Perovskite / crystalline silicon laminated solar cell structure taking tin dioxide thin film as composite layer and preparation method of perovskite / crystalline silicon laminated solar cell structure

Abstract

The invention relates to a perovskite / crystalline silicon laminated solar cell structure taking a tin dioxide thin film as a composite layer and a preparation method of the perovskite / crystalline silicon laminated solar cell structure, and belongs to the technical field of photovoltaics. According to the perovskite / crystalline silicon laminated solar cell structure, the tin dioxide thin film is used as a composite layer, so that the cost of cell preparation is reduced; in the preparation method of the perovskite / crystalline silicon laminated solar cell, the composite layer and the electron transport layer can adopt the same preparation method, so that the equipment cost in the preparation process is reduced; the perovskite / crystalline silicon laminated solar cell obtained by the cell structure and the preparation method provided by the invention is relatively low in preparation cost and relatively high in photoelectric conversion efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of photovoltaics, and in particular relates to a perovskite / crystalline silicon stacked solar cell structure with a tin dioxide film as a composite layer and a preparation method thereof. Background Art

[0002] Due to the wide energy distribution of the solar spectrum, single-junction solar cells cannot fully utilize sunlight. Creating a tandem cell structure can increase the range of sunlight absorption and improve sunlight utilization, offering an effective way to boost solar cell photoelectric conversion efficiency and surpass the theoretical limits of single-junction solar cells. Among common tandem cell structures, perovskite / crystalline silicon tandem cells have attracted considerable attention in the photovoltaic device field due to their high photoelectric conversion efficiency and low production costs.

[0003] Perovskite / crystalline silicon tandem solar cells consist of a perovskite top cell and a crystalline silicon bottom cell, connected in series via a tunneling composite layer. Currently, the tunneling composite layer used in perovskite / crystalline silicon tandem solar cells is primarily made of indium-based transparent conductive oxides, which are expensive to manufacture.

[0004] Tin dioxide has a high work function, low cost, and good transmittance, making it a promising candidate for use as a composite layer in perovskite / crystalline silicon tandem solar cells. Furthermore, various methods exist for preparing tin dioxide materials, including magnetron sputtering, solution deposition, and reactive plasma deposition, all of which can yield uniform, high-quality tin dioxide films. Summary of the Invention

[0005] The purpose of the present invention is to provide a novel perovskite / crystalline silicon tandem solar cell structure and its preparation method, that is, a perovskite / crystalline silicon tandem solar cell structure with a tin dioxide thin film as a composite layer and its preparation method, which solves the problem of high preparation cost of existing perovskite crystalline silicon tandem solar cells.

[0006] In order to achieve the above-mentioned purpose, the present invention provides a perovskite / crystalline silicon stacked solar cell structure with a tin dioxide thin film as a composite layer, comprising a crystalline silicon bottom cell and a perovskite top cell, wherein a tin dioxide thin film is provided between the crystalline silicon bottom cell and the perovskite top cell as a tunneling composite layer.

[0007] The perovskite / crystalline silicon tandem solar cell is a formal tandem structure. Its specific structure from top to bottom is: light-receiving side electrode silver grid line, first transparent conductive layer, hole transport layer, perovskite light absorption layer, electron transport layer, tin dioxide composite layer, P-type doped silicon hole transport layer, first intrinsic amorphous silicon passivation layer, N-type single crystal silicon layer, second intrinsic amorphous silicon passivation layer, N-type doped silicon electron transport layer, second transparent conductive layer and backlight side silver electrode. See the attached structural diagram Figure 1 .

[0008] The first transparent conductive layer and the second transparent conductive layer are indium oxide-based transparent conductive oxide materials, and are made of one or more materials selected from indium tin oxide (ITO), indium tungsten oxide (IWO), indium zinc oxide (IZO) or indium cerium oxide (ICO).

[0009] The hole transport layer is a P-type semiconductor material, and is made of one or more materials selected from molybdenum oxide, nickel oxide, 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), and poly(3-hexylthiophene-2,5-diyl) (P3HT).

[0010] The electron transport layer is a tin dioxide thin film, and by controlling the preparation parameters of the growth process, the performance different from that of the tunneling composite layer is obtained.

[0011] The first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer are intrinsic amorphous silicon passivation layers on the light-receiving side and the backlight side respectively.

[0012] The present invention provides a method for preparing a perovskite / crystalline silicon tandem solar cell with a tin dioxide thin film as a composite layer, comprising the following steps: Step 1: Select N type <100> The CZ silicon wafer is used as the substrate and immersed in hydrofluoric acid to remove the surface oxide layer and obtain the N-type single crystal silicon layer in the battery structure.

