CN111668376A - Polymer solar cell comprising cathode interface layer and preparation method thereof - Google Patents

Polymer solar cell comprising cathode interface layer and preparation method thereof Download PDF

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CN111668376A
CN111668376A CN202010650285.9A CN202010650285A CN111668376A CN 111668376 A CN111668376 A CN 111668376A CN 202010650285 A CN202010650285 A CN 202010650285A CN 111668376 A CN111668376 A CN 111668376A
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pamam
layer
interface layer
solar cell
cathode
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杨上峰
张猛猛
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University of Science and Technology of China USTC
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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Abstract

The application discloses a polymer solar cell comprising a cathode interface layer and a preparation method thereof, wherein the number of terminal amino groups of the cathode interface layer satisfies 2n+2Of Polyamidoamine (PAMAM) branches, wherein the number M of terminal polyamidoamine branches of said n-generation dendrimer PAMAMn＝2n+2N is algebraic and is an integer equal to or greater than zero. Experimental results show that the PAMAM (G0) is introduced to be used as a cathode interface layer to form a smooth and uniform film, the work function of ITO can be reduced, the electron mobility is improved, the energy conversion efficiency of the polymer solar cell reaches 9.13%, and the energy conversion efficiency is higher than that of single ITO and ZnO used as the cathode interface layerThe efficiency of (c). In addition, the cathode interface material is simpler, more effective and lower in cost.

Description

Polymer solar cell comprising cathode interface layer and preparation method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a polymer solar cell comprising a cathode interface layer and a preparation method thereof.
Background
With the rapid development of the world economy and the dramatic increase in the global population, the demand for energy has been increasing. At present, human beings still rely on fossil energy, and fossil fuel is limited in storage, and burning brings a series of problems such as environmental pollution and global warming, so that the development of clean energy is an effective way for realizing sustainable development. Solar energy is an inexhaustible resource, has the advantages of cleanness, no pollution, safety, reliability and the like, and attracts wide attention in the solar cell technology for converting solar energy into electric energy.
Polymer Solar Cells (PSCs) constructed with bulk heterojunctions attract more and more attention because they have features of low cost, light weight, flexibility, solution processibility and large area preparation, etc., and have a wide prospect in application. In order to further improve the device performance, great efforts have been made to develop new materials, interface engineering at the electrode interface, solvent engineering, and the like. Due to the fact that electrons generated by photon absorption of the photoactive layer need to be extracted to the cathode, extraction and transmission of the electrons can be effectively achieved by introducing a cathode interface layer between the cathode and the active layer. The cathode interface layer reduces the energy level potential barrier of electrons injected from the active layer to the electrode by reducing the work function of the cathode, so that the interface charge loss is reduced, and the energy conversion efficiency of the battery is improved. The conventional PSC device structure uses a low work function metal a1 as a cathode, PEDOT: the PSS layer is used as a cavity interface layer, and the ITO layer is used as an anode. However, due to the acidic PEDOT: the corrosion of the PSS layer to ITO and the rapid oxidation of the low work function metal cathode lead to rapid degradation of the cell under ambient conditions. To overcome these disadvantages, an inverted polymer solar cell is obtained using an air-stable high work function metal (e.g., Ag or Au) as the anode for hole collection and ITO as the cathode for electron collection, with greatly improved stability. However, a large energy barrier exists between the work function of ITO (about 4.7eV) and the LUMO level of the n-type fullerene material in the active layer (4.0eV), hindering the extraction process of electrons. Thus, different kinds of materials are applied to the cathode interfacial layer. Among them, ZnO is widely used because of its high electron mobility and visible light transparency. However, the preparation of high quality ZnO generally requires optimization of the sol-gel process, requires high temperature sintering for a long time, and is not suitable for flexible preparation and large-scale industrial processes. Therefore, it is necessary to develop a new cathode interfacial layer which is easy to process and can replace ZnO.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a cathode interface layer that can replace ZnO, and to provide a polymer solar cell that is low in cost, high in efficiency, and/or simple in manufacturing process by using such a cathode interface layer. The inventor of the invention expects that the PAMAM solution is coated on the surface of ITO to form a cathode interface layer, which not only can replace ZnO to be used for the cathode interface layer of a polymer solar cell, but also has simple process and lower cost.
Another object of the present invention is to provide a polymer solar cell comprising the cathode interface layer, wherein the cathode interface layer is composed of PAMAM layer, and PAMAM is a dendrimer composed of different branched polyamidoamine groups.
In a preferred embodiment, the PAMAM ends consist of 4 branched polyamide-amine groups (PAMAM (G0)).
