Perovskite-silicon tandem solar cell and preparation method therefor

Abstract

Provided are a perovskite-silicon tandem solar cell and a preparation method therefor. The perovskite-silicon tandem solar cell comprises a silicon-based battery, an ITO intermediate composite layer, a first hole transport layer, a second hole transport layer, a perovskite light absorption layer, a first electron transport layer, a second electron transport layer, a top transparent conductive layer, and a conductive metal electrode, which are all sequentially stacked. The perovskite-silicon tandem solar cell of the present application can fully achieve the advantages of perovskite batteries and crystalline silicon batteries, reduce the effect of humidity and oxygen on the perovskite material while reducing the optical coupling effect of the perovskite material and the crystalline silicon material, lower the interface effect, and improve the efficiency and stability of the perovskite-silicon tandem solar cell.

Description

A perovskite crystalline silicon stacked battery and its preparation method Technical Field

[0001] The present application belongs to the field of photovoltaic technology and relates to a perovskite crystalline silicon stacked cell and a preparation method thereof. Background Art

[0002] Perovskite-Silicon Tandem Solar Cells (PSCs) are a new type of solar cell structure that stacks perovskite solar cells and crystalline silicon solar cells. This stacked structure is designed to improve solar energy conversion efficiency and achieve a wider range of light absorption across the spectrum. The working principle of PSCs is that in the stacked structure, the perovskite solar cell is located on the top layer to absorb high-energy light, while the crystalline silicon solar cell is located on the bottom layer to absorb low-energy light.

[0003] Perovskite-crystalline silicon tandem cells offer several advantages. First, because perovskite solar cells absorb high-energy light and crystalline silicon solar cells absorb low-energy light, respectively, they can more efficiently utilize solar energy across the entire spectrum. Second, perovskite materials have a high light absorption coefficient and high photoelectric conversion efficiency, while crystalline silicon materials have a long lifespan and good stability. By combining these two materials, their respective advantages can be fully utilized to achieve higher overall performance.

[0004] However, perovskite materials are sensitive to humidity and oxygen and are prone to decomposition and degradation, leading to decreased battery performance.

[0005] CN112582545A discloses a laminated perovskite solar cell and its preparation method, belonging to the field of solar cell device technology. The device comprises a high-transmittance glass layer, a transparent electrode layer, a hole transport layer, a first perovskite active layer, a first electron transport layer, a multifunctional tin oxide layer, a second perovskite active layer, a second electron transport layer, and a metal counter electrode layer, which are sequentially connected to form an integrated solar device. The multifunctional tin oxide layer has a thickness of 10 to 50 nm, and the diameter of the tin oxide nanoparticles in the multifunctional tin oxide layer is 5 to 20 nm.

[0006] CN116033767A discloses a crystalline silicon perovskite tandem solar cell and its preparation method. The cell comprises: a crystalline silicon solar cell, an intermediate transparent conductive layer, a metal oxide layer, and a perovskite solar cell stacked sequentially from bottom to top. The intermediate transparent conductive layer covers a portion of the crystalline silicon solar cell; each edge of the intermediate transparent conductive layer is indented a set distance relative to the edge of the adjacent crystalline silicon solar cell; and the metal oxide layer covers the intermediate transparent conductive layer and the area of ​​the crystalline silicon solar cell not covered by the intermediate transparent conductive layer.

[0007] The preparation cost of the perovskite silicon tandem battery obtained by the above scheme is relatively high, and there are interface problems between the two materials, and the light coupling effect is serious, which affects its photoelectric conversion efficiency. Summary of the Invention

[0008] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0009] The present application provides a perovskite crystalline silicon tandem cell and a preparation method thereof. In the present application, the perovskite crystalline silicon tandem cell can give full play to the advantages of perovskite cells and crystalline silicon cells, while reducing the impact of humidity and oxygen on perovskite materials, reducing the optical coupling effect of perovskite materials and crystalline silicon materials, reducing interface effects, and improving the efficiency and stability of the perovskite crystalline silicon tandem cell.

[0010] In the first aspect, the present application provides a perovskite crystalline silicon stacked cell, which includes a silicon bottom cell, an ITO intermediate composite layer, a first hole transport layer, a second hole transport layer, a perovskite light absorption layer, a first electron transport layer, a second electron transport layer, a top transparent conductive layer and a conductive metal electrode stacked in sequence.

