Perovskite thin film and preparation method thereof, and perovskite solar cell
By introducing haloammonium salt additives during the perovskite thin film preparation process, perovskite surface and bulk defects are passivated, crystallization performance is improved, the efficiency and stability problems of perovskite solar cells are solved, and photoelectric performance and stability are enhanced.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ADVANCED SOLAR TECH INST XUANCHENG
- Filing Date
- 2026-04-24
- Publication Date
- 2026-07-24
AI Technical Summary
The presence of numerous defects in perovskite thin films leads to low efficiency and poor stability in perovskite solar cells.
In the preparation of perovskite thin films, haloammonium salt additives are introduced. The large cations in the haloammonium salt additives passivate the negatively charged defects on the perovskite surface, and the iodine vacancies are passivated by the halide ions, thereby improving the crystallinity of perovskite and reducing the defect density.
This improves the photoelectric performance and stability of perovskite solar cells and reduces the nonradiative recombination loss of photogenerated charges.
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Figure CN122458682A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of perovskite photovoltaic technology, specifically to a perovskite thin film and its preparation method, and a perovskite solar cell. Background Technology
[0002] Perovskite solar cells (PSCs), representing third-generation photovoltaic technology, have become an emerging force in the photovoltaic field since their initial application in 2009. This is due to the superior photoelectric properties exhibited by organic-inorganic hybrid perovskites, such as high absorption coefficient, long carrier lifetime, and tunable bandgap, as well as their significant cost-effectiveness. Organic-inorganic hybrid perovskites have attracted widespread attention due to their numerous advantages, including high absorption coefficient, high defect tolerance, high carrier mobility, and long diffusion length.
[0003] In the two-step process for preparing large-area perovskite thin films, the crystallization rate of perovskite is often relatively fast. However, due to factors such as the soft ion properties of the material, the volatility of organic components, and the dislocations in the perovskite lattice itself, the resulting polycrystalline thin films are prone to generating numerous defects. These defects can induce nonradiative recombination of charge carriers, thereby reducing the efficiency of perovskite solar cells and affecting their stability.
[0004] Therefore, improving the crystallinity of the perovskite layer and passivating defects on the surface of the perovskite layer are key to improving the efficiency and stability of perovskite solar cells. Summary of the Invention
[0005] In view of this, the purpose of the present invention is to solve the problem that there are many defects in the perovskite thin film in the prior art, which leads to low efficiency and poor stability of perovskite solar cells, and to provide a perovskite thin film, a method for preparing the same, and a perovskite solar cell.
[0006] In a first aspect, the present invention provides a method for preparing a perovskite thin film, comprising the following steps: preparing a lead salt layer; preparing an organic salt layer on the lead salt layer; and annealing to obtain the perovskite thin film; The raw materials for the organic salt layer include perovskite precursor organic materials and haloammonium salt additives, wherein the haloammonium salt additives are hydrohalates formed by the structure shown in formula (I).
[0007] Formula (I) In equation (1), n is an integer selected from 0 to 5; a and b are independent integers selected from 0 to 6; R1, R2, and R3 are each independently selected from H, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, or substituted or unsubstituted C1-C6 alkoxy; wherein R2 and R3 can be interconnected to form substituted or unsubstituted C3-C6 aliphatic rings. The substituted C1-C6 alkyl, substituted C2-C6 alkenyl, substituted C1-C6 alkoxy, and substituted C3-C6 aliphatic ring substituents are selected from one or more of halogen, cyano, C1-C6 alkyl, and C1-C6 alkoxy.
[0008] In some alternative implementations, 'a' is selected from 0, 1, 2, 3, 4, 5, and 6.
[0009] In some alternative implementations, b is selected from one of 0, 1, 2, 3, 4, 5, and 6.
[0010] In some alternative implementations, a and b are each independently selected from integers between 0 and 3.
[0011] In some alternative implementations, 'a' is selected from 0, 1, 2, and 3.
[0012] In some alternative implementations, b is selected from 0, 1, 2, and 3.
[0013] In some alternative embodiments, the hydrohalic acid is selected from at least one of hydrochloric acid or hydrobromic acid.
