Perovskite light absorption layer, perovskite crystal silicon laminated cell, preparation method of perovskite crystal silicon laminated cell and photovoltaic module

Abstract

The invention relates to a perovskite light absorption layer, a perovskite crystal silicon laminated cell, a preparation method of the perovskite crystal silicon laminated cell and a photovoltaic module. The preparation method of the perovskite light absorption layer comprises the following steps: preparing an organic halide layer on a substrate by adopting an organic halide solution; preparing a first metal halide layer on the surface of the organic halide layer, and then performing first annealing treatment to form a perovskite intermediate layer; and forming an organic ammonium salt film layer on the surface, far away from the substrate, of the perovskite intermediate layer by adopting an organic ammonium salt solution, and preparing the perovskite absorption layer through second annealing treatment. The preparation method can promote complete reaction of the metal halide and effectively reduce the influence of the metal halide on the stable performance of the device, thereby effectively improving the stable performance of the device.

Description

Technical Field

[0001] The present application relates to the field of batteries, and in particular to a perovskite light-absorbing layer, a perovskite crystalline silicon stacked battery and a preparation method thereof, and a photovoltaic module. Background Art

[0002] Solar energy is a renewable energy source. Using photovoltaic cells to convert solar energy into electrical energy is one of the most effective ways to utilize solar energy. Among them, in halide perovskite solar cells, the formation of excessive lead iodide (PbI2) is not conducive to device stability. In the field of perovskite crystalline silicon stacked cells, in order to increase its short-circuit current density and promote its industrialization, the crystalline silicon bottom cell used has a 2 μm~5 μm velvet structure. The one-step solution method is no longer suitable for preparing high-quality perovskite films on large velvet crystalline silicon bottom cells. The evaporation + solution method has been developed as one of the methods for achieving conformal deposition of perovskites on commercial large velvet crystalline silicon cells. However, residual lead iodide is prone to appear at the bottom of the perovskite prepared by the traditional evaporation + solution method, which will lead to poor stability of the device. Therefore, it is necessary to improve the traditional technology. Summary of the invention

[0003] Based on this, the present application provides a perovskite light-absorbing layer with good stability, a perovskite crystalline silicon stacked cell and its preparation method, and a photovoltaic module.

[0004] The technical solution of this application to solve the above technical problems is as follows.

[0005] The first aspect of the present application provides a method for preparing a perovskite light absorbing layer, comprising the following steps:

[0006] preparing an organic halide layer on a substrate using an organic halide solution;

[0007] Preparing a first metal halide layer on the surface of the organic halide layer, and then performing a first annealing treatment to form a perovskite intermediate layer;

[0008] An organic ammonium salt film layer is formed on the surface of the perovskite intermediate layer away from the substrate using an organic ammonium salt solution, and a perovskite absorption layer is prepared through a second annealing treatment.

[0009] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the organic halide in the organic halide solution includes one or more of formamidine hydroiodide, formamidine hydrobromide, formamidine hydrochloride, tetraethylammonium chloride, propylenediamine iodide and phenethylammonium iodide.

[0010] In some of the embodiments, in the method for preparing the perovskite light-absorbing layer, the solvent in the organic halide solution includes one or more of dimethylamide, dimethyl sulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0011] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the concentration of the organic halide solution is 0.1 mg / mL to 10 mg / mL.

[0012] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the method for preparing the organic halide layer comprises one of spin coating, slit coating and blade coating.

[0013] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the perovskite intermediate layer includes a perovskite thin film layer and a second metal halide layer, the perovskite thin film layer is arranged between the substrate and the second metal halide layer, and the second metal halide layer is a porous metal halide layer.

[0014] In some embodiments, in the method for preparing the perovskite light absorbing layer, the preparation method satisfies at least one of the following characteristics:

[0015] (1) The temperature of the first annealing treatment is 150°C to 200°C, and the time is 2 min to 10 min;

[0016] (2) The temperature of the second annealing treatment is 150°C to 180°C, and the time is 20 min to 30 min.

[0017] In some embodiments, in the method for preparing the perovskite light absorbing layer, the preparation method satisfies at least one of the following characteristics:

[0018] (1) The method for preparing the first metal halide layer includes a thermal evaporation method with a deposition rate of 0.4 Å / s to 1.4 Å / s;

[0019] (2) The thickness of the first metal halide layer is 250 nm to 550 nm;

[0020] (3) The first metal halide layer includes one or more of lead iodide, lead bromide, lead chloride, cesium iodide, cesium bromide and cesium chloride.

[0021] In some embodiments, in the method for preparing the perovskite light absorbing layer, the preparation method satisfies at least one of the following characteristics:

[0022] (1) The method of forming the organic ammonium salt film layer independently includes one of a spin coating method, a slit coating method and a blade coating method;

[0023] (2) The organic ammonium salt solution includes one or more of methylammonium iodide, methylammonium bromide, methylammonium chloride, formamidine hydroiodide, formamidine hydrobromide, formamidine hydrochloride and methylammonium thiocyanate.

