CN118434168A - Perovskite solar cell module with section insulation and preparation method thereof - Google Patents
Perovskite solar cell module with section insulation and preparation method thereof Download PDFInfo
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- Photovoltaic Devices (AREA)
Abstract
The invention relates to the technical field of perovskite solar cells, and discloses a perovskite solar cell module with section insulation and a preparation method thereof. According to the perovskite solar cell module with section insulation, the P2 laser scribing groove and the P3 laser scribing groove are partially overlapped, meanwhile, the first section insulation layer and the second section insulation layer are arranged at the corresponding positions of the P2 laser scribing groove and the P3 laser scribing groove, the exposed sections at the positions of the P2 laser scribing groove and the P3 laser scribing groove are insulated by the section insulation layer, so that the insulation groove is formed on the surface of the transparent conductive layer, and the local crystallinity of the perovskite layer is improved; the P2 and P3 scribing positions are overlapped, so that the dead zone (the scribing position does not generate photo-generated carriers) area can be reduced, the scribing etching section can be ensured to be covered by the insulating layer, and the stability of the battery assembly is improved. The design of the scheme can finally integrally improve the performance of the perovskite solar cell.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell module with section insulation and a preparation method thereof.
Background
With the rapid progress of human society, environmental and energy problems in the background of sustainable development are important points of attention of various countries, and photovoltaic technology, which is the most widely applied clean energy technology in the market at present, is one of the centers of gravity of 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 the bottom transparent conductive layer; p3 is to pattern the electrode after the back electrode layer 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 scribing process basically uses high-frequency high-power laser to carry out one-time penetrating etching, and the scribing position is found to influence the stability of the battery assembly in the practical process.
Therefore, a new technical solution is needed 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 perovskite solar cell module with section insulation and a preparation method thereof.
The invention is realized in the following way:
In a first aspect, the present invention provides a perovskite solar cell module having cross-section insulation, comprising: transparent substrate, transparent conducting layer, first carrier layer, perovskite layer, second carrier layer and back electrode layer, transparent conducting layer deposit in transparent substrate is last, will through P1 laser scribing groove conducting layer cuts apart, first carrier layer perovskite layer with second carrier layer deposits in proper order on the conducting layer and pack in P1 laser scribing groove, will through P2 laser scribing groove second carrier layer perovskite layer with first carrier layer cuts apart, be provided with first section insulating layer on the lateral wall of P2 laser scribing groove, back electrode layer deposits in second carrier layer with the surface of first section insulating layer, cut apart through P3 laser scribing groove will back electrode layer, second carrier layer perovskite layer with first carrier layer, be provided with the second section insulating layer on the lateral wall of P3 laser scribing groove, P2 laser scribing groove with second carrier layer, second section insulating layer, second carrier layer, first section insulating layer, first section cover layer.
In an alternative embodiment, the heights of the first section insulating layer and the second section insulating layer are 700-3000 nm;
And/or the heights of the first section insulating layer and the second section insulating layer exceed the upper surface of the second carrier layer;
And/or the widths of the first section insulating layer and the second section insulating layer are 10-50 mu m;
And/or the distance between the first section insulating layer and the second section insulating layer is 60-200 mu m.
In an alternative embodiment, the materials of the first section insulating layer and the second section insulating layer are at least one of organic matters, inorganic matters and liquid glue;
optionally, the organic matter comprises polyimide;
Optionally, the inorganic substance includes at least one of silicon nitride, silicon oxide, aluminum oxide, and silicon oxynitride;
Optionally, the liquid glue comprises at least one of epoxy, polyurethane and acrylic.
