CN110854272A - Ternary halogen perovskite solar cell and preparation method thereof - Google Patents
Ternary halogen perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a ternary halogen perovskite solar cell and a preparation method thereof, belonging to the technical field of photovoltaics. In the ternary halogen perovskite solar cell, a polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer is inserted between the electron transmission layer and the perovskite light absorption layer, so that the ternary halogen perovskite solar cell has the characteristics of high open-circuit voltage, high conversion efficiency and negligible hysteresis. The preparation method of the ternary halogen perovskite solar cell is simple and easy to operate, has high repeatability, can be popularized in large scale in industrial production, and has potential application value in the aspect of commercialization of solar cells.
Description
Technical Field
The invention belongs to the technical field of photovoltaics, and particularly relates to a ternary halogen perovskite solar cell and a preparation method thereof.
Background
The current energy crisis is becoming more and more severe, and solar cells as a clean and renewable energy can directly convert light energy into electric energy, thus having great application prospect. The research on solar cells has been a hot research in the scientific community, and has been the subject of sustainable development strategy in economic and military equipment in various countries. The first generation of solar technology is silicon-based solar cells, which are the most mature and widely used, but require the use of expensive high-purity silicon (purity requirement is 99.999%), which is an important factor restricting the development thereof. The second generation thin film solar cell has a low defect density, but a large amount of rare elements are needed in the preparation process, so that the production cost of the cell is increased, and the large-scale application of the cell is limited. In order to solve these significant problems, simplify the manufacturing process, reduce the production cost, and improve the photoelectric conversion efficiency, scientists have proposed the third generation solar cell, i.e., the organic/inorganic hybrid perovskite solar cell. In the last decade, the research enthusiasm of perovskite solar cells is raised internationally by virtue of the advantages of low production cost, simple manufacturing process, high photoelectric conversion efficiency and the like.
In recent years, an interface modification method is widely used for passivating an interface between a perovskite light absorption layer and an electron or hole transport layer, so as to reduce the defect density of the interface, reduce the carrier recombination of the interface and improve the photoelectric conversion efficiency of a solar cell. Previous studies have used organic materials such as PMMA or PCBM to passivate the interface between the electron transport layer and the perovskite light absorbing layer or between the perovskite light absorbing layer and the hole transport layer to improve the efficiency of perovskite solar cells. However, PMMA is an insulating material and cannot effectively transport electrons or holes, which inevitably leads to a decrease in the Fill Factor (FF) of the cell, and when the PCBM passivates the interface, the short-circuit current (Jsc) is somewhat reduced due to a decrease in transmittance. Therefore, there is a need for an interface modification material to improve the open circuit voltage and photoelectric conversion efficiency of the perovskite cell.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a ternary halogen perovskite solar cell; the second purpose is to provide a preparation method of the ternary halogen perovskite solar cell.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the ternary halogen perovskite solar cell is formed by sequentially laminating a substrate layer, an electron transport layer, a polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer, a perovskite light absorption layer, a hole transport layer and a metal back electrode from bottom to top.
Preferably, the mass ratio of the polymethyl methacrylate to the [6.6] -phenyl-C61 methyl butyrate in the polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer is 1: 1-3.
Preferably, the polymethyl methacrylate has a molecular weight of 80,000-200,000.
Preferably, the substrate layer is ITO, and the electron transport layer is SnO2The perovskite light absorption layer is Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3A perovskite light-absorbing layer; the hole transport layer is a Spiro-OMeTAD hole transport layer, and the metal back electrode is Ag.
2. The preparation method of the ternary halogen perovskite solar cell comprises the following steps:
(1) pretreating the conductive substrate;
(2) spin-coating on the conductive substrate treated in the step (1) to prepare an electron transport layer;
(3) preparing a polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer by spin coating on the electron transport layer in the step (2);
(4) preparing a perovskite light absorption layer on the polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer in the step (3) in a spin coating manner;
(5) spin coating on the perovskite light absorption layer in the step (4) to prepare a hole transport layer;
(6) and (5) evaporating a metal back electrode on the hole transmission layer in the step (5).