[0011] In this application, crystalline silicon cells and perovskite cells are combined into stacked cells, which can more effectively utilize solar energy within the spectral range. Perovskite materials have a higher light absorption coefficient and a higher photoelectric conversion efficiency, while crystalline silicon materials have a longer life and better stability. By combining these two materials, their advantages can be fully utilized, thereby achieving higher overall performance. Two hole transport layers of different materials are provided in the perovskite cell. The synergistic effect between the first hole transport layer and the second hole transport layer can produce a multiple gain effect to reduce charge loss, thereby improving the performance of the battery and thus improving the photoelectric conversion efficiency. Two electron transport layers of different materials are provided in the perovskite cell, C60 plays an electron transport role, and tin oxide plays an electron transport and protection role in blocking PVD sputtering damage.

[0012] Preferably, the silicon bottom cell comprises a back conductive metal electrode, a bottom transparent conductive layer, a p-type amorphous silicon layer, a first intrinsic amorphous silicon layer, a silicon wafer, a second intrinsic amorphous silicon layer and an n-type amorphous silicon layer stacked in sequence.

[0013] Preferably, the n-type amorphous silicon layer is connected to the ITO intermediate composite layer.

[0014] Preferably, the first transport layer comprises a nickel oxide hole transport layer.

[0015] Preferably, the second hole transport layer comprises a PACz-based hole transport layer.

[0016] Preferably, the material of the second hole transport layer includes any one or a combination of at least two of [2-(9-carbazol-9-yl)ethyl]phosphonic acid (2PACz), [2-(dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz), [2-(3,6-diphenyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Me-2PACz), [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid (MeO-4PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) or [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz).

[0017] Preferably, the second hole transport layer comprises formamidine hydroiodide.

[0018] In this application, by incorporating formamidine hydroiodide into the hole transport layer and forming an interpenetrating interface heterojunction structure between the hole transport layer and the perovskite, the performance of the solar cell can be significantly improved. By reducing the hole transport distance, improving the carrier transport efficiency, increasing the open-circuit voltage and short-circuit current, and improving the fill factor, the photoelectric conversion efficiency of the perovskite crystalline silicon tandem cell is improved.

[0019] Preferably, the first electron transport layer comprises a C60 thin film electron transport layer.

[0020] Preferably, the second electron transport layer comprises a SnO2 thin film electron transport layer.

[0021] Preferably, the top transparent conductive layer comprises an ITO film.

[0022] Preferably, the conductive metal electrode comprises a silver metal electrode.

[0023] Preferably, the thickness of the ITO intermediate composite layer is 15-25 nm, for example, 15 nm, 18 nm, 20 nm, 22 nm or 25 nm.

[0024] Preferably, the thickness of the first hole transport layer is 10-20 nm, for example, 10 nm, 12 nm, 15 nm, 18 nm or 20 nm.

[0025] Preferably, the thickness of the second hole transport layer is 2-5 nm.

[0026] Preferably, the thickness of the perovskite light-absorbing layer is 350-600 nm, for example, 350 nm, 400 nm, 450 nm, 500 nm or 600 nm.

[0027] Preferably, the thickness of the first electron transport layer is 15-25 nm, for example, 15 nm, 18 nm, 20 nm, 22 nm or 25 nm.

[0028] Preferably, the second electron transport layer has a thickness of 10 to 20 nm, for example, 10 nm, 12 nm, 15 nm, 18 nm or 20 nm.

[0029] Preferably, the thickness of the top transparent conductive layer is 100-150 nm, for example, 100 nm, 110 nm, 120 nm, 140 nm or 150 nm.

[0030] Preferably, the thickness of the conductive metal electrode is 800-1000 nm, for example, 800 nm, 850 nm, 900 nm, 950 nm or 1000 nm.

[0031] In a second aspect, the present application provides a method for preparing the perovskite crystalline silicon tandem cell as described in the first aspect, the preparation method comprising the following steps:

[0032] (1) After depositing an ITO composite layer on the N-face microcrystalline silicon of a crystalline silicon cell substrate, sputtering a first hole transport layer on the ITO composite layer, and spin-coating a second hole transport layer on the first hole transport layer;

[0033] (2) vapor-depositing a divalent metal halide on the second hole transport layer, spin-coating a halogenated organic solution on the vapor-deposited film layer, and annealing to obtain a perovskite light-absorbing layer;

[0034] (3) evaporating a first electron transport layer on the perovskite light absorbing layer, and depositing a second electron transport layer on the first electron transport layer using an atomic deposition technique;

[0035] (4) sputtering a top transparent conductive layer on the second electron transport layer, and evaporating a conductive metal electrode on the top transparent conductive layer to obtain the perovskite crystalline silicon stacked cell.

