CN115224200A

CN115224200A - Method for producing perovskite cells and use thereof

Info

Publication number: CN115224200A
Application number: CN202210715966.8A
Authority: CN
Inventors: 常洲; 冯治华; 孙朋超; 邵君; 锁真阳; 简成杰
Original assignee: Wuxi Utmolight Technology Co Ltd
Current assignee: Wuxi Utmolight Technology Co Ltd
Priority date: 2022-06-22
Filing date: 2022-06-22
Publication date: 2022-10-21

Abstract

The invention discloses a method for preparing a perovskite battery and application thereof. The method comprises the following steps: carrying out P1 laser etching on the bottom electrode layer, and marking P2 etching and P3 etching positioning points; forming a first carrier transmission layer, a perovskite photoresponse layer and a second carrier transmission layer and carrying out P2 laser etching based on a P2 etching positioning point; forming a top electrode layer and carrying out P3 laser etching on the basis of a P3 etching positioning point to obtain a perovskite battery component with a series structure, wherein beam splitting processing is carried out on laser emitted by a laser light source by a beam splitting system respectively and independently in P1 laser etching, P2 laser etching and P3 laser etching to obtain a plurality of sub-beams which are parallel to each other and vertical to a layer to be etched, and meanwhile, a plurality of sub-beams can be combined with a focus etching process to form the same etching line or a plurality of etching lines which are arranged at intervals. By adopting the method, the line widths of the P1, P2 and P3 lines can be accurately controlled, the dead zone area of the perovskite battery is reduced, the photoelectric conversion efficiency is improved, the etching process is simplified, and the production efficiency is improved.

Description

Method for producing perovskite cells and use thereof

Technical Field

The invention belongs to the field of perovskite batteries, and particularly relates to a method for preparing a perovskite battery and application of the perovskite battery.

Background

In recent years, perovskite solar cells are a new favorite in the photovoltaic field, and are favored by research experts due to the advantages of weak light power generation, adjustable band gap, simple preparation, flexible substrate and the like. At present, the efficiency of a laboratory single perovskite solar cell is reported to be close to 26%, wherein the world maximum single perovskite cell (3500 cm) ² ) The efficiency is 15.5 percent. Furthermore, the 300cm prepared by the latest research organization ² The silicon solar cell module is more than 18 percent and completely not inferior to the current crystalline silicon solar cell, and shows great commercial value.

At present, the perovskite solar cell module mainly adopts a mechanical scribing or laser scribing mode to serially connect the sub-cells. Wherein, the mechanical scribing uses the interaction force between the point of SPM (scanning probe microscope) and the sample, so that the nano-scale structure is generated by scraping, indenting, pulling or pushing the particles on the film surface. After the perovskite battery is used for a long time, the probe is seriously worn, the scribing precision is influenced, and meanwhile, the bonding force between the back electrode prepared in the perovskite battery and the lower-layer membrane surface is weak, so that the whole electrode is easily torn off by contact type scribing. The laser scribing has the advantages of easy operation, non-contact processing, good reproducibility, high material removal speed and the like, can be compatible with various rigid or flexible materials, can perform various pattern type etching on glass, plastic, stainless steel meshes or Ni meshes, and is widely applied to the preparation of perovskite solar cell components, but the scribing process of the perovskite solar cell components mostly adopts a single light source defocusing etching process, and if a single wider scribed line or a plurality of scribed lines need to be processed, the process is generally realized by adopting an etching process of superposing a plurality of scribed lines or repeatedly scribing, the process is long in time consumption, and the efficiency is low; in the defocusing etching, laser spots are amplified, and the processing energy in unit area can be dispersed by larger spots, so that the scribed lines displayed after etching are wider, and the GFF (geometric filling factor) of the component is influenced.

Disclosure of Invention

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a method for preparing a perovskite cell and a use thereof, so as to precisely control the line width of the etching lines (P1, P2 and P3), reduce the "dead zone" area of the perovskite cell, improve the photoelectric conversion efficiency, simplify the laser process, and improve the production efficiency.

In one aspect of the invention, a method of making a perovskite battery is presented. According to an embodiment of the invention, the method comprises:

(1) Carrying out P1 laser etching on the bottom electrode layer, and marking positioning points of P2 etching and P3 etching;

(2) Sequentially forming a first current carrier transmission layer, a perovskite photoresponse layer and a second current carrier transmission layer on the bottom electrode layer and the P1 etching region, and carrying out P2 laser etching on the first current carrier transmission layer, the perovskite photoresponse layer and the second current carrier transmission layer based on the P2 etching positioning points;

(3) Forming a top electrode layer on the second carrier transmission layer and the P2 etching region, and performing P3 laser etching on the top electrode layer, the first carrier transmission layer, the perovskite absorption layer and the second carrier transmission layer based on the positioning point of the P3 etching so as to obtain a perovskite battery component with a series structure,

in the P1 laser etching, the P2 laser etching and the P3 laser etching, a beam splitting system is respectively and independently used for performing beam splitting processing on laser emitted by a laser source so as to obtain a plurality of sub-beams which are parallel to each other and perpendicular to a layer to be etched, and the plurality of sub-beams are used for forming a same etching line or a plurality of etching lines which are arranged at intervals.

Further, the method of preparing a perovskite battery further comprises: and focusing the sub-beams, wherein the distance from the focused sub-beams to the layer to be etched is equal to the laser focal length of the sub-beams.

Further, after the plurality of sub-beams are focused, a plurality of laser spots with equal intervals are formed on the layer to be etched.

Furthermore, the beam splitting system comprises a beam splitter and a light path shaping system, laser emitted by the laser source is sequentially split by the beam splitter and shaped by the light path shaping system to obtain a plurality of sub beams, the effective area of laser radiation is controlled by adjusting the splitting angle of a beam splitter in the beam splitter, and the distance between two adjacent sub beams is controlled by adjusting the sub splitting angle and the distance between the beam splitter and the light path shaping system.

Further, the separation angle is 0-180 degrees, the sub-separation angle is 0-90 degrees, the sub-separation angle is not greater than the separation angle, and the distance between the optical splitter and the optical path shaping system is not greater than 30mm.

