer and the anode.
In some embodiments, the solar cell comprises the following structure stacked in sequence: the anode comprises a conductive cathode substrate, a cathode modification layer, an interface modification layer, a front battery active layer, a hole collection layer, an electron collection layer, a rear battery active layer, an anode modification layer and an anode.
In some embodiments, the conductive cathode substrate is made of a material selected from Indium Tin Oxide (ITO).
In some embodiments, the cathode modification layer comprises ZnO nanoparticles.
In some embodiments, the interface-modifying layer comprises PFN-Br.
In some embodiments, the front cell active layer is an active layer comprising PBDB-T and F-M in both the first cell active layer and the second cell active layer. In some embodiments, the PBDB-T: the mass ratio of F to M is 1.6-1.4, or 1.
In some embodiments, the hole-collecting layer comprises poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS, e.g., PEDOT: PSS 4083).
In some embodiments, the electron collection layer comprises zinc oxide nanoparticles.
In some embodiments, the post-battery active layer comprises PTB7-Th, O6T-4F and PC in both the first and second battery active layers 71 The other active layer of BM. In some embodiments, PTB7-Th: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 0-1.5:0-1.5 (e.g., 1.
In some embodiments, the anode modification layer comprises MoO 3 。
In some embodiments, the anode comprises silver.
In some embodiments, the cathode modification layer has a thickness of from about 10nm to about 40nm (e.g., 10nm, 111nm, 12nm,13nm,14nm,15nm, 116nm, 17nm,18nm,19nm,20nm, 211nm, 22nm,23nm,24nm,25nm,26nm,27nm,28nm,29nm,30nm,31nm,32nm,33nm,34nm,35nm,36nm,37nm,38nm,39nm, or 40nm, etc.), or from about 15nm to about 30nm.
In some embodiments, the interface-modifying layer has a thickness of from about 5nm to about 15nm (e.g., 5nm,6nm,7nm,8nm,9nm,10nm, 1nm,12nm,13nm,14nm, or 15nm, etc.), or from about 8nm to about 12nm.
In some embodiments, the thickness of the active layer comprising F-M in the first and second battery active layers is from about 120nm to about 200nm (e.g., 120nm,130nm,140nm,150nm,160nm,170nm,180nm,190nm, or 200nm, etc.), or from about 140nm to about 160nm.
In some embodiments, the hole-collecting layer has a thickness of from about 40nm to about 65nm (e.g., 40nm,41nm,42nm,43nm,44nm,45nm,46nm,47nm,48nm,49nm,50nm,51nm,52nm,53nm,54nm,55nm,56nm,57nm,58nm,59nm,60nm,61nm,62nm,63nm,64nm, or 65nm, etc.), or from about 45nm to about 55nm.
In some embodiments, the electron collection layer has a thickness of from about 15nm to about 50nm (e.g., 15nm, 169m, 17nm,18nm,19nm,20nm,21nm,22nm,23nm,24nm,25nm,26nm,27nm,28nm,29nm,30nm,31nm,32nm,33nm,34nm,35nm,36nm,37nm,38nm,39nm,40nm,41nm,42nm,43nm,44nm,45nm,46nm,47nm,48nm,49nm,50nm, etc.), or from about 15nm to about 30nm.
In some embodiments, the thickness of the further active layer is from about 90nm to about 120nm (e.g., 90nm,95nm,100nm,105nm,110nm,115nm, or 120nm, etc.), or from about 100nm to about 115nm.
In some embodiments, the thickness of the anode modification layer is from about 3nm to about 15nm (e.g., 3nm,4nm,5nm,6nm,7nm,8nm,9nm,10nm, 112nm, 13nm,14nm, or 15nm, etc.), or from about 5nm to about 10nm.
In some embodiments, the anode has a thickness of about 65nm to about 120nm (e.g., 65nm,70nm,75nm,80nm,85nm,90nm,95nm,100nm,105nm,110nm,115nm, or 120nm, etc.), or about 70nm to about 100nm.
