Preparation method of perovskite solar cell module
By using multiple spacer grooves and filling in insulating substances during the preparation of perovskite solar cell modules, the problems caused by craters during the back electrode laser etching are solved, the stability and yield of the module are improved, and the cost is reduced.
Patent Information
- Application Number
- CN202411678531.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-22
- Publication Date
- 2025-03-14
AI Technical Summary
Perovskite solar cell back electrode is prone to craters during laser etching, resulting in poor components, leakage or short circuits. The prior art is difficult to effectively prevent and is costly.
During the preparation of perovskite solar cell modules, multiple spacer grooves (P1, P2, P3, P2.5) are used and insulating substances are filled at the overlap of P3 and P2.5, the laser etching effect of the back electrode is improved, the adsorption force of the back electrode is enhanced, and the generation of craters is reduced.
It effectively reduces the generation of P3 craters, improves the stability of the back electrode and the yield of the components, reduces equipment costs, and promotes the low-cost industrial mass production of perovskite components.
Smart Images
Figure CN119630245A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of solar cells, and in particular relates to a method for preparing a perovskite solar cell assembly. Background Art
[0002] Perovskite cells are usually composed of a transparent conductive layer, a lower carrier transport layer, a perovskite layer, an upper carrier transport layer and a back electrode stacked in sequence. In order to construct multiple sub-cells in this stacked structure and connect them in series to form a battery module, P1, P2, and P3 laser etching processes are often used. Although laser etching technology has been widely used in the field of perovskite components, the etching morphology will have adverse effects in actual use. For example, the back electrode of a perovskite cell often uses a pure metal or a composite electrode containing metal. The bottom layer of the electrode is a perovskite layer and a carrier transport layer, which have weak adsorption to the back electrode, and P3 etching is prone to produce craters.
[0003] The P3 crater is mainly caused by the back electrode being affected by the heat of laser etching or the gasification explosion at the moment of etching, which causes the surrounding electrodes to be lifted or lifted, forming a large burr. This burr can easily cause component failure. On the one hand, the burr may be connected to the front electrode or the electrode of the adjacent sub-cell, causing battery leakage or more serious short circuit; further, the back electrode burr of the crater, after the battery component is laminated and packaged, may cause the burr to go down due to lamination, connecting to the exposed front electrode in the P3 wire slot, or the larger burr may connect to the adjacent back electrode that should be cut off by P3, causing leakage or short circuit; further, after the component is packaged, the withstand voltage test is carried out, and the internal discharge and ablation of the component is caused due to the burr.
[0004] At present, the most effective protection for the P3 crater is to only etch the broken back electrode without damaging other layers; however, the laser commonly used in industry is a nanosecond picosecond laser, and the distance between the TCO electrode and the back electrode is only nanometer or submicron, making it difficult to only etch the broken back electrode without exposing the underlying TCO electrode. In order to solve the problem of the P3 crater, a more expensive and energy-consuming femtosecond laser (such as a nanosecond picosecond laser) can be used, but this will increase the cost of the equipment and is not conducive to the low-cost industrial mass production of perovskite components.
[0005] To this end, the present invention designs a method for improving the laser etching of the back electrode of a perovskite cell to improve stability and yield. Summary of the invention
[0006] The object of the present invention is to provide a method for preparing a perovskite solar cell module, comprising the following steps: Step 1, providing a base layer, and depositing a transparent conductive layer on the base layer; Step 2, scribing the transparent conductive layer to form the first spacing groove P1 penetrating the transparent conductive layer; Step 3, preparing a lower carrier transport layer on the transparent conductive layer, preparing a perovskite layer on the lower carrier transport layer, and preparing an upper carrier transport layer on the perovskite layer; Step 4, scribing the upper carrier transport layer to form the second spacing groove P2 penetrating the lower carrier transport layer; Step 5: Scrape the upper carrier transport layer on one side of the second spacing groove P2 in a direction away from the first spacing groove P1 to form the fourth spacing groove P2 penetrating the lower carrier transport layer. 2.5 , to the fourth spacing groove P 2.5 Filled with insulating material; Step 6, preparing a back electrode on the upper carrier transport layer; Step 7: Scribing the back electrode to form the third spacing groove P3 penetrating the lower carrier transport layer.