In a second aspect, the present invention provides a method for preparing a perovskite solar cell module having section insulation according to any one of the previous embodiments, comprising:
Depositing the transparent conductive layer on the surface of the transparent substrate, depositing an insulating column on the surface of the transparent conductive layer at a position corresponding to the P2 laser scribing and a position corresponding to the P3 laser scribing, dividing the conductive layer by adopting the P1 laser scribing to form the P1 laser scribing groove, then depositing the first carrier layer, the perovskite layer and the second carrier layer, dividing the second carrier layer, the perovskite layer and the first carrier layer by adopting the P2 laser scribing on the insulating column to form the P2 laser scribing groove with a first section insulating layer, depositing the back electrode layer on the surfaces of the second carrier layer and the first section insulating layer, and dividing the back electrode layer, the second carrier layer, the perovskite layer and the first carrier layer by adopting the P3 laser scribing on the insulating column to form the P3 laser scribing groove with a second section insulating layer.
In an alternative embodiment, the insulating column has a height of 700-3000 nm and a width of 90-300 μm;
Optionally, the scribing width of the P2 laser scribing is 30-100 μm, the scribing edge is 10-50 μm away from the edge width of the first section insulating layer, and the scribing edge is 50-150 μm away from the edge width of the second section insulating layer;
Optionally, the scribing width of the P3 laser scribing is 30-100 μm, the scribing edge is 50-150 μm away from the edge width of the first section insulating layer, and the scribing edge is 10-50 μm away from the edge width of the second section insulating layer.
In alternative embodiments, the method of fabricating the insulating column includes coating, plasma enhanced chemical vapor deposition, atomic layer deposition, physical vapor deposition, or photolithography;
preferably, the method of plasma enhanced chemical vapor deposition includes performing sputter deposition of the insulating column using a reticle;
preferably, the photoetching method comprises the steps of depositing an insulating layer on the surface of the transparent conductive layer, gluing the surface of the insulating layer, exposing and developing the area to be etched through a mask, exposing the area to be etched, etching, and stripping and cleaning the residual photoresist to form the insulating column.
In an alternative embodiment, the P1 laser scribing, the P2 laser scribing, and the P3 laser scribing are all performed with a femto-second laser device.
In an alternative embodiment, the thickness of the transparent conductive layer is 50-500 nm, the thickness of the first carrier layer is not more than 100nm, the thickness of the perovskite layer is 500-2000 nm, and the thickness of the second carrier layer is not more than 100nm;
Preferably, the material of the transparent conductive layer includes at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene, and carbon nanotubes;
preferably, the material of the first carrier layer includes 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 second carrier 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 back electrode layer is at least one of Au, ag, and Cu.
In a third aspect, the present invention provides a packaging structure of a perovskite solar cell module, which comprises the perovskite solar cell module with section insulation, a packaging adhesive film and a packaging cover plate, wherein the packaging cover plate is adhered to the perovskite solar cell module with section insulation 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, laminating equipment is adopted to package the perovskite solar cell module with section insulation, the packaging adhesive film and the packaging cover plate;
Preferably, the lamination melting temperature in the lamination apparatus is 100 ℃ to 150 ℃.
In a fourth aspect, the present invention provides a perovskite solar cell, comprising the encapsulation structure of the perovskite solar cell module according to the previous embodiment.
The invention has the following beneficial effects:
According to the perovskite solar cell module with section insulation, the P2 laser scribing groove and the P3 laser scribing groove are partially overlapped, meanwhile, the first section insulation layer and the second section insulation layer are arranged at the corresponding positions of the P2 laser scribing groove, the exposed section at the position of the P2 laser scribing groove is insulated by the first section insulation layer, the exposed section at the position of the P3 laser scribing groove is insulated by the second section insulation layer, the side walls of the partially overlapped P2 laser scribing groove and P3 laser scribing groove are covered by the insulation layers under the action of the first section insulation layer and the second section insulation layer, the insulation grooves are formed on the surfaces of the transparent conductive layers, and therefore the local crystallinity of the perovskite layer can be improved; the P2 and P3 scribing positions are overlapped, so that the dead zone (the scribing position does not generate photo-generated carriers) area can be reduced, the scribing etching section can be ensured to be covered by the insulating layer, and the stability of the battery assembly is improved. The design of the scheme can finally integrally improve 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 schematic structural diagram of a perovskite solar cell module with section insulation provided by the invention;
Fig. 2 is a process diagram of a perovskite solar cell module with section insulation provided by the invention;
Fig. 3 is a packaging process diagram of a perovskite solar cell module with section insulation provided by the invention;
Fig. 4 is another process diagram of the fabrication of an insulating column of a perovskite solar cell module with cross-section insulation provided by the invention;
Fig. 5 is another manufacturing process diagram of the perovskite solar cell module with section insulation provided by the invention.