[0024] In some of the embodiments, in the method for preparing the perovskite light absorbing layer, the thickness of the perovskite light absorbing layer is 300 nm to 800 nm.

[0025] A second aspect of the present application provides a perovskite light absorbing layer, which is prepared using the above-mentioned method for preparing a perovskite light absorbing layer.

[0026] The third aspect of the present application provides a perovskite crystalline silicon stacked cell, comprising a suede crystalline silicon cell, the above-mentioned perovskite light-absorbing layer and a first conductive layer stacked in sequence.

[0027] A fourth aspect of the present application provides a method for preparing a perovskite crystalline silicon tandem cell, comprising the following steps:

[0028] Provide velvet crystalline silicon cells;

[0029] The perovskite light absorbing layer is prepared on one surface of the textured crystalline silicon cell by using the above-mentioned method for preparing the perovskite light absorbing layer;

[0030] A first conductive layer is prepared on the surface of the perovskite light-absorbing layer away from the textured crystalline silicon cell.

[0031] In a fifth aspect, the present application provides a photovoltaic module, comprising a perovskite light-absorbing layer, the above-mentioned perovskite crystalline silicon tandem cell, or a perovskite crystalline silicon tandem cell prepared by the preparation method of the above-mentioned perovskite crystalline silicon tandem cell.

[0032] Compared with the prior art, the preparation method of the perovskite light absorbing layer of the present application has the following beneficial effects:

[0033] The preparation method of the perovskite light-absorbing layer of the present application first uses an organic halide solution to prepare an organic halide layer, and then prepares a first metal halide layer on the surface of the organic halide layer. After the organic halide layer and the first metal halide layer are subjected to a first annealing treatment, the organic halide in the organic halide layer reacts with the metal halide in the first metal halide layer close to the organic halide layer to generate a perovskite thin film layer; the metal halide layer in the first metal halide layer that has not reacted with the first organic halide reacts with the organic ammonium salt in the organic ammonium salt film layer, so that the metal halide in the first metal halide layer reacts completely, effectively reducing the influence of the metal halide on the stability performance of the device, thereby effectively improving the stability performance of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0035] Figure 1 A schematic diagram of the structure of a perovskite crystalline silicon tandem cell provided in one embodiment.

[0036] Reference numerals:

[0037] 100: Perovskite crystalline silicon stacked cell; 101: Single crystal silicon substrate; 102: i-type a-Si:H layer; 103: n-type a-Si:H layer; 104: Second conductive transparent layer; 105: Second metal electrode layer; 106: i-type a-Si:H layer; 107: n-type a-Si:H layer; 108: Carrier recombination layer; 109: Hole transport layer; 110: Perovskite light absorption layer; 111: Passivation layer; 112: Electron transport layer; 113: Buffer layer; 114: First conductive transparent layer; 115: First metal electrode layer. DETAILED DESCRIPTION

[0038] References to embodiments of the present invention will now be provided in detail, one or more examples of which are described below. Each example is provided as an explanation rather than a limitation of the present invention. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the present invention. For example, a feature illustrated or described as part of one embodiment may be used in another embodiment to produce a further embodiment.

[0039] Therefore, it is intended that the present invention covers such modifications and variations that fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are obvious from the following detailed description. Those of ordinary skill in the art will appreciate that this discussion is only a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0041] The term "comprises", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment. In the absence of more restrictions, the elements defined by the sentence "comprising one..." do not exclude the presence of other identical elements in the process, method, article or equipment including the elements. The indefinite articles "a kind of" and "an" before the elements or components of the present invention are not restrictive to the quantity requirements (i.e., the number of occurrences) of the elements or components. Therefore, "a" or "a kind of" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the number clearly refers only to the singular form. The meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0042] The weight of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also indicate the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the description of the embodiments of the present invention, it is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0043] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to indicate the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the attached claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0044] The study found that directly evaporating metal halides on the surface of the hole transport layer, because the metal halide layer prepared by the evaporation process is relatively dense and not easily penetrated by the organic ammonium salt solution, the metal halide at the bottom is not easily completely reacted, resulting in poor device stability.

[0045] An embodiment of the present application provides a method for preparing a perovskite light absorbing layer, comprising the following steps:

[0046] Step S10: preparing an organic halide layer on a substrate using an organic halide solution.

[0047] In some of the examples, in step S10 , the organic halide in the organic halide solution includes an organic ammonium halide.

[0048] In some of the examples, in step S10, the organic halide in the organic halide solution includes one or more of formamidine hydroiodide (FAI), formamidine hydrobromide (FABr), formamidine hydrochloride (FACl), tetraethylammonium chloride (TEACl), propylenediamine iodide (PDADI) and phenethylammonium iodide (PEAI).