In a preferred embodiment, the PAMAM ends consist of 8 branched polyamide-amine groups (PAMAM (G1)).
In a preferred embodiment, the PAMAM ends consist of 16 branched polyamide-amine groups (PAMAM (G2)).
In a preferred embodiment, the thickness of the PAMAM layer is 8-15 nm.
In another aspect, the present invention provides a method for preparing the above cathode interfacial layer, the method comprising:
the cathode interface layer was obtained by spin coating a solution of PAMAM on ITO to form a thin film of PAMAM layer.
In a preferred embodiment, the solution of PAMAM is a methanolic solution of PAMAM.
In a preferred embodiment, the thickness of the photoactive layer is 90 to 200 nm.
In a preferred embodiment, the present invention provides a polymer solar cell, comprising:
a transparent substrate;
a transparent electrode ITO as a cathode disposed on the substrate;
a cathode interface layer disposed on the cathode;
an active layer disposed on the cathode interfacial layer;
an anode interfacial layer disposed on the active layer; and
an anode disposed on the anode interfacial layer,
the preparation method is characterized in that the cathode interface layer is a dendritic macromolecular PAMAM layer consisting of branched polyamide-amine groups.
In a preferred embodiment, the PAMAM consists of 4 branched polyamide-amine groups (PAMAM (G0)).
In a preferred embodiment, the thickness of the PAMAM layer is 8-15 nm.
In a preferred embodiment, the transparent electrode ITO is indium tin oxide.
In a preferred embodiment, the photoactive layer is a photoactive layer consisting of a poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b' ] dithiophene-co-3-fluorothieno [3, 4-b ] thiophene-2-carboxylate ] and [6, 6] -phenylcarbon 71-butyric acid methyl ester.
In a preferred embodiment, the anode interfacial layer MoO3The thickness of (A) is 6-10 nm.
In a preferred embodiment, the anode is comprised of metallic silver.
In another aspect, the present invention provides a method for preparing the above polymer solar cell, the method comprising:
forming a PAMAM layer on the transparent electrode by coating PAMAM solution to obtain a cathode interface layer;
coating an active layer solution on the cathode interface layer to obtain an optical active layer;
forming an anode interface layer on the photoactive layer; and
and forming an anode on the anode interface layer to obtain the polymer solar cell.
In a preferred embodiment, the solution of PAMAM is a methanolic solution of PAMAM.
In a preferred embodiment, the photoactive layer is formed by coating a poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b' ] dithiophene-co-3-fluorothieno [3, 4-b ] thiophene-2-carboxylate ] and [6, 6] -phenylcarbon 71-butyric acid methyl ester.
In a preferred embodiment, the anodic interfacial layer is formed by evaporation or deposition of MoO on the photoactive layer3Thereby forming the composite material.
In a preferred embodiment, the anode is formed by evaporating or depositing metallic Ag as an anode on the anode interfacial layer.
In the invention, the PAMAM solution is coated on the ITO to form a PAMAM layer, and the PAMAM layer is used as a cathode interface layer to prepare a battery, so that the PAMAM solution can replace ZnO. The cost is very low in consideration of the advantages that the commercial dendritic macromolecule is low in price and extremely small in usage amount in the battery, and the film can be formed through a wet process without subsequent annealing, so that the cost of the cathode interface layer prepared by the method is low and the process is simple. In addition, polymer solar cells prepared using such cathode interfacial layers have energy conversion efficiencies comparable to or better than those of cells using ZnO or ITO alone.
Drawings
Fig. 1 is a schematic view of a polymer solar cell structure according to an embodiment of the present invention.
Fig. 2 is a current-voltage characteristic curve of polymer solar cells prepared according to examples of the present invention and comparative examples.
Fig. 3 is a current-voltage characteristic curve of polymer solar cells prepared according to examples of the present invention and comparative examples.
FIG. 4 is a current-voltage characteristic curve of polymer solar cells prepared according to examples of the present invention and comparative examples
Detailed Description
In order to solve the technical problems in the prior art, the present invention provides a polymer solar cell including a cathode interface layer and a method for preparing the same, that is, the present application proposes to use a dendrimer (PAMAM) including polyamide-amine groups having different numbers of branches as a cathode interface layer of a PSC. The cathode interface layer in the present invention is a PAMAM cathode interface layer obtained by coating a PAMAM solution on a cathode (e.g., an ITO electrode). PAMAM has a well-defined structure with terminal amino functionality, is well soluble in methanol, and provides orthogonal solubility in the preparation of multi-layered PSCs.
