CN118338694A - Solar cell module, preparation method thereof and solar cell - Google Patents
Solar cell module, preparation method thereof and solar cell Download PDFInfo
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- CN118338694A CN118338694A CN202410774246.8A CN202410774246A CN118338694A CN 118338694 A CN118338694 A CN 118338694A CN 202410774246 A CN202410774246 A CN 202410774246A CN 118338694 A CN118338694 A CN 118338694A
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Abstract
The application discloses a solar cell module, a preparation method thereof and a solar cell. The solar cell module comprises a substrate, a first transmission layer, an interface modification layer, an active layer and a second transmission layer which are arranged in a stacked mode. The first transmission layer, the active layer and the second transmission layer realize the photoelectric conversion function of the solar cell. The interface modification layer is arranged between the first transmission layer and the active layer, and the material of the interface modification layer is used for ionizing hydrogen ions, so that the interface modification layer coordinates free ions on the surface of the first transmission layer, which is close to the active layer, so that vacancy ions on the surface of the first transmission layer are reduced, passivation on the surface of the first transmission layer is realized, free ions on the surface of the active layer, which is close to the first transmission layer, can be coordinated, vacancy ions on the buried surface of the active layer are reduced, passivation on the buried surface of the active layer is realized, interface defects of the solar cell module are reduced, and device performance of the solar cell module is improved.
Description
Technical Field
The application relates to the technical field of solar cells, in particular to a solar cell module, a preparation method thereof and a solar cell.
Background
The development of semiconductor technology has a significant role in the advancement of the electronics industry. Perovskite is used as a novel semiconductor, has the advantages of long carrier diffusion length, high defect tolerance, adjustable band gap, large absorption coefficient and the like, and has the advantages of simple preparation process, lower cost and great advantages in the field of semiconductors compared with the traditional organic and inorganic semiconductors. Up to now, perovskite solar cell efficiency has broken through 26%, and T95 has exceeded thousands of hours. In addition to this, the process is carried out, the light-emitting diode detector has research and application in the aspects of light-emitting diodes, detectors, lasers and the like. Perovskite has shown great potential as an emerging semiconductor material.
Solar cells are a realization route for green low-carbon energy sources. Perovskite solar cells have the advantages of higher photoelectric conversion efficiency, lower cost, environmental protection by using materials and the like, and are becoming a popular solar cell gradually, and are the key development direction of the solar cell industry.
At present, some problems still exist between interfaces of all film layers of the solar cell, and further improvement of the performance of the solar cell is affected.
Disclosure of Invention
The embodiment of the application provides a solar cell module, a preparation method thereof and a solar cell, and aims to improve the interface defect problem of the solar cell.
An embodiment of a first aspect of the present application provides a solar cell module, including: a substrate; the first transmission layer, the interface modification layer, the active layer and the second transmission layer are sequentially stacked on one side of the substrate, and the first transmission layer is positioned on one side, close to the substrate, of the interface modification layer; the interface modification layer is used for passivating the surface of the first transmission layer, which is close to the active layer, the interface modification layer is used for passivating the surface of the active layer, which is close to the first transmission layer, the molecular formula of the material of the interface modification layer comprises carbonyl, and/or the material of the interface modification layer is used for ionizing out hydrogen ions.
According to an embodiment of the first aspect of the application, the molecular formula of the material of the interface modification layer comprises a carboxyl group.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the interface modification layer comprises at least one of auxin or auxin-like.
According to any of the foregoing embodiments of the first aspect of the application, the auxin-like substance comprises 4-chloro-IAA, 5-hydroxy-IAA, indolebutyric acid.
According to any one of the above embodiments of the first aspect of the present application, the thickness of the interface modification layer is 1nm to 20nm.
According to any one of the above embodiments of the first aspect of the present application, the thickness of the interface modification layer is 1nm to 6nm.
According to any of the preceding embodiments of the first aspect of the application, the active layer comprises a perovskite material.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the active layer comprises at least one of an auxin or auxin-like material.
According to any of the foregoing embodiments of the first aspect of the present application, further comprising: the first electrode layer is positioned between the substrate and the first transmission layer, and the second electrode layer is positioned on one side of the second transmission layer away from the substrate; the first electrode layer is a positive electrode, the first transport layer is a hole transport layer, the second transport layer is an electron transport layer, and the second electrode layer is a negative electrode.
According to any of the preceding embodiments of the first aspect of the present application, the material of the first transport layer comprises a metal oxide.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the first transport layer comprises at least one of NiO x,SnO2,ZnO2.
According to any of the foregoing embodiments of the first aspect of the present application, the thickness of the first transmission layer is 50nm to 60nm.
According to any of the foregoing embodiments of the first aspect of the present application, the thickness of the first transmission layer is 5nm to 40nm.
According to any of the foregoing embodiments of the first aspect of the present application, the thickness of the second transmission layer is 10nm to 30nm.
According to any of the preceding embodiments of the first aspect of the present application, the material of the second transport layer comprises a metal oxide or a carbon-based material.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the second transport layer includes at least one of SnO 2,ZnO2, fullerenes or fullerene derivatives.
According to any one of the foregoing embodiments of the first aspect of the present application, the active layer has a thickness of 200nm to 800nm.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the first electrode layer includes a transparent conductive material.
According to any of the preceding embodiments of the first aspect of the present application, the material of the first electrode layer comprises a transparent conductive oxide.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the first electrode layer includes indium tin oxide or fluorine doped tin oxide.
According to any of the preceding embodiments of the first aspect of the application, the material of the second electrode comprises a conductive oxide or a conductive metal or a conductive carbon-based material.
According to any of the foregoing embodiments of the first aspect of the present application, the thickness of the first electrode layer and/or the second electrode layer is 100nm to 500nm.
According to any of the foregoing embodiments of the first aspect of the present application, further comprising: and the auxiliary functional layer is positioned between the second transmission layer and the second electrode layer.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the auxiliary functional layer includes small organic molecules, BCP, TPBI, snO 2、LiF、MgF2, and an organic metal salt.
According to any of the foregoing embodiments of the first aspect of the present application, the material of the auxiliary functional layer includes an organic material or an inorganic material.