[0013] Step 2: Take the silicon wafer prepared in step 1 and use plasma enhanced chemical vapor deposition (PECVD) to prepare intrinsic amorphous silicon passivation layers on the light-receiving side and the backlight side of the silicon wafer, which are the first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer respectively.

[0014] Step 3: Take the silicon wafer prepared in step 2 and, on the first intrinsic amorphous silicon passivation layer on the light-receiving surface, also use PECVD technology to prepare a P-type doped silicon hole transport layer thereon.

[0015] Step 4: Take the silicon wafer prepared in step 3 and prepare an N-type doped silicon electron transport layer on the second intrinsic amorphous silicon passivation layer on the backlight side using PECVD technology.

[0016] Step 5: Take the silicon wafer prepared in step 4 and grow a tin dioxide composite layer and an electron transport layer on the P-type doped silicon hole transport layer.

[0017] Step 6: Take the sample with the electron transport layer prepared in step 5, prepare a perovskite film on it using a spin coating method, and obtain a perovskite light absorbing layer after annealing at 100-120°C.

[0018] Step 7: Take the sample of the perovskite light absorbing layer prepared in step 6, and prepare a hole transport layer thereon using a spin coating method.

[0019] Step 8: Take the sample prepared in step 7 and grow a first transparent conductive layer and a second transparent conductive layer thereon using reactive plasma deposition (RPD) technology.

[0020] Step 9: Take the sample prepared in step 8 and use thermal evaporation technology to prepare light-receiving side electrode silver grid lines and backlight side silver electrodes.

[0021] The preparation methods of the tin dioxide composite layer and the electron transport layer in step 5 include magnetron sputtering, spin coating, atomic layer deposition, reactive plasma deposition, etc.

[0022] The perovskite / crystalline silicon tandem solar cell structure with a tin dioxide film as a composite layer and the preparation method thereof proposed in the present invention have the following advantages: (1) The present invention uses tin dioxide as the tunneling composite layer of the perovskite / crystalline silicon stacked solar cell structure, which has low preparation cost, good film uniformity, high visible light transmittance, and a large number of recombination centers; (2) In the perovskite / crystalline silicon tandem solar cell structure of the present invention, the tin dioxide composite layer and the electron transport layer can be prepared in the same manner, saving equipment costs; (3) The perovskite / crystalline silicon stacked solar cell prepared by the method of the present invention using a tin dioxide thin film as a composite layer has a low preparation cost and a high photoelectric conversion efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic diagram of the structure of a perovskite / crystalline silicon tandem solar cell with a tin dioxide film as the composite layer; Figure 1 In the figure, 1 is the silver grid line of the light-receiving surface electrode, 2 is the first transparent conductive layer, 3 is the hole transport layer, 4 is the perovskite light absorption layer, 5 is the electron transport layer, 6 is the tin dioxide composite layer, 7 is the P-type doped silicon hole transport layer, 8 is the first intrinsic amorphous silicon passivation layer, 9 is the N-type single crystal silicon layer, 10 is the second intrinsic amorphous silicon passivation layer, 11 is the N-type doped silicon electron transport layer, 12 is the second transparent conductive layer, and 13 is the backlight silver electrode.

[0024] Figure 2 This is the IV curve of the perovskite / crystalline silicon tandem solar cell using the tin dioxide thin film as the composite layer and the ICO as the composite layer in Example 4. DETAILED DESCRIPTION

[0025] In the following description, specific details such as specific system structures and techniques are provided for purposes of illustration rather than limitation to facilitate a thorough understanding of the embodiments of the present application. However, it will be apparent to those skilled in the art that the present application may be implemented in other embodiments without these specific details. In other cases, detailed descriptions of well-known systems, devices, circuits, and methods are omitted to avoid obscuring the description of the present application with unnecessary detail.

[0026] It should be understood that when used in the present specification and the appended claims, the term "comprising" indicates the presence of described features, integers, steps, operations, elements and / or components, but does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or collections thereof.

[0027] It will also be understood that the term "and / or" used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.

[0028] As used in this specification and the appended claims, the term "if" can be interpreted as "when" or "upon" or "in response to determining" or "in response to detecting," depending on the context. Similarly, the phrase "if it is determined" or "if [described condition or event] is detected" can be interpreted as meaning "upon determination" or "in response to determining" or "upon detection of [described condition or event]" or "in response to detecting [described condition or event]," depending on the context.

[0029] In addition, in the description of the present application specification and the appended claims, the terms "first", "second", "third", etc. are only used to distinguish the descriptions and cannot be understood as indicating or implying relative importance.

