CN118251105A - Patterned conductive compensation substrate, perovskite battery module and preparation method of perovskite battery module - Google Patents
Patterned conductive compensation substrate, perovskite battery module and preparation method of perovskite battery module Download PDFInfo
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Classifications
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- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
- H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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Abstract
The invention discloses a patterned conductive compensation substrate, a perovskite battery module and a preparation method thereof, and relates to the technical field of solar cells. The patterned conductive compensation substrate comprises a conductive substrate and a conductive compensation column deposited on the conductive substrate, wherein the deposition position of the conductive compensation column is at least one of etching positions corresponding to a P2 laser scribing and a P3 laser scribing. The conductive compensation column provided by the invention can reduce the depth of P2 and/or P3 laser etching, reduce laser energy, improve etching precision, and reduce phenomena of edge collapse and peeling on two sides of an etched line, uneven surface of the etched line, saw-tooth cross section and the like; the contact resistance is reduced, and the problems of easy reaction and corrosiveness between the metal back electrode layer and the perovskite layer are solved; and the method is also beneficial to reducing gaps between the packaging adhesive film and the grooves, reducing the existence of air in the gaps and improving the packaging stability, thereby improving the performance of the perovskite solar cell as a whole.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a patterned conductive compensation substrate, a perovskite battery module and a preparation method of the perovskite battery module.
Background
Photovoltaic technology, which is the most widely used clean energy technology in the market at present, will become one of the centers of gravity for future development. Monocrystalline silicon-based solar cells occupy more than 95% of the photovoltaic market by virtue of their high efficiency and high stability. However, the problems of high cost, industrial chain length, high energy consumption of upstream enterprises and the like of the silicon-based solar cell limit the development speed, and meanwhile, the efficiency of the silicon-based solar cell gradually approaches to the theoretical limit (29.4%), so that the growth of the silicon-based solar cell is slow in recent years, and therefore, the development of a novel photovoltaic technology with low cost, high theoretical efficiency and simple manufacturing industry line is very important.
Perovskite solar cells are a novel photovoltaic technology with low cost and high theoretical efficiency (-31%). Perovskite solar cells generally comprise: the front electrode is transparent conductive glass or flexible transparent conductive film; the first carrier transmission layer is made of a P-type or N-type semiconductor material; the perovskite light absorption layer ABX3 material A is monovalent groups or ions such as methylamino MA, formamidino FA, cesium Cs and the like; b is bivalent element such as Pb, sn or two monovalent element ions; x is a halogen element or other negative monovalent group; the second carrier transmission layer is made of N-type or P-type semiconductor material and is made of metal oxide or organic semiconductor material; the back electrode may be a metallic material, graphite or a conductive oxide. Since 2009, the photoelectric conversion efficiency of the small-area battery in the laboratory is over 26.1% at present, which is comparable to that of the silicon-based battery. Especially in the next half of 2021, the industrialization process of perovskite solar cells is accelerated, and early industrialization attempts such as laboratory technology amplification, pilot production line construction, sample display and the like are well-developed.
Currently, for perovskite solar cell modules used in industrialization, sub-cells are often connected in series by laser scribing, and the laser scribing step usually includes three steps (named P1, P2, and P3), where P1 is to pattern a transparent conductive electrode and divide the transparent conductive electrode into a plurality of sub-modules; p2 is to pattern the prepared first carrier transmission layer/perovskite layer/second carrier transmission layer structure together to expose a small part of bottom transparent electrode; p3 is to pattern the electrode after the electrode is prepared; finally, a perovskite solar module with a plurality of separated sub-cells connected in series is formed.
In the prior art, the laser etching process basically uses high-frequency high-power laser to carry out one-time penetrating etching, and the method saves etching time, but the laser is highly concentrated on the film surface of the battery module, so that edge breakage and peeling occur on two sides of an etched line, and the surface of the etched line is uneven, and the section of the etched line is saw-toothed. Particularly, in the P2/P3 process, the laser etching depth at least penetrates through the two carrier transmission layers and the perovskite layer, in the process, a large part of heat can act on the two charge transmission layers and the perovskite layer, and is limited by the thickness of the film layer and the interface bonding energy of each film layer, a large amount of heat energy can be released randomly and unevenly from the laser etching position, so that the sections of the P2 and P3 etching trunking are uneven, the risk of short circuit among sub-batteries in the battery module is increased due to edge breakage and peeling, the stability of the battery module is also influenced, and the integral performance of the perovskite battery module is finally influenced. Therefore, a new technical solution is required to be developed to improve the above problems, so as to effectively ensure the efficient performance of the perovskite battery assembly.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a patterned conductive compensation substrate, a perovskite battery module and a preparation method thereof.
The invention is realized in the following way:
In a first aspect, the present invention provides a patterned conductive compensation substrate, which includes a conductive substrate and a conductive compensation post deposited on the conductive substrate, where a deposition position of the conductive compensation post is at least one of an etching position corresponding to a P2 laser scribe and a P3 laser scribe.
In an alternative embodiment, when the deposition position of the conductive compensation column corresponds to the etching position corresponding to the P2 laser scribing and the P3 laser scribing simultaneously, the thickness of the conductive compensation column is 100-2000 nm;
when the deposition position of the conductive compensation column only corresponds to the etching position corresponding to the P2 laser scribing or the P3 laser scribing, the thickness of the conductive compensation column is 100-3000 nm.