Further, the original laser intensity, the separation angle, the sub-separation angle, the distance between the beam splitter and the light path shaping system, whether the sub-beams are focused, the distance from the focused sub-beams to the layer to be etched, and the laser focal length of the sub-beams are comprehensively regulated, and the distance between laser spots formed on the layer to be etched after the plurality of sub-beams are focused and the intensity of the sub-beams are regulated.

Further, the method of manufacturing a perovskite battery satisfies at least one of the following conditions: the laser power adopted by the P1 laser etching is 15-40% of the rated laser power, the laser pulse width is 2-150 ns, the laser frequency is 10-150 KHz, the laser processing speed is 0.1-2 m/s, the laser focal length of the sub-beam after the beam splitting is 54mm, and the width of the obtained single P1 etching line is 15-50 mu m; the laser power adopted by the P2 laser etching is 15-90% of the rated laser power, the laser pulse width is 2-150 ns, the laser frequency is 10-150 KHz, the laser processing speed is 0.1-2 m/s, the laser focal length of the sub-beam after the beam splitting is 54mm, and the width of the obtained single P2 etching line is 15-400 mu m; the laser power adopted by the P3 laser etching is 15-90% of the rated laser power, the laser pulse width is 2-150 ns, the laser frequency is 10-150 KHz, the laser processing speed is 0.1-2 m/s, the laser focal length of the sub-beam after the beam splitting is 54mm, and the width of the obtained single P3 etching line is 15-300 mu m; and laser light sources adopted by the P1 laser etching, the P2 laser etching and the P3 laser etching are respectively and independently selected from an infrared light source, a green light source and an ultraviolet light source.

Further, the bottom electrode layer is formed on a substrate, and the P1 laser etching, the P2 laser etching and the P3 laser etching independently and respectively act on the layer to be etched, or act on the layer to be etched through the substrate.

Further, the method of manufacturing a perovskite battery satisfies at least one of the following conditions: the first carrier transport layer is an electron/hole transport layer, and the second carrier transport layer is a hole/electron transport layer; the bottom electrode layer is a first transparent conductive layer, and the top electrode is a second transparent conductive layer or a metal layer; the bottom electrode layer is formed on a rigid substrate or a flexible substrate.

Further, the method of manufacturing a perovskite battery satisfies at least one of the following conditions: the first transparent conductive layer includes at least one selected from FTO, ITO, AZO, BZO, ATO, and IGO; the second transparent conductive layer includes at least one selected from FTO, ITO, AZO, BZO, ATO, and IGO, and the metal layer includes at least one selected from Ag, cu, al, cr, ni, and Ti; the hole transport layer comprises a material selected from the group consisting of nickel oxide, vanadium oxide, molybdenum oxide, copper sulfide, cuprous thiocyanate, copper oxide, cuprous oxide, cobalt oxide, 1' -meta (bis-4-tolylaminobenzene) cyclohexylamine, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine]At least one of polydioxyethyl-silophene, polytriphenylamine and 2,2', 7' -tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene; the electron transport layer comprises titanium dioxide, zinc oxide, cadmium sulfide, tin dioxide, indium oxide, tungsten oxide, cerium oxide, C ₆₀ And derivatives thereof, C ₇₀ And derivatives thereof and alkyl fullerene phenyl-C ₆₁ -at least one of methyl butanoate and derivatives thereof; the perovskite photoresponsive layer is ABX ₃ A layer of a perovskite material of the type wherein A is selected from Cs ⁺ 、K ⁺ 、Ru ⁺ 、CH ₃ NH ₃ ⁺ 、C(NH ₂ ) ₃ ⁺ 、CH(NH ₂ ) ₂ ⁺ B is selected from Pb ²⁺ 、Sn ²⁺ At least one of X is Br ^- 、I ^- 、Cl ^- At least one of (1).

Compared with the prior art, the method for preparing the perovskite battery provided by the embodiment of the invention has at least the following advantages: 1) By the aid of the spectroscopic laser etching process, line widths and mutual intervals of a P1 etching line, a P2 etching line and a P3 etching line can be controlled more accurately, dead zone area is reduced greatly, cross sections of the etching lines can be optimized, geometric filling factors of the perovskite battery are further increased accurately, and efficiency of a battery component is improved; 2) The distance between the sub-beams can be regulated by regulating the parameter range of the light splitting system through adopting the light splitting system for light splitting treatment, and when the line width of a single etching line to be processed is wider or a plurality of etching lines need to be processed, the method can be realized without adopting an etching process of overlapping a plurality of scribed lines or scribing for a plurality of times, so that the time consumption of the process is short, the production efficiency can be obviously improved, and the production cost can be favorably reduced; 3) The large-scale production can be realized, and the marketization of the perovskite battery is promoted; 4) The prepared perovskite battery has higher photoelectric conversion efficiency and stronger market competitiveness.

According to a further aspect of the invention, the invention proposes the use of a process for the preparation of a perovskite cell as described above in the preparation of perovskite cells and photovoltaic modules. Compared with the prior art, the perovskite cell or photovoltaic module prepared by the method for preparing the perovskite cell has higher photoelectric conversion efficiency and stronger market competitiveness.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

fig. 1 is a flow diagram of a method of making a perovskite battery according to one embodiment of the invention.

Fig. 2 is a schematic diagram of obtaining a plurality of P1 etching lines (as shown in fig. 2 (a)) or obtaining a wider P1 etching line (as shown in fig. 2 (b)) by etching the bottom electrode after splitting laser light by using the optical splitting system according to an embodiment of the present invention.

Fig. 3 is a schematic diagram of a plurality of sub-beams obtained by splitting a laser light source with a splitting system according to an embodiment of the invention.

FIG. 4 is a schematic diagram of P1 laser etching in conjunction with a spectroscopy system according to one embodiment of the invention.

FIG. 5 is a schematic diagram of P2 laser etching in conjunction with a spectroscopy system according to one embodiment of the invention.

FIG. 6 is a schematic diagram of P3 laser etching in conjunction with a spectroscopy system according to one embodiment of the invention.

