Manufacturing method of perovskite cell, perovskite cell and laminated cell

Abstract

The invention provides a manufacturing method of a perovskite cell, the perovskite cell and a laminated cell. The manufacturing method comprises the following steps: providing a semiconductor substrate, wherein one side of the semiconductor substrate is provided with a hole transport layer; forming a passivation layer on one side, far away from the semiconductor substrate, of the hole transport layer; a perovskite precursor solution added with a passivating agent is coated on the side, away from the hole transport layer, of the passivation layer to form a perovskite absorption layer, and the material of the passivation layer is the same as that of the passivating agent; forming an electron transport layer on one side, far away from the passivation layer, of the perovskite absorption layer; and forming an electrode layer on one side, far away from the perovskite absorption layer, of the electron transport layer. According to the application, the interface energy level and the performance of perovskite crystal are synchronously improved by using the same material, the purpose of improving the crystal quality of the perovskite absorption layer is achieved, and the production takt can be faster, so that the yield of the perovskite cell is improved, and the production cost is reduced. The problem of high production cost of the perovskite battery caused by long production takt time can be solved.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite cells, and in particular to a method for manufacturing a perovskite cell, a perovskite cell and a stacked cell. Background Art

[0002] The performance improvement of perovskite / crystalline silicon tandem solar cells mainly comes from the improvement of perovskite crystal quality. High-quality perovskite films can have more efficient carrier generation and transmission, thereby improving the performance of the cell. Currently, the methods for improving the quality of perovskite crystals include the following: additive engineering and surface modification engineering. In order to achieve rapid growth in the efficiency of perovskite solar cells, multiple modification processes are usually required at the same time, which will lengthen the production cycle of the cell and increase its production cost. Summary of the invention

[0003] The main purpose of the present invention is to provide a method for manufacturing a perovskite cell, a perovskite cell and a stacked cell, so as to at least solve the problems of poor crystallization quality and more interface defects of the perovskite absorption layer in the prior art.

[0004] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a method for manufacturing a perovskite battery is provided, comprising: providing a semiconductor substrate, one side of the semiconductor substrate having a hole transport layer; forming a passivation layer on a side of the hole transport layer away from the semiconductor substrate; coating a perovskite precursor solution added with a passivator on a side of the passivation layer away from the hole transport layer to form a perovskite absorption layer, wherein the passivation layer and the passivator are made of the same material; forming an electron transport layer on a side of the perovskite absorption layer away from the passivation layer; and forming an electrode layer on a side of the electron transport layer away from the perovskite absorption layer.

[0005] Furthermore, the step of forming the above-mentioned passivation layer includes: dissolving the passivation material into an organic solvent to prepare a passivation solution; applying the above-mentioned passivation solution to the side of the above-mentioned hole transport layer away from the above-mentioned semiconductor substrate to form a passivation precursor film; and heat-treating the above-mentioned passivation precursor film to form the above-mentioned passivation layer.

[0006] Furthermore, the passivation precursor film is formed by a spin coating process, the spin coating speed of the spin coating process is 3000 rpm to 5000 rpm, and the spin coating time of the spin coating process is 30s to 40s.

[0007] Furthermore, the concentration of the passivation solution is 0.1 mg / ml to 1 mg / ml.

[0008] Furthermore, the above-mentioned passivating agent is 6-bromohexyltriethylammonium bromide.

[0009] Furthermore, the concentration of the passivating agent in the perovskite precursor solution is 0.1 mg / ml to 1 mg / ml.

[0010] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a perovskite cell is provided, which is manufactured by the manufacturing method of the perovskite cell as described above, and the perovskite cell comprises a semiconductor substrate, a hole transport layer, a passivation layer, a perovskite absorption layer, an electron transport layer and an electrode layer stacked in sequence.

[0011] Furthermore, the thickness of the passivation layer is 10-15 nm.

[0012] According to another aspect of the present invention, there is provided a stacked battery, comprising a first battery and a second battery stacked in layers, wherein at least one of the first battery and the second battery is the perovskite battery.

[0013] Furthermore, the first battery is a crystalline silicon battery, and the second battery is the perovskite battery.