[0049] In some of the examples, in step S10 , the solvent in the organic halide solution includes one or more of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP).

[0050] In some of the examples, in step S10, the concentration of the organic halide solution is 0.1 mg / mL to 10 mg / mL.

[0051] It will be appreciated that the concentration of the organic halide solution includes, but is not limited to, 0.1 mg / mL, 0.5 mg / mL, 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, and 10 mg / mL; in some examples, the concentration may be within a range consisting of any two of these point values ​​as end values, the same below.

[0052] Optionally, the concentration of the organic halide solution is 1 mg / mL to 10 mg / mL.

[0053] Furthermore, the concentration of the organic halide solution is 1 mg / mL to 5 mg / mL.

[0054] It can be understood that the method for preparing the organic halide layer is a solution method.

[0055] In some of the examples, in step S10, the method of preparing the organic halide layer includes one of spin coating, slit coating and blade coating.

[0056] Optionally, for a small substrate, a spin coating method or a scraping method is used; for example, for a 2.5cm*2.5cm substrate, the amount of the organic halide solution used by the spin coating method is 100 μL~200 μL, and the amount used by the scraping method is 3 μL~10 μL. For a large substrate, a slit coating method is used, for example, for a 10cm*10cm substrate, the amount of the organic halide solution used by the spin coating method is 50 μL~100 μL.

[0057] In some examples, in step S10 , the substrate is a suede substrate.

[0058] Step S20: preparing a first metal halide layer on the surface of the organic halide layer, and then performing a first annealing treatment to form a perovskite intermediate layer.

[0059] It can be understood that step S20 includes step S21 and step S22:

[0060] Step S21: preparing a first metal halide layer on the surface of the organic halide layer.

[0061] In some examples, in step S21, the first metal halide layer includes Pb 2+ and Cs + At least one of .

[0062] In some of the examples, in step S21, the first metal halide layer includes one or more of lead iodide (PbI2), lead bromide (PbBr2), lead chloride (PbCl2), cesium iodide (CsI), cesium bromide (CsBr), and cesium chloride (CsCl).

[0063] In some of the examples, in step S21, the thickness of the first metal halide layer is 250 nm to 550 nm.

[0064] It can be understood that the thickness of the first metal halide layer includes but is not limited to 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, and 550 nm.

[0065] In some of the examples, in step S21 , the method of preparing the first metal halide layer includes thermal evaporation.

[0066] In some of the examples, in step S21, the deposition rate of the thermal evaporation method is 0.4 Å / s to 1.4 Å / s.

[0067] It is understood that the deposition rate of the thermal evaporation method includes but is not limited to 0.4 Å / s, 0.5 Å / s, 0.6 Å / s, 0.8 Å / s, 1 Å / s, 1.1 Å / s, 1.2 Å / s, 1.3 Å / s, and 1.4 Å / s.

[0068] Optionally, in the step of preparing the first metal halide layer by thermal evaporation, Pb 2+ The deposition rate is 1 Å / s ~1.4 Å / s, and the evaporated Cs + The deposition rate is 0.4 Å / s ~0.6 Å / s,

[0069] By controlling the deposition rate, the adhesion properties of the first metal halide layer are ensured.

[0070] Step S22: subjecting the organic halide layer and the first metal halide layer prepared in step S21 to a first annealing treatment to form a perovskite intermediate layer.

[0071] In some of the examples, in step S22, the perovskite intermediate layer includes a perovskite thin film layer and a second metal halide layer, and the perovskite thin film layer is disposed between the substrate and the second metal halide layer.

[0072] It can be understood that after the organic halide layer and the first metal halide layer are subjected to the first annealing treatment, the organic halide in the organic halide layer reacts with the metal halide in the first metal halide layer close to the organic halide layer to generate a perovskite thin film layer, and the second metal halide layer is the remaining metal halide layer in the first metal halide layer that has not reacted with the organic halide.

[0073] In some of the examples, in step S22 , the second metal halide layer is a porous metal halide layer.

[0074] It can be understood that in some of the examples, the organic halide solution in step S10 includes a solvent that can dissolve the metal halide in the first metal halide layer, and the solvent is volatilized during the first annealing treatment, so that the remaining metal halide layer that has not reacted with the organic halide is porous, thereby preparing a porous inorganic framework layer (second metal halide layer). It can be further understood that the above-mentioned specific types of dimethylamide, dimethyl sulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone can achieve the preparation of a porous metal halide layer.

[0075] In some of the examples, in step S22, the temperature of the first annealing treatment is 150°C to 200°C, and the time is 2 min to 10 min.

[0076] It can be understood that the temperature of the first annealing treatment includes but is not limited to 150°C, 160°C, 170°C, 180°C, 190°C, and 200°C, and the time includes but is not limited to 2 min, 3 min, 5 min, 8 min, and 10 min.