[0036] Preferably, the concentration of the PACz compound in the spin-coating solution for spin-coating the second hole transport layer in step (1) is 0.5-1.5 mmol / L, for example: 0.5 mmol / L, 0.8 mmol / L, 1 mmol / L, 1.2 mmol / L or 1.5 mmol / L.

[0037] Preferably, the spin coating speed is 2000-4000 rad / s, for example, 2000 rad / s, 2500 rad / s, 3000 rad / s, 3500 rad / s or 4000 rad / s.

[0038] Preferably, the spin coating liquid contains formamidine hydroiodide.

[0039] Preferably, the concentration of formamidine hydroiodide in the spin coating solution is 5-15 mg / mL, for example, 5 mg / mL, 8 mg / mL, 10 mg / mL, 12 mg / mL or 15 mg / mL.

[0040] Preferably, annealing is performed after the spin coating.

[0041] Preferably, the annealing treatment temperature is 80-120°C, for example, 80°C, 90°C, 100°C, 110°C or 120°C.

[0042] Preferably, the annealing treatment time is 8 to 12 minutes, for example, 8 minutes, 9 minutes, 10 minutes, 11 minutes or 12 minutes.

[0043] Preferably, the divalent metal halide in step (2) comprises any one of lead iodide, cesium iodide or lead bromide, or a combination of at least two of them.

[0044] Preferably, the evaporation rate of lead iodide is For example: or wait.

[0045] Preferably, the evaporation rate of cesium iodide is For example: or wait.

[0046] Preferably, the evaporation rate of lead bromide is For example: or wait.

[0047] Preferably, the solute of the halogenated organic solution in step (2) includes any one of methylamine iodide, methylamine bromide, methylamine iodide or methylamine chloride, or a combination of at least two thereof.

[0048] Preferably, the solvent of the halogenated organic solution includes isopropyl alcohol.

[0049] Preferably, the concentration of the halogenated organic solution is 1 to 1.5 mol / L, for example, 1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L or 1.5 mol / L.

[0050] Preferably, the annealing temperature is 100-150°C, for example, 100°C, 110°C, 120°C, 130°C or 150°C.

[0051] Preferably, the annealing time is 10 to 15 minutes, for example, 10 minutes, 11 minutes, 12 minutes, 13 minutes or 15 minutes.

[0052] Compared with the related art, this application has the following beneficial effects:

[0053] (1) The perovskite crystalline silicon tandem cell described in this application can give full play to the advantages of perovskite cells and crystalline silicon cells. While reducing the impact of humidity and oxygen on the perovskite material, it also reduces the optical coupling effect between the perovskite material and the crystalline silicon material, reduces the interface effect, and improves the efficiency and stability of the perovskite crystalline silicon tandem cell.

[0054] (2) After the addition of formamidine hydroiodide into the hole transport layer, the open circuit voltage, short circuit current and fill factor of the stacked battery were improved, and the conversion efficiency was also improved. This is because the addition of formamidine hydroiodide into the hole transport layer forms an interpenetrating interface heterojunction structure between the hole transport layer and the perovskite, shortening the hole transmission distance and improving the hole carrier transport performance.

[0055] Still other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 is a schematic structural diagram of a perovskite crystalline silicon stacked cell according to an embodiment of the present application; wherein, 101 is a back conductive metal electrode; 102 is a back transparent conductive layer; 103 is a p-type amorphous silicon layer; 104 is a first intrinsic amorphous silicon layer; 105 is a silicon wafer; 106 is a second intrinsic amorphous silicon layer; 107 is an n-type amorphous silicon layer; 108 is an ITO intermediate composite layer; 109 is a nickel oxide hole transport layer (a first hole transport layer); 110 is a PACz type hole transport layer (a second hole transport layer); 111 is a perovskite absorption layer; 112 is a C60 thin film electron transport layer (a first electron transport layer); 113 is a SnO2 thin film electron transport layer (a second electron transport layer); 114 is a top transparent conductive layer; and 115 is a conductive metal electrode. DETAILED DESCRIPTION

[0057] The technical solution of the present application is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0058] The crystalline silicon cells used in the embodiments and comparative examples of the present application all include a back conductive metal electrode, a bottom transparent conductive layer, a p-type amorphous silicon layer, a first intrinsic amorphous silicon layer, a silicon wafer, a second intrinsic amorphous silicon layer and an n-type amorphous silicon layer stacked in sequence.