[0014] The technical solution of the present invention is applied to provide a method for manufacturing a perovskite battery, firstly, a semiconductor substrate is provided, and one side of the semiconductor substrate has a hole transport layer, and then a passivation layer is formed on the side of the hole transport layer away from the semiconductor substrate, so that after the perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer, the passivation layer can adjust the interface energy level of the perovskite absorption layer. And because the perovskite in the perovskite absorption layer close to the passivation layer can also undergo a cross-linking reaction with the passivation material in the passivation layer and form a mixed layer, the crystallization quality of the perovskite absorption layer can be further improved. In addition, in the process of forming the above-mentioned perovskite absorption layer, since a passivator is also added to the perovskite precursor solution, the crystallization quality of the perovskite absorption layer can be improved simultaneously, so that the perovskite crystallization process is regulated to obtain a perovskite absorption layer with a larger grain size and lower defects. Furthermore, since the material of the passivation layer and the passivating agent can be the same, the present solution can use the same material to simultaneously improve the interface performance of the perovskite and the performance of the perovskite crystallization, that is, the purpose of improving the efficiency in both directions is achieved by using one material, and then an electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer, and an electrode layer is formed on the side of the electron transport layer away from the perovskite absorption layer. As can be seen from the above, when the perovskite battery is manufactured by the manufacturing method of the present application, the same material can be used to achieve the purpose of simultaneously improving the interface energy level and improving the crystallization quality of the perovskite absorption layer, and the improvement of the bidirectional efficiency is achieved, so that the perovskite battery can have a faster production cycle, thereby increasing the output of the perovskite battery, and at the same time solving the problem of high production cost of the perovskite battery due to the long production cycle in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0016] Figure 1 A schematic cross-sectional structure diagram of a crystalline silicon perovskite stacked cell according to an embodiment of the present invention is shown.

[0017] The above drawings include the following reference numerals:

[0018] 10. Crystalline silicon cell; 20. Transparent oxide layer; 30. Hole transport layer; 40. Passivation layer; 50. Perovskite absorption layer; 60. Electron transport layer; 70. Transparent conductive layer; 80. Metal electrode layer. DETAILED DESCRIPTION

[0019] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0020] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0021] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged where appropriate, so as to describe the embodiments of the present invention described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0022] As described in the background technology, the current methods for improving the crystal quality of perovskite in the perovskite absorption layer mainly include additive engineering and surface modification engineering. That is, in order to achieve rapid growth in the efficiency of perovskite cells, it is usually necessary to use multiple modification processes at the same time, but the simultaneous use of multiple modification processes will cause the production cycle of perovskite cells to be lengthened, thereby increasing the production cost of perovskite cells. In order to solve the above technical problems, the applicant of this application provides a method for manufacturing a perovskite cell, a perovskite cell and a laminated cell.

[0023] According to one aspect of the present application, a method for manufacturing a perovskite battery is provided, and the manufacturing method includes: providing a semiconductor substrate, one side of the semiconductor substrate having a hole transport layer; forming a passivation layer on a side of the hole transport layer away from the semiconductor substrate; coating a perovskite precursor solution added with a passivator on a side of the passivation layer away from the hole transport layer to form a perovskite absorption layer, wherein the material of the passivation layer is the same as the passivator; forming an electron transport layer on a side of the perovskite absorption layer away from the passivation layer; and forming an electrode layer on a side of the electron transport layer away from the perovskite absorption layer.

[0024] Specifically, the semiconductor substrate may be a transparent conductive glass. Exemplarily, the semiconductor substrate may include but is not limited to indium tin oxide (ITO, In 2 O 3 :Sn), aluminum-doped zinc oxide (AZO, ZnO:Al), fluorine-doped tin oxide (FTO, SnO 2 :F) and antimony-doped tin oxide (ATO, Sn 2 Those skilled in the art can make reasonable selections according to actual needs, and this application does not make specific limitations.

[0025] In some other optional embodiments, the semiconductor substrate may also be a polymer film. For example, the semiconductor substrate may also include, but is not limited to, tin-doped indium oxide-polyethylene terephthalate (ITO-PET) film and polyethylene naphthalate (ITO-PEN) film. Those skilled in the art may make reasonable selections according to actual needs, and this application does not make specific limitations.

[0026] Specifically, the material of the hole transport layer can be independently selected from 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly[3,4-ethynyldioxythiophene]:poly[styrenesulfonate] (PEDOT:PSS) and nickel oxide (NiO x) One or more of the above. Those skilled in the art can make reasonable selections according to actual needs, and this application does not make specific limitations.

[0027] Specifically, the material of the passivation layer can be 6-bromohexyltriethylammonium bromide. Those skilled in the art can make a reasonable selection according to actual needs, and this application does not make any specific limitation.