[0077] Step S30: forming an organic ammonium salt film layer on the surface of the perovskite intermediate layer away from the substrate using an organic ammonium salt solution, and performing a second annealing treatment to prepare a perovskite absorption layer.

[0078] The preparation method of the perovskite light-absorbing layer of the present application first uses an organic halide solution to prepare an organic halide layer, and then prepares a first metal halide layer on the surface of the organic halide layer. After the organic halide layer and the first metal halide layer are subjected to a first annealing treatment, the organic halide in the organic halide layer reacts with the metal halide in the first metal halide layer close to the organic halide layer to generate a perovskite thin film layer; the metal halide layer in the first metal halide layer that has not reacted with the first organic halide reacts with the organic ammonium salt in the organic ammonium salt film layer, so that the metal halide in the first metal halide layer reacts completely, effectively reducing the influence of the metal halide on the stability performance of the device, thereby effectively improving the stability performance of the device.

[0079] It can be understood that the perovskite absorption layer prepared in step S30 includes the perovskite thin film layer prepared in step S22 and the perovskite thin film layer obtained by reacting the second metal halide layer with the organic ammonium salt in the organic ammonium salt film layer in step S30.

[0080] In some examples, in step S30, the temperature of the second annealing treatment is 150° C. to 180° C., and the time is 20 min to 30 min.

[0081] It can be understood that the temperature of the second annealing treatment includes but is not limited to 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, and 180°C, and the time includes but is not limited to 20 min, 23 min, 25 min, 28 min, and 30 min.

[0082] In some of the examples, in step S30, the method of forming the organic ammonium salt film layer independently includes one of spin coating, slit coating and blade coating.

[0083] In some of the examples, in step S30, the organic ammonium salt solution includes one or more of methylammonium iodide (MAI), methylammonium bromide (MABr), methylammonium chloride (MACl), formamidine hydroiodide (FAI), formamidine hydrobromide (FABr), formamidine hydrochloride (FACl) and methylammonium thiocyanate (MASCN).

[0084] In some of the examples, in step S30, the thickness of the perovskite light absorbing layer is 300 nm to 800 nm.

[0085] It can be understood that the thickness of the perovskite light absorbing layer includes but is not limited to 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, and 800 nm.

[0086] Before preparing the metal halide layer, the present application first prepares the organic halide layer by solution method, reacts the metal halide at the bottom which is not easily reacted, and evaporates the high boiling point solvent which is easy to dissolve the metal halide by heating to prepare the porous inorganic framework layer (second metal halide layer). At the same time, the organic halide layer introduced can passivate the buried interface of the perovskite, reduce defects, promote carrier transport, and improve the photoelectric conversion performance of the device.

[0087] One embodiment of the present application provides a perovskite light absorbing layer, which is prepared by the above-mentioned method for preparing a perovskite light absorbing layer.

[0088] One embodiment of the present application provides the use of the above-mentioned perovskite light-absorbing layer in the preparation of a perovskite battery.

[0089] One embodiment of the present application provides a perovskite cell, comprising the above-mentioned perovskite light-absorbing layer.

[0090] One embodiment of the present application provides the use of the above-mentioned perovskite light-absorbing layer or the above-mentioned perovskite perovskite cell in the preparation of a stacked cell.

[0091] An embodiment of the present application provides a perovskite crystalline silicon stacked cell, comprising a suede crystalline silicon cell, the above-mentioned perovskite light-absorbing layer and a first conductive layer stacked in sequence.

[0092] Using the above-mentioned perovskite light-absorbing layer in the perovskite crystalline silicon tandem cell can give the perovskite crystalline silicon tandem cell better stability and conversion efficiency performance.

[0093] In some of these examples, in perovskite crystalline silicon tandem cells, the crystalline silicon bottom cell has a 2 μm~5 μm velvet structure.

[0094] In some of the examples, in the perovskite crystalline silicon tandem cell, the first conductive layer includes a first conductive transparent layer and a first metal electrode layer, and the first conductive transparent layer is disposed between the perovskite light absorbing layer and the first metal electrode layer.

[0095] Optionally, the first conductive transparent layer includes at least one of indium tin oxide (ITO), indium zinc oxide (IZO) and aluminum zinc oxide (AZO).

[0096] Optionally, the first metal electrode layer includes at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al) and carbon (C).

[0097] In some of the examples, in the perovskite crystalline silicon stacked cell, the textured crystalline silicon cell includes a stacked single crystal silicon substrate, an i-type a-Si:H layer, an n-type a-Si:H layer, a second conductive transparent layer, and a second metal electrode layer.

[0098] Optionally, the second conductive transparent layer includes at least one of indium tin oxide (ITO), indium zinc oxide (IZO) and aluminum zinc oxide (AZO).

[0099] Optionally, the second metal electrode layer includes at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al) and carbon (C).