[0059] Example 1

[0060] This embodiment provides a perovskite crystalline silicon tandem cell, which is prepared by the following method:

[0061] (1) depositing an ITO composite layer with a thickness of 20 nm on the N-side microcrystalline silicon of the crystalline silicon cell substrate, sputtering a nickel oxide hole transport layer (first hole transport layer) with a thickness of 15 nm on the ITO composite layer by magnetron, and spin-coating a PACz hole transport layer on the nickel oxide hole transport layer. The concentration of [2-(dimethoxy-9-9-yl)ethyl]phosphonic acid (MeO-2PACz) in the spin-coating solution used is 1 mmol / L, and the concentration of formamidine hydroiodide is 10 g / L, to obtain a PACz hole transport layer (second hole transport layer) with a thickness of 2-5 nm;

[0062] (2) Using the co-evaporation technology, lead iodide, cesium iodide and lead bromide are evaporated on the second hole transport layer. The lead iodide evaporation rate is The evaporation rate of cesium lead iodide is The lead bromide evaporation rate is A mixture of 1.2 mol / L methylammonium iodide and isopropyl alcohol was spin-coated on the evaporated film layer and annealed at 120°C for 12 minutes to obtain a perovskite light-absorbing layer with a thickness of 530 nm.

[0063] (3) a 20 nm thick C60 electron transport layer (first electron transport layer) was prepared on the perovskite light absorption layer, and a 15 nm thick tin oxide film (second electron transport layer) was deposited on the C60 electron transport layer using atomic deposition technology;

[0064] (4) Sputter a layer of 120nm thick on the surface of the tin oxide film layer An ITO film (top transparent conductive layer) is deposited, and a silver metal electrode (conductive metal electrode) with a thickness of 900 nm is evaporated on the surface of the ITO to obtain the perovskite crystalline silicon stacked battery. The structural schematic diagram of the perovskite crystalline silicon stacked battery is shown in Figure 1, wherein 101 is a back conductive metal electrode; 102 is a back transparent conductive layer; 103 is a p-type amorphous silicon layer; 104 is a first intrinsic amorphous silicon layer; 105 is a silicon wafer; 106 is a second intrinsic amorphous silicon layer; 107 is an n-type amorphous silicon layer; 108 is an ITO intermediate composite layer; 109 is a nickel oxide hole transport layer (first hole transport layer); 110 is a PACz-type hole transport layer (second hole transport layer); 111 is a perovskite absorption layer; 112 is a C60 thin film electron transport layer (first electron transport layer); 113 is a SnO2 thin film electron transport layer (second electron transport layer); 114 is a top transparent conductive layer; and 115 is a conductive metal electrode.

[0065] Example 2

[0066] This embodiment provides a perovskite crystalline silicon tandem cell, which is prepared by the following method:

[0067] (1) depositing an ITO composite layer with a thickness of 15 nm on the N-side microcrystalline silicon of the crystalline silicon cell substrate, sputtering a nickel oxide hole transport layer (first hole transport layer) with a thickness of 10 nm on the ITO composite layer by magnetron, and spin-coating a PACz hole transport layer on the nickel oxide hole transport layer. The concentration of [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACz) in the spin-coating solution used is 0.5 mmol / L, and the concentration of formamidine hydroiodide is 5 g / L, to obtain a PACz hole transport layer (second hole transport layer) with a thickness of 2-5 nm;

[0068] (2) Using the co-evaporation technology, lead iodide, cesium iodide and lead bromide are evaporated on the second hole transport layer. The lead iodide evaporation rate is The evaporation rate of cesium lead iodide is The lead bromide evaporation rate is A mixture of 1 mol / L methylammonium iodide and isopropyl alcohol was spin-coated on the evaporated film layer and annealed at 100°C for 15 minutes to obtain a 350 nm thick perovskite light-absorbing layer.

