A perovskite photovoltaic module and preparation method thereof

Abstract

The present invention relates to a perovskite photovoltaic module, including a substrate, a conductive material layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, and a top electrode layer. A cutting line groove P1 is arranged on the conductive material layer, and the cutting line groove P1 cuts the conductive material layer, and the cutting line groove P1 is filled with the same preparation material as the first carrier transport layer. A cutting line groove P4 is arranged on the top electrode layer, and the bottom thereof exposes the conductive material layer. The sides of the perovskite layer on both sides of each cutting line groove P4 are respectively provided with a 2D perovskite protective layer to shield it, and one side of the cutting line groove P4 is filled with the same preparation material as the top electrode layer and is conductively connected to the top electrode layer. The present invention also discloses a preparation method of the perovskite photovoltaic module. The present invention introduces a 2D perovskite protective layer to protect the exposed surface after the perovskite film layer is cut, so as to avoid the perovskite active material from water oxygen erosion and the chemical reaction of metal-halide ions, thereby improving the stability of the photovoltaic module.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite photovoltaic module preparation, and in particular relates to a perovskite photovoltaic module and a preparation method thereof. Background Art

[0002] Perovskite is a class of ABX 3 A general term for materials with a crystal structure. In the structure of organic halide perovskites, A is usually a cation such as methylammonium (MA) or formamidine (FA), B is a metal cation such as lead or tin, and X is an anion such as chlorine, bromine, or iodine. This type of organic halide perovskite has excellent semiconductor properties and can achieve high-quality conversion between light energy and electrical energy, so it can be made into photovoltaic cells, light-emitting diodes, detectors, etc.

[0003] In the industrial process of making optoelectronic devices on a large scale, active materials are usually isolated into several small parts and then connected in series to improve the performance of the entire active area. For perovskite materials, the active side exposed after isolation has extremely high reactivity, and it reacts with water and oxygen in the air, causing the material to degrade; in addition, the halogen anions in the perovskite come into contact with the metal electrode, and a chemical reaction occurs, causing the metal's conductivity to decrease. Therefore, protecting the side of the perovskite material helps improve the performance and stability of the device.

[0004] The patent with publication number CN110534651A discloses perovskite solar cells and modules and their preparation methods, using high molecular polymers, oxides, graphene and other materials as isolation layers on the sides of perovskite films after cutting, and applied to perovskite solar cells. However, the dispensing method used in the patent to coat the isolation layer has many defects in practical applications. For example, the dispensing operation is exposed to the air for a long time, and the perovskite is seriously corroded by water and oxygen; the dispensing method requires a large cutting interval, which reduces the area of ​​the photoactive region; the high-energy ultraviolet rays used for glue curing will cause perovskite degradation; the glue will expand or shrink in volume after curing, affecting the protective effect on the side of the perovskite. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a perovskite photovoltaic module and a preparation method thereof, wherein a 2D perovskite protective layer is introduced to protect the exposed surface after the perovskite thin film layer is cut, so as to prevent the perovskite active substance from being corroded by water and oxygen and the chemical reaction of metal-halogen ions, thereby improving the stability of the photovoltaic module.

[0006] The present invention is implemented in this way. A perovskite photovoltaic module is provided. Its internal structure includes, from bottom to top, a substrate, a conductive material layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, and a top electrode layer. n-1 cutting line grooves P1 are arranged on the conductive material layer. The cutting line grooves P1 cut the conductive material layer. The cutting line grooves P1 are filled with the same preparation material as the first carrier transport layer and are conductively connected to the first carrier transport layer. n-1 cutting line grooves P4 are arranged on the top electrode layer. Each cutting line groove P4 is located on one side of the corresponding cutting line groove P1. The conductive material layer is exposed at the bottom of the cutting line groove P4. 2D perovskite protective layers are respectively arranged on the sides of the perovskite layer on both sides of the cutting line groove P4 to shield it. One side of the cutting line groove P4 is filled with the same preparation material as the top electrode layer and is conductively connected to the top electrode layer. The perovskite photovoltaic module is divided into n perovskite photovoltaic sub-modules under the joint action of the n-1 cutting line grooves P1 and the cutting line grooves P4.

