CN113871532B - Preparation method of perovskite solar cell module - Google Patents
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- CN113871532B CN113871532B CN202111138024.XA CN202111138024A CN113871532B CN 113871532 B CN113871532 B CN 113871532B CN 202111138024 A CN202111138024 A CN 202111138024A CN 113871532 B CN113871532 B CN 113871532B
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Abstract
The invention discloses a preparation method of a perovskite solar cell module, belonging to the technical field of solar cells, and the preparation method comprises the following specific steps: p1 scribing, functional layer preparation, P2 scribing, metal back electrode layer preparation, P3 scribing and P4 scribing. The series integration of the components is realized by adopting laser scribing, the extra series resistance introduced by P2 scribing is eliminated, the high filling factor of the large-area components is realized, the high-efficiency power generation of the components is ensured, and the filling factor of the components is greatly improved after the P2 parameters are optimized; the P3 scribing and the P4 edge cleaning scribing of the assembly are optimized, so that a short-circuit area possibly existing in the assembly is eliminated, the influence of a non-effective power generation area on the performance of the assembly is reduced, and the stability of the assembly is improved; a532 nm laser is adopted in the whole process, the scribing cost is low, the process is simple, the assembly efficiency is high, the stability is good, and the reproducibility is good.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method of a perovskite solar cell module.
Background
With the increasing severity of global ecological environment and energy shortage problems, clean and renewable solar photovoltaic power generation is generally regarded by all countries. Perovskite solar cells have been first reported since 2009 to attract the interest of a large number of researchers. After a few years of development, the device efficiency is improved from 3.8% to 22%. The perovskite solar cell is highly concerned in the photovoltaic field all over the world, and besides it reaches the high efficiency level of the first generation crystalline silicon cell in a short time, more importantly, its low cost preparation method, which brings about the eosin for the low-minded photovoltaic industry.
At present, as a photovoltaic technology with a wide prospect, perovskite thin film solar cells have become a worldwide research hotspot in recent years by virtue of the remarkable advantages of low manufacturing cost, high efficiency and the like. From the current research trend, the perovskite solar cell technology has the potential of being applied in a marketization mode. The preparation of the small-area efficient cell in a laboratory is transited to the preparation of the marketized, efficient and highly stable perovskite solar cell module, the series connection integration technology of the sub-cells is a key, and the photovoltaic performance and stability of the module are determined by the quality of the series connection integration technology.
However, the current-voltage curve of the battery assembly obtained by the traditional preparation method of the thin-film battery assembly is not ideal, the filling factor is low, and the photoelectric conversion efficiency is low. The optimized series integration technology can reduce the efficiency loss of the solar cell device when the solar cell device is transited from a small-area cell to a large-scale component, and particularly can reduce the series resistance of the component, reduce a leakage channel, increase the parallel resistance and improve the filling factor, thereby realizing the common improvement and optimization of the efficiency and the stability of the component.
Therefore, how to provide a method for preparing a perovskite solar cell module is a problem that needs to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a perovskite solar cell module, which overcomes the defects of low module efficiency and poor stability in the prior art.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a perovskite solar cell module comprises the following specific steps:
p1 score: carrying out P1 scribing on a glass substrate prepared with a transparent conductive film to obtain a scribed conductive substrate and form a plurality of P1 scribed lines;
preparing a functional layer: the functional layer comprises an electron transport layer, a perovskite absorption layer and a hole transport layer, and the preparation of the electron transport layer, the perovskite absorption layer and the hole transport layer is respectively carried out on the scribed conductive substrate;
p2 score: depositing an electron transport layer, a perovskite absorption layer and a hole transport layer, carrying out P2 scribing by a 532nm laser to form a plurality of P2 scribed lines,
completely removing the functional layer in the area on one side of the P2 scribing line to obtain the scribed functional layer;
preparing a metal back electrode layer: depositing a metal back electrode layer on the scribed functional layer, and forming a positive electrode in the scribed side area of P2;
p3 score: carrying out P3 scribing on the prepared metal back electrode layer to form a plurality of P3 scribing lines, and removing all the functional layers in the area on one side of the P3 scribing line to form a negative electrode;
p4 score: and carrying out P4 edge-clearing scribing, and removing all functional layers in the edge areas of two sides of the substrate in the direction vertical to the P1 scribing line to obtain the perovskite solar cell module.