According to any of the foregoing embodiments of the first aspect of the present application, the thickness of the auxiliary functional layer is 2nm to 60nm.
According to any of the foregoing embodiments of the first aspect of the present application, the thickness of the auxiliary functional layer is 2nm to 40nm.
An embodiment of the second aspect of the present application provides a method for manufacturing a solar cell module, including:
sequentially preparing a first electrode layer and a first transmission layer on a substrate;
Preparing an interface modification layer on one side of the first transmission layer, which is away from the first electrode layer;
And sequentially preparing an active layer, a second transmission layer and a second electrode layer on one side of the interface modification layer, which is far away from the first transmission layer, wherein the interface modification layer is used for passivating the surface of the first transmission layer, which is close to the active layer, and the interface modification layer is used for passivating the surface of the active layer, which is close to the first transmission layer, and the molecular formula of the material of the interface modification layer comprises carbonyl groups, and/or the material of the interface modification layer is used for ionizing hydrogen ions.
According to an embodiment of the second aspect of the present application, in the step of preparing the interface modification layer on a side of the first transport layer facing away from the first electrode layer, the method further comprises:
Preparing an auxin solution or an auxin-like solution;
Coating an auxin solution or an auxin-like solution on one side of the first transmission layer, which is away from the first electrode layer;
and carrying out heating annealing on the auxin solution or the auxin-like solution to form an interface modification layer.
According to any one of the foregoing embodiments of the second aspect of the present application, in the step of sequentially preparing the first electrode layer and the first transport layer, the method further includes:
Preparing a nanoparticle solution;
coating a nanoparticle solution on one side of the first electrode layer;
the nanoparticle solution is thermally annealed to form a first transport layer.
According to any one of the foregoing embodiments of the second aspect of the present application, in the step of sequentially preparing the active layer, the second transport layer, and the second electrode layer on a side of the interface modification layer facing away from the first transport layer, the method further includes:
preparing a perovskite precursor solution;
coating perovskite precursor solution on one side of the interface modification layer, which is away from the first transmission layer;
Dropwise adding an antisolvent into the perovskite precursor solution;
the perovskite precursor solution is thermally annealed to form an active layer.
An example of the third aspect of the present application provides a solar cell comprising the solar cell module of any one of the embodiments described above or the solar cell module prepared by the preparation method of any one of the embodiments.
According to the solar cell module provided by the embodiment of the application, the solar cell module comprises a substrate, a first transmission layer, an interface modification layer, an active layer and a second transmission layer which are arranged in a stacked manner. The first transmission layer, the active layer and the second transmission layer realize the photoelectric conversion function of the solar cell. The interface modification layer is arranged between the first transmission layer and the active layer, the molecular formula of the material of the interface modification layer comprises carbonyl, and/or the material of the interface modification layer is used for ionizing hydrogen ions, so that the interface modification layer coordinates free ions on the surface of the first transmission layer, which is close to the active layer, vacancy ions on the surface of the first transmission layer are reduced, passivation on the surface of the first transmission layer is realized, free ions on the surface of the active layer, which is close to the first transmission layer, are coordinated, vacancy ions on the buried surface of the active layer are reduced, passivation on the buried surface of the active layer is realized, interface defects of the solar cell module are reduced, and device performance of the solar cell module is improved.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading the following detailed description of non-limiting embodiments, taken in conjunction with the accompanying drawings, in which like reference characters designate the same or similar features, and in which the figures are not to scale.
Fig. 1 is a partial cross-sectional view of a solar cell module according to an embodiment of the present application;
fig. 2 is a graph of current versus voltage for a solar cell module according to an embodiment of the present application;
FIG. 3 is a partial cross-sectional view of a solar cell module in another embodiment;
Fig. 4 is a schematic flow chart of a method for manufacturing a solar cell module according to an embodiment of the present application;
Fig. 5 to 10 are schematic views illustrating a manufacturing process of a solar cell module according to an embodiment of the application.
Reference numerals illustrate:
10. A solar cell module; 11. a substrate;
100. A first electrode layer;
200. a first transport layer;
300. an interface modification layer;
400. An active layer;
500. A second transport layer;
600. A second electrode layer;
700. an auxiliary functional layer.
Detailed Description
Features and exemplary embodiments of various aspects of the present application will be described in detail below, and in order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail below with reference to the accompanying drawings and the detailed embodiments. It should be understood that the specific embodiments described herein are merely configured to illustrate the application and are not configured to limit the application. It will be apparent to one skilled in the art that the present application may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the application by showing examples of the application.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
It will be understood that when a layer, an area, or a structure is described as being "on" or "over" another layer, another area, it can be referred to as being directly on the other layer, another area, or another layer or area can be included between the layer and the other layer, another area. And if the component is turned over, that layer, one region, will be "under" or "beneath" the other layer, another region.
Embodiments of the present application provide a solar cell and a method for manufacturing the same, and various embodiments of the solar cell and the method for manufacturing the same will be described below with reference to the accompanying drawings.
Referring to fig. 1, fig. 1 is a partial cross-sectional view of a solar cell module according to an embodiment of the application.
As shown in fig. 1, the first embodiment of the present application provides a solar cell module 10, where the solar cell module 10 includes a substrate 11, a first transmission layer 200, an interface modification layer 300, an active layer 400, and a second transmission layer 500 that are stacked, and the first transmission layer 200 is located on a side of the interface modification layer 300 close to the substrate 11; the interface modification layer 300 is used for passivating the surface of the first transmission layer 200 close to the active layer 400, the interface modification layer 300 is used for passivating the surface of the active layer 400 close to the first transmission layer 200, the molecular formula of the material of the interface modification layer 300 comprises carbonyl, and/or the material of the interface modification layer 300 is used for ionizing hydrogen ions.