[0014] In some alternative embodiments, R1, R2, and R3 are each independently selected from H, F, Br, Cl, cyano, substituted or unsubstituted group A, or substituted or unsubstituted ring B formed by the interconnection of R2 and R3. Wherein, group A is selected from methyl, ethyl, propyl, isopropyl, trifluoromethyl, n-butyl, and tert-butyl; The ring B is selected from cyclopropyl, cyclobutyl, cyclopentane, and cyclohexane; The substituents of the substituted group A and the substituted ring B are each independently selected from one or more of F, Br, Cl, and cyano.
[0015] In some alternative implementations, equation (I) includes any of the following structures: .
[0016] In some optional embodiments, the lead salt layer is prepared by physical vapor deposition.
[0017] In some optional embodiments, the method for preparing the lead salt layer includes at least one of vacuum evaporation and sputtering.
[0018] In some alternative embodiments, the raw material for the lead salt layer includes at least one of cesium iodide, lead bromide, and lead iodide.
[0019] In some optional embodiments, the method for preparing the organic salt layer includes the following steps: mixing a solution of a perovskite precursor organic material and an additive to obtain a precursor solution, and then coating the precursor solution onto one side surface of a lead salt layer to obtain the organic salt layer.
[0020] In some alternative embodiments, the perovskite precursor organic material includes at least one of formamidine iodide, formamidine bromide, methylamine iodide, and methylamine chloride.
[0021] In some alternative embodiments, the concentration of the additive in the precursor solution is 1 mg / mL to 5 mg / mL.
[0022] In some optional embodiments, the total concentration of the perovskite precursor organic material in the precursor solution is 0.8 mol / L to 1.2 mol / L.
[0023] In some alternative embodiments, the coating method includes at least one of slot coating, blade coating, spin coating, and spray coating.
[0024] In some alternative embodiments, the solvent of the solution of the perovskite precursor organic material includes at least one of isopropanol and ethanol.
[0025] In some alternative embodiments, the thickness of the lead salt layer is 350 nm to 450 nm.
[0026] In some alternative embodiments, the thickness of the perovskite film is 500 nm to 800 nm.
[0027] In some optional embodiments, the annealing temperature is 120°C-150°C, and the annealing time is 10 min-15 min.
[0028] In a second aspect, the present invention provides a perovskite thin film, which is prepared by the preparation method described in the first aspect.
[0029] Thirdly, the present invention provides a perovskite solar cell, wherein the perovskite thin film described in the second aspect of the present invention or the perovskite thin film prepared by the preparation method described in the first aspect of the present invention is a perovskite thin film.
[0030] The technical solution of the present invention has the following advantages: This invention provides a method for preparing a perovskite thin film, comprising the following steps: preparing a lead salt layer; preparing an organic salt layer on the lead salt layer; annealing to obtain the perovskite thin film; the raw materials of the organic salt layer include a perovskite precursor organic material and a haloammonium salt additive, wherein the haloammonium salt additive is a hydrohalate formed by the structure shown in formula (I). In the method for preparing the perovskite thin film provided by this invention, by introducing a haloammonium salt additive into the organic salt layer, the large cations in the haloammonium salt additive can passivate the negatively charged defects on the perovskite surface, reducing the nonradiative recombination of charge carriers at the interface; halide ions can enter the bulk phase of the perovskite and passivate iodine vacancies, reducing the defect density of the perovskite layer, improving the crystallinity of the perovskite, increasing the grain size while further reducing the nonradiative recombination loss of photogenerated charges, thereby improving the photoelectric performance and stability of the perovskite device. Attached Figure Description
[0031] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0032] Figure 1 This is a cross-sectional SEM image of the perovskite thin film of Example 1; Figure 2 The image shows a cross-sectional SEM image of the perovskite film in Comparative Example 1. Figure 3 The image shows a cross-sectional SEM image of the perovskite film in Comparative Example 2. Figure 4 The figures show the decay curves of the device efficiency over time obtained in Examples 1-8 and Comparative Examples 1 and 2. Detailed Implementation
[0033] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments. It should be understood that the embodiments described herein are merely illustrative of the invention and not intended to limit it. Furthermore, it should be noted that, for ease of description, only the parts relevant to the present invention are shown in the drawings, not the entire structure.
[0034] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.
[0035] Example 1 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 3-(4-fluorophenyl)prop-1-amine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 3-(4-fluorophenyl)prop-1-amine hydrochloride was 2 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub gate has a width of 50 μm and a thickness of 1000 nm.
