A perovskite solar cell, its preparation method, and photovoltaic module

Abstract

This invention provides a perovskite solar cell, its fabrication method, and a photovoltaic module. The perovskite solar cell comprises a substrate layer, a conductive functional layer, an intermediate anchoring layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, a conductive layer, and a metal electrode layer, stacked sequentially. The intermediate anchoring layer is made of a lanthanide metal salt. This invention utilizes the extranuclear multiple electrons of lanthanide metal salts and self-assembled monomolecular layers to achieve a multi-coordination structure, improving the adhesion and uniformity of the self-assembled monomolecules, mitigating interface defects, and thus enhancing the photoelectric efficiency of the photovoltaic module.

Description

Technical Field

[0001] This invention belongs to the field of solar cells, and relates to a perovskite solar cell, its preparation method, and a photovoltaic module. Background Technology

[0002] Perovskite solar cells are among the most promising competitors in the photovoltaic market due to their high efficiency, low cost, flexibility, and excellent photoelectric performance. Despite these significant advantages, the commercialization of perovskite cells still faces core challenges, such as susceptibility to corrosion from water, oxygen, light, or heat, which reduces their stability.

[0003] Perovskite solar cells are generally stacked structures of multilayer functional thin films. Assembled monolayers (SAMs) have been widely used in perovskite solar cells, especially in hole transport layers, where the single-cell efficiency of SAM-based perovskite cells has exceeded 27%. However, the coverage of SAMs on the transparent conductive oxide (TCO) layer is often insufficient and prone to detachment, resulting in voids and defects between the SAM and TCO layers. This uneven coverage can lead to direct contact between the perovskite and TCO layers, forming a poor interface that affects energy level matching and carrier transport, ultimately degrading device performance.

[0004] Therefore, new methods need to be developed to improve the coverage of SAM on the TCO layer and ensure good contact between layers, thereby improving the stability and efficiency of the device. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a perovskite solar cell, its preparation method, and a photovoltaic module. By introducing a functional layer with lanthanide metals, the multi-electron sites and holes are well coordinated, solving the problem of poor adhesion of the hole transport layer, improving the contact interface, and thus enhancing the stability and conversion efficiency of the photovoltaic module.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a perovskite battery, the perovskite battery comprising a substrate layer, a conductive functional layer, an intermediate anchoring layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, a conductive layer and a metal electrode layer stacked sequentially, wherein the material of the intermediate anchoring layer comprises a lanthanide metal salt.

[0008] This invention introduces a lanthanide metal salt between the conductive functional layer and the hole transport layer. The lanthanide salt has a large number of extranuclear electrons and forms a multi-coordination structure with holes, which firmly anchors the hole transport layer to the substrate layer, improves the coverage and uniformity of the hole transport layer, and significantly reduces interface defects.

[0009] As a preferred embodiment of the present invention, the general formula of the lanthanide metal salt is LnX3·yH2O.

[0010] Ln is selected from La, Ce, Pr, Nd, Sm, Eu, or Gd.

[0011] X is Cl - Or NO3 - y is an integer from 0 to 9.

[0012] In this invention, y is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably an integer from 0 to 7.

[0013] As a preferred embodiment of the present invention, the concentration of the lanthanide metal salt in the material of the intermediate anchoring layer is 0.01~0.10 mol / L, for example, it can be 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L or 0.10 mol / L, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0014] As one embodiment of the present invention, the thickness of the intermediate anchoring layer is 0.1~3.0nm, for example, it can be 0.1nm, 0.5nm, 0.8nm, 1.0nm, 1.2nm, 1.5nm, 2.0nm, 2.3nm, 2.5nm, 2.8nm or 3.0nm, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0015] As a preferred embodiment of the present invention, the conductive functional layer includes at least one of ITO, FTO, IZO and IWO.

[0016] The hole transport layer is a self-assembled monolayer.