In an alternative embodiment, the width of the conductive compensation column is larger than or equal to the width of the etching position, and the single side width of the scribing edge of the etching position from the edge of the compensation column is 0-10 μm;
preferably, the width of the conductive compensation column is 30-100 μm.
In an alternative embodiment, the material of the conductive compensation post includes at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene, carbon nanotubes, au, al, cu, ni, fe, zn, ti, al 2O3、ZnO、NiOx、SnO2, and TiO 2;
preferably, the conductive substrate comprises a transparent substrate and a conductive layer deposited on the transparent substrate, wherein the material of the conductive layer comprises at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene and carbon nanotubes;
Preferably, the conductive compensation post is made of the same material as the conductive layer.
In a second aspect, the present invention provides a method of preparing a patterned conductive compensation substrate according to any of the preceding embodiments, comprising: depositing a conductive compensation column on the surface of the conductive substrate at least one of etching positions corresponding to the P2 laser scribing and the P3 laser scribing;
Preferably, the deposition method comprises the step of performing sputter deposition on the conductive compensation column by using a mask;
Preferably, the deposition method includes depositing a conductive compensation layer on the surface of the conductive substrate, coating a glue on the surface of the conductive compensation layer, exposing and developing a region to be etched through a mask, exposing the region to be etched, etching, and stripping and cleaning the residual photoresist to form the conductive compensation column.
In a third aspect, the present invention provides a method for preparing a perovskite battery module, comprising preparing a perovskite battery module using a patterned conductive compensation substrate as described in any one of the preceding embodiments;
Preferably, scribing the patterned conductive compensation substrate by using a P1 laser scribing process on the patterned conductive compensation substrate to form a P1 channel, and then depositing a hole transport layer, a perovskite layer and an electron transport layer; then, carrying out scribing treatment on the electron transport layer, the perovskite layer and the hole transport layer by adopting P2 laser scribing to form a P2 channel; depositing a metal back electrode layer on the top of the device; and finally, carrying out scribing treatment on the metal back electrode layer, the electron transport layer, the perovskite layer and the hole transport layer by adopting P3 laser scribing so as to form a P3 channel.
In an alternative embodiment, the scribing width of the P1 laser scribing is 30-100 mu m, the scribing depth is 50-500 nm, and the laser energy is 5-150 mu J;
preferably, the width of the P2 laser scribing is 10-80 mu m, the single side width of the scribing edge from the edge of the conductive compensation column is 0-10 mu m, the scribing depth is 100-3000 nm, and the laser energy is 5-150 mu J;
Preferably, the width of the P3 laser scribing is 10-80 mu m, the single side width of the scribing edge from the edge of the conductive compensation column is 0-10 mu m, the scribing depth is 100-3000 nm, and the laser energy is 5-150 mu J;
preferably, the P1 laser scribing, the P2 laser scribing and the P3 laser scribing are all performed by using a femtosecond laser device.
In an alternative embodiment, the thickness of the hole transport layer is not more than 100nm, the thickness of the perovskite layer is 500-2000 nm, and the thickness of the electron transport layer is not more than 100nm;
Preferably, the material of the hole transport layer comprises at least one of Spiro-OMeTAD, PEDOT: PSS, TPD, PTAA, P 3HT、PCPDTBT、NiOx、V2O5、CuI、MoO3, cuO and Cu 2 O;
Preferably, the perovskite layer material has a chemical formula ABX 3, wherein a is at least one of CH3NH3 +(MA+)、NH2＝CHNH2 +(FA+)、C4H9NH3 +、Cs+ and Rb +; b is at least one of Pb 2+、Sn2+、Ge2+、Sb3+、Bi3+、Ag+、Au3+ and Ti 4+; x is at least one of Cl -,Br-,I- or halogen-like;
preferably, the material of the electron transport layer includes at least one of titanium oxide, zinc oxide, tin oxide, nickel oxide, magnesium oxide, copper oxide, C60 fullerene derivative thereof, cuprous oxide, and tungsten oxide;
preferably, the material of the metal back electrode layer is at least one of Au, ag and Cu.
In a fourth aspect, the present invention provides a perovskite battery module, which is prepared by the method for preparing a perovskite battery module according to any one of the previous embodiments.
In a fifth aspect, the present invention provides a packaging structure of a perovskite battery module, which comprises the perovskite battery module, a packaging adhesive film and a packaging cover plate according to the foregoing embodiment, wherein the packaging cover plate is adhered to the perovskite battery module through the packaging adhesive film;
Preferably, the packaging adhesive film comprises at least one of EVA, POE and PVB;
Preferably, the thickness of the packaging adhesive film is 50-500 mu m;
Preferably, the perovskite battery module, the packaging adhesive film and the packaging cover plate are packaged by adopting lamination equipment;
Preferably, the lamination melting temperature in the lamination apparatus is 100 ℃ to 150 ℃.