[0036] Example 2 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 3-(4-fluorophenyl)prop-1-amine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 3-(4-fluorophenyl)prop-1-amine hydrochloride was 1 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub-gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub-gate has a width of 50 μm and a thickness of 1000 nm.
[0037] Example 3 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 3-(4-fluorophenyl)prop-1-amine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 3-(4-fluorophenyl)prop-1-amine hydrochloride was 5 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub-gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub-gate has a width of 50 μm and a thickness of 1000 nm.
[0038] Example 4 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 3-methyl-3-phenylbut-1-amine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 3-methyl-3-phenylbut-1-amine hydrochloride was 2 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub-gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub-gate has a width of 50 μm and a thickness of 1000 nm.
[0039] Example 5 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 3-(2-chloro-4-fluorophenyl)prop-1-amine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 3-(2-chloro-4-fluorophenyl)prop-1-amine hydrochloride was 2 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub gate has a width of 50 μm and a thickness of 1000 nm.
[0040] Example 6 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 3-phenylpropylamine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 3-phenylpropylamine hydrochloride was 2 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub gate has a width of 50 μm and a thickness of 1000 nm.
[0041] Example 7 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 2-(1-phenylcyclopropyl)ethyl-1-amine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 2-(1-phenylcyclopropyl)ethyl-1-amine hydrochloride was 2 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub gate has a width of 50 μm and a thickness of 1000 nm.
[0042] Example 8 This embodiment provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then phenylpropyl ammonium bromide was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of phenylpropyl ammonium bromide was 2 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub gate has a width of 50 μm and a thickness of 1000 nm.
[0043] Comparative Example 1 This comparative example provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) Organic materials are dissolved in isopropanol at a concentration of 1.0 mol / L to obtain a precursor solution. The organic materials include methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20). The precursor solution is coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the cutting head during coating is 200 μm, the coating rate is 15 mm / s, and the liquid discharge rate is 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub gate has a width of 50 μm and a thickness of 1000 nm.
[0044] Comparative Example 2 This comparative example provides a method for fabricating a perovskite-crystalline silicon heterojunction tandem solar cell, including the following steps: (1) Magnetron sputtering was used to sputter 166*166mm 2 ITO layers are prepared on both sides of the textured silicon substrate, wherein the thickness of the ITO on the N-side is about 30 nm and the thickness of the ITO on the P-side is about 100 nm. (2) A back silver electrode with a thickness of 1µm is prepared on the surface of the P-plane ITO layer away from the silicon substrate by thermal evaporation, wherein the deposition rate is 10Å / s; (3) A NiO layer with a thickness of 18 nm is prepared on the surface of the N-plane ITO layer facing away from the silicon substrate. x Layer, then anneal at 180°C for 20 minutes; (4) NiO is deposited using a hot evaporation method. x Cesium iodide, lead bromide, and lead iodide are deposited together on the surface of the layer opposite to the ITO substrate to obtain an inorganic layer with a thickness of 380 nm. The evaporation rate of cesium iodide is 0.5 Å / s, the evaporation rate of lead bromide is 1 Å / s, and the evaporation rate of lead iodide is maintained at 12 Å / s. (5) The organic material was dissolved in isopropanol at a concentration of 1.0 mol / L, and then 2,2,2-trifluoroethylamine hydrochloride was added to obtain a precursor solution. The organic material included methylamine iodide, formamidine iodide, methylamine chloride, and formamidine bromide (mass ratio of 10:40:7:20), and the concentration of 2,2,2-trifluoroethylamine hydrochloride was 2 mg / mL. The precursor solution was coated on the surface of the inorganic salt layer away from the ITO substrate using a slit coating process, and then annealed at 150°C for 10 min to obtain a perovskite layer with a thickness of 700 nm. The height of the slit was 200 μm, the coating rate was 15 mm / s, and the liquid discharge rate was 15 μL / s. (6) A C layer with a thickness of 20 nm is deposited on the surface of the perovskite layer away from the silicon substrate using a thermal evaporation method. 60 Layer, wherein the deposition rate is 0.5 Å / s; (7) Atomic layer deposition technology was used in C 60 A SnO2 layer with a thickness of 20 nm is prepared on the surface of the layer opposite to the silicon substrate. (8) A top ITO conductive layer with a thickness of 100 nm is prepared on the surface of the SnO2 layer away from the silicon substrate by magnetron sputtering. (9) A top silver gate electrode is prepared on the surface of the top ITO conductive layer away from the silicon substrate by thermal evaporation. The silver gate electrode is divided into a main gate and a sub gate. The main gate has a width of 60 μm and a thickness of 1000 nm. The sub gate has a width of 50 μm and a thickness of 1000 nm.
