Quasi-two-dimensional perovskite silicon laminated solar cell and preparation method thereof

Abstract

The invention provides a quasi-two-dimensional perovskite silicon laminated solar cell and a preparation method thereof. The quasi-two-dimensional perovskite silicon laminated solar cell comprises a passivated quasi-two-dimensional perovskite top cell with a transparent electrode and a silicon bottom cell. The laminated solar cell structurally comprises an antireflection film, a metal electrode, a transparent conductive layer, an electron transport layer, a top electrode buffer layer, a passivation layer, a quasi-two-dimensional perovskite absorption layer, a hole transport layer, an intermediate composite layer and a silicon solar bottom cell from top to bottom in sequence. The laminated solar cell is simple in preparation process, low in cost, high in conversion efficiency and stability and suitable for various industrial and civil fields.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite-silicon tandem solar cells, and particularly relates to a quasi-two-dimensional perovskite thin film-silicon tandem solar cell and a preparation method thereof. Background Art

[0002] The perovskite-silicon tandem solar cell is a new type of solar cell with high potential for photovoltaic conversion. It uses perovskite and silicon as photovoltaic materials and combines the perovskite layer and the silicon layer through a tandem structure. In this tandem cell, each layer structure can absorb sunlight of different wavelengths respectively, so as to maximize the photovoltaic conversion efficiency and realize more efficient utilization of solar energy. The working principle of the perovskite-silicon tandem solar cell is that when sunlight shines on the cell surface, light of different wavelengths is divided into several continuous parts. Light with shorter wavelengths is absorbed by the wide-bandgap material located in the outer layer, while light with longer wavelengths passes through the outer layer and enters the inner layer, which is absorbed and utilized by the narrow-bandgap silicon material, thereby maximizing the conversion of light energy into electrical energy.

[0003] In the tandem structure, the silicon material has a small bandgap and can effectively absorb sunlight with longer wavelengths. The perovskite material becomes an ideal upper light-absorbing material due to its high light absorption coefficient and excellent optoelectronic properties. Among them, the quasi-two-dimensional perovskite exhibits higher stability due to its unique structural advantages: its hydrophobicity and the long organic cation part can effectively prevent water from penetrating into the lattice and simultaneously inhibit ion migration, thereby enhancing the long-term durability of the cell. It is an ideal combination with silicon to form a highly stable and efficient tandem solar cell. Summary of the Invention

[0004] The present invention provides a perovskite-silicon tandem solar cell and a preparation method thereof. The present invention forms a tandem solar cell by combining highly stable quasi-two-dimensional perovskite and silicon, improving the stability and photovoltaic conversion efficiency of the solar cell.

[0005] To achieve the above object, the technical solution of the present invention is: a perovskite-silicon tandem solar cell, which is characterized by including an antireflection film, a metal electrode, a transparent conductive layer, an electron transport layer, a top electrode buffer layer, a passivation layer, a quasi-two-dimensional perovskite absorption layer, a hole transport layer, an intermediate composite layer, and a silicon solar bottom cell.

[0006] The antireflection layer includes, but is not limited to, one or more of SiO2, ZnS, MgF2, TiO2, AI2O3, LiF, Si3N4, and the thickness is 0.001 - 5 mm. The metal electrode includes, but is not limited to, one or more of gold, silver, copper, aluminum, titanium, nickel, and the thickness is 0.001 - 10 μm.

[0007] The transparent conductive layer includes, but is not limited to, one or more of ITO, IZO, AZO, graphene, or metal (gold, silver, copper, aluminum) nanowires, with a thickness of 1 - 1000 nm.

[0008] The electron transport layer includes, but is not limited to, one or more of ZnO, SnO2, ZrO2, fullerene derivatives (C 60 , C 70 ), TiO2, ICBA, BCP, with a thickness of 1 - 1000 nm.

[0009] The top electrode buffer layer includes, but is not limited to, one or more of microcrystalline silicon, amorphous silicon, fullerene derivatives (C 60 , C 70 ), SnO2, Si3N4, ZnO, Ag, Au, Al2O3, SiO2, PMMA, with a thickness of 1 - 100 nm.