Fig. 7 is a graph comparing current and voltage of battery modules prepared according to examples 1 to 2 of the present invention and comparative examples 1 to 2.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

The present application is primarily based on the following problems: 1. most of the existing scribing processes of perovskite solar cell modules adopt a defocusing etching mode, but the laser spot size of the process is large, so that scribed lines appearing after etching are wide, the area of dead zones (the area occupied by P1/P2/P3 is called as the dead zone of the solar module) of the modules is increased, and the dead zone area cannot effectively convert sunlight into electric energy, so that the efficiency of the modules is reduced to a certain extent, and the accurate processing advantage of laser is also severely restricted; 2. the laser basically adopts a single beam of light to perform scribing on the processed film surface, if a single scribing line to be processed is wider or a plurality of scribing lines are needed, the scribing is generally realized by adopting an etching process of overlapping a plurality of scribing lines or scribing for a plurality of times, the process time is longer, the production beat of a production line is increased, and the production efficiency is reduced; 3. when the perovskite solar cell module etches a P3 line, the conducting material of the top electrode, the upper carrier transmission layer, the perovskite photoresponse layer and the lower carrier transmission layer are required to be penetrated and scribed, and meanwhile, the TCO conducting substrate is not damaged; by adopting the defocusing etching process, enlarged laser spots can disperse processing energy on a unit area, and after P3 line etching, the cross section of an electrode is generally low in energy effect, so that the electrode is peeled and curled, and the electrode is more likely to be connected with a conductive substrate or two adjacent sub-battery strips in a small manner, so that the short circuit phenomenon of a battery assembly is caused.

To this end, in one aspect of the invention, a method of making a perovskite battery is presented. As understood with reference to fig. 1, the method includes: (1) Carrying out P1 laser etching on the bottom electrode layer, and marking positioning points of P2 etching and P3 etching; (2) Sequentially forming a first current carrier transmission layer, a perovskite photoresponse layer and a second current carrier transmission layer on the bottom electrode layer and the P1 etching region, and carrying out P2 laser etching on the first current carrier transmission layer, the perovskite photoresponse layer and the second current carrier transmission layer based on a P2 etching positioning point; (3) Forming a top electrode layer on the second carrier transmission layer and the P2 etching area, and carrying out P3 laser etching on the top electrode layer, the first carrier transmission layer, the perovskite absorption layer and the second carrier transmission layer based on a positioning point of the P3 etching so as to obtain the perovskite battery component with a series structure, wherein in the P1 laser etching, the P2 laser etching and the P3 laser etching, light splitting processing is respectively and independently carried out on laser emitted by a laser light source by using a light splitting system so as to obtain a plurality of sub-beams which are parallel to each other and vertical to the layer to be etched, and a plurality of sub-beams are used for forming the same etching line or a plurality of etching lines which are arranged at intervals. The method for preparing the perovskite battery is added with light splitting treatment on the basis of the existing laser etching process, single laser is converted into multiple sub-beams by using a light splitting system, the multiple sub-beams simultaneously act on a layer to be etched, and the distance between the multiple sub-beams can be regulated by using the light splitting system, so that the method is favorable for accurately controlling the line width of the etching line (P1, P2 and P3), reducing the dead zone area of the perovskite battery, improving the photoelectric conversion efficiency, simplifying the laser process and improving the production efficiency.

The above-described method of manufacturing a perovskite battery according to the present invention will be described in detail with reference to fig. 1 to 7.

According to the embodiment of the invention, in the P1 laser etching, the P2 laser etching and the P3 laser etching, the sub-beams can be independently focused respectively, and the distance from the focused sub-beams to the layer to be etched is equal to the laser focal length of the sub-beams; on the other hand, the intensity of the sub-beams can be controlled through the laser intensity output by the laser light source, and the space between the sub-beams is controlled through the light splitting system, so that the line width of the formed single etching line and the space between different etching lines are further controlled; in addition, compared with the defocusing etching process, the laser spot formed on the surface to be etched in the invention has smaller area and high energy of the spot, and can be further favorable for accurately controlling the line width of an etched line, improving the section of the etched line and reducing the dead zone area. According to some embodiments of the present invention, the plurality of sub-beams may be focused to form a plurality of sub-beams parallel to each other and perpendicular to the surface to be etched, and the plurality of sub-beams form an etching line with a wider line width (as shown in (b) of fig. 2) or form a plurality of etching lines (as shown in (a) of fig. 2), thereby further facilitating to improve the line width accuracy of the etching line and control the distance between the etching line and other etching lines. It can be understood that a plurality of sub-beams can form a plurality of laser spots with equal intervals on the layer to be etched after being focused, so that the uniformity of an etching region can be ensured when a wider etching line is obtained, and the intervals between the etching lines can be ensured to be equal when a plurality of etching lines are obtained, thereby being more beneficial to improving the precision of the etching line and optimizing the section of the etching line, being more beneficial to reducing the area of a dead zone, improving the geometric filling factor and improving the efficiency of the perovskite battery.

In order to facilitate understanding of the embodiments of the present invention, a light splitting system, a light splitting principle, and a light splitting effect used in the present invention are described below with reference to fig. 3. According to the embodiment of the invention, the optical splitting system is a Diffractive Optical Element (DOE) optical splitting system, which comprises a DOE optical splitter and an optical path shaping system, wherein laser (processed by a laser preprocessing system) emitted by a laser source is sequentially split by the optical splitter and shaped by the optical path shaping system to obtain a plurality of sub-beams, an effective area of laser radiation, namely an etching area formed on a surface to be etched, is controlled by adjusting a splitting angle alpha of a splitter in the optical splitter, and a distance Y between two adjacent sub-beams is controlled by adjusting a sub-splitting angle beta and a distance x between the optical splitter and the optical path shaping system, wherein the optical path shaping system shown in fig. 3 shapes the plurality of parallel sub-beams, which are not only shaped to obtain parallel beams, but also can be further focused to obtain parallel beams, wherein the distance from the focused parallel beams to the surface to be etched (understood by referring to a processing action platform in fig. 3) is preferably equal to a focusing focal length, so that the problem that processing energy is dispersed and an etching line is caused by the increase of a laser spot size formed on the surface to be etched line can be avoided. It should be noted that, the DOE generally adopts a micro-nano etching process to form diffraction units in two-dimensional distribution, and each diffraction unit can have a specific morphology to finely regulate and control the laser wavefront phase distribution. The laser is diffracted after passing through each diffraction unit, and generates interference at a certain distance (usually infinite distance or a lens focal plane) to form specific light intensity distribution; the laser preprocessing system comprises an attenuator, a beam expander, a reflector system, a light path modification system and the like; the light path shaping system is used for shaping laser emitted by the DOE light splitter into parallel light paths so as to enable the parallel light paths to act on the processing operation platform.