[0045] Perovskite layer surface morphology test The cross-sections of the perovskite thin films of the perovskite-crystalline silicon heterojunction tandem solar cells prepared in Example 1, Comparative Example 1, and Comparative Example 2 were measured using scanning electron microscopy (SEM). The test results for Example 1 are as follows: Figure 1 As shown, the test results of Comparative Example 1 are as follows: Figure 2 As shown, the test results for Comparative Example 2 are as follows: Figure 3 As shown.
[0046] Figure 2 In the example, the cross-sectional SEM image of the perovskite tandem solar cell prepared in Comparative Example 1 (without any additives) shows that there are a large amount of unconverted lead salts in the perovskite layer. Figure 3 In Comparative Example 2 (with the addition of 2,2,2-trifluoroethylamine hydrochloride), the perovskite layer of the prepared perovskite tandem solar cell also contained unconverted lead salts; while Figure 1In Example 1, after the addition of 3-(4-fluorophenyl)prop-1-amine hydrochloride, the lead salt was completely converted into perovskite, and the crystallization performance was significantly better than that of Comparative Example 1 and Comparative Example 2, with larger grains. This indicates that by adding hydrohalate formed with the structure shown in Formula (I) to the organic salt layer, the full conversion of lead salt can be effectively promoted and the crystallization performance of perovskite can be improved.
[0047] Performance testing 1) Photoelectric conversion efficiency test Under standard solar test conditions (AM 1.5G, 1000 W / m²) 2 The efficiency of the perovskite-crystalline silicon heterojunction tandem solar cells prepared in the examples and comparative examples was tested at 25℃. The test results are shown in Table 1, where Voc represents the open-circuit voltage, Jsc represents the short-circuit current density, FF represents the fill factor, and PCE represents the photoelectric conversion efficiency.
[0048] 2) Stability test The perovskite-crystalline silicon heterojunction tandem solar cells prepared in the examples and comparative examples were placed in an air environment, and the photoelectric conversion efficiency was tested and recorded at different times. The photoelectric conversion efficiency after 0 hours in the environment was denoted as PCE0, and the photoelectric conversion efficiency after m hours in the environment was denoted as PCEm. The ratio of PCEm to PCE0 is the PCE retention rate of the cell, and the time when the PCE retention rate reaches 80% is denoted as T80. The T80 of each example and comparative example is shown in Table 1. The decay curves of the device efficiency as a function of time prepared in Examples 1-8 and Comparative Examples 1 and 2 are shown in Table 1. Figure 4 As shown.
[0049] Table 1 Performance test results of perovskite-crystalline silicon heterojunction tandem solar cells prepared in each embodiment and comparative example
[0050] As shown in Table 1, compared with Comparative Example 1 which does not contain haloammonium salt, Example 1 significantly improved the photoelectric conversion efficiency and cycle stability of perovskite solar cells by introducing additives containing large cations and halide ions. This indicates that the introduction of haloammonium salt additives effectively improves the crystallinity of perovskite, reduces bulk defects in perovskite, thereby suppressing nonradiative recombination in perovskite solar cells, and thus greatly improves the photoelectric conversion efficiency and stability of perovskite solar cells.
[0051] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
[0052] The above description is merely a preferred embodiment of the present invention and the technical principles employed. Those skilled in the art will understand that the present invention is not limited to the specific embodiments described above, and various obvious changes, readjustments, combinations, and substitutions can be made without departing from the scope of protection of the present invention. Therefore, although the present invention has been described in detail through the above embodiments, the present invention is not limited to the above embodiments, and may include many other equivalent embodiments without departing from the concept of the present invention.
[0053] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.
[0054] In this invention, "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more substituents. When there are multiple substituents, they can be the same or different.
[0055] In this document, the term "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment can be included in at least one embodiment or implementation of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. The term "implementation" as used herein has a similar understanding. Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.