Preferably, the P1 scoring specific steps are as follows: carrying out P1 scribing on a glass substrate prepared with a transparent conductive film according to preset scribing parameters, and thoroughly dividing the transparent conductive film into a plurality of mutually insulated strips;
wherein the P1 scoring parameters include: the distance between the center positions of two adjacent P1 scribing lines is 0.5-1 cm, the light source is pulse Nd: YAG laser with the wavelength of 532nm, the repetition frequency PRF is 10-40kHz, the average power is 1-4W, the scribing speed is 100-1000mm/s, and the spot diameter is 30-100 microns.
The beneficial effects through the above technical scheme are: through the setting of the scribing parameters of the P1, the transparent conductive film can be completely removed, so that the resistance between two adjacent transparent conductive film layers is infinite, the parallel resistance of the assembly can be increased, the filling factor is improved, and the photoelectric conversion efficiency is improved.
Preferably, the functional layer is prepared by the following specific steps: cleaning and drying the scribed conductive substrate, and respectively preparing an electron transport layer, a perovskite absorption layer and a hole transport layer on 1/2 of the scribed conductive substrate;
wherein, the thickness range of the electron transport layer is 10-50 nanometers, the thickness range of the perovskite absorption layer is 450-650 nanometers, and the thickness range of the hole transport layer is 100-250 nanometers.
Preferably, the electron transport layer, the perovskite absorption layer and the hole transport layer can be prepared by solution spin coating, spray pyrolysis, blade coating and the like.
The beneficial effects through the above technical scheme are: the thickness range of the electron transmission layer can be set to introduce parasitic resistance as low as possible on the premise of ensuring that the surface fluctuation of the transparent conductive film is completely covered by the electron transmission layer; the thickness range of the absorption layer can ensure that the incident sunlight is completely absorbed and converted; the thickness range of the hole transport layer can play a good role in transporting holes and reflecting electrons.
Preferably, the P2 scoring specific steps are as follows: after the electron transport layer, the perovskite absorption layer and the hole transport layer are deposited, P2 scribing is carried out according to preset scribing parameters, the central position of P2 is based on the central position of each P1 line, the deviation is carried out towards one side by 300 mu m, and all functional layers in the scribing region at the one side are completely removed;
wherein the P2 scoring parameters include: the laser wavelength is 532nm, the pulse repetition frequency PRF is 10-20kHz, the average power is 0.3-0.6W, the scribing speed is 10-100mm/s, the spot diameter is 50-100 microns, and the processing times are 1-5 times.
The beneficial effects through the above technical scheme are: after the optimization of the P2 scribing parameter, the functional layer introducing the parasitic series resistance is effectively removed, and meanwhile, the filling factor of the component after the optimization of the P2 scribing parameter is greatly improved.
Preferably, the thickness of the metal back electrode layer is 80-200 nm.
Preferably, the preparation method of the metal back electrode layer can be vacuum evaporation, magnetron sputtering or blade coating method and the like.
Preferably, the P3 scoring specific steps are as follows: and the positions of the P3 scribing lines are deviated from the other side by 5.3-10.9mm based on each P1 line, wherein the scribing line on the other side removes all the functional layers in the side area to obtain the cathode.
Preferably, the P4 scoring specific steps are as follows: and (3) carrying out P4 edge cleaning scribing by a 532nm laser, and removing the functional layers in the width regions of 5-20mm on the two side edges of the substrate in the direction perpendicular to the P1 scribing direction to obtain the perovskite solar cell module.
The beneficial effects through the above technical scheme are: by optimizing the P3 scoring parameters and the P4 scoring parameters, possible short-circuit areas of the assembly are eliminated, the influence of non-effective power generation areas on the performance of the assembly is reduced, and the stability of the assembly is improved.