[0028] Specifically, the perovskite precursor solution can be CsPbI 2 Br solution, CsPbIBr 2 Solution, CsPbI 3 Solution, CsPbBr 3 Solution and FASnI 3 Any one or more of the solutions, and a passivator may be dissolved in any of the above perovskite precursor solutions. Optionally, the material of the above passivator may be the same as the material of the passivation layer. Those skilled in the art may make reasonable selections according to actual needs, and this application does not make specific limitations.

[0029] Optionally, the process of coating the perovskite precursor solution added with the passivator on the side of the passivation layer away from the hole transport layer can be a spin coating process, wherein the spin coating speed of the spin coating process can be 1000rpm~5000rpm, and the spin coating time can be 10s~30s.

[0030] Specifically, the material of the electron transport layer can be independently selected from tin oxide (SnO 2 ), zinc oxide (ZnO), titanium oxide (TiO 2 ), methylfullerene (PCBM) and C 60 Those skilled in the art can make reasonable selections according to actual needs, and this is not specifically limited in this application.

[0031] Specifically, the electrode layer is at least one of a transparent conductive layer and a metal layer. In the case where the electrode layer includes a transparent conductive layer and a metal layer, the transparent conductive layer can be located on a side of the electron transport layer away from the perovskite absorption layer, and the metal layer can be located on a side of the transparent conductive layer away from the electron transport layer.

[0032] Optionally, the material of the transparent conductive layer may include, but is not limited to, oxides of indium (In), antimony (Sb), zinc (Zn) and cadmium (Cd) and composite multi-element oxide thin film materials thereof. Optionally, the material of the metal layer may include, but is not limited to, gold (Au), silver (Ag), copper (Cu) and aluminum (Al). Those skilled in the art may make reasonable selections according to actual needs, and this application does not make specific limitations.

[0033] In the above embodiment, a semiconductor substrate is first provided, and one side of the semiconductor substrate has a hole transport layer, and then a passivation layer is formed on the side of the hole transport layer away from the semiconductor substrate, so that after the perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer, the passivation layer can adjust the interface energy level of the perovskite absorption layer. And because the perovskite in the perovskite absorption layer close to the side of the passivation layer can also undergo a cross-linking reaction with the passivation material in the passivation layer and form a mixed layer, the crystallization quality of the perovskite absorption layer can be further improved. In addition, in the process of forming the above-mentioned perovskite absorption layer, since a passivator is also added to the perovskite precursor solution, the crystallization quality of the perovskite absorption layer can be improved simultaneously, so that the perovskite crystallization process is regulated to obtain a perovskite absorption layer with a larger grain size and lower defects. Furthermore, since the materials of the passivation layer and the passivator can be the same, the present solution can use the same material to simultaneously improve the interface performance of the perovskite and the performance of the perovskite crystallization, that is, use one material to achieve the purpose of bidirectional efficiency improvement, and then form an electron transport layer on the side of the perovskite absorption layer away from the passivation layer, and form an electrode layer on the side of the electron transport layer away from the perovskite absorption layer.

[0034] From the above, it can be seen that when the manufacturing method of the present application is used to manufacture perovskite cells, the same material can be used to simultaneously improve the interface energy level and enhance the performance of perovskite crystallization, thereby achieving the purpose of improving the crystallization quality of the perovskite absorption layer, and realizing the improvement of bidirectional efficiency, so that the perovskite cell can have a faster production cycle, thereby increasing the output of the perovskite cell, and at the same time solving the problem of high production cost of perovskite cells caused by long production cycle in the prior art.

[0035] Optionally, the hole transport layer located on one side of the semiconductor substrate can be formed by magnetron sputtering, atomic layer deposition (ALD) or spin coating.

[0036] Optionally, in some embodiments, Figure 1 As shown, the semiconductor substrate may also include a crystalline silicon cell 10, so that the method for making the perovskite cell is a method for making a crystalline silicon perovskite stacked cell. Specifically, the method for making the crystalline silicon perovskite stacked cell may include: first making a crystalline silicon cell 10; then forming a transparent oxide layer 20 on one side of the crystalline silicon cell 10; then forming a hole transport layer 30 on the side of the transparent oxide layer 20 away from the crystalline silicon cell 10; forming a passivation layer 40 on the side of the hole transport layer 30 away from the transparent oxide layer 20; applying a perovskite precursor solution added with a passivator on the side of the passivation layer 40 away from the hole transport layer 30 to form a perovskite absorption layer 50; forming an electron transport layer 60 on the side of the perovskite absorption layer 50 away from the passivation layer 40; and forming an electrode layer on the side of the electron transport layer 60 away from the perovskite absorption layer 50.