The invention has the following beneficial effects:
The patterned conductive compensation substrate provided by the invention is mainly used for solving the problem of poor P2/P3 laser etching effect, and particularly, a conductive layer is deposited on the surface of a transparent conductive layer at the position corresponding to P2 and/or P3 laser etching to form a conductive compensation column, and the conductive compensation column can reduce the depth of P2 and/or P3 laser etching, so that the laser energy is reduced, the etching precision is improved, and the phenomena of edge breakage, peeling, uneven surface of an etched line, saw-tooth cross section and the like are reduced; particularly, the conductive compensation column is added at the P2 position, which is favorable for increasing the thickness of the contact surface between the metal back electrode layer and the conductive substrate, thereby reducing the contact resistance and also reducing the problems of easy reaction and corrosiveness between the metal back electrode layer and the perovskite layer; the conductive compensation column can also be used as a filler to be filled in the grooves etched by the P2 and P3 laser, so that gaps between the packaging adhesive film and the grooves are reduced, and air in the gaps is reduced. The patterned conductive compensation substrate designed by the invention can improve the laser etching process and the packaging stability, thereby integrally improving the performance of the perovskite solar cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a process for preparing a patterned conductive compensation substrate according to embodiment 1 of the present invention;
Fig. 2 is a schematic diagram of a process flow for preparing a perovskite solar cell module provided in embodiment 1 of the invention;
Fig. 3 is a schematic process flow diagram of the perovskite solar cell module package provided in embodiment 1 of the invention;
Fig. 4 is a process flow chart of the preparation of the patterned conductive compensation substrate based on the photolithography process according to embodiment 6 of the present invention;
Fig. 5 is a schematic diagram of a process flow of preparing a perovskite solar cell module based on P2 position design according to embodiment 7 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a patterned conductive compensation substrate which comprises a conductive substrate and a conductive compensation column deposited on the conductive substrate, wherein the deposition position of the conductive compensation column is at least one of etching positions corresponding to P2 laser scribing and P3 laser scribing.
Aiming at the problem of poor P2/P3 laser etching effect, the invention deposits the conductive compensation column on the surface of the conductive substrate corresponding to the subsequent P2 laser scribing and the etching position corresponding to the P3 laser scribing, and the conductive compensation column can reduce the depth of P2/P3 laser etching, thereby reducing the laser energy, improving the etching precision, reducing the phenomena of edge breakage and peeling on two sides of the etched line, uneven surface of the etched line, saw-tooth cross section and the like; particularly, the P2 position is added with the conductive compensation column, so that the thickness of the contact surface between the metal back electrode layer and the conductive substrate is increased, the contact resistance is reduced, and the problems of easy reaction and corrosiveness between the metal back electrode layer and the perovskite layer can be relieved; the conductive compensation column can also be used as a filler to be filled in the grooves etched by the P2 and P3 laser, so that gaps between the packaging adhesive film and the grooves are reduced, and air in the gaps is reduced. The patterned conductive compensation substrate designed by the invention can improve the laser etching process and the packaging stability, thereby integrally improving the performance of the perovskite solar cell.
The conductive substrate comprises a transparent substrate and a conductive layer deposited on the transparent substrate, and the transparent substrate can be made of common glass, flexible plastic and other transparent materials. The material of the conductive layer includes at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene, and carbon nanotubes. The thickness of the conductive layer may be, for example, 50 to 500nm.
The material of the conductive compensation column comprises at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene, carbon nanotubes, au, al, cu, ni, fe, zn, ti, al 2O3、ZnO、NiOx、SnO2 and TiO 2; preferably, the material of the conductive compensation post is the same as the material of the conductive layer.
Further, when the deposition position of the conductive compensation column corresponds to the etching position corresponding to the P2 laser scribing and the P3 laser scribing at the same time, the thickness of the conductive compensation column is 100-2000 nm; at the moment, the highest point of the conductive compensation column and the hole transport layer can be ensured to be lower than the surface height of the perovskite after annealing crystallization, so that the compensation column and the hole transport layer can be completely covered by the perovskite layer after annealing crystallization, the surface of the perovskite layer is ensured to be flat, and the preparation of the electron transport layer and the metal back electrode layer is facilitated.
When the deposition position of the conductive compensation column only corresponds to the etching position corresponding to the P2 laser scribing or the P3 laser scribing, the thickness of the conductive compensation column is 100-3000 nm. It can be seen that the highest point of the conductive compensation column and the hole transport layer can be higher than the surface height of the perovskite after annealing crystallization, so that the metal back electrode layer is not in contact with the perovskite layer in the section to generate chemical reaction, carrier recombination is reduced, and the efficiency and stability of the battery are improved; the highest point of the compensation column and the carrier transmission layer can be lower than the surface height of the perovskite after annealing crystallization, so that the contact area between the metal back electrode layer and the perovskite layer in the section can be reduced, the occurrence of chemical reaction and carrier recombination are reduced, and the efficiency and the stability of the battery are improved.
Further, the width of the conductive compensation column is larger than or equal to the width of the etching position, and the single side width of the scribing edge of the etching position from the edge of the compensation column is 0-10 mu m; preferably, the width of the conductive compensation post is 30-100 μm.
The preparation method of the patterned conductive compensation substrate is simple, and as long as the conductive compensation column can be deposited on the surface of the conductive substrate at least one of etching positions corresponding to the P2 laser scribing and the P3 laser scribing, the deposition method can comprise the steps of performing sputtering deposition on the conductive compensation column by using a mask plate; the deposition method may further include, for example, depositing a conductive compensation layer on the surface of the conductive substrate, spreading a glue on the surface of the conductive compensation layer, exposing a region to be etched through a mask, etching, and stripping and cleaning the remaining photoresist to form a conductive compensation column.