In another aspect, the present application provides a method of making a solar cell comprising a first cell active layer and a second cell active layer, wherein one of the first cell active layer and the second cell active layer comprises an acceptor material F-M and the other of the two active layers comprises an acceptor material selected from the group consisting of: O6T-4F, PC 71 Any one of or a combination of BMs; the preparation method comprises the following steps:
acceptor materials (e.g., F-M, or O6T-4F with PC) to be used in the first and second battery active layers, respectively 71 BM mixture) are mixed with a solvent (e.g., chlorobenzene, chloroform, etc.) to form two mixed solutions, and the two mixed solutions are spin-coated to form a first battery active layer and a second battery active layer, respectively.
In some embodiments of the preparation method, the solvent is selected from any one of chlorobenzene, chloroform, o-dichlorobenzene, and dichloromethane, or any combination thereof.
In some embodiments of the method of making, the mixed liquor further comprises an additive selected from the group consisting of: 1, 8-diiodooctane, chloronaphthalene, methylnaphthalene, mercaptonaphthalene, 1, 8-octanedithiol, phenylnaphthalene, or any combination thereof.
In some embodiments of the method of making, the additive is present in a fraction by volume relative to the solvent of 0.1% to 2% (e.g., 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2.0%, etc.), or 0.2% to 1%.
In some embodiments of the methods of making, when the first and second battery active layers further comprise at least one donor material, the total concentration of donor material and acceptor material in the mixed liquor is 16mg/mL to 25mg/mL (e.g., 16mg/mL, 17mg/mL, 18mg/mL, 19mg/mL, 20mg/mL, 21mg/mL, 22mg/mL, 23mg/mL, 24mg/mL, or 25mg/mL, etc.), or 18mg/mL to 22mg/mL.
In some embodiments of the method of making, the solar cell further comprises one or more of a cathode, a cathode modification layer, an interface modification layer, a hole collection layer, an electron collection layer, an anode modification layer, and an anode, wherein optionally the cathode is used as a conductive substrate or the anode is used as a conductive substrate; and wherein:
when the cathode is used as a conductive substrate, all the layers except the anode modification layer and the anode are prepared by evaporation, and all the other layers are prepared by adopting a spin coating method;
when the anode is used as a conductive substrate, all the layers except the cathode modification layer and the cathode are prepared by evaporation, and all the other layers are prepared by adopting a spin-coating method.
In some embodiments of the method of making, the method of making comprises the steps of:
performing surface pretreatment on the conductive cathode substrate;
forming a cathode modification layer on the surface of the conductive cathode substrate through spin coating;
forming an interface modification layer on the cathode modification layer through spin coating;
forming an F-M-containing active layer of the first and second battery active layers by spin coating on the interface-modifying layer, in some embodiments, as a pre-battery active layer;
forming a hole-collecting layer on the active layer including F-M by spin coating;
forming an electron collection layer on the hole collection layer by spin coating;
forming the further active layer on the electron collection layer by spin coating, in some embodiments as a post-cell active layer;
forming an anode modification layer on the other active layer by evaporation;
and forming an anode layer on the anode modifying layer by evaporation.
In some embodiments of the method of making, the step of pre-treating the surface of the conductive substrate comprises: the conductive substrate (e.g., indium tin oxide glass ITO) is washed with deionized water and an organic solvent (e.g., acetone, isopropyl alcohol, etc.) (e.g., under ultrasonic conditions) and blown dry with nitrogen and optionally subsequently treated in an ultraviolet ozone cleaner.
In some embodiments of the method of making, the step of forming a cathode modification layer comprises: will be selected from ZnO and TiO 2 And SnO 2 Spin-coating a precursor solution of a metal oxide (such as ZnO nanoparticles) of any one or any combination thereof on a conductive cathode substrate to obtain the cathode modification layer; in some embodiments, the spin coating is followed by a thermal annealing treatment. In some embodiments, the thermal annealing step comprises heating at 150 ℃ to 200 ℃ for 30min to 60min. In some embodiments, the cathode modification layer has a thickness of from about 10nm to about 40nm, or from about 15nm to about 30nm.