[0100] In some of the examples, in the perovskite crystalline silicon tandem cell, the perovskite crystalline silicon tandem cell further includes a hole transport layer and an electron transport layer, the hole transport layer is arranged between the suede crystalline silicon cell and the perovskite light absorbing layer, and the electron transport layer is arranged between the perovskite light absorbing layer and the first conductive layer.

[0101] In some of the examples, in the perovskite crystalline silicon tandem cell, the hole transport layer includes but is not limited to at least one of [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) and [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB).

[0102] In some of these examples, in the perovskite silicon tandem cell, the electron transport layer includes at least one of fullerene and its derivatives.

[0103] It can be understood that fullerene and its derivatives include but are not limited to at least one of C60, C70 and PCBM.

[0104] In some of the examples, in the perovskite crystalline silicon tandem cell, the perovskite crystalline silicon tandem cell further includes a carrier recombination layer, and the carrier recombination layer is arranged between the suede crystalline silicon cell and the hole transport layer.

[0105] In some of these examples, in the perovskite crystalline silicon tandem cell, the carrier recombination layer includes an ITO recombination layer.

[0106] In some of the examples, the perovskite crystalline silicon tandem cell further includes a passivation layer, which is disposed between the perovskite light absorbing layer and the electron transport layer.

[0107] In some of the examples, in the perovskite crystalline silicon tandem cell, the passivation layer includes but is not limited to at least one of propylenediamine iodide, propylenediamine bromide (PDADBr), butylammonium chloride (BACl), butylammonium bromide (BABr), butylammonium iodide (BAI), N,N-dimethyl-1,3-propylenediamine hydrochloride (DMePDADCl), dodecanediaminium bromide (DDDADBr), magnesium fluoride, lithium fluoride (LiF), sodium fluoride (NaF), etc.

[0108] In some of the examples, in the perovskite crystalline silicon tandem cell, the perovskite crystalline silicon tandem cell further includes a buffer layer, and the buffer layer is disposed between the electron transport layer and the first conductive layer.

[0109] In some of these examples, in the perovskite crystalline silicon tandem cell, the buffer layer includes at least one of bathocuproine (BCP) and tin dioxide (SnO2).

[0110] See also Figure 1 In some examples, a perovskite crystalline silicon stacked cell 100 is provided, including a single crystal silicon substrate 101, an i-type a-Si:H layer 102, an n-type a-Si:H layer 103, a second conductive transparent layer 104, and a second metal electrode layer 105, which are sequentially arranged on the back side of the single crystal silicon substrate 101, and an i-type a-Si:H layer 106, an n-type a-Si:H layer 107, a carrier recombination layer 108, a hole transport layer 109, a perovskite light absorption layer 110, a passivation layer 111, an electron transport layer 112, a buffer layer 113, a first conductive transparent layer 114, and a first metal electrode layer 115, which are sequentially arranged on the front side of the single crystal silicon substrate 101.

[0111] An embodiment of the present application provides a method for preparing a perovskite crystalline silicon stacked cell, comprising the following steps:

[0112] Provide velvet crystalline silicon cells;

[0113] The perovskite light absorbing layer is prepared on one surface of the textured crystalline silicon cell by using the above-mentioned method for preparing the perovskite light absorbing layer;

[0114] The first conductive layer is sequentially prepared on the surface of the perovskite light-absorbing layer away from the textured crystalline silicon cell.

[0115] The preparation method of the above-mentioned perovskite crystalline silicon stacked battery uses the above-mentioned preparation method of the perovskite light-absorbing layer to prepare a perovskite light-absorbing layer on one surface of a suede crystalline silicon battery, which can effectively promote the complete reaction of metal halides and reduce the impact of metal halides on the stability performance of the device, thereby effectively improving the stability performance of the device.

[0116] In some of the examples, the method for preparing the perovskite crystalline silicon tandem cell includes the following steps:

[0117] Provide velvet crystalline silicon cells;

[0118] An organic halide solution is used to prepare an organic halide layer on the surface of a textured crystalline silicon cell;

[0119] Prepare a first metal halide layer on the surface of the organic halide layer away from the textured crystalline silicon cell;

[0120] The organic halide layer and the first metal halide layer are subjected to a first annealing treatment to form a perovskite intermediate layer; the perovskite intermediate layer comprises a perovskite thin film layer and a second metal halide layer, and the perovskite thin film layer is arranged between the suede crystalline silicon cell and the second metal halide layer;

[0121] After an organic ammonium salt solution is disposed on the surface of the second metal halide layer away from the perovskite thin film layer, a perovskite absorption layer is formed on the surface of the textured crystalline silicon cell through a second annealing treatment;

[0122] The first conductive layer is sequentially prepared on the surface of the perovskite light-absorbing layer away from the textured crystalline silicon cell.