Preferably, in the step (2), the spin coating is used for preparing the electron transport layerThe method comprises the following steps: SnO2Dropping the colloid water solution onto the conductive substrate, spin-coating at 3000-4000rpm for 30-40s, and annealing at 120-180 deg.C for 30-60 min.
Preferably, in the step (3), the spin coating method for preparing the passivation layer of polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate is as follows: after cooling the composite layer formed by laminating the substrate layer and the electron transport layer to room temperature, dropping polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate chlorobenzene solution on the electron transport layer, spin-coating at 4000-.
Preferably, in the step (4), the method for preparing the perovskite light absorption layer by spin coating comprises the following steps: will consist of a substrate layer, an electron transport layer and polymethyl methacrylate/[ 6.6]]Preheating a composite layer formed by stacking-phenyl-C61 methyl butyrate passivation layers at 30-40 ℃ for 1-2min, and then adding Cs at the temperature of 30-40 DEG C0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite precursor is added dropwise to polymethyl methacrylate/[ 6.6 [ ]]The passivation layer of methyl-phenyl-C61 is spin-coated at a speed of 800-1000rpm for 10-15s, then at a speed of 4000-6000rpm for 20-35s, and finally annealed at a temperature of 100-120 ℃ for 30-60min, wherein the Cs is in the passivation layer0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3When 5-10s before the precursor solution is spin-coated, 100-200 μ L of extraction liquid is dropped within 1-2 s.
Preferably, the extract is one of chlorobenzene, ethyl acetate or anisole.
Preferably, in step (5), the method for preparing the hole transport layer by spin coating is as follows: the material comprises a substrate layer, an electron transport layer, and polymethyl methacrylate/[ 6.6]]-phenyl-C61 methyl butyrate passivation layer and Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3After the composite layer formed by stacking perovskite light absorption layers is cooled to room temperature, a Spiro-OMeTAD chlorobenzene solution is dropwise added
Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite light absorption layer is spin-coated for 30-40s at 3000-.
The invention has the beneficial effects that: the invention provides a ternary halogen perovskite solar cell and a preparation method thereof, the ternary halogen perovskite solar cell has the characteristics of high open-circuit voltage, high conversion efficiency and negligible retardation, and a layer of polymethyl methacrylate/[ 6.6] is inserted between an electron transmission layer and a perovskite light absorption layer of the ternary halogen perovskite solar cell]-phenyl-C61 methyl butyrate as a passivation layer, and mixing the layer with polymethyl methacrylate and [6.6]]The mass ratio of methyl-phenyl-C61 butyrate is controlled to be 1:1-3, so that the efficiency of the battery is optimized. The PMMA is a passivation material with excellent performance, and can well passivate defects on the surface of the perovskite and reduce carrier recombination centers on the perovskite, so that the open-circuit voltage of the battery is improved. However, PMMA is an insulating material and is not beneficial to electron transmission, PCBM can be used as an electron transmission layer and a passivation layer, the defect of perovskite can be passivated and electrons can be effectively transmitted by utilizing the synergistic effect of PMMA and PCBM, and short-circuit current (J) is not reducedsc) Under the condition of increasing the voltage (V) of the incoming pathoc) Thereby improving the efficiency of the battery and simultaneously reducing the hysteresis effect of the positive scanning and the reverse scanning of the battery. The preparation method of the perovskite solar cell is simple and easy to operate, has high repeatability, can be popularized in large scale in industrial production, and has potential application value in the aspect of commercialization of solar cells.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
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For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
fig. 1 is a schematic structural diagram of a ternary halogen perovskite solar cell in examples 1 to 3 in fig. 1;
FIG. 2 is a cross-sectional scanning electron micrograph of a ternary halogen perovskite solar cell according to examples 1 to 3;