[0017] As a preferred embodiment of the present invention, the thickness of the conductive functional layer is 5~50nm, for example, it can be 5nm, 8nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0018] As one embodiment of the present invention, the thickness of the self-assembled monolayer is 0.1~5.0 nm, for example, it can be 0.1 nm, 0.5 nm, 1.0 nm, 1.5 nm, 1.6 nm, 2.0 nm, 2.3 nm, 2.5 nm, 3.0 nm, 3.5 nm, 4.0 nm, 4.5 nm or 5.0 nm, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0019] In this invention, the self-assembled monolayer is extremely thin, highly ordered, and has controllable energy level arrangement, which can form a high-density coating, greatly reducing interfacial recombination and thus improving the open-circuit voltage of the photovoltaic module.

[0020] As a preferred embodiment of the present invention, an interface modification layer is further provided between the perovskite absorption layer and the electron transport layer.

[0021] The interface modification layer of the present invention can suppress interface recombination, optimize charge extraction and transport, and at the same time isolate water and oxygen erosion, effectively improving interface contact.

[0022] In one embodiment of the present invention, a hole blocking layer is further provided between the electron transport layer and the conductive layer.

[0023] In one embodiment of the present invention, an anti-reflection layer is provided on the side of the metal electrode layer away from the conductive layer.

[0024] This invention introduces an antireflection layer into perovskite solar cells, which reduces light reflection loss and significantly improves short-circuit current and photoelectric conversion efficiency. It also provides protection by preventing the erosion of moisture from the external environment.

[0025] In a second aspect, the present invention provides a method for preparing the perovskite solar cell described in the first aspect. The method includes: providing a substrate layer; depositing a conductive functional layer on the surface of the substrate layer; depositing a slurry containing a lanthanide metal salt on the surface of the conductive functional layer; and sequentially annealing and UVO (Ultraviolet / Ozone Treatment) surface modification to form an intermediate anchoring layer; subsequently depositing a hole transport layer, a perovskite absorption layer, an electron transport layer, and a conductive layer sequentially on the surface of the intermediate anchoring layer, and fabricating a metal electrode layer to obtain a perovskite solar cell.

[0026] As a preferred embodiment of the present invention, the concentration of the lanthanide metal salt in the slurry is 0.01~0.10 mol / L, for example, it can be 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L or 0.10 mol / L, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0027] As one embodiment of the present invention, the slurry further includes a solvent, which includes at least one selected from water, ethanol, isopropanol, butanol, acetonitrile, and tetrahydrofuran.

[0028] As one embodiment of the present invention, the slurry is deposited by a solution method or a vapor deposition method.

[0029] As one embodiment of the present invention, the UVO surface modification time is 1 to 10 minutes, for example, it can be 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0030] As one embodiment of the present invention, the annealing temperature is 60~110℃, for example, it can be 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃ or 110℃, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0031] As one embodiment of the present invention, the annealing time is 1 to 20 minutes, for example, it can be 1 minute, 5 minutes, 6 minutes, 8 minutes, 10 minutes, 13 minutes, 15 minutes, 18 minutes, 19 minutes or 20 minutes, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0032] Thirdly, the present invention provides a photovoltaic module, the photovoltaic module comprising the perovskite cell described in the first aspect.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] This invention provides a perovskite solar cell, its preparation method, and a photovoltaic module. By introducing an intermediate anchoring layer containing lanthanide metal salts between the transparent conductive functional layer and the hole transport layer, the uniformity and compactness of the hole transport layer molecules are increased, thereby enhancing its stability. At the same time, lanthanide metals have more extranuclear electrons, which coordinate with holes to form a multi-coordination structure, firmly anchoring the hole transport layer to the substrate, improving the adhesion of the hole transport layer, reducing interface defects, and inhibiting ion migration, thereby effectively improving the conversion efficiency and stability of the photovoltaic module. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the structure of the perovskite single-cell battery provided in Example 1.

[0036] Figure 2 This is a schematic diagram of the contact interface between the conductive functional layer, the intermediate anchoring layer, and the hole transport layer provided in Example 1.