[0007] The present invention is implemented in this way, providing a perovskite photovoltaic module, whose internal structure includes a substrate, a conductive material layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, and a top electrode layer in order from bottom to top, and n-1 cutting grooves P1 are arranged on the conductive material layer, and the cutting grooves P1 cut the conductive material layer, and the cutting grooves P1 are filled with the same preparation material as the first carrier transport layer and are conductively connected to the first carrier transport layer, and n-1 cutting grooves P1 are arranged on the top electrode layer. Line groove P4, each cutting line groove P4 is located on one side of the corresponding cutting line groove P1, the conductive material layer is exposed at the bottom of the cutting line groove P4, and 2D perovskite protective layers are respectively provided on the side and top surfaces of the perovskite layer on both sides of the cutting line groove P4 to shield it, and one side of the cutting line groove P4 is filled with the same preparation material as the top electrode layer and is conductively connected to the top electrode layer, and the perovskite photovoltaic module is divided into n perovskite photovoltaic sub-modules under the joint action of n-1 cutting line grooves P1 and cutting line grooves P4.

[0008] The present invention is implemented by providing a method for preparing the perovskite photovoltaic module as described above, comprising the following steps:

[0009] Step 1: Scratching a substrate having a conductive material layer to obtain a cutting line groove P1, and then sequentially preparing a first carrier transport layer and a perovskite layer on the conductive material layer;

[0010] Step 2: preparing a sacrificial layer on the perovskite layer; the sacrificial layer material includes a high molecular weight organic substance that is easily soluble in a non-polar solvent such as chlorobenzene, ether or ethyl acetate;

[0011] Step 3: The base film layer processed in step 2 is scratched to obtain a cutting groove P2, the bottom of which exposes the conductive material layer, and the 2D perovskite protective layer material reacts with the materials on both sides of the perovskite layer (i.e., both sides of the cutting groove P2) to respectively generate a layer of 2D perovskite protective layer;

[0012] Step 4: remove the sacrificial layer and the unreacted 2D perovskite protective layer preparation material, and sequentially prepare the second carrier transport layer on the perovskite layer;

[0013] Step 5: Re-scribing the position of the original cutting groove P2 to obtain a cutting groove P3, the bottom of which exposes the conductive material layer, and then preparing the top electrode layer;

[0014] Step six: The area where the cutting groove P3 is located is scratched to obtain a cutting groove P4, and the conductive material layer is also exposed at the bottom. The width of the cutting groove P4 is smaller than the cutting groove P3. The preparation material of the top electrode layer is retained on one side of the cutting groove P4 close to the cutting groove P1, and the other side is close to the 2D perovskite protective layer.

[0015] The present invention is implemented by providing a method for preparing the perovskite photovoltaic module as described above, comprising the following steps:

[0016] Step 1: Scratching a substrate having a conductive material layer to obtain a cutting line groove P1, and then sequentially preparing a first carrier transport layer and a perovskite layer on the conductive material layer;

[0017] Step 2: The base film layer processed in step 1 is scratched to obtain a cutting groove P2, the bottom of which exposes the conductive material layer, and then a solution containing a 2D perovskite protective layer preparation material is coated and annealed, and the 2D perovskite protective layer material reacts with the material on the top surface and both side surfaces (i.e., both sides of the cutting groove P2) of the perovskite layer to respectively generate a layer of 2D perovskite protective layer;

[0018] Step 3, removing the unreacted 2D perovskite protective layer preparation material, and sequentially preparing a second carrier transport layer on the 2D perovskite protective layer;

[0019] Step 4: Re-scratching is performed at the position of the original cutting groove P2 to obtain a cutting groove P3, the bottom of which exposes the conductive material layer, and then a top electrode layer is prepared;

[0020] Step 5: Scrape the area where the cutting groove P3 is located to obtain a cutting groove P4, and the conductive material layer is also exposed at the bottom. The width of the cutting groove P4 is smaller than the cutting groove P3. The preparation material of the top electrode layer is retained on one side of the cutting groove P4 close to the cutting groove P1, and the other side is close to the 2D perovskite protective layer.