[0010] The passivation layer includes, but is not limited to, one or more of lithium fluoride (LiF), rubidium fluoride (RbF), graphene, bis(acetylacetone)benzoic acid hydrochloride (PBGH), potassium L - aspartate (PL - A), histamine diiodide (HADI), ammonium sulfamate (AS), multidentate ligand (BTP), N - chlorosuccinimide (NCS), amino - functionalized polymer (PN4N), heparin potassium (HP), graphdiyne (GDY), methylammonium chloride (MACl), formamidinium chloride (FACl), europium metal - organic framework (Eu - MOF), black phosphorene (BP), 3,4 - difluorothiophene (TzNDI - 2FT), polymethyl methacrylate - co - acrylamide polymer (PMMA - AM), ammonium fluoride (NH4F), guanidinium iodide (GAI), benzylamine hydroiodide (BAHI), and two - dimensional perovskites, with a thickness of 0.001 - 50 nm.

[0011] The quasi - two - dimensional perovskite absorption layer has a chemical general formula of A'(A) n-1 B n X 3n+1 , where A' is a large - sized organic cation, including, but not limited to, guanidinium, phenethylamine, octylamine, or a combination thereof; A is a small - sized monovalent cation, including, but not limited to, methylammonium, cesium, or a combination thereof; B is a divalent cation, including, but not limited to, lead, tin, or a combination thereof; X is a monovalent anion, including, but not limited to, chlorine, bromine, iodine, or one or more pseudohalogens; n is a positive integer with a range of 2 to 10. This absorption layer has a quasi - two - dimensional layered structure, where the large - sized organic cation A' isolates the inorganic perovskite layer, forming a periodic organic - inorganic interface, with a thickness of 1 - 5000 nm. The optimized specific chemical composition is GA(MA)5Pb5I 16 , where GA is guanidinium, MA is methylammonium, Pb is lead, and I is iodine.

[0012] The hole transport layer includes, but is not limited to, one or more of SAM, PEDOT:PSS, TPD, PTAA, NiO, 2PACz, DMAcPA, Me-4PACz, Me-2PACz, MPA2FPh-BT-BA, Sprio-OMeTAD, Spiro-TTB, TAPC, CuI, WO x and has a thickness of 1 - 1000 nm.

[0013] The intermediate composite layer includes, but is not limited to, one or several of a transparent conductive film, a metal, and graphene, and has a thickness of 0.001 - 1000 nm.

[0014] The silicon solar bottom cell includes, but is not limited to, a crystalline silicon solar bottom cell with a homojunction, a heterojunction, or a hybrid structure, and has a thickness of 0.01 - 10 mm.

[0015] The present invention provides a method for preparing a perovskite / silicon tandem solar cell. The preparation method includes the following steps: S1. Provide a crystalline silicon bottom cell substrate, where the crystalline silicon bottom cell is a crystalline silicon solar bottom cell with a homojunction, a heterojunction, or a hybrid structure; S2. Prepare a hole transport layer on the crystalline silicon bottom cell by methods including, but not limited to, spin coating, evaporation, sputtering, and spraying; S3. Prepare a quasi-two-dimensional perovskite absorption layer on the hole transport layer by methods including, but not limited to, spin coating, evaporation, sputtering, and spraying; S4. Prepare a passivation layer on the quasi-two-dimensional perovskite layer by methods including, but not limited to, spin coating, evaporation, sputtering, and spraying; S5. Prepare a top electrode buffer layer on the passivation layer by methods including, but not limited to, spin coating, evaporation, spraying, and atomic layer deposition; S6. Prepare an electron transport layer on the electrode buffer layer by methods including, but not limited to, spin coating, evaporation, spraying, and atomic layer deposition; S7. Prepare a transparent conductive layer on the electron transport layer by methods including, but not limited to, spin coating, evaporation, sputtering, and spraying; S9. Prepare a metal electrode on the transparent conductive layer by methods including, but not limited to, evaporation, sputtering, and atomic layer deposition; S10. Prepare an antireflection layer on the top of the cell by methods including, but not limited to, evaporation, sputtering, and atomic layer deposition to complete the preparation of the tandem solar cell. Description of the Drawings

[0016] Figure 1 It is a schematic structural diagram of the tandem solar cell described in the present invention; Among them, (1) is an antireflection layer, (2) is a metal electrode, (3) is a transparent conductive layer, (4) is an electron transport layer, (5) is a top electrode buffer layer, (6) is a passivation layer, (7) is a quasi-two-dimensional perovskite absorption layer, (8) is a hole transport layer, (9) is an intermediate composite layer, and (10) is a silicon solar bottom cell. Specific implementation

[0017] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0018] See Figure 1 , where (1) is an antireflection film, (2) is a metal electrode, (3) is a transparent conductive layer, (4) is an electron transport layer, (5) is a top electrode buffer layer, (6) is a passivation layer, (7) is a quasi-two-dimensional perovskite absorption layer, (8) is a hole transport layer, (9) is an intermediate composite layer, and (10) is a silicon solar bottom cell.