Icon: 100-perovskite solar cell module with section insulation; 110-a transparent substrate; 120-a transparent conductive layer; 130-a first carrier layer; 140-perovskite layer; 150-a second carrier layer; 160-a back electrode layer; 170-a first section insulating layer; 180-second section insulating layer.
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.
According to the invention, the research discovers that the P2 and P3 scribing positions can influence the stability of the battery assembly, because the P2 position is subjected to laser scribing and cutting to form a bare section, and the back electrode layer is subjected to chemical reaction with a perovskite layer in the bare section after being deposited to influence the stability of the battery assembly; and the P3 position is laser-scribed, the exposed section is formed after the laser cutting, and a water-oxygen channel is still formed after the battery module is packaged, so that the stability of the battery module is affected.
To this end, the present invention provides a perovskite solar cell module having section insulation, which can improve the stability of a cell assembly by performing an insulation treatment on the sidewalls of grooves formed at the positions of P2 and P3 scribe lines.
Specifically, referring to fig. 1, the perovskite solar cell module 100 with section insulation in the present invention includes a transparent substrate 110, a transparent conductive layer 120, a first carrier layer 130, a perovskite layer 140, a second carrier layer 150 and a back electrode layer 160, wherein the transparent conductive layer 120 is deposited on the transparent substrate 110, the transparent conductive layer 120 is divided by a P1 laser scribing groove (not shown), the first carrier layer 130, the perovskite layer 140 and the second carrier layer 150 are sequentially deposited on the transparent conductive layer 120 and filled in the P1 laser scribing groove, the second carrier layer 150, the perovskite layer 140 and the first carrier layer 130 are divided by a P2 laser scribing groove (not shown), a first section insulating layer 170 is disposed on a sidewall of the P2 laser scribing groove, the back electrode layer 160 is deposited on a surface of the second carrier layer 150 and the first section insulating layer 170, the back electrode layer 160, the second carrier layer 150, the perovskite layer 140 and the first carrier layer 130 are sequentially deposited on the transparent conductive layer 120 by a P3 laser scribing groove (not shown), the second carrier layer 180 is disposed on a sidewall of the P3 laser scribing groove, and the second section insulating layer 180 is covered by the P3 laser scribing groove, and the second section insulating layer 180 is partially covered by the P3 laser scribing groove and the second carrier layer 130.
Wherein the heights of the first section insulating layer 170 and the second section insulating layer 180 are 700-3000 nm; and/or the heights of the first section insulating layer 170 and the second section insulating layer 180 exceed the upper surface of the second carrier layer 150; and/or the first section insulating layer 170 and the second section insulating layer 180 each have a width of 10 to 50 μm; and/or the distance between the first section insulating layer 170 and the second section insulating layer 180 is 60 to 200 μm.
The first section insulating layer 170 and the second section insulating layer 180 are made of at least one of organic matters, inorganic matters and liquid glue; wherein the organic matter includes, but is not limited to, polyimide; the inorganic substances include, but are not limited to, at least one of silicon nitride, silicon oxide, aluminum oxide, and silicon oxynitride; the liquid glue includes, but is not limited to, at least one of epoxy, polyurethane, and acrylic.
Further, referring to fig. 2, the invention also provides a preparation method of the perovskite solar cell module with section insulation, which comprises the following steps:
i. And (3) depositing a transparent conductive layer.
And cleaning the transparent substrate, and depositing a transparent conductive layer on the surface of the transparent substrate. 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 transparent conductive layer is 50-500 nm.
The transparent substrate can be made of common glass, flexible plastic and other transparent materials. The transparent conductive layer material may be Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), silver nanowires, graphene, carbon nanotubes, or the like.