[0021] Compared with the prior art, the perovskite photovoltaic module and the preparation method thereof of the present invention have the following characteristics:

[0022] 1. Generate a 2D perovskite protective layer on the side and top of the exposed perovskite layer, which has the function of inhibiting ion migration and blocking water and oxygen, thus reducing the damage of environmental factors such as water and oxygen to the perovskite active material during the preparation process;

[0023] 2. The process is simple and easy to produce on a large scale;

[0024] 3. The stability of perovskite thin film optoelectronic components has been improved through structural and process improvements. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic plan view of the internal structure of the perovskite photovoltaic module according to Embodiment 1, Embodiment 3 and Embodiment 4 of the present invention;

[0026] Figure 2 It is a schematic plan view of the internal structure of the perovskite photovoltaic module according to Embodiment 2 and Embodiment 6 of the present invention;

[0027] Figure 3 This is a schematic plan view of the internal structure of the perovskite photovoltaic module according to Example 5 of the present invention. DETAILED DESCRIPTION

[0028] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0029] Example 1

[0030] Please refer to Figure 1 As shown, the first preferred embodiment of the perovskite photovoltaic module of the present invention has an internal structure that includes, from bottom to top, a substrate 1, a conductive material layer 2, a first carrier transport layer 3, a perovskite layer 4, a second carrier transport layer 5, and a top electrode layer 7, and a barrier layer 6 is also arranged between the second carrier transport layer 5 and the top electrode layer 7.

[0031] n-1 cutting grooves P1 are provided on the conductive material layer 2, and the cutting grooves P1 cut the conductive material layer 2. The cutting grooves P1 are filled with the same preparation material as the first carrier transport layer 3 and are conductively connected to the first carrier transport layer 3. The width of the cutting grooves P1 is 50nm~200μm, and the distance between two adjacent cutting grooves P1 is 1mm~30mm.

[0032] n-1 cutting grooves P4 are arranged on the top electrode layer 7, each of which is located on one side of the corresponding cutting groove P1, and the conductive material layer 2 is exposed at the bottom of the cutting groove P4. 2D perovskite protective layers 8 are respectively arranged on the sides of the perovskite layer 4 on both sides of the cutting groove P4 to shield it. One side of the cutting groove P4 is filled with the same preparation material as the top electrode layer 7 and is conductively connected to the top electrode layer 7. The perovskite photovoltaic module is divided into n perovskite photovoltaic sub-modules 9 under the joint action of the n-1 cutting grooves P1 and the cutting grooves P4.

[0033] The preparation material of the 2D perovskite protective layer 8 includes an organic amine halide, and the radius of the organic amine cation is larger than that of the formamidinium cation. The organic amine halide refers to the product of the reaction of an organic molecule containing at least one amine group with a hydrogen halide. Commonly used organic amine halides include guanidinium cations (C(NH 2 ) 3 + ), butylamine cation (CH 3 (CH 2 ) 3 NH 3 + ), phenylethylamine cation (C 6 H 5 (CH 2 ) 2 NH 3 + ). Commonly used preparation materials include butylamine hydroiodide (BAI), phenylethylamine hydroiodide (PEAI), etc. The thickness of the 2D perovskite protective layer 8 is 5nm~100nm.

[0034] The preparation material of the perovskite layer 4 is a material having ABX 3 A halide crystal of type structure, wherein A is a methylamino group (CH 3 NH 3 + ), carboxamidino (CH(NH 2 ) 2 + ), cesium (Cs + ) at least one of the monovalent cations, B is a lead ion (Pb 2 + ) or stannous ions (Sn 2+ ) at least one of the divalent cations, X is Cl - Br - ,I - At least one halogen anion.

[0035] Ion dopants are added to the preparation material of the perovskite layer 4, and the ion dopants include guanidinium cations (C(NH2 ) 3 + ), butylamine cation (CH 3 (CH 2 ) 3 NH 3 + ), phenylethylamine cation (C 6 H 5 (CH 2 ) 2 NH 3 + ) or at least one of the cations of an inorganic element including lithium, sodium, potassium, rubidium, boron, silicon, germanium, arsenic, antimony, beryllium, magnesium, calcium, strontium, barium, aluminum, indium, gallium, tin, thallium, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, and gold, or at least one of the cations of an inorganic element including thiocyanate (SCN - ), acetate ion (CH 3 COO - ) at least one anion.