[0037] Optionally, the electrode layer may be at least one of a transparent conductive layer 70 and a metal electrode layer 80 .

[0038] Optionally, in the case where the electrode layer includes a transparent conductive layer 70 and a side of a metal electrode layer 80, the transparent conductive layer 70 may be located on a side of the electron transport layer 60 away from the perovskite absorption layer 50, and the metal electrode layer 80 may be located on a side of the transparent conductive layer 70 away from the electron transport layer 60. It can be understood that the materials of the hole transport layer 30, the passivation layer 40, the perovskite precursor solution, the passivator, the perovskite absorption layer 50, the electron transport layer 60 and the electrode layer mentioned in this embodiment may correspond to the materials described in the above-mentioned method for manufacturing a perovskite battery, and therefore, they will not be described in detail here.

[0039] In some optional embodiments, in order to form a passivation layer for adjusting the interface energy level between the hole transport layer and the perovskite absorption layer, the step of forming the above-mentioned passivation layer may include: dissolving the passivation material into an organic solvent to prepare a passivation solution; applying the above-mentioned passivation solution to the side of the above-mentioned hole transport layer away from the above-mentioned semiconductor substrate to form a passivation precursor film; and heat-treating the above-mentioned passivation precursor film to form the above-mentioned passivation layer.

[0040] Specifically, the organic solvent may be dimethyl sulfoxide. The passivation material may be 6-bromohexyltriethylammonium bromide. That is, in the process of forming the passivation layer, 6-bromohexyltriethylammonium bromide may be first dissolved in the dimethyl sulfoxide reagent to form the passivation solution. Specifically, the heat treatment may be an annealing treatment, and the annealing conditions may be 100°C / 10min.

[0041] Furthermore, in the process of coating the passivation solution to the side of the hole transport layer away from the semiconductor substrate, in order to enable the passivation solution to form a film quickly, a spin coating process can be used to first prepare a passivation precursor film. Optionally, the spin coating speed of the above spin coating process can be 3000 rpm to 5000 rpm, and the spin coating time can be 30s to 40s.

[0042] In order to adjust the interface energy level, in some optional embodiments, the concentration of the passivation solution may be 0.1 mg / ml to 1 mg / ml.

[0043] In some optional embodiments, in order to play a regulatory role in the perovskite crystallization process, the passivating agent may be 6-bromohexyltriethylammonium bromide.

[0044] In some optional embodiments, in order to regulate the process of perovskite crystallization and obtain a perovskite absorber layer with larger grain size and lower defects, the concentration of the above passivator in the perovskite precursor solution can be 0.1 mg / ml to 1 mg / ml.

[0045] According to another aspect of the present application, a perovskite cell is also provided, which can be manufactured using the above-mentioned method for manufacturing a perovskite cell. Optionally, the perovskite cell may include a semiconductor substrate, a hole transport layer, a passivation layer, a perovskite absorption layer, an electron transport layer, and an electrode layer arranged in a stacked manner. Furthermore, the electrode layer may include a transparent conductive layer and a metal electrode layer arranged in a stacked manner, and the transparent conductive layer is located on the side of the electron transport layer away from the perovskite absorption layer, and the metal electrode layer is located on the side of the transparent conductive layer away from the electron transport layer.

[0046] In the above embodiment, since the perovskite battery can be manufactured by the above-mentioned method for manufacturing the perovskite battery, there is a passivation layer between the hole transport layer and the perovskite absorption layer of the perovskite battery, so that the interface energy level of the perovskite absorption layer can be adjusted. In the process of forming the perovskite absorption layer, there is also a passivating agent to regulate the crystallization process of the perovskite, so that a perovskite absorption layer with a larger grain size and lower defects can be obtained. Therefore, the perovskite battery of this embodiment can achieve more efficient carrier generation and transmission due to the high-quality perovskite absorption layer, thereby improving the performance of the perovskite battery.

[0047] In some optional implementations, in order to make the passivation layer have a good ability to adjust the interface energy level, the thickness of the passivation layer may be 10-15 nm.

[0048] According to another aspect of the present application, in order to further improve the photoelectric conversion efficiency of the perovskite cell, a stacked cell is also provided, which may include a first cell and a second cell stacked together, and at least one of the first cell and the second cell is the above-mentioned perovskite cell.