Ii. And (5) depositing an insulating column.
Depositing insulating columns on the surfaces of the transparent conductive layers at positions corresponding to the P2 laser scribing and the P3 laser scribing, wherein the heights of the insulating columns are 700-3000 nm, and the widths of the insulating columns are 90-300 mu m;
The preparation method of the insulating column comprises coating, plasma Enhanced Chemical Vapor Deposition (PECVD), atomic Layer Deposition (ALD), physical Vapor Deposition (PVD) or photoetching; preferably, the method of plasma enhanced chemical vapor deposition comprises sputtering deposition of the insulating column by using a mask; preferably, the photoetching method comprises the steps of depositing an insulating layer on the surface of a transparent conductive layer, gluing the surface of the insulating layer, exposing and developing the area to be etched through a mask, exposing the area to be etched, etching, and stripping and cleaning the residual photoresist to form the insulating column.
Iii, laser scribing P1.
The conductive layer is divided into P1 laser scribing grooves by P1 laser scribing, laser scribing P1 is carried out by femtosecond laser scribing equipment, different laser power parameters and scribing conditions are selected for different transparent conductive layer types, and the scribing width of the P1 laser scribing is 30-100 mu m.
IV, depositing a first carrier layer (hole transport layer).
The material of the hole transport layer comprises at least one of organic or inorganic P-type semiconductor materials such as Spiro-OMeTAD, PEDOT: PSS, TPD, PTAA, P 3HT、PCPDTBT、NiOx、V2O5、CuI、MoO3, cuO, cu 2 O and the like; 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
Dividing the second carrier layer, the perovskite layer and the first carrier layer by adopting P2 laser scribing on the insulating column to form a P2 laser scribing groove with a first section insulating layer; the laser scribing P2 is performed by using a femtosecond laser scribing device, different laser power parameters and scribing conditions are selected for different transparent conductive layer types, preferably, the scribing width of the P2 laser scribing is 30-100 μm, the width of the scribing edge from the edge of the first section insulating layer is 10-50 μm, and the width of the scribing edge from the edge of the second section insulating layer is 50-150 μm.
Viii, depositing a back electrode layer;
And depositing a back electrode layer on the surfaces of the second carrier layer and the first section insulating layer, wherein the back electrode layer is made of at least one of Au, ag and Cu. The 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 back electrode layer, the second carrier layer, the perovskite layer and the first carrier layer by adopting P3 laser scribing on the insulating column, and dividing to form a P3 laser scribing groove with the insulating layer with the second section. The laser scribing P3 is performed by using a femtosecond laser scribing device, different laser power parameters and scribing conditions are selected for different transparent conductive layer types, preferably, the scribing width of the P3 laser scribing is 30-100 μm, the width of the scribing edge from the edge of the first section insulating layer is 50-150 μm, and the width of the scribing edge from the edge of the second section insulating layer is 10-50 μm.
The invention also provides a packaging structure of the perovskite solar cell module, which comprises the perovskite solar cell module with the section insulation, a packaging adhesive film and a packaging cover plate, wherein the packaging cover plate is adhered with the perovskite solar cell module with the section insulation 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 solar cell module with section insulation, the packaging adhesive film and the packaging cover plate by adopting lamination equipment; the lamination melting temperature in the lamination equipment is 100-150 ℃.
In addition, the invention also provides a perovskite solar cell, which comprises the encapsulation structure of the perovskite solar cell module.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
Referring to fig. 2 and 3, the present embodiment provides a perovskite solar cell module with section insulation, and the preparation method thereof includes:
i. Sequentially using deionized water, acetone, an optical glass cleaner, deionized water and isopropanol to ultrasonically clean the transparent glass substrate, and drying the transparent glass substrate in an oven at 60 ℃ for 6 hours. And sputtering an ITO transparent 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/≡.
Ii. And preparing the SiNx insulating column with the thickness of 2000nm and the width of 150 mu m on the surface of the transparent conductive layer by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and utilizing a mask.