[0036] The material of the substrate 1 includes any one of glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polyimide (PI). The preparation material of the conductive material layer 2 includes any one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide (AZO). The substrate 1 and the conductive material layer 2 form a transparent conductive substrate, which is highly transparent in the visible light and near-infrared light bands, and in particular, the light transmittance in the wavelength range of 350nm to 800nm ​​is not less than 80%.

[0037] The first carrier transport layer 3 and the second carrier transport layer 5 are made of hole transport material and electron transport material respectively. The hole transport material includes nickel oxide, vanadium oxide, molybdenum oxide, copper sulfide, cuprous thiocyanate, copper oxide, cuprous oxide, cobalt oxide, TAPC (1,1'-bis-4-methylphenylaminophenyl) cyclohexylamine), PTAA (poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine]), PEDOT, Poly-TPD, Spiro-MeOTAD (2,2',7,7'-tetrakis (N,N-paramethoxyanilino) -9,9'-spirobifluorene) and any one of their dopants, and the thickness of the layer is 5nm~200nm. The electron transport material includes titanium dioxide, zinc oxide, cadmium sulfide, tin dioxide, indium trioxide, tungsten oxide, cerium oxide, C 60 , C 70, PCBM (alkylfullerene phenyl-C61-butyric acid-methyl ester) and any one of their derivatives and dopants, and the layer thickness is 5nm~300nm.

[0038] The barrier layer 6 is a functional layer that blocks carrier recombination, ion migration, water and oxygen diffusion, etc. The material used to make the barrier layer 6 includes chromium or bismuth, which are metal ion diffusion barrier materials, or any one of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP), which is a hole barrier material, and polyvinylidene chloride (PVDC), which is a water and oxygen barrier material. The thickness of the barrier layer 6 is 2nm~100nm.

[0039] Example 2

[0040] Please refer to Figure 2 As shown, the second preferred embodiment of the perovskite photovoltaic module of the present invention has an internal structure that includes, from bottom to top, a substrate 1, a conductive material layer 2, a first carrier transport layer 3, a perovskite layer 4, a second carrier transport layer 5, and a top electrode layer 7, and a barrier layer 6 is also arranged between the second carrier transport layer 5 and the top electrode layer 7.

[0041] n-1 cutting grooves P1 are arranged on the conductive material layer 2, and the cutting grooves P1 cut the conductive material layer 2. The cutting grooves P1 are filled with the same preparation material as the first carrier transport layer 3 and are conductively connected to the first carrier transport layer 3.

[0042] n-1 cutting grooves P4 are arranged on the top electrode layer 7, each of which is located on one side of the corresponding cutting groove P1, and the conductive material layer 2 is exposed at the bottom of the cutting groove P4. A 2D perovskite protective layer 8 is respectively arranged on the side and top surface of the perovskite layer 4 on both sides of the cutting groove P4 to shield it. One side of the cutting groove P4 is filled with the same preparation material as the top electrode layer 7 and is conductively connected to the top electrode layer 7. The perovskite photovoltaic module is divided into n perovskite photovoltaic sub-modules under the joint action of the n-1 cutting grooves P1 and the cutting grooves P4.

[0043] The other structures and features are the same as those in Example 1 and will not be described in detail.

[0044] Example 3

[0045] Please refer to Figure 1 As shown, the first embodiment of the method for preparing the perovskite photovoltaic module of embodiment 1 of the present invention comprises the following steps:

[0046] Step 11: Scribe (laser cut) the conductive glass substrate 1 deposited with the ITO conductive material layer 2, and etch away the ITO with a width of 100 μm to obtain a cutting line groove P1. Then clean the conductive glass substrate 1, blow dry with nitrogen, and treat with ultraviolet ozone.

[0047] The scribing method includes laser cutting and physical scribing, and the laser cutting method is used in this step. The same applies to the following.