[0037] Figure 3 The diagram below shows the structure of a single perovskite cell for Comparative Example 1.

[0038] Figure 4 A schematic diagram of the contact interface between the conductive functional layer, the intermediate anchoring layer and the hole transport layer provided for Comparative Example 1.

[0039] Figure 5 This is a schematic diagram of the perovskite tandem solar cell provided in Example 4.

[0040] Figure 6 This is a schematic diagram of the contact interface between the conductive functional layer, the intermediate anchoring layer, and the hole transport layer provided in Example 4.

[0041] Figure 7 The diagram shows the structure of the perovskite tandem solar cell provided for Comparative Example 2.

[0042] Figure 8 A schematic diagram of the contact interface between the conductive functional layer, the intermediate anchoring layer and the hole transport layer provided for Comparative Example 2.

[0043] Figure 9 This is a comparison chart of the maximum power point output curves of Example 5 and Comparative Example 2.

[0044] Among them, 1-first metal electrode layer; 2-antireflection layer; 3-first transparent conductive layer; 4-hole blocking layer; 5-electron transport layer; 6-interface modification layer; 7-perovskite absorption layer; 8-hole transport layer; 9-conductive functional layer; 10-silicon substrate layer; 11-second transparent conductive layer; 12-second metal electrode layer; 13-substrate layer; 14-intermediate anchoring layer. Detailed Implementation

[0045] It should be understood that in the description of this invention, the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. These terms are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0046] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0047] In one specific embodiment, the present invention provides a perovskite solar cell, comprising a substrate layer, a conductive functional layer, an intermediate anchoring layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, a conductive layer, and a metal electrode layer stacked sequentially, wherein the material of the intermediate anchoring layer comprises a lanthanide metal salt.

[0048] The substrate layer described in this invention can be a simple silicon substrate, such as a rigid substrate or a flexible conductive substrate with a TCO, or it can be a bottom cell structure to form a tandem cell with a perovskite cell, such as a crystalline silicon cell. This invention does not specifically limit the composition and structure of the substrate layer; those skilled in the art can make adaptive adjustments according to actual needs.

[0049] For single-cell perovskite solar cells, the conductive functional layer serves as a conductive layer on the substrate surface; for tandem perovskite solar cells, the conductive functional layer serves as a conductive composite layer connecting the top and bottom cells. The conductive functional layer is a transparent conductive oxide layer, including at least one of ITO, FTO, IZO, and IWO, with a thickness of 5-50 nm. When the substrate is a simple silicon substrate, the conductive functional layer and the silicon substrate constitute a conductive substrate; when the substrate is the bottom cell, the conductive functional layer can act as a tunneling layer, realizing the composite and connection of the bottom cell and the perovskite solar cell.

[0050] The intermediate anchoring layer contains a lanthanide metal salt with a concentration of 0.01~0.10 mol / L, having the general formula LnX3·yH2O, where Ln is selected from La, Ce, Pr, Nd, Sm, Eu, or Gd, and X is Cl. - Or NO3 -y is an integer from 0 to 9, preferably from 0 to 7. The lanthanide metal salt is preferably CeCl3·7H2O. The thickness of the intermediate anchoring layer is 0.1~3.0 nm, which reduces interface defects.

[0051] The hole transport layer is a self-assembled monolayer with a thickness of 0.1–5.0 nm. This self-assembled monolayer exhibits Lewis acidity, and its internal phosphate groups combine with multiple extranuclear electrons in the intermediate anchoring layer to form a multi-coordination structure, significantly improving its uniformity and density. Specifically, the materials used in the self-assembled monolayer include, but are not limited to, molecules containing acidic functional groups such as 4PADCB, MeO-2PACz, 2PACz, and Poly-2PACz.

[0052] The perovskite precursor in the perovskite absorber layer has the general formula ABX3, wherein A is a monovalent cation, including but not limited to at least one element selected from FA (formamidinyl), MA (methylamino), Cs and Rb; B is a divalent cation, including but not limited to Pb and / or Sn; and X is a monovalent anion, including but not limited to at least one element selected from iodine, bromine and chlorine.