According to the embodiment of the invention, as can be understood by referring to fig. 3, after laser is emitted by a light source, the laser passes through a laser preprocessing system and then passes through a DOE beam splitter, the separation angle β of the beam splitter can be adjusted to be 0-180 degrees to control the effective area of laser radiation, for example, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75 degrees, 90 degrees, 120 degrees, 150 degrees or the like, preferably 90 degrees, so that a proper separation angle can be selected according to the actual conditions of the area to be etched of a layer to be etched and the like, so as to simplify the etching process and achieve the purpose of obtaining a wider single etching line by one-time etching or obtaining a plurality of etching lines by one-time etching; further, the sub-separation angle α and the distance χ between the DOE beam splitter and the optical path shaping system may be adjusted, and the distance Y between the sub-beams may be controlled in the effective region of the laser radiation, so as to adjust and control the distance between the sub-cells in the perovskite cell, wherein the sub-separation angle α is not greater than the separation angle β, specifically, the sub-separation angle α may be 0 to 90 degrees, such as 20 degrees, 30 degrees, 45 degrees, 60 degrees, or 75 degrees, and the like, and the distance χ between the beam splitter and the optical path shaping system is not greater than 30mm, preferably, α may be 45 degrees, and χ may be 8mm.

According to the embodiment of the invention, the laser intensity, the separation angle beta, the sub-separation angle alpha, the distance chi between the beam splitter and the light path shaping system, whether the sub-beams are focused, the distance from the focused sub-beams to the layer to be etched and the laser focal length of the sub-beams can be comprehensively regulated, and the distance between laser spots formed on the layer to be etched and the intensity of the sub-beams after the plurality of sub-beams are focused can be regulated, so that the process parameters can be flexibly selected according to different etching requirements (such as the line width of an etching line and the distance between the etching lines) of P1 laser etching, P2 laser etching and P3 laser etching, the expected etching effect (such as the etching precision and the like) and the like, so as to improve the efficiency and the effect of the laser etching and simultaneously improve the geometric filling factor and the photoelectric efficiency of the perovskite battery.

According to the embodiment of the invention, the bottom electrode layer can be formed on the substrate, and the P1 laser etching, the P2 laser etching and the P3 laser etching can respectively and independently act on the layer to be etched for etching, or act on the layer to be etched through the substrate for etching. In addition, the laser light sources used for P1 laser etching, P2 laser etching and P3 laser etching may be respectively and independently selected from an infrared light source, a green light source and an ultraviolet light source, for example, any one of an infrared light source of 1064nm, a green light laser of 532nm or an ultraviolet light source of 355nm may be selected, and further, for example, a green light laser of 532nm with a power of 20W may be selected. In addition, the kind of the substrate in the present invention is not particularly limited, and those skilled in the art can flexibly select the substrate according to actual needs, for example, the substrate may be a transparent substrate; for another example, the substrate may be a rigid substrate or a flexible substrate, such as transparent glass or the like.

According to the embodiment of the invention, the method is understood by referring to fig. 4, the bottom electrode layer is subjected to P1 laser etching, and positioning points of P2 etching and P3 etching are marked, wherein during the P1 laser etching, light beams are subjected to splitting and focusing treatment, so that the distance from the focused light beams to a layer to be etched is equal to the focusing focal length, and therefore, the area of light spots formed on the surface to be etched is the minimum, and processing energy is not dispersed. In addition, the bottom electrode layer is formed on the substrate, the substrate can be cleaned in advance before the bottom electrode layer is formed on the substrate, and specifically, the substrate can be cleaned by a cleaning agent and deionized high-temperature high-pressure washing in sequence and then dried by hot compressed air; or sequentially ultrasonic cleaning with hot cleaning agent diluent, ultrapure water, ethanol (such as hot industrial alcohol) and/or acetone (such as 15 min), and drying to remove impurities on the surface of the substrate. After the cleaning is finished, the bottom electrode layer can be placed on the laser etching platform upwards, the clamp is aligned to the position, the platform adsorption function is started, two top angles at the left and right sides of the upper edge of the bottom electrode layer are used as initial positioning points, etching is carried out after the dust removal air suction system is started, and meanwhile, mark points (positioning points) of later stages P2 and P3 are etched based on the preset distance between a P1 etching line and a P2 etching line and a P3 etching line in the process of P1 patterning. The P1 laser etching can be directly acted on the layer to be etched for etching, and can also be acted on the layer to be etched for etching through the substrate. Further, the laser power adopted by the P1 laser etching may be 15-40% of the rated laser power, for example, 20%, 25%, 30%, 35%, 40%, or the like; the laser pulse width can be 2-150 ns, such as 2ns, 10ns, 20ns, 30ns, 50ns, 80ns, 100ns, 130ns or 150 ns; the laser frequency may be 10 to 150KHz, for example, 10KHz, 20KHz, 50KHz, 80KHz, 120KHz, 150KHz, or the like; the laser processing rate may be 0.1 to 2m/s, for example, 0.2m/s, 0.5m/s, 0.8m/s, 1.2m/s, 1.5m/s, 1.8m/s, 2m/s, or the like; the focal distance of the laser of the sub-beam after light splitting is 54mm, and the width of the obtained single P1 etching line can be 15-50 μm, so that the process condition of P1 laser etching can be flexibly adjusted according to actual needs so as to form a P1 etching area, wherein the width of the single P1 etching line is controlled to be in the range, so that the bottom conducting layer can form a plurality of sub-conducting layers and the adjacent two sub-conducting layers are not conducting, and the influence on the effective width and the geometric filling factor of the battery due to the overlong distance of a dead zone caused by the overlarge P1 etching line can be avoided.