According to the solar cell module 10 of the embodiment of the present application, the solar cell module 10 includes the substrate 11, the first transmission layer 200, the interface modification layer 300, the active layer 400, and the second transmission layer 500, which are stacked. The first transmission layer 200, the active layer 400, and the second transmission layer 500 implement a photoelectric conversion function of the solar cell. The interface modification layer 300 is disposed between the first transmission layer 200 and the active layer 400, and the molecular formula of the material of the interface modification layer 300 includes carbonyl (c=o), and/or the material of the interface modification layer 300 is used for ionizing hydrogen ions, so that the interface modification layer 300 coordinates free ions of the surface of the first transmission layer 200, which is close to the active layer 400, to reduce vacancy ions of the surface of the first transmission layer 200, to implement passivation of the surface of the first transmission layer 200, and can coordinate free ions of the surface of the active layer 400, which is close to the surface of the first transmission layer 200, to reduce vacancy ions of the buried surface of the active layer 400, to implement passivation of the buried surface of the active layer 400, thereby reducing interface defects of the solar cell module 10 and improving device performance of the solar cell module 10.
For example, O in the carbonyl of the interface modification layer 300 can coordinate with metal ions in the active layer 400, thereby reducing vacancy ions in the buried surface of the active layer 400, and achieving passivation of the buried surface of the active layer 400. The interface modification layer 300 can ionize hydrogen ions, and the hydrogen ions can coordinate with the vacancies O in the first transmission layer 200, so that the vacancies O on the surface of the first transmission layer 200 are reduced, and passivation on the surface of the first transmission layer 200 is realized.
Alternatively, the material of the active layer 400 comprises a perovskite material, and the perovskite active layer 400 has a composition having a chemical formula ABX 3, wherein a is a monovalent metal cation or an organic cation, and may be selected from: at least one of CH 3NH3、C4H9NH3、NH2＝CHNH2 and Cs; b is a divalent metal cation and can be at least one selected from Pb and Sn; x - is a monovalent anion, and can be selected from at least one or more of halogen ions such as Cl -、Br- or I -, pseudohalogen ions such as SCN -, and the like, for example, a plurality of X ions are selected, and the total proportion of the X ions meets the chemical formula of the perovskite active layer 400. Such as one or more of CsPbI 3、CsPbI2Br、CsPbIBr2、CsPbBr3、CsSnI3, or organic-inorganic hybrid perovskite, such as one or more of FAPbI 3、MAPbI3、FAPbBr3、MAPbBr3, or multi-system organic-inorganic hybrid perovskite, such as one or more of Cs0.05FA0.9MA0.05Pb(I0.95Br0.05)3、Cs0.05FA0.95PbI3.
Optionally, the molecular formula of the material of the interface modification layer includes a carboxyl group (-COOH), where the carboxyl group can include a carbonyl group and ionize hydrogen ions, and the hydrogen ions combine with the vacancies O of the first transport layer 200 to reduce the number of vacancies O of the first transport layer 200, so as to implement passivation of the first transport layer 200. And O of carbonyl in carboxyl can coordinate with vacancy Pb ion or vacancy Sn ion of the active layer 400 to reduce the number of vacancy ions of the active layer 400 and realize passivation of the buried interface of the active layer 400, thereby reducing interface defects of the solar cell module 10 and improving device performance of the solar cell module 10.
For example, in some alternative embodiments, the material of interface modification layer 300 includes at least one of an auxin (IAA) or an auxin-like.
In these alternative embodiments, the carboxyl groups of the auxin or auxin-like species are capable of ionizing hydrogen ions to combine with the vacancies O of the first transport layer 200 to reduce the number of vacancies O of the first transport layer 200 to effect passivation of the first transport layer 200. And the carboxyl (-COOH) of the auxin or the auxin-like can coordinate with the vacancy Pb ions or the vacancy Sn ions of the active layer 400 to reduce the number of the vacancy ions of the active layer 400 and realize passivation of the buried interface of the active layer 400, thereby reducing the interface defect of the solar cell module 10 and improving the device performance of the solar cell module 10. The auxin is a natural product, the material has simple structure, easy preparation and low cost.
Alternatively, the chemical nature of auxin is indoleacetic acid.
Optionally, the auxin comprises 4-chloro-IAA, 5-hydroxy-IAA, indolebutyric acid, and the like.
Referring to fig. 2 and table 1 together, fig. 2 is a current-voltage graph of a solar cell module according to an embodiment of the application; the following table shows the solar cell device characteristics of the examples of the present application compared with the comparative examples.
TABLE 1
As shown in fig. 2 and table 1, HTL is a hole transport layer, voc is a device open circuit voltage, jsc short circuit current density, FF is a fill factor, and PCE is photoelectric conversion efficiency. It can be seen that, in embodiment 1 of the present application, the interface modification layer 300 of IAA is added between the first transmission layer 200 and the active layer 400, and compared with the comparative example in which only NiO x is provided between the first electrode layer 100 and the active layer, the open circuit voltage and the short circuit current density of the device are significantly improved, and the efficiency of the device is significantly improved. In embodiment 2 of the present application, the interface modification layer 300 of 4-chloro-IAA is added between the first transmission layer 200 and the active layer 400, and compared with the comparative example in which only NiO x is provided between the first electrode layer 100 and the active layer, the open circuit voltage and the short circuit current density of the device are significantly improved, and the efficiency of the device is significantly improved. In embodiment 3 of the present application, the interface modification layer 300 of 5-hydroxy-IAA is added between the first transmission layer 200 and the active layer 400, and compared with the comparative example in which only NiO x is provided between the first electrode layer 100 and the active layer, the open circuit voltage and the short circuit current density of the device are significantly improved, and the efficiency of the device is significantly improved. In embodiment 4 of the present application, the interface modification layer 300 of naphthylacetic acid (NAA) is added between the first transmission layer 200 and the active layer 400, and compared with the comparative example in which only NiO x is provided between the first electrode layer 100 and the active layer, the open circuit voltage and the short circuit current density of the device are significantly improved, and the efficiency of the device is significantly improved. The 4-chloro-IAA, the 5-hydroxy-IAA, the Naphthalene Acetic Acid (NAA) and the like have the same structure as IAA, namely carboxyl (-COOH), and have the same beneficial effects as IAA.
In some alternative embodiments, the thickness of the interface modification layer 300 is 1nm to 20nm, for example, the thickness of the interface modification layer 300 is 1nm, 2 nm, 3 nm, 6nm, 20nm, etc.