[0049] Specifically, in some optional embodiments, the first battery may be a crystalline silicon battery, and the second battery may be a perovskite battery, wherein the band gap of the perovskite battery is greater than the band gap of the crystalline silicon battery; in other optional embodiments, both the first battery and the second battery may be perovskite batteries. Further, in the case where both the first battery and the second battery are perovskite batteries, the band gap of the perovskite absorption layer of the first battery may be greater than or less than the band gap of the perovskite absorption layer of the second battery.

[0050] The crystalline silicon perovskite tandem battery formed by the method for manufacturing the crystalline silicon perovskite tandem battery of the present invention will be further described below in conjunction with the embodiments and comparative examples.

[0051] Example 1

[0052] Provide crystalline silicon cells;

[0053] A transparent conductive layer is formed on one side of the crystalline silicon cell, the transparent conductive layer is an indium tin oxide (ITO) layer, and the thickness of the indium tin oxide (ITO) layer is 100 nm;

[0054] A hole transport layer is formed on one side of the indium tin oxide (ITO) layer, wherein the material of the hole transport layer is nickel oxide (NiOx) and the thickness is 20 nm;

[0055] A passivation layer is formed on the side of the hole transport layer away from the transparent conductive layer. The steps of forming the passivation layer are as follows: dissolving 6-bromohexyltriethylammonium bromide in a dimethyl sulfoxide solution to obtain a passivation solution with a concentration of 0.1 mg / ml, spin-coating the passivation solution to the side of the hole transport layer away from the transparent conductive layer using a spin coating process at 3000 rpm / 30 s, and annealing at a temperature of 100° C. for 10 minutes;

[0056] A perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer. The steps of forming the perovskite absorption layer are as follows: first, a perovskite precursor solution (mixed ion perovskite precursor solution of CsFAMA) is prepared, wherein a passivator of 6-bromohexyltriethylammonium bromide is added to the perovskite precursor solution, and the concentration of the passivator in the perovskite precursor solution is 0.5 mg / ml, and the perovskite precursor solution added with the above 6-bromohexyltriethylammonium bromide is spin-coated to the side of the passivation layer away from the hole transport layer by a spin coating process with a spin coating speed of 3000 rpm and a spin coating time of 30 s;

[0057] An electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer. The material of the electron transport layer is methyl fullerene (PCBM) with a thickness of 20 nm.

[0058] A transparent electrode layer is formed on a side of the electron transport layer away from the perovskite absorption layer, wherein the material of the transparent electrode layer is an indium zinc oxide (IZO) layer with a thickness of 100 nm;

[0059] A metal electrode layer is formed on a side of the transparent electrode layer away from the electron transport layer. The material of the metal electrode layer is silver (Ag) and the thickness is 90 nm.

[0060] Example 2

[0061] Provide crystalline silicon cells;

[0062] A transparent conductive layer is formed on one side of the crystalline silicon cell, the transparent conductive layer is an indium tin oxide (ITO) layer, and the thickness of the indium tin oxide (ITO) layer is 100 nm;

[0063] A hole transport layer is formed on one side of the indium tin oxide (ITO) layer, wherein the material of the hole transport layer is nickel oxide (NiOx) and the thickness is 20 nm;

[0064] A passivation layer is formed on the side of the hole transport layer away from the transparent conductive layer. The steps of forming the passivation layer are as follows: dissolving 6-bromohexyltriethylammonium bromide in a dimethyl sulfoxide solution to obtain a passivation solution with a concentration of 1 mg / ml, spin-coating the passivation solution to the side of the hole transport layer away from the transparent conductive layer by a spin-coating process at a spin-coating speed of 3000 rpm for 30 seconds, and annealing at an annealing temperature of 100°C for 10 minutes;

[0065] A perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer. The steps of forming the perovskite absorption layer are as follows: first, a perovskite precursor solution (mixed ion perovskite precursor solution of CsFAMA) is prepared, wherein a passivator of 6-bromohexyltriethylammonium bromide is added to the perovskite precursor solution, and the concentration of the passivator in the perovskite precursor solution is 0.5 mg / ml, and the perovskite precursor solution added with the above 6-bromohexyltriethylammonium bromide is spin-coated to the side of the passivation layer away from the hole transport layer by a spin coating process with a spin coating speed of 3000 rpm and a spin coating time of 30 s;

[0066] An electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer. The material of the electron transport layer is methyl fullerene (PCBM) with a thickness of 20 nm.

[0067] A transparent electrode layer is formed on a side of the electron transport layer away from the perovskite absorption layer, wherein the material of the transparent electrode layer is an indium zinc oxide (IZO) layer with a thickness of 100 nm;

[0068] A metal electrode layer is formed on a side of the transparent electrode layer away from the electron transport layer. The material of the metal electrode layer is silver (Ag) and the thickness is 90 nm.