The term "PAMAM" means that the number of terminal amino groups satisfies 2n+2The n-generation dendritic macromolecule composed of polyamide-amine branched chain is shown as the general formula Mn＝2n+2，MnIs the number of n generations of polyamide-amine branches at the end of the dendrimer, n being the number of generations and an integer equal to or greater than zero. Without being limited by any theory, the applicant believes that when the amino functional group at the terminal of the PAMAM with the dendritic structure acts with ITO, the work function of the ITO can be effectively reduced, the energy level barrier for injecting electrons from the active layer to the electrode can be reduced, and the loss of interface charges can be reduced, so that the energy conversion efficiency of the battery can be improved. In view of synthesis technology, the upper limit of the number of generations n of PAMAM may be, for example, 10 or less, preferably 8 or less, more preferably 5 or less, and still more preferably 3 or less. In the present invention, PAMAM dendrimers of generation 0 (G0), generation 1 (G1) or generation 2 (G2) are preferably used, the specific structure of which is as follows:
Figure BDA0002571255470000051
accordingly, the present disclosure provides a polymer solar cell, generally comprising: the light-emitting diode comprises a substrate, and a cathode layer, a cathode interface layer, a light activity layer, an anode interface layer and an anode which are sequentially stacked on the substrate.
In the present disclosure, the substrate is not particularly limited, but is preferably a transparent substrate, and examples thereof may include glass, flexible substrate PET, PEN, and the like, for example.
In the present disclosure, the cathode layer is stacked on the substrate, and is not particularly limited, and for example, examples thereof may include transparent electrodes ITO, AZO, silver nanowires, and the like.
In the present disclosure, the photoactive layer is stacked on the cathode layer, and is not particularly limited, and examples thereof may preferably include poly 3-hexylthiophene (P3 HT): [6,6]Methyl 61 butyrate (PC) phenyl carbon61BM) mixed solution, poly [ (4, 8-bis- (2-ethylhexyloxy) -benzo (1, 2-b: 4, 5-b') dithiophene) -2, 6-diyl- (4- (2-ethylhexanoyl) -thieno [3, 4-b ]]Thiophene) -2-6-diyl](PBDTTT-C)：[6，6]-phenyl carbon 71 methyl butyrate (PC)71BM), poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters](PTB7-TH)：[6，6]-phenyl carbon 71-methyl butyrate mixed solution (PC)71BM) and the like, wherein the mass ratio of the two components is 10: 6-10: 10. But a preferred example thereof is a solar cell formed of poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters]And [6, 6]]-a mixture of phenyl carbon 71-methyl butyrate. For example, a coating of, for example, poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters]And [6, 6]]-phenyl carbon 71-methyl butyrate in chlorobenzene to obtain the photoactive layer.
In the present disclosure, the method for coating the cathode interfacial layer is not particularly limited, but a coating method of spin coating is preferred from the aspect of control of the film thickness.
In the present disclosure, the anode interfacial layer is disposed on the photoactive layer, and the anode is disposed on the anode interfacial layer. The anode interfacial layer and the anode are also not particularly limited. For example, an example of the anode interfacial layer may include MoO3PEDOT: PSS, etc., and examples of the anode may include Ag, Au, etc.
Thus, in one particular example, the solar cell provided by the present disclosure is a polymer solar cell comprising:
a transparent substrate and a transparent electrode ITO as a cathode disposed on the substrate;
a cathode interface layer PAMAM arranged on the transparent electrode ITO;
a photoactive layer disposed on the cathode interfacial layer;
an anode interface layer MoO disposed on the photoactive layer3(ii) a And
an anode disposed on the anode interface layer,
wherein the number of terminal amino groups of the cathode interface layer PAMAM satisfies 2n+2Wherein the number M of terminal polyamidoamine branches of the n-generation dendrimer PAMAM isn＝2n+2N is algebraic and is an integer equal to or greater than zero.
The present invention is described in detail below with reference to the attached drawings. It is to be understood that such description is for the purpose of illustrating the invention and is not to be taken in a limiting sense.
The present invention provides a polymer solar cell, as shown in fig. 1, which includes: the composite film comprises a substrate 6, an ITO transparent electrode 5 (as a cathode), a PAMAM layer 4 (as a cathode interface layer), a photoactive layer 3, an anode interface layer 2 and an anode 1 which are sequentially stacked, wherein the cathode interface layer 4 is a dendritic macromolecule PAMAM layer consisting of branched polyamide-amine groups. Preferably, the PAMAM layer is 8-15nm thick and consists of 4 branched polyamide-amine groups (PAMAM (G0)).