[0053] The electron transport layer includes, but is not limited to, C. 60 At least one of PCBM or ICBA.

[0054] In some embodiments, an interface modification layer is further disposed between the perovskite absorber layer and the electron transport layer. Specifically, the interface modification layer includes PDAI2.

[0055] The conductive layer is a transparent oxide conductive layer, including but not limited to at least one of ITO, FTO, AZO or ATO.

[0056] In some embodiments, a hole-blocking layer is further disposed between the electron transport layer and the conductive layer. Specifically, the hole-blocking layer includes SnO. x .

[0057] The material of the metal electrode layer includes at least one of silver, aluminum, copper, or gold.

[0058] In some embodiments, an antireflection layer is provided on the side of the metal electrode layer away from the conductive layer. Specifically, the antireflection layer includes, but is not limited to, at least one of magnesium fluoride, lithium fluoride, zinc oxide, and tin oxide.

[0059] In another specific embodiment, the present invention provides a method for preparing a perovskite solar cell according to a specific embodiment, the method comprising the following steps.

[0060] S1: Provide a substrate layer, on which a conductive functional layer is deposited.

[0061] The deposition method of the conductive functional layer includes, but is not limited to, at least one of magnetron sputtering, sol-gel method, and atomic layer deposition. The present invention does not specifically limit the method steps and process parameters.

[0062] S2: A slurry containing lanthanide metal salts is deposited on the surface of the conductive functional layer, and then annealed and UVO surface modified in sequence to form an intermediate anchoring layer.

[0063] The concentration of the lanthanide metal salt in the slurry is 0.01~0.10 mol / L, and its general formula is LnX3·yH2O, where Ln is selected from La, Ce, Pr, Nd, Sm, Eu, or Gd, and X is Cl. - Or NO3 - y is an integer from 0 to 9, preferably from 0 to 7. The lanthanide metal salt is preferably CeCl3·7H2O. The slurry also includes a solvent, which includes at least one selected from water, ethanol, isopropanol, butanol, acetonitrile, and tetrahydrofuran.

[0064] The slurry is deposited via a solution method or an evaporation method. The present invention preferably employs a solution method, specifically spin coating, blade coating, or slot coating. More preferably, a spin coating process is used for slurry deposition, wherein the spin coating speed is 1000~4000 rpm and the spin coating time is 10~60 s.

[0065] The annealing temperature is 60~110℃, and the annealing time is 1~20min.

[0066] The UVO surface modification utilizes ultraviolet light irradiating the material surface in an oxygen environment to decompose the oxygen and generate ozone, thereby introducing hydrophilic functional groups into the material surface for activation and enhancing its wettability. The UVO surface modification uses ultraviolet light with a wavelength of 185nm, and the modification time is 1~10min.

[0067] S3: Subsequently, a hole transport layer, a perovskite absorption layer, an electron transport layer and a conductive layer are sequentially deposited on the surface of the intermediate anchoring layer, and a metal electrode layer is fabricated to obtain a perovskite solar cell.

[0068] This invention does not impose specific limitations on the deposition methods and process parameters of the hole transport layer, perovskite absorption layer, electron transport layer and conductive layer, as well as the preparation methods and process parameters of the metal electrode layer. Any preparation process that can achieve the corresponding functional layer can be applied to this invention.

[0069] In another specific embodiment, the present invention provides a photovoltaic module including a perovskite cell as described in a specific embodiment.

[0070] The photovoltaic module can be a crystalline silicon-perovskite tandem solar cell, comprising a first metal electrode layer, a first transparent conductive layer, a crystalline silicon sub-cell, a conductive functional layer, an intermediate anchoring layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, a transparent conductive layer, and a second metal electrode layer stacked sequentially. The crystalline silicon sub-cell includes an HJT sub-cell or a TOPCon sub-cell.