[0069] That is, the passivation solutions in Example 2 and Example 1 have different concentrations.

[0070] Example 3

[0071] Provide crystalline silicon cells;

[0072] A transparent conductive layer is formed on one side of the crystalline silicon cell, the transparent conductive layer is an indium tin oxide (ITO) layer, and the thickness of the indium tin oxide (ITO) layer is 100 nm;

[0073] A hole transport layer is formed on one side of the indium tin oxide (ITO) layer, wherein the material of the hole transport layer is nickel oxide (NiOx) and the thickness is 20 nm;

[0074] A passivation layer is formed on the side of the hole transport layer away from the transparent conductive layer. The steps of forming the passivation layer are as follows: dissolving 6-bromohexyltriethylammonium bromide in a dimethyl sulfoxide solution to obtain a passivation solution with a concentration of 0.5 mg / ml, spin-coating the passivation solution to the side of the hole transport layer away from the transparent conductive layer by a spin-coating process at a spin-coating speed of 3000 rpm for 30 seconds, and annealing at an annealing temperature of 100°C for 10 minutes;

[0075] A perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer. The steps of forming the perovskite absorption layer are as follows: first, a perovskite precursor solution (mixed ion perovskite precursor solution of CsFAMA) is prepared, wherein a passivator of 6-bromohexyltriethylammonium bromide is added to the perovskite precursor solution, and the concentration of the passivator in the perovskite precursor solution is 0.5 mg / ml, and the perovskite precursor solution added with the above 6-bromohexyltriethylammonium bromide is spin-coated to the side of the passivation layer away from the hole transport layer by a spin coating process with a spin coating speed of 3000 rpm and a spin coating time of 30 s;

[0076] An electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer. The material of the electron transport layer is methyl fullerene (PCBM) with a thickness of 20 nm.

[0077] A transparent electrode layer is formed on a side of the electron transport layer away from the perovskite absorption layer, wherein the material of the transparent electrode layer is an indium zinc oxide (IZO) layer with a thickness of 100 nm;

[0078] A metal electrode layer is formed on a side of the transparent electrode layer away from the electron transport layer. The material of the metal electrode layer is silver (Ag) and the thickness is 90 nm.

[0079] That is, the present embodiment 3 has a passivation solution with different concentrations from the above-mentioned embodiments 1 and 2.

[0080] Example 4

[0081] Provide crystalline silicon cells;

[0082] A transparent conductive layer is formed on one side of the crystalline silicon cell, the transparent conductive layer is an indium tin oxide (ITO) layer, and the thickness of the indium tin oxide (ITO) layer is 100 nm;

[0083] A hole transport layer is formed on one side of the indium tin oxide (ITO) layer, wherein the material of the hole transport layer is nickel oxide (NiOx) and the thickness is 20 nm;

[0084] A passivation layer is formed on the side of the hole transport layer away from the transparent conductive layer. The steps of forming the passivation layer are as follows: dissolving 6-bromohexyltriethylammonium bromide in a dimethyl sulfoxide solution to obtain a passivation solution with a concentration of 0.1 mg / ml, spin-coating the passivation solution to the side of the hole transport layer away from the transparent conductive layer by a spin-coating process at a spin-coating speed of 3000 rpm for 30 seconds, and annealing at an annealing temperature of 100°C for 10 minutes;

[0085] A perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer. The steps of forming the perovskite absorption layer are as follows: first, a perovskite precursor solution (mixed ion perovskite precursor solution of CsFAMA) is prepared, wherein a passivator of 6-bromohexyltriethylammonium bromide is added to the perovskite precursor solution, and the concentration of the passivator in the perovskite precursor solution is 0.1 mg / ml, and the perovskite precursor solution added with the above 6-bromohexyltriethylammonium bromide is spin-coated to the side of the passivation layer away from the hole transport layer by a spin coating process with a spin coating speed of 3000 rpm and a spin coating time of 30 s;

[0086] An electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer. The material of the electron transport layer is methyl fullerene (PCBM) with a thickness of 20 nm.

[0087] A transparent electrode layer is formed on a side of the electron transport layer away from the perovskite absorption layer, wherein the material of the transparent electrode layer is an indium zinc oxide (IZO) layer with a thickness of 100 nm;

[0088] A metal electrode layer is formed on a side of the transparent electrode layer away from the electron transport layer. The material of the metal electrode layer is silver (Ag) and the thickness is 90 nm.