[0069] (3) a C60 electron transport layer (first electron transport layer) with a thickness of 15 nm was prepared on the perovskite light absorbing layer, and a tin oxide film (second electron transport layer) with a thickness of 10 nm was deposited on the C60 electron transport layer using atomic deposition technology;

[0070] (4) Sputter a layer of 100 nm thick tin oxide film on the surface An ITO film (top transparent conductive layer) is deposited, and a silver metal electrode (conductive metal electrode) with a thickness of 800 nm is evaporated on the surface of the ITO to obtain the perovskite crystalline silicon stacked battery. The structural schematic diagram of the perovskite crystalline silicon stacked battery is shown in Figure 1, wherein 101 is a back conductive metal electrode; 102 is a back transparent conductive layer; 103 is a p-type amorphous silicon layer; 104 is a first intrinsic amorphous silicon layer; 105 is a silicon wafer; 106 is a second intrinsic amorphous silicon layer; 107 is an n-type amorphous silicon layer; 108 is an ITO intermediate composite layer; 109 is a nickel oxide hole transport layer (first hole transport layer); 110 is a PACz type hole transport layer (second hole transport layer); 111 is a perovskite absorption layer; 112 is a C60 thin film electron transport layer (first electron transport layer); 113 is a SnO2 thin film electron transport layer (second electron transport layer); 114 is a top transparent conductive layer; and 115 is a conductive metal electrode.

[0071] Example 3

[0072] This embodiment provides a perovskite crystalline silicon tandem cell, which is prepared by the following method:

[0073] (1) depositing an ITO composite layer with a thickness of 25 nm on the N-side microcrystalline silicon of the crystalline silicon cell substrate, sputtering a nickel oxide hole transport layer (first hole transport layer) with a thickness of 20 nm on the ITO composite layer by magnetron, and spin-coating a PACz hole transport layer on the nickel oxide hole transport layer. The concentration of [4-(9H-carbazole-9-yl)butyl]phosphonic acid (4PACz) in the spin-coating solution used is 1.5 mmol / L, and the concentration of formamidine hydroiodide is 15 g / L, to obtain a PACz hole transport layer (second hole transport layer) with a thickness of 2-5 nm;

[0074] (2) Using the co-evaporation technology, lead iodide, cesium iodide and lead bromide are evaporated on the second hole transport layer. The lead iodide evaporation rate is The evaporation rate of cesium lead iodide is The lead bromide evaporation rate is A mixture of 1.5 mol / L methylammonium iodide and isopropyl alcohol was spin-coated on the evaporated film layer and annealed at 150°C for 10 min to obtain a 600 nm thick perovskite light-absorbing layer.

[0075] (3) a C60 electron transport layer (first electron transport layer) with a thickness of 25 nm was prepared on the perovskite light absorbing layer, and a tin oxide film (second electron transport layer) with a thickness of 20 nm was deposited on the C60 electron transport layer using atomic deposition technology;

[0076] (4) Sputter a layer of 150nm thick tin oxide film on the surface An ITO film (top transparent conductive layer) is deposited, and a silver metal electrode (conductive metal electrode) with a thickness of 1000 nm is evaporated on the surface of the ITO to obtain the perovskite crystalline silicon stacked battery. The structural schematic diagram of the perovskite crystalline silicon stacked battery is shown in Figure 1, wherein 101 is a back conductive metal electrode; 102 is a back transparent conductive layer; 103 is a p-type amorphous silicon layer; 104 is a first intrinsic amorphous silicon layer; 105 is a silicon wafer; 106 is a second intrinsic amorphous silicon layer; 107 is an n-type amorphous silicon layer; 108 is an ITO intermediate composite layer; 109 is a nickel oxide hole transport layer (first hole transport layer); 110 is a PACz-type hole transport layer (second hole transport layer); 111 is a perovskite absorption layer; 112 is a C60 thin film electron transport layer (first electron transport layer); 113 is a SnO2 thin film electron transport layer (second electron transport layer); 114 is a top transparent conductive layer; and 115 is a conductive metal electrode.

[0077] Example 4

[0078] The only difference between this embodiment and embodiment 1 is that the concentration of formamidine hydroiodide in the spin coating solution is 1 mg, and the other conditions and parameters are exactly the same as those in embodiment 1.

[0079] Example 5

[0080] The only difference between this embodiment and embodiment 1 is that the concentration of formamidine hydroiodide in the spin-coating solution is 20 mg, and the other conditions and parameters are exactly the same as those in embodiment 1.

[0081] Example 6

[0082] The only difference between this embodiment and embodiment 1 is that formamidine hydroiodide is not added to the spin coating solution, and other conditions and parameters are exactly the same as those in embodiment 1.