[0071] Example 1

[0072] This embodiment provides a perovskite single-cell battery and its preparation method, such as... Figure 1 and Figure 2 As shown, the perovskite single-cell solar cell includes a substrate layer 13, a conductive functional layer 9, an intermediate anchoring layer 14, a hole transport layer 8, a perovskite absorber layer 7, an interface modification layer 6, an electron transport layer 5, a hole blocking layer 4, a first transparent conductive layer 3, and a first metal electrode layer 1, stacked sequentially. The conductive functional layer 9 is an ITO layer with a thickness of 100 nm. The intermediate anchoring layer 14 is a coating containing a lanthanide metal salt with a thickness of 0.5 nm. The hole transport layer 8 is a self-assembled monolayer with a thickness of 1 nm. The perovskite absorber layer 7 has a thickness of 300 nm. The interface modification layer 6 is a PDAI2 coating with a thickness of 1 nm. The electron transport layer 5 is a C… 60 The layer has a thickness of 15 nm. Hole blocking layer 4 is made of SnO. x The thickness is 10 nm. The first transparent conductive layer 3 is a transparent IZO layer with a thickness of 45 nm. The first metal electrode layer 1 is a silver electrode with a thickness of 100 nm. An antireflection layer 2, made of MgF2, with a thickness of 100 nm is disposed on the back side of the substrate layer 13.

[0073] The preparation method in this embodiment specifically includes the following steps:

[0074] (1) Provide a substrate layer 13, and use magnetron sputtering process to form ITO on the substrate layer 13 to obtain a conductive functional layer 9.

[0075] (2) Spin-coating an aqueous solution of Nd(NO3)3·6H2O with a concentration of 0.01mol / L onto the conductive functional layer 9, controlling the rotation speed at 3000rpm and the time at 30s. After spin-coating, annealing is performed at 100℃ for 10min, followed by UVO surface modification for 10min to increase the wettability of the coating surface, thus obtaining the intermediate anchoring layer 14.

[0076] (3) Spin-coat a 0.3 mol / L isopropanol solution of 4 PADCB onto the intermediate anchoring layer 14, control the spin-coating speed to be 3000 rpm and the time to be 30 s, and anneal at 100℃ for 10 min after spin-coating to obtain the hole transport layer 8.

[0077] (4) Prepare 1.68 eV Cs 0.05FA 0.85 MA 0.10 Pb(I 0.75 Br 0.25 3. A perovskite precursor solution with a concentration of 1.2 mol / L was prepared using a mixture of DMF and DMSO in a volume ratio of 4:1, with an additional 0.8 mg of phenylethylamine hydrochloride added per milliliter of the perovskite precursor solution. The perovskite precursor solution was then filtered, and the filtered perovskite precursor solution was dropped onto the surface of hole transport layer 8. The solution was first spin-coated at 3000 rpm for 10 s, then at 5000 rpm for 20 s, and finally at 7000 rpm for 15 s. In the last 7 s, 150 μL of anisole was added as a poor solvent to promote perovskite crystallization. After spin-coating, the solution was annealed at 100 °C for 10 min to obtain perovskite absorber layer 7.

[0078] (5) Dissolve 1,3-diaminopropane dihydroiodide (PDAI2) in isopropanol solvent to a concentration of 1 mg / mL, stir thoroughly, filter, and spin-coat it onto the surface of the perovskite absorber layer 7. The spin-coating speed is 6000 rpm and the time is 30 s. Then, anneal at 100 °C to obtain the interface modification layer 6.

[0079] (6) Deposit C on interface modification layer 6 60 As electron transport layer 5, SnOx is deposited on the surface of electron transport layer 5 by atomic layer deposition, with tetramethylaminotin and water as precursors and nitrogen as working carrier gas, to obtain hole blocking layer 4.

[0080] (7) IZO is deposited on the hole blocking layer 4 by magnetron sputtering to obtain the first transparent conductive layer 3. The first metal electrode layer 1 is fabricated on the first transparent conductive layer 3 by vapor deposition. The anti-reflection layer 2 is formed on the back side of the substrate layer 13 by vapor deposition to complete the preparation of the perovskite solar cell.