In some embodiments of the method of making, the step of forming an interface-modifying layer comprises: and spin-coating a solution of a conductive polymer (such as PFN-Br) selected from any one of PFN-Br and PFN or a combination thereof in a solvent (such as methanol) selected from any one of methanol, isopropanol and ethanol or a combination thereof on the cathode modification layer. In some embodiments, the concentration of the conducting polymer in the solution is from 0.5mg/mL to 1.5mg/mL. In some embodiments, the interface-modifying layer has a thickness of about 5nm to about 15nm, or about 8nm to about 12nm.
In some embodiments of the method of making, the step of forming an active layer comprising F-M in both the first battery active layer and the second battery active layer (e.g., a previous battery active layer) comprises: a mixture of a donor material (e.g., PBDB-T) selected from any one or a combination of PBDB-T, PBDB-TF, J52-2F, PDBT-T1 and F-M is mixed with a solvent (i.e., any one or a combination of the aforementioned solvents for dispersing an acceptor material, such as chlorobenzene, chloroform, o-dichlorobenzene and dichloromethane) to form a mixed solution, and the mixed solution is spin-coated on the interface modification layer to obtain the active layer including F-M. In some embodiments, the donor material in the mixed liquor: the mass ratio of acceptor material F-M is 1. In some embodiments, the total concentration of donor material and acceptor material F-M in the mixed solution is 15mg/mL to 25mg/mL or 18mg/mL to 20mg/mL. In some embodiments, the volume fraction of additive (e.g., 1, 8-diiodooctane) in the mixed liquor relative to the solvent is from 0.1% to 0.5%. In some embodiments, the active layer comprising F-M has a thickness of about 120nm to about 200nm, or about 140nm to about 160nm.
In some embodiments of the method of making, the step of making the hole-collecting layer comprises: will be selected from MoO 3 、WO 3 Neutral PDEOT, and poly 3, 4-ethylenedioxythiophene: and a hole collection layer material (such as PEDOT: PSS, for example PEDOT: PSS 4083) of any one or any combination of the PEDOT: PSS and a solvent (such as isopropanol) selected from isopropanol, methanol and ethanol, or any one or any combination of the isopropanol and the solvent is spin-coated on the surface of the active layer containing the F-M to obtain the hole collection layer. In some embodiments, the volume ratio of the hole collection layer material (such as PEDOT: PSS, e.g. PEDOT: PSS 4083) to the solvent is from 1.5 to 2 (e.g. 1. In some embodiments, the spin coating is followed by a thermal annealing treatment. In some embodiments, the thermal annealing treatment step comprises annealing the wafer at a temperature of 80 ℃ to 150 ℃ (e.g., 80 ℃,85 ℃,90 ℃,95 ℃,100 ℃,105 ℃,110 ℃,115 ℃, 120 ℃, 125 ℃,130 ℃, 135 ℃,140 ℃, 145 ℃,150 ℃, or the like) Heating for 5min-30min (such as 5min, 8min, 10min, 15min, 18min, 20min, 25min, 28min or 30 min). In some embodiments, the hole-collecting layer has a thickness of about 40nm to about 65nm, or about 45nm to about 55nm.
In some embodiments of the method of making, the step of making the electron collecting layer comprises: selected from zinc oxide nano particles, PFN, tiO 2 A solution of an electron collecting layer material (e.g., zinc oxide nanoparticles) in a solvent (e.g., n-butanol) selected from any one of n-butanol, methanol, isopropanol, or any combination thereof is spin coated on the surface of the hole collecting layer to obtain the electron collecting layer. In some embodiments, the spin coating is followed by a thermal annealing treatment. In some embodiments, the thermal annealing treatment step comprises heating at 80 ℃ to 150 ℃ (e.g., 80 ℃,85 ℃,90 ℃,95 ℃,100 ℃,105 ℃,110 ℃,115 ℃, 120 ℃, 125 ℃,130 ℃, 135 ℃,140 ℃, 145 ℃, or 150 ℃, etc.) for 5min to 30min (e.g., 5min, 8min, 10min, 15min, 18min, 20min, 25min, 28min, or 30min, etc.). In some embodiments, the electron-collecting layer has a thickness of from about 15nm to about 50nm, or from about 15nm to about 30nm.