And iii, carrying out P1 laser scribing on the transparent conductive layer by using a femtosecond laser device, wherein the etching width is 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.
And (3) preparing a NiOx layer by using a magnetron sputtering device through a mask plate, wherein the thickness of the NiOx layer is 100nm, namely the hole transport layer, annealing the NiOx layer for 10mins at a heating stage of 100 degrees, and performing ultraviolet ozone treatment to enhance the wettability of the surface of the NiOx layer.
And V, preparing the perovskite layer by using a mask plate by adopting vacuum evaporation equipment, and continuously carrying out high-temperature (100 ℃) annealing on a heating table for 50 minutes to form a uniform perovskite layer.
Vi, evaporating C60 by using a mask plate by adopting vacuum evaporation equipment, wherein the thickness is 50nm; and (3) depositing SnO 2 by using ALD (Atomic Layer Deposition ) equipment through a mask plate, and forming a double electron transport layer with the thickness of 30 nm.
And carrying out P2 laser etching by using femto-second laser equipment, wherein the etching parameters are adjusted and optimized to reduce the damage to perovskite and the functional layer, the asymmetric scribing is carried out, the scribing width is 50 mu m, the scribing edge is 30 mu m away from the edge of the first section insulating layer, and the edge width is 70 mu m away from the second section insulating layer.
Viii, depositing a 100nm Ag back electrode layer on the scribed quasi device by vacuum thermal evaporation.
Ix, further adopt femto second laser equipment to carry out P3 laser etching, scribing width 50 mu m, scribing edge is 70 mu m apart from the edge width of first section insulating layer, is 30 mu m apart from the edge width of second section insulating layer. And cutting off the surface back electrode layer to form effective series connection of sub-cells, thereby realizing the preparation of perovskite modules.
X, placing the hot melt adhesive film POE on the surface of the back electrode layer, and arranging the packaging glass on the surface of the hot melt adhesive film POE.
Xi, adopting a lamination process, and adhering packaging glass and a perovskite solar cell module by using a hot melt adhesive film POE to form a complete cell module, wherein the temperature is 120 ℃.
Example 2
This embodiment is substantially the same as embodiment 1, except that the parameters of step ii, vii, ix are different, specifically:
ii. And preparing the SiNx insulating column by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method on the surface of the transparent conductive layer and utilizing a mask plate, wherein the thickness is 700nm, and the width is 90 mu m.
And carrying out P2 laser etching by using femto-second laser equipment, wherein the etching parameters are adjusted and optimized to reduce the damage to perovskite and the functional layer, the scribing width is 30 mu m, the scribing edge is 10 mu m away from the edge of the first section insulating layer, and the scribing edge is 50 mu m away from the edge of the second section insulating layer.
Ix, further adopt femto second laser equipment to carry out P3 laser etching, scribing width 30 mu m, scribing edge is 10 mu m apart from the edge width of first section insulating layer, is 50 mu m apart from the edge width of second section insulating layer. And cutting off the surface back electrode layer to form effective series connection of sub-cells, thereby realizing the preparation of perovskite modules.
Example 3
This embodiment is substantially the same as embodiment 1, except that the parameters of step ii, vii, ix are different, specifically:
ii. And preparing the SiNx insulating column by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method on the surface of the transparent conductive layer and utilizing a mask plate, wherein the thickness is 3000nm, and the width is 300 mu m.
And carrying out P2 laser etching by using femto-second laser equipment, wherein the etching parameters are adjusted and optimized to reduce the damage to perovskite and the functional layer, the width of the asymmetric scribing line is 100 mu m, the width of the scribing line edge is 50 mu m away from the edge of the first section insulating layer, and the width of the scribing line is 150 mu m away from the edge of the second section insulating layer.
Ix, further adopt femto second laser equipment to carry out P3 laser etching, scribing width 100 mu m, scribing edge is 150 mu m apart from the edge width of first section insulating layer, is 50 mu m apart from the edge width of second section insulating layer. And cutting off the surface back electrode layer to form effective series connection of sub-cells, thereby realizing the preparation of perovskite modules.