[0089] That is, the perovskite precursor solutions of Example 4 and Example 1 contain different concentrations of passivating agents.

[0090] Example 5

[0091] Provide crystalline silicon cells;

[0092] A transparent conductive layer is formed on one side of the crystalline silicon cell, the transparent conductive layer is an indium tin oxide (ITO) layer, and the thickness of the indium tin oxide (ITO) layer is 100 nm;

[0093] A hole transport layer is formed on one side of the indium tin oxide (ITO) layer, wherein the material of the hole transport layer is nickel oxide (NiOx) and the thickness is 20 nm;

[0094] A passivation layer is formed on the side of the hole transport layer away from the transparent conductive layer. The steps of forming the passivation layer are as follows: dissolving 6-bromohexyltriethylammonium bromide in a dimethyl sulfoxide solution to obtain a passivation solution with a concentration of 0.1 mg / ml, spin-coating the passivation solution to the side of the hole transport layer away from the transparent conductive layer by a spin-coating process at a spin-coating speed of 3000 rpm for 30 seconds, and annealing at an annealing temperature of 100°C for 10 minutes;

[0095] A perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer. The steps of forming the perovskite absorption layer are as follows: first, a perovskite precursor solution (mixed ion perovskite precursor solution of CsFAMA) is prepared, wherein a passivator of 6-bromohexyltriethylammonium bromide is added to the perovskite precursor solution, and the concentration of the passivator in the perovskite precursor solution is 1 mg / ml, and the perovskite precursor solution added with the above 6-bromohexyltriethylammonium bromide is spin-coated to the side of the passivation layer away from the hole transport layer by a spin coating process with a spin coating speed of 3000 rpm and a spin coating time of 30 s;

[0096] An electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer. The material of the electron transport layer is methyl fullerene (PCBM) with a thickness of 20 nm.

[0097] A transparent electrode layer is formed on a side of the electron transport layer away from the perovskite absorption layer, wherein the material of the transparent electrode layer is an indium zinc oxide (IZO) layer with a thickness of 100 nm;

[0098] A metal electrode layer is formed on a side of the transparent electrode layer away from the electron transport layer. The material of the metal electrode layer is silver (Ag) and the thickness is 90 nm.

[0099] That is, the perovskite precursor solutions corresponding to the present embodiment 5 and the above-mentioned embodiments 1 and 4 have different concentrations of passivating agents.

[0100] Comparative Example 1

[0101] Provide crystalline silicon cells;

[0102] A transparent conductive layer is formed on one side of the crystalline silicon cell, the transparent conductive layer is an indium tin oxide (ITO) layer, and the thickness of the indium tin oxide (ITO) layer is 100 nm;

[0103] A hole transport layer is formed on one side of the indium tin oxide (ITO) layer, wherein the material of the hole transport layer is nickel oxide (NiOx) and the thickness is 20 nm;

[0104] A passivation layer is formed on the side of the hole transport layer away from the transparent conductive layer. The steps of forming the passivation layer are as follows: dissolving 6-bromohexyltriethylammonium bromide in a dimethyl sulfoxide solution to obtain a passivation solution with a concentration of 0.1 mg / ml, spin-coating the passivation solution to the side of the hole transport layer away from the transparent conductive layer by a spin-coating process at a spin-coating speed of 3000 rpm for 30 seconds, and annealing at an annealing temperature of 100°C for 10 minutes;

[0105] A perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer. The steps of forming the perovskite absorption layer are as follows: firstly, a perovskite precursor solution (mixed ion perovskite precursor solution of CsFAMA) is prepared, and the perovskite precursor solution is spin-coated to the side of the passivation layer away from the hole transport layer by a spin coating process with a spin coating speed of 3000 rpm and a spin coating time of 30 seconds;

[0106] An electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer. The material of the electron transport layer is methyl fullerene (PCBM) with a thickness of 20 nm.

[0107] A transparent electrode layer is formed on a side of the electron transport layer away from the perovskite absorption layer, wherein the material of the transparent electrode layer is an indium zinc oxide (IZO) layer with a thickness of 100 nm;

[0108] A metal electrode layer is formed on a side of the transparent electrode layer away from the electron transport layer. The material of the metal electrode layer is silver (Ag) and the thickness is 90 nm.

[0109] That is, the difference between Comparative Example 1 and Example 1 is that a passivator is added to the perovskite precursor solution in Example 1, while no passivator is added to the perovskite precursor solution in Comparative Example 1.