[0083] Example 7

[0084] The only difference between this embodiment and embodiment 1 is that the concentration of the halogenated organic solution is 0.5 mol / L, and the other conditions and parameters are exactly the same as those in embodiment 1.

[0085] Example 8

[0086] The only difference between this embodiment and embodiment 1 is that the concentration of the halogenated organic solution is 2 mol / L, and the other conditions and parameters are exactly the same as those in embodiment 1.

[0087] Comparative Example 1

[0088] The only difference between this comparative example and Example 1 is that no nickel oxide hole transport layer is provided, and only one PACz type hole transport layer is provided. Other conditions and parameters are exactly the same as those in Example 1.

[0089] Comparative Example 2

[0090] The only difference between this comparative example and Example 1 is that no PACz-type hole transport layer is provided, and only one nickel oxide hole transport layer is provided. Other conditions and parameters are exactly the same as those in Example 1.

[0091] Performance testing:

[0092] The photoelectric conversion efficiency of the perovskite crystalline silicon tandem cells prepared in the examples and comparative examples was tested under standard test conditions (1.5 AM). The test results are shown in Table 1:

[0093] Table 1

[0094] As can be seen from Table 1 and Examples 1-3, formamidine hydroiodide can play the same role in different PACz-type hole transport layers.

[0095] By comparing Example 1 with Examples 4-5, it can be seen that during the preparation process of the perovskite crystalline silicon stack cell described in the present application, the concentration of formamidine hydroiodide in the spin-coating solution affects its performance. When the concentration of formamidine hydroiodide in the spin-coating solution is controlled at 5-15 mg / mL, the performance of the obtained perovskite crystalline silicon stack cell is better. If the concentration of formamidine hydroiodide in the spin-coating solution is too high, the excess formamidine hydroiodide will block charge transfer. If the concentration of formamidine hydroiodide in the spin-coating solution is too low, an interpenetrating interface heterojunction structure cannot be formed between the hole transport layer and the perovskite.

[0096] Comparison of Examples 1 and 6 shows that in this application, the incorporation of formamidine hydroiodide into the hole transport layer and the formation of an interpenetrating interface heterojunction structure between the hole transport layer and the perovskite can significantly improve the performance of the solar cell. By reducing the hole transport distance, improving the carrier transport efficiency, increasing the open circuit voltage and short circuit current, and improving the fill factor, the photoelectric conversion efficiency of the perovskite crystalline silicon tandem cell is improved.

[0097] By comparing Example 1 with Examples 7-8, it can be seen that during the preparation process of the perovskite crystalline silicon stacked battery described in the present application, the concentration of the halogenated organic solution will affect its performance. When the concentration of the halogenated organic solution is controlled at 1 to 1.5 mol / L, the performance of the obtained perovskite crystalline silicon stacked battery is better. If the concentration of the halogenated organic solution is too high, the excess halogenated organic matter will cover the perovskite layer, blocking charge transfer and reducing efficiency. If the concentration of the halogenated organic solution is too low, the reaction with the underlying inorganic layer is insufficient, and the inorganic layer will have residues, reducing efficiency.

[0098] By comparing Example 1 and Comparative Examples 1-2, it can be seen that the perovskite battery described in the present application is provided with two hole transport layers of different materials. The synergistic effect between the first hole transport layer and the second hole transport layer can produce a multiple gain effect to reduce charge loss, improve the performance of the battery, and thus improve the photoelectric conversion efficiency.

[0099] The applicant declares that the above is only a specific implementation method of the present application, but the protection scope of the present application is not limited thereto. Technical personnel in the relevant technical field should understand that any changes or substitutions that can be easily thought of by technical personnel in the relevant technical field within the technical scope disclosed in this application fall within the protection scope and disclosure scope of this application.

Claims

1. A perovskite crystalline silicon stacked cell, which includes a silicon bottom cell, an ITO intermediate composite layer, a first hole transport layer, a second hole transport layer, a perovskite light absorption layer, a first electron transport layer, a second electron transport layer, a top transparent conductive layer and a conductive metal electrode stacked in sequence.

2. The perovskite crystalline silicon tandem cell according to claim 1, wherein: The silicon bottom cell comprises a back conductive metal electrode, a bottom transparent conductive layer, a p-type amorphous silicon layer, a first intrinsic amorphous silicon layer, a silicon wafer, a second intrinsic amorphous silicon layer and an n-type amorphous silicon layer which are stacked in sequence; Preferably, the n-type amorphous silicon layer is connected to the ITO intermediate composite layer.