In addition, the invention also provides a preparation method of the perovskite battery module, which comprises the steps of adopting the patterned conductive compensation substrate according to any one of the previous embodiments to prepare the perovskite battery module;
Specifically, referring to fig. 1 and 2, the preparation method includes the following steps:
i. And (3) depositing a transparent conductive layer.
And cleaning the transparent substrate and depositing a transparent conductive layer. The method comprises the steps of cleaning a transparent substrate by sequentially using deionized water, acetone, an optical glass cleaner, deionized water and isopropanol, ultrasonically cleaning the transparent substrate, and drying the transparent substrate in an oven at 60 ℃ for 6 hours. The deposition thickness of the conductive layer is 50-500 nm.
Ii. And depositing conductive compensation columns.
And depositing a conductive compensation column on the surface of the conductive substrate at least one of etching positions corresponding to the P2 laser scribing and the P3 laser scribing. The thickness is 100-3000 nm, and the width is 30-100 μm.
Iii, laser scribing P1.
And (3) carrying out scribing treatment on the patterned conductive compensation substrate by adopting P1 laser scribing to form a P1 channel, wherein the laser scribing P1 is carried out by adopting femtosecond laser scribing equipment, different laser power parameters and scribing conditions are selected for different conductive substrate types, the scribing width of the P1 laser scribing is 30-100 mu m, the scribing depth is 50-500 nm, and the laser energy is 5-150 mu J.
IV, depositing a first carrier layer (hole transport layer).
Preferably, the material of the hole transport layer includes, but is not limited to, at least one of organic or inorganic P-type semiconductor materials such as Spiro-ome tad, PEDOT PSS, TPD, PTAA, P 3HT、PCPDTBT、NiOx、V2O5、CuI、MoO3, cuO, and Cu 2 O; the thickness of the hole transport layer is not more than 100nm, and the preparation method of the hole transport layer comprises, but is not limited to, uniform film forming methods such as physical sputtering and vapor deposition.
V, depositing a perovskite layer.
The chemical formula of the material of the perovskite layer is ABX 3, wherein a is at least one of CH3NH3 +(MA+)、NH2＝CHNH2 +(FA+)、C4H9NH3 +、Cs+ and Rb +; b is at least one of Pb 2+、Sn2+、Ge2+、Sb3+、Bi3+、Ag+、Au3+ and Ti 4+; x is at least one of Cl -,Br-,I- or halogen-like; the thickness of the perovskite layer is 500-2000 nm, and the deposition method of the perovskite layer comprises any solution or vapor deposition method such as a slit coating method, a knife coating method, a screen printing method, a vacuum evaporation method, an ink-jet printing method and the like.
Vi deposition of a second charge carrier layer (electron transport layer)
Materials of the electron transport layer include, but are not limited to, at least one of titanium oxide, zinc oxide, tin oxide, nickel oxide, magnesium oxide, copper oxide, C60 fullerene derivatives thereof, cuprous oxide, and tungsten oxide; wherein the derivative of C60 fullerene includes, but is not limited to, at least one of PC61BM and PC71 BM; the thickness of the electron transport layer is not more than 100nm; methods for preparing the electron transport layer include, but are not limited to, uniform film formation methods such as material solution coating, vapor deposition, and the like.
Vii, laser scribing P2
Carrying out scribing treatment on the electron transport layer, the perovskite layer and the hole transport layer by adopting P2 laser scribing to form a P2 channel; the laser scribing P1 is performed by using a femtosecond laser scribing device, different laser power parameters and scribing conditions are selected according to different conductive substrate types, preferably, the width of the P2 laser scribing is 10-80 mu m, the single side width of the scribing edge from the edge of the conductive compensation column is 0-10 mu m, the scribing depth is 100-3000 nm, and the laser energy is 5-150 mu J.
Viii, depositing a metal back electrode layer;
The material of the metal back electrode layer is at least one of Au, ag and Cu. The metal back electrode layer can be prepared by adopting a vacuum thermal evaporation method.
Ix, laser scribing P3
And finally, carrying out scribing treatment on the metal back electrode layer, the electron transport layer, the perovskite layer and the hole transport layer by adopting P3 laser scribing to form a P3 channel. The laser scribing P3 is carried out by using a femtosecond laser scribing device, different laser power parameters and scribing conditions are selected according to different conductive substrate types, preferably, the width of the P3 laser scribing is 10-80 mu m, the single side width of the scribing edge from the edge of the conductive compensation column is 0-10 mu m, the scribing depth is 100-3000 nm, and the laser energy is 5-150 uJ.
In addition, referring to fig. 3, the invention further provides a packaging structure of the perovskite battery module, which comprises the perovskite battery module, a packaging adhesive film and a packaging cover plate, wherein the packaging cover plate is adhered with the perovskite battery module through the packaging adhesive film;
Wherein the packaging adhesive film comprises at least one of EVA, POE and PVB; the thickness of the packaging adhesive film is 50-500 mu m; packaging the perovskite battery module, the packaging adhesive film and the packaging cover plate by adopting lamination equipment; the lamination melting temperature in the lamination equipment is 100-150 ℃.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
Referring to fig. 1,2 and 3, the present embodiment provides a method for preparing and packaging a perovskite battery module, which includes the following steps:
s1, sequentially using deionized water, acetone, an optical glass cleaner, deionized water and isopropanol to ultrasonically clean a transparent glass substrate, and drying the transparent glass substrate in an oven at 60 ℃ for 6 hours.