[0123] See also Figure 1 In some of these examples, the method for preparing the perovskite crystalline silicon tandem cell includes the following steps:

[0124] Step S200: providing a textured silicon substrate 101 .

[0125] Step S210: depositing an i-type a-Si:H layer 106 and an n-type a-Si:H layer 107 in sequence on the front surface of the textured silicon substrate.

[0126] Step S220: depositing an i-type a-Si:H layer 102 and an n-type a-Si:H layer 103 in sequence on the back side of the textured silicon substrate.

[0127] Optionally, in step S210 and step S220, the deposition temperatures for depositing the i-type a-Si:H layer and the n-type a-Si:H layer are independently 100°C to 300°C; optionally, the thicknesses of the i-type a-Si:H layer and the n-type a-Si:H layer are independently 1 nm to 10 nm; optionally, the methods for depositing the i-type a-Si:H layer and the n-type a-Si:H layer independently include but are not limited to PECVD.

[0128] Step S230 : depositing a second transparent conductive layer 104 and a second metal electrode 105 in sequence on a surface of the n-type a-Si:H layer 103 prepared in step S220 away from the i-type a-Si:H layer 102 .

[0129] Optionally, in step S230, a method of depositing the second transparent conductive layer includes but is not limited to a magnetron sputtering method.

[0130] Optionally, in step S230, a method of depositing the second metal electrode includes but is not limited to a thermal evaporation method.

[0131] Step S240 : depositing a carrier recombination layer 108 on a surface of the n-type a-Si:H layer 107 prepared in step S210 away from the i-type a-Si:H layer 106 .

[0132] Optionally, in step S240, a method of depositing the carrier recombination layer includes but is not limited to a magnetron sputtering method.

[0133] Step S250 : depositing a hole transport layer 109 on the surface of the carrier recombination layer 108 prepared in step S240 away from the n-type a-Si:H layer 107 .

[0134] Optionally, in step S250, the method of depositing the hole transport layer includes but is not limited to spin coating.

[0135] Step S260: using an organic halide solution to prepare an organic halide layer on the surface of the hole transport layer 109 away from the carrier recombination layer 108;

[0136] Preparing a first metal halide layer on a surface of the organic halide layer away from the hole transport layer;

[0137] The organic halide layer and the first metal halide layer are subjected to a first annealing treatment to form a perovskite intermediate layer; the perovskite intermediate layer comprises a perovskite thin film layer and a second metal halide layer, and the perovskite thin film layer is disposed between the hole transport layer and the second metal halide layer;

[0138] After an organic ammonium salt solution is disposed on the surface of the second metal halide layer away from the perovskite thin film layer, a perovskite absorption layer 110 is formed on the surface of the hole transport layer 109 through a second annealing treatment;

[0139] Step S270: sequentially preparing a passivation layer 111 , an electron transport layer 112 , a buffer layer 113 , a first conductive transparent layer 114 and a first metal electrode layer 115 on a surface of the perovskite light absorbing layer 110 away from the hole transport layer 109 .

[0140] Optionally, in step S270, the method of preparing the passivation layer includes but is not limited to thermal evaporation.

[0141] Optionally, in step S270, the method of preparing the electron transport layer includes but is not limited to thermal evaporation.

[0142] Optionally, in step S270, the method of preparing the buffer layer includes but is not limited to ALD deposition method.

[0143] Optionally, in step S270, the method of preparing the first conductive transparent layer includes but is not limited to magnetron sputtering.

[0144] Optionally, in step S270, the method of preparing the first metal electrode layer includes but is not limited to thermal evaporation.

[0145] One embodiment of the present application provides a photovoltaic module, including the above-mentioned perovskite crystalline silicon tandem cell or the perovskite crystalline silicon tandem cell prepared by the preparation method of the above-mentioned perovskite crystalline silicon tandem cell.

[0146] It can be understood that photovoltaic modules can be used in photovoltaic power stations, such as ground power stations, rooftop power stations, water power stations, etc., and can also be used in equipment or devices that use solar energy to generate electricity, such as user solar power supplies, solar street lights, solar cars, solar buildings, etc. It can also be understood that the application scenarios of photovoltaic systems include but are not limited to this, that is, photovoltaic systems can be used in all fields that require solar energy to generate electricity. Taking the photovoltaic power generation system network as an example, the photovoltaic system may include a photovoltaic array, a junction box and an inverter. The photovoltaic array can be an array combination of multiple photovoltaic modules. For example, multiple photovoltaic modules can form multiple photovoltaic arrays. The photovoltaic array is connected to the junction box. The junction box can converge the current generated by the photovoltaic array. The converged current flows through the inverter and is converted into the alternating current required by the mains power grid, and then connected to the mains network to achieve solar power supply.

[0147] The photovoltaic module provided in the present application can be used in, but is not limited to, electrical devices such as vehicles, ships or aircraft.