It should be noted that the strength and material of the bottom electrode layer in the present invention are not particularly limited, and those skilled in the art can flexibly select the material according to actual needs, for example, the bottom electrode layer may be a first transparent conductive layer, and the first transparent conductive layer may include at least one selected from FTO (fluorine doped tin oxide), ITO (indium doped tin oxide), AZO (aluminum doped zinc oxide), BZO (boron doped zinc oxide), ATO (aluminum doped tin oxide), and IGO (indium doped gallium oxide).

According to the embodiment of the invention, as can be understood by referring to fig. 5, after a first carrier transmission layer, a perovskite photoresponse layer and a second carrier transmission layer are sequentially formed on a bottom electrode layer and a P1 etching region, the bottom electrode layer and the P1 etching region are placed on a laser etching platform, the position of a clamp is aligned, the adsorption function of the platform is started, a reserved Mark point is found for positioning, then a dedusting suction system is started, and then laser etching is performed, namely, the first carrier transmission layer, the perovskite photoresponse layer and the second carrier transmission layer are subjected to P2 laser etching based on the positioning point of the P2 etching, so that the etching structure shown in fig. 5 is obtained. The laser power adopted by the P2 laser etching can be 15-90% of the rated laser power, for example, 20%, 30%, 40%, 50%, 60%, 70% or 80% and the like; the laser pulse width can be 2-150 ns, for example, 2ns, 10ns, 20ns, 30ns, 50ns, 80ns, 100ns, 130ns or 150 ns; the laser frequency can be 10-150 KHz, such as 15kHz, 30kHz, 45kHz, 60kHz, 75kHz, 90kHz, 110kHz or 130 kHz; the laser processing rate may be 0.1 to 2m/s, and for example, may be 0.2m/s, 0.5m/s, 0.8m/s, 1.2m/s, 1.5m/s, 1.8m/s, 2m/s, or the like; the laser focal length of the sub-beam after the light splitting can be 54mm, and the width of the obtained single P2 etching line can be 15-400 μm. Therefore, the process conditions of P2 laser etching can be flexibly adjusted according to actual needs so as to form a P2 etching area, wherein the width of a single P2 etching line is controlled as a range, so that the requirement for passing of a large current between two adjacent series sub-batteries in a finally formed perovskite battery small assembly can be met, and the influence on the effective width and geometric filling factors of the battery due to overlong dead zone distance caused by the excessively wide P2 etching area can be avoided.

According to some embodiments of the present invention, the P2 laser etching may be performed by using infrared laser with a wavelength of 1064nm, or by using green laser with a wavelength of 532nm or ultraviolet laser with a wavelength of 355nm, and the inventors have found that the etching of the first carrier transport layer, the perovskite photoresponse layer and the second carrier transport layer 3 thin film can be achieved by using infrared laser, and thus the etching of the P2 etching region can be achieved by using at least one of the three kinds of laser. In addition, it should be noted that P2 laser etching can be performed by directly acting on the layer to be etched, or by acting on the layer to be etched through the substrate, and the process parameters of P2 laser etching controlled in the present invention are not enough to etch the substrate and the bottom electrode layer, so that the etching of the 3 layers of thin films of the first carrier transport layer, the perovskite photoresponse layer and the second carrier transport layer can be completed even though the substrate is penetrated.

According to the embodiment of the invention, it can be understood that the first carrier transport layer may be an electron transport layer or a hole transport layer, and when the first carrier transport layer is an electron transport layer, the second carrier transport layer may be a hole transport layer, at this time, the bottom electrode layer, the electron transport layer, the perovskite light response layer, the hole transport layer, and the top electrode are arranged layer by layer, and the perovskite cell is in a formal structure; when the first carrier transmission layer is a hole transmission layer, the second carrier transmission layer can be an electron transmission layer, and at the moment, the bottom electrode layer, the hole transmission layer, the perovskite photoresponse layer, the electron transmission layer and the top electrode are arranged layer by layer, and the perovskite electricity is distributedThe pool is of a trans-structure. In addition, it should be noted that the materials of the first carrier transport layer, the perovskite photo-responsive layer and the second carrier transport layer in the present invention are not particularly limited, and those skilled in the art can flexibly select them according to actual needs, for example, the hole transport layer may include one selected from nickel oxide, vanadium oxide, molybdenum oxide, copper sulfide, cuprous thiocyanate, cupric oxide, cuprous oxide, cobalt oxide, TAPC (1, 1' -meta (bis-4-tolylaminobenzene) cyclohexylamine), PTAA (poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine)]) At least one of PEDOT (polydioxyethylelenophene), poly-TPD (polytriphenylamine), and Spiro-MeOTAD (2, 2', 7' -tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene); the electron transport layer can include a material selected from the group consisting of titanium dioxide, zinc oxide, cadmium sulfide, tin dioxide, indium oxide, tungsten oxide, cerium oxide, C ₆₀ And derivatives thereof, C ₇₀ And derivatives thereof and PCBM (alkyl fullerene phenyl-C) ₆₁ -methyl butyrate and derivatives and dopants thereof); the perovskite photoresponsive layer may be ABX ₃ A perovskite material layer, wherein A may be selected from Cs ⁺ 、K ⁺ 、Ru ⁺ 、CH ₃ NH ₃ ⁺ 、C(NH ₂ ) ₃ ⁺ 、CH(NH ₂ ) ₂ ⁺ B may be Pb selected from ²⁺ 、Sn ²⁺ X may be Br ^- 、I ^- 、Cl ^- At least one of (1).