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 insulating column in this embodiment is different, specifically, in this embodiment, a transparent conductive layer is deposited on the surface of transparent glass, an insulating layer is deposited on the surface of transparent conductive layer, coating photoresist is coated on the surface of insulating 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 insulating column, as shown in fig. 4.
Example 7
The embodiment is basically the same as embodiment 1, except that in step S7 of the embodiment, a vacuum evaporation device is used to evaporate C60, and a mask is not used, with a thickness of 50nm; snO 2 was deposited using ALD (Atomic Layer Deposition ) equipment, without using a mask, to a thickness of 30nm, to form a dual electron transport layer, as shown in fig. 5.
Comparative example 1
This comparative example is substantially the same as example 1 except that no insulating column is provided in this comparative example, that is, step S3 is omitted, step S2 is performed directly after depositing the transparent conductive layer, and steps S4 to S11 are omitted, while the scribing edge in step S8 is 30 μm from the edge width of the first section insulating layer and 100 μm from the edge width of the second section insulating layer. The scribe line edge in S10 is omitted to have an edge width of 100 μm from the first section insulating layer and an edge width of 30 μm from the second section insulating layer.
Comparative example 2
This comparative example is substantially the same as example 1 except that the positions of the P2 laser scribe line and the P3 laser scribe line in this comparative example are independent of each other and there is no overlap, the first section insulating layers are provided on both side walls of the P2 laser scribe line, and the second section insulating layers are provided on both side walls of the P3 laser scribe line.
Comparative example 3
This comparative example is substantially the same as example 1 except that the method of forming the first-section insulating layer and the second-section insulating layer is different. In the comparative example, step S3 is omitted, no insulating column is arranged, a first section insulating layer is directly deposited on the side wall of the P2 laser scribing groove, and a second section insulating layer is deposited on the side wall of the P3 laser scribing groove.
Specifically, the method of this comparative example comprises the steps of:
i. Sequentially using deionized water, acetone, an optical glass cleaner, deionized water and isopropanol to ultrasonically clean the transparent glass substrate, and drying the transparent glass substrate in an oven at 60 ℃ for 6 hours. And sputtering an ITO transparent 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/≡.
Ii. And carrying out P1 laser scribing on the transparent conductive layer by using a femtosecond laser device, wherein the etching width is 30-100 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.
And iii, preparing a NiOx layer by using a magnetron sputtering device by using a mask plate, wherein the thickness of the NiOx layer is 1-100 nm, namely the hole transport layer, annealing the NiOx layer for 10mins at a heating stage of 100 degrees, and performing ultraviolet ozone treatment to enhance the wettability of the surface of the NiOx layer.
And iV, preparing the perovskite layer by using a mask plate by adopting vacuum evaporation equipment, and continuously carrying out high-temperature (100 DEG) annealing on a heating table for 50min to form a uniform perovskite layer.
V, evaporating C60 by using a mask plate by adopting vacuum evaporation equipment, wherein the thickness is 50nm; and (3) depositing SnO 2 by using ALD (Atomic Layer Deposition ) equipment through a mask plate, and forming a double electron transport layer with the thickness of 30 nm.
Vii, P2 laser etching is carried out by adopting a femtosecond laser device, etching parameters are adjusted and optimized to reduce damage to perovskite and a functional layer, and the scribing width is 30-100 mu m.
Viii, a Mask is matched, a SiNx insulating shielding layer is deposited by adopting a low-temperature PECVD technology, the thickness is 500nm, and the insulating shielding layer covers the width of 2 mu m of the cross section at the position of the P2 scribing.
Ix, depositing an Ag back electrode layer of 100nm on the standard device after scribing by vacuum thermal evaporation.
X, further adopting a femtosecond laser device to carry out P3 laser etching, wherein the scribing width is 30-100 mu m, cutting off the surface back electrode layer, forming effective series connection of sub-cells, and realizing the preparation of the perovskite module.