[0048] Step 12: Deposit a 20 nm thick hole transport material NiOx on the conductive substrate 1 as the first carrier transport layer 3 (hole transport layer). After drying, the prepared perovskite precursor solution is continuously coated in the slits, wherein the amount of methylamine hydroiodide and lead iodide is equal, dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1, the concentration of lead iodide is 0.7 mol / L, and annealed at 100°C for 10 minutes to obtain a 500 nm thick perovskite layer 4.

[0049] Step 13: Scrape a 10 mg / mL chlorobenzene solution of polymethyl methacrylate onto the surface of the perovskite layer 4 to deposit a sacrificial layer with a thickness of 30 nm. The sacrificial layer material includes a high molecular organic substance that is easily soluble in chlorobenzene, ether or ethyl acetate non-polar solvents. Commonly used sacrificial layer materials include polymethyl methacrylate (PMMA), polystyrene (PS), etc.

[0050] Step 14: Scrape the substrate film layer processed in step 13 to obtain a cutting groove P2, the bottom of which exposes the ITO conductive material layer 2. The cutting groove P2 is located 100 nm to the right of the cutting groove P1 and is parallel to the cutting groove P1. The width of the cutting groove P2 is 300 μm.

[0051] Step 15: Slit-coat 4 mg / mL PEAI (C 6 H 5 (CH 2 ) 2 NH 3 I) isopropanol solution, annealed at 100° C. for 10 min, and a 2D perovskite protective layer 8 is in situ grown on the surface of the 3D perovskite layer 4 on both sides of the cutting groove P2.

[0052] Step 16: First, use isopropanol to dissolve and remove the residual PEAI, and then use chlorobenzene to dissolve and remove the sacrificial layer.

[0053] Step 17: Evaporate 30nm thick C on the film treated in step 16. 60 , 5 nm thick BCP serves as the second carrier transport layer 5 (electron transport layer) and the blocking layer 6 (hole blocking layer).

[0054] Step 18: Remove the excess material in the original cutting groove P2 area by laser etching to expose the ITO conductive material layer 2 at the bottom to obtain the cutting groove P3. Vacuum evaporate 150nm of silver as the top electrode layer 7 on the surface of the film after the cutting groove P3 treatment.

[0055] Step 19: The silver electrode in the original cutting groove P3 area is separated by a physical scribing method with a width of 100 μm, exposing the ITO conductive material layer 2, ensuring that the silver in the right section of P4 is completely removed, and obtaining the cutting groove P4. The width of the cutting groove P4 is smaller than that of the cutting groove P3, and the preparation material of the top electrode layer 7 is retained on the left side of the cutting groove P4.

[0056] Example 4

[0057] Please refer to Figure 1 As shown, the second embodiment of the method for preparing the perovskite photovoltaic module of embodiment 1 of the present invention comprises the following steps:

[0058] Step 21, the conductive glass substrate 1 deposited with the FTO conductive material layer 2 is scribed (laser cut), and the FTO with a width of 50 μm is etched away to obtain a cutting line groove P1. The conductive glass substrate 1 is then cleaned, dried with nitrogen, and treated with ultraviolet ozone.

[0059] Step 22: deposit a 20 nm thick layer of electron transport material TiO on the conductive substrate 1. 2 As the first carrier transport layer 3 (electron transport layer), there are a 20nm thick dense layer and a 100nm thick mesoporous layer. After drying, the substrate is heated to 70℃ and the prepared perovskite precursor solution Cs 0.05 FA 0.80 MA 0.15 Pb(I 0.85 Br 0.15 ) 3 , sprayed onto the substrate, wherein the concentration of the solution is 0.3 mol / L, the solvent is 2-methoxyethanol and a small amount of dimethyl sulfoxide, annealed at 100°C for 30 minutes, and a 400 nm thick perovskite layer 4 is obtained.

[0060] Step 23: Spray a 4 mg / mL polystyrene toluene solution on the surface of the perovskite layer 4 to deposit a sacrificial layer with a thickness of 10 nm.

[0061] Step 24: Scrape the substrate film layer processed in step 23 to obtain a cutting groove P2, the bottom of which exposes the FTO conductive material layer 2. The cutting groove P2 is located 500 nm to the right of the cutting groove P1 and is parallel to the cutting groove P1. The width of the cutting groove P2 is 150 μm.