In these alternative embodiments, the thickness of the interface modification layer 300 is greater than or equal to 1nm, so as to avoid the problem that the preparation difficulty of the interface modification layer 300 is high due to the too small thickness of the interface modification layer 300. The thickness of the interface modification layer 300 is less than or equal to 20nm, so that the problem that quantum tunneling cannot occur in the interface modification layer 300 (namely, quantum behaviors that microscopic particles such as carriers can penetrate or cross a potential barrier) due to overlarge interface modification layer 300, namely, the interface modification layer 300 is an insulating layer, and the device function of the solar cell module 10 cannot be realized is avoided.
Optionally, the thickness of the interface modification layer 300 is 1nm to 6nm, for example, the thickness of the interface modification layer 300 is 1nm, 2nm, 3 nm, 4 nm, 5nm, 6nm, and the like, and the interface modification layer 300 within the thickness range has smaller preparation difficulty and can enable the carrier to generate quantum tunneling in the interface modification layer 300, so as to realize the device function of the solar cell module 10.
Optionally, the material of the active layer 400 includes an auxin or auxin-like material, i.e., the active layer 400 is doped with an auxin or auxin-like material, e.g., the perovskite active layer 400 is doped with an auxin or auxin-like material, to further enable the vacancies Pb ions or vacancies Sn ions in the active layer 400 to coordinate with the carboxyl groups (-COOH) of the auxin or auxin-like material, thereby improving the device performance of the solar cell module 10. Optionally, the material of the active layer 400 includes auxin, which is a natural product, and the material has a simple structure, is easy to prepare, and has low cost.
Alternatively, one of the first transport layer 200 and the second transport layer 500 is a hole transport layer, and the other is an electron transport layer. The active layer 400 is used to convert incident light into electric charges. The hole transport layer is used to transport holes generated by absorption of photons in the active layer 400; meanwhile, the hole transport layer can also block the following electrons, so that the recombination of the holes and the electrons is reduced. The electron transport layer is used for transporting electrons generated by absorption of photons in the perovskite active layer 400, and at the same time, the electron transport layer can also block holes and reduce recombination of the holes and the electrons. Holes and electrons are collectively referred to herein as carriers.
TABLE 2
Referring to table 2 above, the above table is a comparison of different O1s peak area ratios in XPS spectra of the film surface of the sample of the present application and the comparative example.
As shown in the table 2 above, in example1, the surface non-coordinated O characteristic peak area of NiO x/IAA is obviously reduced compared with the surface of bare NiO x, which indicates that IAA has passivation effect on the surface defect of NiO x, namely, hydrogen ions ionized by IAA have passivation effect. I.e., the auxin is capable of ionizing out hydrogen ions to combine with the vacancies O of the first transport layer 200 to reduce the number of vacancies O of the first transport layer 200, thereby accomplishing passivation of the first transport layer 200. In example2, the non-coordinated O characteristic peak area of the NiO x/4-chloro-IAA surface is obviously reduced relative to the surface of the bare NiO x, which shows that the 4-chloro-IAA has passivation effect on the NiO x surface defect. In example 3, the non-coordinated O characteristic peak area of the NiO x/5-hydroxy-IAA surface is significantly reduced relative to the surface of the bare NiO x, indicating that the 5-hydroxy-IAA has a passivation effect on the NiO x surface defects. In example 4, the non-coordinated O characteristic peak area of NiO x/naphthylacetic acid (NAA) surface was significantly reduced relative to the bare NiO x surface, indicating that naphthylacetic acid (NAA) has a passivating effect on NiO x surface defects.
Referring to table 3 below, the following table shows different Pb characteristic peak positions in XPS spectra of the film surfaces of the samples of the examples and the comparative examples.
TABLE 3 Table 3
As shown in Table 3 above, in example 1, the Pb 4f 7/2 characteristic peak and the Pb 4f 5/2 characteristic peak of the perovskite/IAA were shifted with respect to the surface of the bare perovskite, indicating that the carboxyl group of the IAA was coordinated with Pb 2+, and the uncomplexed Pb in the perovskite film layer could be passivated. That is, the auxin has carboxyl (-COOH) groups, and can coordinate with the vacancy Pb ions or the vacancy Sn ions of the active layer 400, so as to reduce the number of the vacancy ions of the active layer 400 and realize passivation of the buried interface of the active layer 400. In example 2, the Pb 4f 7/2 characteristic peak and the Pb 4f 5/2 characteristic peak of the perovskite/4-chloro-IAA are shifted relative to the surface of the bare perovskite, which shows that the carboxyl group of the IAA coordinates with Pb 2+, and the uncomplexed Pb in the perovskite film layer can be passivated. In example 3, the Pb 4f 7/2 characteristic peak Pb 4f 5/2 characteristic peak of perovskite/5-hydroxy-IAA was shifted relative to the surface of bare perovskite, indicating that the carboxyl group of IAA was coordinated with Pb 2+ to passivate the uncomplexed Pb in the perovskite film. In example 4, the Pb 4f 7/2 characteristic peak and the Pb 4f 5/2 characteristic peak of perovskite/Naphthalene Acetic Acid (NAA) are shifted relative to the surface of bare perovskite, which shows that the carboxyl group of IAA coordinates with Pb 2+, and the uncomplexed Pb in the perovskite film layer can be passivated.
The solar cell assembly further comprises a first electrode layer 100 and a second electrode layer 600, wherein the first electrode layer 100 is positioned between the substrate 11 and the first transmission layer 200, and the second electrode layer 600 is positioned on one side of the second transmission layer 500 away from the substrate 11; the first electrode layer 100 is a positive electrode, the first transport layer 200 is a hole transport layer, the second transport layer 500 is an electron transport layer, and the second electrode layer 600 is a negative electrode. I.e., the solar cell module 10 is of a trans-configuration. When the solar cell module 10 is irradiated by sunlight, the active layer 400 absorbs photons to generate electron-hole pairs. Due to the difference in exciton binding energy of the active layer 400 material, these carriers either become free carriers or form excitons. Moreover, because these active layer 400 materials tend to have lower carrier recombination probability and higher carrier mobility, the diffusion distance and lifetime of carriers are longer. Then, these uncomplexed electrons and holes are collected by the electron transport layer and the hole transport layer, respectively, i.e., electrons are transported from the active layer 400 to the electron transport layer and finally absorbed by the first electrode layer 100 or the second electrode layer 600; holes are transported from the perovskite layer to the hole transport layer and finally collected by the first electrode layer 100 or the second electrode layer 600; the photocurrent is realized by a circuit connecting the first electrode layer 100 and the first electrode layer 100. The first transport layer 200 is a hole transport layer, and the second transport layer 500 is an electron transport layer, so that electrons are transported from the active layer 400 to the second transport layer 500 and finally collected by the second electrode layer 600.