FIG. 3 is a view showing an ITO transparent conductive substrate layer, which is composed of an ITO transparent conductive substrate layer and SnO in step (2) of comparative example 12A composite layer formed by an electron transport layer, in the step (3) of comparative example 2, an ITO transparent conductive substrate layer and SnO2A composite layer formed by the electron transmission layer and the PMMA passivation layer, in the step (3) of the comparative example 3, an ITO transparent conductive substrate layer and SnO2A composite layer formed by the electron transmission layer and the PCBM passivation layer and the ITO transparent conductive substrate layer and SnO in the steps (3) of the embodiments 1, 2 and 32A transmission rate test result chart of a composite layer formed by the electron transport layer and the PMMA/PCBM passivation layer;
FIG. 4 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in step (4) of comparative examples 2 and 3 and examples 1, 2 and 30.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Scanning electron micrographs of the perovskite light-absorbing layer;
FIG. 5 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in comparative examples 2 and 3 and in step (4) of example 20.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3XRD pattern of perovskite light-absorbing layer;
FIG. 6 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in step (4) of comparative examples 2 and 3 and examples 1, 2 and 30.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Absorption profile of perovskite light absorption layer;
FIG. 7 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in comparative examples 2 and 3 and in step (4) of example 20.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Fluorescence profiles of perovskite light absorbing layers;
FIG. 8 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in comparative examples 2 and 3 and in step (4) of example 20.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3A fluorescence lifetime map of the perovskite light absorption layer;
FIG. 9 is an I-V plot of perovskite solar cells prepared in comparative examples 1 to 3 and examples 1 to 3;
FIG. 10 is a plot of the forward-scan, reverse-scan I-V curves of perovskite solar cells prepared in comparative example 1 and example 2;
fig. 11 is an IPCE graph of the perovskite solar cells prepared in comparative example 1 and example 2.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The PMMA/[ 6.6] -phenyl-C61 methyl butyrate passivation layer is abbreviated as PMMA/PCBM passivation layer in each of the following examples.
Example 1
Preparation of ternary halogen perovskite solar cell
(1) Sequentially ultrasonically cleaning ITO (indium tin oxide) with the thickness of 15mm multiplied by 15mm by using detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30min, blow-drying by using a nitrogen gun, and then carrying out ozone treatment for 30 min;
(2) SnO2Dropwise adding a colloidal aqueous solution onto the ITO treated in the step (1), spin-coating at the speed of 4000rpm for 30s, and finally annealing at 150 ℃ for 30min to prepare SnO2An electron transport layer;
(3) will be made of ITO and SnO2After the composite layer formed by laminating the electron transport layers is cooled to room temperature, 40 mu L of PMMA/PCBM chlorobenzene solution is dripped into SnO in the step (2)2Spin-coating on the electron transport layer at 8000rpm for 30s, and annealing at 100 deg.C for 10min to obtain PMMA/PCBM passivation layer, wherein the mass ratio of PMMA to PCBM in PMMA/PCBM chlorobenzene solution is 1:1, and the molecular weight of PMMA is 200,000;
(4) will be made of ITO, SnO2Preheating a composite layer formed by laminating an electron transport layer and a PMMA/PCBM passivation layer at 30 ℃ for 1min, and then preheating 50 mu L of Cs with the temperature of 30 DEG C0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Dropwise adding the perovskite precursor on the PMMA/PCBM passivation layer obtained in the step (3), spin-coating at the speed of 1000rpm for 10s, then spin-coating at the speed of 6000rpm for 30s, and finally annealing at 100 ℃ for 45min to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer, in which at Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3When the precursor solution is coated for 10s before the end of the spin coating, 100 mu L of ethyl acetate is dripped in 2 s;
(5) will be made of ITO, SnO2Electron transport layer, PMMA/PCBM passivation layer and Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3After the composite layer formed by stacking the perovskite light-absorbing layers was cooled to room temperature, 40. mu.L of a Spiro-OMeTAD chlorobenzene solution was added dropwise to the step (4)Middle Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Spin-coating the perovskite light absorption layer at 3000rpm for 40s to obtain a Spiro-OMeTAD hole transport layer;
(6) under high vacuum (< 2.5X 10)-5Pa), depositing an Ag film with the thickness of 100nm on the Spiro-OMeTAD hole transport layer in the step (5) by thermal evaporation.