According to the technical scheme, compared with the prior art, the invention discloses the preparation method of the perovskite solar cell module, and the preparation method has the following beneficial effects:
(1) the series integration of the components is realized by adopting laser scribing, the extra series resistance introduced by P2 scribing is eliminated, the high filling factor of the large-area components is realized, the high-efficiency power generation of the components is ensured, and the filling factor of the components is greatly improved after the P2 parameters are optimized;
(2) the P3 scribing and the P4 edge cleaning scribing of the assembly are optimized, so that a short-circuit area possibly existing in the assembly is eliminated, the influence of a non-effective power generation area on the performance of the assembly is reduced, and the stability of the assembly is improved;
(3) a532 nm laser is adopted in the whole process, the scribing cost is low, the process is simple, the assembly efficiency is high, the stability is good, and the reproducibility is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic illustration of a P1 scribe according to an embodiment;
fig. 2 is a schematic view of a functional layer preparation structure provided in this embodiment;
FIG. 3 is a schematic view of a P2 scribe provided in the present embodiment;
fig. 4 is a schematic view of a preparation structure of the metal back electrode provided in this embodiment;
FIG. 5 is a schematic view of a P3 scribe provided in the present embodiment;
FIG. 6 is a schematic top view of a perovskite solar cell module according to the present invention;
FIG. 7 is a graph comparing the stability of the components before and after scoring with the addition of P4 provided in this example.
In the drawings:
the solar cell comprises a 1-glass substrate, a 2-transparent conductive thin film layer, a 3-P1 scribing line, a 4-electron transport layer, a 5-perovskite absorption layer, a 6-hole transport layer, a 7-P2 scribing line, an 8-metal back electrode layer, a 9-P3 scribing line and a 10-P4 scribing line.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a perovskite solar cell component, which is based on a 532nm laser and comprises the following steps: the preparation method comprises the following specific steps of:
the method comprises the following steps: the material of the transparent conductive thin film layer 2 is fluorine-doped tin dioxide, equidistant channels with the interval of 7.3mm are scribed on 1/2 of a glass substrate 1 which is 70mm x 70mm and contains the fluorine-doped tin dioxide transparent conductive oxide by a 532nm laser, and the laser scribing divides the fluorine-doped tin dioxide into eight completely insulated parts, namely P1 scribing. The laser parameters used for scribing line 3 of P1 were: the pulse repetition frequency PRF of 532nm laser is 10-40kHz, the average power is 1-4W, the scribing speed is 150mm/s, the spot diameter is 50 microns, and the processing times are 2 times.
In one embodiment, through setting of the P1 scribing parameters, complete removal of the transparent conductive film can be realized, so that the resistance between two adjacent transparent conductive film layers is infinite, the parallel resistance of the assembly can be increased, and the fill factor can be improved, thereby improving the photoelectric conversion efficiency.
Step two, the preparation of the functional layer comprises the following steps: preparing an electron transport layer 4, a perovskite absorption layer 5 and a hole transport layer 6;
specifically, 1/2 of the scribed conductive substrate is cleaned and dried;
preparing an electron transport layer 4 on the substrate scribed with P1, wherein the material of the electron transport layer 4 can be selected from tin dioxide, and the preparation method is a spin coating method or a spray pyrolysis method, and the thickness is 10-50 nm;
specifically, the electron transport layer 4 is used for extracting electrons and improving the photoelectric conversion efficiency of the solar cell. The electron transport layer 4 is generally made of metal oxide and has a high resistivity, so the electron transport layer 4 should have a thickness as small as possible while ensuring complete coverage of the transparent conductive substrate. The thickness of the electron transport layer 4 is selected to be kept in the range of 10 to 50nm in this embodiment to satisfy the requirements of high light transmittance and small parasitic resistance.
The perovskite absorption layer 5 is prepared, the preparation method of the perovskite absorption layer 5 can adopt a spin coating method or a blade coating method, and the thickness is 450-650 nm;
specifically, the thickness of the absorption layer of 450-650nm refers to the thickness of the perovskite thin film light absorber, and enough sunlight is absorbed within the diffusion length (1 μm) of the carriers for photoelectric conversion.