Optionally, the first transport layer 200 is an electron transport layer, and the second transport layer 500 is a hole transport layer, that is, the solar cell module 10 with a formal structure. In the solar cell module 10 with the formal structure, the interface modification layer 300 should be disposed between the active layer 400 and the second transmission layer 500, and when the interface modification layer 300 is prepared on the surface of the active layer 400, but when the interface modification layer 300 is IAA with carboxyl groups, the interface modification layer 300 is a polar material, and the solubility in a polar solvent is good, but the polar solvent may damage the active layer 400 of the perovskite material. And the second transport layer 500 is a metal oxide, the raw material fluidity is good, and it is difficult to prepare on the active layer 400 of perovskite material. Therefore, IAA is more effective in application to the solar cell module 10 of the trans structure.
Optionally, the material of the first transport layer 200 includes a metal oxide, for example NiO x,SnO2,ZnO2, where the first transport layer 200 includes a metal oxide, more vacancies O exist on the surface of the first transport layer 200 near the active layer 400, and an interface modification layer 300 is disposed between the first transport layer 200 and the active layer 400, where the hydrogen ions ionized by the interface modification layer 300 can coordinate with the vacancies O, so as to reduce the vacancies O on the surface of the first transport layer 200, and implement passivation on the surface of the first transport layer 200.
Optionally, the thickness of the first transmission layer 200 is 5nm to 60nm, for example, the thickness of the first transmission layer 200 is 5nm, 10nm, 15nm, 40nm, 60nm, etc.
In these alternative embodiments, the thickness of the first transmission layer 200 is greater than or equal to 5nm, so that the problem that the adhesion effect between the first transmission layer 200 and the active layer 400 is affected due to the fact that the thickness of the first transmission layer 200 is too small and the surface of the first electrode layer 100 is rough, which results in that the surface of the first transmission layer 200 is rough after the first transmission layer 200 covers the first electrode layer 100 is avoided. The thickness of the first transmission layer 200 is less than or equal to 60nm, so that the problem that the carrier transmission efficiency is reduced, namely the conductivity of the first transmission layer 200 is reduced due to the fact that the transmission path of the carrier in the first transmission layer 200 is too long because of the overlarge thickness of the first transmission layer 200 is avoided.
Optionally, the thickness of the first transmission layer 200 is 5nm to 40nm, for example, the thickness of the first transmission layer 200 is 5nm, 10nm, 15nm, 20nm, 30nm, 40nm, and the like, and in this thickness range, the first transmission layer 200 can ensure the flatness of the first transmission layer 200 and can ensure the transfer efficiency of carriers.
Alternatively, the second output is an electron transport layer, and electrons are transported from the active layer 400 to the second transport layer 500 and finally collected by the second electrode layer 600 to realize the device function of the solar cell assembly 10.
Optionally, the thickness of the second transmission layer 500 is 10nm to 30nm, for example, the thickness of the second transmission layer 500 is 10nm, 15nm, 20nm, 30nm, etc.
In these alternative embodiments, the thickness of the second transmission layer 500 is greater than or equal to 10nm, so that the problem that the resistance of the second transmission layer 500 is too high and it is difficult to transmit electrons due to the too small thickness of the second transmission layer 500 can be avoided. The thickness of the second transport layer 500 is less than or equal to 30nm, and thus, problems of an excessive electron transport distance and a reduced electron transport efficiency due to an excessive thickness of the second transport layer 500 can be avoided.
Optionally, the material of the second transmission layer 500 includes a metal oxide or a carbon-based material. For example, the material of the second transmission layer 500 includes SnO 2,ZnO2, fullerene (C60) or fullerene derivative (PCBM), and the like, which combines better conductivity and lower cost. When the material of the second transmission layer 500 is fullerene (C60), the preparation may be performed by thermal evaporation, and when the material of the second transmission layer 500 is PCBM, the preparation may be performed by a solution coating method.
Optionally, the thickness of the active layer 400 is 200nm to 800nm, for example, the thickness of the active layer 400 is 200nm, 300nm, 500nm, 800nm, etc.
In these alternative embodiments, the thickness of the active layer 400 is greater than or equal to 200nm, avoiding the problem of insufficient absorption of light and thus reduction of the Photoelectric Conversion Efficiency (PCE) of the solar cell due to the reduced overall volume of the active layer 400 caused by the too small thickness of the active layer 400. The thickness of the active layer 400 is less than or equal to 800nm, so that the problem that when the thickness of the active layer 400 is too large, the active layer 400 is formed by a plurality of layers of crystals, the carrier transmission efficiency between the crystals is low, namely the carrier transmission efficiency of the active layer 400 is reduced is avoided.
Alternatively, the material of the first electrode layer 100 includes a transparent conductive material, and the transparent first electrode layer 100 serves as the light incident side of the solar cell module 10, so that light can reach the active layer 400 through the first electrode layer 100 and the first transmission layer 200.
Optionally, the material of the first electrode layer 100 includes a transparent conductive oxide, such as Indium Tin Oxide (ITO) or fluorine doped tin oxide (FTO), which has better light transmittance and conductivity.
Optionally, the material of the second electrode includes a conductive oxide or a conductive metal or a conductive carbon-based material, such as Au, ag, cu, cr, al, ITO, FTO, graphite, graphene, carbon nanotubes, etc., and the conductive oxide or the conductive metal has better conductivity and the conductive carbon-based material has lower cost.
Optionally, the thickness of the first electrode layer 100 is 100nm to 500nm, for example, the thickness of the first electrode layer 100 is 100nm, 200nm, 300nm, 500nm, etc.