S2, sputtering an ITO conductive layer on the surface of the transparent substrate by adopting magnetron sputtering, wherein the thickness of the ITO conductive layer is 130nm, and the resistance is 15 omega/≡.
S3, forming a conductive compensation column by utilizing a mask plate on the surface of the conductive layer and sputtering and depositing an ITO conductive layer, wherein the thickness of the conductive compensation column is 500nm, and the width of the conductive compensation column is 100 mu m.
S4, carrying out P1 laser scribing on the conductive layer by using a femtosecond laser device, and etching the conductive layer to a width of 100 mu m. And then sequentially adopting deionized water, acetone, an optical glass cleaner, deionized water and isopropanol for ultrasonic cleaning, and carrying out ultraviolet ozone treatment to enhance the wettability of the surface of the substrate.
S5, preparing a NiOx layer by using magnetron sputtering equipment, wherein the thickness of the NiOx layer is 100nm, namely the hole transport layer, annealing the NiOx layer for 10min at the temperature of a heating table of 100 ℃, and carrying out ultraviolet ozone treatment to enhance the wettability of the surface of the NiOx layer.
S6, preparing a perovskite layer by adopting a slit coating device, coating a FAPbI 3 perovskite solution (V DMF/VDMSO =4:1) with the concentration of 1.35M, and then performing VCD (Vacuum concentrate drying, vacuum drying and concentration) vacuum flash evaporation (10S reaches 20 Pa) to remove a low-boiling-point solvent and promote nucleation; and (3) continuously carrying out high-temperature (100 ℃) annealing for 50 minutes on a heating table to promote crystallization and form a uniform perovskite layer with the thickness of 700nm.
S7, evaporating C60 by adopting vacuum evaporation equipment, wherein the thickness is 50nm; snO 2 was deposited to a thickness of 30nm using ALD (Atomic Layer Deposition ) equipment to form a dual electron transport layer.
S8, carrying out P2 laser scribing by using a femtosecond laser device, wherein the etching parameter is adjusted and optimized to reduce damage to perovskite and a functional layer, the scribing width is 80 mu m, the single side width of the scribing edge from the edge of the compensation column is 10 mu m, the scribing depth is 380nm, and the laser energy is 12 mu J.
S9, depositing an Ag electrode of 100nm on the scribed quasi device through vacuum thermal evaporation.
S10, carrying out P3 laser scribing by using a femtosecond laser device, wherein the scribing width is 80 mu m, the scribing edge is 10 mu m from the single side width of the edge of the compensation column, the scribing depth is 480nm, and the laser energy is 20uJ. And cutting off the surface metal electrode to form effective series connection of sub-cells, so as to realize the preparation of perovskite modules.
S11, adhering the packaging glass and the perovskite solar cell module by adopting a lamination process through a hot melt adhesive film POE to form a complete cell module, wherein the temperature is 120 ℃.
Example 2
The embodiment provides a preparation and packaging method of a perovskite battery module, which comprises the following steps:
s1, sequentially using deionized water, acetone, an optical glass cleaner, deionized water and isopropanol to ultrasonically clean a transparent glass substrate, and drying the transparent glass substrate in an oven at 60 ℃ for 6 hours.
S2, sputtering an ITO conductive layer on the surface of the transparent substrate by adopting magnetron sputtering, wherein the thickness of the ITO conductive layer is 130nm, and the resistance is 15 omega/≡.
S3, forming a conductive compensation column by utilizing a mask plate on the surface of the conductive layer and sputtering and depositing an ITO conductive layer, wherein the thickness of the conductive compensation column is 400nm, and the width of the conductive compensation column is 100 mu m.
S4, carrying out P1 laser scribing on the conductive layer by using a femtosecond laser device, and etching the conductive layer to a width of 100 mu m. And then sequentially adopting deionized water, acetone, an optical glass cleaner, deionized water and isopropanol for ultrasonic cleaning, and carrying out ultraviolet ozone treatment to enhance the wettability of the surface of the substrate.
S5, preparing a NiOx layer by using magnetron sputtering equipment, wherein the thickness of the NiOx layer is 100nm, namely the hole transport layer, annealing the NiOx layer for 10min at the temperature of a heating table of 100 ℃, and carrying out ultraviolet ozone treatment to enhance the wettability of the surface of the NiOx layer.
S6, preparing a perovskite layer by adopting a slit coating device, coating a FAPbI 3 perovskite solution (V DMF/VDMSO =4:1) with the concentration of 1.35M, and then performing VCD (Vacuum concentrate drying, vacuum drying and concentration) vacuum flash evaporation (10S reaches 20 Pa) to remove a low-boiling-point solvent and promote nucleation; and (3) continuously carrying out high-temperature (100 ℃) annealing for 50 minutes on a heating table to promote crystallization and form a uniform perovskite layer with the thickness of 700nm.