[0081] Example 2

[0082] This embodiment provides a perovskite single-cell battery and its preparation method. The difference from Embodiment 1 is that the intermediate anchoring layer 14 is prepared by using an aqueous solution of Nd(NO3)3·6H2O with a concentration of 0.10 mol / L, and the thickness of the intermediate anchoring layer 14 is 2 nm. The remaining structure, preparation method and process parameters are the same as those in Embodiment 1.

[0083] Example 3

[0084] This embodiment provides a perovskite single-cell battery and its preparation method. The difference from Example 4 is that the intermediate anchoring layer 14 is prepared by using an aqueous solution of Nd(NO3)3·6H2O with a concentration of 0.15mol / L, and the thickness of the intermediate anchoring layer 14 is 4nm. The remaining structure, preparation method and process parameters are the same as those in Example 4.

[0085] Comparative Example 1

[0086] This comparative example provides a perovskite single-cell solar cell and its preparation method, such as... Figure 3 and Figure 4 As shown, the difference from Example 1 is that no intermediate anchoring layer 14 is set, while the rest of the structure, preparation method and process parameters are the same as those in Example 1.

[0087] Example 4

[0088] This embodiment provides a perovskite tandem solar cell and its fabrication method, such as... Figure 5 and Figure 6 As shown, the perovskite tandem solar cell includes, in sequence, a second metal electrode layer 12, a second transparent conductive layer 11, a silicon substrate layer 10, a conductive functional layer 9, an intermediate anchoring layer 14, a hole transport layer 8, a perovskite absorber layer 7, an interface modification layer 6, an electron transport layer 5, a hole blocking layer 4, a first transparent conductive layer 3, a first metal electrode layer 1, and an antireflection layer 2. The second transparent conductive layer 11 and the conductive functional layer 9 are ITO layers with thicknesses of 100 nm and 20 nm, respectively. The intermediate anchoring layer 14 is a coating containing a lanthanide metal salt with a thickness of 0.5 nm. The hole transport layer 8 is a self-assembled monolayer with a thickness of 2 nm. The perovskite absorber layer 7 has a thickness of 600 nm. The interface modification layer 6 is a PDAI2 coating with a thickness of 1 nm. The electron transport layer 5 is C 60 The first metal electrode layer 11nm thick has a hole-blocking layer 4 made of SnOx with a thickness of 10nm. The first transparent conductive layer 3 is a transparent IZO layer with a thickness of 50nm. The second metal electrode layer 12 and the first metal electrode layer 1 are both silver electrodes with a thickness of 400nm. The antireflection layer 2 is a magnesium fluoride coating with a thickness of 100nm.

[0089] The preparation method in this embodiment specifically includes the following steps:

[0090] (1) Provide a silicon substrate 10, and deposit ITO at the bottom and top of the silicon substrate 10 respectively using a magnetron sputtering process to obtain a second transparent conductive layer 11 and a conductive functional layer 9, and deposit a second metal electrode layer 12 on the second transparent conductive layer 11.

[0091] (2) Spin-coating an aqueous solution of CeCl3·7H2O with a concentration of 0.01mol / L onto the conductive functional layer 9, controlling the rotation speed at 3000rpm and the time at 30s. After spin-coating, annealing is performed at 100℃ for 10min, followed by UVO surface modification for 10min to increase the wettability of the coating surface, thus obtaining the intermediate anchoring layer 14.

[0092] (3) Spin-coat a 0.3 mol / L isopropanol solution of 4 PADCB onto the intermediate anchoring layer 14, control the spin-coating speed to be 3000 rpm and the time to be 30 s, and anneal at 100℃ for 10 min after spin-coating to obtain the hole transport layer 8.