According to the embodiment of the invention, as shown in fig. 6, a top electrode layer is formed on a second carrier transmission layer and a P2 etching region, then the top electrode layer is placed on a laser etching platform, the position of a clamp is aligned, the adsorption function of the platform is started, a reserved Mark point is found for positioning, then a dedusting and air suction system is started, and then laser etching is performed, namely P3 laser etching is performed on the top electrode layer, the first carrier transmission layer, the perovskite absorption layer and the second carrier transmission layer based on the positioning point of P3 etching, so that the perovskite battery component with the series structure as shown in fig. 6 is obtained. And before the top electrode layer is formed, deionized water high-temperature high-pressure washing or deionized water ultrasonic cleaning can be performed on the product subjected to the P2 laser etching in advance. Further, the laser power adopted by the P3 laser etching may be 15 to 90% of the rated laser power, for example, 20%, 30%, 40%, 50%, 60%, 70%, or 80% and the like; the laser pulse width can be 2-150 ns, for example, 2ns, 10ns, 20ns, 30ns, 50ns, 80ns, 100ns, 130ns or 150 ns; the laser frequency can be 10-150 KHz, such as 15kHz, 30kHz, 45kHz, 60kHz, 75kHz, 90kHz, 110kHz or 130 kHz; the laser processing rate may be 0.1 to 2m/s, and for example, may be 0.2m/s, 0.5m/s, 0.8m/s, 1.2m/s, 1.5m/s, 1.8m/s, 2m/s, or the like; the laser focal length of the sub-beam after light splitting can be 54mm, and the width of the obtained single P3 etching line can be 15-300 mu m; therefore, the process conditions of P3 laser etching can be flexibly adjusted according to actual needs so as to form a P3 etching area, wherein the width of a single P3 etching line is controlled as a range, so that the condition that a larger current can pass between two adjacent series sub-batteries in a finally formed perovskite battery small assembly can be met, and the influence on the effective width and the geometric filling factor of the battery due to the overlong distance of a dead zone caused by the overlarge P3 etching area can be avoided. It should be noted that the P3 laser etching may be performed by directly acting on the layer to be etched, or by acting on the layer to be etched through the substrate, and in addition, the P3 laser etching may be performed by using infrared laser with a wavelength of 1064nm, green laser with a wavelength of 532nm, or ultraviolet laser with a wavelength of 355 nm.

It should be noted that, the strength and material of the top electrode layer in the present invention are not limited in particular, and those skilled in the art can select the top electrode layer flexibly according to actual needs, for example, the top electrode layer may be a rigid conductive layer or a flexible conductive layer; for another example, the top electrode may be a second transparent conductive layer or a metal layer, wherein the second transparent conductive layer may include at least one selected from FTO (fluorine doped tin oxide), ITO (indium doped tin oxide), AZO (aluminum doped zinc oxide), BZO (boron doped zinc oxide), ATO (aluminum doped tin oxide), and IGO (indium doped gallium oxide), and the metal layer may include at least one selected from Ag, cu, al, cr, ni, and Ti.

In summary, compared with the prior art, the method for preparing the perovskite battery according to the above embodiment of the invention has at least the following advantages: 1) Through the spectroscopic laser etching process, the line widths and the mutual intervals of a P1 etching line, a P2 etching line and a P3 etching line can be more accurately controlled, the dead zone area is greatly reduced, meanwhile, the cross section of the etching line can be optimized, the geometric filling factor of the perovskite battery is further accurately increased, and the efficiency of a battery component is improved; 2) The distance between the sub-beams can be regulated by regulating the parameter range of the light splitting system through adopting the light splitting system for light splitting treatment, and when the line width of a single etching line to be processed is wider or a plurality of etching lines need to be processed, the method can be realized without adopting an etching process of overlapping a plurality of scribed lines or scribing for a plurality of times, so that the time consumption of the process is short, the production efficiency can be obviously improved, and the production cost can be favorably reduced; 3) The large-scale production can be realized, and the marketization of the perovskite battery is promoted; 4) The prepared perovskite battery has higher photoelectric conversion efficiency and stronger market competitiveness.

According to a further aspect of the invention, the invention proposes the use of a process for the preparation of a perovskite cell as described above in the preparation of perovskite cells and photovoltaic modules. Compared with the prior art, the perovskite cell or photovoltaic module prepared by the method for preparing the perovskite cell has higher photoelectric conversion efficiency and stronger market competitiveness. It should be noted that the features and effects described for the above-mentioned method for preparing a perovskite battery are also applicable to this application, and are not described in detail here.

The following describes in detail embodiments of the present invention. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.

Comparative example 1

The laser uses a single beam of light to scribe the processed film surface (i.e. the layer to be etched).

(1) Cleaning FTO transparent conductive substrate (comprising a substrate and a bottom electrode layer formed on the substrate)

Firstly, using absorbent cotton to dip a proper amount of cleaning agent, wiping the front and back surfaces of a conductive substrate, then respectively carrying out ultrasonic treatment for 15min by using hot cleaning agent diluent, ultrapure water, hot industrial alcohol and acetone, and finally putting the conductive substrate into a blast drying oven for drying for later use;

(2) P1 line patterning is carried out on FTO transparent conductive substrate

Placing the cleaned FTO transparent conductive base film on a laser etching platform with the surface facing upwards, aligning the position of a clamp and starting the adsorption function of the platform; taking the left and right vertex angles on the upper edge of the conductive substrate as initial positioning points, and etching after starting the dedusting and air suction system; and simultaneously, mark points (positioning points) of P2 and P3 at the later stage are etched in the process of P1 patterning. The laser etching parameters were as follows: the laser power is 22%, the laser pulse width is 50ns, the laser frequency is 100KHz, the laser processing speed is 0.6m/s, the laser focal length is-54 mm, and the distance from a light beam to the film surface is equal to the focal length, namely the laser spot area formed on the film surface is minimum and the energy is highest; after etching the P1 line, cleaning the conductive substrate again, wherein the cleaning process is the same as the process 1 and is not described again; wherein, the line width of the P1 etched line is 20 μm. The laser light source adopted in the embodiment is green laser with the wavelength of 532nm, and the rated power is 20W.

(3) Preparing a first carrier transport layer

And (3) carrying out ultraviolet ozone treatment on the cleaned FTO transparent conductive substrate for 15min, and immediately preparing NiOx after treatment.

(4) Preparation of perovskite photoresponsive layer

Preparing perovskite precursor liquid, weighing a proper amount of CsFA system perovskite precursor, adding a certain amount of anhydrous DMF (N, N-dimethylformamide), 2-ME (ethylene glycol methyl ether) and NMP (N-methyl pyrrolidone) solution, then adding a stirrer, stirring in a glove box for one night, and filtering for later use.