[0148] The embodiments of the present application provide an electric device, which may be, but is not limited to, a mobile phone, a tablet, a laptop, an electric toy, an electric tool, a battery car, an electric car, a ship, a spacecraft, etc. Among them, the electric toy may include a fixed or mobile electric toy, such as a game console, an electric car toy, an electric ship toy, and an electric airplane toy, etc., and the spacecraft may include an airplane, a rocket, a space shuttle, and a spacecraft, etc.

[0149] The present application is further described in detail below in conjunction with specific implementation methods, but the implementation methods of the present application are not limited thereto.

[0150] Example 1

[0151] (1) A 150 μm thick n-type polished silicon wafer was selected and placed in a KOH solution at 85°C for texturing. Then, standard RCA cleaning was performed to remove surface organic matter and metal ions to obtain a single crystal silicon substrate with a texture size of 2-5 μm.

[0152] (2) Using PECVD to deposit a 5 nm i-type a-Si:H layer and a 5 nm n-type a-Si:H layer on the front side of the single crystal silicon substrate at a deposition temperature of 200°C;

[0153] (3) Using PECVD to deposit a 5 nm i-type a-Si:H layer and a 5 nm n-type a-Si:H layer on the back side of a single crystal silicon substrate at a deposition temperature of 180°C;

[0154] (4) Deposit an ITO transparent conductive layer on the back side by magnetron sputtering with a thickness of 200 nm, and then deposit a silver electrode by thermal evaporation with a thickness of 200 nm;

[0155] (5) Deposit an ITO composite layer on the front side by magnetron sputtering with a thickness of 20 nm;

[0156] (6) Prepare the Me0-2PACz hole transport layer by spin coating with a thickness of about 1-5 nm;

[0157] (7) Spin coating an organic halide solution (FAI DMSO solution) with a concentration of 1 mg / mL on the hole transport layer by a spin coating method to prepare an organic halide layer;

[0158] (8) The first metal halide layer of PbI2 and CsBr was simultaneously deposited by evaporation, with the deposition rate of PbI2 being 1.2 Å / s and the deposition rate of CsBr being 0.5 Å / s;

[0159] After the first annealing treatment, a perovskite intermediate layer is prepared. The temperature of the first annealing treatment is 130°C to 150°C, the time is 5 min, and the thickness is 400 nm.

[0160] (9) Spin coating an organic ammonium salt solution (FAI, FABr, MACl, and MASCN in IPA in a mass ratio of 1:0.73:0.1:0.13) on the first metal halide layer by a spin coating method, and then performing a second annealing treatment to prepare a perovskite light absorbing layer (Cs 0.1 MA 0.15 FA 0.75 PbI 2.4 Br 0.6 ), the second annealing temperature is 150℃, the time is 20 min, the band gap of the perovskite light absorbing layer is about 1.68 eV, and the thickness is about 550 nm;

[0161] (10) The LiF passivation layer is deposited by thermal evaporation with a thickness of about 1 nm to 2 nm;

[0162] (11) A C60 electron transport layer was deposited by thermal evaporation with a thickness of 15 nm;

[0163] (12) A SnO2 buffer layer was deposited by ALD with a thickness of 20 nm;

[0164] (13) The IZO transparent conductive layer was deposited by magnetron sputtering with a thickness of 50 nm;

[0165] (14) Thermal evaporation was used to deposit silver electrodes with a thickness of 500 nm to produce perovskite crystalline silicon stacked cells.

[0166] Example 2

[0167] The method is basically the same as Example 1, except that in step (7), the concentration of the organic halide solution is 5 mg / mL.

[0168] Example 3

[0169] The method is basically the same as Example 1, except that in step (7), the concentration of the organic halide solution is 10 mg / mL.

[0170] Example 4

[0171] The method is basically the same as Example 1, except that in step (7), the concentration of the organic halide solution is 0.1 mg / mL.

[0172] Example 5

[0173] The method is basically the same as Example 1, except that in step (7), the organic halide solution is a DMF solution of FAI.

[0174] Example 6

[0175] The method is basically the same as Example 1, except that in step (7), the organic halide solution is a DMSO solution of PEAI (phenethylammonium iodide).

[0176] Comparative Example 1

[0177] The method is basically the same as Example 1, except that step (7) of Example 1 is omitted in Comparative Example 1, and a first metal halide layer of PbI2 and CsBr is directly evaporated on the hole transport layer.

[0178] Comparative Example 2

[0179] The method is basically the same as Example 1, except that in step (7), FAI is evaporated on the hole transport layer by an evaporation method to prepare an organic halide layer.

[0180] The perovskite crystalline silicon stacked cells prepared in each embodiment and comparative example were subjected to performance tests of open circuit voltage, short circuit current density, fill factor and energy conversion efficiency. The IV curve was used for the test. The test conditions were: AM 1.5G standard solar spectrum, irradiance of 1000W / m 2 The experimental test results are shown in Table 1. PCE represents the energy conversion efficiency in %, Voc represents the open circuit voltage in V, and Jsc represents the short circuit current density in mA / cm 2 , FF stands for fill factor, the unit is %.