[0062] Step 25: Slit-coat 4 mg / mL BAI (CH 3 (CH 2 ) 3 NH 3 +) in an isopropanol solution, annealed at 100° C. for 10 min, and a 2D perovskite protective layer 8 was in situ grown on the surface of the 3D perovskite layer 4 on both sides of the cutting groove P2.

[0063] Step 26: First, use isopropanol to dissolve and remove the residual BAI, and then use toluene to dissolve and remove the sacrificial layer.

[0064] Step 27: Deposit 30nm thick PTAA as the second carrier transport layer 5 (hole transport layer) on the film treated in step 26, and evaporate 10nm thick MoO 3 As barrier layer 6.

[0065] Step 28: Remove the excess material in the original cutting groove P2 area by laser etching to expose the FTO conductive material layer 2 at the bottom to obtain the cutting groove P3. Vacuum evaporate 100nm of gold as the top electrode layer 7 on the surface of the film after the cutting groove P3 treatment.

[0066] Step 29: The gold electrode in the original cutting groove P3 area is separated by a physical scribing method with a width of 50 μm, exposing the FTO conductive material layer 2, ensuring that the gold on the right side of P4 is completely removed, and obtaining the cutting groove P4. The width of the cutting groove P4 is smaller than that of the cutting groove P3, and the preparation material of the top electrode layer 7 is retained on the left side of the cutting groove P4.

[0067] Example 5

[0068] Please refer to Figure 3 As shown, the third embodiment of the method for preparing the perovskite photovoltaic module of embodiment 1 of the present invention comprises the following steps:

[0069] Step 31, the conductive glass substrate 1 deposited with the AZO conductive material layer 2 is scribed (laser cut), and 200 μm wide AZO is etched away to obtain a cutting line groove P1. The conductive glass substrate 1 is then cleaned, dried with nitrogen, and treated with ultraviolet ozone.

[0070] Step 32: Deposit a 25 nm thick SnO layer of electron transport material on the conductive substrate 1. 2 As the first carrier transport layer 3 (electron transport layer). After drying, the substrate is heated to 60°C in a nitrogen atmosphere using the roll-to-roll technology, and the prepared perovskite precursor solution Cs 0.15 FA 0.85 PbI 3 Coated onto substrate 1, wherein the concentration of the solution is 1 mol / L, and the solvent is 1,4-butyrolactone and a small amount of N-methylpyrrolidone. Then quickly immersed in and passed through chlorobenzene solution, and then annealed at 100°C for 30 minutes to obtain a 600nm thick perovskite layer 4.

[0071] Step 33: evaporate PVDC onto the surface of the perovskite layer 4 to deposit a sacrificial layer with a thickness of 20 nm.

[0072] Step 34: Scrape the base film layer processed in step 33 to obtain a cutting groove P2, the bottom of which exposes the AZO conductive material layer 2. The cutting groove P2 is located 10 μm to the left of the cutting groove P1 and is parallel to the cutting groove P1. The width of the cutting groove P2 is 500 μm.

[0073] Step 35, 20 nm of guanidine bromide is evaporated on the film treated in step 34, annealed at 100° C. for 30 min in a solvent atmosphere containing an appropriate amount of isopropanol, and a 2D perovskite protective layer 8 is in situ grown on the surface of the 3D perovskite layer 4 on both sides of the cutting groove P2.

[0074] Step 36: first use isopropanol to dissolve and remove the residual guanidine bromide, and then use chlorobenzene to dissolve and remove the sacrificial layer.

[0075] Step 37 , coating 100 nm thick Spiro-MeOTAD (internal doping with lithium bis(trifluoromethanesulfonyl)imide and tert-butylpyridine) on the film treated in step 36 as the second carrier transport layer 5 (hole transport layer), and evaporating 20 nm thick bismuth as the barrier layer 6 .

[0076] Step 38: Remove the excess material in the original cutting groove P2 area by laser etching to expose the bottom AZO conductive material layer 2 to obtain the cutting groove P3. Sputter 70nm of ITO as the top electrode layer 7 on the surface of the film after the cutting groove P3.