In a preferred embodiment of the present invention, substrate 6 is preferably a glass or transparent polymeric substrate such as a polyethylene terephthalate (PET) substrate. The transparent electrode 5 is preferably ITO. The PAMAM layer 4 is preferably composed of 4 branched polyamide-amine groups (PAMAM (G0)). The photoactive layer 3 is preferably poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters]And [6, 6]]-phenylcarboncarbon 71-methyl butyrate in chlorobenzene solution. The anode interface layer 2 is preferably MoO3. The anode 1 is preferably made of metallic silver.
In a preferred embodiment of the present invention, there is also provided a method for manufacturing a polymer solar cell, including:
coating the PAMAM solution on an ITO electrode to obtain a cathode interface layer, preferably a 0 generation PAMAM layer (PAMAM (G0)) consisting of 4 branched polyamide-amine groups, wherein the thickness of the PAMAM (G0) is preferably 8-15 nm;
coating a poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b' ] dithiophene-co-3-fluorothieno [3, 4-b ] thiophene-2-carboxylate ] and [6, 6] -phenylcarbon 71-butyric acid methyl ester in chlorobenzene solution to give a photoactive layer. Preferably, the poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: the concentration of the 4, 5-b' ] dithiophene-co-3-fluorothieno [3, 4-b ] thiophene-2-carboxylate ] solution is preferably 10mg/ml, and the concentration of the [6, 6] -phenylcarbon 71-butyric acid methyl ester solution is preferably 8 mg/ml. Preferably, the volume ratio of the 1, 8-diiodooctane additive to the chlorobenzene is 3: 97;
and forming an anode interface layer and an anode on the photoactive layer, thereby obtaining the polymer solar cell.
In this embodiment, the substrate is preferably a glass or transparent polymer substrate and the anodic interfacial layer is preferably MoO3The anode is preferably made of metallic silver.
Preferably, in one embodiment of the present invention, the PAMAM cathode interface layer may be prepared as follows:
cleaning and drying the etched thin strip-shaped ITO conductive glass;
and (3) placing the ITO substrate on a bracket of a spin coater, and preferably, uniformly coating a methanol solution of PAMAM (G0) on the substrate to form a PAMAM (G0) film on the substrate. The thickness of the PAMAM (G0) thin film is preferably 8-15 nm;
in a preferred embodiment of the present invention, the specific operation of forming the anode interfacial layer and the anode on the photoactive layer to obtain the polymer solar cell may be:
transferring the substrate with the cathode, the PAMAM cathode interface layer and the optical activity layer into a vacuum coating machine for evaporation. Vapor deposition MoO3And an anode interface layer, wherein the thickness of the anode interface layer is preferably 6-10nm, and then a silver electrode is evaporated as an anode, wherein the thickness of the silver electrode is preferably 70-120nm, so that the polymer solar cell is obtained.
In the present invention, a poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters](PTB7-Th) may be the OneMateral product, and the receptor material [6, 6]]-phenyl carbon 71-butyric acid methyl ester (PC)71BM) may be the product of solenone BV.. The PAMAM can be MoO, a product of molecular new material of Weihaichen origin3The Alfa Aesar product may be used.
The polymer solar cell prepared by the invention is AM1.5 at 100mW/cm2The xenon lamp solar simulator is tested under a light source, and the cell performance parameters (including open-circuit voltage V) under illumination can be obtained from a Keithley 2400 digital source tableoc(V) short-circuit current Jsc(mA/cm2) Fill factor FF (%) and energy conversion efficiency PCE (%). As can be seen from the test results, the polymer solar cell prepared by the invention has higher short-circuit current and energy conversion efficiency.
Examples
To further illustrate the technical solutions of the present invention, the following preferred embodiments of the present invention are described with reference to examples, but it should be understood that these examples are only for further specifically illustrating the features and advantages of the present invention, and do not limit the scope of the present invention.
Example 1
Washing the etched ITO conductive glass with a certain width by RBS washing liquor, water, acetone and isopropanol in sequence and drying;
putting a clean ITO substrate on a bracket of a spin coater, uniformly coating a 0 generation PAMAM (G0) methanol solution consisting of 4 branched-chain polyamide-amine groups at the tail end on the substrate to form a PAMAM film on the substrate, and controlling the rotating speed and time to ensure that the thickness of the PAMAM film is about 10 nm;
poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl)-benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters](PTB7-Th) and [6, 6]-phenyl carbon 71-butyric acid methyl ester (PC)71BM) is dissolved in chlorobenzene solution according to the mass ratio of 10: 8 to prepare 18mg/mL chlorobenzene solution, the volume ratio of the additive 1, 8-diiodooctane to the chlorobenzene is 3: 97, and the active layer precursor mixed solution is obtained by uniformly stirring.