In some embodiments of the method of making, the step of forming the further active layer (e.g. a later battery active layer) comprises: a donor material selected from PTB7-Th and an acceptor material selected from any one or the combination of O6T-4F and PC71BM (such as O6T-4F and PC) 71 BM) is mixed with a solvent (i.e., any one or any combination of the aforementioned solvents for dispersing the acceptor material, such as chlorobenzene, chloroform, o-dichlorobenzene, and methylene chloride) to form a mixture, and the mixture is spin-coated onto the electron-collecting layer to form the further active layer. In some embodiments, the donor material in the mixed liquor: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 0-1.5:0-1.5 (e.g., 1. In some embodiments, the mixed solution includes donor material and acceptor material (e.g., O6T-4F and PC) 71 BM) is 15mg/mL to 25mg/mL or 18mg/mL to 20mg/mL. In some embodiments, the addition in the mixed liquorThe volume fraction of additive (e.g. 1, 8-diiodooctane, if any) relative to the solvent is 0.5% to 1.5%. In some embodiments, the thickness of the further active layer is from about 90nm to about 120nm, or from about 100nm to about 115nm.
In some embodiments of the method of making, the step of forming an anode modification layer comprises: depositing a material selected from the group consisting of: moO 3 Polyethylene oxide, niO, V 2 O 5 Or WO 3 Any one of or any combination thereof (e.g., moO) 3 ) And obtaining the anode modification layer. In some embodiments, the evaporation is at less than 2 x 10 - 4 Pa under vacuum. In some embodiments, the thickness of the anode modification layer is from about 3nm to about 15nm, or from about 5nm to about 10nm.
In some embodiments of the method of making, the step of forming the anode comprises: evaporating and plating a metal material selected from the following metal materials on the surface of the anode modification layer: any one of silver, gold, aluminum, or any combination thereof (e.g., silver), resulting in the anode. In some embodiments, the anode has a thickness of about 65nm to about 120nm, or about 70nm to about 100nm.
In yet another aspect, the present application provides a solar cell fabricated according to the fabrication method of the present disclosure.
The inventions of the present application provide one or more of the following advantages:
(1) The solar cell disclosed by the invention adopts non-fullerene molecules with complementary light absorption as acceptor materials in active layers of front and rear sub-cells, such as PBDB-T: F-M and PTB7-Th: O6T-4F 71 The ultraviolet-visible absorption spectra of BM are complementary, so that sunlight can be more fully utilized, and the solar cell device based on the two acceptor materials can obtain matched short-circuit current density of front and rear sub-cells, thereby obtaining high performance of the solar cell device. For example, in some embodiments, solar cell devices of the present disclosure can achieve a voltage of not less than 1.4V (e.g., 1.4V,1.45v,1.48v,1.5v,1.55V,1.58V,1.6V,1.62V,1.64V,1.67V,1.68V,1.7V,1.75V,1.8V,1.9V or 2.0V, etc.), an open circuit voltage of not less than 1.5V or not less than 1.6V. In some embodiments, the solar cell devices of the present disclosure have a short circuit current density of not less than 10mA/cm 2 (e.g., 10 mA/cm) 2 ，11mA/cm 2 ，12mA/cm 2 ，13mA/cm 2 ，14mA/cm 2 ，15mA/cm 2 ，16mA/cm 2 ，17mA/cm 2 Or 18mA/cm 2 Etc.), not less than 14mA/cm 2 Or not less than 17mA/cm 2 (ii) a The fill factor is 60% or more (e.g., 60%, 62%, 65%, 68%, 70%, 72%, 73%, 74%, 75%, 76%, or 80%, etc.), 70% or more, or 80% or more. In some embodiments, the solar cell devices of the present disclosure have an energy conversion efficiency of no less than 15% (e.g., 15%, 16%, 17%, 18%, 19%, 20%, 21%, or 22%, etc.), no less than 17%, or no less than 19%.