[0030] References to "one embodiment" or "some embodiments" in this specification mean that a particular feature, structure, or characteristic described in conjunction with that embodiment is included in one or more embodiments of the present application. Thus, phrases such as "in one embodiment," "in some embodiments," "in other embodiments," and "in other embodiments" appearing in various places in this specification do not necessarily refer to the same embodiment, but rather mean "one or more but not all embodiments," unless otherwise specifically emphasized. The terms "including," "comprising," "having," and variations thereof all mean "including but not limited to," unless otherwise specifically emphasized. Example 1

[0031] This embodiment provides a method for preparing a perovskite / crystalline silicon tandem solar cell with a tin dioxide thin film as a composite layer, comprising the following steps: Step 1: Select N type <100> The CZ silicon wafer was used as the substrate and immersed in 2% hydrofluoric acid for 1 minute to remove the surface oxide layer and obtain the N-type single crystal silicon layer in the battery structure.

[0032] Step 2: Take the silicon wafer prepared in step 1 and use plasma enhanced chemical vapor deposition (PECVD) to prepare 7 nm and 10 nm intrinsic amorphous silicon passivation layers on the light-receiving side and backlight side of the silicon wafer, respectively, which are the first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer.

[0033] Step 3: Take the silicon wafer prepared in step 2 and, using the same PECVD technology, prepare a 12 nm P-type doped amorphous silicon hole transport layer on the first intrinsic amorphous silicon passivation layer on the light-receiving surface.

[0034] Step 4: Take the silicon wafer prepared in step 3 and prepare an N-type heavily doped amorphous silicon electron transport layer on the second intrinsic amorphous silicon passivation layer on the backlight side using PECVD technology.

[0035] Step 5: Take the silicon wafer prepared in step 4 and prepare a tin dioxide composite layer and an electron transport layer on the P-type doped amorphous silicon hole transport layer by spin coating, wherein the tin dioxide composite layer is prepared at a rotation speed of 5000 r / min, and the electron transport layer is prepared at a rotation speed of 2000 r / min.

[0036] Step 6: Take the sample with the electron transport layer prepared in step 5, prepare a perovskite film on it using a spin coating method, and obtain a perovskite light absorbing layer after annealing at 100°C.

[0037] Step 7: Take the sample of the perovskite light absorbing layer prepared in step 6, and prepare a hole transport layer thereon using a spin coating method.

[0038] Step 8: Take the sample prepared in step 7 and grow a first transparent conductive layer and a second transparent conductive layer thereon using reactive plasma deposition (RPD) technology.

[0039] Step 9: Take the sample prepared in step 8 and use thermal evaporation technology to prepare light-receiving side electrode silver grid lines and backlight side silver electrodes. Example 2

[0040] This embodiment provides a method for preparing a perovskite / crystalline silicon tandem solar cell with a tin dioxide thin film as a composite layer, comprising the following steps: Step 1: Select N type <100> The CZ silicon wafer is used as the substrate and immersed in 2% hydrofluoric acid for 2 minutes to remove the surface oxide layer and obtain the N-type single crystal silicon layer in the battery structure.

[0041] Step 2: Take the silicon wafer prepared in step 1 and use plasma enhanced chemical vapor deposition (PECVD) to prepare 6 nm and 8 nm intrinsic amorphous silicon passivation layers on the light-receiving side and backlight side of the silicon wafer, respectively, which are the first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer.

[0042] Step 3: Take the silicon wafer prepared in step 2 and, using the same PECVD technology, prepare a 10 nm thick P-type doped microcrystalline silicon hole transport layer on the first intrinsic amorphous silicon passivation layer on the light-receiving surface.

[0043] Step 4: Take the silicon wafer prepared in step 3 and prepare an N-type doped microcrystalline silicon electron transport layer on the second intrinsic amorphous silicon passivation layer on the backlight side using PECVD technology.

[0044] Step 5: Take the silicon wafer prepared in step 4 and use magnetron sputtering to prepare a tin dioxide composite layer and an electron transport layer on the P-type doped microcrystalline silicon hole transport layer, wherein 1.2 sccm H2 doping is used to prepare the tin dioxide composite layer, and 40 sccm O2 doping is used to prepare the electron transport layer.

[0045] Step 6: Take the sample with the electron transport layer prepared in step 5, prepare a perovskite film on it using a spin coating method, and obtain a perovskite light absorbing layer after annealing at 100°C.

[0046] Step 7: Take the sample of the perovskite light absorbing layer prepared in step 6, and prepare a hole transport layer thereon using a spin coating method.