Placing the ITO glass coated with the PAMAM (G0) film on a tray of a spin coater, uniformly coating the fully dissolved active layer solution on the whole surface of the PAMAM (G0) film, and controlling the rotating speed and the time to ensure that the mixture forms a layer of PTB7-Th with the thickness of about 100nm on the surface of the PAMAM (G0): PC (personal computer)71BM thin film to obtain the optical active layer of the polymer solar cell;
finally, the coating layer coated with PTB 7-Th: PC (personal computer)71The substrate of the photoactive layer of the BM film is placed in a vacuum coater at 4 × 10-4Vapor deposition of MoO under Pa3And Ag electrode, MoO3Has a thickness of about 8nm, a silver electrode thickness of about 90nm, and a cell effective area of 10mm2The prepared structure is ITO/PAMAM (G0) (10nm)/(PTB 7-Th: PC71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 1 and fig. 2.
Example 2
The structure and preparation method of the polymer solar cell are similar to example 1, the methanol solution of 1 generation PAMAM (G1) composed of 8 branched chain polyamide-amine groups at the end is uniformly coated on the substrate, the rotating speed and time are controlled to make the thickness of the PAMAM (G1) film about 10nm, and the film is used as a cathode interface layer to prepare the structure of ITO/PAMAM (G1) (10nm)/(PTB 7-Th: PC71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 1 and fig. 2.
Example 3
The structure and preparation method of the polymer solar cell are similar to those of example 1, and the polymer solar cell is composed of 16 branched polyamide-amine groups at the tail endUniformly coating a methanol solution of 2-generation PAMAM (G2) on the substrate, controlling the rotation speed and time to make the thickness of the PAMAM (G2) film about 10nm, and using the film as a cathode interface layer to prepare the ITO/PAMAM (G2) (10nm)/(PTB 7-Th: PC71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 1 and fig. 2.
Comparative example 1
Washing the etched ITO conductive glass with a certain width by RBS washing liquor, water, acetone and isopropanol in sequence and drying;
preparing a ZnO precursor solution: 1g of zinc acetate dihydrate is weighed and dispersed in 10mL of ethylene glycol monomethyl ether, 300 mu L of ethanolamine is dropwise added, and the mixture is stirred overnight at 60 ℃ to obtain a ZnO precursor solution. And uniformly coating the ZnO precursor solution on an ITO substrate by controlling the rotating speed and time, heating the film at 200 ℃ for 10min in a nitrogen environment after spin coating, then heating at 200 ℃ for 60min in the air, and controlling the rotating speed and time to obtain a ZnO layer with the thickness of about 10nm as a cathode interface layer. The preparation methods of the active layer, the anode interface layer and the anode were the same as in example 1. The prepared structure is ITO/ZnO (10nm)/(PTB 7-Th: PC71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 1 and fig. 2.
Comparative example 2
Preparing a ZnO precursor solution: 1g of zinc acetate dihydrate is weighed and dispersed in 10mL of ethylene glycol monomethyl ether, 300 mu L of ethanolamine is dropwise added, and the mixture is stirred overnight at 60 ℃ to obtain a ZnO precursor solution. And uniformly coating the ZnO precursor solution on an ITO substrate by controlling the rotating speed and time, heating the film at 200 ℃ for 10min in a nitrogen environment after spin coating, then heating at 200 ℃ for 60min in the air, and controlling the rotating speed and time to obtain a ZnO layer with the thickness of about 40nm as a cathode interface layer. The preparation methods of the active layer, the anode interface layer and the anode were the same as in example 1. The prepared structure is ITO/ZnO (40nm)/(PTB 7-Th: PC71BM)(100nm)/MoO3(8nm)/Ag (90nm) polymerA solar cell. The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 1 and fig. 2.
Comparative example 3
Washing the etched ITO conductive glass with a certain width by RBS washing liquor, water, acetone and isopropanol in sequence and drying;
directly spin-coating an active layer solution on an ITO substrate without a cathode interface layer to prepare the ITO/(PTB7-Th PC)71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 1 and fig. 2.