(2) In the preparation process of the solar cell disclosed by the disclosure, for example, except for the anode modification layer and the metal anode (when the cathode is used as a conductive substrate), the film of each layer is prepared by adopting a solution spin coating method, and the solvent is reasonably selected, so that each step of solution treatment is ensured not to erode and damage the lower layer, and the preparation method is beneficial to industrial printing production.
Examples
The following examples are for the purpose of illustration only and are not intended to limit the scope of the present application.
Example 1:
the double-junction organic solar cell device comprises conductive cathode ITO glass, a zinc oxide cathode modification layer, a PFN-Br interface modification layer, a front cell active layer, a PEDOT (power of plant) PSS (hole System) collecting layer, a zinc oxide nano particle electron collecting layer, a rear cell active layer, moO (molybdenum oxide) and a metal oxide semiconductor) layer, wherein the conductive cathode ITO glass is used for forming a double-junction organic solar cell device shown in figure 1 3 The anode modification layer and the silver anode form a laminated structure, and the thicknesses of the layers are respectively as follows: 120nm of ITO cathode, 15nm of zinc oxide nanoparticle cathode modification layer, 10nm of PFN-Br interface modification layer, 150nm of front battery active layer, 50nm of PEDOT (PSS hole collection layer), 15nm of zinc oxide nanoparticle electron collection layer and 110nm of rear battery active layernm、MoO 3 The anode modification layer is 6nm, and the silver anode is 70nm.
The preparation method of the double-junction organic solar cell device comprises the following steps:
1) And (3) sequentially carrying out ultrasonic cleaning on Indium Tin Oxide (ITO) glass by using a detergent, deionized water, acetone and an isopropanol solvent for 15 minutes respectively, taking out the ITO glass, drying the ITO glass by using a nitrogen gun, and treating the ITO glass in an ultraviolet ozone cleaning machine for 20 minutes.
2) Spin-coating zinc oxide nanoparticle cathode modification layer on pretreated ITO glass
Preparing a precursor solution of zinc oxide nano particles, spin-coating the precursor solution on the conductive cathode substrate to form a film with the thickness of about 15nm, and then performing thermal annealing treatment on the film for 60 minutes at 200 ℃ on a heating plate.
3) Forming an interface modification layer on the cathode modification layer by spin coating
A1 mg/mL methanol solution of PFN-Br was spin coated on the cathode modification layer to a thickness of about 10nm.
4) Spin coating a pre-cell active layer on the cathode modification layer
Preparing a mixture of PBDB-T and F-M with the mass ratio of 1.
5) Spin coating PEDOT PSS hole-collecting layer on the front cell active layer
And (3) spin-coating PEDOT: PSS 4083 and isopropanol in a volume ratio of 1.
6) Spin coating zinc oxide nanoparticles electron collection layer on the front hole collection layer
Spin coating the n-butanol solution of zinc oxide nanoparticles on the active layer of the front battery, and heating at 120 deg.C for 20min to form a film of about 15nm.
7) Spin coating a post-cell active layer on the hole-collecting layer
Preparing a mixture of PTB7-Th: O6T-4F.
8) Placing the substrate in a vacuum chamber with a pressure below 2 × 10 -4 Pa, 6nm of MoO vapor-deposited 3 And forming an anode modification layer.
9) Then, the preparation of the device is finished by evaporating 70nm silver anode, and the area of the device is about 4mm 2 。
In standard sunlight (AM 1.5G, 100mW/cm) 2 ) The device performance was tested using a computer controlled Keithley 2400 digital source meter under irradiation conditions, with the performance parameters listed in table 1 below.
Table 1: non-fullerene acceptor double junction device performance parameters
Figure BDA0003812054710000211
a The data in parentheses are the best values for multiple measurements, and the data outside parentheses are the average values for multiple measurements.