Preparing a hole transport layer 6, wherein the hole transport layer 6 is made of spiro-OMeTAD, and the preparation method is a spin coating method with the thickness of 100-200 nm;
specifically, the hole transport layer 6 is a functional layer for selectively transporting holes and reflecting electrons, and the hole transport layer 6 is a non-light-receiving surface, so that the hole transport layer 6 does not have a thickness that affects absorption by the absorbing layer. In the present embodiment, the hole transport layer 6 has a high hole-extracting and electron-reflecting capability, and the hole transport layer 6 has a thickness of 100-250 nm.
More specifically, the electron transport layer 4, the perovskite absorption layer 5 and the hole transport layer 6 can be prepared by any one or more of solution spin coating, spray pyrolysis and blade coating.
The beneficial effects through the above technical scheme are: the thickness range of the electron transport layer 4 can be set to introduce the parasitic resistance as low as possible on the premise of ensuring that the surface fluctuation of the transparent conductive film is completely covered by the electron transport layer 4; the thickness range of the absorption layer can ensure that the incident sunlight is completely absorbed and converted; the hole-transporting layer 6 can be arranged in a thickness range to play a good role in transporting holes and reflecting electrons.
And step three, after the step two is completed, the cross section of the substrate object is shown in the attached figure 2.
The substrate is scribed by P2 with a 532nm laser, the position of the P2 scribe line 7 is shifted by 150um to the right with respect to each P1 scribe line 3, and all functional layers in the right area are removed by the rightmost scribe line.
The cross-section of the sample object after the P2 scoring is complete is shown in fig. 3. The P2 scribe line 7 completely removes the electron transport layer 4, perovskite light absorbing layer 5 and hole transport layer 6 in the scribed region.
Specifically, the laser parameters used for P2 scribing were: 532nm laser, pulse repetition frequency PRF is 10-20kHz, average power is 0.3-0.6W, scribing speed is 10-100mm/s, spot diameter is 50-100 microns, and processing times are 1-5.
The beneficial effects through the above technical scheme are: after the optimization of the P2 scribing parameter, the functional layer introducing the parasitic series resistance is effectively removed, and meanwhile, the filling factor of the component after the optimization of the P2 scribing parameter is greatly improved.
And step four, preparing a back electrode layer, wherein in a specific embodiment, an Au layer is deposited on the hole transport layer 6 by adopting a vacuum evaporation coating mode on the electrode layer, and the thickness of the Au layer is 80-200 nm.
More specifically, the method for preparing the metal back electrode layer 8 may be any one or more of vacuum evaporation, magnetron sputtering, or blade coating.
And step five, after the step four is completed, the cross section of the substrate object is shown in the attached figure 4.
The multilayer film was P3 scribed using a 532nm laser, the P3 scribe line 9 position shifted 6.7mm to the left with respect to each P1 line, with the leftmost scribe line removing all functional layers (4/5/6/8) in the left area to give the negative electrode. The resulting cross-sectional view is shown in fig. 5.
And sixthly, referring to the attached figure 6, carrying out P4 edge-clearing scribing on the substrate by adopting a 532nm laser to obtain a P4 scribing line 10, and finishing the preparation of the finished perovskite solar cell module, specifically, removing all the electron transport layer 4, the perovskite layer 5, the hole transport layer 6 and the metal back electrode layer 8 in the regions with the width of 10mm respectively at the edges of two sides of the substrate in the direction perpendicular to the P1 scribing line, and obtaining the finished perovskite solar cell module.
More specifically, the scribing of the P4 scribe line 10 was performed using exactly the same laser settings as for the P3 scribe.
The beneficial effects through the above technical scheme are: by optimizing the P3 scoring parameters and the P4 scoring parameters, possible short-circuit areas of the assembly are eliminated, the influence of non-effective power generation areas on the performance of the assembly is reduced, and the stability of the assembly is improved.
More specifically, referring to FIG. 7, increasing the normalized efficiency of the pre-P4 scribe assembly to 0.85 of the initial value after 2000 hours of operation and increasing the normalized efficiency of the post-P4 scribe assembly to 0.95 of the initial value after 2000 hours of operation clearly shows that the post-P4 scribe assembly stability is higher.