Example 2
Preparation of ternary halogen perovskite solar cell
(1) Sequentially ultrasonically cleaning ITO (indium tin oxide) with the thickness of 15mm multiplied by 15mm by using detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30min, blow-drying by using a nitrogen gun, and then carrying out ozone treatment for 30 min;
(2) SnO2Dropwise adding a colloidal aqueous solution onto the ITO treated in the step (1), spin-coating at 3000rpm for 40s, and finally annealing at 120 ℃ for 60min to obtain SnO2An electron transport layer;
(3) will be made of ITO and SnO2After the composite layer formed by laminating the electron transport layers is cooled to room temperature, 40 mu L of PMMA/PCBM chlorobenzene solution is dripped into SnO in the step (2)2Spin-coating the electron transport layer at 4000rpm for 60s, and annealing at 110 ℃ for 12min to obtain a PMMA/PCBM passivation layer, wherein the mass ratio of PMMA to PCBM in the PMMA/PCBM chlorobenzene solution is 1:2, and the molecular weight of PMMA is 120,000;
(4) will be made of ITO, SnO2Preheating a composite layer formed by laminating an electron transport layer and a PMMA/PCBM passivation layer at 35 ℃ for 2min, and then preheating 50 mu L of Cs with the temperature of 35 DEG C0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Dropwise adding the perovskite precursor on the PMMA/PCBM passivation layer obtained in the step (3), spin-coating at the speed of 900rpm for 12s, then spin-coating at the speed of 4000rpm for 35s, and finally annealing at 120 ℃ for 30min to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer, in which at Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Dripping 200 mu L chlorobenzene in 2s when the precursor liquid finishes the spin coating for 8 s;
(5) will be made of ITO, SnO2Electron transport layer, PMMA/PCBM passivation layer and Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3After the composite layer formed by stacking the perovskite light absorption layers is cooled to room temperature, 40 mu L of Spiro-OMeTAD chlorobenzene solution is dropwise added to the Cs in the step (4)0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Spin-coating the perovskite light absorption layer at 3500rpm for 35s to obtain a Spiro-OMeTAD hole transport layer;
(6) under high vacuum (< 2.5X 10)-5Pa), depositing an Ag film with the thickness of 100nm on the Spiro-OMeTAD hole transport layer in the step (5) by thermal evaporation.
Example 3
Preparation of ternary halogen perovskite solar cell
(1) Sequentially ultrasonically cleaning ITO (indium tin oxide) with the thickness of 15mm multiplied by 15mm by using detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol for 30min, blow-drying by using a nitrogen gun, and then carrying out ozone treatment for 30 min;
(2) SnO2Dropwise adding a colloidal aqueous solution onto the ITO treated in the step (1), then spin-coating at 3500rpm for 35s, and finally annealing at 180 ℃ for 45min to prepare SnO2An electron transport layer;
(3) will be made of ITO and SnO2After the composite layer formed by laminating the electron transport layers is cooled to room temperature, 40 mu L of PMMA/PCBM chlorobenzene solution is dripped into SnO in the step (2)2Spin-coating on the electron transport layer at 6000rpm for 45s, and annealing at 120 ℃ for 15min to obtain a PMMA/PCBM passivation layer, wherein the mass ratio of PMMA to PCBM in a PMMA/PCBM chlorobenzene solution is 1:3, and the molecular weight of PMMA is 80,000;
(4) will be made of ITO, SnO2Preheating a composite layer formed by laminating an electron transport layer and a PMMA/PCBM passivation layer at 40 ℃ for 1min, and then preheating 50 mu L of Cs with the temperature of 40 DEG C0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Dropwise adding the perovskite precursor on the PMMA/PCBM passivation layer obtained in the step (3), spin-coating at the speed of 800rpm for 15s, then spin-coating at the speed of 5000rpm for 20s, and finally annealing at 110 ℃ for 60min to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer, in which at Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3When the precursor solution is coated for 5s before the end of the spin coating, 150 mu L of anisole is dripped in 1 s;
(5) will be made of ITO, SnO2Electron transport layer, PMMA/PCBM passivation layer and Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3After the composite layer formed by stacking the perovskite light absorption layers is cooled to room temperature, 40 mu L of Spiro-OMeTAD chlorobenzene solution is dropwise added to the Cs in the step (4)0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Spin-coating the perovskite light absorption layer for 30s at the speed of 4000rpm to prepare a Spiro-OMeTAD hole transport layer;
(6) under high vacuum (< 2.5X 10)-5Pa), depositing an Ag film with the thickness of 100nm on the Spiro-OMeTAD hole transport layer in the step (5) by thermal evaporation.