S7, evaporating C60 by adopting vacuum evaporation equipment, wherein the thickness is 50nm; snO 2 was deposited to a thickness of 30nm using ALD (Atomic Layer Deposition ) equipment to form a dual electron transport layer.
S8, carrying out P2 laser scribing by using a femtosecond laser device, wherein the etching parameter is adjusted and optimized to reduce damage to perovskite and a functional layer, the scribing width is 80 mu m, the single side width of the scribing edge from the edge of the compensation column is 10 mu m, the scribing depth is 480 mu m, and the laser energy is 20 mu J.
S9, depositing an Ag electrode of 100nm on the scribed quasi device through vacuum thermal evaporation.
S10, carrying out P3 laser scribing by using a femtosecond laser device, wherein the scribing width is 80 mu m, the scribing edge is 10 mu m from the single side width of the edge of the compensation column, the scribing depth is 580 mu m, and the laser energy is 25 mu J. And cutting off the surface metal electrode to form effective series connection of sub-cells, so as to realize the preparation of perovskite modules.
S11, adhering the packaging glass and the perovskite solar cell module by adopting a lamination process through a hot melt adhesive film POE to form a complete cell module, wherein the temperature is 120 ℃.
Example 3
The embodiment provides a preparation and packaging method of a perovskite battery module, which comprises the following steps:
s1, sequentially using deionized water, acetone, an optical glass cleaner, deionized water and isopropanol to ultrasonically clean a transparent glass substrate, and drying the transparent glass substrate in an oven at 60 ℃ for 6 hours.
S2, sputtering an ITO conductive layer on the surface of the transparent substrate by adopting magnetron sputtering, wherein the thickness of the ITO conductive layer is 130nm, and the resistance is 15 omega/≡.
S3, forming a conductive compensation column by utilizing a mask plate on the surface of the conductive layer and sputtering and depositing an ITO conductive layer, wherein the thickness of the conductive compensation column is 600nm, and the width of the conductive compensation column is 100 mu m.
S4, carrying out P1 laser scribing on the conductive layer by using a femtosecond laser device, and etching the conductive layer to a width of 100 mu m. And then sequentially adopting deionized water, acetone, an optical glass cleaner, deionized water and isopropanol for ultrasonic cleaning, and carrying out ultraviolet ozone treatment to enhance the wettability of the surface of the substrate.
S5, preparing a NiOx layer by using magnetron sputtering equipment, wherein the thickness of the NiOx layer is 100nm, namely the hole transport layer, annealing the NiOx layer for 10min at the temperature of a heating table of 100 ℃, and carrying out ultraviolet ozone treatment to enhance the wettability of the surface of the NiOx layer.
S6, preparing a perovskite layer by adopting a slit coating device, coating a FAPbI 3 perovskite solution (V DMF/VDMSO =4:1) with the concentration of 1.35M, and then performing VCD (Vacuum concentrate drying, vacuum drying and concentration) vacuum flash evaporation (10S reaches 20 Pa) to remove a low-boiling-point solvent and promote nucleation; and (3) continuously carrying out high-temperature (100 ℃) annealing for 50 minutes on a heating table to promote crystallization and form a uniform perovskite layer with the thickness of 700nm.
S7, evaporating C60 by adopting vacuum evaporation equipment, wherein the thickness is 50nm; snO 2 was deposited to a thickness of 30nm using ALD (Atomic Layer Deposition ) equipment to form a dual electron transport layer.
S8, carrying out P2 laser scribing by using a femtosecond laser device, wherein the etching parameter is adjusted and optimized to reduce damage to perovskite and a functional layer, the scribing width is 80 mu m, the single side width of the scribing edge from the edge of the compensation column is 10 mu m, the scribing depth is 280 mu m, and the laser energy is 10 mu J.
S9, depositing an Ag electrode of 100nm on the scribed quasi device through vacuum thermal evaporation.
S10, carrying out P3 laser scribing by using a femtosecond laser device, wherein the scribing width is 80 mu m, the scribing edge is 10 mu m from the single side width of the edge of the compensation column, the scribing depth is 380 mu m, and the laser energy is 12 mu J. And cutting off the surface metal electrode to form effective series connection of sub-cells, so as to realize the preparation of perovskite modules.
S11, adhering the packaging glass and the perovskite solar cell module by adopting a lamination process through a hot melt adhesive film POE to form a complete cell module, wherein the temperature is 120 ℃.
Example 4
The present embodiment is substantially the same as embodiment 1, except that the transparent glass in step S1 of embodiment 1 is replaced with a PET flexible substrate in the present embodiment, and the flexible perovskite solar cell module can be realized by adopting the subsequent steps as well.
Example 5
The present embodiment is substantially the same as embodiment 1, except that in this embodiment, the p-type NiOx transmission layer in S5 of embodiment 1 is replaced with an n-type SnO 2 transmission layer, and simultaneously the n-type C60/SnO 2 transmission layer in step S7 of embodiment 1 is replaced with a p-type spira-ome transmission layer, so that the preparation of the regular perovskite solar cell module (n-i-p structure) can be achieved.
Example 6
The difference between this embodiment and embodiment 1 is that the preparation method of the conductive compensation column in this embodiment is different, specifically, in this embodiment, a transparent conductive layer is deposited on the surface of transparent glass, a compensation column layer is deposited on the surface of transparent conductive layer, coating photoresist is coated on the surface of the compensation column layer, exposing/developing is performed by using a mask, the area to be etched is exposed, etching is performed again, the exposed area is etched, and finally, the remaining photoresist is stripped and washed to form the conductive compensation column, as shown in fig. 4.