[0047] Step 8: Take the sample prepared in step 7 and grow a first transparent conductive layer and a second transparent conductive layer thereon using reactive plasma deposition (RPD) technology.

[0048] Step 9: Take the sample prepared in step 8 and use thermal evaporation technology to prepare light-receiving side electrode silver grid lines and backlight side silver electrodes. Example 3

[0049] This embodiment provides a method for preparing a perovskite / crystalline silicon tandem solar cell with a tin dioxide thin film as a composite layer, comprising the following steps: Step 1: Select N type <100> The CZ silicon wafer was used as the substrate and immersed in 2% hydrofluoric acid for 1 minute to remove the surface oxide layer and obtain the N-type single crystal silicon layer in the battery structure.

[0050] Step 2: Take the silicon wafer prepared in step 1 and use plasma enhanced chemical vapor deposition (PECVD) to prepare 7 nm and 10 nm intrinsic amorphous silicon passivation layers on the light-receiving side and backlight side of the silicon wafer, respectively, which are the first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer.

[0051] Step 3: Take the silicon wafer prepared in step 2 and, using the same PECVD technology, prepare a 12 nm P-type heavily doped amorphous silicon hole transport layer on the first intrinsic amorphous silicon passivation layer on the light-receiving surface.

[0052] Step 4: Take the silicon wafer prepared in step 3 and prepare an N-type doped amorphous silicon electron transport layer on the second intrinsic amorphous silicon passivation layer on the backlight side using PECVD technology.

[0053] Step 5. Take the silicon wafer prepared in step 4, and for one part, use reactive plasma deposition to prepare a tin dioxide composite layer and an electron transport layer on the P-type heavily doped amorphous silicon hole transport layer, wherein the tin dioxide composite layer is prepared by 1.2 sccmH2 doping, and the electron transport layer is prepared by 40 sccmO2 doping; for the other part, use reactive plasma deposition to prepare an ICO composite layer and a tin dioxide electron transport layer on the P-type heavily doped amorphous silicon hole transport layer.

[0054] Step 6: Take the two samples of the electron transport layer prepared in step 5, prepare a perovskite film on them using a spin coating method, and obtain a perovskite light absorbing layer after annealing at 100°C.

[0055] Step 7: Take the two samples of the perovskite light absorbing layer prepared in step 6 and prepare a hole transport layer thereon using a spin coating method.

[0056] Step 8: Take the two samples prepared in step 7 and grow a first transparent conductive layer and a second transparent conductive layer thereon using reactive plasma deposition (RPD) technology.

[0057] Step 9: Take the two samples prepared in step 8 and use thermal evaporation technology to prepare light-receiving side electrode silver grid lines and backlight side silver electrodes. Example 4

[0058] This embodiment provides a method for preparing a perovskite / crystalline silicon tandem solar cell with a tin dioxide thin film as a composite layer, comprising the following steps: Step 1: Select N type <100> The CZ silicon wafer was used as the substrate and immersed in 2% hydrofluoric acid for 1 minute to remove the surface oxide layer and obtain the N-type single crystal silicon layer in the battery structure.

[0059] Step 2: Take the silicon wafer prepared in step 1 and use plasma enhanced chemical vapor deposition (PECVD) to prepare 7 nm and 10 nm intrinsic amorphous silicon passivation layers on the light-receiving side and backlight side of the silicon wafer, respectively, which are the first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer.

[0060] Step 3: Take the silicon wafer prepared in step 2 and, using the same PECVD technology, prepare a 12 nm P-type heavily doped amorphous silicon hole transport layer on the first intrinsic amorphous silicon passivation layer on the light-receiving surface.

[0061] Step 4: Take the silicon wafer prepared in step 3 and prepare an N-type doped amorphous silicon electron transport layer on the second intrinsic amorphous silicon passivation layer on the backlight side using PECVD technology.

[0062] Step 5: Take the silicon wafer prepared in step 4, and prepare a tin dioxide composite layer on the P-type heavily doped amorphous silicon hole transport layer by reactive plasma deposition on one part; and prepare a tin dioxide electron transport layer on the other part by spin coating.

[0063] Step 6: Take the two samples of the electron transport layer prepared in step 5, prepare a perovskite film on them using a spin coating method, and obtain a perovskite light absorbing layer after annealing at 100°C.

[0064] Step 7: Take the two samples of the perovskite light absorbing layer prepared in step 6 and prepare a hole transport layer thereon using a spin coating method.

[0065] Step 8: Take the two samples prepared in step 7 and grow a first transparent conductive layer and a second transparent conductive layer thereon using reactive plasma deposition (RPD) technology.