Comparative example 1
The difference from example 1 is that in SnO2Preparation of Cs by direct spin coating of electron transport layer0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3A perovskite light absorbing layer.
Comparative example 2
The difference from example 1 is that the PMMA/PCBM chlorobenzene solution in step (3) was replaced by a PMMA-chlorobenzene solution.
Comparative example 3
The difference from example 1 is that the PMMA/PCBM chlorobenzene solution in step (3) was replaced by a PCBM chlorobenzene solution.
FIG. 1 is a schematic view of the structure of a ternary halogen perovskite solar cell in examples 1 to 3FIG. 2 is a cross-sectional scanning electron microscope image of the ternary halogen perovskite solar cell in examples 1 to 3, and as can be seen from FIG. 1 and FIG. 2, the ternary halogen perovskite solar cell in examples 1 to 3 comprises an ITO transparent conductive substrate layer and SnO in sequence from bottom to top2Electron transport layer, PMMA/PCBM passivation layer, Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite light absorption layer, the Spiro-OMeTAD hole transport layer and the Ag electrode are stacked.
FIG. 3 is a view showing an ITO transparent conductive substrate layer, which is composed of an ITO transparent conductive substrate layer and SnO in step (2) of comparative example 12A composite layer formed by an electron transport layer, in the step (3) of comparative example 2, an ITO transparent conductive substrate layer and SnO2A composite layer formed by the electron transmission layer and the PMMA passivation layer, in the step (3) of the comparative example 3, an ITO transparent conductive substrate layer and SnO2A composite layer formed by the electron transmission layer and the PCBM passivation layer and the ITO transparent conductive substrate layer and SnO in the steps (3) of the embodiments 1, 2 and 32And the transmission rate test result chart of the composite layer formed by the electron transport layer and the PMMA/PCBM passivation layer. As can be seen from fig. 3, the transmittance curves of the 6 composite layers are substantially overlapped, i.e., there is no significant change in transmittance of the 6 composite layers, indicating that the insertion of each passivation layer does not affect Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Absorption by the perovskite light-absorbing layer has a large influence.
FIG. 4 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in step (4) of comparative examples 2 and 3 and examples 1, 2 and 30.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Scanning Electron micrograph of perovskite light-absorbing layer, it can be seen from FIG. 4 that Cs prepared in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The crystal grains in the perovskite light absorption layer are compared with those in comparative examples 2 and 3 and example 1,2 and 3 Cs produced in step (4)0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The crystal grains in the perovskite light absorption layer have no great change, and the white crystal in the figure is lead iodide (PbI)2)，PbI2Is formed by perovskite degradation, PbI is inserted along with the insertion of a passivation layer2The amount of PbI in the PMMA/PCBM passivation layer is gradually reduced compared with that in the PMMA passivation layer and the PCBM passivation layer2The amount of (A) is small, indicating that the insertion of the PMMA/PCBM passivation layer inhibits the degradation of the perovskite.
FIG. 5 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in comparative examples 2 and 3 and in step (4) of example 20.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3XRD Pattern of perovskite light-absorbing layer, as can be seen from FIG. 5, Cs prepared in each example0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The characteristic peaks of the perovskite light absorption layer are basically consistent, which shows that the insertion of each passivation layer does not influence the composition of the light absorption layer, but the PbI is inserted into the PMMA/PCBM passivation layer2Compared with PbI after inserting PMMA passivation layer and PCBM passivation layer2Is reduced, compared to the PbI in PMMA/PCBM passivation layer shown in FIG. 4, in the PMMA and PCBM passivation layers2The result of the smaller amount of (A) is consistent, i.e. the insertion of the PMMA/PCBM passivation layer inhibits the degradation of the perovskite.