[0110] An Oriel 300W solar simulator with a spectrum distribution of AM1.5G and a light intensity of 100mw / cm2 was used as the light source to test the photoelectric performance of the devices obtained in the above embodiments and comparative examples. The effective area of ​​the battery was 0.01cm 2 The JV curve was measured by Keithly 2400 digital source meter, and the devices obtained in the above-mentioned Examples 1 to 5 and Comparative Example 1 were tested, and then the photoelectric performance test parameters shown in Table 1 were obtained:

[0111] Table 1

[0112]

[0113] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0114] First, a semiconductor substrate is provided, and one side of the semiconductor substrate has a hole transport layer, and then a passivation layer is formed on the side of the hole transport layer away from the semiconductor substrate, so that after the perovskite absorption layer is formed on the side of the passivation layer away from the hole transport layer, the passivation layer can adjust the interface energy level of the perovskite absorption layer. And because the perovskite in the perovskite absorption layer close to the passivation layer can also undergo a cross-linking reaction with the passivation material in the passivation layer and form a mixed layer, the crystallization quality of the perovskite absorption layer can be further improved. In addition, in the process of forming the above-mentioned perovskite absorption layer, since a passivator is also added to the perovskite precursor solution, the crystallization quality of the perovskite absorption layer can be improved simultaneously, so that the perovskite crystallization process can be regulated to obtain a perovskite absorption layer with a larger grain size and lower defects. Furthermore, since the materials of the passivation layer and the passivation agent can be the same, the present solution can use the same material to simultaneously improve the interface performance of the perovskite and the performance of the perovskite crystallization, that is, the purpose of improving the efficiency in both directions is achieved by using one material, and then an electron transport layer is formed on the side of the perovskite absorption layer away from the passivation layer, and an electrode layer is formed on the side of the electron transport layer away from the perovskite absorption layer. As can be seen from the above, when the perovskite battery is manufactured using the manufacturing method of the present application, the same material can be used to achieve the purpose of simultaneously improving the interface energy level and improving the performance of the perovskite crystallization, so as to achieve the purpose of improving the crystallization quality of the perovskite absorption layer, and realize the improvement of the bidirectional efficiency, so that the perovskite battery can have a faster production cycle, thereby increasing the output of the perovskite battery, and at the same time solving the problem of high production cost of the perovskite battery due to the long production cycle in the prior art.

[0115] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for manufacturing a perovskite battery, characterized in that: include: Providing a semiconductor substrate, wherein one side of the semiconductor substrate has a hole transport layer; forming a passivation layer on a side of the hole transport layer away from the semiconductor substrate; Coating a perovskite precursor solution added with a passivator on a side of the passivation layer away from the hole transport layer to form a perovskite absorption layer, wherein the material of the passivation layer is the same as the passivator; forming an electron transport layer on a side of the perovskite absorption layer away from the passivation layer; An electrode layer is formed on a side of the electron transport layer away from the perovskite absorption layer.

2. The method according to claim 1, characterized in that: The step of forming the passivation layer comprises: Dissolving the passivation material in an organic solvent to prepare a passivation solution; Applying the passivation solution to the side of the hole transport layer away from the semiconductor substrate to form a passivation precursor film; The passivation precursor film is thermally treated to form the passivation layer.

3. The method according to claim 2, characterized in that: The passivation precursor film is formed by a spin coating process, the spin coating speed of the spin coating process is 3000 rpm to 5000 rpm, and the spin coating time of the spin coating process is 30s to 40s.

4. The method according to claim 2, characterized in that: The concentration of the passivation solution is 0.1 mg / ml to 1 mg / ml.

5. The method according to any one of claims 1 to 4, characterized in that: The passivating agent is 6-bromohexyltriethylammonium bromide.

6. The method according to claim 5, characterized in that: The concentration of the passivating agent in the perovskite precursor solution is 0.1 mg / ml to 1 mg / ml.

7. A perovskite battery, characterized in that: The perovskite cell is manufactured by the manufacturing method of any one of claims 1 to 6, wherein the perovskite cell comprises a semiconductor substrate, a hole transport layer, a passivation layer, a perovskite absorption layer, an electron transport layer and an electrode layer stacked in sequence.

8. The perovskite cell according to claim 7, characterized in that: The thickness of the passivation layer is 10-15 nm.

9. A laminated battery, characterized in that: It comprises a first battery and a second battery which are stacked, and at least one of the first battery and the second battery is the perovskite battery according to claim 6 or 7.

10. The laminated battery according to claim 9, characterized in that: The first battery is a crystalline silicon battery, and the second battery is the perovskite battery.

Images