In these alternative embodiments, the thickness of the first electrode layer 100 is greater than or equal to 100nm, so that the problems of the first electrode layer 100 having a relatively large resistance and a reduced conductivity due to the excessively small thickness of the first electrode layer 100 can be avoided. The thickness of the first electrode layer 100 is 500nm or less, and thus, the problem of reduction in the photoelectric conversion efficiency of the solar cell module 10 due to reduction in the transmittance of the first electrode layer 100 and reduction in the relationship of the transmittance of the first electrode layer 100 to the active layer 400 caused by excessive thickness of the first electrode layer 100 can be avoided. And also to avoid the problem of cost increase caused by the excessive thickness of the first electrode layer 100.
Optionally, the thickness of the second electrode layer 600 is 100nm to 500nm, for example, the thickness of the second electrode layer 600 is 100nm, 120nm, 200nm, 300nm, 500nm, etc.
In these alternative embodiments, the thickness of the second electrode layer 600 is greater than or equal to 100nm, so that the problems of the second electrode layer 600 having a large resistance and a reduced conductivity due to the too small thickness of the second electrode layer 600 can be avoided. The thickness of the second electrode layer 600 is less than or equal to 500nm, and thus, the problem of an increase in material cost of the second electrode layer 600 due to an excessive thickness of the second electrode layer 600 can be avoided.
Referring to fig. 3, fig. 3 is a partial cross-sectional view of a solar cell module according to another embodiment.
As shown in fig. 3, in some alternative embodiments, an auxiliary functional layer 700 is further included, the auxiliary functional layer 700 being located between the second transport layer 500 and the second electrode layer 600.
In these alternative embodiments, the material of the auxiliary functional layer 700 includes an organic material or an inorganic material. For example, small organic molecules, BCP (2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline), TPBI, snO 2、LiF、MgF2, organic Metal Salts (MOFs), etc., for example, BCP is disposed between the second transmission layer 500 and the second electrode layer 600, which can significantly improve the electron collection rate of the second electrode layer 600 and also can effectively improve the PCE of the solar cell module 10. When the material of the auxiliary functional layer 700 is small organic molecules, the preparation can be performed by thermal evaporation, and when the material of the auxiliary functional layer 700 is inorganic material such as SnO 2, the preparation can be performed by vacuum plating such as PVD or ALD.
Optionally, the thickness of the auxiliary functional layer 700 is 2nm to 60nm, for example, the thickness of the auxiliary functional layer 700 is 2nm, 7nm, 10nm, 20nm, 40nm, 60nm, etc.
In these alternative embodiments, the thickness of the auxiliary functional layer 700 is greater than or equal to 2mm, so that the difficulty in preparing the auxiliary functional layer 700 is prevented from being increased due to the excessively small thickness of the auxiliary functional layer 700. The thickness of the auxiliary functional layer 700 is less than or equal to 40nm, so that the problem that quantum tunneling cannot occur in the auxiliary functional layer 700 due to excessive thickness of the auxiliary functional layer 700, that is, the interface modification layer 300 is an insulating layer, and the device function of the solar cell module 10 cannot be realized is avoided. For example, when the material of the auxiliary functional layer 700 is small organic molecules, the thickness of the auxiliary functional layer 700 is 2nm to 10nm, and when the material of the auxiliary functional layer 700 is an inorganic material such as SnO 2, the thickness of the auxiliary functional layer 700 is 10nm to 40nm.
Optionally, the thickness of the auxiliary functional layer 700 is 2 nm-40 nm, for example, the thickness of the auxiliary functional layer 700 is 2nm, 7nm, 10nm, 20nm, 30nm, 40nm, and the like, and in the thickness range, the auxiliary functional layer 700 has lower preparation difficulty, and can ensure that the quantum tunneling of carriers occurs in the auxiliary functional layer 700, so that the device function of the solar cell module 10 is realized.
The structural design in the present embodiment can be applied to other solar cell modules 10, and specifically can be selected according to practical situations, and the present application is not limited thereto.
Referring to fig. 4 to 10 together, fig. 4 is a schematic flow chart of a method for manufacturing a solar cell module according to an embodiment of the application; fig. 5 to 10 are schematic views illustrating a manufacturing process of a solar cell module according to an embodiment of the application.
As shown in fig. 4 to 10, an embodiment of a second aspect of the present application provides a method for manufacturing a solar cell module, including:
step S01: a first electrode layer and a first transport layer are sequentially prepared on a substrate.
Step S02: an interface modification layer is prepared on the side of the first transmission layer facing away from the first electrode layer.
Step S03: and sequentially preparing an active layer, a second transmission layer and a second electrode layer on one side of the interface modification layer, which is far away from the first transmission layer, wherein the interface modification layer is used for passivating the surface of the first transmission layer, which is close to the active layer, and the interface modification layer is used for passivating the surface of the active layer, which is close to the first transmission layer, and the molecular formula of the material of the interface modification layer comprises carbonyl groups, and/or the material of the interface modification layer is used for ionizing hydrogen ions.
According to the manufacturing method of the second aspect embodiment of the present application, the solar cell module 10 includes the substrate 11, the first electrode layer 100, the first transport layer 200, the interface modification layer 300, the active layer 400, the second transport layer 500, and the second electrode layer 600, which are stacked. The first electrode layer 100, the first transport layer 200, the active layer 400, the second transport layer 500, and the second electrode layer 600 implement a photoelectric conversion function of the solar cell. The interface modification layer 300 is disposed between the first transmission layer 200 and the active layer 400, and the molecular formula of the material of the interface modification layer 300 includes carbonyl (c=o), and/or the material of the interface modification layer 300 is used for ionizing hydrogen ions, so that the interface modification layer 300 coordinates free ions of the surface of the first transmission layer 200, which is close to the active layer 400, to reduce vacancy ions of the surface of the first transmission layer 200, to implement passivation of the surface of the first transmission layer 200, and can coordinate free ions of the surface of the active layer 400, which is close to the surface of the first transmission layer 200, to reduce vacancy ions of the buried surface of the active layer 400, to implement passivation of the buried surface of the active layer 400, thereby reducing interface defects of the solar cell module 10 and improving device performance of the solar cell module 10.
Optionally, in step S02, the method further includes:
Preparing an auxin solution or an auxin-like solution;
coating an auxin solution or auxin-like solution on a side of the first transport layer 200 facing away from the first electrode layer 100;
The auxin solution or auxin-like solution is thermally annealed to form the interface modification layer 300.