3. The perovskite crystalline silicon tandem cell according to claim 1 or 2, wherein: The first transport layer includes a nickel oxide hole transport layer.

4. The perovskite crystalline silicon tandem cell according to any one of claims 1 to 3, wherein: The second hole transport layer comprises a PACz-based hole transport layer; Preferably, the material of the second hole transport layer includes any one of [2-(9-carbazole-9-yl)ethyl]phosphonic acid, [2-(dimethoxy-9-9-yl)ethyl]phosphonic acid, [2-(3,6-diphenyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid or [4-(9H-carbazole-9-yl)butyl]phosphonic acid or a combination of at least two thereof; Preferably, the second hole transport layer comprises formamidine hydroiodide.

5. The perovskite crystalline silicon tandem cell according to any one of claims 1 to 4, wherein: The first electron transport layer comprises a C60 thin film electron transport layer; Preferably, the second electron transport layer comprises a SnO2 thin film electron transport layer.

6. The perovskite crystalline silicon tandem cell according to any one of claims 1 to 5, wherein: The top transparent conductive layer includes an ITO film; Preferably, the conductive metal electrode comprises a silver metal electrode.

7. The perovskite crystalline silicon tandem cell according to any one of claims 1 to 6, wherein: The thickness of the ITO intermediate composite layer is 15 to 25 nm; Preferably, the thickness of the first hole transport layer is 10 to 20 nm; Preferably, the thickness of the second hole transport layer is 2-5 nm; Preferably, the thickness of the perovskite light absorbing layer is 350-600 nm; Preferably, the thickness of the first electron transport layer is 15 to 25 nm; Preferably, the thickness of the second electron transport layer is 10 to 20 nm; Preferably, the thickness of the top transparent conductive layer is 100-150 nm; Preferably, the thickness of the conductive metal electrode is 800-1000 nm.

8. A method for preparing a perovskite crystalline silicon tandem cell according to any one of claims 1 to 7, comprising the following steps: (1) after depositing an ITO composite layer on the N-side microcrystalline silicon of a crystalline silicon cell substrate, sputtering a first hole transport layer on the ITO composite layer, and spin coating a second hole transport layer on the first hole transport layer; (2) evaporating a divalent metal halide on the second hole transport layer, spin-coating a halogenated organic solution on the evaporated film layer, and annealing to obtain a perovskite light absorbing layer; (3) evaporating a first electron transport layer on the perovskite light absorption layer, and depositing a second electron transport layer on the first electron transport layer using an atomic deposition technique; (4) sputtering a top transparent conductive layer on the second electron transport layer, and evaporating a conductive metal electrode on the top transparent conductive layer to obtain the perovskite crystalline silicon stacked cell.

9. The preparation method according to claim 8, wherein The concentration of the PACz compound in the spin coating solution for spin coating the second hole transport layer in step (1) is 0.5 to 1.5 mmol / L; Preferably, the spin coating speed is 2000-4000 rad / s; Preferably, the spin coating solution contains formamidine hydroiodide; Preferably, the concentration of formamidine hydroiodide in the spin coating solution is 5 to 15 mg / mL.

10. The preparation method according to claim 8 or 9, wherein: After the spin coating, annealing is performed; Preferably, the annealing temperature is 80-120°C; Preferably, the annealing treatment time is 8 to 12 minutes.

11. The preparation method according to any one of claims 8 to 10, wherein: The divalent metal halide in step (2) comprises any one of lead iodide, cesium iodide or lead bromide, or a combination of at least two thereof; Preferably, the evaporation rate of lead iodide is Preferably, the evaporation rate of cesium iodide is Preferably, the evaporation rate of lead bromide is 12. The preparation method according to any one of claims 8 to 11, wherein: The solute of the halogenated organic solution in step (2) comprises any one of methylamine iodide, methylamine bromide, methylamine iodide or methylamine chloride, or a combination of at least two thereof; Preferably, the solvent of the halogenated organic solution comprises isopropanol; Preferably, the concentration of the halogenated organic solution is 1 to 1.5 mol / L.

13. The preparation method according to any one of claims 8 to 12, wherein: The annealing temperature in step (2) is 100-150° C. Preferably, the annealing time is 10 to 15 minutes.

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