[0093] (4) Prepare 1.68 eV Cs 0.05 FA 0.85 MA 0.10 Pb(I 0.75 Br 0.25 3. A perovskite precursor solution with a concentration of 1.7 mol / L was prepared using a mixture of DMF and DMSO in a volume ratio of 4:1, with an additional 0.8 mg of phenylethylamine hydrochloride added per milliliter of the perovskite precursor solution. The perovskite precursor solution was then filtered, and the filtered perovskite precursor solution was dropped onto the surface of hole transport layer 8. The solution was first spin-coated at 3000 rpm for 10 s, then at 5000 rpm for 20 s, and finally at 7000 rpm for 15 s. In the last 7 s, 150 μL of anisole was added as a poor solvent to promote perovskite crystallization. After spin-coating, the solution was annealed at 100 °C for 10 min to obtain perovskite absorber layer 7.

[0094] (5) Dissolve 1,3-diaminopropane dihydroiodide (PDAI2) in isopropanol solvent to a concentration of 1 mg / mL, stir thoroughly, filter, and spin-coat it onto the surface of the perovskite absorber layer 7. The spin-coating speed is 6000 rpm and the time is 30 s. Then, anneal at 100 °C to obtain the interface modification layer 6.

[0095] (6) Deposit C on interface modification layer 6 60 As electron transport layer 5.

[0096] (7) SnOx was deposited on the surface of electron transport layer 5 by atomic layer deposition, with tetramethylaminotin and water as precursors and nitrogen as working carrier gas, to obtain hole blocking layer 4.

[0097] (8) IZO is deposited on the hole blocking layer 4 by magnetron sputtering to obtain the first transparent conductive layer 3. The first metal electrode layer 1 is fabricated on the first transparent conductive layer 3 by vapor deposition. Then, magnesium fluoride is deposited on the first metal electrode layer 1 to form an anti-reflection layer 2, thus completing the preparation of the perovskite battery.

[0098] Example 5

[0099] This embodiment provides a perovskite solar cell and its preparation method. The difference from Embodiment 4 is that the intermediate anchoring layer 14 is prepared using an aqueous solution of CeCl3·7H2O with a concentration of 0.1 mol / L, and the thickness of the intermediate anchoring layer 14 is 2 nm. The remaining structure, preparation method and process parameters are the same as those in Embodiment 4.

[0100] Example 6

[0101] This embodiment provides a perovskite solar cell and its preparation method. The difference from Embodiment 4 is that the intermediate anchoring layer 14 is prepared using an aqueous solution of CeCl3·7H2O with a concentration of 0.15 mol / L, and the thickness of the intermediate anchoring layer 14 is 4 nm. The remaining structure, preparation method and process parameters are the same as those in Embodiment 4.

[0102] Comparative Example 2

[0103] This comparative example provides a perovskite tandem solar cell and its fabrication method, such as... Figure 7 and Figure 8 As shown, the difference from Example 4 is that the intermediate anchoring layer 14 is not set, while the rest of the structure, preparation method and process parameters are the same as those in Example 4.

[0104] Performance tests were conducted on the perovskite solar cells in Examples 1-6 and Comparative Examples 1-2 of this invention (test conditions: AM1.5G, 100mW / cm). 2 (25℃), the results are shown in Table 1.

[0105] Table 1

[0106]

[0107] For single-cell cells, as shown in Table 1, the perovskite cells provided in Examples 1 and 2 all exhibited good electrical performance, with high conversion efficiency, open-circuit voltage, and fill factor. In Example 3, the excessively high concentration and thickness of the lanthanide metal salt within the intermediate anchoring layer 14 led to an accumulation of excessive lanthanide metal salt at the bottom, hindering carrier transport and thus reducing device performance. Comparative Example 1 lacked the intermediate anchoring layer 14, resulting in lower adhesion between the conductive functional layer 9 and the hole transport layer 8. This led to a less dense arrangement of the hole transport layer 8 and its tendency to detach, thereby affecting the photoelectric performance of the perovskite cell.