Example 7
The difference between this embodiment and embodiment 1 is that the conductive compensation column is designed only at the position of the P2 laser scribing, in this embodiment, the thickness of the conductive compensation column is 3000nm, and at this time, the highest point of the conductive compensation column and the hole transport layer is higher than the surface height of the perovskite after annealing and crystallization, so that the metal electrode does not contact with the perovskite layer in the cross section to generate chemical reaction, reduce carrier recombination, and improve the efficiency and stability of the battery, as shown in fig. 5.
Comparative example 1
This comparative example is substantially the same as example 1 except that the conductive compensation column is not provided in this comparative example, that is, step S3 is omitted, and step S2 is directly performed after the conductive layer is deposited in step S4 to S11, wherein the scribing depth of the P2 laser scribing in step S8 is 880 μm and the laser energy is 40 μj. In step S10, the scribing depth of the P3 laser scribing was 980. Mu.m, and the laser energy was 45. Mu.J.
Comparative example 2
This comparative example is substantially the same as example 1 except that the deposition thickness of the conductive compensation column in this comparative example is 50nm.
Comparative example 3
This comparative example is substantially the same as example 1 except that the deposition thickness of the conductive compensation column in this comparative example is 4000nm.
Experimental example
The perovskite battery modules prepared in the above examples 1 to 7 and comparative examples 1 to 3 were examined, wherein the state of both sides of the etched line was evaluated as good if it exhibited a state without edge chipping or peeling; if the state of slight edge breakage and slight skinning is presented, the evaluation is good, and if the state of severe edge breakage and skinning is presented, the evaluation is poor; among them, the stability of the state without edge chipping and peeling was evaluated as good, the stability of the state with slight edge chipping and slight peeling was evaluated as good, and the stability of the state with severe edge chipping and severe peeling was evaluated as poor. The test results are shown in the following table.
From the table, the proper thickness of the conductive compensation column can reduce the laser cutting energy, optimize the shape of the cutting section and improve the encapsulation effect. Wherein, the states of both sides of the etched line after the P2 laser scribing of the embodiments 1-7 are evaluated as better or better, wherein, the thickness of the conductive compensation column of the embodiment 2 is slightly lower than that of other embodiments, so that the laser energy of the embodiment is increased, and meanwhile, the states of both sides of the etched line are evaluated as better, and the corresponding P3 laser scribing and overall performance are also evaluated as better. In example 7, the conductive compensation column was designed only at the P2 laser scribing position, so that the state of both sides of the etched line after the P2 laser scribing was evaluated as good, but the state of both sides of the etched line after the P3 laser scribing was evaluated as poor, but the final stability was evaluated as good, and it was confirmed that the stability was improved to some extent by designing the conductive compensation column only at the P2 laser scribing position, and correspondingly, the stability was improved to some extent by designing the conductive compensation column only at the P3 laser scribing position. In contrast, in comparative example 1, no conductive compensation column was provided, at this time, the laser energy of P2 and P3 was significantly increased, and both the etched line side state and the package stability were poor, while as can be seen from comparative examples 2 and 3, the deposition thickness of the conductive compensation column was too low or too high, the effect was still poor, and both the etched line side state and the package stability were poor.
In summary, the patterned conductive compensation substrate provided by the invention is mainly aimed at the problem of poor P2/P3 laser etching effect, and specifically, a conductive layer is deposited on the surface of a transparent conductive layer at the position corresponding to P2 and/or P3 laser etching to form a conductive compensation column, and the conductive compensation column can reduce the depth of P2 and/or P3 laser etching, thereby reducing laser energy, improving etching precision, reducing edge breakage and peeling on two sides of an etched line, and reducing the phenomena of uneven surface of the etched line, saw-tooth cross section and the like; particularly, the conductive compensation column is added at the P2 position, which is favorable for increasing the thickness of the contact surface between the metal back electrode layer and the conductive substrate, thereby reducing the contact resistance and also reducing the problems of easy reaction and corrosiveness between the metal back electrode layer and the perovskite layer; the conductive compensation column can also be used as a filler to be filled in the grooves etched by the P2 and P3 laser, so that gaps between the packaging adhesive film and the grooves are reduced, and air in the gaps is reduced. The patterned conductive compensation substrate designed by the invention can improve the laser etching process and the packaging stability, thereby integrally improving the performance of the perovskite solar cell.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The patterned conductive compensation substrate is characterized by comprising a conductive substrate and a conductive compensation column deposited on the conductive substrate, wherein the deposition position of the conductive compensation column is at least one of etching positions corresponding to a P2 laser scribing and a P3 laser scribing.
2. The patterned conductive compensation substrate of claim 1, wherein the conductive compensation post has a thickness of 100-2000 nm when the deposition location of the conductive compensation post corresponds to the etch locations corresponding to both the P2 laser scribe and the P3 laser scribe;
when the deposition position of the conductive compensation column only corresponds to the etching position corresponding to the P2 laser scribing or the P3 laser scribing, the thickness of the conductive compensation column is 100-3000 nm.