[0077] Step 39, the ITO in the original cutting groove P3 area is separated by a physical scribing method, with a width of 200 μm, exposing the AZO conductive material layer 2, ensuring that the ITO on the left side of P4 is completely removed, and obtaining the cutting groove P4. The width of the cutting groove P4 is smaller than that of the cutting groove P3, and the preparation material of the top electrode layer 7 is retained on the right side of the cutting groove P4.

[0078] Example 6

[0079] Please refer to Figure 2 As shown, the first embodiment of the method for preparing the perovskite photovoltaic module of embodiment 2 of the present invention comprises the following steps:

[0080] Step 41, the conductive glass substrate 1 deposited with the FTO conductive material layer 2 is scribed (laser cut), and the FTO with a width of 80 μm is etched away to obtain a cutting line groove P1. The conductive glass substrate 1 is then cleaned, dried with nitrogen, and treated with ultraviolet ozone.

[0081] Step 42, deposit a 20nm thick hole transport material PEDOT:PSS on the conductive substrate 1 as the first carrier transport layer 3 (hole transport layer). After drying, spin-coat a methylamine acetic acid solution of lead iodide on the substrate, anneal at 60°C for 2min, and obtain a 300nm thick lead iodide precursor layer. Spin-coat a mixed isopropanol solution of formamidine hydroiodide and methylamine hydrochloride with a molar ratio of 10:1 on it. Among them, the concentration of formamidine hydroiodide is 60mg / mL. Then anneal at 150°C for 60min. After cooling, quickly dissolve and remove the residual formamidine hydroiodide and methylamine hydrochloride on the surface with ethanol, and then anneal at 100°C for 10min to obtain a perovskite layer 4.

[0082] Step 43, the base film layer processed in step 42 is scratched to obtain a cutting groove P2, the bottom of which exposes the FTO conductive material layer 2. The cutting groove P2 is located 1 μm to the right of the cutting groove P1 and is parallel to the cutting groove P1. The width of the cutting groove P2 is 300 μm.

[0083] Step 44 , spin-coat 3 mg / mL dimethylamine hydroiodide tert-butyl alcohol solution on the film treated in step 43 , anneal at 100° C. for 20 min, and in-situ grow a 2D perovskite protective layer 8 on the surface of the 3D perovskite layer 4 .

[0084] Step 45: Dissolve and remove excess dimethylamine hydroiodide with tert-butyl alcohol.

[0085] Step 46: Spin-coat PC on the film treated in step 45 71 BM is used to form a 30 nm thick second carrier transport layer 5 (electron transport layer), and zinc sulfide with a thickness of 10 nm and chromium with a thickness of 10 nm are sequentially evaporated as a barrier layer 6 .

[0086] Step 47: Remove the excess material in the original cutting groove P2 area by laser etching to expose the FTO conductive material layer 2 at the bottom to obtain the cutting groove P3. Vacuum evaporate 120nm of copper as the top electrode layer 7 on the surface of the film after the cutting groove P3 treatment.

[0087] Step 48, the metal copper electrode in the original cutting groove P3 area is separated by a physical scribing method, with a width of 70 μm, exposing the FTO conductive material layer 2, ensuring that the copper on the right side of P4 is completely removed, and obtaining the cutting groove P4. The width of the cutting groove P4 is smaller than that of the cutting groove P3, and the preparation material of the top electrode layer 7 is retained on the left side of the cutting groove P4.