[0019] The antireflection layer (1) includes, but is not limited to, one or more of SiO2, ZnS, MgF2, TiO2, AI2O3, LiF, and Si3N4, and the thickness is 0.001 - 5 mm.

[0020] The metal electrode (2) includes, but is not limited to, one or more of gold, silver, copper, aluminum, titanium, and nickel, and the thickness is 0.001 - 10 μm.

[0021] The transparent conductive layer (3) includes, but is not limited to, one or more of ITO, IZO, AZO, graphene, or metal (gold, silver, copper, aluminum) nanowires, and the thickness is 1 - 1000 nm.

[0022] The electron transport layer (4) includes, but is not limited to, one or more of ZnO, SnO2, ZrO2, fullerene derivatives (C 60 , C 70 ), TiO2, ICBA, and BCP, and the thickness is 1 - 1000 nm.

[0023] The top electrode buffer layer (5) includes, but is not limited to, one or more of microcrystalline silicon, amorphous silicon, fullerene derivatives (C 60 , C 70 ), SnO2, Si3N4, ZnO, Ag, Au, Al2O3, SiO2, and PMMA, and the thickness is 1 - 100 nm.

[0024] The passivation layer (6) includes, but is not limited to, one or more of lithium fluoride (LiF), rubidium fluoride (RbF), graphene, p-benzoylbenzoic acid hydrochloride (PBGH), potassium L-aspartate (PL-A), histamine diiodide (HADI), ammonium sulfamate (AS), multidentate ligand (BTP), N-chlorosuccinimide (NCS), amino-functionalized polymer (PN4N), potassium heparin (HP), graphdiyne (GDY), methylammonium chloride (MACl), formamidinium chloride (FACl), europium metal-organic framework (Eu-MOF), black phosphorus (BP), 3,4-difluorothiophene (TzNDI-2FT), polymethyl methacrylate co-acrylamide polymer (PMMA-AM), ammonium fluoride (NH4F), guanidine iodide (GAI), benzylamine hydroiodide (BAHI), and two-dimensional perovskite, with a thickness of 0.001 - 50 nm.

[0025] The quasi-two-dimensional perovskite absorption layer (7) has a chemical general formula of A'(A) n-1 B n X 3n+1 , where A' is a large-sized organic cation, including, but not limited to, guanidinium, phenethylamine, octylamine, or a combination thereof; A is a small-sized monovalent cation, including, but not limited to, methylammonium, cesium, or a combination thereof; B is a divalent cation, including, but not limited to, lead, tin, or a combination thereof; X is a monovalent anion, including, but not limited to, chlorine, bromine, iodine, or one or more pseudohalogens; n is a positive integer with a range of 2 to 10. This absorption layer has a quasi-two-dimensional layered structure, where the large-sized organic cation A' isolates the inorganic perovskite layer, forming a periodic organic-inorganic interface, with a thickness of 1 - 5000 nm. The specific chemical composition after optimization is GA(MA)5Pb5I 16 , where GA is guanidinium, MA is methylammonium, Pb is lead, and I is iodine.

[0026] The hole transport layer (8) includes, but is not limited to, one or more of SAM, PEDOT:PSS, TPD, PTAA, NiO, 2PACz, DMAcPA, Me-4PACz, Me-2PACz, MPA2FPh-BT-BA, Spiro-OMeTAD, Spiro-TTB, TAPC, CuI, WO x , with a thickness of 1 - 1000 nm.

[0027] The intermediate composite layer (9) includes, but is not limited to, one or several of transparent conductive film, metal, and graphene, with a thickness of 0.001 - 1000 nm.

[0028] The silicon solar bottom cell (10) includes, but is not limited to, a crystalline silicon solar bottom cell with a homojunction, heterojunction, or hybrid structure, with a thickness of 0.001 - 10 mm.