FIG. 6 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in step (4) of comparative examples 2 and 3 and examples 1, 2 and 30.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3As can be seen from FIG. 6, the absorption curve of the perovskite light-absorbing layer shows that Cs is present0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The absorption curve of the perovskite light absorption layer has no obvious change, which indicates that the insertion of the passivation layer does not cause Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The absorption properties of the perovskite light-absorbing layer have a significant effect.
FIG. 7 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in comparative examples 2 and 3 and in step (4) of example 20.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Fluorescence profile of perovskite light-absorbing layer, as can be seen from FIG. 7, Cs prepared in step (4) of comparative example 20.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite light absorption layer has the strongest fluorescence intensity because PMMA is an insulating material and cannot effectively transmit electrons, so that the electrons and holes are compounded; comparative example 3 Cs produced in step (4)0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite light absorption layer has the weakest fluorescence intensity, because the PCBM can effectively transmit electrons except as a passivation layer and an electron transmission layer; example 2 Cs produced in step (4)0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Fluorescence intensity ratio of perovskite light-absorbing layer to Cs prepared in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite light-absorbing layer has strong fluorescence intensity, which indicates that the insertion of the PMMA/PCBM passivation layer reduces the non-radiative recombination between the perovskite layer and the electron transport layer.
FIG. 8 shows Cs produced in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite light-absorbing layer and Cs prepared in comparative examples 2 and 3 and in step (4) of example 20.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3As can be seen from fig. 8, the trend of the fluorescence lifetime of each perovskite light-absorbing layer is consistent with the trend of the fluorescence intensity thereof. Example 2 Cs produced in step (4)0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Fluorescence lifetime of perovskite light-absorbing layer compared with Cs prepared in step (3) of comparative example 10.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite light absorption layer has long fluorescence life, which shows that the PMMA/PCBM passivation layer effectively passivates the defects on the surface of the perovskite layer, inhibits the non-radiative recombination of charge carriers, and improves the open-circuit voltage, thereby improving the efficiency of the battery.
Fig. 9 is an I-V plot of the perovskite solar cells prepared in comparative examples 1 to 3 and examples 1 to 3, from which the data are shown in table 1.
TABLE 1
| Voc(V) | Jsc(mA cm-2) | FF(％) | PCE(％) | |
| Comparative example 1 | 1.11 | 23.12 | 66.88 | 17.32 |
| Comparative example 2 | 1.13 | 21.98 | 70.63 | 17.52 |
| Comparative example 3 | 1.16 | 21.00 | 72.30 | 17.63 |
| Example 1 | 1.16 | 21.51 | 72.67 | 18.25 |
| Example 2 | 1.17 | 22.73 | 69.87 | 18.63 |
| Example 3 | 1.17 | 21.88 | 70.98 | 18.26 |
As can be seen from table 1, the open circuit voltage of the perovskite solar cells prepared in comparative examples 2 and 3 and examples 1, 2 and 3 was higher than that of the perovskite solar cell prepared in comparative example 1, because PMMA, PCBM or PMMA/PCBM can effectively passivate the surface defects of the perovskite, suppress non-radiative recombination of charge carriers, and increase the open circuit voltage, but the PMMA/PCBM passivation layer has the best effect.
Fig. 10 is a forward-scan and reverse-scan I-V curve diagram of the perovskite solar cells prepared in comparative example 1 and example 2, and it can be seen from fig. 10 that the perovskite solar cell prepared in example 2 exhibits negligible hysteresis phenomenon compared to the perovskite solar cell prepared in comparative example 1, because the reduction of the surface defects of the perovskite makes the transport of electrons and holes more balanced, reduces the accumulation of charges, and suppresses the hysteresis phenomenon.