TABLE 1 Performance parameters of Polymer solar cells prepared in examples and comparative examples
Cathode interface layer Voc(V) Jsc(mA/cm2) FF(％) PCE(％)
Comparative example 1 ZnO 0.76 16.12 58.34 7.13
Comparative example 2 ZnO 0.78 16.56 66.75 8.62
Example 1 PAMAM(G0) 0.78 17.30 67.64 9.13
Example 2 PAMAM(G1) 0.77 17.33 65.48 8.73
Example 3 PAMAM(G2) 0.77 17.36 60.77 8.11
Comparative example 3 Is free of 0.41 15.89 51.84 3.34
Example 4
Washing the etched ITO conductive glass with a certain width by RBS washing liquor, water, acetone and isopropanol in sequence and drying;
putting a clean ITO substrate on a bracket of a spin coater, uniformly coating the substrate with a methanol solution of 0 generation PAMAM (G0) consisting of 4 branched-chain polyamide-amine groups at the tail end to form a PAMAM film on the substrate, and controlling the rotating speed and time to ensure that the thickness of the PAMAM film is about 10 nm.
Poly [ (4, 8-bis- (2-ethylhexyloxy) -benzo (1, 2-b: 4, 5-b') dithiophene) -2, 6-diyl- (4- (2-ethylhexanoyl) -thieno [3, 4-b ]]Thiophene) -2-6-diyl](PBDTTT-C) and [6, 6]-phenyl carbon 71 methyl butyrate (PC)71BM) is dissolved in chlorobenzene solution according to the mass ratio of 10: 8 to prepare 18mg/mL chlorobenzene solution, the volume ratio of the additive 1, 8-diiodooctane to the chlorobenzene is 3: 97, and the active layer precursor mixed solution is obtained by uniformly stirring.
Placing the ITO glass coated with the PAMAM (G0) film on a tray of a spin coater, uniformly coating the fully dissolved active layer solution on the surface of the whole PAMAM (G0) film, and controlling the rotating speed and the time to ensure that the mixture forms a layer of PBDTTT-C with the thickness of about 100nm on the surface of the PAMAM (G0): PC (personal computer)71BM thin film to obtain the optical active layer of the polymer solar cell;
finally coating with PBDTTT-C: PC (personal computer)71The substrate of the photoactive layer of the BM film is placed in a vacuum coater at 4 × 10-4Vapor deposition of MoO under Pa3And Ag electrode, MoO3Has a thickness of about 8nm, a silver electrode thickness of about 90nm, and a cell effective area of 10mm2The prepared structure is ITO/PAMAM (G0) (10 nm)/(PBDTTT-C: PC71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 2 and fig. 3.
Example 5
The structure and fabrication of the polymer solar cell were similar to example 4, with 8 endsUniformly coating a methanol solution of 1-generation PAMAM (G1) composed of branched polyamide-amine groups on the substrate, controlling the rotating speed and time to make the thickness of the PAMAM (G1) film about 10nm, and using the PAMAM (G1) film as a cathode interface layer to prepare the ITO/PAMAM (G1) (10 nm)/(PBDTTT-C: PC)71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 2 and fig. 3.
Example 6
The structure and preparation method of the polymer solar cell are similar to example 4, the methanol solution of 2 generation PAMAM (G2) composed of 16 branched chain polyamide-amine groups at the end is uniformly coated on the substrate, the rotating speed and time are controlled to make the thickness of the PAMAM (G2) film about 10nm, and the film is used as a cathode interface layer to prepare the structure of ITO/PAMAM (G2) (10 nm)/(PBDTTT-C: PC71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 2 and fig. 3.
Comparative example 4
Preparing a ZnO precursor solution: 1g of zinc acetate dihydrate is weighed and dispersed in 10mL of ethylene glycol monomethyl ether, 300 mu L of ethanolamine is dropwise added, and the mixture is stirred overnight at 60 ℃ to obtain a ZnO precursor solution. And (3) uniformly coating the ZnO precursor solution on the ITO substrate by controlling the rotating speed and time, heating the film for 10min at 200 ℃ in a nitrogen environment after spin coating, and then heating for 60min at 200 ℃ in the air. Preferably, the rotation speed and time are controlled to obtain a ZnO layer with the thickness of about 40nm as the cathode interface layer. The preparation methods of the active layer, the anode interface layer and the anode were the same as in example 1. The prepared structure is ITO/ZnO (40 nm)/(PBDTTT-C: PC71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 2 and fig. 3.
Comparative example 5
Washing the etched ITO conductive glass with a certain width by RBS washing liquor, water, acetone and isopropanol in sequence and drying;
directly spin-coating an active layer solution on an ITO substrate without a cathode interface layer to prepare the ITO/(PBDTTT-C: PC)71BM)(100nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 2 and fig. 3.