[0029] A perovskite / silicon tandem solar cell and a preparation method thereof, comprising the following steps: S1. Provide a crystalline silicon bottom cell substrate, which is a crystalline silicon solar bottom cell with a homojunction, heterojunction or hybrid structure; S2. Prepare a hole transport layer on the bottom crystalline silicon cell by methods including but not limited to spin coating, evaporation, sputtering, and spraying; S3. Prepare a quasi-two-dimensional perovskite absorption layer on the hole transport layer by methods including but not limited to spin coating, evaporation, sputtering, and spraying; S4. Prepare a passivation layer on the quasi-two-dimensional perovskite layer by methods including but not limited to spin coating, evaporation, sputtering, and spraying; S5. Prepare a top electrode buffer layer on the passivation layer by methods including but not limited to spin coating, evaporation, spraying, and atomic layer deposition; S6. Prepare an electron transport layer on the electrode buffer layer by methods including but not limited to spin coating, evaporation, spraying, and atomic layer deposition; S7. Prepare a transparent conductive layer on the electron transport layer by methods including but not limited to spin coating, evaporation, sputtering, and spraying; S9. Prepare a metal electrode on the transparent conductive layer by methods including but not limited to evaporation, sputtering, and atomic layer deposition; S10. Prepare an antireflection layer on the top of the cell by methods including but not limited to evaporation, sputtering, and atomic layer deposition to complete the preparation of the tandem solar cell.

[0030] The following is a more detailed description with more specific examples: Example 1 In this example, a tandem solar cell is prepared using an antireflection layer / silver grid / ITO / SnO2 / C 60 / guanidinium iodide / quasi-two-dimensional perovskite / MeO-2PACz / ITO / heterojunction silicon structure. The specific preparation process is as follows: Sputter deposit a 20 nm ITO intermediate composite layer on the heterojunction crystalline silicon bottom cell; Spin coat a MeO-2PACz hole transport layer on the intermediate composite layer; Spin coat a GA(MA)5Pb5I 16 quasi-two-dimensional perovskite absorption layer on the hole transport layer; Spin coat a GAI passivation layer on the quasi-two-dimensional perovskite absorption layer; Prepare a 15 nm C 60 top cell buffer layer on the passivation layer by evaporation; ALD a 20 nm SnO2 electron transport layer on the top cell buffer layer; Prepare a 100 nm ITO transparent conductive layer on the electron transport layer by sputtering; Deposit a 200 nm silver metal grid on the transparent conductive layer by thermal evaporation; Evaporate a textured PDMS antireflection layer on the front of the cell to complete the preparation of the tandem solar cell.

[0031] Table 1 shows the optoelectronic and stability performance of the stacked solar cell described in Example 1.

[0032]

[0033] The above embodiments are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, various changes, modifications, substitutions, and deformations can be made to these embodiments. The technical solutions obtained by equivalent substitution of the claims of the present invention all fall within the protection scope of the present invention. The protection scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A quasi-two-dimensional perovskite / silicon tandem solar cell, characterized in that: The stacked solar cell includes an antireflection film, a metal electrode, a transparent conductive layer, an electron transport layer, a top electrode buffer layer, a passivation layer, a perovskite absorption layer, a hole transport layer, a transparent conductive layer, n-type amorphous silicon, an amorphous silicon buffer layer, n-type monocrystalline silicon, an amorphous buffer layer, p-type amorphous silicon, a transparent charge layer, and a metal bottom electrode.

2. The quasi-two-dimensional perovskite silicon tandem solar cell according to claim 1, wherein: The antireflection layer includes one or more of SiO2, ZnS, MgF2, TiO2, AI2O3, LiF, and Si3N4, and has a thickness of 0.001 - 5 mm.

3. The quasi-two-dimensional perovskite / silicon tandem solar cell according to claim 1, wherein: The metal electrode includes one or more of gold, silver, copper, aluminum, titanium, and nickel, and has a thickness of 0.001 - 10 μm.

4. The quasi-two-dimensional perovskite-silicon tandem solar cell according to claim 1, wherein: The transparent conductive layer includes one or more of ITO, IZO, AZO, graphene, or metal (gold, silver, copper, aluminum) nanowires, and has a thickness of 1 - 1000 nm.