Carrying out ultraviolet ozone treatment on the sample obtained in the step (3) for 15min; coating a modification layer on the surface of the NiOx layer by adopting a Slot-die coating method, and then annealing; coating perovskite precursor liquid by adopting Slot-die to form a photoresponse layer, and annealing at 120 ℃ after coating; and then coating a passivation layer by adopting Slot-die, and then annealing for later use.

(5) Preparing a second carrier transport layer

Adopting an electron beam device to sequentially deposit C on the film prepared in the step (4) ₆₀ 、SnO ₂ The materials, totaling to a thickness of about 25nm, were obtained as a thin film.

(6) P2 line etching

Placing the substrate film prepared in the step (5) on a laser etching platform with the surface facing upwards, aligning the position of a clamp and starting the adsorption function of the platform; and finding a Mark point of P2 for positioning, and then starting a dust removal air suction system for laser etching. The laser etching parameters were as follows: the laser power is 32%, the laser pulse width is 50ns, the laser frequency is 50KHz, the laser processing speed is 1m/s, the laser focal length is-54 mm, and the distance from a light beam to the film surface is equal to the focal length, namely the area of a laser spot formed on the film surface is the smallest and the energy is the highest. Wherein, the line width of the P2 etched line is 100 μm.

(7) Preparation of top electrode conductive material

And (4) depositing Au of about 100nm on the sample film prepared in the step (6) by adopting a thermal evaporation device to obtain a top electrode layer.

(8) P3 line etching:

placing the base film prepared in the step (7) on a laser etching platform with the surface facing upwards, aligning the position of a clamp and starting the adsorption function of the platform; and finding a Mark point of P3 for positioning, and then starting a dust removal air suction system for laser etching. The laser etching parameters were as follows: the laser power is 40%, the laser pulse width is 50ns, the laser frequency is 50KHz, the laser processing speed is 1m/s, the laser focal length is-54 mm, and the distance from a light beam to the film surface is equal to the focal length, namely the area of a laser spot formed on the film surface is minimum, and the energy is highest. Wherein, the line width of the P3 etched line is 60 μm.

(9) Component testing

And (4) testing the perovskite cell component by adopting standard sunlight.

Comparative example 2

The difference from comparative example 1 is that: in the step (2), the step (6) and the step (8), the laser etching adopts defocusing etching, and the positive defocusing focal length is-50 mm. Wherein, the line width of the P1 etching line is 25 μm, the line width of the P2 etching line is 170 μm, and the line width of the P3 etching line is 100 μm.

Example 1

In contrast to comparative example 1: in the step (2), the step (6) and the step (8), the laser in the comparative example 1 adopts a single beam to act on the processed film surface for scribing and is replaced by a single beam emitted by a laser light source to pass through a laser pretreatment system and a DOE light splitting system to obtain a plurality of sub-beams, and the plurality of sub-beams act on the processed film surface for scribing. Wherein, the line width of the P1 etching line is 20 μm, the line width of the P2 etching line is 100 μm, and the line width of the P3 etching line is 60 μm.

Example 2

The difference from example 1 is that: and replacing the FTO transparent conductive substrate with an ITO transparent conductive substrate.

Example 3

The difference from example 1 is that: and replacing the FTO transparent conductive substrate with a PET flexible transparent conductive substrate.

Example 4

The difference from example 1 is that:

only comprises the steps (1) and (2), in the step (2), technological parameters of the light splitting system are adjusted to enable the separation angle to be 2.4 degrees, the sub-separation angle to be 0.6 degrees, the distance between the DOE light splitter and the light path shaping system to be 5mm, the distance between a plurality of sub-beams obtained after the sub-beams pass through the light path shaping system to be 50 mu m, the plurality of sub-beams act on a processed film surface to be scribed, the line width of an etched line of P1 is 200 mu m, the etched line is clean and flat in section, and concave-convex debris residue is avoided.

Example 5

The difference from example 1 is that:

only comprising the steps (1) and (2), in the step (2), adjusting the technological parameters of the light splitting system to enable the separation angle to be 90 degrees, the sub-separation angle to be 45 degrees, the distance between the DOE light splitter and the light path shaping system to be 10mm, enabling the distance between a plurality of sub-beams obtained after the light path shaping system to be 10mm, enabling the plurality of sub-beams to act on the processed film surface for scribing to obtain a plurality of P1 etching lines, enabling the distance between every two adjacent P1 etching lines to be 10mm, enabling the sections of the etching lines to be clean and flat, and enabling no concave-convex chips to remain.

Results and conclusions:

the results of performance tests of the perovskite battery modules manufactured in comparative examples 1 to 2 and comparative examples 1 to 2 under the same test conditions are shown in table 1 and fig. 7.

Table 1 results of performance test of perovskite battery modules manufactured in examples 1 to 2 and comparative examples 1 to 2 under the same test conditions

Variables of	Current Density Jsc (mA/cm) ² )	Open circuit voltage Voc (V)	Fill factor FF (%)	Conversion efficiency PCE (%)
					Comparative example 1	0.90	24.26	74.23	16.21
Comparative example 2	0.88	24.04	74.38	15.74
					Example 1	0.92	24.23	71.91	16.03
Example 2	0.90	23.92	72.09	15.52