3. The patterned conductive compensation substrate of claim 1, wherein the conductive compensation post has a width that is greater than or equal to the width of the etched location, and wherein the scribe line edge of the etched location is 0-10 μιη from the single edge width of the compensation post edge;
preferably, the width of the conductive compensation column is 30-100 μm.
4. The patterned conductive compensation substrate of claim 1, wherein the conductive compensation post material comprises at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene, carbon nanotubes, au, al, cu, ni, fe, zn, ti, al 2O3、ZnO、NiOx、SnO2, and TiO 2;
preferably, the conductive substrate comprises a transparent substrate and a conductive layer deposited on the transparent substrate, wherein the material of the conductive layer comprises at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene and carbon nanotubes;
Preferably, the conductive compensation post is made of the same material as the conductive layer.
5. The method of preparing a patterned conductive compensation substrate according to any of claims 1-4, comprising: depositing a conductive compensation column on the surface of the conductive substrate at least one of etching positions corresponding to the P2 laser scribing and the P3 laser scribing;
Preferably, the deposition method comprises the step of performing sputter deposition on the conductive compensation column by using a mask;
Preferably, the deposition method includes depositing a conductive compensation layer on the surface of the conductive substrate, coating a glue on the surface of the conductive compensation layer, exposing and developing a region to be etched through a mask, exposing the region to be etched, etching, and stripping and cleaning the residual photoresist to form the conductive compensation column.
6. A method of manufacturing a perovskite battery module, comprising manufacturing a perovskite battery module using the patterned conductive compensation substrate as claimed in any one of claims 1 to 4;
Preferably, scribing the patterned conductive compensation substrate by using a P1 laser scribing process on the patterned conductive compensation substrate to form a P1 channel, and then depositing a hole transport layer, a perovskite layer and an electron transport layer; then, carrying out scribing treatment on the electron transport layer, the perovskite layer and the hole transport layer by adopting P2 laser scribing to form a P2 channel; depositing a metal back electrode layer on the top of the device; and finally, carrying out scribing treatment on the metal back electrode layer, the electron transport layer, the perovskite layer and the hole transport layer by adopting P3 laser scribing so as to form a P3 channel.
7. The method for manufacturing a perovskite battery module according to claim 6, wherein the P1 laser scribing has a scribing width of 30 to 100 μm, a scribing depth of 50 to 500nm, and a laser energy of 5 to 150 μj;
preferably, the width of the P2 laser scribing is 10-80 mu m, the single side width of the scribing edge from the edge of the conductive compensation column is 0-10 mu m, the scribing depth is 100-3000 nm, and the laser energy is 5-150 mu J;
Preferably, the width of the P3 laser scribing is 10-80 mu m, the single side width of the scribing edge from the edge of the conductive compensation column is 0-10 mu m, the scribing depth is 100-3000 nm, and the laser energy is 5-150 mu J;
preferably, the P1 laser scribing, the P2 laser scribing and the P3 laser scribing are all performed by using a femtosecond laser device.
8. The method for manufacturing a perovskite battery module according to claim 6, wherein the thickness of the hole transport layer is not more than 100nm, the thickness of the perovskite layer is 500 to 2000nm, and the thickness of the electron transport layer is not more than 100nm;
Preferably, the material of the hole transport layer comprises at least one of Spiro-OMeTAD, PEDOT: PSS, TPD, PTAA, P 3HT、PCPDTBT、NiOx、V2O5、CuI、MoO3, cuO and Cu 2 O;
Preferably, the perovskite layer material has a chemical formula ABX 3, wherein a is at least one of CH3NH3 +(MA+)、NH2＝CHNH2 +(FA+)、C4H9NH3 +、Cs+ and Rb +; b is at least one of Pb 2+、Sn2+、Ge2+、Sb3+、Bi3+、Ag+、Au3+ and Ti 4+; x is at least one of Cl -,Br-,I- or halogen-like;
preferably, the material of the electron transport layer includes at least one of titanium oxide, zinc oxide, tin oxide, nickel oxide, magnesium oxide, copper oxide, C60 fullerene derivative thereof, cuprous oxide, and tungsten oxide;
preferably, the material of the metal back electrode layer is at least one of Au, ag and Cu.
9. A perovskite battery module, characterized in that it is prepared by the preparation method of the perovskite battery module as claimed in any one of claims 7 to 8.
10. A packaging structure of a perovskite battery module, which is characterized by comprising the perovskite battery module, a packaging adhesive film and a packaging cover plate, wherein the packaging cover plate is adhered with the perovskite battery module through the packaging adhesive film;
Preferably, the packaging adhesive film comprises at least one of EVA, POE and PVB;
Preferably, the thickness of the packaging adhesive film is 50-500 mu m;
Preferably, the perovskite battery module, the packaging adhesive film and the packaging cover plate are packaged by adopting lamination equipment;
Preferably, the lamination melting temperature in the lamination apparatus is 100 ℃ to 150 ℃.
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| CN119141006A (en) * | 2024-11-13 | 2024-12-17 | 能丰(杭州)光电科技有限公司 | Laser processing method and device for OPV organic photovoltaic cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN119141006A (en) * | 2024-11-13 | 2024-12-17 | 能丰(杭州)光电科技有限公司 | Laser processing method and device for OPV organic photovoltaic cell |
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