Xi, matching with Mask, adopting low temperature PECVD technology to deposit SiNx insulating shielding layer with thickness of 500nm, and covering the width of 2 μm of cross section of each insulating shielding layer around the P3 scribing position.
And Xii, adhering the encapsulation 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 ℃.
Experimental example
The perovskite solar cell modules prepared in the examples and the comparative examples are tested, wherein the test items comprise the efficiency and the stability of the perovskite solar cell module, the efficiency test method comprises the steps of adopting a JV curve for test, the evaluation index is that the battery efficiency is compared, the battery efficiency is higher than 22%, the battery efficiency is lower than 22%, the stability test method comprises the steps of standing in a glove box, testing the JV curve once every 5 days, and testing 6 times. The evaluation index is battery efficiency contrast, the battery efficiency after stability test is more than 20% and is poor, and the detection result is shown in the following table.
From the above table, it can be seen that the addition of the cross-section insulating layer in the embodiments 1 to 7 of the present application can effectively improve the efficiency and stability of the device, while the efficiency and stability of the device in the comparative example 1 are significantly inferior to those in the embodiment 1, and the positions of the P2 laser scribe line and the P3 laser scribe line in the comparative example 2 are independent from each other and do not overlap, so that although good stability can be achieved, the efficiency is lower, which is due to the complicated process and the difficulty of manufacturing of the comparative example 2. In comparative example 3, the positions of the P2 laser scribing and the P3 laser scribing are independent of each other and there is no overlap, and at this time, although good stability can be achieved, the efficiency is also low, which is due to the high deposition difficulty, and the deposition width and thickness are difficult to control.
In summary, according to the perovskite solar cell module with section insulation provided by the invention, the P2 laser scribing groove and the P3 laser scribing groove are partially overlapped, meanwhile, the first section insulation layer and the second section insulation layer are arranged at the corresponding positions, the exposed section at the position of the P2 laser scribing is insulated by using the first section insulation layer, the exposed section at the position of the P3 laser scribing is insulated by using the second section insulation layer, the side walls of the partially overlapped P2 laser scribing groove and P3 laser scribing groove are covered by the insulation layers under the action of the first section insulation layer and the second section insulation layer, and the insulation grooves are formed on the surfaces of the transparent conductive layers, so that the local crystallinity of the perovskite layer is improved; the P2 and P3 scribing positions are overlapped, so that the dead zone (the scribing position does not generate photo-generated carriers) area can be reduced, the scribing etching section can be ensured to be covered by the insulating layer, and the stability of the battery assembly is improved. The design of the scheme can finally integrally improve 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. Perovskite solar cell module with section insulation, characterized in that it includes: the solar cell comprises a transparent substrate, a transparent conductive layer, a first carrier layer, a perovskite layer, a second carrier layer and a back electrode layer, wherein the transparent conductive layer is deposited on the transparent substrate, the transparent conductive layer is divided through a P1 laser scribing groove, the first carrier layer, the perovskite layer and the second carrier layer are sequentially deposited on the transparent conductive layer and filled in the P1 laser scribing groove, the second carrier layer, the perovskite layer and the first carrier layer are divided through a P2 laser scribing groove, a first section insulating layer is arranged on the side wall of the P2 laser scribing groove, the back electrode layer is deposited on the surfaces of the second carrier layer and the first section insulating layer, the back electrode layer, the second carrier layer, the perovskite layer and the first carrier layer are divided through a P3 laser scribing groove, a second section insulating layer is arranged on the side wall of the P3 laser scribing groove, the second carrier layer, the second section insulating layer, the second carrier layer and the second section insulating layer are covered by the P2 laser scribing groove, and the second section insulating layer.
2. The perovskite solar cell module with section insulation of claim 1, wherein the first section insulation layer and the second section insulation layer are both 700-3000 nm in height;
And/or the heights of the first section insulating layer and the second section insulating layer exceed the upper surface of the second carrier layer;
And/or the widths of the first section insulating layer and the second section insulating layer are 10-50 mu m;
And/or the distance between the first section insulating layer and the second section insulating layer is 60-200 mu m.