5. The quasi-two-dimensional perovskite-silicon tandem solar cell according to claim 1, wherein: The electron transport layer includes one or more of ZnO, SnO2, ZrO2, fullerene derivatives (C 60 , C 70 ), TiO2, ICBA, and BCP, and has a thickness of 1 - 1000 nm.

6. The quasi-two-dimensional perovskite silicon tandem solar cell according to claim 1, wherein: The top electrode buffer layer includes one or more of microcrystalline silicon, amorphous silicon, fullerene derivatives (C 60 , C 70 ), SnO2, Si3N4, ZnO, Ag, Au, Al2O3, SiO2, PMMA, and has a thickness of 1 - 100 nm.

7. The quasi-two-dimensional perovskite-silicon tandem solar cell according to claim 1, wherein: The passivation layer includes one or more of lithium fluoride (LiF), rubidium fluoride (RbF), graphene, bis(acetylacetone)benzoic acid hydrochloride (PBGH), potassium L-aspartate (PL-A), histamine diiodide (HADI), ammonium sulfamate (AS), multidentate ligand (BTP), N-chlorosuccinimide (NCS), amino-functionalized polymer (PN4N), heparin potassium (HP), graphdiyne (GDY), methylammonium chloride (MACl), formamidinium chloride (FACl), europium metal-organic framework (Eu-MOF), black phosphorus (BP), 3,4-difluorothiophene (TzNDI-2FT), polymethyl methacrylate co-acrylamide polymer (PMMA-AM), ammonium fluoride (NH4F), guanidinium iodide (GAI), benzylamine hydroiodide (BAHI), and two-dimensional perovskite, and has a thickness of 0.001 - 50 nm.

8. The quasi-two-dimensional perovskite silicon tandem solar cell according to claim 1, characterized in that: The quasi-two-dimensional perovskite absorption layer has a chemical general formula of A'(A) n-1 B n X 3n+1 , where A' is a large-sized organic cation, including guanidinium, phenethylamine, octylamine or a combination thereof, A is a small-sized monovalent cation, including methylammonium, cesium or a combination thereof, B is a divalent cation, including lead, tin or a combination thereof, X is a monovalent anion, including chlorine, bromine, iodine or one or more of pseudohalogens, n is a positive integer, ranging from 2 to 10, and the absorption layer has a quasi-two-dimensional layered structure, in which the large-sized organic cation A' isolates the inorganic perovskite layer, forming a periodic organic-inorganic interface, with a thickness of 1 - 5000 nm. The specific chemical composition after optimization is GA(MA)5Pb5I 16 , where GA is guanidinium, MA is methylammonium, Pb is lead, and I is iodine.

9. The quasi-two-dimensional perovskite-silicon tandem solar cell according to claim 1, characterized in that: The hole transport layer includes one or more of SAM, PEDOT:PSS, TPD, PTAA, NiO, 2PACz, DMAcPA, Me-4PACz, Me-2PACz, MPA2FPh-BT-BA, Sprio-OMeTAD, Spiro-TTB, TAPC, CuI, WO x with a thickness of 1 - 1000 nm.

10. A method for preparing the quasi-two-dimensional perovskite silicon tandem solar cell according to any one of claims 1-9, characterized in that, It includes the following steps: S1. Provide a crystalline silicon bottom cell substrate, and the crystalline silicon bottom cell is a crystalline silicon solar bottom cell with a homojunction, heterojunction, or hybrid structure; S2. Prepare a hole transport layer on the crystalline silicon bottom cell by one of spin coating, evaporation, sputtering, and spraying; S3. Prepare a quasi-two-dimensional perovskite absorption layer on the hole transport layer by one of spin coating, evaporation, sputtering, and spraying; S4. Prepare a passivation layer on the quasi-two-dimensional perovskite layer by one of spin coating, evaporation, sputtering, and spraying; S5. Prepare a top electrode buffer layer on the passivation layer by one of spin coating, evaporation, spraying, and atomic layer deposition; S6. Prepare an electron transport layer on the electrode buffer layer by one of spin coating, evaporation, spraying, and atomic layer deposition; S7. Prepare a transparent conductive layer on the electron transport layer by one of spin coating, evaporation, sputtering, and spraying; S9. Prepare a metal electrode on the transparent conductive layer by one of evaporation, sputtering, and atomic layer deposition; S10. Prepare an antireflection layer on the top of the cell by one of evaporation, sputtering, and atomic layer deposition to complete the preparation of the stacked solar cell.

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