TABLE 2 Performance parameters of Polymer solar cells prepared in examples and comparative examples
Cathode interface layer Voc(V) Jsc(mA/cm2) FF(％) PCE(％)
Comparative example 4 ZnO 0.70 13.61 60.73 5.79
Example 4 PAMAM(G0) 0.70 14.59 62.38 6.37
Example 5 PAMAM(G1) 0.70 14.64 59.29 6.07
Example 6 PAMAM(G2) 0.70 14.61 51.94 5.31
Comparative example 5 Is free of 0.40 14.41 43.89 2.53
Example 7
Washing the etched ITO conductive glass with a certain width by RBS washing liquor, water, acetone and isopropanol in sequence and drying;
putting a clean ITO substrate on a bracket of a spin coater, uniformly coating a 0 generation PAMAM (G0) methanol solution consisting of 4 branched-chain polyamide-amine groups at the tail end on the substrate to form a PAMAM film on the substrate, and controlling the rotating speed and time to ensure that the thickness of the PAMAM film is about 10 nm;
poly 3-hexylthiophene (P3HT) and [6, 6]]Methyl 61 butyrate (PC) phenyl carbon61BM) mixed solution is dissolved into o-dichlorobenzene solution according to the mass ratio of 10: 8 to preparePreparing an o-dichlorobenzene solution with the concentration of 36mg/mL, and uniformly stirring to obtain an active layer precursor mixed solution.
Placing the ITO glass coated with the PAMAM (G0) film on a tray of a spin coater, uniformly coating the fully dissolved active layer solution on the whole surface of the PAMAM (G0) film, and controlling the rotating speed and the time to ensure that the mixture forms a layer of P3HT with the thickness of about 180nm on the surface of the PAMAM (G0): PC (personal computer)61Annealing the BM thin film for 10min at 135 ℃ to obtain an optical active layer of the polymer solar cell;
finally, the coating will be coated with P3 HT: PC (personal computer)61The substrate of the photoactive layer of the BM film is placed in a vacuum coater at 4 × 10- 4Vapor deposition of MoO under Pa3And Ag electrode, MoO3Has a thickness of about 8nm, a silver electrode thickness of about 90nm, and a cell effective area of 10mm2The prepared structure is ITO/PAMAM (G0) (10nm)/(P3 HT: PC)61BM)(180nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 3 and fig. 4.
Example 8
The structure and preparation method of the polymer solar cell are similar to example 7, the methanol solution of 1 generation PAMAM (G1) composed of 8 branched chain polyamide-amine groups at the end is uniformly coated on the substrate, the rotating speed and time are controlled to make the thickness of the PAMAM (G1) film about 10nm, and the film is used as a cathode interface layer to prepare the structure of ITO/PAMAM (G1) (10nm)/(P3 HT: PC61BM)(180nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 3 and fig. 4.
Example 9
The structure and preparation method of the polymer solar cell are similar to example 7, the methanol solution of 2 generation PAMAM (G2) composed of 16 branched polyamidoamine groups at the end is uniformly coated on the substrate, the rotating speed and time are controlled to make the thickness of the PAMAM (G2) film about 10nm, and the film is used as a cathode interface layer to prepare the structure of ITO/PAMAM (G2) (10nm)/(P3 HT: PC61BM)(180nm)/MoO3(8nm)/Polymer solar cell of Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 3 and fig. 4.
Comparative example 6
Preparing a ZnO precursor solution: 1g of zinc acetate dihydrate is weighed and dispersed in 10mL of ethylene glycol monomethyl ether, 300 mu L of ethanolamine is dropwise added, and the mixture is stirred overnight at 60 ℃ to obtain a ZnO precursor solution. And (3) uniformly coating the ZnO precursor solution on the ITO substrate by controlling the rotating speed and time, heating the film for 10min at 200 ℃ in a nitrogen environment after spin coating, and then heating for 60min at 200 ℃ in the air. Preferably, the rotation speed and time are controlled to obtain a ZnO layer with the thickness of about 40nm as the cathode interface layer. The preparation methods of the active layer, the anode interface layer and the anode were the same as in example 1. The prepared structure is ITO/ZnO (40nm)/(P3 HT: PC61BM)(180nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 3 and fig. 4.
Comparative example 7
Washing the etched ITO conductive glass with a certain width by RBS washing liquor, water, acetone and isopropanol in sequence and drying;
without a cathode interface layer, an active layer is directly prepared on an ITO substrate to obtain an ITO/(P3 HT: PC) structure61BM)(180nm)/MoO3(8nm)/Ag (90 nm). The polymer solar cell prepared in the embodiment is 100mW/cm2The performance parameters under xenon lamp illumination are shown in table 3 and fig. 4.