3. The perovskite solar cell module with section insulation according to claim 1, wherein the material of the first section insulation layer and the second section insulation layer is at least one of organic matter, inorganic matter and liquid glue;
optionally, the organic matter comprises polyimide;
Optionally, the inorganic substance includes at least one of silicon nitride, silicon oxide, aluminum oxide, and silicon oxynitride;
Optionally, the liquid glue comprises at least one of epoxy, polyurethane and acrylic.
4. A method for manufacturing a perovskite solar cell module having insulation on a cross section as claimed in any one of claims 1 to 3, comprising:
Depositing the transparent conductive layer on the surface of the transparent substrate, depositing an insulating column on the surface of the transparent conductive layer at a position corresponding to the P2 laser scribing and a position corresponding to the P3 laser scribing, dividing the conductive layer by adopting the P1 laser scribing to form the P1 laser scribing groove, then depositing the first carrier layer, the perovskite layer and the second carrier layer, dividing the second carrier layer, the perovskite layer and the first carrier layer by adopting the P2 laser scribing on the insulating column to form the P2 laser scribing groove with a first section insulating layer, depositing the back electrode layer on the surfaces of the second carrier layer and the first section insulating layer, and dividing the back electrode layer, the second carrier layer, the perovskite layer and the first carrier layer by adopting the P3 laser scribing on the insulating column to form the P3 laser scribing groove with a second section insulating layer.
5. The method for manufacturing a perovskite solar cell module with section insulation according to claim 4, wherein the height of the insulation column is 700-3000 nm and the width is 90-300 μm;
Optionally, the scribing width of the P2 laser scribing is 30-100 μm, the scribing edge is 10-50 μm away from the edge width of the first section insulating layer, and the scribing edge is 50-150 μm away from the edge width of the second section insulating layer;
Optionally, the scribing width of the P3 laser scribing is 30-100 μm, the scribing edge is 50-150 μm away from the edge width of the first section insulating layer, and the scribing edge is 10-50 μm away from the edge width of the second section insulating layer.
6. The method for manufacturing a perovskite solar cell module with section insulation according to claim 4, wherein the method for manufacturing an insulation column comprises coating, plasma enhanced chemical vapor deposition, atomic layer deposition, physical vapor deposition or lithography;
preferably, the method of plasma enhanced chemical vapor deposition includes performing sputter deposition of the insulating column using a reticle;
preferably, the photoetching method comprises the steps of depositing an insulating layer on the surface of the transparent conductive layer, gluing the surface of the insulating layer, exposing and developing the area to be etched through a mask, exposing the area to be etched, etching, and stripping and cleaning the residual photoresist to form the insulating column.
7. The method for manufacturing a perovskite solar cell module with section insulation according to claim 4, wherein 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 of manufacturing a perovskite solar cell module with section insulation according to claim 4, wherein the thickness of the transparent conductive layer is 50-500 nm, the thickness of the first carrier layer is not more than 100nm, the thickness of the perovskite layer is 500-2000 nm, and the thickness of the second carrier layer is not more than 100nm;
Preferably, the material of the transparent conductive layer includes at least one of indium tin oxide, fluorine doped tin oxide, aluminum doped zinc oxide, silver nanowires, graphene, and carbon nanotubes;
preferably, the material of the first carrier layer includes 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 second carrier 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 back electrode layer is at least one of Au, ag, and Cu.
9. A packaging structure of a perovskite solar cell module, which is characterized by comprising the perovskite solar cell module with section insulation, a packaging adhesive film and a packaging cover plate, wherein the packaging cover plate is adhered with the perovskite solar cell module with section insulation 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, laminating equipment is adopted to package the perovskite solar cell module with section insulation, the packaging adhesive film and the packaging cover plate;
Preferably, the lamination melting temperature in the lamination apparatus is 100 ℃ to 150 ℃.
10. A perovskite solar cell, characterized in that it comprises the encapsulation structure of a perovskite solar cell module as claimed in claim 9.
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