[0007] The first spacing groove P1 has a line width of 10~100μm, and the insulation resistance on both sides of the scribe line is required to be greater than 1MΩ; the second spacing groove P2 has a line width greater than 10μm, and the edge is 0.01~500μm away from the first spacing groove P1; the third spacing groove P3 has a line width greater than 20μm, and the edge is 10~500μm away from the second spacing groove P2; the fourth spacing groove P 2.5 The line width is greater than 20 μm and is 0.01 to 500 μm away from the second spacing groove P2.
[0008] Furthermore, the insulating material is an organic or inorganic substance. The organic substance is such as silica gel, rubber, various hydrocarbon polymers, etc.; the inorganic substance is such as aluminum oxide, tin oxide, calcium carbonate, etc.
[0009] Furthermore, the third spacing groove P3 and the fourth spacing groove P 2.5 overlapping.
[0010] Furthermore, the transparent conductive layer is made of transparent conductive oxide.
[0011] Furthermore, the back electrode is made of transparent conductive oxide or metal material.
[0012] Furthermore, the transparent conductive oxide is selected from FTO (fluorine doped tin oxide), ITO (indium doped tin oxide), AZO (aluminum doped zinc oxide), ATO (aluminum doped tin oxide), IGO (indium doped gallium oxide) or BZO (boron doped zinc oxide). The metal material is selected from Ag, Cu, Al, Cr, Ni or Ti.
[0013] In the present invention, the lower carrier transport layer, the perovskite layer, and the upper carrier transport layer can be prepared using general materials and preparation methods known to those skilled in the art without any special requirements.
[0014] For example, the material of the perovskite layer is an ABX3 type perovskite material, wherein A is selected from Cs + , K + 、Ru + 、CH3NH3 + 、C(NH2)3 + or CH(NH2) 2+ , B is Pb 2+ and / or Sn 2+ , X is selected from Br - ,I - or Cl - The preparation method of the perovskite layer is selected from any one of spin coating, wire rod coating, slit coating, screen printing or inkjet printing, or a combination of at least two thereof.
[0015] For example, the types of charges transported by the lower carrier transport layer and the upper carrier transport layer are opposite. The perovskite battery component in the present invention can be a pin structure or a nip structure. When it is a pin structure, the lower carrier transport layer is a hole transport layer and the upper carrier transport layer is an electron transport layer; when it is a nip structure, the lower carrier transport layer is an electron transport layer and the upper carrier transport layer is a hole transport layer. Preferably, the lower carrier transport layer is a hole transport layer and the upper carrier transport layer is an electron transport layer. The material of the hole transport layer is selected from 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 ((3,4-ethylenedioxythiophene monomer) polymer), Poly-TPD (poly [bis (4-phenyl) (4-butylphenyl) amine]), Spiro-MeOTAD (2,2',7,7'-tetrakis (N,N-p-methoxyanilino) -9,9'-spirobifluorene). The material of the electron transport layer is selected from titanium dioxide, zinc oxide, cadmium sulfide, tin dioxide, indium trioxide, tungsten oxide, cerium oxide, C60, C70, PCBM (alkyl fullerene phenyl-C61-butyric acid-methyl ester).
[0016] The preparation methods of the transparent conductive layer, the lower carrier transport layer, the upper carrier transport layer and the back electrode in the present invention are selected from one or more combinations of chemical reagent spin coating, wire rod coating, slit coating, electron beam evaporation, magnetron sputtering and vacuum thermal evaporation. Beneficial Effects
[0017] 1. The third spacing groove P3 and the fourth spacing groove P 2.5 Overlapping, due to the effect of the filler, the adsorption force on the back electrode is stronger, and P3 can produce almost no crater; 2. Since the filler has a lower laser absorption rate than functional layers such as perovskite and is more resistant to lasers, it will remain after etching, blocking the back electrode and TCO electrode, reducing the risk of leakage.
[0018] 3. After lamination, the back electrode cannot be connected to the TCO electrode, which will eventually improve the yield of package lamination. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 Schematic diagram of the preparation process of the perovskite solar cell module in Example 1.