[0181] The stability performance test of the perovskite crystalline silicon stacked cells prepared in each embodiment and comparative example was carried out, and the retention rate = energy conversion efficiency after running for 720 hours / initial energy conversion efficiency. The results are shown in Table 1.

[0182] Table 1

[0183]

[0184] As can be seen from Table 1, depositing an organic halide layer on the buried interface using a solution method using an organic halide solution can significantly improve the performance of the stacked battery, wherein when the concentration of the organic halide solution is 1 mg / mL, the battery performance is relatively better; Comparative Example 2 uses an evaporation method to deposit an organic halide layer, which has limited improvement on battery performance.

[0185] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0186] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. A method for preparing a perovskite light-absorbing layer, It is characterized in that The following steps are involved: preparing an organic halide layer on a substrate using an organic halide solution; Preparing a first metal halide layer on the surface of the organic halide layer, and then performing a first annealing treatment to form a perovskite intermediate layer; An organic ammonium salt film layer is formed on the surface of the perovskite intermediate layer away from the substrate using an organic ammonium salt solution, and a perovskite absorption layer is prepared through a second annealing treatment.

2. The preparation method according to claim 1, It is characterized in that The organic halide in the organic halide solution includes one or more of formamidine hydroiodide, formamidine hydrobromide, formamidine hydrochloride, tetraethylammonium chloride, propylenediamine iodide and phenethylammonium iodide.

3. The preparation method according to claim 1, It is characterized in that The solvent in the organic halide solution includes one or more of dimethylamide, dimethyl sulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.

4. The preparation method according to claim 1, It is characterized in that The concentration of the organic halide solution is 0.1 mg / mL to 10 mg / mL.

5. The preparation method according to claim 1, It is characterized in that The method of preparing the organic halide layer includes one of a spin coating method, a slit coating method and a blade coating method.

6. The preparation method according to claim 1, It is characterized in that The perovskite intermediate layer includes a perovskite thin film layer and a second metal halide layer. The perovskite thin film layer is disposed between the substrate and the second metal halide layer. The second metal halide layer is a porous metal halide layer.

7. The preparation method according to any one of claims 1 to 6, It is characterized in that The preparation method meets at least one of the following characteristics: (1) The temperature of the first annealing treatment is 150°C to 200°C, and the time is 2 min to 10 min; (2) The temperature of the second annealing treatment is 150°C to 180°C, and the time is 20 min to 30 min.

8. The preparation method according to any one of claims 1 to 6, It is characterized in that The preparation method meets at least one of the following characteristics: (1) The method for preparing the first metal halide layer includes a thermal evaporation method with a deposition rate of 0.4 Å / s to 1.4 Å / s; (2) The thickness of the first metal halide layer is 250 nm to 550 nm; (3) The first metal halide layer includes one or more of lead iodide, lead bromide, lead chloride, cesium iodide, cesium bromide and cesium chloride.

9. The preparation method according to any one of claims 1 to 6, It is characterized in that The preparation method meets at least one of the following characteristics: (1) The method of forming the organic ammonium salt film layer includes one of a spin coating method, a slit coating method and a blade coating method; (2) The organic ammonium salt solution includes one or more of methylammonium iodide, methylammonium bromide, methylammonium chloride, formamidine hydroiodide, formamidine hydrobromide, formamidine hydrochloride and methylammonium thiocyanate.

10. The preparation method according to any one of claims 1 to 6, It is characterized in that The thickness of the perovskite light-absorbing layer is 300 nm to 800 nm.

11. A perovskite light absorbing layer, It is characterized in that The method is prepared according to any one of claims 1 to 10.

12. A perovskite crystalline silicon tandem battery, It is characterized in that It comprises a textured crystalline silicon cell, a perovskite light-absorbing layer as claimed in claim 11 and a first conductive layer which are stacked in sequence.

13. A method for preparing a perovskite crystalline silicon stacked cell, It is characterized in that The following steps are involved: Provide velvet crystalline silicon cells; The perovskite light absorbing layer is prepared on one surface of the textured crystalline silicon cell by using the method for preparing the perovskite light absorbing layer according to any one of claims 1 to 10; A first conductive layer is prepared on the surface of the perovskite light-absorbing layer away from the textured crystalline silicon cell.

14. A photovoltaic module, It is characterized in that A perovskite crystalline silicon tandem battery comprising the perovskite light-absorbing layer as claimed in claim 11, the perovskite crystalline silicon tandem battery as claimed in claim 12, or a perovskite crystalline silicon tandem battery prepared by the preparation method of the perovskite crystalline silicon tandem battery as claimed in claim 13.

Images