FIG. 3 shows the non-fullerene acceptor double-junction organic solar cell device of example 1 in standard sunlight (AM 1.5G,100mW cm) -2 ) The current density-voltage curves measured under irradiation conditions show: the device can obtain higher open-circuit voltage reaching 1.642V and short-circuit current density reaching 14.35mA/cm 2 The filling factor is 73.7%, and the energy conversion efficiency reaches 17.36%.
While the invention has been described in detail by way of the general description and the specific embodiments, it will be apparent to those skilled in the art that certain modifications or improvements may be made in the invention and any combination may be made as required. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.

Claims (10)

1. A solar cell comprising a first cell active layer and a second cell active layer, wherein one of the first and second cell active layers comprises an acceptor material F-M and the other of the two active layers comprises an acceptor material selected from the group consisting of: O6T-4F, PC 71 Any one of BM or a combination thereof.
2. The composite material of claim 1, wherein:
optionally, the solar cell is a double or multijunction solar cell;
optionally, the further active layer comprises O6T-4F and PC 71 BM；
Optionally, the first and second cell active layers further comprise at least one donor material, and optionally, the donor material in the first cell active layer and the donor material in the second cell active layer are each independently selected from any one of PBDB-T, PBDB-TF, PTB7-Th, J52-2F, PDBT-T1, or any combination thereof;
optionally, the donor material in the active layer comprising F-M in both the first and second cell active layers is selected from any one or combination of PBDB-T, PBDB-TF, J52-2F, PDBT-T1, and the donor material in the other active layer is selected from PTB7-Th;
optionally, the donor material in the F-M containing active layer in both the first and second cell active layers is selected from PBDB-T and the donor material in the other active layer is selected from PTB7-Th;
optionally, in the active layer comprising F-M, the donor material: the mass ratio of F to M is 1;
optionally, in the further active layer, the donor material: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 1:0-1.5:0 to 1.5;
optionally, the active layer comprising F-M in both the first and second battery active layers serves as a front battery active layer, and the other active layer serves as a rear battery active layer.
3. The composite material of claim 1 or 2, wherein:
optionally, the solar cell further comprises one or more of a cathode, a cathode modification layer, an interface modification layer, a hole collection layer, an electron collection layer, an anode modification layer, and an anode;
optionally, the cathode serves as a conductive substrate, or the anode serves as a conductive substrate;
optionally, when the cathode is the conductive substrate, the anode comprises a metal;
optionally, when the anode is used as a conductive substrate, the cathode comprises a metal;
optionally, the metal is selected from any one of silver, gold, aluminum or any combination thereof;
optionally, the material of the conductive substrate is selected from any one of Indium Tin Oxide (ITO) and fluorine-doped tin oxide (FTO), or a combination thereof.
Optionally, the cathode modification layer comprises a metal oxide, and optionally, the metal oxide is selected from ZnO, tiO 2 And SnO 2 Any one or any combination thereof;
optionally, the interface modification layer comprises a conductive polymer, and optionally, the conductive polymer is selected from any one or a combination of PFN-Br and PFN;
optionally, the hole-collecting layer comprises MoO 3 、WO 3 Neutral PDEOT, and poly 3, 4-ethylenedioxythiophene: PSS, PSS or any combination thereof;
optionally, the electron collecting layer comprises zinc oxide nanoparticles, PFN, tiO 2 Any one or any combination thereof;
optionally, the anode modification layer comprises MoO 3 、V 2 O 5 Or WO 3 Any one of them or any combination thereof.