[0020] Figure 2 Schematic diagram of the preparation process of the perovskite solar cell module in Example 2.
[0021] Figure 3 The performance test results of the perovskite solar cell module in Example 1 and the perovskite solar cell module in Example 2 are compared. DETAILED DESCRIPTION
[0022] The preferred embodiments of the present invention will be described in detail below in conjunction with examples. It should be understood that the following examples are provided only for the purpose of illustration and are not intended to limit the scope of the present invention. Those skilled in the art may make various modifications and substitutions to the present invention without departing from the purpose and spirit of the present invention.
[0023] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.
[0024] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources. Example 1
[0025] like Figure 1 As shown, the perovskite solar cell module of this embodiment is prepared by the following steps: Step 1, take FTO glass with a thickness of 3.2 mm, and remove dust particles or other foreign matter on the surface by brushing thoroughly to serve as the front electrode; Step 2, P1 laser etching is performed on the obtained front electrode substrate, infrared 1064nm laser is used for positive focus scribing, laser power is 20W, laser frequency is 100kHz, laser pulse width is 100ns, laser processing rate is 0.5m / s, and P1 line grooves with a width of 25μm are formed; P1 cuts through the FTO conductive layer but does not damage the glass, the scribing insulation resistance is greater than 1MΩ, and the substrate with P1 pattern is fully cleaned again; Step 3: On the obtained substrate with P1 pattern, a 20 nm thick nickel oxide is prepared by magnetron sputtering process as a carrier transport layer; a perovskite precursor solution is prepared, and the precursor solution is Cs 0.3 Fa 0.7 PbBr0 .5 I 2.5 A precursor combination of , weighing each component and stirring and dissolving it in DMF (N, N-dimethylformamide) to obtain a precursor solution, scraping the precursor solution on the lower carrier transport layer by a doctor blade coating process, transferring the substrate to a hot plate at 140° C., crystallization annealing for 30 minutes, and obtaining a 500 nm thick perovskite film; on the perovskite film, a 20 nm thick C60 material is prepared by a vacuum heating evaporation process as an upper carrier transport layer; Step 4, performing P2 laser etching on the substrate obtained in step 3, using a green 532nm laser with a positive focus to scribe, with a laser power of 1W, a laser frequency of 50kHz, a laser pulse width of 10ps, and a laser processing rate of 0.5m / s to form a P2 line groove with a width of 50μm; the P2 line passes through the C60 layer, the perovskite layer, and the nickel oxide layer to expose the front electrode; Step 5, performing back electrode coating on the substrate obtained in step 4, depositing 100 nm of Cu as a back electrode on the surface by a magnetron sputtering process, and the back electrode can be connected to the exposed front electrode through the P2 groove; Step 6, the substrate obtained in step 5 is subjected to P3 laser etching, and ultraviolet 355nm laser is used for focus scribing, with a laser power of 0.5W, a laser frequency of 30kHz, a laser pulse width of 10ps, and a laser processing rate of 0.5m / s to form a P3 line groove with a width of 50μm; the P3 line passes through the Cu electrode to disconnect the electrode from the P3 line. Example 2
[0026] like Figure 2 As shown, the perovskite solar cell module of this embodiment is prepared by the following steps: Step 1, take FTO glass with a thickness of 3.2 mm, and remove dust particles or other foreign matter on the surface by brushing thoroughly to serve as the front electrode; Step 2, P1 laser etching is performed on the obtained front electrode substrate, infrared 1064nm laser is used for positive focus scribing, laser power is 20W, laser frequency is 100kHz, laser pulse width is 100ns, and laser processing rate is 0.5m / s, to form a P1 line groove with a width of 25μm; P1 cuts through the FTO conductive layer but does not damage the glass, the scribing insulation resistance is greater than 1MΩ, and the substrate with P1 pattern is fully cleaned again; Step 3: On the obtained substrate with P1 pattern, a 20 nm thick nickel oxide is prepared by magnetron sputtering process as a carrier transport layer; a perovskite precursor solution is prepared, and the precursor solution is Cs 0.3 Fa 0.7 PbBr0 .5 I 2.5 A