As can be seen by combining fig. 7 and various parameters in table 1, PCE (component efficiency) of the perovskite battery component prepared by the defocused etching process in comparative example 2 is lower than the efficiency of the battery component prepared by the focused etching process in comparative example 1, and the difference between the PCE (component efficiency) and the efficiency of the perovskite battery component is found to be larger because Jsc (current density) of comparative example 2 is lower than Jsc of comparative example 1, which is caused by that etching lines generated by the defocused etching are wider, so that dead zones are increased, absorption of light by the components is influenced, and PCE of comparative example 2 is lower than that of comparative example 1, which can also be verified from the current-voltage curve in fig. 7; in addition, compared with the comparative example 1, in the embodiment 1, after the DOE spectroscopic system is added, the deviation of the battery assembly PCE prepared by laser scribing is very small and negligible compared with that of the comparative example 1, so that the laser scribing speed can be obviously improved by adopting the embodiment of the application on the premise of ensuring that the PCE of the perovskite battery assembly is basically unchanged; comparing example 2 with example 1, it can be seen that the embodiment of the present invention is not only applicable to FTO conductive substrates, but also applicable to other conductive substrates, and it should be noted that the reason why the PCE of the perovskite battery component prepared in example 2 in the present application is lower than that of comparative examples 1-2 is that the material of the bottom electrode layer is changed, and the PCE of the battery component is decreased by using ITO instead of FTO in example 2. In addition, as can be seen from embodiments 4 to 5, the separation angle and the sub-separation angle, and the distance between the DOE beam splitter and the optical path shaping system can be adjusted to change the distance between the plurality of sub-beams, and the same wider etching line can be prepared or a plurality of etching lines can be simultaneously prepared by using each sub-beam, and the cross section of the obtained etching line is clean and flat without concave-convex debris residue no matter the wider etching line or the plurality of etching lines distributed at intervals are prepared.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. A method of making a perovskite battery, comprising:

2. The method of claim 1, further comprising: focusing the sub-beams, wherein the distance from the focused sub-beams to the layer to be etched is equal to the laser focal length of the sub-beams,

optionally, after being focused, a plurality of sub-beams form a plurality of laser spots with equal intervals on the layer to be etched.

3. The method according to claim 1 or 2, wherein the optical splitting system comprises an optical splitter and an optical path shaping system, the laser emitted from the laser source is sequentially split by the optical splitter and shaped by the optical path shaping system to obtain a plurality of sub-beams, the effective area of the laser radiation is controlled by adjusting the splitting angle of the optical splitter in the optical splitter, and the distance between two adjacent sub-beams is controlled by adjusting the sub-splitting angle and the distance between the optical splitter and the optical path shaping system.

4. The method of claim 3, wherein the separation angle is 0 to 180 degrees, the sub-separation angle is 0 to 90 degrees, the sub-separation angle is not greater than the separation angle, and the distance between the beam splitter and the optical path shaping system is not greater than 30mm.

5. The method as claimed in claim 4, wherein the original laser intensity, the separation angle, the sub-separation angle, the distance between the beam splitter and the optical path shaping system, whether the sub-beams are focused, the distance from the focused sub-beams to the layer to be etched, the laser focal length of the sub-beams are adjusted, and the distance between the laser spots formed on the layer to be etched after the plurality of sub-beams are focused and the intensity of the sub-beams are adjusted.

6. The method according to claim 1 or 4, characterized in that at least one of the following conditions is fulfilled:

the laser power adopted by the P1 laser etching is 15-40% of the rated laser power, the laser pulse width is 2-150 ns, the laser frequency is 10-150 KHz, the laser processing speed is 0.1-2 m/s, the laser focal length of the sub-beam after the beam splitting is 54mm, and the width of the obtained single P1 etching line is 15-50 mu m;

the laser power adopted by the P2 laser etching is 15-90% of the rated laser power, the laser pulse width is 2-150 ns, the laser frequency is 10-150 KHz, the laser processing speed is 0.1-2 m/s, the laser focal length of the sub-beam after the beam splitting is 54mm, and the width of the obtained single P2 etching line is 15-400 mu m;

the laser power adopted by the P3 laser etching is 15-90% of the rated laser power, the laser pulse width is 2-150 ns, the laser frequency is 10-150 KHz, the laser processing rate is 0.1-2 m/s, the laser focal length of the sub-beam after the beam splitting is 54mm, and the width of the obtained single P3 etching line is 15-300 mu m;

and laser light sources adopted by the P1 laser etching, the P2 laser etching and the P3 laser etching are respectively and independently selected from an infrared light source, a green light source and an ultraviolet light source.

7. The method as claimed in claim 6, wherein the bottom electrode layer is formed on a substrate, and the P1 laser etching, the P2 laser etching and the P3 laser etching are independently applied to the layer to be etched directly or through the substrate.

8. The method according to claim 1 or 4, characterized in that at least one of the following conditions is fulfilled:

the first carrier transport layer is an electron/hole transport layer, and the second carrier transport layer is a hole/electron transport layer;

the bottom electrode layer is a first transparent conductive layer, and the top electrode is a second transparent conductive layer or a metal layer;

the bottom electrode layer is formed on a rigid substrate or a flexible substrate.

9. The method of claim 8, wherein at least one of the following conditions is satisfied:

the first transparent conductive layer includes at least one selected from FTO, ITO, AZO, BZO, ATO, and IGO;

the second transparent conductive layer includes at least one selected from FTO, ITO, AZO, BZO, ATO, and IGO, and the metal layer includes at least one selected from Ag, cu, al, cr, ni, and Ti;

the hole transport layer includes at least one selected from the group consisting of nickel oxide, vanadium oxide, molybdenum oxide, copper sulfide, cuprous thiocyanate, copper oxide, cuprous oxide, cobalt oxide, 1 '-meta (bis-4-tolylaminobenzene) cyclohexylamine, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ], polydioxyethilphene, polytriphenylamine, and 2,2',7 '-tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene;

the electron transport layer comprises titanium dioxide, zinc oxide, cadmium sulfide, tin dioxide, indium oxide, tungsten oxide, cerium oxide, C ₆₀ And derivatives thereof, C ₇₀ And derivatives thereof and alkyl fullerene phenyl-C ₆₁ -at least one of methyl butanoate and derivatives thereof;

the perovskite photoresponsive layer is ABX ₃ A layer of perovskite material of the type wherein A is selected from Cs ⁺ 、K ⁺ 、Ru ⁺ 、CH ₃ NH ₃ ⁺ 、C(NH ₂ ) ₃ ⁺ 、CH(NH ₂ ) ₂ ⁺ B is selected from Pb ²⁺ 、Sn ²⁺ At least one of, X is selected from Br ^- 、I ^- 、Cl ^- At least one of (a).

10. Use of the process according to any one of claims 1 to 9 in the preparation of perovskite cells and photovoltaic modules.