[0088] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a perovskite photovoltaic module, characterized in that: The perovskite photovoltaic module has an internal structure that includes, from bottom to top, a substrate, a conductive material layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, and a top electrode layer. n-1 cutting grooves P1 are provided on the conductive material layer, the cutting grooves P1 cut the conductive material layer, the cutting grooves P1 are filled with the same preparation material as the first carrier transport layer and are conductively connected to the first carrier transport layer, n-1 cutting grooves P4 are provided on the top electrode layer, each cutting groove P4 is located on one side of the corresponding cutting groove P1, the conductive material layer is exposed at the bottom of the cutting groove P4, 2D perovskite protective layers are provided on the sides of the perovskite layer on both sides of the cutting groove P4 to shield it, one side of the cutting groove P4 is filled with the same preparation material as the top electrode layer and is conductively connected to the top electrode layer, and the perovskite photovoltaic module is divided into n perovskite photovoltaic sub-modules under the joint action of the n-1 cutting grooves P1 and the cutting grooves P4; The preparation method of the perovskite photovoltaic module comprises the following steps: Step 1: Scratching a substrate having a conductive material layer to obtain a cutting line groove P1, and then sequentially preparing a first carrier transport layer and a perovskite layer on the conductive material layer; Step 2: preparing a sacrificial layer on the perovskite layer; the sacrificial layer material includes a high molecular weight organic substance that is easily soluble in a non-polar solvent such as chlorobenzene, ether or ethyl acetate; Step 3: The base film layer processed in step 2 is scratched to obtain a cutting line groove P2, the bottom of which exposes the conductive material layer, and the 2D perovskite protective layer material reacts with the materials on both sides of the perovskite layer to respectively generate a layer of 2D perovskite protective layer; Step 4: remove the sacrificial layer and the unreacted 2D perovskite protective layer preparation material, and sequentially prepare the second carrier transport layer on the perovskite layer; Step 5: Re-scribing the position of the original cutting groove P2 to obtain a cutting groove P3, the bottom of which exposes the conductive material layer, and then preparing the top electrode layer; Step six: The area where the cutting groove P3 is located is scratched to obtain a cutting groove P4, and the conductive material layer is also exposed at the bottom. The width of the cutting groove P4 is smaller than the cutting groove P3. The preparation material of the top electrode layer is retained on one side of the cutting groove P4 close to the cutting groove P1, and the other side is close to the 2D perovskite protective layer.

2. A method for preparing a perovskite photovoltaic module, characterized in that: The perovskite photovoltaic module has an internal structure that includes, from bottom to top, a substrate, a conductive material layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, and a top electrode layer. n-1 cutting grooves P1 are provided on the conductive material layer, the cutting grooves P1 cut the conductive material layer, the cutting grooves P1 are filled with the same preparation material as the first carrier transport layer and are conductively connected to the first carrier transport layer, n-1 cutting grooves P4 are provided on the top electrode layer, each cutting groove P4 is located on one side of the corresponding cutting groove P1, the conductive material layer is exposed at the bottom of the cutting groove P4, 2D perovskite protective layers are provided on the side and top surfaces of the perovskite layer on both sides of the cutting groove P4 to shield it, one side of the cutting groove P4 is filled with the same preparation material as the top electrode layer and is conductively connected to the top electrode layer, and the perovskite photovoltaic module is divided into n perovskite photovoltaic sub-modules under the joint action of the n-1 cutting grooves P1 and the cutting grooves P4; The preparation method of the perovskite photovoltaic module comprises the following steps: Step 1: Scratching a substrate having a conductive material layer to obtain a cutting line groove P1, and then sequentially preparing a first carrier transport layer and a perovskite layer on the conductive material layer; Step 2, the base film layer processed in step 1 is scratched to obtain a cutting line groove P2, the bottom of which exposes the conductive material layer, and then a solution containing a 2D perovskite protective layer preparation material is coated and annealed, and the 2D perovskite protective layer material reacts with the materials on the top surface and both side surfaces of the perovskite layer to respectively generate a layer of 2D perovskite protective layer; Step 3, removing the unreacted 2D perovskite protective layer preparation material, and sequentially preparing a second carrier transport layer on the 2D perovskite protective layer; Step 4: Re-scratching is performed at the position of the original cutting groove P2 to obtain a cutting groove P3, the bottom of which exposes the conductive material layer, and then a top electrode layer is prepared; Step 5: Scrape the area where the cutting groove P3 is located to obtain a cutting groove P4, and the conductive material layer is also exposed at the bottom. The width of the cutting groove P4 is smaller than the cutting groove P3. The preparation material of the top electrode layer is retained on one side of the cutting groove P4 close to the cutting groove P1, and the other side is close to the 2D perovskite protective layer.

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