According to the technical scheme, compared with the prior art, the invention discloses the preparation method of the perovskite solar cell module, and the preparation method has the following beneficial effects:
(1) the series integration of the components is realized by adopting laser scribing, the extra series resistance introduced by P2 scribing is eliminated, the high filling factor of the large-area components is realized, the high-efficiency power generation of the components is ensured, and the filling factor of the components is greatly improved after the P2 parameters are optimized;
(2) the P3 scribing and the P4 edge cleaning scribing of the assembly are optimized, so that a short-circuit area possibly existing in the assembly is eliminated, the influence of a non-effective power generation area on the performance of the assembly is reduced, and the stability of the assembly is improved;
(3) a532 nm laser is adopted in the whole process, the scribing cost is low, the process is simple, the assembly efficiency is high, the stability is good, and the reproducibility is good.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (2)
1. The preparation method of the perovskite solar cell module is characterized by comprising the following specific steps:
p1 score: carrying out P1 scribing on a glass substrate prepared with a transparent conductive film to obtain a scribed conductive substrate and form a plurality of P1 scribed lines;
preparing a functional layer: the functional layer comprises an electron transport layer, a perovskite absorption layer and a hole transport layer, and the preparation of the electron transport layer, the perovskite absorption layer and the hole transport layer is respectively carried out on the scribed conductive substrate;
p2 score: depositing the electron transport layer, the perovskite absorption layer and the hole transport layer, and then scribing P2 by a 532nm laser to form a plurality of P2 scribed lines, and completely removing the functional layer in the region on one side of the P2 scribed line to obtain the scribed functional layer;
preparing a metal back electrode layer: depositing a metal back electrode layer on the scribed functional layer, and forming a positive electrode in the scribed side area of P2;
p3 score: carrying out P3 scribing on the prepared metal back electrode layer to form a plurality of P3 scribing lines, and removing all the functional layers in the area on one side of the P3 scribing line to form a negative electrode;
p4 score: carrying out P4 edge-cleaning scribing, and removing all functional layers in the edge areas of two sides of the substrate in the direction vertical to the P1 scribing direction to obtain the perovskite solar cell module;
the P1 scoring comprises the following specific steps: performing P1 scribing on a glass substrate with a transparent conductive film according to preset scribing parameters, and thoroughly dividing the transparent conductive film into a plurality of mutually insulated strips;
wherein the P1 scoring parameters include: the distance between the center positions of two adjacent P1 scribing lines is 0.5-1 cm, the light source is pulse Nd with the wavelength of 532nm, YAG laser, the repetition frequency PRF is 10-40kHz, the average power is 1-4W, the scribing speed is 100-1000mm/s, and the spot diameter is 30-100 microns;
the preparation method of the functional layer comprises the following specific steps: cleaning and drying the scribed conductive substrate, and respectively preparing an electron transport layer, a perovskite absorption layer and a hole transport layer on the scribed conductive substrate;
wherein, the thickness range of the electron transport layer is 10-50 nanometers, the thickness range of the perovskite absorption layer is 450-650 nanometers, and the thickness range of the hole transport layer is 100-250 nanometers;
the P2 scoring comprises the following specific steps: depositing the electron transport layer, the perovskite absorption layer and the hole transport layer, and then scribing P2 according to preset scribing parameters, wherein the central position of P2 is based on the central position of each P1 line, the right deviation is 150um, and the right-most scribing line removes all functional layers in the right region;
wherein the P2 scoring parameters include: the laser wavelength is 532nm, the pulse repetition frequency PRF is 10-20kHz, the average power is 0.3-0.6W, the scribing speed is 10-100mm/s, and the diameter of a light spot is 50-100 microns;
the P3 scoring comprises the following specific steps: the position of a P3 scribing line is based on each P1 line, the left deviation is 6.7mm, and the leftmost scribing line completely removes all functional layers in the left area to obtain a negative electrode;
the specific steps of the P4 scoring are as follows: and (3) carrying out P4 edge cleaning scribing by a 532nm laser, and removing the functional layers in the width regions of 5-20mm on the two side edges of the substrate in the direction perpendicular to the P1 scribing direction to obtain the perovskite solar cell module.
2. The method of claim 1, wherein the thickness of the metal back electrode layer is 80-200 nm.
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