In these alternative embodiments, the auxin or auxin-like solution is prepared using a solution process, e.g., the IAA solution is an IAA ethanol solution at a concentration of 0.1-10mg/mL, e.g., 0.2 mg/mL, 0.5 mg/mL, 1 mg/mL, 10mg/mL, etc. And coating IAA ethanol solution on the side of the first transmission layer 200 facing away from the first electrode layer 100 by any one of spin coating, knife coating, soaking, slit coating, spray coating, printing, vacuum deposition and film drawing, for example, in a spin coating method, the rotation speed is 3000rpm-3500 rpm, and the spin coating is 30s-60s. Finally, annealing is carried out for 10min-20min at the temperature of 100-120 ℃ to form a dry IAA film layer, namely an interface modification layer 300, on the surface of the first transmission layer 200.
Optionally, in the spin coating method, the spin coating is performed at 3000rpm for 30s, and the annealing is performed at 100 ℃ for 10min, or at 3200rpm, and the spin coating is performed for 40s, and the annealing is performed at 110 ℃ for 12min, or at 3500rpm, and the spin coating is performed for 60s, and the annealing is performed at 120 ℃ for 20min.
Optionally, in step S01, the method further includes:
Preparing a nanoparticle solution;
Coating a nanoparticle solution on one side of the first electrode layer 100;
The nanoparticle solution is thermally annealed to form the first transport layer 200.
In these alternative embodiments, the nanoparticle solution is prepared by a solution method, and the nanoparticles may be nanoparticles of metal oxides such as NiO x,SnO2,ZnO2, and are coated on the surface of the first electrode layer 100 by PVD magnetron sputtering or nanoparticle solution coating, or may be processed by any one of spin coating, knife coating, soaking, slot coating, spraying, printing, vacuum deposition, and film drawing. For example, an aqueous nanoparticle solution having a concentration of 10mg/mL-20 mg/mL is prepared and spin-coated at a spin speed of 3000rpm-3500 rpm for 30s-60s, and finally annealed at 100-120℃for 10min-20min to form a dried first transport layer 200 on the surface of the first electrode layer 100.
Optionally, preparing a nanoparticle aqueous solution with the concentration of 10mg/mL, spin-coating at 3500rpm for 60s, and finally annealing at 100 ℃ for 10min; or preparing a nanoparticle aqueous solution with the concentration of 15mg/mL, spin-coating for 35s at the speed of 3200rpm, and finally annealing for 20min at 120 ℃; or preparing a nanoparticle aqueous solution with the concentration of 20mg/mL, spin-coating for 30s at a speed of 3000rpm, and finally annealing for 10min at 110 ℃.
Optionally, in step S03, the method further includes:
preparing a perovskite precursor solution;
coating a perovskite precursor solution on a side of the interface modification layer 300 facing away from the first transport layer 200;
Dropwise adding an antisolvent into the perovskite precursor solution;
The perovskite precursor solution is thermally annealed to form the active layer 400.
In these alternative embodiments, the perovskite precursor solution is prepared and the active layer 400 is prepared by a solution method such as slot coating, doctor blade coating, spray coating, ink jet printing, screen printing, or by a method such as vacuum thermal evaporation. For example, csI (0.05-0.15 equiv), FAI (0.5-1 equiv), pbI 2 (0.8-1.2 equiv), MACl (0.2-0.4 equiv) are weighed in molar proportions and dissolved in DMF: in dmso=4:1 solution to prepare a perovskite precursor solution with a solution concentration of 1mol/ml to 1.4mol/ml, spin-coating the perovskite precursor solution at a speed of 3000rpm to 3500rpm for 30s to 60s, dropping ethyl acetate anti-solvent at the last 5s, and annealing at 100 ℃ to 150 ℃ for 30min to 45min to form a dried active layer 400 on the side of the interface modification layer 300 facing away from the first transport layer 200. Wherein, the addition of the antisolvent can increase the crystallization rate of the perovskite active substance. The preparation efficiency is improved. CsI (0.1 equiv) means that the equivalent of CsI is 0.1, in other words, the molar ratio of CsI to the whole solute is 0.1, for example, when the equivalent of CsI is 0.1 and the equivalent of PbI 2 is 1, if PbI 2 is 1mol, csI is 0.1mol, and the other materials are the same.
Alternatively, csI (0.05 equiv), FAI (0.5 equiv), pbI 2 (0.8 equiv), MACl (0.2 equiv) were weighed in molar proportions and dissolved in DMF: dmso=4:1 to prepare a perovskite precursor solution having a solution concentration of 1mol/ml to 1.4 mol/ml; or CsI (0.1 equiv), FAI (0.9 equiv), pbI 2 (1.0 equiv), MACl (0.35 equiv) were weighed in molar proportions and dissolved in DMF: dmso=4:1 to prepare a perovskite precursor solution having a solution concentration of 1mol/ml to 1.4 mol/ml; alternatively, csI (0.15 equiv), FAI (1 equiv), pbI 2 (1.2 equiv), MACl (0.4 equiv) were weighed in molar proportions and dissolved in DMF: dmso=4:1 to prepare a perovskite precursor solution with a solution concentration of 1mol/ml to 1.4mol/ml. The perovskite precursor solution concentration may be 1mol/ml, 1.1mol/ml, 1.3mol/ml, 1.4mol/ml.
An example of the third aspect of the present application provides a solar cell including the solar cell module 10 of any one of the above embodiments or the solar cell module 10 manufactured by any one of the manufacturing methods of the embodiments. Since the solar cell provided by the embodiment of the third aspect of the present application includes the solar cell module 10 of any one of the embodiments, the solar cell provided by the embodiment of the third aspect of the present application has the beneficial effects of the solar cell module 10 of any one of the embodiments, and will not be described herein.
These embodiments are not exhaustive or to limit the application to the precise embodiments disclosed, and according to the application described above. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the application and the practical application, to thereby enable others skilled in the art to best utilize the application and various modifications as are suited to the particular use contemplated. The application is limited only by the claims and the full scope and equivalents thereof.