FIG. 11 is a graph showing the IPCE curves of the perovskite solar cells prepared in comparative example 1 and example 2. from FIG. 11, it can be seen that the IPCE curve of the perovskite solar cell prepared in example 2 is slightly higher than that of the perovskite solar cell prepared in comparative example 1, indicating that the PMMA/PCBM passivation layer accelerates electrons from Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The transmission of the perovskite light absorption layer to the electron transport layer increases the short circuit current.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The ternary halogen perovskite solar cell is characterized by being formed by sequentially laminating a substrate layer, an electron transport layer, a polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer, a perovskite light absorption layer, a hole transport layer and a metal back electrode from bottom to top.
2. The ternary halogen perovskite solar cell of claim 1, wherein the mass ratio of polymethylmethacrylate to [6.6] -phenyl-C61 methyl butyrate in the polymethylmethacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer is 1: 1-3.
3. The ternary halogen perovskite solar cell of claim 2, wherein the polymethyl methacrylate has a molecular weight of 80,000-200,000.
4. The ternary halogen perovskite solar cell of any one of claims 1 to 3, wherein the substrate layer is ITO and the electron transport layer is SnO2The perovskite light absorption layer is Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3A perovskite light-absorbing layer; the hole transport layer is a Spiro-OMeTAD hole transport layer, and the metal back electrode is Ag.
5. The method for producing a ternary halogen perovskite solar cell as claimed in any one of claims 1 to 4, wherein the method comprises the steps of:
(1) pretreating the conductive substrate;
(2) spin-coating on the conductive substrate treated in the step (1) to prepare an electron transport layer;
(3) preparing a polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer by spin coating on the electron transport layer in the step (2);
(4) preparing a perovskite light absorption layer on the polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate passivation layer in the step (3) in a spin coating manner;
(5) spin coating on the perovskite light absorption layer in the step (4) to prepare a hole transport layer;
(6) and (5) evaporating a metal back electrode on the hole transmission layer in the step (5).
6. The method of claim 5, wherein in step (2), the spin coating is performed to prepare the electron transport layer by: SnO2Dropping the colloid water solution onto the conductive substrate, spin-coating at 3000-4000rpm for 30-40s, and annealing at 120-180 deg.C for 30-60 min.
7. The method of claim 5, wherein in the step (3), the spin coating method for preparing the passivation layer of polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate comprises the following steps: after cooling the composite layer formed by laminating the substrate layer and the electron transport layer to room temperature, dropping polymethyl methacrylate/[ 6.6] -phenyl-C61 methyl butyrate chlorobenzene solution on the electron transport layer, spin-coating at 4000-.
8. The method of claim 5, wherein in step (4), the spin coating is used to prepare the perovskite light absorbing layer by: will consist of a substrate layer, an electron transport layer and polymethyl methacrylate/[ 6.6]]Preheating a composite layer formed by stacking-phenyl-C61 methyl butyrate passivation layers at 30-40 ℃ for 1-2min, and then adding Cs at the temperature of 30-40 DEG C0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite precursor is added dropwise to polymethyl methacrylate/[ 6.6 [ ]]The passivation layer of methyl-phenyl-C61 is spin-coated at a speed of 800-1000rpm for 10-15s, then at a speed of 4000-6000rpm for 20-35s, and finally annealed at a temperature of 100-120 ℃ for 30-60min, wherein the Cs is in the passivation layer0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3When 5-10s before the precursor solution is spin-coated, 100-200 μ L of extraction liquid is dropped within 1-2 s.
9. The method of claim 8, wherein the extraction solution is one of chlorobenzene, ethyl acetate, or anisole.
10. As claimed in claimThe method of (5), wherein in step (5), the method for preparing the hole transport layer by spin coating comprises the following steps: the material comprises a substrate layer, an electron transport layer, and polymethyl methacrylate/[ 6.6]]-phenyl-C61 methyl butyrate passivation layer and Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3After the composite layer formed by stacking the perovskite light absorption layers is cooled to room temperature, a Spiro-OMeTAD chlorobenzene solution is dripped into Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite light absorption layer is spin-coated for 30-40s at 3000-.
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