[0056] In this invention, terms such as "multiple", "multiple", "several", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more types.
[0057] In this invention, terms such as "preferred" and "better" merely describe implementation methods or embodiments with better effects and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.
[0058] In this invention, "optionally" or "optionally" means that something is optional, that is, it refers to either "with" or "without". If multiple "options" appear in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "option" is independent.
[0059] In this invention, open-ended technical features or solutions described using terms such as "containing," "comprising," or "including" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and features or solutions where "A includes not only a1, a2, and a3, but also other members."
[0060] Furthermore, in this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.
Claims
1. A method for preparing a perovskite thin film, characterized in that, Includes the following steps: Preparation of lead salt layer; An organic salt layer was prepared on a lead salt layer; Annealing yields the perovskite film; The raw materials for the organic salt layer include perovskite precursor organic materials and haloammonium salt additives, wherein the haloammonium salt additives are hydrohalates formed by the structure shown in formula (I). Formula (I) In equation (1), n is an integer selected from 0 to 5; a and b are independent integers selected from 0 to 6; R1, R2, and R3 are each independently selected from H, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, or substituted or unsubstituted C1-C6 alkoxy; wherein R2 and R3 can be interconnected to form substituted or unsubstituted C3-C6 aliphatic rings. The substituted C1-C6 alkyl, substituted C2-C6 alkenyl, substituted C1-C6 alkoxy, and substituted C3-C6 aliphatic ring substituents are selected from one or more of halogen, cyano, C1-C6 alkyl, and C1-C6 alkoxy.
2. The method for preparing perovskite thin films according to claim 1, characterized in that, a and b are each independent integers selected from 0 to 3; Preferably, the hydrohalic acid is selected from at least one of hydrochloric acid or hydrobromic acid; Preferably, R1, R2, and R3 are each independently selected from H, F, Br, Cl, cyano, substituted or unsubstituted group A, or substituted or unsubstituted ring B formed by the interconnection of R2 and R3; Wherein, group A is selected from methyl, ethyl, propyl, isopropyl, trifluoromethyl, n-butyl, and tert-butyl; The ring B is selected from cyclopropyl, cyclobutyl, cyclopentane, and cyclohexane; The substituents of the substituted group A and the substituted ring B are each independently selected from one or more of F, Br, Cl, and cyano.
3. The method for preparing perovskite thin films according to claim 1 or 2, characterized in that, Equation (I) includes any of the following structures: 。 4. The method for preparing perovskite thin films according to claim 1, characterized in that, The method for preparing the lead salt layer includes thermal evaporation deposition. Preferably, the raw materials for the lead salt layer include cesium iodide, lead bromide, and lead iodide.
5. The method for preparing perovskite thin films according to any one of claims 1-3, characterized in that, The method for preparing the organic salt layer includes the following steps: A solution of the perovskite precursor organic material and an additive are mixed to obtain a precursor solution. The precursor solution is then coated onto one side of a lead salt layer to obtain the organic salt layer.
6. The method for preparing perovskite thin films according to claim 5, characterized in that, The perovskite precursor organic material includes at least one of formamidine iodide, formamidine bromide, methylamine iodide, and methylamine chloride; Preferably, the concentration of the additive in the precursor solution is 1 mg / mL to 5 mg / mL; Preferably, the total concentration of the perovskite precursor organic material in the precursor solution is 0.8 mol / L-1.2 mol / L; Preferably, the coating method includes at least one of slot coating, blade coating, spin coating, and spray coating; Preferably, the solvent of the solution of the perovskite precursor organic material includes at least one of isopropanol and ethanol.
7. The method for preparing perovskite thin films according to any one of claims 1-6, characterized in that, The thickness of the lead salt layer is 350nm-450nm; Preferably, the thickness of the perovskite film is 500nm-800nm.
8. The method for preparing perovskite thin films according to claim 1, characterized in that, The annealing temperature is 120℃-150℃, and the annealing time is 10min-15min.
9. A perovskite thin film, characterized in that, The perovskite thin film is prepared by the preparation method according to any one of claims 1-8.
10. A perovskite solar cell, characterized in that, The perovskite solar cell comprises the perovskite thin film of claim 9 or the perovskite thin film prepared by the preparation method of any one of claims 1-8.