Claims (26)
1. A solar cell module, comprising:
A substrate;
the first transmission layer, the interface modification layer, the active layer and the second transmission layer are sequentially stacked on one side of the substrate, and the first transmission layer is positioned on one side, close to the substrate, of the interface modification layer;
wherein the material of the interface modification layer comprises at least one of auxin or auxin-like.
2. The solar module of claim 1, wherein the auxin comprises 4-chloro-IAA, 5-hydroxy-IAA, indolebutyric acid.
3. The solar cell module of claim 1, wherein the interface modification layer has a thickness of 1nm to 20nm.
4. The solar cell module of claim 3, wherein the interface modification layer has a thickness of 1nm to 6nm.
5. The solar cell assembly of claim 1, wherein the active layer comprises a perovskite material.
6. The solar cell module of claim 5, wherein the material of the active layer comprises at least one of auxin or auxin-like.
7. The solar cell assembly of claim 1, further comprising: a first electrode layer and a second electrode layer, the first electrode layer being located between the substrate and the first transport layer, the second electrode layer being located on a side of the second transport layer remote from the substrate; the first electrode layer is an anode, the first transport layer is a hole transport layer, the second transport layer is an electron transport layer, and the second electrode layer is a cathode.
8. The solar cell assembly of claim 1, wherein the material of the first transmission layer comprises a metal oxide.
9. The solar cell module of claim 8 wherein the material of the first transport layer comprises at least one of NiO x,SnO2,ZnO2.
10. The solar cell module of claim 1, wherein the thickness of the second transmission layer is 5nm to 60nm.
11. The solar cell module of claim 10, wherein the thickness of the first transmission layer is 5nm to 40nm.
12. The solar cell module of claim 1, wherein the thickness of the second transmission layer is 10nm to 30nm.
13. The solar cell module of claim 1 wherein the material of the second transmission layer comprises a metal oxide or a carbon-based material.
14. The solar cell module of claim 13 wherein the material of the second transport layer comprises at least one of SnO 2,ZnO2, fullerenes or fullerene derivatives.
15. The solar cell module of claim 1, wherein the active layer has a thickness of 200nm to 800nm.
16. The solar cell module according to claim 7, wherein the thickness of the first electrode layer and/or the second electrode layer is 100 nm-500 nm.
17. The solar cell module of claim 7, further comprising:
and the auxiliary functional layer is positioned between the second transmission layer and the second electrode layer.
18. The solar cell module of claim 17 wherein the material of the auxiliary functional layer comprises an organic material or an inorganic material.
19. The solar cell module of claim 18 wherein the material of the auxiliary functional layer comprises small organic molecules, BCP, TPBI, snO 2、LiF、MgF2, organometallic salts.
20. The solar cell module of claim 17, wherein the thickness of the auxiliary functional layer is 2nm to 60nm.
21. The solar cell module of claim 20, wherein the thickness of the auxiliary functional layer is 2nm to 40nm.
22. A method of manufacturing a solar cell module, comprising:
sequentially preparing a first electrode layer and a first transmission layer on a substrate;
preparing an interface modification layer on one side of the first transmission layer, which is away from the first electrode layer;
And sequentially preparing an active layer, a second transmission layer and a second electrode layer on one side of the interface modification layer, which is far away from the first transmission layer, wherein the material of the interface modification layer comprises at least one of auxin or auxin-like.
23. The method of preparing according to claim 22, wherein in the step of preparing an interface modification layer on a side of the first transport layer facing away from the first electrode layer, the method further comprises:
Preparing an auxin solution or an auxin-like solution;
Coating the auxin solution or auxin-like solution on one side of the first transmission layer facing away from the first electrode layer;
and carrying out heating annealing on the auxin solution or the auxin-like solution to form the interface modification layer.
24. The method of manufacturing according to claim 22, wherein in the step of sequentially manufacturing the first electrode layer and the first transport layer, the method further comprises:
Preparing a nanoparticle solution;
coating the nanoparticle solution on one side of the first electrode layer;
and performing thermal annealing on the nanoparticle solution to form the first transmission layer.
25. The method of claim 22, wherein in the step of sequentially preparing an active layer, a second transport layer, and a second electrode layer on a side of the interface modification layer facing away from the first transport layer, the method further comprises:
preparing a perovskite precursor solution;
coating the perovskite precursor solution on one side of the interface modification layer away from the first transmission layer;
Dropwise adding an antisolvent into the perovskite precursor solution;
And heating and annealing the perovskite precursor solution to form the active layer.
26. A solar cell comprising the solar cell module of any one of claims 1-21 or the solar cell module prepared by the method of any one of claims 22-25.
Priority Applications (1)
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| CN111244305A (en) * | 2018-11-29 | 2020-06-05 | Tcl集团股份有限公司 | Light emitting device, display apparatus, and method of manufacturing display apparatus |
| CN115650871A (en) * | 2022-10-21 | 2023-01-31 | 陕西师范大学 | Universal cesium-based perovskite battery interface material, perovskite battery and preparation method |
| CN115915788A (en) * | 2022-12-30 | 2023-04-04 | 无锡极电光能科技有限公司 | Perovskite solar cell and preparation method thereof |
| CN117750862A (en) * | 2023-12-27 | 2024-03-22 | 极电光能有限公司 | Perovskite battery and preparation method thereof |
| CN118201379A (en) * | 2024-03-14 | 2024-06-14 | 天合光能股份有限公司 | Solar cell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111244305A (en) * | 2018-11-29 | 2020-06-05 | Tcl集团股份有限公司 | Light emitting device, display apparatus, and method of manufacturing display apparatus |
| CN115650871A (en) * | 2022-10-21 | 2023-01-31 | 陕西师范大学 | Universal cesium-based perovskite battery interface material, perovskite battery and preparation method |
| CN115915788A (en) * | 2022-12-30 | 2023-04-04 | 无锡极电光能科技有限公司 | Perovskite solar cell and preparation method thereof |
| CN117750862A (en) * | 2023-12-27 | 2024-03-22 | 极电光能有限公司 | Perovskite battery and preparation method thereof |
| CN118201379A (en) * | 2024-03-14 | 2024-06-14 | 天合光能股份有限公司 | Solar cell and preparation method thereof |
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