TABLE 3 Performance parameters of Polymer solar cells prepared in examples and comparative examples
Cathode interface layer Voc(V) Jsc(mA/cm2) FF(％) PCE(％)
Comparative example 6 ZnO 0.62 8.57 65.18 3.46
Example 7 PAMAM(G0) 0.62 8.95 68.10 3.78
Example 8 PAMAM(G1) 0.61 8.80 64.06 3.43
Example 9 PAMAM(G2) 0.60 8.72 56.76 2.97
Comparative example 7 Is free of 0.56 6.14 45.09 1.55
As can be seen from the above examples and comparative examples, the introduction of PAMAM (G0), PAMAM (G1) or PAMAM (G2) is very suitable for use as the cathode interface layer of the polymer solar cell, and even the energy conversion efficiency of the polymer solar cell prepared by the present invention can be as high as 9.13%, which exceeds the energy conversion efficiency of ITO alone and ZnO as the cathode interface layer. Moreover, the cathode interface layer is simpler, more effective and lower in cost. Thus, it is expected that the present invention will have a wide industrial application prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A polymer solar cell comprising a cathode interface layer comprises a substrate, and a cathode layer, a cathode interface layer, a photoactive layer, an anode interface layer and an anode which are sequentially stacked on the substrate, wherein the number of terminal amino groups of the cathode interface layer satisfies 2n+2Of Polyamidoamine (PAMAM) branches, wherein the number M of terminal polyamidoamine branches of said n-generation dendrimer PAMAMn＝2n+2N is algebraic and isAn integer equal to or greater than zero.
2. The polymer solar cell according to claim 1, wherein n is an integer of 0, 1 or 2.
3. The polymer solar cell according to claim 1, wherein the thickness of the PAMAM layer as the cathode interface layer is 8-15 nm.
4. The polymer solar cell according to claim 1, wherein the photoactive layer comprises at least one selected from the group consisting of: poly-3-hexylthiophene (P3 HT): [6, 6]]Methyl 61 butyrate (PC) phenyl carbon61BM) mixed solution; poly [ (4, 8-bis- (2-ethylhexyloxy) -benzo (1, 2-b: 4, 5-b') dithiophene) -2, 6-diyl- (4- (2-ethylhexanoyl) -thieno [3, 4-b ]]Thiophene) -2-6-diyl](PBDTTT-C) and [6, 6]-phenyl carbon 71-butyric acid methyl ester (PC)71BM); poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters](PTB7-TH)∶[6，6]-phenyl carbon 71-butyric acid methyl ester (PC)71BM).
5. The polymer solar cell according to claim 1, wherein the chemical structure of the 0, 1 or 2 generation of the polyamidoamine branch composed dendrimer PAMAM is as follows:
Figure FDA0002571255460000011
Figure FDA0002571255460000021
6. the polymer solar cell according to claim 1, wherein the photoactive layer has a thickness of 90 to 200 nm.
7. A method for making a polymer solar cell, the method comprising:
disposing a transparent electrode as a cathode on a substrate;
arranging a cathode interface layer on the transparent electrode;
an optical activity layer is arranged on the cathode interface layer;
an anode interface layer is arranged on the photoactive layer; and
an anode is arranged on the anode interface layer,
wherein the number of terminal amino groups in the cathode interface layer satisfies 2n+2Wherein n is the number of generations of the dendrimer PAMAM and is an integer equal to or greater than zero.
8. The method of claim 7, wherein the disposing a cathode interface layer PAMAM on the transparent electrode comprises forming a thin film PAMAM layer by coating a solution of PAMAM on the cathode.
9. The method of claim 7, wherein the thickness of the PAMAM layer as the cathode interface layer is 8-15 nm.
10. The method of claim 7, wherein the disposing a photoactive layer on the cathode interfacial layer is performed by coating any one selected from the group consisting of: poly 3-hexylthiophene (P3 HT): [6, 6]]Methyl 61 butyrate (PC) phenyl carbon61BM) mixed solution; poly [ (4, 8-bis- (2-ethylhexyloxy) -benzo (1, 2-b: 4, 5-b') dithiophene) -2, 6-diyl- (4- (2-ethylhexanoyl) -thieno [3, 4-b ]]Thiophene) -2-6-diyl](PBDTTT-C) and [6, 6]-phenyl carbon 71-butyric acid methyl ester (PC)71BM); poly [4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) -benzo [1, 2-b: 4, 5-b']Dithiophene-co-3-fluorothieno [3, 4-b]Thiophene-2-carboxylic acid esters](PTB7-TH)∶[6，6]-phenyl carbon 71-butyric acid methyl ester (PC)71BM).
CN202010650285.9A 2020-07-06 2020-07-06 Polymer solar cell comprising cathode interface layer and preparation method thereof Pending CN111668376A (en)

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