4. The composite material of claim 3, wherein:
optionally, the solar cell comprises the following structure stacked in sequence: the conductive cathode substrate, the cathode modification layer, the interface modification layer, the active layer comprising F-M, the hole collection layer, the electron collection layer, the other active layer, the anode modification layer and the anode in the first battery active layer and the second battery active layer;
optionally, the solar cell comprises the following structure stacked in sequence: the battery comprises a conductive cathode substrate, a cathode modification layer, an interface modification layer, a front battery active layer, a hole collection layer, an electron collection layer, a rear battery active layer, an anode modification layer and an anode;
optionally, the conductive cathode substrate is made of Indium Tin Oxide (ITO);
optionally, the cathode modification layer comprises ZnO nanoparticles;
optionally, the interface-modifying layer comprises PFN-Br;
optionally, the front cell active layer comprises PBDB-T and F-M; and optionally, PBDB-T: the mass ratio of F to M is 1;
optionally, the hole-collecting layer comprises poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate PEDOT PSS;
optionally, the electron collection layer comprises zinc oxide nanoparticles;
optionally, the rear cell active layer comprises PTB7-Th, O6T-4F and PC 71 BM; and optionally, PTB7-Th: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 1:0-1.5:0 to 1.5;
optionally, the anode modification layer comprises MoO 3 ；
Optionally, the anode comprises silver;
optionally, the cathode modification layer has a thickness of about 10nm to about 40nm, or about 15nm to about 30nm;
optionally, the interface-modifying layer has a thickness of from about 5nm to about 15nm, or from about 8nm to about 12nm;
optionally, the thickness of the active layer comprising F-M of the first and second battery active layers is from about 120nm to about 200nm, or from about 140nm to about 160nm;
optionally, the hole-collecting layer has a thickness of about 40nm to about 65nm, or about 45nm to about 55nm;
optionally, the electron collection layer has a thickness of about 15nm to about 50nm, or about 15nm to about 30nm;
optionally, the further active layer has a thickness of about 90nm to about 120nm, or about 100nm to about 115nm;
optionally, the thickness of the anode modification layer is from about 3nm to about 15nm, or from about 5nm to about 10nm;
optionally, the anode has a thickness of about 65nm to about 120nm, or about 70nm to about 100nm.
5. A method of manufacturing a solar cell comprising a first cell active layer and a second cell active layer, wherein one of the first cell active layer and the second cell active layer comprises an acceptor material F-M and the other of the two active layers comprises an acceptor material selected from the group consisting of: O6T-4F, PC 71 Any one of or a combination of BMs;
the preparation method comprises the following steps:
and respectively mixing the receptor materials respectively used for the first battery active layer and the second battery active layer with a solvent to form two mixed solutions, and respectively carrying out spin coating on the two mixed solutions to obtain the first battery active layer and the second battery active layer.
6. The production method according to claim 5, wherein:
optionally, the solvent is selected from any one or any combination of chlorobenzene, chloroform, o-dichlorobenzene and dichloromethane;
optionally, the mixed solution further comprises an additive selected from the following: any one of 1, 8-diiodooctane, chloronaphthalene, methylnaphthalene, mercaptonaphthalene, 1, 8-octanedithiol and phenylnaphthalene or any combination thereof; and optionally, the volume fraction of the additive relative to the solvent is 0.1% to 2% or 0.2% to 1%;
optionally, when the first cell active layer and the second cell active layer further comprise at least one donor material, the total concentration of the donor material and the acceptor material in the mixed solution is 16mg/mL to 25mg/mL or 18mg/mL to 22mg/mL.
7. The method according to claim 5 or 6, wherein the solar cell further comprises one or more of a cathode, a cathode modification layer, an interface modification layer, a hole collection layer, an electron collection layer, an anode modification layer, and an anode; wherein optionally the cathode or the anode is used as a conductive substrate; and wherein:
when the cathode is used as a conductive substrate, all the layers except the anode modification layer and the anode are prepared by evaporation, and all the other layers are prepared by adopting a spin coating method;
when the anode is used as a conductive substrate, all the layers except the cathode modification layer and the cathode are prepared by evaporation, and all the other layers are prepared by adopting a spin coating method.
8. The method of claim 7, comprising the steps of:
performing surface pretreatment on the conductive cathode substrate;
forming a cathode modification layer on the surface of the conductive cathode substrate through spin coating;
forming an interface modification layer on the cathode modification layer through spin coating;
forming an active layer containing F-M in the first battery active layer and the second battery active layer on the interface modification layer through spin coating; wherein optionally, the active layer comprising F-M is used as a front cell active layer;
forming a hole collecting layer on the active layer including F-M by spin coating;
forming an electron collection layer on the hole collection layer by spin coating;
forming the further active layer on the electron collecting layer by spin coating, wherein optionally the further active layer acts as a post-cell active layer;
forming an anode modification layer on the other active layer by evaporation;
and forming an anode layer on the anode modifying layer by evaporation.