[0108] For tandem solar cells, it is evident from Table 1 that the thickness of the intermediate anchoring layer 14 shows a similar trend to that of single-cell cells, indicating that different lanthanide materials all possess good anchoring properties. Compared to Comparative Example 2, Examples 4 and 5 show improved open-circuit voltage and fill factor. This is mainly due to the introduction of an intermediate anchoring layer 14 containing lanthanide metal salts, which increases the uniformity and density of the hole transport layer 8 molecules at the bottom, reduces interface defects, and thus improves the efficiency and stability of the perovskite solar cell.

[0109] Furthermore, the present invention places the perovskite solar cells from Example 5 and Comparative Example 2 under a solar simulator (100 mW·cm²). -2 The maximum power point output curve (MPP) of the battery was tested separately, and the results are as follows: Figure 9 As shown, the photoelectric efficiency of the perovskite solar cell decreased to 67% of its initial efficiency after 160 hours, and the output fluctuated greatly in the first 30 hours, indicating that its cell structure was unstable. In contrast, the solar cell of Example 5 achieved a photoelectric efficiency of 101% of its initial efficiency after 160 hours, indicating a more stable cell structure. This invention prepares an intermediate anchoring layer 14 on the conductive functional layer 9, which can effectively anchor the self-assembled monolayer, improve its uniformity and density, reduce defect-induced interfacial recombination and ion migration, thereby enhancing cell performance.

[0110] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A perovskite solar cell, characterized in that, The perovskite solar cell comprises a substrate layer, a conductive functional layer, an intermediate anchoring layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, a conductive layer, and a metal electrode layer stacked sequentially. The material of the intermediate anchoring layer includes lanthanide metal salts. The general formula of the lanthanide metal salt is LnX3·yH2O; Wherein, Ln is selected from Ce or Nd; X is Cl - Or NO3 - y is an integer from 0 to 9.

2. The perovskite solar cell according to claim 1, characterized in that, In the material of the intermediate anchoring layer, the concentration of the lanthanide metal salt is 0.01~0.10 mol / L; And / or, the thickness of the intermediate anchoring layer is 0.1~3.0 nm.

3. The perovskite solar cell according to claim 1, characterized in that, The conductive functional layer includes at least one of ITO, FTO, IZO and IWO; The hole transport layer is a self-assembled monolayer.

4. The perovskite solar cell according to claim 3, characterized in that, The thickness of the conductive functional layer is 5~50nm; And / or, the thickness of the self-assembled monolayer is 0.1~5.0 nm.

5. The perovskite solar cell according to any one of claims 1, 3, or 4, characterized in that, An interface modification layer is further provided between the perovskite absorption layer and the electron transport layer; And / or, a hole blocking layer is further provided between the electron transport layer and the conductive layer; And / or, an anti-reflection layer is provided on the side of the metal electrode layer away from the conductive layer.

6. A method for preparing a perovskite solar cell according to any one of claims 1-5, characterized in that, The preparation method includes: A substrate layer is provided, and a conductive functional layer is deposited on the surface of the substrate layer; A slurry containing lanthanide metal salts is deposited on the surface of the conductive functional layer, and then annealed and UVO surface modified in sequence to form an intermediate anchoring layer. Subsequently, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a conductive layer are sequentially deposited on the surface of the intermediate anchoring layer, and a metal electrode layer is fabricated to obtain a perovskite solar cell.

7. The method for preparing a perovskite solar cell according to claim 6, characterized in that, The concentration of the lanthanide metal salt in the slurry is 0.01~0.10 mol / L; And / or, the slurry further includes a solvent, the solvent including at least one selected from water, ethanol, isopropanol, butanol, acetonitrile and tetrahydrofuran; And / or, the deposition method of the slurry includes solution deposition or vapor deposition.

8. The method for preparing a perovskite solar cell according to claim 6 or 7, characterized in that, The UVO surface modification time is 1~10 min; And / or, the annealing temperature is 60~110℃; And / or, the annealing process takes 1 to 20 minutes.

9. A photovoltaic module, characterized in that, The photovoltaic module includes the perovskite cell according to any one of claims 1-5.

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