[0066] Step 9: Take the two samples prepared in step 8 and use thermal evaporation technology to prepare the silver grid lines of the light-receiving side electrode and the silver electrode of the backlight side. The IV curves of the two stacked solar cell structures are as follows: Figure 2 shown.

[0067] The above-described embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present application, and should all be included in the scope of protection of the present application.

Claims

1. The present invention provides a perovskite / crystalline silicon tandem solar cell structure with a tin dioxide thin film as a composite layer. This cell structure is a formal tandem structure, and its specific structure, from top to bottom, is as follows: a light-receiving side electrode silver grid line, a first transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a tin dioxide composite layer, a P-type doped silicon hole transport layer, a first intrinsic amorphous silicon passivation layer, an N-type single crystal silicon layer, a second intrinsic amorphous silicon passivation layer, an N-type doped silicon electron transport layer, a second transparent conductive layer, and a backlight side silver electrode; The first transparent conductive layer and the second transparent conductive layer are indium oxide-based transparent conductive oxide materials, and are made of one or more materials selected from the group consisting of indium tin oxide (ITO), indium tungsten oxide (IWO), indium zinc oxide (IZO), and indium cerium oxide (ICO); The hole transport layer is a P-type semiconductor material, and is made of one or more of molybdenum oxide, nickel oxide, 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), poly[bis(4-phenyl)(4-butylphenyl)amine] (Poly-TPD), and poly(3-hexylthiophene-2,5-diyl) (P3HT); The electron transport layer is a tin dioxide thin film, and by controlling the preparation parameters of the growth process, the performance different from that of the tunneling composite layer is obtained; The first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer are intrinsic amorphous silicon passivation layers on the light-receiving side and the backlight side respectively; The P-type doped silicon hole transport layer can be made of one or more materials selected from the group consisting of P-type doped amorphous silicon, P-type doped nanocrystalline silicon, P-type doped microcrystalline silicon, P-type doped polycrystalline silicon, P-type doped amorphous silicon oxide, P-type doped nanocrystalline silicon oxide, and P-type doped microcrystalline silicon oxide by controlling the growth process and process parameters; The N-type doped silicon electron transport layer can be made of one or more materials selected from N-type doped amorphous silicon, N-type doped nanocrystalline silicon, N-type doped microcrystalline silicon, N-type doped polycrystalline silicon, N-type doped amorphous silicon oxygen, N-type doped nanocrystalline silicon oxygen, and N-type doped microcrystalline silicon oxygen by controlling the growth process and process parameters.

2. The present invention provides a method for preparing the perovskite / crystalline silicon tandem solar cell structure according to claim 1, characterized in that: The preparation method of the perovskite / crystalline silicon tandem solar cell structure comprises the following steps: Step 1: Select N type <100> The CZ silicon wafer is used as the substrate and immersed in 2% hydrofluoric acid for 1 minute to remove the surface oxide layer and obtain the N-type single crystal silicon layer in the battery structure; Step 2: Take the silicon wafer prepared in step 1 and use plasma enhanced chemical vapor deposition (PECVD) to prepare intrinsic amorphous silicon passivation layers on the light-receiving side and the backlight side of the silicon wafer, respectively, which are the first intrinsic amorphous silicon passivation layer and the second intrinsic amorphous silicon passivation layer; Step 3: Take the silicon wafer prepared in step 2 and, on the first intrinsic amorphous silicon passivation layer on the light-receiving surface, also use PECVD technology to prepare a P-type doped silicon hole transport layer thereon; Step 4: Take the silicon wafer prepared in step 3 and prepare an N-type doped silicon electron transport layer on the second intrinsic amorphous silicon passivation layer on the backlight side using PECVD technology; Step 5: Take the silicon wafer prepared in step 4 and grow a tin dioxide composite layer and an electron transport layer on the P-type doped silicon hole transport layer; Step 6: Take the sample prepared with the electron transport layer in step 5, prepare a perovskite film on it by spin coating, and obtain a perovskite light absorbing layer after annealing at 100-120°C; Step 7: Take the sample of the perovskite light absorbing layer prepared in step 6 and prepare a hole transport layer thereon; Step 8: Take the sample prepared in step 7 and grow a first transparent conductive layer and a second transparent conductive layer on it using reactive plasma deposition (RPD) technology; Step 9: Take the sample prepared in step 8 and use thermal evaporation technology to prepare light-receiving surface electrode silver grid lines and backlight surface silver electrodes; The preparation methods of the tin dioxide composite layer and the electron transport layer in step 5 include magnetron sputtering, spin coating, atomic layer deposition, reactive plasma deposition, etc.

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