precursor combination of , weighing each component and stirring and dissolving it in DMF (N, N-dimethylformamide) to obtain a precursor solution, scraping the precursor solution on the lower carrier transport layer by a doctor blade coating process, transferring the substrate to a hot plate at 140° C., crystallization annealing for 30 minutes, and obtaining a 500 nm thick perovskite film; on the perovskite film, a 20 nm thick C60 material is prepared by a vacuum heating evaporation process as an upper carrier transport layer; Step 4, P2 laser etching is performed on the substrate obtained in step 3, and green light 532nm laser is used for positive focus scribing, and a laser power of 1W, a laser frequency of 50kHz, a laser pulse width of 10ps, and a laser processing rate of 0.5m / s are used to form a P2 line groove with a width of 50μm; the P2 scribing runs through the C60 layer, the perovskite layer, and the nickel oxide layer to expose the front electrode; P2.5 etching is completed on the P2 side away from P1, and the width of the P2.5 line groove is 30μm, and the target etching passes through the back electrode layer, the upper carrier transport layer, the perovskite layer, and the lower carrier transport layer; polypropylene glue is filled in the P2.5 groove by a dispensing method, and organic matter with high adhesion; Step 5, performing back electrode coating on the substrate obtained in step 4, depositing 100 nm of Cu as a back electrode on the surface by a magnetron sputtering process, and the back electrode can be connected to the exposed front electrode through the P2 groove; Step 6, the substrate obtained in step 5 is subjected to P3 laser etching, and ultraviolet 355nm laser is used for focus etching, with a laser power of 0.5W, a laser frequency of 30kHz, a laser pulse width of 10ps, and a laser processing rate of 0.5m / s to form a P3 line groove with a width of 50μm. The P3 line passes through the Cu electrode to disconnect the electrode from the P3 line.
[0027] like Figure 3As shown, 50 groups of perovskite solar cell modules were prepared respectively by the steps of Example 1 and Example 2. After adding the P2.5 slot, there was no significant difference in the mean performance of the modules prepared by Example 1 and Example 2, but the discreteness of Example 1 was higher, a small number of low performance existed, and the yield was not as good as that of Example 2.
Claims
1. A method for preparing a perovskite solar cell module, characterized in that: The following steps are involved: Step 1, providing a base layer, and depositing a transparent conductive layer on the base layer; Step 2, scribing the transparent conductive layer to form the first spacing groove P1 penetrating the transparent conductive layer; Step 3, preparing a lower carrier transport layer on the transparent conductive layer, preparing a perovskite layer on the lower carrier transport layer, and preparing an upper carrier transport layer on the perovskite layer; Step 4, scribing the upper carrier transport layer to form the second spacing groove P2 penetrating the lower carrier transport layer; scribing the upper carrier transport layer on one side of the second spacing groove P2 in a direction away from the first spacing groove P1 to form the fourth spacing groove P2 penetrating the lower carrier transport layer. 2.5 , to the fourth spacing groove P 2.5 Filled with insulating material; Step 5, preparing a back electrode on the upper carrier transport layer; Step 6: Scribing the back electrode to form the third spacing groove P3 penetrating the lower carrier transport layer.
2. The preparation method according to claim 1, characterized in that: The insulating material is organic or inorganic.
3. The preparation method according to claim 1, characterized in that: The third spacing groove P3 and the fourth spacing groove P 2.5 overlapping.
4. The preparation method according to claim 1, characterized in that: The transparent conductive layer is made of transparent conductive oxide.
5. The preparation method according to claim 1, characterized in that: The back electrode is made of transparent conductive oxide or metal material.
6. The preparation method according to claim 1, characterized in that: The material of the perovskite layer is an ABX3 type perovskite material, wherein A is selected from Cs + , K + 、Ru + 、CH3NH3 + 、C(NH2)3 + or CH(NH2) 2+ , B is Pb 2+ and / or Sn 2+ , X is selected from Br - ,I - or Cl - .
7. A perovskite solar cell module prepared by the preparation method according to any one of claims 1 to 6.