9. The production method according to claim 7 or 8, wherein:
optionally, the step of forming a cathode modification layer comprises: will be selected from ZnO, tiO 2 And SnO 2 Spin-coating a precursor solution of a metal oxide of any one or any combination of the metal oxide on a conductive cathode substrate to obtain the cathode modification layer; wherein optionally, a thermal annealing treatment is performed after the spin coating; and optionally, the thermal annealing treatment comprises heating at 150-200 ℃ for 30-60 min.
Optionally, the step of forming an interface-modifying layer comprises: and spin-coating a solution of a conductive polymer selected from any one of PFN-Br and PFN or a combination thereof in a solvent selected from any one of methanol, isopropanol and ethanol or a combination thereof on the cathode modification layer. Wherein optionally, the concentration of the conducting polymer in the solution is 0.5mg/mL to 1.5mg/mL;
optionally, the step of forming the active layer comprising F-M comprises: mixing a mixture of a donor material selected from any one of PBDB-T, PBDB-TF, J52-2F and PDBT-T1 or any combination of the PBDB-T, the J52-2F and the PDBT-T1 and a solvent to form a mixed solution, and spin-coating the mixed solution on the interface modification layer to obtain the active layer containing the F-M; wherein optionally, the donor material in the mixed solution: the mass ratio of F to M is 1.
Optionally, the step of preparing the hole-collecting layer comprises: will be selected from MoO 3 、WO 3 Neutral PDEOT, and poly 3, 4-ethylenedioxythiophene: PSS and a solvent selected from isopropanol, methanol and ethanol, wherein the solvent comprises a mixed solution of a hole collecting layer material of any one or any combination of the polystyrene sulfonate PEDOT and the PSS and a solvent selected from isopropanol, methanol and ethanolF-M to obtain the hole collecting layer; wherein: optionally, performing a thermal annealing treatment after the spin coating; optionally, the thermal annealing treatment step comprises heating at 80-150 ℃ for 5-30 min; optionally, the volume ratio of the hole collecting layer material to the solvent is 1;
optionally, the step of preparing the electron collecting layer comprises: selected from zinc oxide nano particles, PFN, tiO 2 A solution of an electron collecting layer material of any one or any combination thereof in a solvent selected from any one or any combination of n-butanol, methanol, isopropanol is spin-coated on the surface of the hole collecting layer to obtain the electron collecting layer, wherein: optionally, performing a thermal annealing treatment after the spin coating; optionally, the thermal annealing treatment step comprises heating at 80-150 ℃ for 5-30 min; optionally, the electron-collecting layer has a thickness of about 15nm to about 50nm;
optionally, the step of forming the further active layer comprises: a donor material selected from PTB7-Th and a donor material selected from O6T-4F, PC 71 The acceptor material of any one of the BMs or the combination thereof is mixed with a solvent to form a mixed solution, and the mixed solution is spin-coated on the electron collection layer to form the other active layer; wherein optionally, the donor material in the mixed solution: O6T-4F: PC (personal computer) 71 The mass ratio of BM is 1:0-1.5:0 to 1.5;
optionally, the step of forming an anode modification layer comprises: depositing a material selected from the group consisting of: moO 3 、V 2 O 5 Or WO 3 Any one or any combination of them to obtain the anode modification layer;
optionally, the step of forming the anode comprises: and (2) evaporating and plating a metal material selected from the following metal materials on the surface of the anode modification layer: any one of silver, gold, aluminum or any combination thereof to obtain the anode.
10. A solar cell fabricated according to the fabrication method of any one of claims 5-9.
CN202211014695.XA 2018-06-29 2018-06-29 Solar cell and preparation method thereof Pending CN115498108A (en)

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